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BACKGROUND OF THE INVENTION
In the container filling industries, liquid filling machines are sometimes used to fill containers with products which require heating to elevated temperatures above ambient in order to be successfully placed into the selected container. In many cases the product must be heated in order to allow the filling machine to successfully move the product through the filling apparatus itself.
In the past, when these requirements have been encountered, numerous solutions have been attempted. These have included heating means such as surrounding the complete filling apparatus with an insulated and heated room or tracing the filling apparatus with suitable heating elements in order to add heat energy to the system. In another case, radiant heat lamps are placed in close proximity to the filling mechanism in order to raise the temperature of the mechanism. In still another case known in the prior art (U.S. Pat. No. 4,142,561), a cabinet is placed around the filling apparatus and heated by injection of heated air from a blower and heater located in the base of the machine. In this arrangement, the filling tubes, used to deliver heated product into the container packages, are specified to periodically be lowered in such a way that they leave the heated enclosure and are positioned about or in the container packages. The container packages are suitably disposed to receive the filling tubes by being positioned on a conveyor. The conveyor is below and outside of the heated enclosure.
This last method offers substantial improvements over the previously cited means of temperature control, but is never-the-less burdened with numerous shortcomings. Among these are that the heated cabinets of known type are of a simple construction with loose fitting single panels. These single panels, generally of transparent plastic, allow substantial heat loss from the area they enclose by their very nature. Further, much hot air is lost by substantial leakage about and around the lossely fitted dpanels. Taken together, these means cause substantial heat loss and severely limit the maximum temperature above ambient to which the enclosure can be elevated, and result in very poor energy efficiency.
Another limitation of the previous heated enclosure designs concerns the variations of relative temperatures within the heated enclosure. Because of the leaky design and the variable placement of apparatus within the heated area and the well recognized property of hot air to rise, the temperature within the heated area can vary by many degrees centigrade from bottom to top of the heated area and within the heated enclosure. This temperature variance is frequently too great and too random as to be allowable and useful in controlling the filling characteristics of many products.
Another problem associated with heated enclosure liquid fillers of previously known types concerns the specified placement of the product container conveyor outside of the heated enclosure and the specified movement of the filling tubes to an area outside of the heated enclosure and above the conveyor during filling. Taken separately and together, this arrangement requires that the filling nozzles be outside of the heated area for a substantial period of time during the actual fluid dispensing period. This period would commonly be of a duration of one to ten seconds, and can be of adequate time for product to thicken or solidify on the filling tubes, particularly at the very tips thereof, and particularly when the product is only slightly elevated above its solidification temperature as is commonly and sensibly the practice.
A further limitation of known heated enclosure liquid fillers concerns operation of such a machine in a hazardous or flammable environment. It is well understood that many products requiring heating for filling give off vapors and gases which can be hazardous or flammable. The use of a motor and blower in conjunction with electrically controlled heaters contained within the machine, as is the case with the previously known types, therefore creates a hazardous and unsafe condition and is thus not allowed.
Still another limitation associated with the single panel construction of heated filling machine enclosures of previous type concerns machine operator safety. Because the enclosure's panels are loose fitting and free moving, it is possible for a person to open the enclosure while the air within is at elevated temperature. This can result in a large discharge or release of heated air onto and about the operator. When such air is at or above about 60° centigrade the operator can experience pain and injury from such exposure. Even when a panel is not opened by an operator, a single layer panel which is touched by an operator when the panel is at or about 60° centigrade will cause pain. At a temperature of about 66° centigrade, skin contact with a panel can cause burns.
Another problem associated with heated enclosure liquid fillers of known type is that the containers into which the heated product is to be dispensed are at ambient temperature. This frequently causes uneven and accelerated cooling and solidification of many heated products. This, in turn, can cause undesirable distortions of the container or product body or even rapid cooling induced separation of the product from the containers wall, or irregular and random changes in product color or texture, or surface appearance.
OBJECTS AND SUMMARY OF THE INVENTION
It is a primary object of the present invention to overcome the numerous disadvantages of heated enclosure liquid fillers of the prior art as set forth above. More specifically, it is the primary object of the present invention to provide a liquid filling machine in which the container conveyor enters a temperature controlled heated enclosure on one side and passes through it and exits on the opposite side, the filling nozzle(s) being within the heated enclosure so that the filling nozzles need never pass out of or leave the temperature controlled enclosure which has tightly and permanently sealed panels free of air leaks and which has a double wall construction with a trapped air space in between the panels, and to provide a heated enclosure which has air jets of heated air located within.
It is a further object of this invention to provide a temperature controlled filling machine which has the forced air heat source located sufficiently remotely from the machine to allow operation in hazardous environments; which has a locking mechanism to prevent entry into the enclosure while its temperature is above a specified level; which provides for a period of forced air circulation at ambient temperature prior to allowing cabinet entry; and which provides for the heating of containers within the cabinet prior to, or during filling.
The present invention relates to a unique and novel means whereby the container conveyor passes through the heated enclosure. By this unique means, the actual dosing procedure, by whatever means and involving one or more filling nozzles is carried out entirely within the temperature controlled cabinet. Because the nozzle tubes never leave the cabinet this, in turn, ensures that the filling nozzles cannot be reduced in temperature during filling which prevents the build-up of solidified or thickened product on or about these nozzles. This aspect of the present invention is particularly important in allowing only a slight elevation of the product and apparatus temperature above that required for the particular case. This allows successful operation on products where overheating is detrimental to product properties or characteristics and further offers much reduced heating costs by reducing the level of heating required.
The present invention further provides for a sealed cabinet in which the heated air exits essentially only from the apertures through which the conveyor enters and exits, said apertures being of the smallest practical dimensions allowable, and said apertures being adjustable as necessary from time to time to allow minimum dimensioning as the specific filling case will allow. This approach allows a predictable and controllable heated enclosure environment in which temperature controlled air loss is held to the absolute minimum and in which it is possible to regulate temperatures in a predictable way. In the present invention, temperature control is actively controlled within the enclosure by use of relatively high velocity temperature controlled air jets. This novel method, in which a main flow of air into the cabinet from a remote source is sub-divided in such a way that separate flows can be directed as necessary to achieve desired temperatures within particular sections or regions of the enclosure. It is particularly important to note that this allows equilibration of temperature within the cabinet regardless of dimensions or inclusions of apparatus within; and equally important in other cases, allows the establishment of separate temperatures in various sections or regions of the cabinet as desired. This capability is particularly important in that additional thermal energy can be precisely delivered onto or about very specific sections of apparatus. Thus, for example, additional heating can be carried out on a device which is particularly prone to accelerated heat loss, as, for example, when a portion of the filling mechanism is fastened to a portion of the machine frame causing accelerated heat loss therefrom.
The ability to direct heat energy variably and separately is particularly crucial when a filling machine is operated at comparatively high elevated temperatures about ambient, as for example up to 125° centigrade. As will presently be explained, operation at these relatively extreme temperatures requires this novel heat control method to be successful.
Still another object of this invention is to allow its operation with flammable products or in hazardous areas. It is well understood and recognized that electrically powered heaters and blowers are not safe in such areas. Thus, this invention provides for a completely separate and isolated heating module which contains all means of heating and blowing air. The air is then novelly directed to the heated filling machine enclosure using a flexible duct of double wall construction with insulation placed between the flexible duct walls, said ducting being constructed of suitable high temperature materials. A double wall duct construction allows the duct to be placed and handled safely even when high temperature air is passing through it.
By remote placement of the heating elements, the air forced into the system can be of known quality and can be assured of being free of any hazardous vapors. Furthermore, all sources of ignition associated with the heating have been removed, the distance of remoting is variable and, in practical terms, substantially unlimited, but in any event is easily greater than twenty-five feet. The heater mechanism in the present invention is controlled by electronic means, with the temperature sensing being accomplished within the cabinet and the level being safely sent to the heater apparatus using intrinsically safe barriers of suitable type.
Another novel aspect of the current invention is that in addition to controlling the temperature of the air being sent to the filling machine, the volume of air is controlled as well. This is a fundamentally important advancement in the state-of-the-air in that it allows a relatively high volume of air at relatively high temperature to be delivered early on in the heat-up process, but then allows a much reduced volume of air at precisely the required final temperature to be delivered to the cabinet, in such a way as to reduce the total thermal energy requirements to the absolute minimum required to maintain a desired temperature. This improvement in efficiency is substantial and can lower energy costs in such a system by a very substantial amount. This efficiency of operation is particularly important in operating a cabinet enclosed filling machine at temperatures about 100° centigrade, where machines of previously known type cannot reach or be maintained in temperature.
Another very important object of the present invention is the unique double wall construction utilized to fashion the heated enclosure. By utilizing an inner panel, frequently of tempered glass, to allow exposure to temperatures well above those allowable with most plastics, said panel being sealed to its supporting frame by common glazing materials, a first heat barrier is established. By constructing an outer panel support frame and affixing and sealing to it an outer panel of metal or plastic or glass, an air barrier of trapped air of suitable dimensions between panels is established. Thus, this air space serves as a second co-existing heat barrier. The outer panel, unto itself, serves as a third co-existing heat barrier. Taken separately, but most crucially as a three barrier structure, this novel arrangement substantially reduces the rate of heat energy loss from the cabinet. This, in turn, greatly reduces the required heat energy to maintain a given temperature above ambient, and this, in turn, greatly lowers the operating costs associated with this machine. These efficiencies and savings are particularly important when the cabinet is operated at particularly high temperatures, since the greater the temperature elevation, the greater the rate of heat loss. It is also important to understand that this reduced rate of heat loss method allows the system to reach much higher operating temperatures than would otherwise be the case, and to do so with a remote heater module of much less wattage capability than would otherwise be the case.
Another novel aspect of the three barrier temperature enclosure of the present invention is its operator safety improvements. Because of the previously described construction of the heated cabinet, the outer wall is only relatively warm to the touch when exposed skin is placed against it. This is true, even for a cabinet operating with an internal temperature of 120° centigrade. Thus, the risk of burns or pain associated with the operation of heated filling machines of previously known types is essentially eliminated.
A further novel aspect of the present invention is that the afore-described heated enclosure is equipped with access doors which are hinged and fitted with a locking mechanism, and are substantially sealed when closed. The locking mechanism is pneumatically operated and thus safe for use even in hazardous environments. In operation, when the heated cabinet reaches a temperature judged in the particular case to be unsafe for operating personnel, the pneumatic lock engages, effectively preventing entry into the interior of the cabinet and thus substantially reducing the risks of injury or pain to said operators. Likewise, when the temperature of the enclosure decends to one below which entry in the interior of the cabinet is safe, the locking mechanism disengages. This apparatus is controlled by sensing the temperature within the cabinet using the same sensor which controls the remotely located heating apparatus or by separate sensor means where further safety enhancement is desired.
Still a further novel feature of the present invention is the use of an intrinsically safe cabinet door interlock switch which prevents the operation of the remote heater whenever the outer wall door cabinet is in an open condition.
A further novel aspect of this invention is the use of a blow-down or cooling sequence when cabinet entry is desired. By intrinsically safe electronic means, the operator may cause the remotely located heating apparatus to be turned off, but the air blower mechanism to remain on at high flow rate. This way, hot air is rapidly forced from the cabinet, greatly reducing the time required to allow safe entry thereto.
An additional novel feature of this invention is the ability of the machine to place product containers completely within the boundaries of the heated enclosure, prior to and during filling. This is possible because of the novel feature of this invention wherein the product container conveyor runs completely though the heated chamber. Because this is so, the containers have a definite residence time within the heated area. Because this is the case, the containers can be heated to some degree above the ambient temperature, particularly on the immediate outer surfaces thereof. This unique feature can have the most beneficial role of allowing less precipitous heat loss from the quantity of product being placed into the container. Thus, the problems associated with too rapid cool down of some products, such as crystallization, changes in color, texture, clarity or chemical changes or separation of various constituents of the product are reduced or avoided.
The foregoing objects and advantage of this invention will become more apparent to one having ordinary skill in the art after a consideration of the following detailed description taken in conjunction with the accompanying drawings in which a preferred form of this invention is illustrated.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front elevational view of the liquid filling machine of this invention.
FIGS. 2 and 3 are side elevation and top views of the liquid filling machine shown in FIG. 1, the upper conveyor flight being omitted in FIG. 3 for purposes of clarity.
FIG. 4 is an enlarged side view of a portion of the liquid filling machine shown in FIG. 2.
FIG. 5 is a sectional view taken generally along the line 5--5 in FIG. 1.
FIGS. 6 and 7 are further sectional views, these views being taken generally along the lines 6--6 and 7--7 in FIG. 1.
FIG. 8 is a sectional view taken generally along the line 8--8 in FIG. 1.
FIG. 9 is a view similar to FIG. 7 but showing an embodiment of an electrical cabinet door interlock switch and key, this view being taken generally along the line 9--9 in FIG. 3.
FIG. 10 is a schematic view illustrating the controls of the embodiment shown in FIGS. 1-9.
DETAILED DESCRIPTION
With reference initially to FIGS. 1, 2 and 3, the liquid filling machine of this invention is indicated generally at 10. The machine includes a frame and housing 12 (FIG. 1) upon which the major components of this invention are mounted. Thus, a product reservoir 14 is carried by the housing 12 as well as a filling nozzle 16. The filling nozzle may be mounted in a stationary manner, but it is preferably interconnected with a diving mechanism 18 carried on the top of the housing, the diving mechanism permitting the filling nozzle to enter into the top of the container to be filled. The product reservoir 14 and filling nozzle 16 are interconnected with each other by flow control means indicated generally at 20 in FIG. 2. Various different types of flow control means can be utilized and in the very simplest form, it may be simply an on-off valve which permits the flow from the reservoir to the filling nozzle when open, and which will prevent the flow when closed. In the embodiment illustrated in this invention though, the flow control means is a pump 22 which is driven by a pump motor 24. While the pump 22 may be connected directly to the output shaft of the motor 24, in the embodiment illustrated it is magnetically coupled to the output of the motor 24. Thus, with reference to FIG. 2, it can be seen that during the operation of the pump 22, product to be filled will flow from the reservoir 14 through a first product conveying tube 26 to the pump 22 and from the pump 22 through a second product conveying tube 28 to the filling nozzle 16.
In order to present suitable containers 30 which are to be filled by the liquid filling machine of this invention, a conveyor 32 is provided, the conveyor including a sub-frame 34 which may be supported by an auxiliary support 36, a conveyor motor 38, drive sprockets 40, and driven sprockets 42. Extending between the sprockets 40 and 42 is a conveyor chain 44. The conveyor chain has a lower flight (or return flight) 44.1 which is supported in part by conveyor return rails 46 (FIG. 5), the conveyor return rails in turn being mounted within a conveyor housing 48 supported by brackets 12.1 on the front of the frame housing 12. Mounted on the upper surface of the conveyor housing 48 are conveyor standoffs 50. The conveyor standoffs 50 in turn support the upper flight 44.2 of the conveyor chain. As can be seen from FIG. 5, each of the cross links of the conveyor chain are provided with suitable lugs 44.3 which are engaged by the drive sprockets 40 for the purpose of driving the chain. The operation of the conveyor motor may be initiated from an operator control 52. In order to provide the container with lateral stability in the area where it is being filled, front and rear stabilizer rails 54 are provided. Each of the front and rear stabilizer rails are in turn mounted on an adjustable bar 56 which is in turn adjustably connected to a stabilizer support bracket via a threaded fastener 60 of any conventional design.
To a large extent, the filling machine so far described is of a type well known in the prior art. As pointed out above, the disadvantage of this form of filling machine, so far described, is in the handling of product which is either solid or highly viscous at room temperature. Accordingly, it is a feature of this invention to provide an enclosure to totally enclose the reservoir 14, filling nozzle 16, and the container while it is in the environment of the filling nozzle. To this end, an enclosure, indicated generally at 62, is provided. In the preferred design of this invention, the enclosure is double walled, having essentially one enclosure within another. The inner and outer enclosures can be considered as cabinets, the back of the cabinets being part of the housing 12. The brackets 12.1 additionally support an inner enclosure indicated generally at 64 in FIG. 2 and an outer enclosure indicated generally at 66. The bottom of each of the enclosures is formed of a steel plate 68 supported by the brackets 12.1. Supported upon the steel plate along the sides thereof are lower horizontal frame members for each of the enclosures, each of the lower side frame members having a generally inverted U-shaped portion as can best be appreciated from an inspection of FIGS. 2 and 4. Thus, the right horizontal frame member 70 for the outer enclosure has an inner horizontal lower side portion 70.1, an intermediate inverted U-shaped portion 70.2, and an outer horizontal lower side frame portion 70.3. It should be appreciated that the left horizontal lower side frame member 70 for the outer enclosure will have an identical structure to that of the right horizontal lower side frame member 70 shown in FIG. 4. In addition, the right and left horizontal lower side frame members 70 for the inner enclosure 64 will be essentially the same as those for the outer enclosure except that each will have a shorter outer portion 70.3. The rear end of each of the horizontal lower side frame members 70 will be connected to a rear vertical frame member 72 which abuts in air tight contact the front wall of the housing 12. Secured to the outer end of the outer portion 70.3 of each of the horizontal lower side frame members 70 is a front vertical frame member 74. The upper end of each of the rear and front vertical frame members in turn supports a horizontal upper side frame member 76. As can be seen from the above, the side of each enclosure is framed by frames 70, 72, 74 and 76. The inner enclosure 64 has side walls formed of a sheet of tempered glass 78, the glass being held in place within the frame 70, 72, 74, 76 by a glazing strip 80 and a silicone seal 82. The outer enclosure is provided with side walls formed of a clear polycarbonate, each sheet of polycarbonate 84 being secured in place by a glazing strips 86 and 88.
It can be seen from FIGS. 1, 2 and 4 that the conveyor housing 48 extends entirely through the outer and inner enclosures 64, 66 respectively. The conveyor housing is sealed against the sides of the for the inner enclosure 64 shaped members 70.2. However, there is an opening above the conveyor housing in the sides for the entry of the upper flight of the conveyor and the containers carried thereon. As the inner enclosure will be provided with forced hot air for heating purposes, it is desired to minimize the loss of hot air from the inner enclosure. To this end, moveable aperture plates 90 are provided, each aperture plate being provided with a suitable cutout, so that when they are in abutting positions as shown in FIG. 4, they will receive the container 30 and the stabilizer rails 54. The moveable aperture plates are supported by aperture guides 92 which are suitably fastened to the clear polycarbonate wall 84 of the outer enclosure by suitable fasteners 94. It should be appreciated that if a container of a different size than that shown in FIG. 4 is to be filled, the aperture plates 90 may be removed and other suitable aperture plates may be substituted therefor. In the preferred design of this invention aperture plates are provided only on the outer enclosure. However, if the heat loss is unacceptable when aperture plates are provided only on the outer enclosure, it may be desirable to add similar aperture plates to the inner enclosure.
The front of each of the enclosures is closed by a suitable door. Thus, the inner enclosure is closed by a suitable door 96, and the outer enclosure is closed by a suitable outer door indicated generally at 98. As can best be seen from FIG. 1, the outer door is formed of a rectangular frame 100, having lower and upper horizontal frame members 100.1, 100.2 respectively, and left and right vertically extending frame members 100.3 and 100.4 respectively. A sheet of clear polycarbonate 102 is mounted within the frame 100 via a glazing strip 104 and a silicone seal 106. The door 98 is hinged to the left front vertical frame member via a piano hinge 108, the hinge 108 being secured to the vertically extending frames 74 and 100.3 by conventional fasteners not shown. The outer door can be opened by engaging a door knob 110 mounted on the right vertical frame member 100.4. A suitable mechanical latch (not illustrated) may be provided for holding the outer door in its closed position. When the door is closed it will abut a stop not shown.
With reference now to FIGS. 1 and 6, the inner door is formed in essentially the same manner as the outer door. Thus, there is an inner door frame 118 having a lower horizontal frame member 118.1, an upper horizontal frame member 118.2, a left vertical frame member 118.3, and a right vertical frame member 118.4. Tempered glass 120 is mounted within the door frame 118 and is secured in place via a glazing strip 122 and a silicone seal 124. This door is also hinged by a piano hinge 126 to the left vertical frame member 74 of the inner enclosure 64. A door knob 128 is provided for opening and closing the inner door. In order to hold the door 96 in its locked position, an air operated door interlock is provided, the interlock being indicated at 112. The interlock has a latch 114 which, when extended to the left as viewed in FIG. 7, will enter a suitable aperture within the door frame 118.4 to hold it in its latched position. The air operated door interlock is operated via pressurized factory air which is suitably controlled in a manner to be set forth below. However, it should be noted that when air under pressure is introduced into the interlock 112 via air tube 116 that the latch 114 will be extended to the left as shown in FIG. 7. When the air pressure is removed a spring (not shown) will return the latch to its normal right hand position where the door is free to open.
In order to heat the product within the product reservoir 14 as well as the filling nozzles and other components within the enclosure 64 hot air is introduced into the inner enclosure 64 by a hot air duct indicated generally at 130. The hot air duct extends from the enclosures to a heater located outside of the enclosure. The hot air duct is well insulated, and to this end it is formed of an inner silicone duct 132 which is in turn wrapped with a ceramic fiber batting 134, the batting and inner duct in turn being received within a silicone outer duct 136. It has been found that with this design of a heating duct that a heater may be located outside of the enclosure at a distance of 25 feet or more. This is desirable when filling containers with highly flammable materials. The heater is indicated schematically at 138 in FIG. 10 and includes a variable output electric heater with a maximum output 10,000 watts. Air is blown over the heater 138 by a blower indicated schematically at 140. (The air received by the blower may be suitably filtered.) The blower is in turn driven by a variable speed electric motor 142. The heater 138 is preferably mounted within a tubular cartridge 144, the upstream end of which is connected to the discharge end of the blower 140, and the downstream end of the tubular cartridge being in turn connected to the hot air duct 130. The heater 138 and motor 140 are both connected via power lines 146 to a suitable source of electric current. The rotational speed of the motor 142 is controlled by control signals carried by control line 148 and the output of the variable output electric heater is controlled by control signals carried by control line 150.
In operation, the operator of the machine will dial in the temperature that is necessary to be maintained for the proper operation of the filling machine. For example, if dealing with a material which is highly viscous at room temperature, it will be necessary to dial in the proper temperature where the material will properly flow though the flow control means to the container. Thus, it may be desirable to maintain the enclosure at 80° C. which temperature will be dialed in by the operator. Once the proper temperature has been established, the operator will initiate operation by pushing the start button 154. When the start button is pushed, the control mechanism 156 will send signals through the motor control line and heater control line to cause the heater to be operated at full output and the motor to be operated at a speed to most quickly heat the enclosure. A sensor 158 is mounted within the enclosure and when a suitable operating temperature has been achieved it will be sensed by the control mechanism 156 which will in turn send further control signals through the motor control line 148 and heater control line 150 to adjust their outputs to the most efficient operation. In the meantime the operation of the conveyor belt will be initiated to bring containers into the machine so that they can be suitably filled and discharged. An interlock will prevent operation of the conveyor if the inner enclosure is not at the desired temperature. The control mechanism will also send a signal through a control line 160 to a valve 162 which is connected to factory air indicated by tube 164, the valve normally being closed, but being opened when the temperature within the enclosure at the location of the sensor reaches a certain level which is considered dangerous to the operator. Air will then flow through the air line 116 to the air operated interlock 112 to cause the latch 114 to be extended. It should be noted that if the air temperature within the enclosure varies that through the sensor 158 and suitable controls that the thermal output of the heater 138 may be varied so as to adequately maintain a relatively constant temperature within the enclosure. This is a desirable feature in order to maintain proper operating efficiencies. In addition, by employing the double walled enclosure with the air barrier between the walls a very energy efficient system has been developed.
At the completion of the operation, the operator will stop the operation by hitting the stop button 166. This will immediately turn off the heater and increase the speed of the blower to its maximum rated output to quickly cool down the enclosure. Once the enclosure has been suitably cooled down, it may be possible to open the door as the latch 114 will become disengaged from the door.
It should be noted that it has been found that it is necessary to direct the hot air received within the enclosure. Thus, the hot air duct is connected to a fitting 168 within the inner enclosure 64. The fitting is in turn is provided with suitable air jets 170. In order to prevent excessive heat transfer away from the pump 22, one of the air jets is connected to an air tube 172 which is directed directly at the pump 22.
In the design described above the inner door 96 can only be opened when the temperature within the inner enclosure 64 is below a predetermined temperature at which time the air operated door interlock latch 114 is withdrawn to permit the opening of the door. In some situations the temperature within the enclosure is not sufficiently high to be dangerous to the operator in which case the door interlock may be omitted. However, in all cases it is desirable to use an electrical door interlock which is illustrated at the top left hand corner of FIG. 2 and in FIG. 9. In this design an electrical door interlock key 174 is provided which, when in its locking position, will engage an electrical door interlock switch 176. When the key 174 is removed to permit opening of the door 98, the electrical door interlock switch 176 will send a signal to the controller 156 to shut down the heater and run the blower on high until the enclosure temperature is reduced.
It should be apparent to one having ordinary skill in the art that by the employment of the foregoing design the objects of this invention have been achieved. While a preferred form of this invention has been described above and shown in the accompanying drawings, it should be understood that applicant does not intend to be limited to the particular details described above and illustrated in the accompanying drawings, but intends to be limited only to the scope of the invention as defined by the following claims. | A filling machine (10) for filling into containers (30), by volume, weight, or level, of products requiring maintenance of a specified temperature. The filling machine includes a product reservoir (14), a filling nozzle (16), a pump (22) and suitable tubes (26, 28) for controlling the flow of product from the reservoir to the nozzle. The above parts are disposed within a double walled enclosure (62). A conveyor (44) having an upper flight (44.2) which supports containers (30) to be filled via the filling nozzle enters and exits the enclosure. A heater (138) is located outside of the enclosure and is connected to the enclosure through an insulated air duct (130) so that forced hot air may be used for heating the enclosure. A heat sensor (158) is provided within the enclosure for controlling the flow of air into the enclosure and also for regulating the output of the heater. The enclosure is provided with two aligned doors (96, 98), and when these doors are opened a blow down cycle is initiated. | 1 |
RELATED APPLICATIONS
[0001] This application is a continuation-in-part of application Ser. No. 13/761,393 filed Feb. 7, 2013, which claims priority from CN201210166508.X filed May 25, 2012 and CN201210282678.4 filed Aug. 9, 2012, each of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The invention relates to a pet groomer and a vacuum cleaner includes the pet groomer.
BACKGROUND OF THE INVENTION
[0003] Generally, pet owners use brushes to comb their pet. The loose hair that combed from pets are comparatively thin and broken, easily flying with the wind, and can contain allergens or various bacteria and throw threats to or even destroy health of people, especially to children and sensitive people. Loose hair combed down by traditional brush can scatter in the air or on the ground or twined in comb teeth, user has to clear twined hair by hand from comb teeth. In the process, user is exposed to or even harmed by bacteria and/or allergen contained in pet hair. Besides, most comb teeth are relatively sharp and intensively arranged, so user may get hurt when clearing twined hair manually.
[0004] In order to solve the problems above, U.S. Pat. No. 6,681,775 (Wang) discloses a pet brush comprised of a front plate and a base plate, lots of holes corresponding to comb teeth are set in the front plate, with many comb teeth planted on base plate which extends outside of corresponding holes in the front plate, when it is necessary to comb a pet, user operate controlling key to extend comb teeth out, then the comb teeth withdraw from corresponding holes by operating the controlling key after pet hair combed, combed hair will be stripped off comb teeth by the front plate and then dumped into trash can. Since combed loose hair can scatter in all directions when falling into trash can from comb teeth, allergens and/or bacteria may spread to pollute environment, and besides, user has to operate the controlling key in every combing process to strip off hair in comb teeth and holding the pet brush, put it into the trash can. It is inconvenience and labor waste.
[0005] Based on the above, CN201010189748.2 discloses a vacuum cleaner attachment. The attachment can be connected with vacuum cleaning equipment through a pipe, the external wall of the pipe serves as an operating handle, the overlying front plate and base plate are at the other end of the pipe, many bristle-type comb teeth are planted in the base plate, the front plate has many holes and an air inlet connected with the main suction channel of vacuum cleaner, and comb teeth in the base plate extend or withdraw through holes in the front plate. A controlling key with a spring is set near the pipe handle, user operate the controlling key to move towards the pipe handle direction, to drive comb teeth to extend outwards through the holes on front plate and enter the combing status. After pet hair transferred to comb teeth, user relaxes finger to let comb teeth withdraw, meanwhile the airflow speed at the air inlet suction hole becomes higher to vacuum loose hair after it is stripped off comb teeth by the front plate. Since loose hair firstly stripped from comb teeth can fall down freely due to insufficient suction force of the main suction channel, and as the air intake direction is vertical to the front plate scattered with stripped hair, the pet hair which is at the rim of the front plate can't be completely vacuumed away easily. Furthermore, in order to avoid excessive suction force which affects comfort of pet, the suction force at the air intake hole cannot be too strong. In practice, hair stripped off from rim comb teeth can stuck on front plate after comb teeth withdrawn, user must extend and withdraw comb teeth repeatedly to move residual hair into suction hole completely, sometimes still have to use fingers to help in the final. This can obviously increase the chance of hair and allergen spreading to cause secondary pollution. Therefore, the risk that furs and allergens spread to cause secondary pollution can be increased. If there have fleas hide inside the hair combed down, they may be exposed in air on the front plate in the end of each incomplete stripping/vacuuming cycle and get chance to jump around. Many stripping and vacuuming cycles needed to comb a pet, incomplete vacuuming can multiply the chance of flea spreading. Moreover, the controlling key of the tool should be pressed to extend comb teeth outwards, and user should press the controlling key constantly during the combing process, it can be tiring for use. As the length of comb teeth is fixed, it is uneasy to control the length of comb teeth extended outside of the front plate to fit different pet hair length. Shorter extended teeth cannot comb deep enough for pets with thick hair, and longer extended teeth can hurt pets with thin hair. In order to maximize effective suction at the air inlet hole in the front plate, the tool welds different components together which makes it very difficult for consumer to replace comb teeth. If one or more comb teeth damaged, consumer will have to buy a new product. Besides, it is unavoidable that some pet hair drop in the gap of welded parts in use, it is hard for user to clean.
BRIEF SUMMARY OF THE INVENTION
[0006] Targeting at the problems above, the present invention provides a pet groomer which is used in conjunction with the suction hose of a vacuum cleaner, comprising: a substance body which has a suction channel that is used to be connected with the suction hose and has at least one air intake which transmits air to the suction channel; a combing assembly which is used to comb pet hair; and a driving assembly which drives said combing assembly so as to make comb teeth in combing assembly to move to the air intake from a comb position.
[0007] As the embodiment 1 of the invention, the pet groomer can also has the following features: the substance body also has a hollow front section which is placed outside of the air intake and the hollow front section has a comb use opening; the combing assembly is consisted of a rotating body and a plurality of groups of the comb teeth distributed in the axial direction of the rotating body; The rotating body is installed inside of the hollow front section, at least one group of the comb teeth extends outwards from the comb use opening to comb pet hair, and a rotation accepting assembly is set at one end of the rotating body; the driving assembly is formed from a knob drive assembly, the knob drive assembly has a drive unit and a knob in conjunction with the drive unit, the drive unit penetrates through aside wall of the hollow front section inosculating with the rotation accepting assembly, and the knob is exposed on external surface of the hollow front section.
[0008] Further, the pet groomer of the invention in embodiment 1 can also has the following features: the driving assembly also has a rotation angle locating section which locates the rotation angle of the rotating body.
[0009] Further, the pet groomer of the invention in embodiment 1 can also has the following features: the rotation angle locating section has a 3-tooth positioning block which surrounds the rotation accepting assembly, and ensures the knob drives the rotating body to rotate by 120° every time; the comb teeth has three groups, the circular pitch between two neighbor groups is 120°, and the air intake is set at the position 120° rotated from the comb position.
[0010] Further, the pet groomer of the invention in embodiment 1 can also has a position limiting unit, a ratchet wheel is set at the other end of the rotating body, the position limiting unit is consisted of the ratchet wheel and a position limiting plate which is meshed with the ratchet wheel, and when the rotating body rotates by the said rotation angle, the position limiting plate and the ratchet wheel are meshed to prevent the comb teeth from leaving the comb position.
[0011] Further, the pet groomer of the invention in embodiment 1 can also has the following features: the hollow front section also has an air leakage opening which may prevents excessive air force in the comb use opening from affecting comfort level of pet when combed.
[0012] Besides, the pet groomer of the invention in embodiment 2 can also has the following features: the substance body also has a hollow front section which is placed outside of the air intake, and the hollow front section has a comb use opening; the combing assembly is consisted of a rotating body and a plurality of groups of the comb teeth distributed in the axial direction of the rotating body. The rotating body is installed inside of the hollow front section, at least one group of the comb teeth extends outwards from the comb use opening to comb pet hair, and a rotation accepting assembly is set at one end of the rotating body; the driving assembly is formed from a lever drive assembly which has a connecting rod driving unit and a lever connected with the connecting rod driving unit, and the connecting rod driving unit is meshed with the rotation accepting assembly.
[0013] Further, the pet groomer of the invention in embodiment 2 can also has the following features: the rotation accepting assembly is a ratchet wheel, the connecting rod driving unit has a driving pawl meshed with the ratchet wheel, and the ratchet wheel and the driving pawl constitute a rotation angle locating section which regulates the rotation angle of the rotating body.
[0014] Further, the pet groomer of the invention in embodiment 2 can also has the following features: the pet groomer also includes a position limiting pawl, a 6-tooth position limiting wheel is also set at the other end of the rotating body, the position limiting pawl and the 6-tooth position limiting wheel constitute a position limiting unit to ensure that the rotating body rotates by the said rotation angle.
[0015] Further, the pet groomer of the invention in embodiment 2 can also has the following features: the ratchet wheel is a 6-tooth ratchet wheel, and when the lever is activated for one time, the rotating body will be driven to rotate by 60°; the comb teeth are in six groups, the circular pitch between two neighbor groups is 60°, and the air intake is set at the place 60° rotated from the comb position.
[0016] Further, the pet groomer of the invention in embodiment 2 can also has the following features: the substance body also has an actuator container which is formed along and separated apart from the suction channel, the actuator container is adjacent to the hollow front section and used to contain the driving assembly, and the lever is exposed outside of the actuator container.
[0017] Further, the pet groomer of the invention in embodiment 2 can also has the following features: the hollow front section also has an air leakage opening which prevents excessive air force in the comb use opening from affecting comfort level of pet when combed.
[0018] Besides, the pet groomer of the invention in embodiment 3 can also has the following features: the substance body has two air intakes as the primary air intake and secondary air intake and a hollow front section which is placed outside of the two air intakes, and the hollow front section has a comb use opening; the combing assembly is consisted of a rotating body and a plurality of groups of the comb teeth distributed in the axial direction of the rotating body. The rotating body is installed inside of the hollow front section, at least one group of the comb teeth extends outwards from the comb use opening to comb pet hair, and a rotation accepting assembly is set at one end of the rotating body; the driving assembly is formed from a press-button drive assembly which has a connecting rod driving unit and a press-button which is connected with the connecting rod driving unit, and the connecting rod driving unit is meshed with the rotation accepting assembly. The comb teeth which have combed pet hair are firstly rotated to the primary air intake and then the secondary air intake in further activation.
[0019] Further, the pet groomer of the invention in embodiment 3 can also has the following features: the rotation accepting assembly is a ratchet wheel, the connecting rod driving unit has a driving pawl which is meshed with the ratchet wheel, and the ratchet wheel and the driving pawl constitute a rotation angle locating section which regulates the rotation angle of the rotating body.
[0020] Further, the pet groomer of the invention in embodiment 3 can also has the following features: the pet groomer also includes a position limiting pawl, a 6-tooth position limiting wheel is set at the other end of the rotating body, and the position limiting pawl and the 6-tooth position limiting wheel constitute a position limiting unit which ensures that the rotating body rotates by the said rotation angle.
[0021] Further, the pet groomer of the invention in embodiment 3 can also has the following features: the ratchet wheel has 6 teeth, and when the press-button is pressed for one time, the rotating body will be driven to rotate by 60°, the comb teeth are in six groups, the circular pitch between two neighbor groups is 60°, the primary air intake is set at the position 60° rotated from the comb position, and the secondary air intake is set at the position 120° rotated from the comb position.
[0022] Further, the pet groomer of the invention in embodiment 3 can also has the following features: the substance body also has an actuator container which is formed along and separated apart from the suction channel, the actuator container is adjacent to the hollow front section which is used to contain the driving assembly, and the press-button is exposed outside of the actuator container.
[0023] Further, the pet groomer of the invention in embodiment 3 can also has the following features: the substance body also has an air leakage opening which prevents excessive air force in the comb use opening from affecting comfort level of pet when combed.
[0024] Further, the pet groomer of the invention in embodiment 4 can also has the following features: the combing assembly is constituted of a rotating body and a plurality of groups of the comb teeth distributed in the axial direction of the rotating body. A ratchet wheel with more than one tooth space is set on one end of the rotating body. The driving assembly is constituted of a cam assembly and a connecting rod driving assembly; the cam assembly has a cam coaxial with the rotating body, a cam track which is integrated with the cam, and a driving pawl unit which is set on the cam; the driving pawl unit has a driving pawl which is meshed with the tooth space, and the connecting rod driving assembly is engaged with the cam track and drives the cam track to move, so the driving pawl can mesh with the tooth space.
[0025] Further, the pet groomer of the invention in embodiment 4 can also has the following features: the driving pawl unit has a driving pawl chamber which is integrated with the cam and used to contain the driving pawl, and has a spring with one end supported by the internal surface of the driving pawl chamber; the connecting rod driving assembly is engaged with the cam track to drive the cam track to move towards the direction opposite to the rotation direction of said rotating body, so the driving pawl acts on the surface of the ratchet wheel under the elastic force of the spring, presses on the surface of the ratchet wheel flexibly in the radial direction of the cam, moves from one tooth space to next one, and meshes with the next one.
[0026] Further, the pet groomer of the invention in embodiment 4 can also has the following features: a spring retaining slot is set at one end of the driving pawl, the other end of the spring is in the spring retaining slot, and the driving pawl always presses on the surface of the ratchet wheel in the radial direction of the cam under the elastic force of the spring, and moves from one tooth space to next one.
[0027] Further, the pet groomer of the invention in embodiment 4 can also has the following features: the substance body also has a hollow front section which is placed outside of the air intake, the hollow front section has a comb use opening, the rotating body is installed inside of the hollow front section, and the comb teeth which is rotated to the comb position extends outside of the comb use opening to comb the pet hair.
[0028] Further, the pet groomer of the invention in embodiment 4 can also has the following features: the cam assembly and the ratchet wheel constitute a rotation angle locating section to regulate the rotation angle of the rotating body.
[0029] Further, the pet groomer of the invention in embodiment 4 can also has the following features: the ratchet wheel is a 6-tooth ratchet wheel, the rotation angle is 60° every time, and at least one air intake is set at the position integral multiples of 60° rotated from the comb position.
[0030] Further, the pet groomer of the invention in embodiment 4 can also has the following features: the comb teeth are in six groups, the circular pitch between two neighbor groups is 60°, every group of comb teeth has two rows of stagger arrangement, and the air intake is set in the position rotated by 120° from the comb position.
[0031] Further, the pet groomer of the invention in embodiment 4 can also has the following features: the comb teeth are in three groups, the circular pitch between two neighbor groups is 120°, the air intake is set at the position rotated by 120° from the comb position, when the first group of the comb teeth extends outside of the comb use opening, the rotating body rotates for two times, and when the second group of the comb teeth is rotated to the comb position, the first group of the comb teeth is rotated to the position right against the air intake; when the rotating body rotates for one time, the comb teeth is rotated to the position with 60° circular pitch from the comb position and therefore withdrawn in the hollow front section to protect the comb teeth.
[0032] Further, the pet groomer of the invention in embodiment 4 can also has the following features: a position limiting pawl is also included, a 6-tooth position limiting wheel is also set at the other end of the rotating body, and the position limiting pawl and the position limiting wheel constitute a position limiting unit which ensures that the rotating body rotates by the said rotation angle.
[0033] Further, the pet groomer of the invention in embodiment 4 can also has the following features: the substance body also has a flexible hose which is connected with the suction channel and an universal adaptor to be connected with the suction hose, and the universal adaptor regulates its inner diameter flexibly to ensure tight connection with the suction hose of different external diameters.
[0034] Further, the pet groomer of the invention in embodiment 4 can also has the following features: an operating and prompting unit is also included which sends corresponding information according to the fact whether the comb teeth are at the comb position or not and informs the user the status of the pet groomer; when no comb teeth are in the comb position, i.e. the pet groomer is under the status of protecting the comb teeth, the operating and prompting unit sends corresponding signals to inform the user it is protecting the comb teeth status, and then drives the connecting rod driving assembly, so a group of the comb teeth will extend outside of the comb use opening; when a group of comb teeth in the comb position is at the comb use opening, i.e. the pet groomer is under combing status, the operating and prompting unit sends corresponding signals to inform the user the combing status available to comb pet hair; if the comb teeth need to be withdrawn and hidden in the pet groomer, the connecting rod driving assembly should be driven.
[0035] Further, the pet groomer of the invention in embodiment 4 can also has the following features: the substance body also has an actuator container which is formed along and separated apart from the suction channel, the actuator container is adjacent to the hollow front section and used to contain the driving assembly. The connecting rod driving assembly has a press-button or a lever drive assembly which is exposed to the outside of the actuator container for selection.
[0036] Further, the pet groomer of the invention in embodiment 4 can also has the following features: the substance body also has at least one air leakage opening which prevents excessive air force in the comb use opening from affecting comfort level of pet when combed.
[0037] Further, according to the present invention, there is provided a vacuum cleaner, comprising:
[0038] a suction hose; and
[0039] a pet groomer to be used in conjunction with the suction hose, wherein the pet groomer is described above.
[0040] The above and other objects and features of the present invention will become apparent from the following detailed description and the appended claims with reference to the accompanying drawings.
[0041] The pet groomer and related vacuum cleaner system with said groomer provided by present invention drives the combing assembly through the driving assembly, to move pet hair combed down from pet body to air intake position so as to be vacuumed away directly, avoiding the intermediate action of stripping off hair from comb teeth or similar actions, so no loose hair can fall off from pet body in grooming to pollute environment or to transmit allergen material.
BRIEF DESCRIPTION OF THE DRAWINGS
[0042] The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown.
[0043] In the drawings:
[0044] FIG. 1 is a side perspective view of the pet groomer in embodiment 1;
[0045] FIG. 2 is a perspective view of the pet groomer in embodiment 1, from bottom side;
[0046] FIG. 3 is an exploded view of the pet groomer in embodiment 1;
[0047] FIG. 4 is a perspective view of the pet groomer in embodiment 1, from bottom side;
[0048] FIGS. 5A-D are structural illustrations of combing assembly of the pet groomer in embodiment 1;
[0049] FIG. 6 is a top view of the pet groomer in embodiment 1;
[0050] FIG. 7 is an A-A section view of FIG. 6 ;
[0051] FIG. 8 is a B-B section view of FIG. 6 ;
[0052] FIG. 9 is a side perspective view of the pet groomer in embodiment 2;
[0053] FIG. 10 is a perspective view of the pet groomer in embodiment 2, from bottom side;
[0054] FIG. 11 is an exploded view of the pet groomer in embodiment 2;
[0055] FIG. 12 is a bottom exploded view of the pet groomer in embodiment 2;
[0056] FIGS. 13A-D are structural illustrations of the combing assembly of the pet groomer in embodiment 2;
[0057] FIG. 14 is an inverted side section view of the pet groomer in embodiment 2;
[0058] FIG. 15 is a top view of the pet groomer in embodiment 2;
[0059] FIG. 16 is an A-A section view of FIG. 15 ;
[0060] FIG. 17 is a B-B section view of FIG. 15 ;
[0061] FIG. 18 is a side perspective view of the pet groomer in embodiment 3;
[0062] FIG. 19 is a perspective view of the pet groomer in embodiment 3, from bottom side;
[0063] FIG. 20 is an exploded view of the pet groomer in embodiment 3;
[0064] FIG. 21 is a semi-exploded view of the pet groomer in embodiment 3;
[0065] FIGS. 22A-D are structural illustrations of the combing assembly of the pet groomer in embodiment 3;
[0066] FIG. 23 is an inverted side section view of the pet groomer in embodiment 3.
[0067] FIG. 24 is a top view of the pet groomer in embodiment 3;
[0068] FIG. 25 is an A-A section view of FIG. 24 ;
[0069] FIG. 26 is a B-B section view of FIG. 24 ;
[0070] FIG. 27 is a side perspective view of the pet groomer in embodiment 4;
[0071] FIG. 28 is a perspective view of the pet groomer in embodiment 4, from bottom side;
[0072] FIG. 29 is an exploded view of the pet groomer in embodiment 4;
[0073] FIG. 30 is a bottom exploded view of the pet groomer in embodiment 4;
[0074] FIGS. 31A-D are structural illustrations of the combing assembly of the pet groomer in embodiment 4;
[0075] FIG. 32 is an inverted side section view of the pet groomer in embodiment 4;
[0076] FIG. 33 is a top view of the pet groomer in embodiment 4;
[0077] FIG. 34 is an A-A section view of FIG. 33 ; and
[0078] FIG. 35 is a B-B section view of FIG. 33 .
DETAILED DESCRIPTION OF THE INVENTION
[0079] Embodiments of the invention will be described in details herein below with reference to the drawings.
Embodiment 1
[0080] FIG. 1 is a side perspective view of a pet groomer in embodiment 1; FIG. 2 is a perspective view of the pet groomer in embodiment 1 from bottom side; FIG. 3 is an exploded view of the pet groomer in embodiment 1; FIG. 4 is a perspective view of the pet groomer in embodiment 1 from bottom side; FIG. 6 is a top view of the pet groomer in embodiment 1; FIG. 7 is an A-A section view of FIG. 6 of the pet groomer in the embodiment; as shown by FIG. 1 , FIG. 2 , FIG. 3 , FIG. 4 , FIG. 6 and FIG. 7 , the pet groomer 10 to be used together with the suction hose of a vacuum cleaner includes a substance body 11 , a combing assembly 12 and a driving assembly 13 .
[0081] The substance body 11 has an upper covering unit 20 and a lower covering unit 28 . The lower covering unit 28 is constituted of the front section and rear section and a suction channel 43 is set at the rear section to be connected with the suction hose of vacuum cleaner. The external wall of suction channel 43 also serves as a handle for users to operate and use the pet groomer 10 ; half circles structure 46 and 47 are set at two side ends of the front section respectively and form circles together with the upper covering unit 20 for mounting the combing assembly 12 . The front section also has a buckle 45 , a slot 53 is set at the front section of the upper covering unit 20 , and the slot 53 and the buckle 45 are fastened so that the upper covering unit 20 and the lower covering unit 28 are tightly combined together.
[0082] A clamp ring 27 is also set in the substance body 11 for combining the half circle structure at the rear end of the upper covering unit 20 with the corresponding half circle at the middle of the lower covering unit 28 to clamp the upper covering unit 20 with the lower covering unit 28 tightly. The clamp ring is detachable. When it is necessary to replace the combing assembly or clean the parts between the upper covering unit 20 and lower covering unit 28 , demount the clamp ring 27 to demount the upper covering unit 20 and the lower covering unit 28 , and obviously the combing assembly mounted between the upper covering unit 20 and the lower covering unit 28 is replaceable.
[0083] After the upper covering unit 20 is combined with the lower covering unit 28 , the baffle 44 b in the upper covering unit 20 forms an air intake 44 (See FIG. 7 ) to transmit air into the suction channel 43 together with the baffle 44 a in the lower covering unit 28 . The best preference for the length of air intake 44 is to be longer than the contour length of any group of comb teeth 21 distributed on rotating body 22 . A hollow front section is placed outside of the air intake 44 , and a comb use opening 50 and an air leakage opening 40 are set in the hollow front section.
[0084] FIGS. 5A-D are structural illustrations of the combing assembly of the pet groomer in embodiment 1, of which views a, b, c and d are structural illustrations of the combing assembly in different directions. As shown by FIGS. 5A-D , the combing assembly 12 is comprised of a rotating body 22 and three groups of comb teeth 21 arranged in axial direction on the rotating body 22 . Every group includes two rows of comb teeth 21 , and the interval of two adjacent groups of comb teeth 21 is 120°, and one group of comb teeth 21 extends outside of the comb use opening 50 to comb pet hair. The air intake 44 is set at the position rotated by 120° from comb position along direction A in FIG. 7 .
[0085] As the best preference for the arrangement of comb teeth 21 on rotating body 22 , for any group of comb teeth 21 , when they are located opposite to the air intake 44 , their orthogonal projection against air intake 44 should not fall beyond the contour of air intake 44 . The recommended length of comb tooth 21 is equivalent to the thickness of pet hair to be combed
[0086] Felts 23 are mounted at two ends of the rotating body 22 , so the rotating body 22 is mounted in the circle 46 between the upper covering unit 20 and lower covering unit 28 to make sure that the rotating body 22 rotates around the axis and the rotating body 22 is tightly combined with the upper covering unit 20 and lower covering unit 28 to avoid furs and other sundries from flying into two side ends. Obviously the rotating body 22 is inside of the hollow front section.
[0087] A driven groove 42 (i.e. rotation accepting assembly) and a 6-tooth positioning block 41 around the driven groove 42 for regulating the rotation angle of the rotating body 22 as 120° are set at one end of the rotating body 22 .
[0088] The 6-tooth positioning block 41 and the positioning gear unit constitute a positioning unit, and the positioning gear unit is comprised of a positioning gear 24 to mesh with the 6-tooth positioning block 41 , a guide holder 26 fixed between the upper covering unit 20 and the lower covering unit 28 , and a spring 25 to connect the two above. The end of the positioning gear 24 connected with the spring 25 is inserted into the guide holder 26 so that the positioning gear is able to flexibly extend in the guide holder 26 under the action of the spring 25 . When the rotating body 22 rotates by 120°, the positioning gear 24 is meshed with the 6-tooth positioning block 41 to make sure that the rotation angle of the rotating body must be integral multiples of 120°.
[0089] The pet groomer 10 also has a position limiting plate 31 , a ratchet wheel 52 meshed with the position limiting plate 31 is set at the other end of the rotating body 22 , the ratchet wheel 52 and the position limiting plate 31 constitute a position limiting unit, so that the ratchet wheel 52 and the position limiting plate 31 are meshed every time after the rotating body 22 rotates to prevent the rotating body 22 from rotating reversely in combing.
[0090] The driving unit 13 is a knob with a rib 48 , rib 48 passes through the side end of the hollow front section and meshes with the driven groove 42 , so when the knob 29 is turned, the moment is transferred to the rotating body 22 from rib 48 to make the comb teeth 21 rotate around the axis. Comb teeth 21 can fix in the place right against air intake 44 and ensure every piece of comb teeth 21 in this group points to air intake 44 and falls inside the air stream into the air intake 44 .
[0091] When the pet groomer is used to comb pet hair, firstly choose the rotating body 22 with corresponding length of comb teeth 21 to mount in the hollow front section according to different pet hair length, so to avoid scratch on pet skin owing to unsuitable lengths of comb teeth in the combing process. Then connect the pet groomer with a vacuum cleaner, and turn on the vacuum cleaner. Then the comb use opening 50 and the air leakage opening 40 transmit airflows to the air intake 44 at the same time, and the airflow enters into vacuum cleaner through the suction channel 43 . Then user holds the external wall of the suction channel 43 as handle to comb pets. In the combing process, the pet's body blocks the comb use opening 50 , the airflow from the air leakage opening 40 to the air intake 44 reduces the suction force at the comb use opening 50 and effectively avoiding excessive suction that affects comfort of pets. After a certain amount of hair is accumulated on the comb teeth, turn the knob 29 to make a new group of comb teeth 21 to the comb position, so user could continue to comb pets with the new group of comb teeth. The two rows of comb teeth 21 just combed hair are rotated by 120° along direction A (See FIG. 7 ), which is just fixed at the position opposite to the air intake 44 , to make sure that every piece of comb teeth in the group of comb teeth 21 points to the middle of the air intake 44 , and sufficient suction force along the comb teeth extending direction will vacuum hair from the comb teeth 21 into the air intake 44 , no need external force to strip hair off comb teeth in advance. Because suction force is on the comb position in the whole process, pet hair will not drop down in the whole process.
[0092] The best total sectional area of the air leakage opening 40 is 1.2 times of total sectional area of the air intake 44 , and the best total sectional area of the air intake is equivalent to the sectional area of the suction hose of the vacuum cleaner. The best airflow at the air intake is equivalent to the actual airflow of the suction hose of a vacuum cleaner, i.e. no air leaking device is between the air intake and the suction hose of the vacuum cleaner.
Function and Effects of Embodiment 1
[0093] In summary, the pet groomer 10 in the embodiment has the knob 29 to drive the rotating body 22 , so pet hair combed are transferred to the air intake 44 and vacuumed into cleaner. No pet hair drops down in the combing process, thus not causing environmental pollution and avoiding allergen spreading. Besides, the substance body is detachable and easy for internal structure cleaning; the rotating body is replaceable, so user can choose suitable comb teeth length for his pet groomer according to different pet hair to improve the comfort level of pets in the combing process and avoid hurting pets, since pet hair is transferred to air intake through knob rotation, even hair wound in comb teeth can also be vacuumed into the air intake along the comb teeth extending direction and they will not scatter, and moreover, intermediate actions like stripping off hair from comb teeth or similar are saved. As a result the pet groomer 10 has the following features: simple structure, convenient use, labor saving, not tiring for use and no threaten to users health.
[0094] The clamp ring 27 in the embodiment can screw back and forth to mesh with the steps of the upper covering unit 20 and the lower covering unit 28 to ensure tight locking between the upper covering unit 20 and the lower covering unit 28 , clamp ring 27 can also lock with the upper covering unit 20 and the lower covering unit 28 through locking slot.
[0095] The comb teeth 21 in the embodiment are in three groups, it can also be in other integral group(s), and every group may has one or more rows; the quantity of the comb teeth 21 in every row is also subject to requirements, such as 20 pieces, 30 pieces, 40 pieces, 50 pieces and 60 pieces; the diameter of the comb teeth 21 is also subject to requirements, for example, φ0.3, φ0.5, φ0.6, φ0.8, φ1.0, φ1.2, φ1.5, etc. The material of the comb teeth 21 is subject to requirements like stainless steel 304, stainless steel 201, 45# plated steel, plastic PP, etc.; the top surface shape of the comb teeth 21 may be flat or others like ball-shape.
[0096] The comb teeth 21 in the embodiment may be directly fixed in the rotating body 22 or firstly connected with other carriers and then fixed in the rotating body 22 . For example, the comb teeth 21 may be firstly connected with a fixing base and then mounted on rotating body 22 . The comb teeth 21 may have a movable structure for convenient of repairing and replacement.
Embodiment 2
[0097] FIG. 9 is a side perspective view of the pet groomer in embodiment 2; FIG. 10 is a bottom perspective view of the pet groomer in embodiment 2; FIG. 11 is an exploded view of the pet groomer in embodiment 2; FIG. 12 is a bottom exploded view of the pet groomer in embodiment 2; FIG. 14 is an inverted side section view of the pet groomer in embodiment 2; FIG. 15 is a top view of the pet groomer in embodiment 2; FIG. 16 is an A-A section view of FIG. 15 ; FIG. 17 is a B-B section view of FIG. 15 . As shown by FIG. 9 , FIG. 10 , FIG. 11 , FIG. 12 , FIG. 14 , FIG. 15 , FIG. 16 and FIG. 17 , a pet groomer 100 to be used together with the suction hose of vacuum cleaner includes a substance body 101 , a combing assembly 102 and a driving assembly 103 .
[0098] The substance body 101 has an upper covering unit 110 and a lower covering unit 122 . The lower covering unit 122 is comprised of a front section and a rear section, a suction channel 144 is set at the rear end to be connected with the suction hose of vacuum cleaner, and the external wall of the suction channel 144 also serves as a handle for users to operate and use the pet groomer 100 ; half circles 145 are set at two side ends of the front section respectively and form circles together with the upper covering unit 100 for mounting the combing assembly 102 . The front section also has a buckle 143 , a slot 151 is set at the front section of the upper covering unit 110 , and the slot 151 and the buckle 143 can be fastened together to lock tightly the upper covering unit 110 and the lower covering unit 122 . Substance body 101 (also named as main body) comprises two side walls, wherein the combing assembly 102 is fixed.
[0099] A clamp ring 123 also set in the substance body 101 for combining the half circle structure which is at the rear end of the upper covering unit 110 with the corresponding half circle which is at the middle of the lower covering unit 122 and clamp the upper covering unit 110 with the lower covering unit 122 tightly. The clamp ring 123 is detachable. When it is necessary to replace the combing assembly 102 or clean the parts between the upper covering unit 110 and lower covering unit 122 , demount the clamp ring 123 to demount the upper covering unit 110 and the lower covering unit 122 , and obviously the combing assembly mounted between the upper covering unit 110 and the lower covering unit 122 is replaceable.
[0100] After the upper covering unit 110 is combined with the lower covering unit 122 , the baffle in the upper covering unit 110 is tightly combined with the corresponding baffle in the lower covering unit 122 . An air transmission channel is set in the lower covering unit 122 and connected with the suction channel 144 . An air intake 142 is set accordingly in the front of the air transmission channel to transmit air into the air transmission channel. A hollow front section is placed outside of the air intake 142 , and a comb use opening 150 and an air leakage opening 130 are set in the hollow front section. The best preference of the length of air intake 142 is to be longer than the contour length of any group of comb teeth 111 distributed on rotating body 117 .
[0101] A back plate 124 is set at the bottom of the lower cover to cover the driving assembly, a screw hole 146 is set at the back plate 124 , a screw boss 152 corresponding to the screw hole 146 is set on the lower covering unit 122 , the back plate 124 is reliably connected with the lower covering unit 122 through the screw 125 , and the area between the back plate 124 and the lower cover of the air transmission channel (i.e. actuator container)-stores driving assembly 103 .
[0102] The driving assembly 103 is comprised of a lever drive assembly, which is consisted of a driving pawl 113 , a connecting rod 114 , and the lever 115 which is exposed outside of the actuator container and near the suction channel 144 . It is convenient for activating when user grasps the external wall of the suction channel 144 as handle. The connecting rod 114 has a positioning cylinder 134 , a motion transmission cylinder 135 connected with the lever 115 , and a motion transmission cylinder 133 connected with the driving pawl 113 . The positioning cylinder 134 is fixed in the positioning block 154 of the lower covering unit 122 . The motion transmission cylinder 133 activates the driving pawl 113 . The driving pawl 113 has a round hole 131 and an elastic reset assembly 132 , the round hole 131 is connected with the motion transmission cylinder 133 , and the elastic reset assembly 132 is pressed on the connecting rod 114 so the driving pawl 113 interacts with the combing assembly 102 continuously. The lever 115 has a rotary positioning cylinder 137 , slotted hole 136 and a supporter groove 138 of spring 116 , the rotary positioning cylinder 137 is fixed in the tab 153 of the lower covering unit 122 , and the slotted hole 136 is connected with the cylinder 135 of the connecting rod 114 to transfer the moment. The spring supporter groove 138 contains spring 116 , so the lever 115 can reset under the action of spring 116 after activated. Lever 115 extends toward center of combing assembly 102 with an arm containing slotted hole 136 extends toward sidewall of substance body 101 .
[0103] FIG. 13 is a structural illustration of the combing assembly in embodiment 2; FIGS. 13A-D are structural illustrations of the combing assembly in different directions. As shown by FIGS. 13A-D , the combing assembly 102 is comprised of a rotating body 117 , a comb teeth base plate 112 and six groups of replaceable comb teeth 111 arranged in the axial direction of the rotating body, the interval between two neighbor groups of the comb teeth 111 is 60°, and a group of comb teeth 111 has one row. The air intake 142 is set at the position rotates by 60° from the comb position along direction B in FIG. 16 .
[0104] Felts 118 are mounted at two ends of the rotating body 117 so the rotating body 117 is mounted in the circle 145 between the upper covering unit 110 and the lower covering unit 122 to ensure the rotating body 117 rotates around the axis and there is no gap between the rotating body 117 , the upper covering unit 110 and the lower covering unit 122 , so that pet hair are prevented from flying into two sides. Obviously the rotating body 117 is mounted inside of the hollow front section. One group of comb teeth 111 extends outside of the opening 150 to comb.
[0105] A 6-tooth ratchet wheel 147 which meshes with the driving pawl 113 is set at one end of the rotating body 117 , and the 6-tooth ratchet wheel 147 and the driving pawl 113 constitute into a rotation angle locating section to regulate that the rotation angle of the rotating body 117 is 60° in every rotation, and prevent rotating body 117 from reversing in use.
[0106] The pet groomer 100 also has a position limiting gear 119 , and a 6-tooth position limiting wheel 139 is set at the other end of the rotating body 117 . The 6-tooth position limiting wheel 139 and the above mentioned position limiting gear 119 , the guide holder 121 fixed between the upper covering unit 110 and the lower covering unit 122 and a spring 120 connect the two parts constitute into a position limiting unit. The end of the position limiting gear 119 connected with the spring 120 is inserted into the guide holder 121 , so the position limiting gear 119 flexibly extends in the guide holder 121 under the action of the spring 120 . When the rotating body 117 rotates by 60°, the position limiting gear 119 is meshed with the 6-tooth position limiting wheel 139 to prevent rotating body 117 from rotating reversely.
[0107] When the pet groomer is used to comb, firstly choose the rotating body 117 with proper length of comb teeth 111 to mount in the hollow front section according to pet hair length to avoid scratching pet skin in combing, or to replace comb teeth 111 in the rotating body 117 with those of best lengths.
[0108] Then connect the pet groomer with a vacuum cleaner, and turn on vacuum cleaner. Then the comb use opening 150 and the air leakage opening 130 transmit airflows to the air intake 142 at the same time, and the airflow enters into vacuum cleaner through the suction channel 144 . Then the user holds the external wall of the suction channel 144 as the handle to comb pets. In the combing process, the pet's body blocks the comb use opening 150 , the airflow from the air leakage opening 130 to the air intake 142 helps reduce the suction force at the comb use opening 150 to avoid excessive suction that affects comfort of pets. After certain amounts of pet hair accumulated on the comb teeth, activate the lever 115 outside of the lower covering unit 122 , the connecting rod 114 drives the driving pawl 113 and the driving pawl 113 pushes the 6-tooth ratchet wheel 147 and therefore drives the rotating body 117 to rotate by 60°. Then a new group of comb teeth 111 is rotated to the comb position, so the user could continue to comb pets with this new group of comb teeth. The comb teeth 111 above mentioned with pet hair are rotated and fixed at the position opposite to the air intake 142 , to make sure sufficient suction airflow along the comb teeth extending direction vacuums hair from the comb teeth 111 into the air intake 142 , no need to strip off hair in the comb teeth 111 with external force. Because suction acts in the comb position in the whole process, no pet hair will drop down in the whole process.
[0109] Besides, if one or more pieces of comb teeth 111 are damaged, new comb teeth can be used to replace.
Function and Effects of Embodiment 2
[0110] The pet groomer 100 provided by the embodiment has a lever drive assembly to drive the rotating body 117 and move pet hair to the front of the air intake 142 , so airflows flowing towards air intake 142 take hair from comb teeth to vacuum cleaner in the comb teeth extending direction, and combed hair does not need to be stripped off from comb teeth with external force in advance, no pet hair would drop down in the combing process, thus not causing environmental pollution and avoiding allergen spreading. Besides, the substance body is detachable and easy for internal structure cleaning; the rotating body is replaceable, so user can choose proper comb length according to different pet hair. Every group of comb teeth is replaceable, so when one or more pieces of comb teeth 111 are damaged, new comb teeth may replace damaged ones, thus being environment-protection. Plus, choosing comb with proper teeth length according to different pet hair can improve the comfort level of pets in the combing process and avoid hurting pets at the same time. Pet hair are moved to air intake and vacuumed away once after the lever is activated. As a result the pet groomer 100 has the following features: simple structure, convenient use, labor saving, not tiring to use and no harm to user's health.
[0111] The clamp ring 123 can screw back and forth to mesh with the steps of the upper covering unit 110 and the lower covering unit 122 to make both covering units lock together tightly; the upper covering unit 110 and the lower covering unit 122 could also be connected together through a locking groove.
[0112] The comb teeth 111 in the embodiment are in six groups, can also be in other integral group(s), and every group may has one or more rows; the quantity of the comb teeth 111 in every row is also subject to requirements, such as 20 pieces, 30 pieces, 40 pieces, 50 pieces and 60 pieces; the diameter of the comb teeth 111 is also subject to requirements, for example, φ0.3, φ0.5, φ0.6, φ0.8, φ1.0, φ1.2, φ1.5, etc. The material of the comb teeth 111 is also subject to requirements like stainless steel 304, stainless steel 201, 45# plated steel, plastic PP, etc.; the top surface shape of the comb teeth 111 may be flat or others like ball-shape.
[0113] The comb teeth 111 are firstly connected with the base plate 112 , then fixes the base plate 112 into the rotating body 117 . The base plate 112 of the comb teeth and the rotating body 117 may also be connected with a pressing plate, or by other methods. Of course the comb teeth 111 may also be mounted on other carriers and then on the rotating body. The comb teeth 111 may be a movable structure convenient for repair and replacement, or permanently fixed in the rotating body 112 .
[0114] Besides, the lower covering unit 122 and the bottom back plate 124 may be connected in others ways, such as through a buckle or by ultrasonic welding.
Embodiment 3
[0115] FIG. 18 is a side perspective view of the pet groomer in embodiment 3; FIG. 19 is a bottom perspective view of the pet groomer in embodiment 3; FIG. 20 is an exploded view of the pet groomer in embodiment 3; FIG. 21 is a semi-exploded view of the pet groomer in embodiment 3; FIG. 23 is an inverted side section view of the pet groomer in embodiment 3; FIG. 24 is a top view of the pet groomer in embodiment 3; FIG. 25 is an A-A section view of FIG. 24 ; FIG. 26 is a B-B section view of FIG. 24 . As shown by FIG. 18 , FIG. 19 , FIG. 20 , FIG. 21 , FIG. 23 , FIG. 24 , FIG. 25 and FIG. 26 , a pet groomer 200 to be used together with the suction hose of vacuum cleaner includes a substance body 201 , a combing assembly 202 and a driving assembly 203 .
[0116] The substance body 201 has an upper covering unit 233 and a lower covering unit 232 . The lower covering unit 232 is consisted of a front section and a rear section; and a suction channel 248 is set at the rear end to be connected together with the suction hose of a vacuum cleaner, and the external wall of the suction channel 248 also serves as a handle for users to operate and use the pet groomer 200 ; half circles 252 are set at two side ends of the front section respectively and form two circles together with the upper covering unit 233 for installing the combing assembly 202 .
[0117] The front section of the lower covering unit 232 has a round hole 258 , a cylinder 253 is set at the front end of the upper covering unit 233 , and the cylinder 253 is installed in the round hole 258 to make the upper covering unit 233 rotate relative to the lower covering unit 232 .
[0118] A locking ring 231 is also set in the substance body 201 which is used to combine the half circle structure at the rear end of the upper covering unit 233 with the corresponding circle in the junction area of the front and rear section of the lower covering unit 232 and clamp the upper covering unit 233 with the lower covering unit 232 tightly. The locking ring 231 is detachable.
[0119] When it is necessary to replace the combing assembly 202 or clean the parts between the upper covering unit 233 and lower covering unit 232 , demount the locking ring 231 to twist and turn the upper covering unit 233 relative to the lower covering unit 232 , and obviously the combing assembly 202 installed between the upper covering unit 233 and the lower covering unit 232 is replaceable.
[0120] An air transmission channel is set in the lower covering unit 232 and connected with the suction channel 248 . A primary air intake 270 is set accordingly in front of the air transmission channel to transmit air into the air transmission channel. After the upper covering unit 233 and the lower covering unit 232 are combined, the baffle 251 b in upper covering unit 233 and the corresponding baffle 251 a in the lower covering unit 232 form a secondary air intake 251 (See FIG. 25 ) to transmit air to the suction channel 248 . The best preference of air intake length is, at least one air intake to be longer than the contour length of any group of comb teeth 225 distributed on rotating body 226 . A hollow front section is placed outside of the primary air intake 270 and the secondary air intake 251 . A comb use opening 257 and an air leakage opening 256 are set in the hollow front section.
[0121] A separating plate 221 is fixed between the upper covering unit 233 and the lower covering unit 232 , and the separating plate 221 and the lower covering unit form an actuator container, which is used to store the driving assembly 203 , to make sure pet hairs vacuumed from the air intake enter into the suction channel 248 directly and not affect normal movements of the driving assembly.
[0122] The driving assembly 203 is formed from press-button drive assembly, which is consisted of a driving pawl 222 , a connecting rod 223 and a press-button 220 which passes through the separating plate 221 and the upper covering unit 233 and is near the suction channel 248 .
[0123] The connecting rod 223 has a positioning cylinder 245 , a slotted hole 262 connected with the button 220 , a driving cylinder 243 connected with the driving pawl 222 and a spring 260 . The positioning cylinder 245 is fixed on the locating tab 250 in the lower covering unit 232 . The driving cylinder 243 transmits force to move the driving pawl 222 . One end of the spring 260 is fixed with the spring fixing cylinder 259 in the lower covering unit 232 to make sure the button could reset automatically after pressed down.
[0124] The button 220 has a cylinder 240 which is clamped into the slotted hole 262 in the connecting rod 223 to drive the connecting rod 223 , so the user could operate the button with his thumb when holding the external wall of the suction channel 248 to drive the combing assembly 202 .
[0125] A round hole 242 and a resetting spring 241 are set in the driving pawl 222 , the round hole 242 is connected with the driving cylinder 243 , and the resetting spring 241 is pressed on the connecting rod 223 to produce elastic force which ensures interaction between the driving pawl 222 and the combing assembly 202 .
[0126] FIGS. 22A-D are structural illustrations of the combing assembly of the pet groomer in embodiment 3, of which views a, b, c and d are structural illustrations of the combing assembly in different directions. As shown by FIGS. 22A-D , the combing assembly 202 is consisted of a rotating body 226 and six groups of replaceable comb teeth 225 distributed in axial direction in the rotating body 226 . The circular pitch of two adjacent groups of comb teeth 225 is 60°, of which every group includes one row of comb teeth 225 . The primary air intake 270 is set at the position rotated by 60° from the comb position along direction C in FIG. 27 , and the secondary air intake 251 is set at the position rotated by 120° from the comb position along direction C in FIG. 27 . The comb teeth 225 which has combed pet hair is turned to the primary air intake 270 firstly and then the secondary air intake 251 .
[0127] Felts 227 are installed at two ends of the rotating body 226 , so the rotating body 226 is installed in the circle 252 between the upper covering unit 233 and lower covering unit 232 to make sure that the rotating body 226 rotates around the axis and the rotating body 226 is tightly combined with the upper covering unit 233 and lower covering unit 232 to avoid hairs and other sundries from flying to two sides. Obviously the rotating body 226 is inside of the hollow front section. A group of comb teeth 225 extends outside of the comb use opening 257 to comb pet hairs.
[0128] A 6-tooth ratchet wheel 255 which meshes with the driving pawl 222 is set at one end of the rotating body 226 , and the 6-tooth ratchet wheel 255 and the driving pawl 222 constitute into a rotation angle locating section to regulate that the rotation angle of the rotating body 226 is 60° in every time, and prevent it from reversing in use.
[0129] The pet groomer 200 also has a position limiting pawl 228 , and a 6-tooth position limiting wheel 247 is set at the other end of the rotating body 226 . The 6-tooth position limiting wheel 247 and the above mentioned position limiting pawl 228 , the guide holder 230 fixed between the upper covering unit 233 and the lower covering unit 232 and a spring 229 connect the two constitute into a position limiting unit. The end of the position limiting pawl 228 connected with the spring 229 is inserted into the guide holder 230 , so the position limiting pawl 228 flexibly extends in the guide holder 230 under the action of the spring 229 . When the rotating body 226 rotates by 60°, the position limiting pawl 228 is meshed with the 6-tooth position limiting wheel 247 to prevent the rotating body 226 from rotating reversely
[0130] When the pet groomer 200 is used to comb pet hair, firstly choose the rotating body 226 with proper length of comb teeth 225 to install in the hollow front section according to different pet hairs, and avoid scratch of pet skin owing to unsuitable lengths of comb teeth during the combing process. Or just replace comb teeth 225 in the rotating body 226 to adapt to lengths of pet hairs to be combed.
[0131] Then connect the pet groomer 200 with a vacuum cleaner, and turn on vacuum cleaner. Then the comb use opening 257 and the air leakage opening 256 transmit airflows to the primary air intake 270 and the secondary air intake 251 at the same time, and the airflow enters into vacuum cleaner through the suction channel 248 . Then the user holds the external wall of the suction channel 248 as the handle to comb pet. In the combing process, the pet body blocks the comb use opening 257 , the airflow from the air leakage opening 256 to the primary air intake 270 and the secondary air intake 251 reduces suction force in comb use opening 257 , so no excessive air force is in the comb use opening 257 to make pet uncomfortable when combed.
[0132] After certain amounts of hairs are accumulated on the comb teeth, press down the button 220 in the upper covering unit 233 . The button 220 drives the connecting rod 223 to move through the cylinder 240 , the connecting rod 223 moves around the cylinder 245 under the driving force of the button 220 , the driving pawl 222 is driven to move by the cylinder 243 when the connecting rod 223 moves, the driving pawl 222 pushes the ratchet wheel 255 in the rotating body 226 to rotate, then the rotating body 226 is driven to rotate in direction C in FIG. 25 , and the comb teeth 225 and the rotating body 226 rotate by 60° synchronously. A new group of comb teeth 225 is at the comb position, and the user may use the group of comb teeth to comb pet continuously. The comb teeth that has combed pet is opposite the primary air intake 270 now, and the comb teeth that faced the primary air intake 270 is now opposite the secondary air intake 251 , and so on, so hairs not cleared away in the primary air intake can be completely vacuumed away in the secondary air intake; as suction always acts at the comb position in the process, hairs will not drop down in the whole combing process. Besides, if one or more pieces of comb teeth 225 are damaged, new comb teeth can be used to replace the group of comb teeth.
Function and Effects of Embodiment 3
[0133] The pet groomer 200 provided by the embodiment has the press-button drive assembly to drive the rotating body 226 and move pet hairs to the front of the primary air intake 270 , so hairs are vacuumed into airflows in the comb teeth extending direction and into vacuum cleaner. As the pet groomer also has the secondary air intake 251 which further clear away hairs left from the primary air intake 270 , hairs need not be stripped off from comb teeth with external force in advance and all hairs on the comb teeth can be vacuumed into vacuum cleaner by the airflow, so no loose hair can fall off from pet body in grooming to pollute environment or to transmit allergen material. Besides, the substance body is detachable and easy for internal structure cleaning; the rotating body is replaceable, so different rotation bodies with suitable comb teeth can be installed on the pet groomer according to different pet hairs. Every group of comb teeth is replaceable, so when one or more pieces of comb teeth 225 are damaged, new comb teeth may replace damaged ones, thus being environment-protection. Plus, proper comb teeth may be chosen according to different pet hairs to make pet more comfortable and avoid hurting pet when combed. Pet hairs are moved to the air intake once the button is pressed, thus avoiding intermediate actions such as stripping off hair from comb teeth or similar actions. As a result the pet groomer 200 has the following features: simple structure, convenient use, labor saving, not tiring for use and no harm to user's health.
[0134] The locking ring 231 in the embodiment can screw back and forth, so the locking ring 231 can be meshed with the steps of the upper covering unit 233 and the lower covering unit 232 , to make the upper covering unit 233 and the lower covering unit 232 are tightly clamped; the upper covering unit 233 and the lower covering unit 232 could also be connected through locking slot to make the upper covering unit 233 and the lower covering unit 232 tightly clamped.
[0135] The comb teeth 225 in the embodiment is in six groups, can also be other integral group(s), and every group may has one or more rows; the quantity of the comb teeth 225 in every row is also subject to requirements, such as 20 pieces, 30 pieces, 40 pieces, 50 pieces and 60 pieces; the diameter of the comb teeth 225 is also subject to requirements, for example, φ0.3, φ0.5, φ0.6, φ0.8, φ1.0, φ1.2, φ1.5, etc. The material of the comb teeth 225 is subject to requirements likewise like stainless steel 304, stainless steel 201, 45# plated steel, plastic PP, etc.; the top surface shape of the comb teeth 225 may be flat or other shape like ball shape.
[0136] The comb teeth 225 in the embodiment is of moveable structure for repair and replacement; or the comb teeth may be firstly installed on carriers and then the comb teeth carrier is connected with the rotating body.
Embodiment 4
[0137] FIG. 27 is a front perspective view of the pet groomer in embodiment 4; FIG. 28 is a bottom perspective view of the pet groomer in embodiment 4; FIG. 29 is an exploded view of the pet groomer in embodiment 4; FIG. 30 is a bottom exploded view of the pet groomer in embodiment 4;
[0138] FIG. 32 is an inverted side section view of the pet groomer in embodiment 4; FIG. 33 is a top view of the pet groomer in embodiment 4; FIG. 34 is an A-A section view of FIG. 33 ; FIG. 35 is a B-B section view of FIG. 33 . As shown by FIG. 27 , FIG. 28 , FIG. 29 , FIG. 30 , FIG. 32 , FIG. 33 , FIG. 34 and FIG. 35 , the pet groomer 300 for connecting with the suction hose of a vacuum cleaner includes a substance body 301 , a combing assembly 302 and a driving assembly 303 . The combing assembly 302 is consisted of a rotating body 316 and multi-rows of comb teeth on the rotating body 316 . One end of the rotating body is a 6-tooth ratchet wheel with many tooth spaces.
[0139] The substance body 301 has an upper covering unit 310 and a lower covering unit 324 . The lower covering unit 324 is comprised of the front section and the rear section and a suction channel 349 is set at the rear section to be connected with the suction hose of cleaner. The external wall of the suction channel 349 also serves as a handle for users to operate and use the pet groomer 300 ; circles 350 are set at two side ends of the front section (See FIG. 29 ), and the circles 350 is used to install the end cap 314 of the rotating body 316 . Besides, the front section also has a buckle 339 , a slot 331 is set at the front section of the upper covering unit 310 , and the slot 331 and the buckle 339 are fastened so that the upper covering unit 310 and the lower covering unit 324 can be tightly combined together. Substance body 301 (also named as main body) comprises two side walls, wherein the combing assembly 302 is fixed.
[0140] A locking ring 323 is also set in the substance body 301 to combine the half circle structure at the rear end of the upper covering unit 310 with the corresponding half circle at the middle of the lower covering unit 324 and clamp the upper covering unit 310 with the lower covering unit 324 tightly. The locking ring 323 is detachable. When it is necessary to replace the combing assembly 302 or clean the parts between the upper covering unit 310 and lower covering unit 324 , demount the locking ring 323 to demount the upper covering unit 310 and the lower covering unit 324 , and obviously the combing assembly 302 installed between the upper covering unit 310 and the lower covering unit 324 is replaceable.
[0141] After the upper covering unit 310 is combined with the lower covering unit 324 , the baffle 347 in the upper covering unit 310 and the corresponding baffle 348 in the lower covering unit 324 combine and form an air intake 346 (See FIG. 34 ) to transmit air into the suction channel 349 . The best preference for the length of air intake 346 is to be longer than the contour length of any group of comb teeth 315 distributed on rotating body 316 . A hollow front section is placed outside of the air intake 346 , and a comb use opening 332 and an air leakage opening 330 are set in the hollow front section.
[0142] Aback-plate 327 is set at the bottom of the lower covering unit 324 , a screw hole 351 is set at the back plate 327 , a screw boss 352 corresponding to the screw hole 351 is set on the lower covering unit 324 , the back plate 327 is reliably connected with the lower covering unit 324 through the screw 328 , and the space between the back plate 327 and the lower covering unit of the air transmission channel (i.e. actuator container) is used to contain the driving assembly 303 .
[0143] The substance body 301 can also has a universal adaptor to be connected with vacuum cleaner (See FIG. 29 ). The universal adaptor includes an adapting tube 390 , a flexible hose 391 , an inner ring 392 , a sealing ring 393 and an adjusting ring 394 . The inner ring 392 , the sealing ring 393 and the adjusting ring 394 constitute a universal adaptor which could adjust its inner diameter to adapt to suction hoses of different outer diameters and realize sealing connection. The adapting tube 390 can be connected with the suction channel 349 of the lower covering unit 324 . The adapting tube 390 and the inner ring 392 are connected with one end of the flexible hose 391 respectively. The sealing ring 393 is for connecting the suction hose of vacuum cleaner.
[0144] The driving assembly 303 is formed from a lever drive assembly, which is consisted of a cam assembly and a connecting rod driving assembly. The connecting rod driving assembly has a connecting rod 318 and a lever 325 exposed outside of the actuator container.
[0145] The lever is integrated from a cap 342 , a cylinder 341 and a driving track 340 . The cap 342 is exposed outside of the actuator container and extends towards the suction channel 349 . User could activate the cap 342 by grasping the external wall of the suction channel 349 . The cylinder 341 is located between the cap 342 and the driving track 340 and fixed on the positioning tab 354 on the lower covering unit 324 (See FIG. 30 ). The driving track 340 is connected with the passive cylinder 336 of the connecting rod 318 to transmit torque force to the connecting rod 318 . The connecting rod 318 has a supporting cylinder 344 , the passive cylinder 336 and a driving cylinder 335 , and the supporting cylinder 344 is fixed in the locating hole 355 of the lower covering unit 324 (See FIG. 30 ). The connecting rod driving assembly also has a connecting rod block 317 which is used to press the connecting rod 318 tightly and prevent the connecting rod 318 from falling off. The cam assembly is consisted of a cam 311 , a cam track 334 and a driving pawl unit, of which the cam 311 has an installing hole 333 (See FIG. 29 ) and a driving pawl chamber 353 which is integrated with the cam 311 (see FIG. 32 ). The rotating body 316 has a 6-tooth ratchet wheel 337 , and the cylinder 345 is installed on the side of the 6-tooth ratchet wheel 337 . The cylinder 345 threads the installing hole 333 in the cam 311 and then is connected with the cap 314 , so the cam 311 is able to rotate coaxially with the rotating body 316 . Lever 325 extends from cap 342 toward center of combing assembly 302 with an arm containing driving track 340 extends toward sidewall of substance body 301 , driving assembly from driving track 340 till combing assembly 302 extends alongside sidewall of main body 301 , and all driving assembly 303 is isolated from suction airflow with cap 342 exposed outside for operation.
[0146] The cam track 334 is engaged with the driving cylinder 335 on the connecting rod 318 and therefore the connecting rod driving assembly and the cam assembly is combined. When the connecting rod 318 rotates, the driving cylinder 335 drives the cam track 334 on the cam 311 to move towards the direction opposite to the rotation direction of said rotating body 316 , so the cam assembly rotates around the cylinder 345 on the rotating body 316 .
[0147] The driving pawl unit has the driving pawl 313 , and the driving pawl 313 is meshed with the tooth space of the 6-tooth ratchet wheel 337 installed on the rotating body 316 . The driving pawl unit also includes the driving pawl chamber 353 within the cam 311 and the spring 312 of which one end is connected with the driving pawl 313 and the other end sticks to the inner wall of the driving pawl chamber 353 . A spring locating hole 356 is set on the driving pawl 313 , one end of the spring 312 is in the spring locating hole 356 , and the other end of the spring 312 extends outside of the driving pawl 313 and sticks to the inner wall of the driving pawl chamber 353 , so the driving pawl 313 acts on the surface of the 6-tooth ratchet wheel 337 . The 6-tooth ratchet wheel 337 is in circular arc shape, the driving pawl sticks to the surface of the ratchet wheel constantly and moves from one tooth space to next and mesh with the next tooth space.
[0148] When the cap 342 of the lever 325 is activated, the lever 325 rotates around the cylinder 341 , then the driving track 340 drives the passive cylinder 336 of the connecting rod 318 to move, then the connecting rod 318 rotates around the supporting cylinder 344 , the driving cylinder 335 of the connecting rod 318 moves to drive the cam track 334 of the cam assembly to move in the peripheral direction of the rotating body 316 , the cam assembly rotates around the installing cylinder 345 of the rotating body 316 , i.e. rotating coaxially with the rotating body. When the cam assembly rotates, the driving pawl 313 is driven to move, and the driving pawl 313 sticks to the surface of the 6-tooth ratchet wheel 337 on the rotating body 316 and meshes with the tooth space of the 6-tooth ratchet wheel, so the driving pawl 313 drives the 6-tooth ratchet wheel 337 to rotate and the rotating body 316 rotates around the installing cylinder 345 (See FIG. 32 ). When the lever 325 is released, the lever 325 rotates around the cylinder 341 to return back under the elastic force of the spring 326 , and the connecting rod 318 and cam reset accordingly at the same time, this makes the cam track 334 move in the direction opposite to the rotation direction of rotating body 316 .
[0149] FIGS. 31A-D are structural illustrations of the combing assembly of the pet groomer in embodiment 4; views a, b, c and d are structural illustrations of the combing assembly in different directions. As shown by FIGS. 31A-D , the combing assembly 302 is consisted of the rotating body 316 and six groups of comb teeth 315 , the pitch of every group of comb teeth 315 is 60°, every group of comb teeth 315 is in two rows, and one group of comb teeth 315 out of the six groups of comb teeth 315 necessarily extends outside of the comb use opening 332 to comb pet hairs. Obviously a group of comb teeth 315 can have one or more rows.
[0150] Two installing cylinders 345 at two ends of the rotating body 316 extend outwards along the axis of the rotating body 316 to install and limit the rotating body 316 is always inside the hollow front section.
[0151] The 6-tooth ratchet wheel 337 which mesh with the driving pawl 313 is set at one end of the rotating body 316 , and the 6-tooth ratchet wheel 337 and the cam assembly constitute a rotation angle locating section to regulate that the rotation angle by which the rotating body 316 rotates every time is 60°, and prevent rotating body 316 from reversing in use. The ratchet wheel may be designed as 8-tooth ratchet wheel and constitutes a rotation angle locating section together with the cam assembly to regulate that rotation angle by which the rotating body 316 rotates every time is 45°. Obviously the shape of the ratchet wheel may be designed on requirements to realize other different rotation angles, and the best plan is to have rotation angles as integral times of 10° or 15°.
[0152] The air intake 346 is set in the position rotated by 120° in direction D in FIG. 34 from the comb position. Necessarily one group of comb teeth is fixed to right face the air intake 346 when the rotating body rotates every time, and air intakes may be set in angles integral times of 60° or 45° if necessary.
[0153] The pet groomer 300 also has a position limiting pawl 319 , and a 6-tooth position limiting wheel 338 is set at the other end of the rotating body 316 . The 6-tooth position limiting wheel 338 and the above mentioned position limiting pawl 319 , the guide holder 321 fixed between the upper covering unit 310 and the lower covering unit 324 and the spring 320 connects the two constitute into a position limiting unit. The end of the position limiting pawl 319 connected with the spring 320 is inserted into the guide holder 338 , so the position limiting pawl 319 flexibly extends in the guide holder 321 under the action of the spring 320 . When the rotating body 316 rotates by 60°, the position limiting pawl 319 is meshed with the 6-tooth position limiting wheel 338 to prevent the rotating body 316 from rotating reversely. The position limiting pawl 338 may be also designed in 8-tooth, and after the rotating body 316 rotates by 45°, the position limiting pawl 319 meshes with the 8-tooth position limiting wheel 338 and prevents the rotating body 316 from rotating reversely.
[0154] The length of the comb teeth on the rotating body 316 may vary. When the pet groomer is used to comb pet hair, firstly choose the rotating body 316 which has corresponding length of comb teeth 315 to be installed inside of the hollow front section according to different pet hairs to avoid hurting pet skin due to improper lengths of comb teeth. Or replace the rotating body 316 directly to adapt to pet hair to be combed.
[0155] When the pet groomer is used, firstly connect the pet groomer with a vacuum cleaner, and turn on the vacuum cleaner. Then the comb use opening 332 and the air leakage opening 330 transmit airflows to the air intake 346 at the same time, and the airflow enters into vacuum cleaner through the suction channel 349 . In the combing process, the pet body blocks the comb use opening 332 , and the airflow from the air leakage opening 330 to the air intake 346 reduces the suction force at the comb use opening 332 to the pet body and effectively preventing excessive suction from affecting the comfort level of pet. After a certain amount of hair is accumulated on the comb teeth, activate the lever 325 , the lever 325 drives the connecting rod 318 through the driving track 340 , the connecting rod 318 drives the cam assembly to rotate, and the cam assembly drives the driving pawl 313 to rotate on the surface of the 6-tooth ratchet wheel and extend flexibly in the axial direction of the cam under the elastic force of the spring, so the 6-tooth ratchet wheel 337 is driven to rotate, then the rotating body 316 is driven to rotate by 60° by every activation. Then a new group of comb teeth 315 is rotated to the comb position, user may continue combing pet hair with the new group of comb teeth, and the comb teeth 315 that has combed pet hair is rotated by 60°. When a certain amount of pet hair is accumulated on the comb teeth at the comb position, activate the lever again, the present comb teeth 315 is rotated by another 60°, the previous comb teeth 315 with hair is rotated to the air intake 346 , and hair will be vacuumed into the air intake 346 from the comb teeth 315 , no external force is needed to strip off hair from comb teeth in advance. Because the suction acts at the comb position in the whole process, hairs will not drop down. The rotation angle of the comb teeth 315 may be other angles if necessary, and the best plan is integral multiples of 10° or 15°.
[0156] When comb teeth with hair are rotated to the position close to the air intake, in order to ensure pet hair wound on comb teeth can be vacuumed away completely, make sure every piece of comb teeth in this group points at the middle of the air intake, so the extending direction of every piece of comb teeth in the group keeps consistent with the vacuuming direction of the main suction airflow, rigorous paralleling is preferred, and make sure every piece of comb teeth in the group is inside of the main vacuuming airstream completely instead of partly, so the suction airflow could clear hairs away by overcoming only the frictional force between hair and smooth comb teeth.
Function and Effects of Embodiment 4
[0157] The driving pawl, which moves flexibly in axial direction of cam and meshes with the tooth space of the ratchet wheel, is adopted in the embodiment and constantly sticks to the surface of the ratchet wheel, moves from one tooth space to the next one, and meshes with the next tooth space to make sure the driving pawl drives the ratchet wheel to rotate by required angle, the structure is stable and reliable; besides, the pet groomer has a lever drive assembly to drive the rotating body 316 , and pet hair is moved to close to the air intake 346 , so pet hair is vacuumed into vacuum cleaner in the extending direction of the comb teeth and does not need external force to strip off hair from comb teeth in advance. No loose hair can fall off from pet body in grooming to pollute environment or to transmit allergen material. Besides, the substance body is detachable and easy for internal structure cleaning; the rotating body is replaceable, so different rotation bodies with proper comb teeth can be installed on the pet groomer according to different pet hair. Every group of comb teeth is replaceable, so when one or more pieces of comb teeth 315 are damaged, new comb teeth may replace damaged ones, thus being environment-protection. Plus, proper comb teeth may be chosen according to different pet hairs to make pet more comfortable and avoid hurting pet at the same time when combed. Pet hairs are moved to the air intake once the lever is activated, so the structure is simple and the operation is convenient. The pet groomer can be connected with the suction hose of vacuum cleaner through a flexible hose to realize convenient grooming, labor saving and not to fatigue the user easily; an adjusting ring is adopted in this case to adjust the sealing ring to be connected with the suction hose of vacuum cleaner which has different diameters, thus making the use more convenient.
[0158] In the pet groomer in embodiment 4, the external wall of the suction channel is used as the handle to grasp the pet groomer. Handles may be set in the upper covering unit or other proper positions of the pet groomer of the present invention to enable the user to operate and control the pet groomer conveniently.
[0159] The connecting rod driving assembly of the present invention extends outside of the substance body, and the part for the user to operate the pet groomer in embodiment 4 is a lever. Obviously the lever may be replaced by a press button and other driving parts.
[0160] One air leakage opening is set on the substance body of the present invention in embodiment 4, and obviously more air leakage openings may be set at other positions of the substance body if necessary to prevent excessive air force at the comb use opening from affecting the comfort level of pet when combed.
[0161] One group of comb teeth is arranged by every 60° in the present invention in embodiment 4, and altogether six groups are arranged, which could also be replaced by three groups of comb teeth uniformly distributed on the rotating body. When the comb teeth are in three groups, the circular pitch of every group is 120° and these three groups are uniformly distributed on the rotating body 316 , after a certain amount of pet hair is accumulated on the comb teeth at the comb position, once the lever 325 is activated, the comb teeth 315 are still rotated by 60°, and there are no comb teeth 315 under combing status at the comb position, so hair from pet body or dropping to the ground may be vacuumed through the comb use opening 332 . When the lever 325 is activated again, the comb teeth 315 with hair are rotated to the air intake 346 , adequate suction is at the air intake 346 to vacuum pet hair from comb teeth 315 to the air intake, and meanwhile another group of comb teeth 315 is under combing status and continues to comb pet hair.
[0162] The comb teeth on the rotating body may also be in four groups which are uniformly distributed on the rotating body with a circular pitch of 90°. After a certain amount of pet hair is accumulated on the comb teeth at the comb position, once the lever 325 is activated, the comb teeth 315 are rotated by 45°, and there are no comb teeth 315 under combing status at the comb position, so hair from pet body or dropping to the ground may be vacuumed through the comb use opening 332 . When the lever 325 is activated again, the comb teeth 315 with hair are rotated by 90° totally from beginning, and then another group of comb teeth 315 is under combing status and continues to comb pet hair. When lever 325 is activated by the 3<rd >time, the 1<st >group of comb teeth 315 with hair are rotated to the air intake 346 , adequate suction is at the air intake 346 to vacuum pet hair from comb teeth 315 , and meanwhile there are no comb teeth 315 under combing status at the comb position, so hair from pet body or dropping to the ground may be vacuumed through the comb use opening 332 .
[0163] Comb teeth on the rotating body may be distributed in different angles if necessary and withdrawn in correspondingly proper circular pitch. In the present invention, when the group number of comb teeth is m (m is an integral number), the quantity of tooth spaces on the ratchet wheel is recommended to be integral multiples of m.
[0164] When the comb teeth could be withdrawn in the pet groomer, in order to facilitate convenient use, an operation unit is set to the main body which sends corresponding information to inform the status of the pet groomer according to the fact whether comb teeth are at the comb position or not. When there are no comb teeth extending outside of the comb use opening, i.e. the pet groomer is under comb teeth protecting status, the operating and prompting unit sends corresponding signals to inform the user of the comb teeth protecting status, and after the lever is activated for n (n is an integral number) times, one group of comb teeth extends outside of the comb use opening; when one group of comb teeth is at the comb use opening, i.e. the pet groomer is under combing status, the operating and prompting unit sends corresponding signals to inform the user of the combing status, the user could comb pet hair, and if the comb teeth need to be withdrawn in the pet groomer, the lever should be activated for m (m is an integral number) times. Obviously under two circumstances that three groups of comb teeth are set when the rotation angle is 60° and four groups of comb teeth are set when the rotation angle is 45°, when there are no comb teeth at the comb position, i.e. the pet groomer is under comb teeth protecting status, the operating and prompting unit sends corresponding signals to inform the user of the comb teeth protecting status, and the connecting rod driving assembly is driven to make one group of comb teeth extend outside of the comb use opening; when one group of comb teeth is under combing status at the comb position, i.e. the pet groomer is under combing status, the operating and prompting unit sends corresponding signals to inform the user of the combing status, the user could comb pet hair, and if the comb teeth need to be withdrawn in the pet groomer, the connecting rod driving assembly should be driven for one time.
[0165] As a specific plan, we may adopt indicators of two different colors to send corresponding signals, and give further descriptions about indicators with words or graphs.
[0166] Besides, if one or more pieces of comb teeth 315 are damaged, new comb teeth can be used to replace or just turn to a new rotating body with proper comb teeth.
[0167] The locking ring 323 in the embodiment connects the upper covering unit 310 with the lower covering unit 324 through the locking groove to make the upper covering unit 310 and the lower covering unit 324 tightly locked.
[0168] The comb teeth 315 in embodiment 4 are in six groups, and it can also be in other integral group(s), for example, three groups, four groups, eight groups, etc., and every group may has one or more rows; the quantity of the comb teeth 315 in every row is also subject to requirements, such as 20 pieces, 30 pieces, 40 pieces, 50 pieces and 60 pieces; the comb teeth of different rows may be distributed on the rotating body in a staggered arrangement way.
[0169] Besides, six groups of comb teeth 315 in the embodiment all are distributed perpendicular to the rotating body, so the pointing direction (i.e. the extending direction of the comb teeth) of every group of comb teeth when rotated to the air intake is consistent with the main direction of the airflow which is vacuumed into the air intake. In the pet groomer of the present invention, the comb teeth may be distributed in the rotating body in other forms (such as curve extending way), as long as every piece of comb teeth in the group points at the air intake and gets in the main channel of vacuuming airflow when rotated to the front of air intake.
[0170] The diameter of the comb teeth in the present invention is also subject to requirements, for example, φ0.3, φ0.5, φ0.6, φ0.8, φ1.0, φ1.2, φ1.5, φ1.8, φ2.0, φ2.5, etc.; the material of the comb teeth 315 is subject to requirements likewise like stainless steel 304, stainless steel 201, 45# chromed steel, plastic PP, plastic PVC etc.; in order to prevent plastic comb teeth 315 from producing static electricity, antistatic agent may be added to the material, or static may be eliminated by adding a metal strip. The top surface shape of the comb teeth 315 may be flat or other shape like ball-shape. Some rectangular or round ventilating slots may be added to the surface of the rotating body 316 to help vacuuming pet hair on the comb teeth. The rotating body surface may have some grooves 343 to clear away pet hair which is winded on the rotating body more easily.
[0171] The comb teeth 315 may be firstly connected with comb teeth base plate, then the comb teeth base plate assembled on the rotating body 316 , and the comb teeth base plate and the rotating body 316 can also be connected through a pressing plate, etc. Of course the comb teeth 315 may also be installed on other carriers and then on the rotating body. The comb teeth 315 may be a movable structure convenient for repair and replacement, or directly fixed in the comb teeth rotating body 316 .
[0172] Besides, the lower covering unit 324 and the bottom back plate 327 may be connected in others ways, such as through a buckle or ultrasonic welding.
[0173] It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims. | A pet groom and vacuum cleaner including the pet groomer are provided. The pet groomer includes a main body having two sidewalls, an actuator container, and a hollow handle for connecting with the suction hose. A comb assembly is fixed between said two sidewalls, and includes a rotatable body, and a comb teeth arranged in an axial direction of the rotatable body. A driving assembly drives the comb teeth to rotate with the rotatable body. The comb teeth rotates between a first position and a second position. The driving assembly is isolated from the suction airflow and includes an actuator element exposed out of the actuator container and extending toward the hollow handle. Motion transmission elements of the driving assembly extends from the actuator element to the comb assembly, and includes three sections. | 0 |
BACKGROUND OF THE INVENTION
This invention relates to dental appliances and, more particularly, to gingival tissue retraction cords.
In dental therapeutics, it is often necessary to retract gingival tissue in order to prepare patients for taking impressions, setting crowns or effecting restorations.
In a widely used procedure for retracting gingival tissue, cotton cord, impregnated with a therapeutic preparation having astringent and hemostatic properties, is disposed about the tooth and placed into the gingival crevice for a limited time period to effect tissue displacement.
The fluid absorbent, cotton cord which is used in gingival retraction may be single or multiple strand of suitable cross-sectional area for dental purposes. The therapeutic preparations which may be absorbed onto the cotton cord to effect gingival retraction include, for example, racemic epinephrine hydrochloride and aluminum compounds such as potassium aluminum sulfate (alum). For a further discussion of gingival retraction with cotton cords as well as absorbent, resilient, circular rings composed of hard or soft leather, see U.S. Pat. No. 3,238,620 (Robertson, 1966).
Although the gingival retraction cord of the prior art is very effective as a tissue displacement device and agent, it has various negating characteristics. The mechanical handling of the prior art cord, which usually consists of twists of cotton strands or filaments has been somewhat difficult and awkward because of the pliable nature of the cord; in particular, it is difficult and awkward to thread the pliable cord between closely adjacent teeth and, where desired, to tie the loose ends prior to the insertion of the therapeutic cord into the gingival crevice. Also, unless the cord is packed into the gingival crevice with instrumentation which is applied in alignment with the twist, the strands or filaments can become unraveled during the packing step. The cotton twist cord may split during packing with the "L" shaped packing instrument whereby the horizontal arm of the instrument traverses the cord and reciprocal removal of the instrument through the body of the cord is somewhat difficult; and, in extreme cases, the traversal of the cotton twist cord by the relatively sharp packing instrument may result in severance of tooth attachment tissue. Since the cotton twist cord is highly pliable, it presents relatively small resistance to gum force and, while disposed in the gingival sulcus, it tends to flatten out thereby decreasing the spaced relationship between the tooth and the gum which can interfere with the taking of an impression. In addition, the tensile strength of the cotton twist cord is relatively weak as a result of which the cord tends to fray and leave therapeutically impregnated lint in the gingival sulcus which may cause tissue irritation.
Accordingly, the principal object of this invention is to provide a moderately firm, flexible, fluid absorbent, gingival retraction cord which (a) facilitates the circumdisposition of the cord about the tooth, (b) resists splitting during the packing of the cord into the gingival sulcus, (c) maintains its shape in the gingival sulcus and (d) is substantially fray resistant and lint free.
SUMMARY OF THE INVENTION
In accordance with one aspect of this invention, there is provided a gingival tissue retraction cord comprising a suitably dimensioned, moderately firm, flexible, multistrand, braided, absorbent cord impregnated with an effective amount of gingival tissue retraction material.
In accordance with a second aspect of this invention, there is provided a method for retracting gingival tissue which comprises inserting into the gingival sulcus a suitably dimensioned, moderately firm, flexible, multistrand, braided, absorbent cord impregnated with an effective amount of gingival tissue retraction material.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partial, schematic, side elevational view of one embodiment of the braided retraction cord of this invention having 4 warp strands, 4 filling strands and 3 axial support strands;
FIG. 1A is a diagramatic view of the cord depicted in FIG. 1 showing the filling strands successively passing over and then under adjacent warp strands and the warp strands successively passing over and then under adjacent filling strands.
FIG. 2 is a partial, schematic, side elevational view of an alternative embodiment of the braided retraction cord of this invention having 4 pairs of warp strands, 4 pairs of filling strands and 1 axial support strand.
FIG. 2A is a diagramatic view of the cord depicted in FIG. 2 showing each pair of filling strands successively passing over and then under adjacent pairs of warp strands and each pair of warp strands successively passing over and then under adjacent pairs of filling strands.
FIG. 3 is a schematic, perspective view showing the braided gingival retraction cord of this invention disposed about a tooth and packed into the gingival crevice.
DETAILED DESCRIPTION
Referring now to the drawings (wherein "F" identifies filling strands and "W" identifies warp strands) and, in particular, to FIGS. 1 and 1A, there is shown, in schematic and diagramatic views, a braided gingival retraction cord 10 having four warp strands, 12, 14, 16 and 18, three axial support strands 20 and four filling strands 22, 24, 26 and 28. As illustrated in FIG. 1A, the filling strands successively pass over and then under adjacent warp strands and the warp strands successively pass over and then under adjacent filling strands.
With reference to FIGS. 2 and 2A, there is shown, in schematic and diagramatic views, a braided gingival retraction cord 30 having four pairs of warp strands 32, 34, 36 and 38 one axial support strand 40 and four pairs of filling strands 42, 44, 46 and 48. As depicted in FIG. 2A each pair of filling strands in this embodiment of the invention successively passes over and then under adjacent pairs of warp strands and each pair of warp strands successively passes over and then under adjacent pairs of filling strands.
The braided retraction cords of this invention comprise longitudinally disposed warp strands, transversely disposed filling strands and, advantageously, may include one or more axially or longitudinally disposed support strands. The individual strands comprise fluid absorbent yarns or thread of suitable size and weight. For example, the warp and filling strands may comprise No. 60/2 cotton thread which is composed of a double cotton filament twist having a length-pound ratio of 25,200 yards per pound and the axial support strands may comprise No. 40/2 cotton thread which is composed of a double cotton filament twist having a length-pound ratio of 16,800 yards per pound. The size and number of strands are so selected as to provide a gingival retraction cord having a diameter from about 0.015 to about 0.05 inch.
In one embodiment of this invention employing No. 60/2 cotton thread for all strands, the braided retraction cord has four warp strands, four filling strands, fifty two picks or plaits per linear inch, and a diameter of about 0.5 mm (0.02 in.). In a second embodiment of this invention employing No. 60/2 cotton thread for the warp and filling strands and No. 40/2 cotton thread for the axial support strands, the braided retraction cord has four warp strands, three axial support strands, four filling strands, thirty eight picks or plaits per linear inch, and a diameter of about 0.635 mm (0.025 in.). In a third embodiment of this invention employing No. 60/2 cotton thread for the warp and filling strands and No. 40/2 cotton thread for the axial support strand, the braided retraction cord has four pairs of warp strands, one axial support strand, four pairs of filling strands, twenty seven picks or plaits per linear inch, and a diameter of about 0.762 mm (0.030 in.).
The braided retraction cord generally has from about 24 to about 60 picks or plaits per linear inch with the number of picks or plaits per linear inch being inversely proportional to the increasing diameter of the cord and being so selected as to provide a flexible cord having a relatively firm body.
One or more of the filling strands may be a suitably dyed strand which can impart a color code to the braided retraction cord to indicate size or for other identification purposes.
The braided retraction cord of this invention may advantageously include from one to three or more axial support strands which, beneficially, enable the substantially annular cord to resist flattening in the gingival sulcus where the gum tissue exerts a positive force and pressure in the direction of the tooth. This resistance of the cord to flattening distortion under use conditions is highly desirable since flattening of the gingival retraction cord can interfere with the taking of an impression.
As schematically illustrated in FIG. 3, the braided retraction cord 50, which comprises interlaced and entwined warp and filling strands, is readily and easily disposed about the tooth and packed into the gingival sulcus 60. The interlaced and entwined strands which form the braided retraction cord resist unraveling and untwisting during the packing step and, at the same time, resist splitting and transversing of the cord by the packing instrument. This latter feature is very significant because traversal of the cord by the relatively sharp packing tool can result in cutting or, in extreme case, severance of tooth attachment tissue. In addition, the braided retraction cord resists fraying and is substantially lint free as a result of which substantially no chemically impregnated lint is left in the gingival sulcus upon removal of the braided cord from the sulcus.
The braided retraction cord may be fabricated by using any suitable braiding machine as, for example, a Wardwell rapid braider having two carrier tiers with eight carriers in each tier as well as central dispensing carriers. By suitably spacing a selected number of thread spools on the upper and lower tiers, a braided cord is obtained in which the filling strands successively pass over and then under adjacent warp strands and warp strands successively pass over and then under adjacent filling strands as diagramatically shown in FIG. 1A, or, in an alternative embodiment, a braided cord is obtained in which pairs of filling strands successively pass over and then under adjacent pairs of warp strands and pairs of warp strands pass over and then under adjacent pairs of filling strands as diagramatically shown in FIG. 2A.
Following the fabrication of the braided cord, it is passed through an impregnating solution containing a suitable concentration of retraction material such as epinephrine, alum, aluminum chloride, or mixtures thereof to saturate the cord with the solution. In an illustrative embodiment, the braided cord is passed through and saturated with a retraction solution containing 8% racemic epinephrine and 7% aluminum potassium sulfate. Upon completion of the soaking and saturation step, the braided cord is dried to remove the fluid carrier. The dried cord may be wound in spool form and packaged in glass dispensers.
For retraction of gingival tissue, the dental practioner passes the treated cord around the neck of the tooth and packs its into the gingival sulcus. Normal tissue moisture, water or gingival retraction solutions activate the impregnated braided cord to retract the gingival tissue.
While in the foregoing description and accompanying drawings there has been shown and described the preferred embodiment of this invention, it will be understood, of course, that minor changes may be made in the details of construction as well as in the combination, arrangement and composition of parts, without departing from the spirit and scope of the invention as claimed. | A gingival tissue retraction cord is provided which comprises a suitably dimensioned, moderately firm, flexible, multistrand, braided, absorbent cord impregnated with an effective amount of gingival tissue retraction material. The retraction cord is adapted to be inserted into the gingival sulcus to effect retraction of gingival tissue. | 0 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This patent application claims priority to U.S. patent application Ser. No. 12/308,481, filed Sep. 13, 2010, which claims the benefit of International Application Ser. No. PCT/US2007/014290 filed on Jun. 18, 2007, which claims the benefit U.S. Provisional Patent Application Ser. No. 60/814,518, filed on Jun. 16, 2006; U.S. Provisional Patent Application Ser. No. 60/900,796 filed on Feb. 7, 2007; U.S. Provisional Patent Application Ser. No. 60/921,881 filed on Apr. 3, 2007, each of which are incorporated herein by reference in their entireties.
BACKGROUND OF THE INVENTION
[0002] This invention relates generally to suspension systems for vehicles, and more particularly, to a leaf suspension arrangement that is useable with independent and semi-independent suspension systems.
DESCRIPTION OF THE RELATED ART
[0003] Leaf spring systems have for many years been used for the suspension of wheeled vehicles. The central element of a leaf spring suspension system for a vehicle is termed a “semi-elliptical” spring configured as an arc-shaped length of spring steel having a rectangular cross-section. At the center of the arc is provided an arrangement for coupling to the axle of the vehicle. At the ends are provided coupler holes for attaching the spring to the vehicle body. For heavy vehicles, leaf springs are stacked on one another to form layers of springs of different lengths. Leaf springs are still used in heavy commercial vehicles and railway carriages. In the case of very heavy vehicles, leaf springs provide the advantage of spreading the load over a larger region of the vehicle's chassis. A coil spring, on the other hand, will transfer the load to a single point.
[0004] The well-known Hotchkiss drive, the name of which derives from the French automobile firm of Hotchkiss, employs a solid axle that is coupled at its ends to the centers of respective semi-elliptical leaf springs. There are a number of problems with this form of drive arrangement. First, this drive system is characterized by high unsprung mass. Additionally, the use of a solid axle results in coupled left/right wheel motion. During heavy cornering and fast acceleration, this known system suffers from vertical deflection and wind-up.
[0005] One prior art effort to address the problems associated with the Hotchkiss system employs a parallel leaf spring arrangement at each end of a solid axle. This known arrangement affords increased axle control, in the form of reduced power hop. Other advantages of this known arrangement include roll under steer, auto load leveling and the gross vehicle weight, and no frame changes are required to convert from a Hotchkiss system. However, the known parallel leaf spring arrangement employs a solid axle, and therefore does not provide the benefits of independent suspension. In addition, this known arrangement is plagued with the disadvantage of high unsprung mass.
[0006] A de Dion tube vehicle suspension arrangement is a form of semi-independent suspension and constitutes an improvement over the Hotchkiss drive. In this type of suspension, universal joints are employed at the wheel hubs and the differential, and there is additionally provided a solid tubular beam that maintains the opposing wheels in parallel. The de Dion tube is not directly connected to the chassis and is not intended to flex.
[0007] The benefits of a de Dion suspension include a reduction in the unsprung weight compared to the Hotchkiss drive. This is achieved by coupling the differential to the chassis. In addition, there are no camber changes during suspension unloading. Since the camber of both wheels is set at zero degrees, the traction from wide tires is improved, and wheel hop under high power operations is reduced compared to an independent suspension. However, the de Dion tube adds unsprung weight.
[0008] It is, therefore, an object of this invention to provide a vehicle suspension arrangement that provides the benefits of independent suspension while using leaf spring technology.
[0009] It is another object of this invention to provide a vehicle suspension arrangement that employs leaf spring technology and yet affords reduced unsprung mass for reduced inertial effects and improved vehicle handling response.
[0010] It is also an object of this invention to provide a vehicle suspension arrangement that employs leaf spring technology and affords reduced suspension inertia.
[0011] It is a further object of this invention to provide a vehicle suspension arrangement that employs leaf spring technology and affords reduced noise, vibration, and harshness (NVH).
[0012] It is additionally an object of this invention to provide a vehicle suspension arrangement that employs leaf spring technology and affords reduced lateral wheel shake.
[0013] It is yet a further object of this invention to provide a vehicle suspension arrangement that employs leaf spring technology and affords reduced side view wind-up at the axle bracket.
[0014] It is also another object of this invention to provide a vehicle suspension arrangement that employs leaf spring technology and affords reduced forward and rearward movement.
[0015] It is yet an additional object of this invention to provide a vehicle suspension arrangement that employs leaf spring technology and affords a semi-independent suspension effect during asymmetric wheel travel.
[0016] It is yet an additional object of this invention to provide a vehicle suspension arrangement that employs leaf spring technology in combination with a coil spring element.
SUMMARY OF THE INVENTION
[0017] These and other advantages and features will become more apparent from the following description taken in conjunction with the drawings.
[0018] The foregoing and other objects are achieved by this invention which provides a vehicle drive arrangement for a vehicle of the type having a chassis extending longitudinally, and a rotary power shaft extending longitudinally along the chassis. The rotary power shaft is coupled at a rearward end thereof to a differential power transmission arrangement that converts the rotary motion of the rotatory power shaft to rotatory motion of first and second drive shafts disposed substantially orthogonal the rotary power shaft. Each of the first and second drive shafts has a respective longitudinal axis. In accordance with the invention, there are provided a differential coupling arrangement for fixedly coupling the differential arrangement to the chassis, and first and second universal coupling arrangements for coupling respective ones of the first and second drive shafts to the differential arrangement, whereby the first and second drive shafts are transaxially displaceable. First and second spring elements are coupled to respective ones of the first and second drive shafts at respective ends distal from the first and second universal coupling arrangements, and to the chassis. In addition, first and second secondary leaf springs are coupled at respective first ends thereof to the first and second drive shafts at respective ends distal from the first and second universal coupling arrangements, and at respective second ends thereof to the chassis. There is additionally provided a beam having first and second ends. The beam is coupled at the first and second ends to respective ones of the first and second drive shafts at respective ends distal from the first and second universal coupling arrangements.
[0019] In one embodiment of the invention, each of the first and second ends of the beam are coupled to the first and second drive shafts at a determined transaxial distance.
[0020] In a highly advantageous embodiment, the first and second spring elements are respective first and second primary leaf springs. Each of the first and second primary leaf springs is coupled at a respective first end thereof to the chassis and at substantially the center thereof to a respective one of the first and second drive shafts. The first and second secondary leaf springs are arranged, in this embodiment, to be substantially parallel to the respective first and second primary leaf springs.
[0021] A beam coupler arrangement is provided for coupling the beam to the chassis. The beam coupler arrangement includes a pivotable beam coupler element pivotally coupled to the beam. A first beam coupler arm is coupled at one end thereof to the pivotable beam coupler element, and at a distal end thereof substantially in the direction of the longitudinal axis of the first drive shaft, to the chassis. There is additionally provided a second beam coupler arm coupled at one end thereof to the pivotable beam coupler element, and at a distal end thereof substantially in the direction of the longitudinal axis of the second drive shaft, to the chassis.
[0022] In a practicable embodiment of the invention, the first and second secondary leaf springs are disposed below the respective first and second primary leaf springs. In other embodiments, however, the first and second secondary leaf springs are disposed above the respective first and second primary leaf springs. In some of such other embodiments, the first and second secondary leaf springs are arranged to extend through the chassis.
[0023] In a highly advantageous embodiment of the invention, there are further provided first and second displaceable pivot coupling arrangements for coupling the respective second ends of the first and second secondary leaf springs to the chassis. The displaceable pivot coupling arrangements facilitate adjustment of the effective spring rate of the secondary leaf springs.
[0024] In other embodiments, there are provided first and second displaceable fulcrum arrangements, also for facilitating the varying of the respective spring rates of the first and second secondary leaf springs.
[0025] In accordance with a further aspect of the invention, there is provided a vehicle drive arrangement for a vehicle of the type having a chassis extending longitudinally, and a rotatory power shaft extending longitudinally along the chassis. The rotary power shaft is coupled at a rearward end thereof to a differential power transmission arrangement that converts the rotary motion of the rotatory power shaft to rotary motion of first and second drive shafts disposed substantially orthogonal the rotary power shaft. Each of the first and second drive shafts has a respective longitudinal axis. In accordance with the invention, there are provided a differential coupling arrangement for fixedly coupling the differential arrangement to the chassis, and first and second universal coupling arrangements for coupling respective ones of the first and second drive shafts to the differential arrangement, whereby the first and second drive shafts are transaxially displaceable. First and second primary leaf springs are each coupled at respective first and second ends thereof to the chassis and at substantially the center thereof to respective ones of the first and second drive shafts at respective ends of the drive shafts distal from the first and second universal coupling arrangements. In addition, first and second secondary leaf springs are coupled at respective first ends thereof to the first and second drive shafts at respective ends distal from the first and second universal coupling arrangements, and at respective second ends thereof to the chassis. There is additionally provided a beam having first and second ends. The beam is coupled at the first and second ends to respective ones of the first and second drive shafts at respective ends distal from the first and second universal coupling arrangements.
[0026] In a highly advantageous embodiment of the invention, there is provided a vehicle suspension arrangement for a vehicle having a chassis and a drive axle. The vehicle suspension arrangement is provided with a primary leaf spring having a substantially longitudinal configuration and first and second ends for coupling to the chassis of the vehicle. A secondary leaf spring has a substantially longitudinal configuration, a first end for coupling to the chassis, and a second end. A coupling element is provided for coupling to the drive axle. In addition, a first pivot joint for pivotally coupling to substantially the center of said primary leaf spring intermediate of its first and second ends for coupling to said coupling element. Finally, a second pivot joint for pivotally coupling the second end of said secondary leaf spring to said coupling element.
[0027] In one embodiment, there is further provided a primary leaf coupler for securing said first pivot joint to substantially the center of said primary leaf spring. The first pivot joint is formed of first and second pivot portions, the first pivot portion being fixedly coupled to said primary leaf coupler, and the second pivot portion being fixedly coupled to the coupling element. The first and second pivot portion being configured to be pivotally coupled to each other.
[0028] In a still further embodiment, the first pivot joint is configured to enable limited pivotal motion between said primary leaf spring and said coupling element. The pivotal motion in this embodiment therefore is directed longitudinally in see-saw like relation to said primary leaf spring.
[0029] In accordance with a further apparatus aspect of the invention, there is provided a vehicle suspension arrangement for a vehicle having a chassis and a drive axle. The vehicle suspension arrangement is provided with a primary spring having a substantially helical configuration, the primary spring having a first end for coupling to the chassis of the vehicle, and a second end for coupling to an axle of the vehicle. A secondary leaf spring that has a substantially longitudinal configuration is further provided. The secondary leaf spring has a first end for coupling to the chassis, and a second end. Additionally, a coupling element couples the second ends of the secondary leaf spring to the drive axle.
[0030] In one embodiment of the vehicle suspension arrangement, the coupling element includes a pivot joint for pivotally coupling the second end of said secondary leaf spring to the drive axle.
[0031] In a still further embodiment of the invention, there is provided a further primary spring having respective first and second ends thereof coupled to the chassis. The further primary spring is coupled at substantially the center thereof to the drive shaft and to the second en of said primary spring. In a highly advantageous embodiment, the further primary spring is a flat locating plate. The flat locating plate is, in some embodiments, a single plate-main leaf spring.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] Comprehension of the invention is facilitated by reading the following detailed description, in conjunction with the annexed drawing, in which:
[0033] FIG. 1 is a perspective representation of a specific illustrative embodiment of the invention;
[0034] FIG. 2 is a side plan view of the embodiment of FIG. 1 ;
[0035] FIG. 3 is a perspective representation of a further specific illustrative embodiment of the invention;
[0036] FIGS. 4 a and 4 b are respective side plan and partially cross-sectional front plan simplified schematic illustrations of a rotary joint arrangement constructed in accordance with the principles of the invention;
[0037] FIGS. 5 a and 5 b are simplified representations of a suspension system constructed in accordance with the principles of the invention ( FIG. 5 a ) and a prior art suspension arrangement ( FIG. 5 b ), both in a simulated static acceleration condition;
[0038] FIGS. 6 a and 6 b are simplified representations of the suspension system constructed in accordance with the principles of the invention of FIG. 5 a and a prior art suspension arrangement of FIG. 5 b , both in a simulated static braking condition;
[0039] FIG. 7 is a simplified schematic representation of a side view of a suspension system constructed in accordance with the principles of the invention with a 1 st stage leaf spring, and further showing the wheel center path, with a fulcrum arranged to communicate with the 2 nd stage lower leaf;
[0040] FIG. 8 is a simplified schematic representation of a side view of a suspension system constructed in accordance with the principles of the invention with a 1 st stage consisting of a substantially equivalent coil spring, or air spring, with the fulcrum of the 2 nd stage lower leaf removed;
[0041] FIG. 9 is a simplified schematic representation of a side view of a suspension system constructed in accordance with the principles of the invention with a 1 st stage consisting of a coil spring or air spring, with an optional fulcrum, arranged to communicate with the secondary stage lower leaf, and further showing an optional locating spring plate in the 1 st stage;
[0042] FIG. 10 is a simplified schematic representation of a clip bracket that can be used to push or pull the main spring or the secondary stage;
[0043] FIGS. 11 a , 11 b , and 11 c are simplified schematic side view representations of a height control arrangement constructed in accordance with the invention that is useful in the loading and unloading of a stationary vehicle, FIG. 11 a showing a simplified system control arrangement in block and line form;
[0044] FIG. 12 is a simplified schematic top plan representation of a splayed suspension arrangement constructed in accordance with the invention wherein secondary leaf springs are shown to be mounted at angles with respect to the primary leaf springs;
[0045] FIG. 13 is a simplified schematic perspective representation of a variable position fulcrum bumper constructed in accordance with the invention that may be active or passive to rotate in a controlled manner to create a variation in the stiffness of the secondary spring rate;
[0046] FIG. 14 is a simplified schematic plan representation of the variable position fulcrum bumper of FIG. 13 ; and
[0047] FIG. 15 is a simplified schematic representation of the variable position fulcrum bumper of FIG. 14 that is useful to illustrate the variation in vehicle height that is achievable, particularly when the vehicle (not shown) is stationary.
DETAILED DESCRIPTION
[0048] FIG. 1 is a perspective representation of a specific illustrative embodiment of the invention. As shown in this figure, a vehicle suspension system 100 has a chassis that is generally designated as chassis 110 . The chassis has a pair of substantially parallel chassis rails 112 a and 112 b that are coupled to one another by cross-braces 116 and 118 .
[0049] A differential drive arrangement 120 is fixedly coupled to the chassis and converts the rotary motion of a drive shaft 122 to substantially orthogonal rotary motion at half shafts 125 a and 125 b . Each half shaft has an associated pair of universal joints (not specifically designated) that are arranged to be proximal and distal with respect to the differential drive arrangement Thus, the half shafts, each of which has an associated longitudinal axis (not shown), accommodate transaxial motion, particularly by operation of the proximal universal joints.
[0050] Half shafts 125 a and 125 b are shown to be coupled at their distal ends to respective leaf springs 130 a and 130 b . Referring to leaf spring 130 a , for example, the leaf spring is, in this specific illustrative embodiment of the invention, pivotally coupled at its forward end to a bracket 132 a . At its rearward end, leaf spring 130 a is pivotally coupled to a link 134 a . As shown in this figure, there is additionally provided a half leaf spring 136 a that is also, in this specific illustrative embodiment of the invention, coupled at its forward end to bracket 132 a . At its rearward end, half leaf spring 136 a is coupled to the distal end of half shaft 125 a . Half leaf spring 136 a is shown in this specific illustrative embodiment of the invention, to engage a fulcrum 133 a.
[0051] There is additionally provided a transverse beam 140 that is coupled to cross-brace 116 by a damper 142 and to cross-brace 118 by a further damper 144 . Transverse beam 140 has installed thereon a pivoting member 150 to which are attached link elements 152 and 154 . The link elements are attached, via brackets (not specifically designated), to cross-brace 118 .
[0052] FIG. 2 is a side plan view of the embodiment of FIG. 1 of vehicle suspension system 100 . Elements of structure that have previously been discussed are similarly designated. As shown in this figure, leaf spring 130 a and half leaf spring 136 a are each coupled at their respective forward ends to bracket 132 a . Leaf spring 130 a is pivotally coupled at a pivot 160 , and half leaf spring 136 a is pivotally coupled at a pivot 162 , at bracket 132 a . In this specific illustrative embodiment of the invention, pivots 160 and 162 are fixed on bracket 132 a , which is fixed in relation to chassis rail 112 a . In other embodiments, and as will be described below, there is provided a mechanism (not shown in this figure) that displaces bracket 132 a , and in some embodiments, only pivot 162 , in relation to chassis rail 112 a . Such displacement of the pivots enables advantageous adjustment of the combined spring rate of leaf spring 130 a and half leaf spring 136 a . Additionally, such displacement is useful to adjust the height of the vehicle (not shown) while stopped, illustratively to facilitate loading and unloading of cargo and passengers (not shown).
[0053] FIG. 3 is a perspective representation of a further specific illustrative embodiment of the invention. Elements of structure that have previously been discussed are similarly designated. As shown in this figure, a vehicle suspension system 170 has a leaf spring 171 and a half leaf spring 172 . In contrast to the embodiment of FIGS. 1 and 2 , leaf spring 171 is arranged to be coupled to the underside of half shaft 125 b . Half leaf spring 172 is coupled above half shaft 125 b.
[0054] Leaf spring 171 is, in this specific illustrative embodiment of the invention, coupled to a bracket 175 . Half leaf spring 172 is coupled to chassis rail 177 at a bracket 180 . Bracket 180 is shown to be disposed within chassis rail 177 . It is particularly noteworthy that in this embodiment half leaf spring 172 is arranged to extend through chassis rail 177 at a fulcrum point 182 . The arrangement of this embodiment advantageously reduces the extent to which the leaf suspension system is visible when installed on a vehicle.
[0055] FIGS. 4 a and 4 b are respective side plan and partially cross-sectional front plan simplified schematic illustrations of a rotary joint arrangement 200 constructed in accordance with the principles of the invention. Elements of structure that bear analogous correspondence to elements of structure that have previously been discussed are similarly designated in this figure. Referring to FIG. 4 a , it is seen that there is provided a leaf spring 130 a that, in this specific illustrative embodiment of the invention, is pivotally coupled at its forward and rear ends, as previously described. There is additionally provided a half leaf spring 210 that is also, in this specific illustrative embodiment of the invention, pivotally coupled at a pivot mount 212 at its end distal to a further pivotal mounting 213 at a coupling member 214 . The coupling member is itself coupled to axle shaft 215 . Half leaf spring 210 is shown in this specific illustrative embodiment of the invention to engage a fulcrum 216 .
[0056] FIG. 4 a further illustrates a pivot link mounting arrangement 220 wherein leaf spring 130 a is securely clamped between clamping member 222 and 224 , as will be described below in relation to FIG. 4 b . Referring once again to FIG. 4 a , clamping member 224 is coupled to a pivot joint 226 that is itself engaged with coupling 214 . This arrangement permits a further degree of motion that reduce system internal loading on the pivot joint arrangement and leaf spring elements.
[0057] FIG. 4 b is a partially cross-sectional front plan simplified schematic illustrations of rotary joint arrangement 200 constructed in accordance with the principles of the invention. Elements of structure that bear analogous correspondence to elements of structure that have previously been discussed are similarly designated in this figure. It is seen in this figure that leaf spring 130 a (shown cross-sectionally) is securely clamped between clamping members 222 and 224 by operation of bolts 230 .
[0058] Pivot joint 226 is shown in FIG. 4 b to be formed of two pivot sections, 214 a and 224 a . More specifically, pivot section 214 a is coupled to coupling 214 (not specifically designated in this figure), and pivot section 224 a is coupled to clamping member 224 . The pivot sections in this specific illustrative embodiment of the invention, are pivotally engaged in this embodiment of the invention in a hinge-like manner. Therefore, in this embodiment, the pivotal motion is directed longitudinally in see-saw like fashion of leaf spring 130 a.
[0059] FIGS. 5 a and 5 b are simplified representations of a suspension system 200 constructed in accordance with the principles of the invention ( FIG. 5 a ) and a prior art suspension arrangement 300 ( FIG. 5 b ), illustratively a conventional parallel leaf suspension, both represented in computer-simulated static acceleration conditions. Elements of structure that have previously been discussed are similarly designated in this figure. FIGS. 5 a and 5 b are situated next to one another for sake of facilitating comparison of the effect of acceleration. It is seen that the prior art embodiment of FIG. 5 b does not comprise the structural equivalent of half leaf spring 210 shown in FIG. 5 a.
[0060] As can be seen in FIG. 5 a , leaf spring 130 a remains essentially without distortion during simulated vehicle acceleration as the vehicle (not shown) travels in the direction shown by arrow 201 . Prior art suspension arrangement 300 , on the other hand, shows during the simulated vehicle acceleration in the direction of arrow 301 a distortion in leaf spring 302 wherein region 313 of leaf spring 302 is distorted downward and region 314 is distorted upward. This condition, which is commonly referred to as “side view windup,” results in the unacceptable condition of power hop during acceleration, as well as a disadvantageous reduction in axle control.
[0061] FIGS. 6 a and 6 b are simplified representations of suspension system 200 of FIG. 5 a and prior art suspension arrangement 300 of FIG. 5 b , both in computer-simulated static braking conditions. Elements of structure that have previously been discussed are similarly designated in this figure. As shown in FIG. 6 a , leaf spring 130 a remains substantially in its base line configuration during simulated acceleration in the direction of arrow 201 . FIG. 6 b , on the other hand, shows leaf spring 302 to undergo significant side view windup. Region 313 of leaf spring 302 is distorted upward significantly, while region 314 is distorted downward. When leaf spring 302 is wound up as shown in this simulation, its spring rate is changed significantly, as well as other suspension parameters, resulting in reduced control, particularly when braking is performed on an uneven or bumpy surface (not shown).
[0062] FIG. 7 is a simplified schematic representation of a side view of a suspension system 400 constructed in accordance with the principles of the invention with a 1 st stage leaf spring 410 , and further showing the path of the center of axle 411 , as indicated by curved arrow 412 with a fulcrum 414 arranged to communicate with 2 nd stage lower leaf spring 416 . The embodiment of the invention represented in this figure is pivotally coupled to 1 st stage leaf spring 410 at a pivot coupling 414 .
[0063] FIG. 8 is a simplified schematic representation of a side view of a suspension system 430 constructed in accordance with the principles of the invention. Elements of structure that previously have been discussed are similarly designated in this figure. In this figure, there is illustrated a 1 st stage consisting of a coil spring 435 , which may, in certain embodiments be a conventional air spring (not shown). In still further embodiments of the invention, coil spring 435 may constitute a combination of a coil spring and an air spring. Coil spring 435 is substantially equivalent in function to 1 st stage leaf spring 410 of the embodiment of FIG. 7 . However, as will be noted below, the use of a coil spring results in a variation in the path of the axle.
[0064] Fulcrum 414 of the 2 nd stage lower leaf has been removed, but is nevertheless illustrated in phantom representation to show that its use is optional in this specific illustrative embodiment of the invention. Its use will depend on the geometric needs of the vehicle (not shown).
[0065] In this embodiment, the path of center of axle 411 is indicated by curved arrow 437 . Curved arrow 412 , which represents the path of the center axle in the embodiment of FIG. 7 , is shown in this figure for comparison purposes.
[0066] A significant aspect of this specific illustrative embodiment of the invention is that lower leaf spring 440 is configured as a lower link subcomponent that allows a measure of compliance. It is not a rigid link.
[0067] FIG. 9 is a simplified schematic representation of a side view of a suspension system 450 constructed in accordance with the principles of the invention with a 1 st stage consisting of a substantially equivalent coil spring 455 , which in some embodiments of the invention may be an air spring or a combination of a coil spring and an air spring. Coil spring 455 provides vertical load support in place of 1 st stage leaf spring 410 shown in FIG. 7 . However, in this specific illustrative embodiment of the invention, added control is achieved by the use of an optional single plate main leaf spring 457 as part of the 1 st stage with coil spring 455 . A lower leaf 460 of the 2 nd stage is employed for additional control. In this embodiment, lower leaf 460 permits a measure of compliance and is not a rigid link.
[0068] Again, Fulcrum 414 of the 2 nd stage lower leaf has been removed, but is illustrated in phantom representation to show that its use is optional in this specific illustrative embodiment of the invention. Its use will depend on the geometric needs of the vehicle (not shown).
[0069] In this specific illustrative embodiment of the invention, the center of axle 411 travels along a path that conforms to curved arrow 462 , as seen in the present side view.
[0070] FIG. 10 is a simplified schematic representation of a clip bracket 500 that can be used to push or pull a stack of spring plates 502 . Spring plates 502 may be the main spring or the secondary stage in the practice of the invention. In operation, clip bracket 500 is urged upward and downward in the direction of arrows 504 and 506 , respectively. Spring plates 502 are contained between rubber bushings 510 and 512 , to prevent damage to the spring plates. The operation of clip bracket 500 will be described below in relation to FIGS. 11 a , 11 b , and 11 c.
[0071] FIGS. 11 a , 11 b , and 11 c are simplified schematic side view representations of a height control arrangement 520 constructed in accordance with the principles of the invention that is useful in the loading and unloading of a stationary vehicle, FIG. 11 a showing a simplified system control arrangement in block and line form. Elements of structure that have previously been discussed are similarly designated in these figures.
[0072] As shown in FIG. 11 a , a primary leaf spring 130 a is coupled at its ends to a chassis rail (not specifically designated) as described in relation to FIGS. 1 and 2 , above. Leaf spring 130 a and secondary spring 502 , which may be the equivalent of half leaf spring 136 a described above, are coupled to the axle (not specifically designated in this figure). Moreover, although clip bracket 500 is shown in this specific illustrative embodiment of the invention, to operate on the secondary spring system, other embodiments can employ clip bracket 500 on the primary spring, i.e., primary leaf spring 130 a . The principle is to provide a way literally push or pull on the spring assembly in a local area to force a temporary camber change This translates into a change in the height “Z” of the vehicle (see, FIG. 15 and its corresponding description below) that can be selectively employed in response to the operation of a height control system that is generally designated as 530 in the figure.
[0073] Height control system 532 includes a height control system 532 that receives vehicle height information from a height sensor 534 . A desired vehicle height is entered by a user (not shown) at user input 536 . In a simple embodiment of the invention, user input 536 may constitute a simple pair of switches (not shown) that enable the user to raise or lower the vehicle height as desired. In other embodiments, user input 536 may constitute a programable arrangement (not shown) wherein several vehicle heights and other conditions can be preprogramed. In response to the data received at user input 536 and the corresponding height data received from height sensor 534 , height control system 532 operates an electrical or hydraulic system (not shown) that exerts a force on clip bracket 500 whereby the clip bracket is urged upward or downward, as the case may be, in the direction of arrows 504 and 506 , respectively, relative to the chassis rail. In this embodiment of the invention, clip bracket 500 can only exert force on secondary spring 502 statically and must be withdrawn to a baseline condition when the vehicle is in use to prevent damage to the spring. More specifically, the compression surface of the spring should not be loaded during dynamic or fatigue loading, and secondary spring 502 should therefore be employed only statically, such as for loading and unloading the vehicle. For this reason, this specific illustrative embodiment of the invention is provided with a vehicle interface 538 that, among other functions, disables the operation of height control system 532 when vehicle motion is detected.
[0074] If the vehicle is lightly loaded, a height sensor 534 provides vehicle height data that indicates that clip bracket 500 must pull on secondary spring 502 such that vehicle trim position is lowered. This allows the vehicle to be loaded more easily by the user. In some embodiments of the invention, when the vehicle is shifted to the “drive” position, vehicle interface 538 instructs height control system 532 to restore the height of the vehicle to a predetermined baseline position to avoid creating a rise in the operational stress applied to secondary spring 502 .
[0075] Referring to FIG. 11 b , it is noted that as the clip bracket (not specifically designated in this figure) is urged upward in the direction of arrow 504 , the vehicle height is reduced from the baseline of Z to Z′, where Z′ 502 upward, a downward force 542 is applied at the distal end of secondary spring 502 .
[0076] In FIG. 11 c , the clip bracket (not specifically designated in this figure) is urged downward in the direction of arrow 506 , the vehicle height is increased from the baseline of Z to Z″, where Z″>Z. As the clip bracket urges secondary spring 502 upward, an upward force 544 is applied at the distal end of secondary spring 502 .
[0077] FIG. 12 is a simplified schematic top plan representation of a splayed suspension arrangement 560 constructed in accordance with the invention wherein secondary leaf springs 562 a and 562 b are shown to be mounted at angles with respect to respective ones of primary leaf springs 130 a and 130 b . Elements of structure that have previously been discussed are similarly designated in this figure. The secondary leaf springs are not parallel to the respective primary leaf springs, as is the case in the embodiments of FIGS. 1 and 2 . In a practical embodiment of the invention, angles of deviation for the secondary leaf springs will be on the order of 5°-10°. Of course, the present invention is not limited to this angular range, which can be determined in response to finite element and kinematic analyses as will be discussed below.
[0078] Further in relation to the embodiment of FIG. 12 , it is noted that the addition of secondary leaf springs 562 a and 562 b , which are mounted in the system at an angle relative to primary leaf springs 130 a and 130 b , enhances axle control, as the present non-parallel arrangement emulates a rigid 4-link rear axle system (not shown).
[0079] However, a key difference is that in the present system leaf springs 562 a and 562 b function as springs, not just rigid links. This significant difference allows for compliance that will affect all aspects of the dynamic and kinematic response, including axle wind-up and roll response. The angularly disposed secondary springs of this embodiment of the invention will increase roll stiffness significantly. The resulting stresses that are applied by this arrangement to the mounting plate (not specifically designated) can be balanced on a case-by-case basis using standard analytical systems, such as finite element analysis (“FEA”). Additionally, kinematic analysis performed using commercially available software, such as the ADAMS software, will on a case-by-case basis identify exact values for the vehicle response to roll inputs. Wheel sideslip and axle steer control are thereby improved.
[0080] FIG. 13 is a simplified schematic perspective representation of a variable position fulcrum bumper 570 constructed in accordance with the invention that may be active or passive to rotate in a controlled manner to create a variation in the stiffness of the secondary spring rate. By allowing the fulcrum bumper (whether passive or active) to rotate in a controlled manner about the ground point on the frame bracket, a change in secondary plate stiffness is produced. Essentially, the bumper ground point at chassis rail 112 b is rotated such that the point of contact on the secondary spring is moved. The resulting stiffness and kinematic effects are significantly affected. The specific value of the amounts of stiffness and kinematic effects is determined on a case-by-case basis with the use of kinematic modeling. Additionally, the resulting change in spring rate thereby calculated.
[0081] In the practice of this aspect of the invention, an electric motor (not shown) is mounted to the frame bracket (not specifically designated) and is actuated to cause the desired rotation after a signal sent from a height transducer identifies how much rotation is needed. A simplified height analysis system is described in relation to FIG. 11 a . The displaceable fulcrum bumper herein described can be used in combination with a bumper having a variable stiffness, whereby numerous combinations of final stiffness and kinematic path result. In some embodiments of the invention, variable position fulcrum bumper 570 comprises a rheological material that changes viscosity or stiffness in response to the application of electrical energy. The stiffness of variable position fulcrum bumper 570 is the focus. By activating the fulcrum bumper to become more (or less) rigid, a desired change in supporting spring stiffness is effected and, correspondingly, the geometric and kinematic attributes of the suspension system are affected.
[0082] The fulcrum bumper is not limited to be used in combination with a rheological material, and can employ an air spring or other mechanical means to effect the engagement of the secondary stage leaf. Although in this embodiment of the invention there would be no “active” vehicle retrim, the system could “passively” allow for the rate change, which as a result of the linked kinematic geometry effect, would affect vehicle dynamic behavior in roll, acceleration, braking, or cornering motions. Once vehicle attitude is effected via suspension displacement activity, the secondary plate contact with the fulcrum bumper would initiate reaction forces. A variable rate bumper made of rubber, urethane, like material that can be voided or otherwise manufactured to cause a nonlinear compression effect that will influence the secondary plate deflection character while under load, albeit to a lesser degree than an active system.
[0083] FIG. 14 is a simplified schematic plan representation of the variable position fulcrum bumper of FIG. 13 , that has been magnified to facilitate the illustration of certain details of its operation. It is seen in this figure that variable position fulcrum bumper 570 is installed on a carrier 575 that is configured to pivot about a pivot coupling 580 to which is also coupled primary leaf spring 130 a . The carrier is coupled to half leaf spring 136 a at pivot coupling 582 . An electric drive arrangement 590 (shown schematically) is actuatable, illustratively in response to the system described in connection with FIG. 11 a , to cause carrier 575 to be rotated about pivot coupling 580 in the direction of arrow 596 . Electric drive arrangement 590 is coupled to carrier 575 by a drive coupler 592 that, in this specific illustrative embodiment of the invention, is urged in the directions of two-headed arrow 593 . The actuation of the carrier by electric drive arrangement 590 causes variable position fulcrum bumper 570 to change the point at which it communicates with half leaf spring 136 a over a range c, whereby half leaf spring 136 a is displaced to position 136 a ′, and primary leaf spring 130 a is displaced to position 130 a′.
[0084] FIG. 15 is a simplified schematic representation of the variable position fulcrum bumper of FIG. 14 that is useful to illustrate the variation in vehicle height that is achievable, particularly when the vehicle (not shown) is stationary. Elements of structure that have previously been discussed are similarly designated in this figure. As shown in this figure, variable position fulcrum bumper 570 causes, as previously noted, half leaf spring 136 a is displaced to position 136 a ′. This displacement is responsive to a displacement of z′ at the point identified by line 600 . The height displacement of the vehicle corresponds substantially to the displacement z′ multiplied by the mechanical advantage nx/x, or n. In a typical vehicle, the value of n may be on the order of 6, and therefore the height of the vehicle will be lowered by approximately 6 z′.
[0085] Although the invention has been described in terms of specific embodiments and applications, persons skilled in the art may, in light of this teaching, generate additional embodiments without exceeding the scope or departing from the spirit of the invention herein claimed. Accordingly, it is to be understood that the drawing and description in this disclosure are proffered to facilitate comprehension of the invention, and should not be construed to limit the scope thereof.
[0086] Having thus described the invention, | A vehicle drive arrangement for a vehicle of the type having differential power transmission arrangement that converts the rotatory motion of the rotatory power shaft to rotatory motion of first and second drive shafts disposed substantially orthogonal the rotatory power shaft. Primary leaf springs are each coupled at their respective centers to respective drive shafts by pivotal arrangements. The first and second primary springs may include helical springs that are used in place of, or in combination with, the primary leaf springs. Secondary leaf springs may be splayed and therefore need not be arranged parallel to the primary leaf springs. Control over vehicle kinematics is enhanced by configuring the resilience of a fulcrum bumper using resilient, rheological, or active systems. An active system will control vehicle height while stationary to facilitate loading and unloading of the vehicle. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a continuation application of U.S. patent application Ser. No. 10/384,110 filed on Mar. 7, 2003 and issued Feb. 28, 2006 as U.S. Pat. No. 7,006,223 entitled Dermoscopy Epiluminescence Device Employing Cross and Parallel Polarization, the substance of which is relied upon and incorporated herein by reference.
STATEMENT RE: FEDERALLY SPONSORED RESEARCH/DEVELOPMENT
(Not Applicable)
FIELD OF THE INVENTION
The present invention relates generally to an epiluminescence device used in dermoscopy. More particularly, the invention comprises an improved apparatus for illuminating the skin for medical examination by providing cross-polarized and parallel-polarized light to aid in viewing internal structures as well as the skin surface.
BACKGROUND OF THE INVENTION
Dermoscopy is the term used to describe methods of imaging skin lesions. Skin is the largest organ in the body and it is the most easily accessible organ for external optical imaging. For early detection of cancers, it is important that the skin be medically examined for lesions.
With over forty (40%) percent of the cancers occurring on the skin (American Cancer Society Statistics 2001, Perelman 1995), and incidence of skin cancer increasing each year, tools and methods of imaging skin lesions are becoming increasingly important. Most of the cancers detected on the skin are Basal Cell Carcinoma (BCC) and Squamous Cell Carcinoma (SSC), which are differentiated from melanoma, a more deadly form of skin cancer. The early detection of skin cancer allows for inexpensive treatment before the cancer causes more severe medical conditions. Thus, there is a great need in the art for simple inexpensive instruments that allow for the early screening for skin cancer.
Because skin is partially translucent, dermoscopy utilizes tools for visualization of the pigmentation of the skin below the surface. In this regard, when attempting to visualize the deeper structure of the skin, it is important to reduce the reflection of light from the skin which may obscure the underlying structures. Methods used to reduce the surface reflection from the skin are referred to as epiluminescence imaging. There are three known methods for epiluminescence imaging of the skin, oil-immersion, cross-polarization, and side-transillumination. Oil-immersion and cross-polarization methods have been extensively validated for early skin cancer detection while side transillumination methods are currently undergoing study and clinical validation.
Oil-immersion devices are generally referred to as Dermatoscopes. Dermatoscopes permit increased visualization of sub surface pigmentation by using a magnification device in association with a light source. In operation, oil is placed between the skin and a glass faceplate. The placement of oil and a glass interface between the eye and the surface of the skin reduces the reflected light from the skin, resulting in deeper visualization of the underlying skin structure.
While oil-immersion has proved to be an excellent method of epiluminescence imaging of the skin, demonstrating improved sensitivity for melanoma detection, it is messy and time consuming for the physician. As a result, the Dermatoscope is used mostly by physicians that specialize in pigmented lesions and for evaluation of suspicious lesions that cannot be diagnosed visually. Also, the oil-immersion of the Dermatoscope has been found to be less effective for BCC and SCC imaging. The pressure created by the compression of the glass faceplate causes blanching of blood vessels in the skin resulting in reduced capability of the Dermatoscope for imaging the telangiectesia that is often associated with BCC or other malignent lesions.
Cross-polarization or orthogonal polarization is another method of reducing the reflection of the light from the surface of the skin to aid in the medical examination of the skin. Light emanating from a light source is first linearly polarized, so that the orientation of the light falling on the skin surface is in the same plane of polarization. As the light enters the skin, its polarization angle changes such that the light is reflected from a deeper structure. However, the light reflected from the surface of the skin is still polarized in the same plane as the incident light. By including a second polarizer in the path of the reflected light from the skin, a selective filtering of light can be achieved.
Most of the light directed to the skin's surface is reflected as the refractive index of skin is higher than that of air. The reflection of light, off of the skin, is analogous to the reflection of light off of the surface of water. Accordingly, the information received by the eye carries mostly information about the contour of the skin surface rather than the deeper structures. Remaining light enters the skin and is absorbed or is reflected back in a scattered fashion. By polarizing the incident light with a second of polarizer, the specular component of the reflected light is blocked by the viewing polarizer, thus producing an enhanced view below the skin surface. Accordingly, inflammation, color, pigmentation, hair follicles and blood vessels may be viewed.
When the incident light and the second polarizer are parallel, the surface topography and properties of the skin are highlighted and enhanced. In this regard, if the polarizer in the path of the light from the skin to the eye is polarized in the same orientation of the incident light, only the light from its polarization angle will be allowed to pass through the lens. Cross-polarization imaging of the body was originally described by R. R. Anderson (“Polarized light examination and photography of the skin.” Archives Dermatology 1991; 127; 1000–1005). Later, Binder introduced the MoleMax manufactured by Derma Instruments (Vienna, Austria) for the examination and mapping of pigmented lesions. Binder further developed the no-oil cross-polarization epiluminescence method. MoleMax, however, while validating clinically the improved diagnosis and accuracy without the use of oil, still used a glass faceplate and video imaging system to execute skin examinations.
In light of many of the difficulties associated with prior dermoscopy systems, a simple and cost-effective diagnostic systems remained unavailable for general dermatologists to use on a routine clinical basis. Dermoscopy, until recently, remained generally a research tool utilized in special clinical cases.
More recently, however, a substantial advancement in skin cancer detection occurred through a simple device identified as DermLite®, manufactured and marketed by 3Gen, LLC. of Monarch Beach, Calif. With this low cost and easy to use DermLite® Device, screening for cancer by dermatologists in routine clinical examination of skin disease has become a reality. The DermLite® device uses cross-polarization epiluminescence imaging through use of white light emitting diodes (LEDs), a high magnification lens (10×), and a lithium ion battery contained in a small lightweight device.
In the DermLite® device, a window is incorporated into a compact housing, and a plurality of white light LEDs encircle a magnifying lens. The DermLite® device incorporates cross-polarization filters that reduce the reflection of light from the surface of the skin and permits visualization of the deeper skin structures. Light from eight (8) LEDs is polarized linearly by a polarizer, which is annular in shape and located in front of the LEDs. The imaging viewed through the magnifying lens is also linearly polarized by using a polarizer that is located in front of the lens. The LEDs have a narrow beam angle that concentrates the light into a small area, pointing the incident light to the center to increase the brightness of the area being viewed. Thus, light from the LEDs passes through the polarizer which enters the skin and reflects back through the viewing polarizer to create cross-polarization allowing examination to look deeper within the skin structure. Although, the DermLite® product has been recognized as a major advancement in the art of routing clinical diagnosis and analysis of skin cancer lesions, DermLite® device does not provide a mechanism for enabling the user to additionally view parallel-polarized light, or a combination of cross-polarized light and parallel-polarized light.
The DermLite® Platinum® product, also manufactured by 3Gen, LLC. was developed to provide variable polarization. Variable polarization is achieved by a rotating dial. Rotation of the polarizer to a cross-polarization cancels out the surface reflection for an in-depth look at the deeper pigmentation in lesion structure. Rotation to parallel polarization allows a clear view of the skin surface. The DermLite® Platinum® product requires manual manipulation of the dial which may cause user to lose the viewing spot, or otherwise interfere with examination. Further, DermLite Platinum® does not provide a user the ability to view the skin with an instantaneous switch over from cross-polarization to parallel polarization.
Recent discoveries in optical fluorescence imaging have identified several molecules having fluorescence properties that are useful in medicine. In dermatology, simple applications such as delta-aminolaevulinic acid (ALA) applied topically have been found to enhance the visualization of basal cell cancer from normal tissue, when illuminated with UV/Blue light. Fluorescein is another fluorescent compound that has been in clinical use in opthamology for several years and has great potential for use in dermatological applications. Indocyanine green (ICG), Methylene Blue, and ethyl nile blue are contrast agents that are used to increase light absorption in blood vessels. There are several FDA approved optical fluorescence tracers already approved for clinical use, and several more new probes may be applicable in the future. However, the use of fluorescence imaging of the skin has been illusive for clinical dermatologist because of the complexity and costs of the associated equipment.
In current applications, such as in the application of ALA topically to a basal cell carcinoma to a BCC, conventional white light visual images of the BCC are displayed next to the fluorescence excited images of ALA in the BCC. The ALA is taken up by the active areas of cancer, converted to porphyrin IX, and fluoresces when exposed to UV/Blue light. It becomes apparent that the fluorescent areas of the BCC may not coincide with the anatomical features of the BCC as shown in white light. Currently the side-by-side comparison is only available by taking two separate images and co-registering these images later in the computer.
Thus, there is a great need in the art for a device that will allow clinical viewing of skin lesions which provides on demand switching from cross-polarized imaging to parallel-polarized imaging and a combination of both. Further there is a great need in the art for a clinical viewing of skin lesions that can toggle back and forth from a white light to a colored or UV light in order to contrast and compare images.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to a dermoscopy epiluminescence device used in the medical diagnosis of skin lesions. The device is a hand held modular housing incorporating a magnification lens and associated lighting scheme for examining the epidermis on humans. The light sources of the lighting scheme are powered by an on board lithium battery and are controlled by a three way switch which provides on demand cross-polarized, parallel-polarized and a combination thereof for epiluminescence.
More particularly, a first embodiment of the present invention comprises a generally circular optical lens incorporated into the housing of the device. The lens produces a magnified image of the skin to be observed by a viewer. In the first embodiment the lens is a 15 mm diameter Hastings lens with a 10× optical gain. The viewer observes the magnified skin through the lens window of the housing. The viewing is aided by a plurality of luminous diodes positioned within the housing and about the circumference of the lens. The diodes direct light upon the skin to be viewed. The LEDs are white high light output Indium Gallium Nitride LEDs. Two light circuits form first and second illumination sources forming a ring of alternating diodes about the lens. A switch is provided that when not in operation has a normal OFF mode. In operation the switch has a first ON mode for initiating the first illumination source (i.e. every other diode on the first light circuit), a second ON mode for initiating the second illumination source (i.e. every other diode on the second light circuit) and a third ON mode for initiating both said first and second illumination sources simultaneously (i.e. all diodes).
A first polarizer filter comprises a planar annular ring defining a generally circular center opening and an outer ring. The center opening of the annular ring of the first polarizer is positioned in alignment with the circular optical lens to provide an unobstructed view of the skin through the lens and the housing. The outer ring of the first polarizer includes a plurality of openings sized and positioned to correspond to the diodes of the second illumination source (i.e. every other diode of the second light circuit) such that light emitted from the diodes of the second illumination source passes through the openings unfiltered by the first polarizer. Because there are no corresponding openings for the diodes of the first illumination source (i.e. every other diode on the first light circuit) light emitted from first source diodes is polarized by the outer ring of the first polarizer filter.
A second polarizer filter comprises a planar annular ring defining a generally circular center opening and an outer ring. The center opening of said annular ring of the second polarizer is positioned in alignment with the circular optical lens to provide an unobstructed view of the skin through the lens and housing. The second polarizer is 90 degrees out of phase with the first polarizer. The outer ring of the second polarizer has a plurality of openings sized and positioned to correspond to the diodes of the first illumination source (i.e. every other diode on the first light circuit) such that light emitted from the diodes of the first illumination source passes through the openings unfiltered by the second polarizer. Because there are no corresponding openings for the diodes of the second illumination source (i.e. every other diode on the second light circuit) light emitted from second source diodes is polarized by the outer ring of the second polarizer filter.
A viewing polarizer is also provided positioned in the housing in line with viewing corridor of the optical lens. The viewing polarizer filters light reflected back from the skin and is cross-polarized relative to said first polarizer and is parallel-polarized relative to said second illumination source. The cross-polarization aids the examiner in viewing deeper structures of the skin while the parallel polarization aids in viewing the topography of the skin.
In a second embodiment of the invention, the ring of diodes that surround the lens incorporate alternating light wavelengths of differing colors. In operation, a user initiates the first light circuit by operating the first ON mode of the housing switch to light every other diode of a first color. The user then can initiate the second ON mode to light every other diode of a second color. Finally the user can initiate a third ON mode and light both sets of diodes to emit both colors simultaneously. For example, one set of lights could be white light LEDs and the second set of light can be a UV/Blue LEDs. Fluorescence imaging provides functional information about the disease, while the standard white light epiluminescence imaging provides the anatomical information that the physician is familiar with in viewing skin disease. Combining the UV/Blue light image with the standard white light image, into a device that is simple and easy to use can be achieved by using a “flicker” method of image integration in the eye, whereby two sets of images are presented one after the other. Switching back and forth between the two sets of images allows the brain to “co-register” the two different images without the need for computers. A third embodiment employs the alternating colored diodes of the second embodiment as well as the cross and parallel polarization of the light from the diodes as found in the first embodiment.
BRIEF DESCRIPTION OF THE DRAWINGS
These as well as other features of the present invention will become more apparent upon reference to the drawings wherein:
FIG. 1 is a is a top perspective view of the device of the present invention;
FIG. 2 is a bottom perspective view of the device of the present invention;
FIG. 3 is an exploded top view of a first embodiment of the present invention;
FIG. 4 is and exploded bottom view of a first embodiment of the present invention;
FIG. 5 is a cross-sectional view of the device of a first embodiment of the present invention;
FIG. 6 is and exploded bottom view of a second embodiment of the present invention; and
FIG. 7 is and exploded bottom view of a third embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The detailed description as set forth below in connection with the appended drawings is intended as a description of the presently preferred embodiments of the present invention, and does not represent the only embodiment of the present invention. It is understood that various modifications to the invention may be comprised by different embodiments and are also encompassed within the spirit and scope of the present invention.
Referring particularly to FIGS. 1 and 2 , there are shown a top and bottom perspective views, respectively, of the dermoscopy epiluminescence device 12 of the present invention. The device 12 is lightweight and compact, and can easily fit within the shirt pocket of a user. The outer structure of the device 12 can be utilized in association with the first embodiment ( FIGS. 3–5 ), the second embodiment ( FIG. 6 ) and third embodiment ( FIG. 7 ). The exterior appearance of the device for each of the first, second and third embodiments would be identical as shown in FIGS. 1 and 2 .
FIG. 1 shows the top perspective view of the device 12 showing the viewing port of the lens 14 incorporated into a housing 20 . A battery cover 22 may be removeably secured to the housing 20 to provide access to an interior compartment for insertion and removal of a battery.
Also shown is a switch 16 for initiating a first light source and a switch 18 for initiating the second light source.
Referring particularly to FIG. 2 , a bottom perspective view of the device 12 is shown. A light portal is incorporated into the housing 20 to expose a viewing polarizer 24 . A plurality of diodes (not shown) encircle the viewing polarizer within the housing 20 and direct light though a multiple layer filter ring 25 . Light from the diodes (not shown) is directed onto the skin surface to aid lighting the magnified area to be viewed.
Referring particularly to FIGS. 3 and 4 , there is shown a first embodiment of the present invention. FIG. 3 is an exploded top view of the device 12 and FIG. 4 is an exploded bottom view of the device 12 . The housing 20 includes top component 20 a and bottom component 20 b . The top component 20 a , bottom component 20 b and battery cover 22 are formed from molded lightweight durable plastic. The plastic is a PVC derivative material and may be formed from acrylic or lexan. Additionally, the housing may be formed from metal such as aluminum. Components 20 a , 20 b and cover 22 are interconnected to form the outer housing 20 as shown in FIGS. 1 and 2 .
The top housing component 20 a includes an aperture 26 for receiving the combination of the optical lens 14 inserted within the lens sleeve 28 . Shown best in FIG. 4 , the underside of the top housing component 20 a is shown wherein the aperture 26 incorporates a downwardly protruding collar for receiving the lens 14 within the lens sleeve 28 . The lens sleeve 28 incorporates an annular lip 29 which engages the sloped sides of the aperture 26 to complete the exterior of the viewing port of the housing 20 . The lens sleeve 28 operates to securely hold the lens 14 in place within the aperture 26 . The lens 14 in the first embodiment is preferably a 15 mm diameter Hastings lens with a 10× optical gain. Although the first embodiment employs a Hastings lens, the lens may be a single convex lens, a combination of two or more lenses, a double achromat lens, or a combination of double achromat lenses. In addition, the lens may incorporate aspherical lenses to accommodate better optics and lower distortion. The lenses coated with an antireflection coating may be used and may additionally include a color filter to selectively filter light passing through the lens.
Although the invention shows a hand held unit without imaging equipment attached, it is contemplated by the present invention that the same could be used with a camera, and that the size and shape of the lens would be modified to accommodate the same.
The protruding collar 30 is part of the unitary structure of the upper housing component 20 a . The cylinder 30 protrudes through the interior components of the housing 20 , including a printed circuit board (PCB) 32 having an opening 33 to extend to the light portal of bottom component 20 b . A battery 34 nests within a battery chamber formed by the top component 20 a and bottom component 20 b . PCB 32 includes electrical contacts 36 a and 36 b for interfacing with the battery 34 contacts 38 a and 38 b . The upper housing 20 a includes slots 40 a and 40 b to allow the PCB contacts 36 a and 36 b to protrude from the circuit board 32 into the battery chamber and contact the battery leads 38 a and 38 b . In all embodiments of the present invention, the battery 34 is an extended charge lithium battery, however, it is understood and contemplated by the present invention that the battery could be any suitable battery package such as a one-time lithium battery or rechargeable lithium battery. The invention additionally contemplates use of a DC power supply that may have a suitable DC output to drive the LEDs.
The bottom component 20 b includes a viewing aperture 42 . The viewing polarizer 24 and sleeve 44 cap off the opening of the collar 30 . Viewing polarizer 24 is composed of acrylic plastic with polarization material embedded within the polarizer. It is contemplated by the invention that the viewing polarizer 24 may be constructed of glass, also with material embedded or coated on the glass. In addition, the viewing polarizer 24 may be coated with a filter material that can selectively filter out some of the light frequencies emanating from the object. Alternatively, the secondary filter assembly made of plastic or glass with the capability of filtering the light may be placed in the path of the viewing lens to filter out some of the light. Bottom housing component 20 b includes a bottom collar 46 formed therein. A lip 48 incorporating a plurality of guide tabs, is formed between the collar 46 and the aperture 42 . The lip 48 and guide tabs are adapted to engage bottom annular polarizer 50 and a top annular polarizer 52 . The top 52 and bottom 50 polarizers are 90 degrees out of phase. The bottom 50 polarizer is in cross polarization with the viewing polarizer 24 and top polarizer 52 is in parallel polarization with the viewing polarizer 24 . The top 52 and bottom 50 polarizers are composed of acrylic plastic and include polarization at different angles. The polarizers 50 and 52 may also be coated with a special material to filter out some of the light emanating from the LEDs, or alternatively the annular polarizer 50 and 52 may be sandwiched with a color filter acrylic material. The aperture 42 is wide enough to permit a viewing corridor from the lens sleeve 28 through the housing 20 to the aperture 42 while allowing portions of the top 52 and bottom 50 polarizers to be exposed and to filter light emitting diodes inside the housing 20 .
Sixteen light emitting diodes 58 ring the circuit board. The diodes are preferably white high light output Indium Gallium Nitride LEDs, however any suitable lighting diodes are appropriate. The even diodes are on a single circuit and the odd diodes are an a separate single circuit. In the shown embodiment, the LEDs 58 are a standard white LED made with phosphorescence phosphors to create white light. It is additionally contemplated by the present invention that tri-colored LEDs, with individual red, green and blue LEDs that can combine form white light may be utilized. It is contemplated by the present invention that the LEDs may have focusing lenses to concentrate the light into a smaller and tighter beam. The LEDs may additionally be comprised of indium gallium arsenide material, or any other like semiconductor material. The PCB board 42 incorporates switch contacts 54 and 56 . The polarizing parallel switch 16 engages switch contact 56 and the parallel-polarizing switch 18 engages with contact 54 . Thus, engaging switch 16 initiates a first light source, which are the eight even diodes 58 and the switch 18 initiates the second light source, which are the other eight odd diodes. Both switches 56 and 54 may be operated simultaneously to light all sixteen diodes 58 simultaneously. It is contemplated by the present invention that the device may employ three or more switches operative to initiate three or more sets of diodes.
A first polarizer filter 50 comprises a planar annular ring defining a generally circular center opening and an outer ring. The center opening of the annular ring of the first polarizer 50 is positioned in alignment with the circular optical lens 14 to provide an unobstructed view of the skin through the lens 14 and the housing 20 . The outer ring of the first polarizer 50 includes a plurality of openings sized and positioned to correspond to the diodes 58 of the second illumination source (i.e. every other diode 58 of the second light circuit) such that light emitted from the diodes 58 of the second illumination source passes through the openings unfiltered by the first polarizer 50 . Because there are no corresponding openings for the diodes of the first illumination source (i.e. every other diode on the first light circuit) light emitted from first source diodes is polarized by the outer ring of the first polarizer filter 50 .
A second polarizer filter 52 comprises a planar annular ring defining a generally circular center opening and an outer ring. The center opening of said annular ring of the second polarizer 52 is positioned in alignment with the circular optical lens 14 to provide an unobstructed view of the skin through the lens 14 and housing 20 . The second polarizer 52 is 90 degrees out of phase with the first polarizer 50 . The outer ring of the second polarizer 52 , like the first polarizer 50 , has a plurality of openings sized and positioned to correspond to the diodes of the first illumination source (i.e. every other diode on the first light circuit) such that light emitted from the diodes of the first illumination source passes through the openings unfiltered by the second polarizer 52 . Because there are no corresponding openings for the diodes 58 of the second illumination source (i.e. every other diode on the second light circuit) light emitted from second source diodes is polarized by the outer ring of the second polarizer 52 . While the switches of the first embodiment 16 and 18 shows only two light sources (i.e. two sets of diodes) three are more sets of diodes are contemplated by the present invention.
Referring particularly to FIG. 5 , there is shown a cross-sectional view of the device 12 of the first embodiment of the present invention. FIG. 5 shows an optional spacer 60 which can engage the viewing portal of the housing 20 . The spacer includes glass 62 to provide a transparent barrier. The spacer can aid in achieving the optimal viewing distance between the device 12 and the skin 64 . Also, the spacer 60 can prevent contamination of the lens 14 during examination.
FIG. 5 illustrates the angle of mounting of the LEDs 58 upon the PCB 32 . The light from the LEDs 58 is angled to concentrate the light onto a focused area are represented by the angled lines shown in phantom. The light from the LEDs 58 is focused into a smaller area, so as to increase the brightness of the LEDs. All of the LEDs 58 in the circle are pointed toward the central area of the region of interest, so as to increase multifold the amount of light directed into the region. It is additionally contemplated by the present invention that some of the LEDs may be directed slightly off center to enlarge the viewing field and to make for uniform lighting.
FIG. 6 is a bottom exploded view of a second embodiment of the present invention. The assembly and structure of the device shown in FIG. 6 is identical to that shown in FIGS. 1–5 of the first embodiment of the present invention (and thus the description is not repeated herein), except that the device shown in FIG. 6 does not include two annular filters 50 and 52 and the LEDs 66 and 68 are of different colors. Preferably, the even diodes 66 are of a particular green wavelength and odd diodes 68 are white diodes. The colored LEDs may be different LEDs available at the time such as 370 nm UV, 470 nm blue, 500 nm aqua, 525 nm green, 570 nm orange, 630 nm red, etc. The combination of different colors will provide different imaging capabilities. As an example, the blue light is more absorbed in skin pigmentation and therefore better visualization of pigmentation is achieved with the blue light. Similarly, the green light is more absorbed by the blood and so it is better for visualizing blood vessels. Some compounds also fluoresce at different wavelength light. An example of this is the multiple fluorescence compounds used in research and medicine such as fluorescein, which fluoresces green when illuminated with a blue light. While the second embodiment herein shows green and white diodes, it is understood that the second embodiment could employ any desirable combinations of colors. Likewise, while the switch contemplates only two light sources (i.e. two sets of diodes) three are more sets of diodes are contemplated by the present invention, employing multiple combinations of colors.
FIG. 7 is a bottom exploded view of a third embodiment of the present invention. The assembly and structure of the device shown in FIG. 7 is identical to that shown in FIGS. 1–5 of the first embodiment of the present invention (and thus the description is not repeated herein), except that the device shown in FIG. 7 includes LEDs 70 and 72 are of different colors. Preferably, the even diodes 70 are of a particular green wavelength and odd diodes 72 are white diodes. The two annular polarizers provide cross polarization and parallel polarization identical to that described with respect to the first embodiment. While the third embodiment herein contemplates green and white diodes, it is understood that the third embodiment could employ any desirable combinations of colors. Likewise, while the switches may only initiate two light sources (i.e. two sets of diodes), three are more sets of diodes are contemplated by the present invention, employing multiple combinations of colors.
It should be noted and understood that with respect to the embodiments of the present invention, the materials suggested may be modified or substituted to achieve the general overall resultant high efficiency. The substitution of materials or dimensions remains within the spirit and scope of the present invention. | The present invention is a hand held dermoscopy epiluminescense device with a magnification lens and an associated ring of luminous diodes powered by an on board battery. Every other diode in the ring operates as first and second light sources. The even diodes are filtered by a first polarization ring and the odd diodes are filtered by a second polarization ring. Each polarization ring has an open center for the lens and openings sized and positioned to correspond to the even or odd diodes to only filter one set. A viewing polarizer is provided and is cross-polarized relative to the first polarization ring and is parallel-polarized with the second polarization ring. A three way switch which provides on demand cross-polarized, parallel-polarized and a combination thereof for epiluminescence. A second embodiment provides even diodes of a first color and odd diodes of a second color. A third embodiment employs the alternating colored diodes of the second embodiment as well as the cross and parallel polarization of the light from the diodes as found in the first embodiment. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 61/432,461, filed Jan. 13, 2011, the full disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to medical apparatus and methods. More particularly, the present invention relates to implantable devices and methods and systems for detecting their dysfunction or impending dysfunction.
Implantable medical devices, particularly those indicated for long term use in the human body, are highly regulated and must meet certain safety requirements. It is known that when a device is implanted in the body, the materials forming the cover and structural elements of the device may degrade and fatigue over time. It is also known that improper or excessive handling during implantation could stress the structural integrity of the device. In devices with movable mechanical parts, the wear and tear of the materials in contact with each other could lead to degradation of the surface, the interior volume, and eventually the structural stability of the part itself. Such wear can also release debris particles which in turn can cause harm in a variety of ways including triggering immune reactions which can cause osteolysis and blocking luminal structures which can cause strokes or bowel obstruction. When large enough, the damaged part of the device could shred healthy cells and tissues from red blood corpuscles to bone. Failure of the structural integrity of the device can cause not only dysfunction but severe injury. Often the wear of the device can be moderated or evened by changes in physical activity. Or the impaired part of the device could be replaced without difficulty before the rest of the device is damaged necessitating more extensive revision procedures and rehabilitation. Not only would this enhance safety and reduce costs, the life of the product can be prolonged. Therefore, it would be desirable to detect, to monitor, or to predict such an event and take measures before any irreparable damage to the device or injury to the patient ensues.
Prosthetic devices implanted in numerous locations in the body are prevalent in medical practice and are expected to be of even greater importance than ever before. With medical advances human longevity has increased the population of elderly needing them. Obesity adds further wear and tear on the body. In today's data driven generation, people are more involved in taking care of their own health. The implications are many. Initial, primary therapeutic procedures are performed at younger ages and revision or replacement procedures are increasingly more common. Device statistical lifecycles are no longer satisfactory as patients need information specific to the device implanted in their own body and individualized counseling. Having a device that can be self monitored economically by the patient would be further helpful and reduce overall healthcare costs.
Many devices, such as cardiovascular valves, have parts that are dynamic when performing their function and cannot be stopped for examination. Thus failure prediction and detection often depend on secondary signs, such as errant flow patterns by imaging such as ultrasound. By the time their function is impaired enough to be detected, the wear and tear to the device has already far progressed to require more urgent treatment. Early detection of partial failure through a direct or primary method would enable more accurate diagnosis and better treatment planning.
Other devices suffer repeated or cyclical stresses from deliberate manipulation or secondary body movement. Devices such as insulin or other drug pumps require refilling of the reservoir, typically through a needle. Repeated stabbing in the same location could induce and propagate these defects in the covering that could allow intrusion of body fluids and impair the precisely calibrated functions. Or the refilled fluid could leak through the defects established or propagated by the injecting device. Electronic stimulation devices, such as neurostimulators, and many mechanically restrictive devices, such as lapbands used in bariatric surgery, require fixation of certain critical components to body tissues. As the device and the body tissues are not isolated from motions of the rest of the body, any movement could cause mechanical stress and, over time, fatigue leading to tears or dislocations of the device.
For these reasons, it would be desirable to provide apparatus and methods to detect, to monitor, or predict an actual or potential breach of a surface, layer, or body of an implantable object or device in the body. Prompt removal and/or replacement of such impaired devices or components thereof could avert many, if not all, of the problems associated with failure of such devices. The methods and apparatus would preferably be adaptable for use in many devices without adversely affecting the device's performance or structural integrity. It would be beneficial if the device could be directly examined while functionally deployed in motion without interfering with its performance, even temporarily. It would be further desirable if the breach of the device were detectable to the patient in an easy, rapid, and reliable fashion at home and in other settings away from the doctor and hospital. Additionally, it would be beneficial if the system were able to monitor the device non-invasively on a frequent basis without incurring significant additional cost for each diagnostic event. At least some of these objectives will be met by the inventions described hereinafter.
2. Description of the Background Art
U.S. 2006/0111777 and U.S. 2006/0111632 describe inflatable and rigid implants having embedded conductors utilizing transponders to signal a breach. U.S. Pat. No. 5,833,603 describes an implantable transponder that can be used to detect breach or wear in implantable devices. Breast implants and methods for their use are described in U.S. Pat. Nos. 6,755,861; 5,383,929; 4,790,848; 4,773,909; 4,651,717; 4,472,226; and 3,934,274; and in U.S. Publ. Appln. 2003/163197. Gastric balloons and methods for their use in treating obesity are described in U.S. Pat. Nos. 6,746,460; 6,736,793; 6,733,512; 6,656,194; 6,579,301; 6,454,785; 5,993,473; 5,259,399; 5,234,454; 5,084,061; 4,908,011; 4,899,747; 4,739,758; 4,723,893; 4,694,827; 4,648,383; 4,607,618; 4,501,264; 4,485,805; 4,416,267; 4,246,893; 4,133,315; 3,055,371; and 3,046,988 and in the following publications: US 2004/0186503; US 2004/0186502; US 2004/0106899; US 2004/0059289; US 2003/0171768; US 2002/0055757; WO 03/095015; WO88/00027; WO87/00034; WO83/02888; EP 0103481; EP0246999; GB2090747; and GB2139902.
BRIEF SUMMARY OF THE INVENTION
The present invention provides devices, systems and methods for detecting partial or complete breach of a surface or volume of solid or other non-inflatable structures or components of an implantable device to predict device dysfunction or failure of the structure, component, or device as a whole. The solid or other non-inflatable structures of the device can be made of any solid material including but not limited to polymers, metals, minerals, ceramics, biologics, and their hybrids. Common examples include articular components of prosthetic joints where the entire volume is solid. Other structures in implantable devices subject to such breach include hermetically sealed rigid-walled enclosures, such as those of implantable defibrillators or neurostimulators, or reservoirs, such as those in implanted insulin or drug pumps, where the volume includes other parts of the device whether gas, liquid, or solid.
Typically the solid structures are subject to breach in areas where there is extensive contact between the device and body tissues or with an external object or between different parts of the device. If the device is manipulated periodically, the area of wear and tear is at the site of stress and fatigue of the manipulation. While the implementation of these systems and methods will be described in detail in connection with orthopedic joints, it will be appreciated that the principles may be applied to other non-inflatable prostheses. The systems of the present invention are incorporated into at least a portion of the surface, layer, or thickness of the non-inflated prosthesis and provide for the emission or transmission of a detectable electronic signal upon breach or partial breach of the same. As used hereinafter, the term “breach” will refer to any partial or full penetration of a surface, layer, or thickness of a structure, or other mechanical disruption which could initiate or lead to the contact of heretofore unexposed device materials with surrounding tissues or body fluids.
The signal emission system of the present invention preferably comprises a signaling circuit having one or more components which become exposed to an exterior or interior environment surrounding or within the prosthesis upon breach or partial breach of the surface, layer, or thickness, wherein such exposure enables, disables, energizes, discharges, and/or changes a signal which is emitted by the system. In particular, the breach will typically close an open region within the signaling circuit to cause, enable, disable, or alter the signal emission.
In a first embodiment, the component of the signaling circuit will generate electrical current when exposed to a body fluid by the breach. In such cases, the generated electrical current can power an unpowered transmission component to emit the signal. Alternatively, the power can alter a signal which has already been continuously or periodically emitted by the signaling circuit. In the latter case, the signaling circuit may require a separate source of energy, such as a battery or circuit components which can be placed on either side of the surface, layer, or thickness so that they are always exposed to fluids to provide for current generation. Devices near parts of the body engaged in movement may utilize piezoelectricity to power the circuit. Optionally, the current can throw a switch irreversibly, i.e., entered into memory, so that its altered state can be detected at a later time.
Alternatively, the circuit components may include spaced-apart conductors which are electrically coupled to the signaling circuit to “close” the signaling circuit to permit current flow when exposed to a body fluid in a breach. In the exemplary embodiments described below, the detection portion of a conductor acting as a probe comprise elongate elements embedded beneath the surface, layer, or thickness of the structure in the location subject to breach with an axis oriented toward the direction of the breach. As used hereinafter, the embedded “conductor” or “probe” refers to the detecting element including, if present, a cover that electrically insulates it from surrounding tissues or body fluids. In this unexposed and electrically isolated position, the probe conducts no current and is electrically inactive. A breach through the surface, layer, or thickness will expose and electrically activate the otherwise isolated probe and provide a channel for the intruding electrically conductive bodily fluids bridging the probe and other conductors. The coupling of the spaced-apart conductors may also cause, alter, or enable a signal emission to alert the patient of the breach or potential breach. The probes can have any one of a variety of shapes or a combination of them to fit the geometry of the structure or the contour of its surface, layer, or thickness and match the geometry of the breach. A single conductor can expand at the distal end, branch out into a multi-pronged configuration, or run in a continuous loop configuration in order to cover a wide area subject to breach to minimize potential disruption to the integrity of the structure. Alternatively, when disposed in a material that is resistant to delamination, the conductor can be shaped in a planar configuration, such as a mesh or a continuous plate, to expand the coverage area of detection. Alternatively, the conductor could be made of a material, such as a polymer or metal, in a three dimensional framework that supports the integrity or stability of the structure. The shallowest sections of the embedded probes can be situated in various locations, preferably near portions of the structure where the most wear and tear is anticipated to enhance sensitivity and reliability of the detection. Conductors separately coupled to the logic circuit can be embedded at different distances from a surface, layer or thickness to detect not only the breach but the extent of it through the volume. They can be separately embedded in different components or sections of them to distinguish the location of the breach. The breadth of the coverage area, the density of probes, and/or the alignment of the probes could be correlated to the seriousness of the breach to minimize the potential that such a breach is missed.
In a preferred embodiment, the signaling circuit will comprise a passive transponder and antenna which are adapted to be powered and interrogated by an external reader. Such transponder circuitry may conveniently be provided by using common radio frequency identification (RFID) circuitry where the transponder and tuned antenna are disposed on or within the prosthesis and connected to remaining portions of the signaling circuit. For example, by connecting the transponder circuitry to “open” conductors which may be closed in the presence of body fluids, the signal transmitted by the transponder upon interrogation by an external reader may be altered. Thus, the patient or medical professional may interrogate the prosthesis and determine whether or not the prosthesis remains intact or a potential breach exists. This is a particularly preferred approach since it allows the user to determine that the transponder circuitry is functional even when a breach has not occurred. In passive circuits where the antenna derive power from incoming radiofrequency signals, the antenna is preferably fixated in a radio frequency privileged location relatively in parallel to the surface of the overlying tissues and/or skin. In this fashion, the plane of the antenna can be orthogonal to the radiofrequency vector in order to maximize radio frequency induction and signal strength. If there is radiofrequency interference from materials nearby, the antenna and/or the circuit will have shielding in the substrate or encased to minimize this effect. To minimize interference even further, the circuitry may be separated from the antenna with the sensitive portions fixated to privileged sites on the device or to the surrounding tissue.
The present invention further provides methods for signaling breach of a surface, layer, or thickness of a structure in a prosthesis. Usually, a wireless signal emission comprises closing a circuit when the surface, layer, or thickness is at least partially breached or generating an electrical current when the surface, layer, or thickness is at least partially breached. The particular signaling circuits and transmission modes have been described above in connection with the methods of the present invention.
The signaling system of the present invention can be designed to function in a variety of algorithms to notify the patient in a simple, unequivocal fashion. For example, in a toggle algorithm, the transmitter is either on in the static state or preferably off in order to reduce the need for power. Upon direct contact with the body fluids and or device contents, the conductors cause the transmitter to turn the signal off or preferably on to be able to send a wireless signal on a continuous basis. The wireless signal or lack thereof is recognized by the detector to notify the patient that the integrity of the device is compromised. Optionally, the conductors can cause a switch to be thrown irreversibly so that its altered state in the memory can be detected at a later time. Optionally, the conductors can cause a switch to be thrown so that other functions of the device are enabled.
Alternatively, the algorithm could be based on time, amplitude, frequency, or some other parameter. For example, the transmitter may be enabled to emit a wireless signal at a predetermined time interval in its static state. The detector recognizes the length of the interval as normal and the existence of the signal as the system in working order. Upon direct contact with the body secretions or device contents by the conductors, the transmitter is enabled to send the same signal at different time intervals or a different signal, which is recognized by the detector to notify the patient that the integrity of the device is compromised. The lack of a signal is recognized by the detector to notify the patient of a detection system malfunction and potential compromise of the integrity of the device.
Optionally, more than one probe or more than one type of probe may be placed internally in different parts or components in the device so that the particular part or component which failed may be identified based on which probe was activated. The transmitter would send different signals for the receiver to display the source of the failure. Optionally, they can be separately embedded in different locations of the same part. Diagnostics amongst the various parts or sections can be easily differentiated with the RFID codes assigned to each part or section. Optionally, probes could be coupled to detect, identify, and/or monitor the cause of the breach, especially in the situation where the material of the structure is subject to a breach by certain chemical or biological agents which may or may not normally be present in the environment. Optionally, two or more probes could be coupled to detect or monitor the extent of the breach in another parameter value. For example, wear and tear often result in the shedding of small debris particles. The detectable presence of these particles, particularly if they have intrinsic or contain ingredients that have electromagnetic properties, and the concentration of them in the surrounding body fluids could be monitored by the coupled probes thereby giving an indication of the site of the debris and the volume of the wear. Optionally, probes activated by the breach could serve as a composite for imaging the location, extent, and depth of the breach. The data from the probes can be plotted on a map to visualize the projections.
The probe is a three dimensional conductor disposed in the material directly underneath the surface, layer, or thickness subject to breach. Embedded in this position, the conductor is directly behind the surface, layer, or thickness in the advancing path of the breach into the structure. Exposing the conductor, therefore, is ipso facto evidence of the breach penetrating through the surface, layer, or thickness overlying the conductor. Depending on the configuration, the conductor can be situated to detect breaches in multiple sides of the structure and from multiple directions. The most sensitive embodiment is planar, such as a fine mesh, lattice, or continuous film of the detection material embedded in the material or in between layers of the materials of the structure. In general, such a configuration optimizes the performance of the system in detecting failures early. If the site of the tear or rupture cannot be predicted, the probe would be unlikely to miss detecting the breach by covering the entire device, as discussed in commonly owned prior patent publications US 2006/0111777 and US 2006/011632, the full disclosures of which are incorporated herein by reference.
A continuous film, mesh, or lattice may be preferred for inflatable or fillable devices where the site of breach is unpredictable and complete failure can result from a very small breach. However, for some non-inflated structures or devices, a continuous film, mesh, or lattice may not be required or even ideal. Most non-inflatable devices do not fail from pinpoint breaches but later from the propagation of them. In orthopedic prostheses, the areas of stress and fatigue are often well identified and circumscribed. For example, in prosthetic orthopedic joints certain structures and parts of them suffer the brunt of the various forces from load bearing. These include but are not limited to compression, dispersion, shear, rotation, friction, and combinations of any of them. Motility usually involves repetitive and cyclical movements of certain body parts. Consequently, particular areas on the articular surfaces suffer the most from these forces and are the most susceptible to degrade and eventually break down from wear and tear. Moreover, the wear and tear is not uniform, layer by layer, because articular surfaces do not experience fixed directional forces applied evenly. This is exacerbated with dedicated sports activities although the particular areas affected are specific for the sport. For others, such as cardiovascular valves, the leaflet edges encounter the most stress from cycles of opening and closing. For devices fixated to body tissues, repetitive and cyclical forces from normal body movements exert strain on particular areas on certain structures. The breaches on these fixation structures, such as locking mechanisms and anchors, again can start at an edge or corner and propagate inward or across the structure. Such mechanisms do not have to have sudden failure to cause a meaningful effect. Mere loosening of a functional part, such as in a lap band, could be the difference between therapeutic success and failure.
A continuous film or lattice could even be disadvantageous for non-inflatable and non-fillable devices. For many, such an embodiment embedded as a layer may actually weaken the structure subject to breach. Corrosion of the device can start in several ways. It could begin as a small crack or tear into the surface or deep in the layer of a load bearing area from a compressive force. Or the surface could begin to pit from friction and shear due to repetitive lateral and rotational movements. Thereafter, shards or small layers of the material are abraded off the protruding edges. As the breach progresses into the volume, the exposed materials continue to erode and wide pits result. If the structure has convexities, they can shear and flatten. This is a continuing material science problem in the design of orthopedic implants for product longevity. Metal and plastic parts are typically titanium or cobalt-chromium alloys and ultra high molecular weight polyethylene, respectively, to balance the needs for strength, flexibility, lubricity, and shape retention. In some instances, synthetic ceramics are also used for their special properties. Surface hardening processes from sintering to special coatings are common. Incorporating the conductors, and if needed, its insulation, as additional planes or layers into different materials introduces surface-to-surface adhesion and differential shear resistance among other problems that could increase susceptibility to propagation of wear and tear and sudden failure. If there is any chemical or biological corrosion, it could travel along the natural plane in the interface between different materials. Therefore, such a planar configuration could even result in accelerated degradation, especially through deformation or delamination.
Given the lower sensitivities required and the non-uniform wear and tear characteristics in certain non-inflatable structures, a probe configuration with minimal potential to change the performance or durability of the structure is desirable. In the preferred embodiment, it is a three dimensional array or arrangement of one or more elongate elements embedded beneath the surface, layer, or thickness subject to breach as described in greater detail below and the accompanying figures. The detecting portions of the probe project from deeper levels in the volume and end at predetermined distances from the surface, layer or thickness. From the surface, an array of points and/or broken lines or curves at predetermined depths is presented to detect the breach. Such an embodiment is minimally disruptive to the overall integrity of the structure while allowing configurations that can maintain coverage of the detection to a wider area.
The probe material could be made of any biocompatible metal, polymer, gel, fiber, particle, ingredient, or combination thereof, with or without any coating or particle impregnation that can generate an electrical charge or enable flow of electric current when in contact with the body fluids or device contents. For example, an electrical charge could be generated from a non-toxic chemical reaction when the elongate element exposed underneath a tear comes in contact with the body secretions. Flow of electric current could be enabled when two ends of an electric circuit hitherto physically separated by electrically non-conductive material in the covering or a structural element of the device are in contact with electrolytes in the body secretions when the intervening electrically non-conductive material is compromised. For example, a charged elongate element is embedded in the core material separate from the ground probe on the external surface of the device. When the elongate element is exposed to the electrolytes in the body fluids in the event of a tear, the circuit is closed. Alternatively, the charged and ground probes could be physically adjacent but electrically separate from each other in the material of the structure and both exposed to body fluids by a breach. Preferred materials include non-corrosive, biocompatible metals and elastomers, inks, or the like which contain electrically conductive particles. They can be rigid or non-rigid. To minimize effects on the material properties and performance characteristics of the structure, it is preferably in the same class of materials or has compatible physical and/or chemical properties as the surrounding materials in the structure subject to breach. So long as the materials of which the elongate element is made are in electrical contact, they can be in any physical composition, even including but not limited to loosely compacted particles or suspensions such as gels. In these alternatives, they can readily assume an altered shape if the structure can deform prior to a breach. If the conductor material is more durable than the material surrounding it, the conductor could even be designed by one skilled in the art to serve an extra function as reinforcement for the structure itself.
Optionally, a conductor material is selected for its intrinsic biochemical effect. For example, silver and gold have natural anti-infectious and anti-inflammatory properties, respectively. Embedded in the structure, the conductor materials are released in doses depending on the magnitude of the breach. Optionally, the probes can be designed by one skilled in the art to function as carriers for biochemical agents, which are eluted and/or activated when exposed by the wear and tear. For example, antibiotics could be delivered to fight infectious organisms or anti-inflammatory agents, such as corticosteroids, to moderate inflammatory responses. Should these agents be electrically non-conductive, they could be incorporated in the insulating cover for the elongate element. Shielded by the intact structure, these agents would lie in waiting for the moment the structure is breached. Given that the release in a breach is immediate and localized, very small amounts of the agents could be effective in controlling these complications early in the process, often far before they become symptomatic. Worn off with the debris of the structure itself, these agents travel with the debris like chaperones. Instead of selecting the materials for their therapeutic value, the materials may be selected for their properties for diagnostic value. For example, the materials could facilitate diagnosis and monitoring for their radio or sono contrast, luminescence, or other chemical or physical properties. Once a breach has been detected, the extent of the distribution and the load of the debris can be imaged non-invasively by readily available radiographic or sonographic equipment. Again, should these agents be electrically non-conductive, they could be incorporated in the insulating cover for the elongate element.
The conductive elongate element in the assembly can be in various configurations to suit the detection criteria and match the contour of the surface, layer, or thickness subject to breach and the geometry of the breach. In its most basic form, the elongate element is a simple cylinder of conductive material. Optionally, it is tapered at the distal end to be minimally disruptive to the structure nearer the surface, layer, or thickness subject to breach. If the material of the structure in which it is embedded is electrically conductive, the elongate element is insulated such that the entire element is of a cylinder or cone in shape. In this configuration, the probe presents a conductive point at the desired depth to detect the breach. This may be sufficiently sensitive if the breach is expected to assume the shape of a shallow and wide depression from shearing and abrasion. Optionally, the conductor is a loop or coil to widen the coverage area or to detect widening breach trajectories. In this configuration, detection of a linear split is enhanced since such a breach could easily miss a point but is likely to extend across and expose a portion of the loop. The coil can be uniform in diameter of a cylinder or has the overall geometry to match the expected path of the breach. For example, an inverted cone might be preferred in a breach that has a small entry but propagates widely deep beneath a surface, layer, or thickness, especially one that has been processed to increase durability. Optionally, the loop can spread out in an expanded pattern within a thickness constituting a patterned conductive line to detect an incoming breach. Optionally, a conductor comprises branches of individual elongate elements arrayed or arranged in a multipronged formation presenting an array of points to detect the breach and the main branches much further behind to minimize the potential disruption to the physical integrity of the structure. These prongs can approach the surface, layer, or thickness at any angle, be in a staggered formation, and/or crisscross each other. Whether the surface, layer, or thickness is flat, convex, or concave, the above configurations or a combination of them could be embedded at suitable depths and densities to detect the existence and extent of the breach. In these configurations, the points or discontinuous lines that end at each uniform distance from the surface, layer, or thickness constitute a line or plane that is parallel to the surface, layer, or thickness.
For surfaces, layers, or thicknesses with complex contours or silhouettes with mixed flats, protuberances, and indentations, it may be problematic to embed precisely the elongate element conductors at uniform depths and/or densities amongst the peaks and valleys of structure or to incorporate multiple conductors without threatening the integrity of the structure. In this situation, the conductive elongate element could be configured as a continuous loop following such contours or silhouettes such that conductive points or broken lines are presented at a uniform distance from such surface, layer, or thickness to detect the breach. Certain portions of the elongate conductor can project out and others depress in to vary the placement of the conductive line within a thickness. The shallowest or detecting sections of the embedded probes can be situated in various locations, preferably near portions of the structure where the most wear and tear is anticipated to enhance sensitivity and reliability of the detection. Such a configuration enables monitoring a large, prescribed area or a specific structural feature with a single conductor. Optionally, the continuous loop following such contours or silhouettes can present conductive points or discontinuous lines or curves at different distances from such surface, layer, or thickness to match the relative probabilities or importance of breaches at different locations.
Regardless of the geometry of the three dimensional formation of the assembled elongate elements, at least one major axis of the configuration is aimed toward the direction of the breach. Usually, this is the axis in alignment with the detection portion of the probe projecting toward the direction of the breach. Typically for a flat surface, layer, or thickness, the axis is the longitudinal which is oriented orthogonal to the surface, layer, or thickness. For a simple convex or concave surface, layer, or thickness this axis is perpendicular or at an angle to the tangential plane depending on the tolerances in manufacturing, impact on the structural integrity, and/or differences in performance characteristics. Where the contour of the surface, layer, or thickness is complex requiring a continuous loop or coil, the preferred axis is the radial intersecting the tangential plane. In this instance, the shallower portions of the conductor project to and are oriented to the contour. Alternatively, if the trajectory of the breach branches out, for example in a cylindrical structure, the radial axis may be directed inward any branch in propagation.
The conductive probes, with or without insulation, can be incorporated into the non-inflatable devices in a variety of manufacturing processes well known to those skilled in the arts. For example, for types of technologies such as casting or molding, the preformed conductor can be placed in the mold at the exact distance from the surface, layer, or thickness and precision casted or molded together with the surrounding core materials to form the structure. Or a bore for the probe can be casted, for example, using the lost wax method. For material removal and forming types of technologies, the component can be precision machined by a computer numerical controlled tool, preferably from behind the surface, layer, or thickness, to form bores or shaped spaces for fixating the conductor. In this direction of machining the component, the surface, layer, or thickness to be monitored would be preserved as a pristine, continuous barrier for the breach. In addition, sources of abrasion or breach, such as any physical deformities or imperfections left behind by machining from the front and any sealing or fixation method, would be obviated. For accretion manufacturing technologies, the conductor can be built into the original substrate or the built part can be machined as above. In the former, for example, the conductor and/or its fixation is held in place as a node and the material of the structure is injected onto and around it from different directions or layer by layer to build up the desired three dimensional structure. If the material is a biologic, the surface of the conductor with its insulation could be engineered to have adhesive properties for the aggregation of the cellular components and growth of the tissue. In the latter, as in the other manufacturing processes, once the bore for the conductor is formed, the conductor can be placed and fixated onto the structure by a variety of processes depending on the material. If it is a solid, the conductor can be inserted directly into the bore and fixated. Alternatively, the bore can be filled with a conductive fluid or paste and then, if needed, transformed into a solid by a variety of means known to those skilled in the art, for example, heat or ultraviolet light curing. The conductor can be uninsulated if the material of the structure is electrically non-conductive. If the material of the structure is conductive, insulation can be preformed over the conductor or placed in the bore prior to introducing the conductor. However, whether the structure material is conductive or not, the conductor is preferably surrounded by insulation along its length to the circuit to form a continuously insulated and electrically isolated appendage prior to placement. In this fashion, there would be no seam that could be poorly sealed or opened after deployment for body fluids to intrude and cause the circuit to send a false positive signal of a breach of the structure. Because of the various axes along which the elongate elements of the conductor are embedded in the structure and potentially tortuous bore, precise machining may be challenging. In this situation, the component can be constructed in three steps. A housing, such as a shaped plug, containing the conductor is first constructed as a male member by any of the processes described above. The component is then precision machined as the female member, preferably from behind the surface, layer, or thickness to hollow out the correspondingly shaped cavity to receive the plug. The plug can be inserted and fixated through a variety of means, including but not limited to mechanical, chemical, physical, or hybrid technologies known to those skilled in the art.
Typically, the component will need to undergo finishing processes. They range from mechanical processes such as polishing to remove imperfections to chemical processes such as coating and sintering to harden the surface. So long as the process does not involve hostile conditions for the conductor assembly and circuitry, the component can be finished with installed conductor. In most situations, however, it will be preferable to complete the surface finishing process before installing the conductor. The treated surfaces can simply be protected during the component assembly. The entire circuitry could be further attached, encased, or hermetically sealed to the assembled component in protective material to form one solid piece, if needed.
The transmitter in the circuit can be a simple wireless signal generator triggered by an electric current or preferably a transponder using the well-established RFID technology, i.e., produces a wireless signal when triggered by an interrogating signal. The electric charge generated or the electric current enabled by the probe in contact with the body fluids or device contents enables the transmitter to emit or causes it to emit a wireless signal. Typically, the transponder is powered by the interrogating radiofrequency signal so that no power source of its own is required. Alternatively, the transmitter could be powered internally by a micro battery or externally by induction. Alternatively, power can be generated by a chemical reaction or piezoelectricity from surrounding body tissues. The circuitry is placed on a substrate which may include shielding to protect it from electromagnetic interference. For protection from degradation by an acidic and electrolyte solution and become potentially toxic, the transmitter or transponder circuit is encased in a highly resistant material, such as silicone rubber, glass, polycarbonate, or stainless steel. The transmitter or transponder circuit can be placed in the interior or on the exterior, preferably away from an area of mechanical stress and electromagnetic interference. The antenna can be placed in a separate radiofrequency privileged location from the circuit but is preferably in an orientation that is most sensitive in sending and receiving signals through body tissue overlying the device. The circuitry and any of its parts may be mechanically fixated to preferred sites on the device or to the tissue in a variety of means known to those skilled in the art. Many of the above teachings are exemplified in the embodiments of the invention in the detailed descriptions of the inventions below.
The wireless signal from the transmitter is recognized by a detector external to the body. The detector could be simply a receiver tuned to the transmitter's signal or, preferably, a combination of both a transmitter of a signal to interrogate the transponder and a receiver to distinguish the different signals from the transponder. The detector is preferably powered by batteries and portable enough to be handheld, worn on a band or belt, or can be placed conveniently near a place where the patient visits often or spends most of his time. Upon receiving a signal that a breach has occurred, the detector will alert the patient to seek medical assistance or alert medical professionals directly through other devices, such as Bluetooth linked to an autodial telephone. The alarm could be auditory, such as beeping sounds, visual, such as flashing LED's or a LCD display, sensory, such as vibrations, or preferably a combination of any or all of the above.
Optionally, the detector could have different auditory, visual, sensory, or different combinations to identify the source of the detected breach, especially with more than one probe or more than one type of probe. For example, LED's of different colors or different sounds could be used. The alarm could further indicate the seriousness of the breach. For example, when multiple probes detect a breach, the volume of the alarm would increase to a higher level. Upon receiving a signal indicating a dysfunction or impending dysfunction of the device, the patient would seek prompt medical care for the timely replacement of the impaired part or component before serious complications. Optionally, the signals indicating the breach from the probes could be compiled into an image to show the location, extent, and depth of the breach.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A-C illustrate the radiofrequency circuitry in three configurations of the breach detection system of the present invention.
FIGS. 2A-2E illustrate the various configurations of the detecting portion of the second conductor as an elongate element.
FIG. 3 illustrates the orientation of the detecting portion of the second conductor as an elongate element to the direction of the breach.
FIG. 4 illustrates an alternative configuration of the elongate element and an example of the method of embedding the elongate element in the material behind the surface, layer, or thickness in the direction of the breach.
FIGS. 5A-5D illustrate additional configurations of the elongate element where the detection portion of the second conductor is spread out in an expanded pattern to cover a wider area and increase the sensitivity.
FIGS. 6A-6D illustrate further configurations of the second conductor where two or more elongate elements are combined and coupled in a multipronged formation aiming toward the direction of the breach.
FIGS. 7A-7B illustrate location and orientation of the elongate elements of the second conductor incorporated in a structure with a convex surface, layer, or thickness over a volume.
FIGS. 8 and 9 illustrate location and orientation of the elongate elements of the second conductor incorporated in a structure with a concave surface, layer, or thickness.
FIGS. 10A-10C illustrate another configuration where the elongate is a long spiral, coil, or helix.
FIGS. 11A-11D illustrate how a loop or coil configuration of the elongate element is incorporated in more complex surfaces, layers, or thicknesses.
FIGS. 12A-12C illustrate a knee prosthesis having the breach detection system of the present invention incorporated in the components on the tibial side.
FIGS. 13A-13B illustrate a knee prosthesis having the breach detection system of the present invention incorporated in the femoral component.
FIGS. 14A-14C illustrate the various wear and tear forces that the knee experiences during stances and movements leading to a breach of a surface, layer, or thickness.
FIGS. 15A-15B illustrate the operation of the passive transponder detection system in the knee prosthesis with a handheld reader.
FIGS. 16A-16B illustrate the various wear and tear forces that the hip experiences during stances and movements leading to a breach of a surface, layer, or thickness and a hip prosthesis having the breach detection system of the present invention incorporated herein.
FIGS. 17A-17B illustrate a hip prosthesis having the breach detection system of the present invention incorporated in the femoral head component.
FIGS. 18A-18D illustrate a hip prosthesis having the breach detection system of the present invention incorporated in the acetabular cup component.
FIG. 19 illustrates the operation of the passive transponder detection system in the hip prosthesis with a handheld reader.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIGS. 1A-1C , the radiofrequency circuitry of the device is shown in three configurations, each with four major parts, a first conductor 110 , a second conductor 120 (a distal end for detection shown in figures below in more detail), a logic circuit 130 , and an antenna 140 . The logic circuit 130 , unless split into distinct parts, for the descriptive purposes here includes the transmitter and transponder. Conductors 110 and 120 are electrically isolated from each other until a breach exposing the conductor 120 to an electrically conductive fluid intruding into said breach bridges them. In circuitry 151 , the logic circuit 130 is on the same substrate as the antenna 140 . In circuitry 152 , the logic circuit 130 is fixed on another substrate apart from the antenna 140 to accommodate design requirements for size and location, esp. to enhance sensitivity, specificity, or robustness. In circuitry 153 , the logic circuitry 130 and a ferrite core antenna 140 is fixed inside a hermetically sealed capsule. It will be obvious to an ordinary person skilled in the art that the circuit could be split further in parts on separate substrates to satisfy design requirements. In passive circuits where the antenna derive power from incoming radiofrequency signals, the antenna is fixated relatively in parallel to the surface of the overlying skin. In this fashion, the plane of the antenna can be orthogonal to the radiofrequency vector in order to maximize capture of radiofrequency energy. The radiofrequency reception can be also be enhanced, such as shown with a ferrite core antenna. Conductor 110 is shown as a single lead wire but can be in any form or shape (not shown here), including the variety of configurations as the conductor 120 below, or electrically coupled to other conducting materials so long as it is electrically exposed to an electrically conductive fluid when the device is implanted in a body or in the event of a breach. Conductors 110 and 120 are shown here in their proximal link to the logic circuit 130 and the double hashed lines indicate the linkage to the distal detecting portion of the conductors.
FIGS. 2A-2E show the distal detecting portion of the second conductor as an elongate element in various configurations. In these and all of the following configurations, should any material be incorporated for enhancement, such as pharmacologic therapeutic or diagnostic agents, whether in the conductor or its insulation, it is not shown separately but represented within the whole. The second conductor 221 is a simple cylinder containing a core of conductive material 202 or a combination of such materials 202 . The conductor can be a bare wire if the device material surrounding it has sufficient impedance to electrical conduction. The overall shape of the second conductor 205 including the conducting material 202 and the optional insulating or fixating material 207 surrounding it can be in any elongate form, here shown as a cylinder in conductor 222 or a cone in conductor 223 . Conductor 203 is shown in a tapered configuration. In conductor 224 , the first conductor 201 is adjacent to the second conductor 202 with insulating material in the middle separating them. At their distal portions, the conductors can be side-by-side, wrapped around each other, loop one around the other, one concentric to the other or form a double helix formation. These close proximity configurations of the first and second conductors 204 is particularly advantageous in specific situations where the first conductor must also be unexposed electrically or, for example, detecting a breach that would expose both conductors simultaneously is desired. If not shown in later figures, this configuration of both the first and second conductors located next to each other may be assumed by figures of only the second conductor. In conductor 225 , the shape at the tip forming the frontline of the detection may be enlarged or enhanced with a plate, lattice, film of conductive material. In this figure and in subsequent figures, the double hashed lines indicate the linkage to the logic circuit 130 in FIG. 1 .
FIG. 3 shows the detection portion of the second conductor as an elongate element with a longitudinal axis oriented toward the direction of a breach. As described in FIG. 2 above, the overall shape may be in any elongate form, here depicted as a cone. The surface, layer, or thickness to be breached is depicted as full or total in 362 or as partial in two layers 361 and 363 . Each surface, layer, or thickness while depicted as separate may themselves be made of thicknesses of different materials or is made of the same material as the core 364 . Thicknesses 361 and 363 could even represent the processed surface of a structure made from a uniform material through a variety of technologies by one skilled in the art to increase durability. The conductors 321 , 322 , and 323 are embedded in the core material 364 beneath the exposed outermost surface 360 extending toward and into the surface, layer, or thickness for a fixed distance. The direction and path of the breach is shown as 370 and the conductors are disposed at the interface or plane between the surface, layer, or thickness subject to breach and the layer or thickness of the material underneath it. In this location, the conductors are directly behind the layer or thickness and in front of the core material in the path of the breach. In conductor 321 , the detection tip 325 closest to the outermost surface extend through layer 363 and end at the partial thickness 361 to detect a partial breach and in conductor 322 , at the full thickness to detect a complete breach. It will be appreciated that the depths of the breach can thus be detected by a number of embedded conductors with tips ending at predetermined levels. The conductor is oriented toward the direction of the anticipated breach with the longitudinal axis perpendicular in conductors 321 and 322 and slanted at an acute angle in conductor 323 . Regardless of the angle of approach, it is readily seen that the longitudinal axis of the elongate element intersects the plane of the surface, layer, or thickness subject to breach. Note that the surface 362 may be exposed to an interior and direction of the breach may be from an interior toward an exterior but the conductors are oriented to intercept the breach.
FIG. 3 also illustrates how the elongate elements 321 , 322 , and 323 intersect a planar region of the implant at different angles, typically between 60° ( 323 ) and 90° ( 321 ).
FIGS. 2A-2E show the distal detecting portion of the second conductor as an elongate element in various configurations. In these and all of the following configurations, should any material be incorporated for enhancement, such as pharmacologic therapeutic or diagnostic agents, whether in the conductor or its insulation, it is not shown separately but represented within the whole. The second conductor 221 is a simple cylinder containing a core of conductive material 202 or a combination of such materials 202 . The conductor can be a bare wire if the device material surrounding it has sufficient impedance to electrical conduction. The overall shape of the second conductor 205 including the conducting material 202 and the optional insulating or fixating material 207 surrounding it can be in any elongate form, here shown as a cylinder in conductor 222 or a cone in conductor 223 . Conductor 203 is shown in a tapered configuration. In conductor 224 , the first conductor 201 is adjacent to the second conductor 202 with insulating material in the middle separating them. At their distal portions, the conductors can be side-by-side, wrapped around each other, loop one around the other, one concentric to the other or form a double helix formation. These close proximity configurations of the first and second conductors 204 is particularly advantageous in specific situations where the first conductor must also be unexposed electrically or, for example, detecting a breach that would expose both conductors simultaneously is desired. If not shown in later figures, this configuration of both the first and second conductors located next to each other may be assumed by figures of only the second conductor. In conductor 225 , the shape at the tip 206 forming the frontline of the detection may be enlarged or enhanced with a plate, lattice, film of conductive material. In this figure and in subsequent figures, the double hashed lines indicate the linkage to the logic circuit 130 in FIG. 1 .
FIG. 3 shows the detection portion of the second conductor as an elongate element with a longitudinal axis 327 oriented toward the direction of a breach. As described in FIG. 2 above, the overall shape may be in any elongate form, here depicted as a cone. The surface, layer, or thickness to be breached is depicted as full or total in 362 or as partial in two layers 361 and 363 . Each surface, layer, or thickness while depicted as separate may themselves be made of thicknesses of different materials or is made of the same material as the core 364 . Thicknesses 361 and 363 could even represent the processed surface of a structure made from a uniform material through a variety of technologies by one skilled in the art to increase durability. The conductors 321 , 322 , and 323 are embedded in the core material 364 beneath the exposed outermost surface 360 extending toward and into the surface, layer, or thickness for a fixed distance. The direction and path of the breach is shown as 370 and the conductors are disposed at the interface or plane between the surface, layer, or thickness subject to breach and the layer or thickness of the material underneath it. In this location, the conductors are directly behind the layer or thickness and in front of the core material in the path of the breach. In conductor 321 , the detection tip 325 closest to the outermost surface extend through layer 363 and end at the partial thickness 361 to detect a partial breach and in conductor 322 , at the full thickness to detect a complete breach. It will be appreciated that the depths of the breach can thus be detected by a number of embedded conductors with tips ending at predetermined levels. The conductor is oriented toward the direction of the anticipated breach with the longitudinal axis perpendicular in conductors 321 and 322 and slanted at an acute angle in conductor 323 .
FIGS. 6A-6D show yet another configuration of the second conductor where two or more elongate elements are assembled and coupled in a multipronged formation pointing toward the direction of the breach. In FIG. 6A , Conductors 621 and 622 have branches ending at layer 363 and 361 , respectively. The prongs of the two conductors are arranged in a staggered array, as shown in a top view FIG. 6B , thus enabling detection coverage over a wider area of a partial and a full thickness breach. A configuration where the branches of two conductors 621 and 622 are crisscrossed is shown in cross sectional views in FIG. 6C and, rotated 90 degrees, in FIG. 6D . If desired, the staggered arrangement can be produced with branches of different lengths. The prongs may be uniform in shape or a combination of different shapes as depicted in the earlier figures above.
FIGS. 7A-7B depict location and orientation of the elongate elements of the second conductor in a cross sectional view with the principles described above in a structure with a convex surface, layer, or thickness. In a structure having a hollow volume 780 , such as an enclosure or luminal structure, the detection portion of the conductors 424 shown in loops terminate distally at different depths below the surface, layer, or thickness to be monitored. With conductors 425 and 426 , the spiral ends transect tangential planes 771 at the full thickness of the surface and 772 at an even deeper layer in the core of the structure, respectively. Regardless of the angle of approach, it is readily seen that the longitudinal axis of the elongate element transects a plane of the convex surface, layer, or thickness subject to breach. Shown with the volume comprising a solid cored structure 790 , the conductors 222 are placed with their longitudinal axes radiating from the core toward the surface, layer, or thickness to be monitored 760 ending at partial thickness 761 and full thickness 763 . In structures that are heterogeneous, shown here as biphasic with material 764 concentrically wrapped around a core material 766 , it may be advantageous to have the core material form optional projections or protuberances here shown as cones 764 and 765 around the conductors. The alternating peaks and valleys of the two materials dovetail to provide mechanical stability to prevent delamination and/or hinder shearing forces at the interface that could tear the conductor and compromise its integrity.
FIGS. 8 and 9 depict location and orientation of the elongate elements of the second conductor in a cross sectional view with the principles described above in a structure with a concave surface, layer, or thickness. The base of the structure 850 is partial and curved in dotted lines for a fastening mechanism to immobilize the component, such as a device housing, to the body. An optional configuration where it is narrowed and/or extended to form a neck 852 for the connection is shown in dashed lines. Alternatively, the concave structure, such as a luminal enclosure or connector component, is fastened to another part of the device. The detection portions of the conductors 821 and 822 radiate distally toward the core of the concavity and terminate in different layers of the structure. They may be combined either singly or grouped in a staggered array (not shown). Conductor 823 has a multipronged formation of elongate elements aimed toward the concavity in the direction of the breach. The conductors typically extend proximally through the structure and drape along the back to reach and connect to the logic circuit, which can be placed in a variety of locations. In FIG. 9 , the base of the concave surface, layer, or thickness is wide and extend to cover its entirety in an optional configuration. Conductors 424 are shown with a spiral configuration with termination distally at various depths. Tangential planes 971 at the full thickness of the surface and 972 at an even deeper layer are transected by their respective conductors, 921 and 922 . Regardless of the angle of approach, it is readily seen that the longitudinal axis of the elongate element transects a plane of the concave surface, layer, or thickness subject to breach.
Referring now to FIGS. 10A-10C show where the elongate element 1021 is in the continuous loop configuration of a long spiral, coil, or helix with radial axes 1031 oriented toward the direction a surface, layer, or thickness subject to breach. In this configuration, the conductor seen from the top (not shown) presents at the desired depth an electrically conductive discontinuous line or curve of dots and/or dashes formed by the peaks 1022 to detect the breach. In a longitudinal sectional view ( FIG. 10B ) and a cross sectional view ( FIG. 10C ), this configuration will enable detection over a cylindrical surface with a single conductor. This configuration ( FIG. 10C ) also enables detection of an internal breach, for example a breach of a concave surface or layer of a housing or luminal structure, initiated in the internal core volume that propagates laterally toward the surface with the radial axis 1032 directed inward.
In FIGS. 11A-11D , how this loop or coil configuration of the elongate element can be applied to surfaces, layers, or thicknesses with more complex contours or silhouettes is shown. In the sectional view FIG. 11A , the detection portion 1021 of the coil presents an electrically conductive spiral to detect a breach in a protuberant or thickened edge commonly used to reinforce and increase durability of an edge, for example, a leaflet of a cardiovascular valve. The radial axis 1131 of the elongate element is shown intersecting the tangential plane 1132 of the surface, layer, or thickness. Surfaces having a mixture of flats, protuberances, and indentations like many naturally occurring in the body, such as joint articular surfaces, are shown from a simplified cross sectional view in FIG. 11B , projectional view in FIG. 11C , and a top view in FIG. 11D . Using the mold for the part, the conductor 1122 can be formed, bent, and wound into shapes that faithfully follow the contour so that it is equidistant at two or more points 1121 along its length closest to the surface, layer, or thickness subject to breach. The shallower portions of the conductor, here shown in a continuous line in FIGS. 11B , 11 C, and 11 D, form conductive curves projecting to the direction of the breach and are oriented to the contour of the surface, layer, or thickness. In all these configurations, the connection to the circuitry is in a deep, protected part of the device and oriented away from the area prone to the breach.
FIGS. 12A-12C , 13 A, 13 B, 14 A- 14 C, 15 A, 15 B, 16 A, 16 B, 17 A, 17 B, 18 A- 18 D, and 19 , illustrate how the breach detection system is deployed in various exemplar applications in orthopedic prosthesis, the hip, a simple ball and socket joint, and the knee, a highly complex joint, encompassing most, if not all, of the types of motions and forces a joint experiences while static or in motion. It will be appreciated that the applications are not limited to these two joints and can be similarly applicable to unicompartmental knee joints and other joints or partial joints in the body. It will further be appreciated that configurations of the elongate elements described in the other figures above, while not shown here, can be deployed in the fashion described to suit the situation. The teachings will be applicable to naturally occurring, synthetic, biologically derived, or hybrid materials used in such devices including but not limited to metal alloys, polymers, ceramics, and biologics, and in articulating contacts whether metal-to-metal, metal-to-polymer, metal-to-ceramic, polymer-to-ceramic, polymer-to-polymer, ceramic-to-ceramic, and to their biologic equivalents and hybrids.
FIGS. 12A-12C , 13 A, 13 B, 14 A- 14 C, 15 A and 15 B show deployment in the total knee replacement joint comprising two components, the femoral 1230 and the tibial 1240 . The patellar component is not shown here as it is not load bearing but the teachings can similarly apply. The tibial component itself typically comprises two parts, an articulating plate or insert 1250 above and a support plate 1260 below as shown in FIGS. 12A and 12B . The femoral component sits on the contoured superior surface of the tibial articulating plate as shown in FIGS. 13A and 13B . FIGS. 14A-14C depict the variety of wear and tear forces that the joint experiences during different stances and movements. In FIGS. 15A and 15B , the operation of the system is depicted. The tibial articulating plate is described in these teachings as made of polymer, such as ultra high density polyethylene, but can be made of any biocompatible material. While the system is not shown embedded in the tibial support plate, the teachings can be similarly applied. The tibial support plate is typically made of alloy and separated from the hostile conditions by the articular plate, which bears the brunt of the wear and tear. Thus, no meaningful wear and tear to this part is anticipated unless the damage to the articulating insert extends far beyond what is detectable. Note that the teachings will be applicable to partial deployment or replacement of only a part, a component, a single articulation, or a combination thereof.
Referring now to FIG. 12A , the tibial component is anchored and fixated inferiorly with a post 1273 to the surgically truncated tibia. The circuit and antenna 151 and a first conductor 110 on a shielded substrate are fixated away from articulating and radiofrequency disadvantaged areas, here placed in an exterior facing area on the anterior surface, of the polymer articulating plate. The polymer plate 1250 with the circuitry 151 fit on top of the adjoining area in the alloy plate 1282 . Optionally, the anterior surfaces of the plates adjacent to the substrate can be undercut, as shown here, in order to form a smooth contour over the anterior surface of the tibial component. The plane of the antenna is relatively in parallel to the surface of the overlying tissues and skin on the anterior part of the knee. In this location, the incoming radiofrequency signals are relatively free from interference by the metallic components, which are behind the antenna and shielding. FIG. 12B shows the superior articular surface of the polymer plate, the concave area of articulation in contact with the femoral component 1255 in dotted lines, and two configurations of the second conductors 221 and 1122 embedded below. In FIG. 12C , the two plates are disassembled like a clamshell. The inferior surface of the polymer plate 1251 mates with the superior surface of the alloy plate 1261 , commonly with female 1252 and male 1262 mechanisms as anchors. While shown near the center of the component, one or more of the fastening mechanisms can be placed at any suitable location. These interlocking mechanisms are preferably non-destructive on the alloy plate side in the removal of only the polymer plate to facilitate the replacement of a worn polymer plate with a new one. Using this method of replacing only the worn part without replacement of the intact alloy plate would simplify the procedure and spare unnecessary bone loss. Two different arrangements of the second conductors are deployed in exemplar fashion. Second conductors 221 isolated from each other run from the logic circuit along the inferior surface of the polymer plate, penetrate through at the desired points, and terminate at the desired depths behind the superior articulating surface. In this configuration, two depths of breach can be detected. Second conductor 1122 runs from the logic circuit along the inferior surface of the polymer plate, penetrates through at the desired point, and forms or connects to a continuous coil of a complex shape with points along its length equidistant in depth from the articulation contact area on the superior surface. In this configuration, the coverage area for the breach of the same depth over the articulation contact area, an uneven contour, is enlarged with a single conductor. Optional additional grooves 1271 or sunken areas can be undercut on the superior surface of the alloy plate to accommodate the section of the second conductor on the inferior surface of the polymer plate. Alternatively, the circuitry can be designed as a package or have its own interlocking mechanisms to fit securely onto either or both plates (not shown). The entire circuitry could be further attached, encased, or hermetically sealed to the polymer plate on its inferior, non-articular, surface in protective material to form one fixed, solid piece, if desired. Alternatively, the polymer insert may be constructed in two or more pieces, medial and lateral, each with its own conductors and circuitry (not shown). In this configuration, each side can be monitored and, when impairment detected, replaced independent of each other.
The system incorporated in the femoral component 1230 , which sits on the tibial component 1240 , in anterior and side views, FIGS. 13A and 13B , respectively. The femoral component is fitted to the surgically shaved femoral head and anchored with posts 1360 . The logic circuit 130 and first conductor 110 is fixated away from articulating areas, here on the shielded interior side wall of the component. The antenna 140 on a shielded substrate is fixated away from articulating and radiofrequency disadvantaged areas, here on the exterolateral side of the component and its plane relatively in parallel to the surface of the overlying tissues and skin. In these locations, the incoming radiofrequency signals are relatively free from interference by the metallic components, which are beneath the antenna. In addition, the plane of the antenna is relatively orthogonal to the radiofrequency vector thereby maximizing the capture of radiofrequency energy and strength of signal. Referring now to FIG. 13B , a lead runs from the antenna, either penetrates the side wall at a desired point or cross over the edge, along the interior side wall to connect electrically to the logic circuit. A second conductor 622 of the double prong configuration is shown. Each prong is embedded in the desired depth and aimed toward the articulation contact area of the femoral component 1380 , runs away from the articulating surface subject to breach, emerges out of the floor, joins the other prong, runs along the floor and interior side wall to connect electrically with the logic circuit. In this configuration, two pinpoint areas, whether close or far, subject to breach could be monitored simultaneously by one conductor. Again, the entire circuitry could be further attached, encased, or hermetically sealed to the assembled femoral component in protective material to form one solid piece, if needed.
In FIGS. 14A-14C , a selection of the various wear and tear forces encountered by the knee are depicted with the articular planes of the components transecting the load bearing axis. In a stationary position, a load or impact 1431 is directly delivered by the most distal portions of the femoral component causing compression and dispersion forces 1432 on articulating contact areas, esp. that of the polymer plate. A change in stance would shift the load and center of such forces to other areas while its axis is still transected by the articular planes. Rotation, abduction and adduction, would cause corresponding shearing forces and load shifts in the same direction 1434 . Flexion and extension causes a mixture of rotational and frictional forces 1433 .
FIGS. 15A-15B shows the progression of the accrued wear and tear resulting in pitting and cracking in the softer polymer plate 1590 thereby exposing the embedded second conductor in the breach. Interstitial fluid enters the breach and the ions electrically bridge the second conductor with the exposed first conductor enabling the logic circuit to send a breach signal. During examination of the device, a radiofrequency reader 1550 is held over the hermetically sealed capsule containing the circuit and antenna and an interrogation signal is sent 1570 and a signal 1580 indicating “breach” or “no breach” is returned and shown on the display panel 1560 . Depending on the configurations of the embedded second conductors, partial breach, breach location, and the extent of the breach could be detected and displayed. If the wear and tear can be detected early, prior to any degradation of the underlying alloy plate or the femoral component, the impaired polymer plate can then be replaced in a relatively minor procedure without replacing the tibially fixated alloy plate, thereby sparing the bone tissue.
In FIGS. 16A-16B , a selection of the various wear and tear forces encountered by the hip are depicted and the system is shown deployed in the total hip replacement joint comprising two components, the acetabular 1651 and the femoral 1652 . In a stationary position, a load or impact 1631 is directly delivered by the femoral head causing compression and dispersion forces (not shown) on articulating contact areas, esp. that of the polymer liner. A change in stance would shift the load and pressure point of such forces to other areas in the liner. Rotation, abduction, adduction, flexion, and extension 1633 would cause corresponding shearing and frictional forces in the same direction. Normal movement of the leg is a mixture of these actions and would result in a combination of these forces in various degrees affecting both the acetabular liner and the femoral component. The logic circuits and their respective antennas 152 and the first conductors 110 are shown oriented toward the outside of the body, typically in an antero-medial or postero-lateral direction with the planes of the antenna fixated relatively in parallel to the surface of the overlying tissues and skin. The logic circuits, antennas, and first conductors are fastened to an external and radiofrequency advantaged area on the respective components or on the bone in which the respective components are anchored. In these locations, the incoming radiofrequency signals are relatively free from interference from the metallic components, which are behind the antenna. In addition, the plane of the antenna can be orthogonal to the radiofrequency vector in order to maximize transmission signal strength and capture of radiofrequency energy.
The two disarticulated components and the disassembled femoral component are shown in FIGS. 17A-17B . FIG. 17A shows how the spherical head fits in the hemispherical cup of the acetabular component. As shown in FIG. 17B , the femoral component typically comprises two parts, a spherical alloy head 1654 with a cylindrical orifice 1740 into which the neck of the alloy femoral shaft 1751 is inserted. A double pronged second conductor 621 is embedded with its tips at the predetermined depth in the head projected outward. The prongs connect electrically in a lead 1752 , which emerges into the cylindrical orifice and runs along its interior wall and out of the head to connect to the logic circuit. Optionally, the circuitry could be further attached, encased, or hermetically sealed to the femoral head in protective material to form one fixed, solid piece, if needed. Grooves 1771 can be undercut either on the interior wall of the orifice or on the neck of the femoral shaft to fit the lead. The area for the logic circuit, antenna, and first conductor 151 is undercut 1772 to fit the circuitry in order for the femoral shaft to have a smooth, continuous contour. Alternatively, not shown here, the circuitry is attached to tissue that moves coterminously with the femoral head and shaft, so that it is not dislocated or torn by movement of the body.
FIGS. 18A-18D depicts the deployment of the system in the acetabular component. The alloy acetabular cup viewed from the side 1653 and front 1653 A are shown. A liner, commonly made of polymer, such as ultra high density polyethylene, but could be any kind of suitable material, viewed from the side 1655 and from the back 1655 A are shown. A spiral second conductor 423 , embedded at a specified depth from and oriented toward the concavity of the liner 1655 , runs outward, emerges from the liner, runs along the convex posterior wall to connect with the logic circuit and antenna on a substrate 151 . When the liner is fixated to the acetabular cup by anchors, the logic circuitry is draped over the exterior of the cup. As analogous to the knee prosthesis, these interlocking anchors are preferably non-destructive on the alloy liner side in the removal of only the polymer liner to facilitate the replacement of a worn liner with a new one. The locations of these fastening mechanisms can be placed at any suitable location so long as the device can function properly. Using this method of replacing only the worn part without replacement of the intact alloy cup would simplify the procedure and spare unnecessary bone loss. A slot on the edge of the cup 1822 and an area on the exterior of the cup 1823 can optionally be undercut such that the lead extension and circuitry could be inserted in place and fastened. Alternatively, the circuitry could be fastened to a wing on the acetabular cup (not shown) or the side of the pubic bone. In the case where the acetabular component is a singular piece, the second conductor can be embedded in the same fashion as the liner, emerges from the liner in the back, runs along the convex posterior wall to connect with the logic circuit and antenna 151 . In this configuration, the circuitry could be fastened to the exterior wall of or a wing on the acetabular cup or the side of the pubic bone. Optionally, the circuitry could be further shielded, attached, encased, or hermetically sealed to the acetabular liner and/or cup in protective material to form one solid piece, if needed. While they are not shown here, it will be appreciated that the circuitry can be designed by one skilled in the art as a package with fixating mechanisms in a myriad of ways to fit securely onto the device.
FIG. 19 shows the system in operation, here with a hermetically encapsulated device with a ferrite core antenna. As in the knee, the progression of the accrued wear and tear resulting in pitting and cracking in the softer acetabular liner exposes the embedded second conductor in the breach to the surrounding interstitial fluid. Naturally occurring ions in the interstitial fluid enters the breach electrically connect the exposed conductor with the exposed first conductor enabling the logic circuit to send a breach signal. During examination of the device, a radiofrequency reader 1950 is held over the antenna of the selected component and an interrogation signal is sent 1970 and a signal 1980 indicating “breach” or “no breach” is returned and shown on the display panel 1960 . Each logic circuitry will have an identifying code to indicate which component, if any, or both have been breached. Depending on the configurations of the embedded second conductors, partial breach, breach location, and the extent of the breach could be detected and displayed. If the wear and tear can be detected early, prior to any degradation of the alloy acetabular cup or the femoral head, only the impaired liner is then replaced in a relatively minor procedure, thereby sparing the bone tissue.
While the present invention has been described herein with respect to the exemplary embodiments and the best mode for practicing the invention, it will be apparent to one of ordinary skill in the art that many modifications, improvements and subcombinations of the various embodiments, adaptations and variations can be made to the invention without departing from the spirit and scope thereof. | An implantable device includes at least one solid structure having an external surface and a volume beneath the surface. One or more of a first conductor or set of conductors is disposed externally and/or internally on or within the structure and an array of elongate electrically conductive elements are disposed radially outwardly within the volume. A breach is detected when a conductive fluid intrudes into the volume through the surface. | 0 |
The invention was made with Government support under contract number F33615-97-C-5021 awarded by the United States Air Force. The Government has certain rights in this invention.
FIELD OF THE INVENTION
The present invention relates to transparent polymeric materials containing sub-micron to nano size bubbles which demonstrate low density, high fracture toughness, high fracture strain, and lower haze than prior art similar such materials, and to a method for their fabrication.
BACKGROUND OF THE INVENTION
Current monolithic and laminated canopies and windscreens for fighter aircraft and the like are fabricated using PMMA (polymethyl methyl methacrylates) acrylics and bisphenol polycarbonates. These materials have relatively low use temperature limits, up to about 220° F. and 300° F. for acrylics and polycarbonates respectively. Wind tunnel testing of such structures conducted at Mach 1.6 to 3.0 at specific altitudes and exposure times showed that the transparency surface temperatures varied from 200° F. to 500° F. Consequently, there is a clearly perceived need for improved transparent materials, which demonstrate a higher temperature capability. Concurrently, in such applications, structural performance, optics (transparency and the avoidance of multiple imaging), and numerous other demanding capabilities are required of the material. As aircraft are produced to fly even faster and under more stringent conditions, these demands will all increase.
In the case of commercial aircraft, acrylics and polycarbonates are commonly used for subsonic canopies, windows and windscreens, since temperature is generally not an issue in such service. However, in the case of supersonic commercial aircraft, the demands will be very much the same as those for military aircraft. Additionally, due to thermal instability in a fire situation, windows of subsonic commercial aircraft tend to pop out, thus allowing air (oxygen) and flame to enter the cabin area more readily. The use of higher temperature capability transparent polymeric materials in these applications, is accordingly also desirable.
Recently, methods have been developed for the production of T g (202-350° C.) transparent polymers. Much of this work has involved the synthesis of new high T g polymers or polymer blends such as blends of polyetherketone with polyethersulfone, miscible sulfonated polyetheretherketone with polyetherimide, melt blends of phenylene ether phosphine oxide based on hydroquinone and bisphenol with polyetheretherketone, synthesis of aromatic polybenzoxazoles in trimethylsilyl polyphosphate, and 6F-polybenzoxazoles to obtain adequate transparency, structural capacity and temperature capability. A particularly interesting class of such materials and the methods of their synthesis are described in U.S. Pat. No. 5,691,442 to Unroe, et al issued November 1997 which is incorporated herein by reference. This patent describes improving the transparency of poly(arylene ether) homopolymers or copolymers by endcapping the polymeric chain with an unsubstituted phenolic-based endcapping agent. Such materials, when cast as thin films from chloroform, yield tough, transparent and colorless films. The T g of these materials is in the range of 207° C. and 281° C., their tensile strengths are in the range of 10.4-12.7 ksi, their tensile modulus in the range of 0.26 and 0.37 msi and their fracture strains in the range of 4% to 58%. When processed as thick sheet by injection molding or compression molding, however, the materials become yellow thus limiting applications as described above, that require good transparency.
Whatever the material used to fabricate canopies according to the prior art, such as thermal forming, injection molding, etc. the resulting structure was a “solid” material having the density of the parent polymeric material. Additionally, the thermal processing of “thick” sections of high T g polymers, of the type required for the aforementioned applications, generally produces an undesirable coloration as the thickness of the structure increases, as in the case of the polymers of Unroe et al. Alternatively, a complex and time consuming laminating process must be used to obtain structures, which demonstrate the required clarity.
The materials of the present invention, produced in accordance with the process of the present invention, contain up to about 30% voids and demonstrate highly desirable optical characteristics that are required for the above described applications while being significantly lighter, i.e. about 16% lighter because of their foamed structure.
DESCRIPTION OF THE DRAWINGS
The invention will be more fully understood from the following detailed description taken in conjunction with the accompanying drawings, which form a part of this application, and in which:
FIG. 1 is a block flow diagram of the process for producing the polymeric foams of the present invention.
FIG. 2 is an SEM photomicrograph of a transparent sample as produced in Example 1.
FIG. 3 is an SEM photomicrograph of a foamed material prepared in accordance with a modified practice of the present invention as described in Example 1.
FIG. 4 is an SEM photomicrograph of a foamed material produced in accordance with the present invention that has received further thermal processing in accordance with Example 2 of this disclosure.
FIG. 5 is an SEM photomicrograph of a foamed material produced in accordance with the present invention that has received further thermal processing in accordance with Example 2 of the present invention.
SUMMARY OF THE INVENTION
The present invention provides a method for the production of novel polymeric foams which, because of the sub-micron or nano size of their component bubbles, is transparent and demonstrates enhanced optical and mechanical properties. High T g polymeric foams produced in accordance with the present invention, when compared to similar materials produced using conventional thermal processing techniques such as injection molding, exhibit lighter weight due to their foamed structure, higher fracture toughness, higher fracture strain, marginally higher fracture strength, in many cases improved optical clarity and modulus.
According to the present invention, polymer foams are produced by forming a desired shape from the desired polymer, heating the shape to a consolidation temperature under pressure, saturating the heated shape with an inert blowing gas at a temperature above the Tg of the polymer at elevated pressure, and controllably releasing the pressure to cause the formation of sub-micron or nano sized bubbles. If thin films of the polymer are transparent to visible radiation, and the bubbles produced by the process are on the order of from about 0.1 to about 0.7 μm in size, since particles smaller than the wavelength of visible light are transparent to the human eye, the polymeric foams of the present invention will appear transparent. The present invention describes a method for producing bubbles of appropriate size in appropriate polymers to provide foamed polymeric materials in useful shapes that, while being transparent, exhibit enhanced mechanical properties.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, polymer foams are produced by forming a shape from the desired polymer, heating the shape to a consolidation temperature under pressure, cooling down and saturating the heated polymer shape under inert gas at a temperature above the T g of the polymer, and controllably releasing the pressure to cause the formation of sub-micron or nano sized bubbles.
The process of the present invention is useful with virtually any polymer, which is capable of being formed into a suitable shape, and treated as described hereinafter. Specifically preferred polymers, however, are those that demonstrate a high T g (glass transition temperature), for example, above about 200° C. because of the utility of such polymers in meeting the high temperature and strength demands of such applications as aircraft canopies, etc.
In the current description, polymers of the type described in the aforementioned U.S. Pat. No. 5,691,442 to Unroe et al will be used to demonstrate a specific preferred process, however, it will be understood that any suitable polymer can be substituted therefor in the process described and claimed herein.
According to the preferred process of the present invention, a disk or other desired shape is produced by compression molding or otherwise, for example, by extrusion, injection molding etc. According to a highly preferred embodiment of the invention, the disk or shape is compression molded from a powder at a pressure above about 12000 psi. Vacuum is drawn inside the die during the compression molding cycle to remove air from the disk or shape as much as possible. The temperature of the disk or shape is then raised, in a pressure vessel, to the softening temperature of the polymer, in the case of the biphenyl endcapped poly(arylene ether) homopolymers of Unroe, between about 360 and 430° C., under a continuous feed of inert gas, for example, carbon dioxide, nitrogen, helium or any of the inert gases, and held under positive pressure for a period of from about 10 to about 50 minutes. This consolidation process serves to assure that the polymer shape has a continuous structure prior to further processing. If the disk or shape is already provided from another source in a transparent and suitably consolidated form, for example, injection molded, i.e. formed under consolidation conditions, then this step of consolidation may be excluded as consolidation has already been performed.
However the disk or shape is provided, after consolidation, the disk or shape is “saturated”, i.e. subjected to heating to a temperature above its T g , and to a pressure above about 9000 psi under an inert atmosphere for a period of from about 1 to about 5 hours. The temperature and soak or saturation time will, of course, be dependent upon the particular polymer being processed, the saturating gas utilized and the solubility of that gas in the particular polymer being foamed, but such parameters are readily determinable by the skilled artisan. According to a particularly preferred embodiment, saturation is performed at a temperature between the T g of the polymer and about 1.2×T g .
After the holding period is complete, the shape is cooled to room temperature. This cooling may be accomplished while either maintaining the soaking pressure or partially releasing the same until the temperature of the polymer shape has reached a temperature somewhat below the T g of the polymer. Once the shape has reached a temperature somewhat below the T g of the polymer or room temperature, the pressure is released. At this stage in the process, the “bubble structure” has been locked into the body of the shape. Further modification of the bubble size or foam morphology can be accomplished by heating the shape in an oven to a temperature at or just below the T g of the polymer.
The principal operating variables for controlling the nucleation rate and hence the cell density of the polymer are the applied saturation pressure and the solubility of the gas in the particular polymer being processed. Increasing either of these variables, i.e. pressure or solubility, increases the nucleation rate of the bubbles and consequently, increases the porosity of the foam.
EXAMPLES
Example 1
An biphenyl endcapped poly(arylene ether) thermoplastic polymer identified in U.S. Pat. No. 5,691,442 to Unroe et al in Example 1 as 6FETPP-E and commercially available from Daychem Laboratories, Inc., 143 Westpark Road, Dayton, Ohio 45459, was obtained in flake form. The material was dried, ground into fine particles and compression molded into sample disks approximately 1.125 to about 2.256 inches in diameter and 0.125 inches thick.
The sample disks were then saturated in a pressure vessel at temperatures ranging from about 320° C. to about 380° C. at pressures between about 9000 and 9200 psi. The densities of the sample disks ranged from about 1.13 g/cc to about 1.20 g/cc depending upon the processing temperature and pressure. A spectrum of transparencies was obtained depending upon the size of the bubbles formed in the processing. Those samples using a higher saturation temperature at the upper end of the previously mentioned range had larger bubbles than those processed at the lower end of the range, and consequently, the former did not demonstrate the same degree of optical clarity as the latter. This is shown in FIGS. 2 and 3. FIG. 2 is an SEM of the most optically clear sample showing only sub-micron bubbles. FIG. 3 is an SEM of a sample produced at a higher saturation temperature range showing that the bubbles are larger than those shown in FIG. 2 . This sample exhibited a lower optical clarity than that shown in FIG. 2 .
Transparent sample materials from this processing tested for haze and transmittance according to ASTM D1003 demonstrated values of between about 19 and 24% for haze and 69 and 73% for transmittance. These values did not change appreciably between room temperature and 330° F.
Mechanical properties for samples from this processing showed ultimate strengths on the order of 10,700 psi, a chord modulus above about 470,000 psi (strain gauges broke before specimens failed). Additionally, these materials demonstrated fracture toughness values up 3.5 times those of the parent material, and higher fracture strain values, up to 81%, than those of the parent material.
Example 2
In order to show the ability to alter the foam morphology after the bubbles are “locked in” by initial processing, samples prepared in Example 1 were slowly heated in an oven to a temperature just above the T g of the polymer. As shown in FIGS. 4 and 5, the bubbles grow as soak time in the oven at elevated temperature just above the T g are lengthened. In FIG. 4 the bubbles have grown to 1-2 microns, while further soaking results in the bubbles growing to 10-20 microns, as shown in FIG. 5 . While such materials are clearly useful in many applications, they are not transparent.
Example 3
A second biphenyl endcapped(arylene ether) polymer identified as BPETPP in Unroe et al in Example V, and commercially available from Eikos, 115 Dean Ave., P.O. Box 328, Franklin, Mass. 02038 was processed similarly to the material processed in Example 1 except that consolidation was performed at between 400 and 430° C. The resulting foam had a T g of about 222° C. and was stable and maintained its transparency up to about 400° F.
Example 4
A third biphenyl endcapped(arylene ether) identified in Example V11 of Unroe et al as FEK-E also available in flake form from Daychem Laboratories, Inc. was processed as described in Example 1 above, except that consolidation was performed at 420° C. and saturation was performed at 250-280° C. Transparent samples having a T g of about 247° C. were obtained.
Example 5
A fourth biphenyl endcapped poly(arylene ether) identified in Unroe et al in Example V111 as FETPP-E also commercially available from Daychem Laboratories, Inc. was processed as described in Example 1 except that consolidation was performed at a temperature of about 410-450° C. and gas saturation was performed above 281-320° C. Transparent samples having a T g of about 281° C. were obtained.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, make various changes and modifications of the invention to adapt it to various usages and conditions. It is therefore intended that the scope of the invention is limited only by the scope of the appended claims. | A novel class of transparent polymeric foams comprising submicron cells and a process for their production is described. The polymers are preferably high glass transition materials and the process comprises saturating a consolidated polymer shape with an inert gas at a temperature above the glass transition temperature of the polymer and under a pressure of at least 9000 psi for a period adequate to dissolve the gas in the polymer shape and then controllably cooling the polymer shape to produce the submicron cell structure. | 2 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an innovative ensilage trolley for containers and to a shuttle with said trolley. This invention also relates to a storage system including said shuttle and trolley.
[0003] 2. State of the Prior Art
[0004] The ensilage trolley or ensiler and the shuttle have the function of transferring containers or other assimilable load units (movable cases or equivalent platforms for intermodal transport of various goods) between the different boxes of a warehouse or handling and sorting system of said load units.
[0005] In the description below, by the word ‘container’ is meant all the possible load units assimilable with a container in its various versions.
[0006] Usually, warehouses automated with ensilage shuttles and trolleys have boxes arranged on several superimposed levels, normally from 6 to 10 (even if solutions are possible with a larger or smaller number of levels). The boxes are realized with a-structure of columns and cross pieces of steel beams having shelves to support the containers. Among the shelves of boxes there are pathways for the transport system including the trolleys and shuttles.
[0007] In the known art of such storage systems, by ‘shuttle’ is meant a trolley transporting the container in a direction perpendicular to the major axis of the container while the ensilage trolley transports the containers in the direction of the major axis while transferring them with this movement from a storage box to the shuttle and vice versa.
[0008] The shuttle transfers the container together with the ensilage trolley, which remains on the shuttle during the movement of same so as to be available for transfer of the container to or from a box when the shuttle is aligned with a new box.
[0009] The ensilage trolley disconnected from a trolley is also used for transferring the containers between two aligned boxes belonging to two different sets of shelves facing each other with the short side. In this case the container is transferred from one box of the shelving to the box of the facing shelving instead of from box to shuttle and vice versa. The ensiler moves only forward and backward between the two boxes and transfers the containers while supporting them on itself in the two flow directions.
[0010] The bulk of the containers handled can easily exceed 30 tonnes while the length can exceed 12 meters and the width be approximately 2.5 meters with height variable on the basis of the intended use of the container.
[0011] The ensiler must therefore be capable of handling containers with rather variable weight and transport them supporting them on itself in different positions. For example, it would be advantageous that the same trolley might support a long or short container transported centered, a short container transported on the right or left side of the ensiler, or two short containers transported simultaneously et cetera.
[0012] In addition to the variability of the dimensions, there is also a variability of the position of the center of gravity of the full container depending on the position of the center of gravity of the goods contained in it. A center of gravity position too far from the symmetry axes of the container can cause handling difficulty in the known transport systems.
[0013] It is clear that the accidental stopping of a shuttle or an ensilage trolley in the warehouse, in addition to the impossibility of taking or depositing the container foreseen, has repercussions of varying gravity on the entire system based on the type and position of the failure. The difficulties of acceding to a failed machine together with the mass and dimensions of the loads transported increase the difficulties of solving a failure situation.
[0014] From the foregoing the need is clear for realizing machines as simple as possible with high reliability, easy to repair even outside the area equipped for programmed maintenance and calling for minimum maintenance even if used in a marine environment. In addition, it is preferable that these machine be capable of completing the work cycle started in the greater part of failure cases foreseen. The whole set remains in minimal dimensions of space occupied in height and reasonable costs.
[0015] The general purpose of the present invention is to remedy the above mentioned shortcomings of known devices and make available an innovative ensilage trolley for containers, a shuttle with said trolley and a storage system including said shuttle and trolley which allow satisfaction of the requirements mentioned.
SUMMARY OF THE INVENTION
[0016] In view of this purpose it was sought to provide in accordance with the present invention a motorized ensilage trolley for entering and exiting from a cell in a container storage system and transfer containers between the cell and the exterior and characterized in that the trolley is equipped with at least one transport unit made up of a base frame with motorized wheels for running on rails for movement of entry and exit of a loading platform arranged over the base frame and designed to support a container with there being between the loading platform and the base frame fluid hoisting sets distributed longitudinally to the trolley for controlled hoisting of the platform and which also realize elastic attenuation parts.
[0017] Again in accordance with this invention it is sought to realize a shuttle for translation between cells in a container storage system including on it such a trolley.
[0018] It is also sought to realize in accordance with this invention a container storage system including a plurality of cells for reception of containers and means of transfer of containers inside and outside of the cells with the transfer means including such a shuttle for translation between the cells and such an ensilage trolley carried on the shuttle to face the cells.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] To clarify the explanation of the innovative principles of the present invention and its advantages compared with the prior art there is described below with the aid of the annexed drawings a possible embodiment thereof by way of non-limiting example applying said principles. In the drawings:
[0020] FIG. 1 shows a diagrammatic side elevation view of a storage system part with shuttle realized in accordance with this invention,
[0021] FIG. 2 shows a diagrammatic plan view of a shuttle of FIG. 1 with an ensilage trolley advanced in a cell of the warehouse,
[0022] FIG. 3 shows a diagrammatic view taken transversely to the axis of a shuttle,
[0023] FIG. 4 shows a diagrammatic side view enlarged by one shuttle in accordance with this invention,
[0024] FIG. 5 shows an enlarged diagrammatic view of a detail of a motorization zone of the shuttle of FIG. 4 ,
[0025] FIG. 6 shows a diagrammatic plan view of an ensilage trolley part of the shuttle of FIG. 4 ,
[0026] FIG. 7 shows a diagrammatic view along line VII-VII of FIG. 6 of the ensilage trolley on the respective shuttle, and
[0027] FIG. 8 shows a diagrammatic view of a control part of the ensilage trolley.
DETAILED DESCRIPTION OF THE INVENTION
[0028] With reference to the figures, FIG. 1 shows part of a warehouse system designated as a whole by reference number 10 and realized in accordance with this invention.
[0029] The system includes a reticular structure or shelving 11 which identifies cells or boxes 12 for housing of containers 13 and corridors 14 between walls of facing cells which define horizontal lanes in which run motorized shuttles 15 for transport, insertion or extraction of the containers. The warehouse can include at the ends of each corridor lifting means for vertical translation of the containers. A similar warehousing structure is well known to the technician and not further described nor shown.
[0030] To introduce containers into and extract them from the cells there are ensilers 16 each transported by a shuttle 15 along the lane so as to align it with the boxes 12 . FIG. 1 shows diagrammatically a shuttle with ensiler withdrawn aboard (upper shuttle) and a shuttle with ensiler inserted in a cell (lower shuttle). The shuttle with ensiler off board and inserted in the cell is also shown in plan view in FIG. 2 .
[0031] As see well in FIG. 2 also, the shuttles run horizontally among the cells along tracks 17 by means of motorized units 18 each one including a wheel 19 and an electric motor reducer 20 .
[0032] The shuttle has a pair of tracks 21 which are aligned with corresponding tracks 22 in each cell and on which run the ensiler 16 by means of a plurality of partially motorized wheels 29 to enter into and exit from the cells of the shelves. As clarified below, the ensiler has a platform which moves vertically for hoisting of the containers from special supports in the cells and aboard the shuttles.
[0033] The ensiler can therefore exit from the shuttle, to enter in a cell sliding on the pathway constituted from tracks 21 , 22 , introducing itself under the container in the cell, to raise the container, releasing it from the supports, to return aboard the shuttle transporting the container and, at last, to put down the container on the appropriate supports aboard the shuttle.
[0034] The container transfer cycle from the box to the shuttle being completed the shuttle can be moved opposite an empty box where, by performing the cycle symmetrical to that described above, it deposits the container on its supports of the new box. The box can also contain a vertical lift for the container.
[0035] The ensiler, in passing from the shuttle to the box, must overcome a break in the pathway deriving from the play necessary between the fixed pathway in the boxes and the movable one on board the shuttle. The play must be sufficiently ample to compensate for the relative movements due to thermal variations, to movements of the shelves, to take-up of play et cetera. In addition, at the end of the pathway beyond the empty space there is also a misalignment on the vertical plane given by the different elastic camber of the two structures in the different load conditions.
[0036] As may be seen in FIG. 3 , the shuttle structure includes shelves 23 to support the container for transportation and among which is arranged the ensiler 16 . Inclined guide and centering floors 24 cooperate advantageously with the shelves.
[0037] The ensiler 16 has the upper loading platform 25 which is supported by means of hoisting sets 26 on the underlying motorized structure 27 which runs along the tracks 21 . The hoisting sets are distributed along the frame and are advantageously realized by means of pneumatic cylinders with bellows.
[0038] Advantageously, the upper movable loading platform is a rigid structure while the base frame is made up of a particularly simple elastic structure which supports the wheels and, having the possibility of deforming in elastic field, inflectionally and torsionally, it adapts to all the irregularities of the pathways and in this manner allows all the wheels to remain in contact therewith without the use of the large quantity of precision balances and articulated arms which would be necessary to allow adaptation to the pathway of the considerable number of wheels which support the load.
[0039] As seen well in FIG. 4 , advantageously the ensiler is made up of two equal units 16 a , 16 b connected in series. As seen in the figure, the two units can collaborate for the transportation of long containers ( FIG. 1 ) or a single unit can support a half-length container ( FIG. 4 ).
[0040] As seen again in FIG. 4 and, more in particular, FIG. 5 , the two load units 16 a and 16 b are connected together by a pair of connecting rods 28 . The two load units making up the ensilage trolley are connected together this way by a coupling allowing a minimum adaptation to the irregularities of the pathway and at the same time constrain rigidly the two units to follow the same acceleration-deceleration law, hence in the translation movement they behave as a single vehicle with twelve motors (six per unit).
[0041] FIGS. 4 and 5 show in greater detail for each unit the upper loading platform 25 movable vertically, the base frame 27 supporting the bearing wheels 29 and the bellows cylinders 26 which in expanding control the hoisting of the upper movable load unit. The tie rods 34 for limiting the hoisting path are also visible.
[0042] In FIG. 5 it is noted how the upper loading platform is realized by means of longitudinal beams which assure rigidity to the loading platform while the base frame part is realized relatively thin to allow the above mentioned elastic flexibility. In this manner the wheels 29 constrained directly to the base frame are kept correctly gripped on the running tracks with no need for other devices. Elimination of the precision balances used generally in the prior art, in addition to the obvious reduction of construction and assembly costs, has a considerable advantage from the operative viewpoint due to elimination of parts (pins, bushings, arms) which require a constant accurate maintenance and the greater simplicity of the machine which consequently reduces the chance of failure.
[0043] FIG. 5 also shows wheels 30 with vertical axis for lateral guidance of the ensiler along the tracks. As shown better in the plan view of FIG. 6 (only one unit of the ensiler is shown for simplicity) and in FIG. 7 the side guidance wheels 30 are arranged in pairs to be supported on two opposite side edges of a single rail of the pair of ensiler running rails. Advantageously, each load unit is guided by three pairs of guide wheels. The first two pairs are near one end of the two units making up the ensiler and the other pair is near the other end, which is the one facing the other unit. In this manner, the complete ensiler will have two pairs of wheels at one end, two pairs in the middle (one pair per unit) and two pairs at the other end.
[0044] The arrangement of the wheels described above allows, with the use of a lower number of guide wheels, crossing of breaks in the pathway without losing the guidance effect because at every moment at least one pair of wheels at each end of each load unit remains gripped on the pathway and in addition, the guide performed acting on the two sides of only one of the two pathways allows accurate guidance of the ensiler trolley conditioned only by the construction tolerance on the width of the pathway and independent of the position errors, parallelism, rectilinearity of the totality of the two pathways.
[0045] Each unit has a good number of supporting wheels 29 of small diameter (for example sixteen wheels) for the purpose of limiting the space occupied in height and distributing the load uniformly over all the entire length of the pathway while reducing the flexion stress and making possible the use of lighter and hence more economical profiles, limiting the specific pressure on the pathway, allowing crossing of the irregularity of the pathway with a limited increase in the load on the wheels which remain supported and must carry the load while a pair of wheels is transiting on the break of the pathway and consequently is totally unloaded.
[0046] Again in FIG. 6 shows the alternating and uniform distribution of supporting wheels 29 and for pneumatic hoisters 26 which was found particularly advantageous. Advantageously, the motor reducers 31 for handling of the wheels are arranged alternatively on the right and left of the trolley and are fitted directly on the shaft of the respective wheel without intermediate transmissions. This together with assembly of the wheel on bearings with watertight rings arranged so as to create an increased reserve of lubricant compared with the normal sealed bearings make practically null the need for maintenance of this whole set with consequent advantages in terms of cost and reliability of the system. The wheels are all identical except for the axle which in the drive wheels is lengthened so that it can couple with the motor reducer so that it is possible to vary the number of drive wheels simply by installing a drive wheel set in place of an idling wheel set.
[0047] To allow rapid replacement of the complete idling wheel unit the supports of the roller bearings which support the axle of the wheels can be disassembled upward by unscrewing only four bolts 32 or the complete drive wheel by unscrewing the same four bolts plus a bolt 33 which holds the reaction arm (as shown also in FIG. 7 ).
[0048] Again advantageously, the drive wheels on the right-hand side and the left-hand side are not arranged on the same axle but are out of phase by one step (where to the right the drive wheel is driving and to the left it is idling and vice versa). This way, a single drive wheel at a time can be at the irregularity of the pathway so that even in this small section of the path the traction is always assured by eleven drive wheels out of twelve.
[0049] Advantageously, between the upper movable loading platform and the base frame there are interposed a high number (eighteen) of pneumatic cylinders with bellows arranged on the same longitudinal axle and alternating with the bearing wheels which can thus perform different functions. Advantageously, the movable frame hoisting means of each unit are controlled independently of those of the other so as to be able to take or deposit independently only one of two short containers (for example 20 ′) which can be stored in a box of 40 ′. When one takes or deposits the 40 ′ container, both the hoists are operated simultaneously.
[0050] In addition to the above mentioned function of hoisting and lowering the upper loading platform and the container, they allow uniform sharing of the load among all the wheels coupled with a bellows set with common powering and allow determining the weight of the container transported and the plan position of its center of gravity and lastly carry out the function of softly amortizing all the jolts and vibrations and the concentrations of stresses which there are with the movement of means in particular when the masses transported are considerable.
[0051] When the two units are not loaded in the same manner or at the limit one is loaded and the other not loaded, the vertical load on the drive wheels of the unit with lightest load is the one which determines most transmissible horizontal force from each of the wheels of the ensiler to avoid its slipping in every load condition.
[0052] Considering that the load transported by each load unit can reach even five times the weight of the empty vehicle, it is clear how penalizing the acceleration limitation is which is obtained by limiting the torque to that defined for accelerating the empty vehicle even when the vehicle is fully loaded with resulting lengthening of the cycle time.
[0053] It is not enough to take with a sensor the presence of a container on board the ensiler to be able to vary consequently the torque delivered by the motor because the content of containers is extremely variable and, consequently, even their weight has considerable variations so that using a mean value one risks slipping when the weight is low and does not utilize all the acceleration possibilities when the weight is high.
[0054] In the subject ensiler one manages to obtain maximum possible acceleration compatibly with the number of driving wheels and with the present friction coefficient between wheels and the pathway by varying the torque of the motors as a function of the load effectively on the driving wheels. The torque is equal between the motors of a unit and can be different from that of the motors of the other unit if the latter is subjected to a different load (for example a heavy container on one unit and no load transported on the other unit).
[0055] Thanks to the pneumatic suspension of the cylinders 26 the load transported is shared equally between all of the bearing wheels (drive and idling) of a unit.
[0056] As shown diagrammatically in FIG. 8 , an electronic control unit 40 manages the trolley functions. In particular the control unit 40 controls electronic operations (inverter) 41 of the motor reducers so as to regulate the torque delivered by the motors as a function of a signal proportionate to the pressure generated by a pressure transducer 42 located on the pneumatic hoisting system 43 . The system controls the pressure so as to balance the load transported. The electrical motor-control equipment is located advantageously on board a shuttle to be easily accessible and commutable on those of backup.
[0057] The movement of hoisting and lowering the movable frame of the ensiler is controlled by the bellows cylinder 26 through a battery of electromagnetic valves 44 motorized by a reserve of compressed air contained in one or more tanks 45 transported by the ensiler trolley which are motorized through flexible tubes 46 connected to a main tank 47 arranged on board the shuttle. The pneumatic powering of the ensiled by the shuttle can be realized with a double flexible tube to be able to continue working even in case of breakage of one of the tubes. The air reserve on board the ensiler is advantageously such as to be able to carry out at least one hoisting cycle even under powering interruption conditions by the shuttle.
[0058] Under normal operating conditions a small compressor 48 on the shuttle provides refilling of the main tank and the tanks on board the ensiler. The energy necessary for fast hoisting of the movable frame with the container loaded is accumulated in the tanks by utilizing little power for a long time and is available for hoisting the container rapidly without having to install a large power supply which would then be used for a few seconds each cycle. Advantageously, the pneumatic circuit can include safety valves which automatically exclude a failed bellows cylinder and allow continuing work with those remaining.
[0059] The hoisting run necessary for releasing the container from the benchmarks in the boxes and on the shuttle is much smaller than that necessary for conventional container handling means (straddle carrier, reach stacker) so that movement for setting down and picking up can be done using low speed even though making the movement in reduced time. As a result the acceleration or shock to which the containers and goods contained therein are subject are considerably reduced and are still more reduced by the mildness of movement of the pneumatic hoisting system.
[0060] With this control system the driving torque is regulated as a function of the load transported by each single unit allowing the best utilization of the acceleration and deceleration possibilities of the ensiler as a whole set. Either the electrical or pneumatic connections between the shuttle and the ensiler can be made by means of quick plugs and connectors to be able to disconnect the ensiler fast from its shuttle so as to be able to perform replacements and repairs rapidly.
[0061] It is now clear that the preset purposes have been achieved. The particular structure of the ensiler trolley allows high reliability even with reduced maintenance. The system also allows reliable and safe management of containers having different dimensions, weights and centers of gravity. The pneumatic hoisting system allows uniform distribution of the load on all wheels and reduced flexion stress on the pathway and the specific contact pressure. The amortized support of the container also allows reduction of vibrations to which the container content is subject, reduction of the stress peaks transmitted to the support structure and to the machines cooperating with the ensiler.
[0062] In addition, thanks to the innovative structure it is possible to rapidly replace a failed ensiler with an efficient one in the maintenance zone. In addition, it is possible to temporarily deposit an ensiler in the maintenance zone and use the shuttle for other functions such as going and picking up an ensiler doing service in the so-called ‘movable box’ and transport it to the overhaul zone for programmed maintenance or for repairs which it is not economical to perform locally. It is also possible to abandon a broken down ensiler which can no longer move in the same box where it broke down so as a to free the shuttle and consequently the corridor to rapidly resume activity with a reserve shuttle. The shuttle without ensiler can be equipped with a new ensiler in the maintenance zone or wait in the same zone until its ensiler is repaired.
[0063] With the structure in accordance with this invention the possibility that an ensiler will undergo a failure preventing it from reaching the maintenance zone is extremely reduced. For example, in case of failure of a motor the remaining eleven allow completing the work cycle. In case of failure of a wheel the other fifteen on which in the worst case the load is distributed allow translation of the ensiler. If the wheel is then completely blocked and it is wanted to avoid its dragging on the pathway, it is possible to raise it slightly from the pathway by acting on the tie rods which limit the hoisting run.
[0064] The motors can be equipped with manual unlocking of the brake to allow opening of the brakes even in case of failed electric power.
[0065] As can be seen in the figures, the structure of the trolley makes it possible to carry out repairs even on an ensiler blocked in a box with a container on board since all the critical mechanical parts (motors, wheels, bellows cylinders, electromagnetic valves) are accessible and replaceable from beneath the ensiler. A special movable maintenance platform can be positioned where necessary using a shuttle.
[0066] In the same manner the shuttle is provided with all the characteristics necessary to make extremely unlikely the possibility that it might stop during a working cycle. For example the motorization is independent on all the four wheels with the possibility of completing the cycle at reduced speed with only two motors on service.
[0067] Thanks to the compressed-air hoisting system, in case of failure of the compressor or the connecting tubes the hoisting system can be supplied by means of a rapid connection to be connected by means of a flexible emergency tube to the tank of a shuttle different from the one on which the ensiler is normally dependent. It is also possible to use the compressed air contained in a normal breathing apparatus cylinder to control the hoisting in case a second shuttle from which to take the compressed air is not quickly available.
[0068] Naturally the above description of an embodiment applying the innovative principles of the present invention is given by way of non-limiting example of said principles within the scope of the exclusive right claimed here. For example, without leaving the ambit of this invention the pneumatic circuit can be realized with several separate circuits for reasons of safety with the use of leveling valves for control of the position of the container and with position and multiple pressure transducers, encoders on the drive and idling wheels and calculation algorithms of the torque to be delivered as a function of the information received.
[0069] By using several pressure sensors each connected to a separate circuit separately feeding groups of pneumatic bellows cylinders it is possible to determine the weight distribution both longitudinally and transversely and in addition to using this information for management of the distribution of the torque among the various motors it is possible to calculate the position of the center of gravity and, if the container risks instability, automatically reduce speed and acceleration for that particular mission. The sensors, circuits and cylinder units can be advantageously four. It is also possible to memorize this information and combine it with the data of that container to signal it at the time of loading on the train, truck or ship so that the appropriate precautions are taken during maneuvering. Movement of the load in the container due to incorrect arrangement of the goods contained and to the dynamic stresses to which it is subjected during the trip is not infrequent and can become a source of accidents if not detected and, in the most serious cases, it is necessary to open the container and proceed with reloading the contents thereof.
[0070] The number of bellows-type pneumatic cylinders, the number of bearing wheels, the distribution among idling and motorized wheels are not binding and can be generously changed to enhance one or the other characteristic of the system described in one of the various possible configurations without leaving the scope of the invention. The pneumatic system can be realized also as hydro-pneumatic or hydraulic with tanks. The movements of ensiler shuttle and trolleys can be oriented along other axes of the container. The warehouse can have a different number of levels even on a single non-reticulate floor and structure. | A storage system for containers including a plurality of cells for reception of containers and means of transferring containers within and outside of the cells. The transfer means include shuttles for translation between the cells and ensilage trolleys which are carried by the shuttles to face a cell and which are motorized to enter and exit from the cell and transfer containers between the cell and the shuttle. The ensilage trolleys are fitted with at least one transport unit made up of a base frame with motorized wheels for running on rails for the entrance and exit movement and with loading platform arranged above the base frame and designed to support a container. Between the platform and the base frame there are fluid hoisting sets distributed longitudinally to the trolley for controlled hoisting of the platform and which also realize elastic attenuation parts. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to buoyancy compensation devices for use by underwater divers, especially recreational SCUBA divers, and more particularly to a buoyancy compensation device that provides relatively constant buoyancy regardless of the diver's depth and a method of providing buoyancy compensation at relatively constant buoyancy for an underwater diver regardless of the diver's depth.
2. Description of the Prior Art
Typically, a SCUBA diver with dive gear, including a wetsuit and air tank, is positively buoyant and must wear lead weights in order to submerge. When the diver enters the water, the wetsuit has maximum buoyancy owing to the air in the pores of the expanded neoprene or butyl rubber from which wetsuits are typically made. As the wetsuit gets soaked with exposure to water and the air in the wetsuit is compressed as the diver descends to depths having pressures greater than atmospheric, it loses some of its buoyancy. Thus, the diver may have to overcome the tendency to sink. SCUBA divers typically use a “buoyancy compensation device” (BCD) to adjust buoyancy during a dive.
The BCD in current, relatively widespread use by divers, referred to herein as a “conventional BCD,” is simply a substantially inelastic, inflatable bladder that can be filled and emptied of air that is always at ambient pressure. That is to say, the internal pressure of a typical inflated BCD bladder corresponds substantially to the external ambient pressure regardless of water depth; at the water surface the BCD bladder internal pressure is 14.7 psia and at about 150 feet water depth the BCD bladder internal pressure is about 80 psia, the ambient pressure in fresh water at about 150 feet depth.
By inflating the conventional BCD when at depth, the diver's tendency to sink owing to the compression of the diver's wetsuit, for example, can be overcome. As the diver uses up compressed air from the air tank, the tank becomes lighter, and thus more positively buoyant, typically, by about 5 lbs., which corresponds to about 5 lbs. of lift or about 2.25 liters of air volume. Thus, at the end of a dive, it may be difficult for a diver to stay submerged for a safety stop (to prevent decompression illness). Should the diver experience such difficulty, the diver can carry more lead on the next dive and, to be safe, can overestimate the lead requirement. Thus, according to this approach, the diver will carry a fairly large amount of lead and then compensate for the added weight by introducing air into the BCD bladder. Apart from having to carry the extra weight, this presents another problem for the diver.
The air that is forced into the conventional BCD bladder from the air tank displaces a given volume of water at a given depth, i.e., the deeper the dive, the more air will be required to produce the same volume displacement of water. The lift or buoyancy generated is equal to the weight of the water displaced from the BCD bladder. It would be desirable for this displacement to remain constant throughout the dive, regardless of the diver's depth. However, the air in the BCD bladder is compressed as the diver descends to deeper depths (producing less displacement and less lift) and expands when the diver ascends toward the surface (producing more displacement and more lift). The former situation is a nuisance; as the diver descends, he may find that he has a tendency to sink faster and must add air to the BCD bladder to compensate for the faster descent. However, the latter situation is not only a nuisance, but can be quite dangerous.
A brief description of lung volumes and their definitions will be helpful in understanding the following description of the prior art devices, as well as the invention and its operation and advantages over the prior art devices. A typical representation of lung volumes measured at atmospheric pressure is shown in the chart of FIG. 10 and in the following table:
Lung Volume
Volume in liters
Description/Definition
Total lung capacity
6.0
The volume of air contained in the lungs at the
(TLC)
IRV + TV + ERV + RV
end of maximum inspiration. Total volume of the
lungs.
Vital capacity
4.6
The volume of air that can be expelled from the
(VC)
IRV + TV + ERV
lungs after a complete maximum inspiration.
Tidal Volume
0.5
The volume of air breathed in or out of the lungs
(TV or VT)
during normal respiration.
Residual Volume
1.2
The volume of air left in the lungs after a
(RV)
maximum exhalation.
Functional Residual
2.4
The volume of air that stays in the lungs during
Capacity (FRC)
ERV + RV
normal breathing.
Inspiratory Reserve
3.0
The maximum volume of air that can be inspired
Volume (IRV)
VC − (TV + ERV)
into the lungs in addition to the tidal volume.
Inspiratory Capacity
3.5
The maximum volume of air that can be inspired
(IC)
TV + IRV
into the lungs following a normal expiration.
Expiratory Reserve
1.2
The volume of air that can be expelled from the
Volume (ERV)
lungs after the expiration of a normal breath.
Based on the chart and table, it can be seen that during normal breathing at tidal volume (TV) ±0.5 liter, a diver changes his buoyancy or lift only about ±1 lb. It can also be seen that if a diver inspires deeply after a normal inspiration, he can increase the air volume in his lungs by about an additional 3.0 liters (IRV) and thus increase his buoyancy by about 6.6 additional pounds. It can also be seen that if a diver exhales deeply after a normal expiration, he can decrease the air volume in his lungs by about an additional 1.2 liters (ERV) and thus decrease his buoyancy by about 2.6 pounds. A skilled diver can maintain a normal tidal volume, but increase his ERV and decrease his IRV so that he is breathing “near the top” of his vital capacity. Similarly, a skilled diver can maintain a normal tidal volume, but decrease his ERV and increase his IRV so that he is breathing “near the bottom” of his vital capacity. This permits the seasoned diver to adjust his buoyancy during the course of a dive to a magnitude that can come close to the changes in buoyancy caused by using up air and compressing his wetsuit.
If a diver ascends to the surface using a conventional BCD without carefully controlling his rate of ascent by releasing air from the BCD, the air in the BCD will increase in volume making him ascend faster, which further increases the BCD volume and so on, resulting in an “uncontrolled ascent.” An uncontrolled ascent can cause two serious problems. One of these problems is decompression sickness, commonly called “the bends,” which is caused by the release of dissolved nitrogen as a gas into the blood stream. An equally, if not more, serious problem can be caused by a rapid increase in the total lung volume. A skilled, relaxed diver knows to allow air to expel from the lungs during such a situation. A novice or panicked diver may keep his glottis closed. This, in turn, will cause an increase in lung volume beyond that which the lungs are capable of accommodating, which may rupture the alveoli, resulting in a pneumothorax. In such a situation the lung collapses and the air escapes into the chest. A pneumothorax can be fatal and is a common cause of death for the novice or panicked diver.
A diver should always ascend to the surface from depth at a slow, controlled rate. If the diver has been at depth for a significant time period, he may need to make a decompression stop to allow the dissolved nitrogen in his blood to slowly and safely come out of solution. Thus, controlled buoyancy is absolutely critical when a diver surfaces. As the air in the conventional BCD bladder expands upon ascending, the diver will tend to ascend faster which, in turn, increases lift more rapidly and causes acceleration of the diver's rate of ascension, an extremely dangerous condition, especially if a decompression stop is necessary before surfacing. In order to prevent this from happening with a conventional BCD, the diver must carefully release air from the BCD during ascension. Occasionally, even experienced divers do not accurately adjust the release of air from the conventional BCD and accidentally bypass a decompression stop.
Another problem can occur when a diver, experienced or not, wears a thick and, therefore, very buoyant wetsuit. To compensate for the extra lift of the wetsuit, the diver must wear more lead in order to descend. Then, when the wetsuit compresses, the diver becomes negatively buoyant to a degree that requires a significant volume of air to be introduced into the BCD. This large volume of air will vary considerably with depth and, thus, require the diver to frequently add to and reduce the BCD volume. Similarly, if a diver is carrying heavy equipment, he will be negatively buoyant to a degree that requires significant air in the BCD, making it necessary for the diver to carefully adjust buoyancy with depth changes so as to avoid the aforementioned “uncontrolled ascent” scenario with its accompanying difficulties.
It would clearly be a desirable objective to have a BCD that provides substantially constant lift or buoyancy, or at least a degree of lift or buoyancy that varies substantially less than that of the conventional BCD, regardless of the diver's depth. Ideally, the change in volume of a BCD during ascent should produce a change in lift that is no greater than the decrease in lift that a diver can achieve with a forced expiration, which, as explained above, is on the order of 3.0 pounds. Such a BCD would result in increased safety, because the diver could then stop an ascent with a forced exhalation only.
One approach that accomplishes the objective of constant or substantially constant lift or buoyancy regardless of depth is a rigid, constant or fixed volume buoyancy tank. However, because it is often necessary to adjust buoyancy, for the reasons mentioned above, e.g., wetsuit compression and tank air depletion, most prior art fixed volume tanks provide means for adjusting buoyancy. In those prior art devices, if it is desired to adjust (increase or decrease) the lift or buoyancy of the tank, the fixed volume of the tank can be changed by a movable piston inside the tank or, more typically, by flooding the tank with water or expelling water from the tank. U.S. Pat. Nos. 3,161,028; 4,009,583; 4,068,657; 4,101,998; 4,114,389; 5,221,161; and U.S. Patent Application No. 2006/0120808 disclose buoyancy compensation devices that utilize such a rigid, constant or fixed volume buoyancy tank with means to adjust the volume. Using such devices, a diver can adjust buoyancy for a given depth to achieve vertical equilibrium and then change depth to some extent with little or no need to readjust buoyancy.
There are, however, several disadvantages to these rigid tank types of buoyancy compensation apparatus. A constant or fixed volume buoyancy tank, as the term implies, is not deflatable and thus increases the overall size (occupied volume) of the BCD regardless of depth. This adds to the cumbersome nature of the already cumbersome array of equipment a SCUBA diver needs in order to enjoy safe and interesting dives. A further disadvantage of a floodable fixed volume buoyancy compensation apparatus is that buoyancy cannot be increased or decreased when the diver is in an inverted position (or in any position in which water or air cannot be expelled to ambient through the air and water valves), unless the constant volume tank is provided with water inlet-outlet valves at both the top and bottom of the constant volume tank. Such additional valves obviously increase the cost and complexity of a fixed volume BCD, as well as make the BCD more difficult for the diver to operate. Moreover, a floodable fixed volume buoyancy tank effectively functions no differently than the conventional BCD because the pressure inside the tank corresponds to ambient pressure (as typified by the aforementioned U.S. Pat. No. 5,221,161 and U.S. Patent Application No. 2006/0120808), unless the valving of the fixed volume BCD is also designed to isolate the fixed volume of air from ambient pressure.
Referring again to the conventional BCD, that prior art device employs a collapsible or substantially flaccid, inelastic bag or bladder, the volume of which can be increased or decreased in order to control the buoyancy of the diver. The bladder is essentially inelastic during its working range of pressures because the pressures inside (internal) and outside (ambient) the bladder are the same and, when completely full or inflated to its full volume, the bladder vents air to ambient surroundings to maintain substantially equal internal and ambient pressures, as well as maintain its inelastic condition and prevent unintended rupture of the bladder. As explained above, a significant disadvantage of such a BCD is that the internal volume of the bag or bladder increases rapidly with during ascent because of the decreasing pressure of the ambient water on the bag or bladder as the diver ascends. Unless the diver offsets this rapidly increasing volume by continuously releasing air to decrease the air volume in the bag or bladder, the diver may “overshoot” his intended decompression stop depth and dangerously and rapidly ascend to the surface thereby increasing the risk of decompression sickness or pneumothorax. To minimize this problem, a number of prior art BCDs utilize automatic buoyancy control systems which include hydrostatic valving systems responsive to ambient pressure to control the volume of the bag or bladder of the BCD during the diver's ascent or descent. Obviously, the cost and complexity of such hydrostatic valving systems and the risk of failure of their numerous components are major drawbacks to this approach.
One additional disadvantage of the prior art BCD's is that the air pocket in the BCD shifts according to the diver's position. Thus, there is generally a plurality of venting valves located at different points on the BCD. Typically, a modern BCD will have three such valves. Furthermore, to fully vent a BCD, a diver must take the large corrugated tube that exits the BCD at the diver's left shoulder and extend it as high as possible above his head to vent air from the BCD. In light of these disadvantages, it would be desirable to provide a BCD that forcibly expels all the air that was introduced during the dive, so that only a single exhaust valve would be necessary and the location of that valve could be arbitrarily positioned.
Yet another disadvantage of the prior art BCD's is the shifting of the air pocket in the bladder during a dive, which can result in imbalance, causing the diver to tilt toward the right or left. It would, therefore, also be desirable to provide a BCD in which the location of the air pocket is controlled, predictable, and balanced across the diver's breadth.
The conventional BCDs in current use comprise one or more inflatable bladders in the form of a belt or vest worn on or about the torso of the diver. A few examples of such prior art BCD are disclosed in U.S. Pat. Nos. 4,913,589; 5,256,094; 5,560,738; 5,562,513; 5,707,177; 6,478,510; 6,592,298; and 6,796,744. As previously mentioned, to control the addition and expulsion of air from the bladder, many prior art BCDs include mechanisms for automatically adjusting the buoyancy of the BCD bladder depending on the water depth or pressure or other parameters. Several of such prior art automatic BCDs are disclosed in U.S. Pat. Nos. 3,820,348; 5,496,136; 5,560,738; and 6,666,623. U.S. Pat. No. 5,551,800 discloses an automatically adjustable BCD which uses an expandable bellows with an internal spring as a buoyancy bladder or tank.
In light of the foregoing, it would be desirable to provide a BCD for a diver which has a relatively constant buoyancy regardless of diving depth, i.e., approaching that of a rigid, or fixed volume BCD, without the disadvantages of having a more complex and cumbersome buoyancy compensation system. It would also be desirable to provide a BCD with a displacement container or volume having a change of buoyancy with depth (lift versus depth characteristic) that approaches the constant lift versus depth characteristic of a rigid tank BCD and has a lift versus depth characteristic substantially better than that of the conventional BCD that employs an ambient pressure inflatable inelastic bladder for buoyancy control. Furthermore, it would be desirable to provide a BCD that overcomes the foregoing limitations and shortcomings of prior art BCD devices, has a minimum number of parts, is economical to manufacture and is easy, convenient and particularly safe for a diver to use.
SUMMARY OF THE INVENTION
The present invention is directed to an improved BCD that comprises one or more elastic members with a given initial internal volume or displacement at atmospheric pressure (“the base volume”) that, during inflation, maintain(s) a substantially constant base volume until an internal pressure is reached (“the base pressure” or “yield point pressure”) that is always substantially greater than the ambient pressure at any dive depth throughout the working range of diving pressures. At internal pressures above the base pressure, the internal volume of the tubular member(s) of the disclosed embodiment increases as described in more detail hereinafter. Although the BCD of the invention can be embodied in many different configurations than the configuration of the embodiment disclosed herein, key features of the invention are that the tubular member is elastic at any volume and that the base pressure is always substantially greater than the ambient pressure at any dive depth throughout the working range of diving pressures. A typical range of dive depth for recreational divers is from zero (14.7 psia) to 150 feet depth (80 psia). Thus, regardless of depth, the base pressure of the tubular member (or members) may be, for example, 20-40 psia or more greater than ambient pressure.
The invention also relates to a method of providing buoyancy compensation by providing a BCD that is always elastic and that has a lift versus depth characteristic that approaches the lift versus depth characteristic of a constant or fixed volume buoyancy compensation device.
According to its apparatus aspects, one embodiment of the BCD invention comprises one or more elastic tubular members connected via the first stage regulator and a manually-operated inflation/dump valve to the pressurized air tank of a SCUBA diving apparatus. The inflation and deflation functions can be accomplished with two valves that are preferably located close to one another so that they can be operated by one hand and so that the diver can easily switch between inflating and deflating the BCD. Alternatively, and preferably, the inflation and deflation functions are accomplished with a conventional single slider valve which has three positions, “neutral,” “inflate” and “deflate.” In the “neutral” position, the valve is closed. In the “inflate” position, the valve connects the BCD tubular members to the pressurized inflation tube. In the “deflate” position, the valve vents the BCD tubular members to ambient. It is common for such slider valves to be spring biased to return to the neutral position after an inflation or deflation function has been performed. In addition, an over-pressure relief valve may be provided as part of the slider valve, or elsewhere in the pneumatic system, to dump air more rapidly than the tubular members can be inflated when a predetermined over-pressure in the system is reached during an inflation condition.
The elastic tubular members may be sealed at both ends with rigid plastic end caps or by other means and contain a given, relatively small total displacement volume at atmospheric pressure (the base volume), e.g., a total of 0.4 to 1.0 liter for four tubular members. The tubular members are made of an elastomeric material, preferably a silicone rubber, such as a high shear and tear resistant Shore A (25-40) silicone rubber manufactured by Dow Chemical Company or Axon AB Plastics. Other elastomeric materials may be used for making the elastic tubular members of the present invention in light of the teachings herein, and such materials will be apparent to, or readily determined by, those of skill in that art.
In the preferred embodiment of the BCD invention disclosed herein, four tubular members are provided, two located on each side of the pressurized air tank at the diver's back along axes substantially parallel to the longitudinal axis of the air tank. The bottom end caps of each pair of tubular members are connected to a respective manifold that includes inlets/outlets for admitting or exhausting high pressure air to/from the tubular members via a passage in the bottom end caps. One manifold connected to a pair of tubular members is mounted on each side of the pressurized air tank by means of a manifold mounting bracket affixed to the frame or jacket of the SCUBA diving apparatus.
To limit the maximum volumetric expansion of the elastomeric tubular members in the radial as well as in the axial or longitudinal direction, each tubular member is provided with an external tubular first sleeve made of a substantially non-stretchable material, such as a woven nylon fabric, that is affixed, e.g., by clamps, at each of its ends to a respective top and bottom end cap. This external or first sleeve prevents over expansion of the tubular member beyond its desired maximum size and internal volume. In the unexpanded or uninflated or base volume condition of the tubular member, the first sleeve is slack or gathered about the tubular member.
A second sleeve, also made of a substantially non-stretchable nylon fabric, loosely surrounds each pair of tubular members and first sleeves and is affixed at its bottom end to a respective manifold and at its top end to the frame or jacket of the SCUBA diving apparatus. The purpose of the second sleeves is to constrain the tubular members to remain close to the diver's body when, for example, the diver is in a horizontal position looking down or to either side. If the tubular members were not so constrained when the diver is in the aforesaid horizontal positions, air in the tubular members may cause them to flex away from the diver's body and create a potential diving hazard for a diver, for example, attempting to pass through a submerged opening. It should be understood that other equivalent means or mechanisms could be employed in lieu of the second sleeves. For example, spring tension could be applied to the upper, free end of the tubular members to keep them parallel to one another and close to the diver's body as they inflate. Alternatively, the uninflated tubular members could be pre-stretched to their maximum inflated length and both top and bottom ends could be affixed to the SCUBA diving apparatus frame or jacket.
A third sleeve or covering made of a stretchable material or an elastic fabric, such as spandex, may be stretched over each second sleeve to snug each pair of tubular members and first and second sleeves up to the diver's back for streamlining and abrasion protection purposes. All the sleeves are preferably porous to air so that in the event of a rupture of one or more tubular members, the air would not be trapped in any of the three sleeves, which, if air were so trapped, could cause a sudden and undesired increase in buoyancy.
As pressurized air from the air tank via the regulator and inflation valve is introduced into the tubular members via the inlets in the bottom caps thereof, the internal pressure in the tubular members increases substantially before the internal volume of the tubular members (the base volume) begins to increase to any great extent. Although not to be considered as limiting the invention, in the embodiment described herein at ambient atmospheric pressure, the internal pressure in the tubular members reaches a base pressure of about 40 psia before the base volume and the rate of change of the base volume (dV/dt) begins to increase significantly, assuming that the rate of increase of pressure (dP/dt) is constant or substantially constant. In other words, the compliance of the tubular members, defined as the change in volume as a function of pressure (dV/dP), is low or substantially zero until the internal base pressure is reached at which point compliance begins to increase more rapidly. The internal base pressure at which compliance begins to increase significantly is also referred to herein as the “yield point pressure” and may be a pressure greater or less than 40 psia above ambient pressure, but is preferably a pressure in excess of about 20 psia above ambient pressure.
Accordingly, as used herein to describe the disclosed embodiment, “yield point pressure” is defined as that given internal pressure in a tubular member at which the compliance of the tubular member is greater than the compliance of the tubular member below the given internal pressure, and corresponds generally to the base pressure. In the disclosed embodiment, yield point pressure is physically manifested by a relatively rapid increase in diameter of a tubular member or a bulging at one longitudinal region of a tubular member that is controlled by the design of the tubular member. To cause this increase in diameter or bulging to occur at a given longitudinal region of the tubular member, the member may be cast or otherwise manufactured with a reduced wall thickness or enlarged diameter at a predetermined longitudinal location, e.g., a predetermined distance from one end of the tubular member. It may also be possible to cast, extrude or otherwise manufacture tubular members that do not manifest the aforementioned bulging at one longitudinal region, but rather increase radially substantially uniformly along substantially the entire longitudinal extent of the pressurized tubular member beginning at the base pressure.
Above the base or yield point pressure, continued introduction of pressurized air into the tubular members causes the volume of the tubular members to increase until each tubular member is constrained to its maximum inflated volume both radially and longitudinally by its surrounding first sleeve. At its maximum inflated volume, each tubular member has an internal pressure substantially greater than ambient, e.g., from about 40 psia to about 60 psia or more greater than ambient up to the maximum pressure of the first stage regulator, which is typically about 140 psia. Because the internal base pressure of the elastic tubular members is always higher than ambient pressure, the change of lift or volume with water depth for the BCD of the invention is advantageously much less than that of the conventional BCD. In other words, the BCD of the invention will maintain a much more constant displacement and lift over a typical dive profile than the conventional BCD. With an appropriate selection of elastomeric materials and design of the elastic tubular members, the lift versus depth characteristic of the BCD of the invention can be made relatively comparable to that of a constant or fixed volume BCD.
When a plurality of elastic members, e.g., four, is used in the BCD of the invention, flow restrictors may be included in the inlet to each elastic member should the elastic members not inflate uniformly together. Such flow restrictors will avoid any unbalance in the lift forces that would otherwise occur, for example, if one of the four elastic members inflates before the other elastic members begin inflating.
According to the method aspects of the present invention, the elastic tubular members of the BCD invention may be inflated to an internal base pressure that is always greater than the ambient pressure at any dive depth throughout the working range of diving pressures. During inflation, there is a pressure, defined hereinabove as the “yield point pressure,” typically at least 20 psia above ambient, above which the compliance of the tubular members is greater than the compliance of the tubular members below the yield point pressure or base pressure. Below and up to about the yield point pressure, the base volume of the tubular members remains relatively constant. The method of the invention differs substantially from the method of providing buoyancy compensation with conventional BCD bladders which are inelastic in that they are inflatable only to internal pressures corresponding essentially to ambient pressure so that the internal pressure is always the same as ambient pressure. Moreover, when the bladder of a conventional BCD is inflated to its maximum volume, any further introduction of air is typically vented so as to retain the inelasticity of the bladder and maintain the pressure in the bladder at ambient pressure, i.e., at a pressure differential of zero between internal and ambient.
With the foregoing and other objects, advantages and features of the invention that may become hereinafter apparent, the nature of the invention may be more clearly understood by reference to the following detailed description of the invention, the appended claims and to the several drawings forming a part hereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of one embodiment of the primary components of the BCD of the present invention shown as they would be positioned on the body of a diver without the other components of a conventional SCUBA diving apparatus;
FIG. 2 is a schematic view of the pneumatic system of the embodiment of the BCD invention shown in FIG. 1 ;
FIGS. 3A and 3B are plan and cross-sectional views of an uninflated elastic tubular member of the embodiment of the BCD invention shown in FIG. 1 , with the cross-sectional view of FIG. 3B taken along plane A-A of FIG. 3A ;
FIGS. 4A and 4B are plan and cross-sectional views of an inflated elastic tubular member of the embodiment of the BCD invention shown in FIG. 1 , with the cross-sectional view of FIG. 4B taken along plane B-B of FIG. 4A ;
FIG. 5 is a perspective view of the embodiment of the BCD invention depicted in FIG. 1 in the uninflated condition shown with the first, second and third sleeves;
FIG. 6 is a perspective view of the embodiment of the BCD invention depicted in FIG. 1 in the inflated condition shown with the first, second and third sleeves;
FIG. 7 is a graph comparing displacement versus inflation pressure at ambient atmospheric pressure of the BCD of the invention, a conventional BCD and a fixed volume BCD and showing the yield point pressure of the BCD of the invention;
FIG. 8 is a graph comparing lift and internal volume versus depth of the BCD of the invention, a conventional BCD and a fixed volume BCD with a start depth of 96 feet and an initial lift of about 3.0 lbs.;
FIG. 9 is a graph comparing internal volume versus depth of the BCD of the invention, a conventional BCD and a fixed volume BCD both up and down from a start depth of 40 feet at an initial lift of 4.0 lbs; and
FIG. 10 is a chart showing a typical representation of lung volumes measured at atmospheric pressure.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIG. 1 of the drawings, an embodiment of the BCD of the invention is illustrated in perspective on the body of a diver D and is designated generally with reference numeral 10 . In the FIG. 1 illustration, the diver's conventional SCUBA equipment is not shown, apart from the first stage regulator 12 and the valve 14 which is connected between the first stage regulator and the pressurized tank of the SCUBA equipment. The BCD 10 of the invention comprises four elastic tubular members 16 a , 16 b , 18 a and 18 b , which are vertically arranged in two pair 16 a , 16 b and 18 a , 18 b , respectively, on opposite sides of the diver's lower back. The structure of the elastic tubular members is described in more detail hereinafter in connection with FIGS. 3A , 3 B, 4 A and 4 B. Each pair of tubular members is connected to a respective left and right manifold 20 , 22 , which, in turn, are affixed to a manifold mounting bracket 24 . Bracket 24 is mounted on the diver's SCUBA equipment (not shown), e.g., on the frame or jacket that supports the pressurized tank of the SCUBA equipment.
A single slide valve 26 having three positions, “neutral” or “off,” “inflate,” and “deflate” or “dump” is connected to the first stage regulator 12 by an inflation hose 28 , which passes over the left shoulder of the diver D. Preferably, the slide valve 26 is manually operated and is spring-biased to the neutral or off position so that no air passes through the slide valve. A first inflation/dump hose 30 is connected between the slide valve 26 and the left manifold 20 also passing over the left shoulder of the diver D. A second inflation/dump hose 32 is connected between the left and right manifolds 20 , 22 .
When the diver D desires to provide lift during a dive, he manually operates the operator lever 34 to move the slide valve 26 from its neutral or off position to the inflate position to admit pressurized air from the pressurized air source (not shown) through the first stage regulator 12 , the inflation hose 28 , slide valve 26 , inflation/dump hoses 30 , 32 , manifolds 20 , 22 and into the bottom of each elastic tubular member 16 a , 16 b , 18 a and 18 b to begin inflating all the tubular members simultaneously. When the desired magnitude of lift is achieved, the diver D releases the operator lever 34 of the slide valve 26 and the slide valve automatically returns to its neutral or off position. If the diver D wishes to decrease lift, he manually operates the operator lever 34 to the deflate or dump position to release air from the tubular members 16 a , 16 b , 18 a and 18 b through the manifolds 20 , 22 , the inflation/dump hoses 30 , 32 and exhaust port 36 on the body of the slide valve to ambient. When the desired decrease in lift has been achieved, the diver D releases the operator lever 34 and the slide valve automatically returns to its neutral or off position. If desired, a relief valve (not shown) may also be provided in the body of the slide valve 26 or elsewhere in the inflation circuit of the BCD 10 to prevent overpressure in the tubular members.
Those skilled in the art will appreciate that there are many other possible valve and hose configurations that may be used to inflate and deflate the tubular members so that the present invention is not to be limited by the particular valve and hose configuration shown in FIG. 1 .
FIG. 2 is a pneumatic schematic of another embodiment of the BCD of the present invention which is designated generally by reference numeral 40 . In this embodiment, a conventional SCUBA tank 42 provides a source of pressurized air for the BCD 40 via a valve 44 and first stage regulator 46 . BCD 40 comprises four elastic members 48 , 50 , 52 , 54 connected to the first stage regulator 46 by inflation hoses 56 , 58 . A two-position inflation valve 60 is connected between hoses 56 , 58 for admitting pressurized air into the elastic members. Air is exhausted to ambient from the elastic members via hose 62 and two-position dump valve 64 . Flow restrictors 66 , 68 , 70 , 72 are provided in the inlet to each elastic member so that the elastic members inflate evenly together. Such flow restrictors will help avoid any unbalance in the lift forces that would otherwise occur if, e.g., one of the four elastic members fully inflates before any other elastic member begins inflating. A flow restrictor 74 may also be provided between hose 56 and valve 60 to limit the flow rate of the air entering the elastic members.
Referring now to FIGS. 3A and 3B , a representative elastic member assembly 80 of the invention is shown in plan and cross-sectional views, respectively, in its unexpanded or uninflated, but still elastic condition. Elastic member assembly 80 comprises a substantially cylindrical tubular member 81 ( FIG. 3B ) cast or otherwise formed of an elastomeric material, preferably a silicone rubber, such as a high shear and tear resistant Shore A (25-40) silicone rubber manufactured by Dow Chemical Company or Axon AB Plastics. Tubular member 81 is formed with a central through passage 82 and at its ends with outwardly extending flanges 84 , 86 . Central through passage 82 is formed with a slightly enlarged portion 83 for a purpose to be described and has a relatively small volume at atmospheric pressure, e.g., about 0.1 liter.
Flanges 84 , 86 are captured and secured in a respective top and bottom end cap 88 , 90 by means of a respective pair of split retainer sleeves 92 , 94 . As shown in FIG. 3B , split retainer sleeves 92 , 94 are threaded on their outer circumferential surfaces so as to threadably engage the threads on the inner circumferential surfaces of the top and bottom end caps 88 , 90 . Split retainer sleeves 92 , 94 are also threaded on their inner circumferential surfaces so that when the split sleeves 92 , 94 are threaded into the end caps 88 , 90 to capture and seal the flanges 84 , 86 against a respective end cap, they also grip the outer circumferential wall surfaces of the tubular member 81 adjacent the flanges 84 , 86 to securely hold the tubular member 81 in the end caps 88 , 90 .
Top end cap 88 is provided with a central elongated pin 96 that extends into and supports the central passage 82 , 83 of the tubular member 81 . Bottom end cap 90 is also provided with a central pin 98 that sealingly extends into the central passage 82 of tubular member 81 . Pin 98 is provided with a central bore 100 through which pressurized air is admitted and exhausted as explained in more detail hereinafter. Bottom end cap 90 also differs from top end cap 88 in that it is provided with a pair of lugs 91 , 93 and screws 95 for securing the elastic member assembly 80 to one of the manifolds 20 , 22 ( FIG. 1 ).
Elastic member assembly 80 also includes a first tubular sleeve 102 , preferably made of a substantially non-stretchable woven nylon fabric, which surrounds the tubular member 81 and is affixed at its sleeve ends to a respective end cap 88 , 90 by means of clamps 104 , 106 or any other suitable fastening means. Sleeve 102 is illustrated in a bellows-like form in FIGS. 3A and 3B only to indicate that, in the uninflated or unexpanded condition of the elastic member assembly 80 , the sleeve is in a slack condition. Accordingly, sleeve 102 may have other regular or irregular shapes gathered about the tubular member 81 . First sleeve 102 serves to limit the maximum expansion of the tubular member 81 in the radial as well as in the axial or longitudinal direction so as to prevent over expansion of the tubular member beyond its desired maximum size and internal volume.
Referring now to FIGS. 4A and 4B , elastic member assembly 80 of the invention and of FIGS. 3A and 3B is shown in plan and cross-sectional views, respectively, in its expanded or inflated condition. In this condition, pressurized air has been admitted through central bore 100 into central passage 82 , 83 and has inflated or expanded the elastic tubular member 81 to its maximum internal volume, e.g., about 2.25 liters. First sleeve 102 is taut in both the axial and longitudinal directions and, thus, substantially prevents further expansion of the tubular member 81 and further increase in its internal volume.
As described above, during introduction of pressurized air into the bore 100 , the central passage 82 , 83 of tubular member 81 remains at a substantially constant volume, e.g., about 0.1 liter, until the base pressure or yield point pressure is reached. Then, at base pressure or yield point pressure, e.g., 20-40 psia, the tubular member 81 begins to expand or increase its internal volume beginning at the enlarged diameter portion 83 of the central passage 82 . Instead of providing an enlarged diameter portion 83 in the central passage 82 to initiate expansion at a specific location along the length of the tubular member 81 , a constant internal diameter of the tubular member with a reduced wall thickness at a specific location will also initiate expansion at that location.
FIGS. 5 and 6 illustrate, in perspective and partially cut away, the BCD of the invention 10 in the uninflated and inflated conditions, respectively, that would be connected to a conventional SCUBA apparatus. A conventional SCUBA tank (not shown) provides a source of pressurized air for the BCD 10 via valve 14 and first stage regulator 12 . The four elastic tubular members are arranged in pairs 16 a , 16 b and 18 a and 18 b and are connected to a respective left and right manifold 20 , 22 affixed to manifold mounting bracket 24 . Bracket 24 is mounted on the diver's SCUBA equipment (not shown), e.g., on the frame or jacket that supports the pressurized tank of the SCUBA equipment. Three position slide valve 26 is connected to the first stage regulator 12 by an inflation hose 28 . Inflation/dump hoses 30 , 32 are connected between the slide valve 26 and the manifolds 20 , 22 .
As seen in the uninflated condition of FIG. 5 and the inflated condition of FIG. 6 , the tubular members 16 a , 16 b and their first sleeves 102 are each loosely enclosed in a second sleeve 120 , also made of a substantially non-stretchable nylon fabric. Each second sleeve 120 is affixed at its bottom end to manifold 20 and at its top end to the frame or jacket of the SCUBA diving apparatus (not shown) by a flap 122 using, e.g., a hook-and-loop fastener. The second sleeves 120 keep the tubular members close to the diver's body as previously described.
A third sleeve 124 or covering made of a stretchable material or an elastic fabric, such as spandex, is stretched over each second sleeve 120 to snug each pair of tubular members 16 a , 16 b and 18 a , 18 b with their first and second sleeves 102 , 120 to the diver's back for streamlining and abrasion protection purposes. All the sleeves 102 , 120 , 124 are porous to air so as not to trap air in any of them.
FIG. 7 is a graphic representation showing the internal displacement versus inflation pressure of a conventional BCD, a rigid BCD and the BCD of the invention when pressurized air is admitted internally to the respective BCD under ambient atmospheric conditions. It should be understood that, except for the rigid BCD, the graphs of FIG. 7 do not illustrate what occurs when the BCDs are inflated at depth, but only at the surface at atmospheric pressure. To illustrate what occurs when the BCDs are inflated at depth, the x-axis of the FIG. 7 graph need only be modified to indicate the “delta pressure,” that is, the difference between the internal pressure and the ambient pressure.
The graph R shows that the rigid tank BCD maintains a constant volume or internal displacement of about 9 liters regardless of the inflation pressure. This, of course, assumes that the walls of the rigid tank BCD are perfectly rigid, that is, the walls do not flex inwardly or outwardly as air is evacuated or introduced into the tank and the tank is not flooded with any water to decrease its total displacement of about 9 liters.
The graph C of the conventional BCD shows that this BCD, when inflated at atmospheric pressure, increases its internal displacement from zero to about 9 liters with no change in internal pressure, i.e., atmospheric pressure. This assumes that the substantially inelastic, inflatable bladder previously described as the “conventional BCD” is not inflated to the point where the material of the bladder is under tension or is stretched, a condition that is never operational for the conventional BCD.
Graph I illustrates the displacement versus inflation pressure of the embodiment of the invention described herein, that is, a BCD using four tubular members constructed according to the embodiment shown in FIGS. 1-6 . The tubular members of the invention have an internal volume of zero when the internal pressure is 0.0 psia (a vacuum) as shown in FIG. 7 at the origin or point O. At atmospheric pressure or 14.7 psia, the combined volume or internal displacement of the four tubular members is about 0.4 liters, or about 0.1 liter for each tubular member as described above in connection with FIGS. 3A and 3B .
Assuming pressurized air is initially introduced into the tubular members of the invention when their internal pressure is at atmospheric pressure (14.7 psia) as in the conventional BCD, it can be seen that the internal pressure of the four tubular members increases up to the yield point pressure of about 40 psia at point Y while their total internal volume remains relatively constant with an increase of only about 0.5-0.6 liter. Thus, in the region from atmospheric pressure to point Y at 40 psia, the compliance of the elastic tubular members, defined above as the change in volume as a function of pressure (dV/dP), is low or substantially zero. At pressures above yield point pressure at point Y, the tubular members are more compliant, but still require a substantial increase in inflation pressure (up to 80 psia) to increase the total internal volume of the four tubular members to 9 liters at point X. In contrast, the compliance of the conventional, inelastic BCD is essentially infinite. This compliance characteristic of the elastic members of the invention is one of the features that distinguishes the BCD of the invention from the prior art BCDs.
FIG. 8 illustrates more particularly how the BCD of the invention differs from the conventional BCD in an operating (diving) environment in sea water. FIG. 8 shows the lift characteristics of each of the three types of BCD (rigid, conventional and the invention) during ascent, assuming a diver's lowest or bottom depth of 96 feet and ending at the water surface or zero depth and assuming no flooding of the rigid BCD and no venting of the air in the BCDs during ascent. Each of the three BCDs has a beginning internal volume of about 1.5-1.75 liters and a lift force of about 3.2 pounds at 96 feet depth (about 57 psia in sea water). Referring first to curve R 1 for the rigid tank BCD, as expected, the internal volume and lift force of the rigid tank BCD remains constant as the diver ascends from the 96 foot depth to the surface. Looking now at the curve C 1 for the conventional BCD, it is seen that, as the diver ascends from 96 feet depth (4 atm. pressure) toward the surface (1 atm. pressure), the internal volume and thereby the lift force of the conventional BCD increase by a factor of four to almost 6 liters volume and about 13 pounds of lift force. It is this lift characteristic of the conventional BCD that has the potential to create a dangerous condition during ascent for the diver, experienced or not, as explained hereinbefore.
Referring now to curve I 1 for the BCD of the invention, as the diver ascends from 96 feet to the surface, the internal volume and lift increase only slightly, i.e., about 0.5 liter increase in volume and about 1.2 pounds lift force. Such a small increase in volume and lift force makes it easy for the diver to maintain complete and safe control of his ascent using the BCD of the invention. It can also be seen that the BCD of the invention has a lift characteristic substantially the same as that of the rigid tank BCD, i.e., constant, when a diver ascends to the surface from depth.
FIG. 9 illustrates the lift versus depth curves for the three BCDs (rigid, conventional and the invention) for a typical dive profile between 100 feet depth and the surface. Assuming all three BCDs are adjusted for a typical lift of 4.0 pounds at a depth of 40 feet, the lift of the rigid tank BCD remains constant at 4.0 pounds. However, it can be seen from FIG. 9 that the lift for the BCD of the invention varies by only 2.0 pounds from 100 feet depth (3.0 pounds lift) to the surface (5.0 pounds lift), whereas the lift of the conventional BCD varies by approximately 7.0 pounds from 100 feet depth (2.25 pounds lift) to the surface (about 9.3 pounds lift).
From the foregoing detailed description and drawings, it will be appreciated by those skilled in the art that the BCD of the invention meets the objectives described above for providing a safer, less complex and cumbersome BCD for divers.
Although certain presently preferred embodiments of the invention have been specifically described herein, it will also be apparent to those skilled in the art to which the invention pertains that variations and modifications of the various embodiments shown and described herein may be made without departing from the spirit and scope of the invention. Accordingly, it is intended that the invention be limited only to the extent required by the appended claims and the applicable rules of law. | An improved buoyancy compensation device having a lesser change in buoyancy with depth than conventional buoyancy compensation devices which use ambient pressure bladders is disclosed. The improved device comprises one or more elastic members that, throughout the working range of diving pressures and volumes, is always elastic and, when pressurized, maintains an internal air pressure that is always greater than the ambient pressure at any dive depth. The invention also relates to a method of providing a buoyancy compensation device with an elastic member having a lift versus depth characteristic that approaches the lift versus depth characteristic of a constant or fixed volume buoyancy compensation device. | 1 |
BACKGROUND
[0001] This invention relates to methods and apparatus for scavenging and using energy caused by changes in pressure. This includes but is not limited to using changes of pressure in closed or substantially closed atmosphere environments to create electrical energy which is then used as a power source.
[0002] The invention will be described in reference to pneumatic devices and in particular pneumatic tires used in vehicles. However, this description is one exemplary embodiment of the invention and systems and methods of the invention are applicable to any circumstance where changes in pressure occur at a frequency that they may be used to convert mechanical energy to electrical energy.
[0003] Tire safety studies show that maintaining proper tire pressure improves vehicle handling, improves fuel economy, increases tire life and helps avoid accidents. An NHTSA research survey of U.S. passenger vehicles found that 27% of passenger cars on U.S. roadways were driven with one or more substantially under-inflated tire. The survey found that 33% of light trucks (including sport utility vehicles, vans and pickup trucks) are driven with one or more substantially under-inflated tire. Other studies have shown that nearly 20% of service stations providing customers with tire pressure gauges on their air pumps use gauges that over report the pressure present in a tire by at least 4 psi (pounds per square inch) or more. At pressure levels that are typical for most passenger cars or SUVs, nearly 10% of service station air pump gauges over report by 6 psi or more. In addition, radial tires can lose much of their tire air pressure and still appear to be fully inflated.
[0004] In response to this safety issue, the federal government has enacted standards which require motor vehicles to become equipped with tire pressure monitoring systems. The standards specify performance requirements for tire pressure monitoring systems to prevent significant under-inflation of tires and the resulting safety problems. The standard applies to passenger cars, multipurpose passenger vehicles, trucks and buses that have a gross vehicle weight rated of 10,000 pounds or less. The tire pressure monitoring system refers to a system that detects when one or more of the vehicles tires are under-inflated and illuminates a low tire pressure warning telltale. The low tire pressure warning telltale must be mounted inside the occupant compartment in front of and in clear view of the driver. The tire pressure monitoring system must continue to meet the requirements of the standard when the vehicle's original tires are replaced with tires of any optional or replacement size.
[0005] Related art tire pressure monitoring systems provide vehicles using pneumatic tires with a system having a sensor to sense conditions of a tire. See U.S. Pat. Nos. 6,438,193 and 6,518,877 which are hereby incorporated by reference. The conditions may include internal pressure, temperature, number of revolutions, etc. Related art systems are mounted in the tire and include a transmitter which communicates sensed data to a receiver located in the vehicle. The sensed data may then be communicated to the vehicle operator via a user interface, such as a display. The related art systems are often powered by batteries which wear out and need to be replaced. This increases labor costs and hazardous waste. This may also result in system failures due to lack of power during the operation of the vehicle.
SUMMARY
[0006] The invention provides a power supply by providing methods and systems that convert mechanical energy to electric energy and in particular the changes in pressure of a rotating tire into electric energy, which is then stored and used to power the tire based components of a tire pressure monitoring system. As a tire rotates, turns and otherwise trundles down a road, its internal volume is constantly changing causing variations of pressure inside the tire. These pressure fluctuations can be used to cause mechanical changes in a mechanical portion which are transmitted to a piezoelectric element. The piezoelectric element is distorted by the mechanical changes and generates electrical energy. The electrical energy is stored and delivered to the tire mounted portion of the tire pressure monitoring system via an electric circuit.
[0007] In an exemplary embodiment of the invention, an aneroid cell is the mechanical portion of the system and is linked to a piezoelectric element so that mechanical changes in the aneroid cell cause mechanical changes in the piezoelectric element.
[0008] In another exemplary embodiment of the invention, a bourdon tube is the mechanical portion of the system and is linked to a piezoelectric element so that mechanical changes in the bourdon tube cause mechanical changes in. the piezoelectric element.
[0009] In another exemplary embodiment of the invention the piezoelectric element is formed to surround the mechanical portion so that mechanical changes in the mechanical portion are directly transmitted to the piezoelectric element.
[0010] In another exemplary embodiment of the invention the piezoelectric element is linked mechanically to the mechanical portion so that mechanical changes in the mechanical portion are transmitted through the mechanism linkages to the piezoelectric element.
[0011] In another exemplary embodiment of the invention, the various exemplary embodiments of the invention are mounted on a valve stem.
[0012] In another exemplary embodiment of the invention, electrical energy created by the piezoelectric element is stored in a capacitor.
[0013] In another exemplary embodiment of the invention, electrical energy created by the piezoelectric element is stored in a battery.
[0014] In another exemplary embodiment of the invention, the tire pressure monitoring system includes a sensor that senses at least one of tire pressure, tire temperature and tire revolutions.
[0015] In another exemplary embodiment of the invention, data sensed by the sensor is transmitted to a receiver and the data received by the receiver is communicated to the user via a user interface.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a schematic of an apparatus for scavenging and using energy caused by changes in pressure according to one exemplary embodiment of the invention;
[0017] FIGS. 2A-2C are schematics of an aneroid chamber used as the pressure reactor according to an exemplary embodiment of the invention;
[0018] FIGS. 3A-3C are schematics of a bourdon tube used as a pressure reactor according to an exemplary embodiment of the invention;
[0019] FIG. 4 is a schematic of a method of mounting an apparatus for scavenging and using energy caused by changes by pressure according to an exemplary aspect of the invention; and
[0020] FIGS. 5A and 5B are schematics of a sensed data receiver and transmitter according to an exemplary aspect of the invention.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0021] FIG. 1 is a schematic of an exemplary embodiment of the invention using a aneroid chamber as the mechanical portion. FIG. 4 is a schematic of the exemplary embodiment of FIG. 1 mounted on the valve stem of a pneumatic tire. However, it should be appreciated that any environment with sufficient changes in pressure over a sufficient time period would be suitable to create the mechanical changes in the mechanical portion necessary to satisfy the requirements of the exemplary embodiments of the invention.
[0022] As the tire trundles down the road, interior pressure P 2 is constantly changing. The changes in pressure ΔP are communicated to the aneroid chamber 18 via the interim atmosphere of the pneumatic tire 11 . The aneroid chamber 18 is a tightly sealed chamber or series of chambers containing air at a predetermined pressure. The pressure P 1 of the aneroid chamber may be matched to the manufacturers recommended cold inflation pressure of the tire. Aneroid chambers are well-known to detect changes in atmospheric pressure. They may be formed from any suitable material, such as stainless steel or brass. The piezoelectric element 20 is placed in relation to the aneroid chamber 18 so that expansions or contractions of the aneroid chamber 18 caused by changes in air pressure P 2 inside the tire 11 cause mechanical changes in the piezoelectric element 20 thus generating electrical energy. The use of piezoelectric elements is well-known. See U.S. Pat. No. 6,438,193 which is hereby incorporated by reference.
[0023] FIGS. 2A-2C are schematics showing the effects of the changes of pressure P 2 on the aneroid chamber 18 . It should be appreciated that FIGS. 2A-2C are not drawn to scale and features are exaggerated for representation and explanation purposes.
[0024] FIG. 2A shows an aneroid chamber 18 . In the wall 18 A of the aneroid chamber 18 , there are formed circular corrugations 19 . The corrugations are formed in any suitable size, number and shape to make the wall 18 A flexible to provide a desired mechanical change in the shape of the aneroid chamber 18 when subjected to changes in pressure P 2 . It should be appreciated that the corrugations 19 are optional. Furthermore, it should be appreciated that the aneroid chamber 18 may be any suitable size or shape so long as the aneroid chamber 18 is able to be influenced mechanically by the changes in pressure P 2 .
[0025] In FIG. 2A , the pressure P 1 is equal to pressure P 2 . There are no mechanical changes in the aneroid chamber 18 . Thus, the piezoelectric element 20 does not experience any mechanical changes and no electricity is generated.
[0026] FIGS. 2A-2C show an exemplary embodiment of the invention where the piezoelectric element 30 is formed to surround the aneroid chamber 20 . However, it should be appreciated the various exemplary embodiments of the invention include forming or positioning a piezoelectric element in any suitable relationship such that mechanical changes caused by changes in pressure P 2 cause mechanical changes in the piezoelectric element 20 . For example, it is well known to transmit mechanical changes in aneroid chambers using mechanical linkages.
[0027] In FIG. 2B the pressure P 1 is greater than P 2 . This causes the wall 18 A to deflect outward at those portions where the corrugations 19 are formed. The deflection of the wall 18 A causes a similar deflection in the piezoelectric element 20 . Thus, electrical energy is generated. Similarly, FIG. 2C shows the result when the pressure P 1 is less than P 2 . This causes the wall 18 A to deflect outward at those portions where the corrugations are formed. The deflection of the wall 18 A causes a similar deflection in the piezoelectric element 20 . Thus, electricity is generated.
[0028] FIGS. 3A-3C are schematics of an exemplary embodiment of the invention using a bourdon tube 30 as the pressure reactor.
[0029] FIG. 3A is a schematic of a C-shaped bourdon tube 30 . The bourdon tube 30 has a hollow elliptical cross section as shown in FIG. 3B . One end 30 A of the bourdon tube 30 is closed. The other end 30 B is open to the pressure P 2 . The walls 30 C are thin and change shape when there are changes in pressure P 2 . The open end 30 B is fixed. Thus, changes in pressure P 2 cause changes in the position of the closed end 30 A. The tube 30 is formed to be bent into an arc of a circle generally between 270 to 300 degrees. When pressure P 2 is increased, the cross section becomes more circular as shown in FIG. 3C . This causes the tube to straighten out until the force of the fluid pressure is balanced by the elastic resistance of the tube 30 .
[0030] A piezoelectric element 20 is put in mechanical relation through the use of well known mechanical linking elements to either the tube walls or the closed end of the tube, so that changes in the shape or position of either will cause mechanical changes to the piezoelectric element and electricity is generated. The piezoelectric element 20 may be placed in any suitable relationship to the bourdon tube 30 to transfer the mechanical change. FIG. 3A shows a mechanical linkage 32 . Mechanical linkages for transferring mechanical changes of bourdon tubes are well known. FIGS. 3B and 3C show a configuration where the piezoelectric element 20 is formed to surround the bourdon tube 20 .
[0031] The electrical energy generated by the piezoelectric element 20 is ac. The energy is conditioned by the rectifier 25 and the regulator 26 to convert the ac signals to a stable DC power supply. The power supply is stored in storage 26 and used to supply power to sensor 27 , digital circuit 28 and transmitter 29 . Storage 26 may be any suitable electricity storage device such as a capacitor on battery. The digital circuit processes the sensor signals and communicates with the transmitter 29 which conditions the signals generated by the sensors 27 for transmission and broadcasts a signal representative of at least one of the vehicle tire parameters being monitored via antenna 42 . The broadcast signal is received by antenna 44 which is in communication with receiver 40 . The receiver 46 processes the received signal which is then communicated to a user through a user interface, such as a display or an audio warning system.
[0032] In the exemplary embodiment of FIG. 4 the apparatus of an exemplary embodiment of the invention is mounted on valve stem 40 which in turn is mounted on a tire rim 10 on pneumatic tire 11 . It should be appreciated that the apparatus of an exemplary embodiment of the invention may be formed integrally with the valve stem 40 to facilitate mounting during vehicle manufacture or when new tires are mounted. Alternatively, the apparatus of an exemplary embodiment of the invention may be formed to be mounted on the valve system 40 by any suitable means such as threads, clips, etc. It should further be appreciated that the apparatus of an exemplary embodiment of the invention may be mounted in any suitable location so long that the pressure changes of the environment create mechanical changes in the apparatus of the exemplary embodiments of the invention.
[0033] In the exemplary embodiment of FIG. 4 a housing 12 is provided to enclose the apparatus. The housing 12 may be formed of any suitable material to provide protection during handling, installation and use of the apparatus of the exemplary embodiment of the invention. The housing 12 includes inlets 14 and vents 16 to allow the pressure changes of the interior of the tire to reach the mechanical portion.
[0034] In various exemplary embodiments of the invention, the mechanical portion may also be used as a pressure sensor.
[0035] While the invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the exemplary embodiments or constructions. While the various elements of the exemplary embodiments are shown in various combinations and configurations, which are exemplary, other combinations and configurations, including more, less or only a single element, are also within the spirit and scope of the invention. | An apparatus to scavenge energy caused by changes in interior pressure of a container, including at least one flexible chamber containing a fluid at a predetermined pressure; a piezoelectric element coupled to the flexible chamber so as to generate electricity when the flexible chamber is flexed by a change in pressure of the container. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates to emitters for drip irrigation, and specifically to pressure compensating emitters.
BACKGROUND OF THE INVENTION
[0002] Conventionally, a drip tube product with a continuous flow path with inlets is separated into individual emitters by the design of the inserted ribbon using a crossover. The ribbon is bonded into the main tube via insertion through a crosshead die and then pressed against the tube to bond the ribbon to the tube. An outlet is then laser shot or slit at the appropriate point. This type of process has been used in the irrigation industry by several companies. The flow rates of the products made using this process are dependent on pressure in the desired range of operation. These products are energy efficient and run in a pressure range of 6 to 15 psi. Depending on the design the flow rate of the emitters can fall off as much as 50% or more.
[0003] Hence, there is a need to compensate for pressure and allow for a uniform distribution of water greatly improving crop uniformity and energy usage.
OBJECTIVE OF THE INVENTION
[0004] 1. It is the primary objective of the present invention to compensate pressure variations of incoming water
[0005] 2. It is another objective of the present invention to allow uniform distribution and output of water
SUMMARY OF THE INVENTION
[0006] According to an aspect of an invention there is disclosed an emitter for discharging liquid. The emitter comprises an elongated frame such that the periphery encloses a cavity therewith, the periphery enabling attachment of the elongated frame to an interior surface of a fluid conduit. The base is arranged to deflect in response to a pressure differential between a pressure in the cavity and a pressure in a fluid flow passage of the fluid conduit. The emitter further comprises a plurality of intervals disposed in the periphery at a first end of the elongated frame, the plurality of intervals enabling fluid communication between the cavity and the fluid flow passage and arranged to receive fluid from the fluid flow passage. The emitter further comprises a plurality of projections disposed approximately at a middle portion of the elongated frame and extending from the periphery on both sides of the elongated frame towards a center of the cavity. Each of the plurality of projections has a first surface that slopes downwards from the periphery towards the center of the cavity. The plurality of projections are arranged to reduce the pressure of fluid flowing through the cavity and wherein the plurality of projections are arranged to deflect with the deflection of the base. The cavity at a second end is arranged to receive pressure compensated fluid from the middle portion and wherein the cavity is arranged to communicate fluidly through an aperture on the fluid conduit, wherein the first end and the second end are linearly opposite end portions of the elongated frame.
BRIEF DESCRIPTION OF DRAWINGS
[0007] Exemplary embodiments of the present invention are described hereinafter with reference to the following drawings, in which:
[0008] FIG. 1 shows an isometric view of an emitter for discharging liquid
[0009] FIG. 2 shows an enlarged view of a plurality of projections in the emitter
[0010] FIG. 3 shows an aperture in a fluid conduit for discharge of fluid
DETAILED DESCRIPTION OF THE INVENTION
[0011] Discrete emitters have been produced for a period of time using a silicone diaphragm that deflects under varying pressure onto a metering groove. This metering groove is sufficiently small to allow only a certain amount of water to pass regardless of the pressure. While this technique has been used, the nature of this design can cause plugging and the use of a thermoset silicone is expensive and limits the design of the product. These emitters are also individually molded units and do lend themselves to continuous production easily. A novel approach to solve this problem would be to use a continuously formed ribbon as the emitter and have that ribbon compensate for pressure. By using a special flexible olefin block copolymer; this ribbon can easily be bonded to the main body of the tube. The flexibility of the polymer is only one aspect of the compensation technique. The teeth of the flow path that would normally be bonded to the tube are not in this case bonded but instead a rail that rides slightly above the teeth is bonded to the tube. This allows for varying number of teeth to engage the body of the tube depending on pressure and consequently compensates for pressure. Conventional design techniques require a pressure reduction area or labyrinth prior to the metering groove. This area is also prone to plugging causing variations in the compensation capabilities as well as plugging of the metering groove. The advantage provided by the invention is that the compensation starts at the distal end of the flow path and progresses towards the proximal end as the pressure increases. If there are any debris in the emitter, the backpressure will increase causing the entire flow path to disengage from the main body of the tube causing the debris to pass. The advantage of this design is that when pressure is relieved the flow path again becomes a straight through path flowing over the teeth and allowing any built up debris to pass through. Also during operation if the path becomes clogged the pressure will open the flow path and allow the debris to pass. The unique nature of the polymer allows the bonding of the rails and the flexibility of the teeth of the flow path to both compensate and be clog resistant.
[0012] The design of the flow path described above coupled with the unique characteristics of the olefin block copolymer allow the flowpath to be formed in a very precise manner and be bonded in a unique manner to the main body of the tube. Since both materials are of an olefinic base a strong bond is insured. The design of the teeth is precisely radiused to compensate for the structure of the tube. The teeth can also be tapered along the length of the flowpath to further aid in compensation. To achieve this type of performance requires a combination of precise rotary mold design, product design and polymer properties to work effectively.
[0013] The number of intervals that interact with the fluid flow passage depends on the pressure differential starting at the outlet end and progressing towards inlet at increasing main body pressure channels.
[0014] FIG. 1 shows an isometric view of an emitter 100 for discharging liquid. The liquid that the emitter is capable of emitting can be water or any solution. The emitter 100 can be used for purposes of irrigation and specifically drip irrigation where water or any water based solution has to be supplied to the irrigated area. The solution can be a solution of any water soluble compound in water that is to be supplied to the plants in the irrigated area.
[0015] As illustrated in FIG. 1 , the emitter 100 comprises an elongated frame 105 with a periphery 110 . The periphery can also be referred to as an edge running completely around the elongated frame 105 . The periphery 110 is higher than a base 115 of the elongated frame 105 . The base 115 runs throughout the entire length of the elongated frame 105 . The periphery 110 running around the elongated frame 105 encloses a cavity 120 . The periphery 110 enables attaching the emitter to an internal surface of a fluid conduit (not shown). The working of the emitter 100 in conjunction with the fluid conduit is described hereinafter. To elaborate, the emitter 100 is fitted or attached to the inside surface or internal surface of the fluid conduit and the fluid from the fluid conduit enters the cavity 120 of the emitter 100 and flows out through an aperture 190 on the fluid conduit, as illustrated in FIG. 3 . FIG. 3 shows the aperture 190 in the fluid conduit for discharge of fluid from the emitter. FIG. 3 illustrates that any fluid conduit can accommodate a plurality of emitters with the plurality of emitters communicating to the environment through a plurality of apertures 190 arranged linearly.
[0016] The emitter 100 comprises a plurality of intervals 125 disposed in the periphery 110 at a first end 130 of the elongated frame 105 . The plurality of intervals 125 enables fluid communication between the cavity 120 and a fluid flow passage (not shown) of the fluid conduit to receive fluid from the fluid flow passage. In other words, when in use, the fluid passes through the plurality of intervals 125 from the fluid flow passage to the cavity 120 .
[0017] The emitter 100 further comprises a plurality of projections or teeth 140 disposed in a middle portion 145 of the elongated frame 105 . The middle portion 145 is disposed between the first end 130 and a second end 150 . The plurality of projections 140 extend from the periphery 110 on both sides of the elongated frame 105 towards the center of the cavity 120 . In other words, the plurality of projections 140 extends towards each other from the periphery 110 on both sides of the elongated frame 105 . The plurality of projections 140 from the opposite sides of the periphery 110 do not touch or contact each other, such that fluid from the first end 130 can flow through the plurality of projections 140 to the second end 150 . Each of the plurality of projections 140 has a first surface 155 that slopes downwards from the periphery towards the center of the cavity 120 . The surface of each of the plurality of projections 140 opposite the first surface 155 is a second surface 160 (as shown in FIG. 2 ). FIG. 2 shows an enlarged view of the plurality of projections 140 in the emitter 100 . The second surface 160 is mounted on the base 115 of the elongated frame 105 .
[0018] To elaborate, if the first surface 155 is oriented towards the top, then the second surface 160 is oriented towards the bottom. Alternately, if the first surface 155 is oriented towards the bottom, then the second surface 160 is oriented towards the top. Since the plurality of projections 140 are mounted on the base 115 , a deflection of the base 115 deflects the plurality of projections 140 as well depending on the direction of deflection of the base 115 . The deflection of the base 115 is caused by a pressure gradient between the pressure in the cavity 120 and the pressure in the fluid conduit. To elaborate, if the pressure in the fluid conduit is higher than the pressure in the cavity 120 , then the base 115 is deflected in a direction towards the internal surface of the fluid conduit, such that the cross-sectional surface area and the volume of the cavity is reduced. The plurality of projections 140 in the cavity 120 enables obstruction of the flow of the fluid through the emitter so that the speed and pressure of the flowing fluid is reduced. The pressure of the fluid flowing through the teeth 140 gradually reduces from an initial portion 165 of the plurality of projections 140 to a terminating portion 170 of the plurality of projections 140 . Moreover, the arrangement of the plurality of projections 140 as illustrated in FIG. 2 provides a flow path that is winding for the fluid which enables a reduction of the speed of flow of the fluid from the initial portion 165 of the teeth 140 to the terminating portion 170 of the teeth 140 .
[0019] When in use, the fluid passing through the plurality of teeth 140 flows into the cavity 120 at the second end 150 . The fluid conduit in the proximity of the second end 150 comprises aperture 190 open to the atmosphere. The pressure compensated fluid flowing into the cavity 120 at the second end 150 egresses out of the aperture 190 in the fluid conduit to the outside atmosphere for irrigation or other suitable purposes. The first end 130 and the second end 150 are linearly opposite end portions of the elongated frame 105 .
[0020] The plurality of intervals 125 are disposed on the periphery 110 on both sides of the elongated frame 105 . The advantage of this arrangement is that fluid can enter the cavity 120 of the elongated frame 105 from both sides of the cavity 120 . The fluid then flows from the first end 130 of the elongated frame 105 to the second end 150 of the elongated frame 105 and flows out of the elongated frame 105 . The plurality of intervals 125 extends from the first surface 155 of the periphery 110 to the base 115 of the elongated frame 105 . There are a set of hemispherical structures 175 mounted linearly on the base 115 of the elongated frame 105 in the first end 130 between the periphery 110 .
[0021] The elongated frame 105 comprises an intermediate portion 180 between the first end 130 and the middle portion 145 . The periphery of the intermediate portion 180 has a width which is greater than a width of the periphery 110 in the first end 130 , the second end 150 and the middle portion 145 . The increased width of the periphery 110 in the intermediate portion 180 reduces width of the cavity 120 of the elongated frame 105 in the intermediate portion 180 . The width of the periphery 110 in the intermediate portion 180 on both sides can increase from an end proximal to the first end to an end proximal to the middle portion. In other words, the width of the cavity is greater at the end proximal to the first end than the width of the cavity at the end proximal to the middle portion.
[0022] The plurality of projections or the teeth 140 are made of the same material as the base 115 and therefore imparts the same flexibility as the base 115 . The teeth 140 are disposed such that they make an angle with the periphery 110 . In other words, they are not arranged normal to the periphery 110 . The teeth 140 are arranged such that they project towards the second end 150 . The teeth from the opposite periphery do not touch each other, thus providing a winding pathway for the fluid to flow from the first end 130 to the second 150 . The fluid when flowing through the winding pathway is reduced in pressure from the inlet pressure existing at the first end 130 to the outlet pressure existing at the second end 150 .
[0023] The pressure of the fluid flowing through the cavity 120 of the elongated frame 105 reduces gradually from the first end 130 to the second end 150 . However, the pressure of the fluid flowing through the fluid flow passage in the fluid conduit is constant. As the pressure reduces along the elongated frame 105 from the first end 130 to the second end 150 , a pressure gradient increases gradually from the first end 130 to the second end 150 .
[0024] Higher the inlet pressure, higher the pressure gradient in the middle portion 100 proximal to the second end 150 . Higher the pressure gradient across the base 115 of the elongated frame 105 in the middle portion 100 proximal to the second end 150 , there will be a greater push by the fluid in the fluid flow passage of the fluid conduit on the base 115 to push the base 115 and the second end towards the interior surface of the fluid conduit. For example, if the inlet pressure is 6 psi, a few teeth in the middle portion 100 proximal to the second end 150 are pushed towards the interior surface of the fluid conduit. For example, if the inlet pressure is 10 psi, more teeth in the middle portion 100 proximal to the second end 150 are pushed towards the interior surface of the fluid conduit. For example, if the inlet pressure is 14 psi, even more teeth in the middle portion 100 proximal to the second end 150 are pushed towards the interior surface of the fluid conduit. This pressure gradient and the subsequent deflection of the base 115 towards the interior surface of the fluid conduit helps in pushing the fluid out of the aperture.
[0025] The second portion 150 has a set of hemispherical balls 180 mounted on the base 115 .
[0026] It is to be understood that the foregoing description is intended to be purely illustrative of the principles of the disclosed techniques, rather than exhaustive thereof, and that changes and variations will be apparent to those skilled in the art, and that the present invention is not intended to be limited other than as expressly set forth in the following claims. | The emitter attachable to a fluid conduit comprises a fluid inlet portion capable of taking in fluid from the fluid conduit. The fluid from the inlet portion moves to the pressure compensating or reducing portion which comprises a set of teeth which are arranged in a way so as to impede the flow of liquid thereby reducing the pressure. Downstream the pressure compensating portion is the output portion which communicates with an aperture in the fluid conduit to enable distributing the fluid to the environment. The base of the emitter is flexible allowing movement of the base by virtue of the pressure gradient. When the pressure of the fluid is reduced in the pressure compensating portion, a pressure gradient is created across the base and this result in the fluid in the fluid conduit moving the base towards the fluid conduit thereby reducing the volume of the cavity of the emitter. | 0 |
BACKGROUND OF THE INVENTION
It is highly desirable to have the cap of a container secured in place from accidental removal, or from being tampered with or removed. This is particularly desirable to protect children from removing caps from containers which may contain harmful substances. It is common practice to enclose the portion of a cap and a portion of a spout or neck of a container or bottle with metal or layer of plastic material which may be removed or torn.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a locking element or tamperproof element as a separate part which can be installed when the cap is screwed into place and which prevents the cap from being unscrewed. The separate element or lock-band may be made from a plastic material which is relatively strong but which has a tab whereby the lock-band may be torn and removed, thus freeing the cap so that it can be unscrewed.
It is an object of the present invention to provide a lock band or lock member which is assembled with the cap and is non-rotatable with respect thereto and has a shoulder positioned between the cap and the wall from which the spout projects so that when the cap is screwed into place one-way teeth on the shoulder of the lock band engage oppositely directed one-way teeth on the container adjacent to the spout, thus permitting the cap to be screwed into place but preventing the cap from being unscrewed unless the lock band is first removed.
It is a further object of our invention to provide a cap and lock arrangement of the character described in which the locking means is a separate element and is separately removable, and in which at any time it is desired to lock the cap from removal or to render it tamper-proof another lock band may be installed in place. In fact, the cap and lock-band arrangement may be provided with extra bands for use when desired.
It is a further object of our invention to provide an arrangement of the character described in which there is a lock element compressed between the lower end face of the cap and the top surface of the container, said lock means being releasably connected to said cap and being associated with said container so as to be rotatable only in a direction in which the cap is screwed onto the spout of the container.
Other objects and advantages will be made evident during the course of the following detailed description of a preferred form of our invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view showing the tamperproof screw cap of our invention applied to a container.
FIG. 2 is a plan view of our invention as applied to the container shown in FIG. 1;
FIG. 3 is a sectional view on the line 3--3 of FIG. 2;
FIG. 4 is a fragmentary bottom plan view of the lock member or lock band of our invention taken on line 4--4 of FIG. 3;
FIG. 5 is a fragmentary view taken on line 5--5 of FIG. 3; and
FIG. 6 is a fragmentary view taken on approximately line 6--6 of FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As shown in FIGS. 1 and 3, the numeral 10 represents a container having a top wall 11, having a filling and pouring opening provided by a cylindrical wall 12 which extends from the wall 11 and forms a passageway for filling the container or pouring material from it, this part being referred to as a spout 14. The wall 12 has external threads 15, a cylindrical inner surface 16 and an end surface 17.
Our invention provides a screw cap 18 having a cylindrical wall 19 provided with threads 20 adapted to screw onto the spout 14. An end wall 23 of the cap 18 closes the spout and extending from the end wall 23 toward the spout 14 is a conical wall 24 which fits into the spout and mates with the surface 16 in order to form a seal.
In order to secure the cap 18 in place, making it tamperproof and back-off proof, we provide a lock member or lock band or lock ring 30 which has a cylindrical wall 31 surrounding the wall 19 of the cap 18 and being a slidable fit thereon. To restrain the cap 18 and lock member 30 from relative rotation there is a connecting means which is composed of grooves 33 formed in the inner surface of the cylindrical wall 31 and axial ribs 34 formed on the outer surface of the wall 19 of the cap. The ribs fit in the grooves as shown in FIGS. 2 and 3. The groove 33 may be formed in the wall 19 and the ribs 34 may be formed on the wall 31, if desired.
The lock member 30 has an inwardly extending shoulder 35 which projects from the lower portion of the wall 31 and has a surface 36 engaged by the end surface 37 of the cap 18, this shoulder comprising a lock element. The shoulder 35 has locking teeth 39 projecting therefrom toward the wall 11 of the container 10, the teeth 39 are formed by intersecting vertical walls 40 and inclined walls 41 making the teeth saw-shaped. Stationary teeth 44 comprised by intersecting vertical walls 46 and inclined walls 47 (FIG. 6) are formed on the container wall 11 in one or two or more groups. These groups are cylindrically arranged around the area where the spout projects from the wall 11. The stationary teeth 44 and the movable teeth 39 are of substantially the same size and pitch, and faced in complementary directions so that the walls 40 will abut walls 46 while cap 18 is screwed down on spout 14. FIG. 6 shows the manner in which the walls 40 and 46 engage each other.
The lock member 30 has a pull tab 49 and the wall 31 may be scored so that when the pull tab 49, FIG. 4, is pulled quite strongly, it will tear away from the main portion of the lock band and sever it.
After the container has been filled, the screw cap is then put into place. The first step is to assemble the cap and lock-band. This may be done by slipping the cap into the lock-band so that the end shoulder 37 engages the shoulder or the end face 36 of the shoulder 35. The ribs 34 fit into the grooves 33 and thus render these two parts nonrotatable relative to each other.
This assembly of the cap and lock-band is then screwed onto the spout 14, the assembly being rotated in the direction of the arrow 50 of FIG. 6. As the cap reaches the position where the sealing flange moves into contact with the cylindrical surface 16, the inclined surfaces 41 and 47 will engage, and as rotation of the cap is continued the teeth will be deformed to permit further rotation of the cap and lock-band. When the parts are thus in place the shoulder or lock element 35 is compressed between the lower surface 36 of the cap and the teeth 44 which comprise a part of the top wall of the container.
When the cap has been screwed tightly in place and a good seal formed at the end of the spout, the teeth will occupy the positions shown in FIG. 6 and because of the vertical or axial shoulders 40 and 46 the locking ring cannot be rotated in the opposite direction to the arrow 50. Also, the cap 18 may not be moved in the opposite or unscrewing direction because of the engagement of the ribs 34 in the grooves 33.
With the parts in the positions described, the cap cannot be unscrewed and the lock member surrounds parts in such a way that there can be no tampering which would enable a removal of the cap without breaking the lock member or band. The parts are made from a relatively strong material, and the lock-ring imparts strength in the areas of pressure and impact. In order to break the band, a substantial pull must be made on the tab 49. When it is desired to remove the cap 18, the tab is engaged very tightly with the fingers or by use of a pair of pliers, and pulled outwardly in order to tear a strip from the band. The band is then removed which frees the cap so that it can be twisted in the reverse direction relative to said shoulder or lock element in order to remove it from the spout. | A tamperproof screw cap for a container which may be locked in place on the container spout, including a lock-band surrounding the cap and having one-way teeth thereon engageable with one-way teeth surrounding the spout which permits the cap to be screwed into place but prevents the cap from being unscrewed until said lock-band is removed. | 1 |
RELATED APPLICATION
This is a continuation, of application Ser. No. 960,894 filed 11/15/78, now abandoned, which is a CIP of application Ser. No. 792,424, filed 4/29/77, now abandoned.
BACKGROUND
This invention relates to lithographic printing and more particularly to improving the printing characteristics of lithographic printing plates.
Lithographic printing is an ancient art based on the principle of oil and water immiscibility. The art has been greatly advanced by the use of anodized aluminum substrates on which a printing surface is formed using photochemicals and photopolymers. The printing surface is made up of an image area which is oleophilic and hydrophobic (ink attracting and water repelling) and a nonprinting or background area which is hydrophilic and oleophobic (water attracting and ink repelling).
Successful printing requires a delicate balance between ink and water. Water has been used in spray and other, types of dampening systems; but with the conventional system using molleton on cloth covers, the dampeners grease rapidly when only plain water is used in the fountain. Greasing of the dampeners causes poor wetting as well as spreading of the ink into non-image areas, especially in halftones and reverse lettering. The use of solutions containing gum arabic or cellulose gum as a fountain solution greatly reduces this tendency of dampeners to grease. Greasing of cloth dampeners, however, always occurs to some extent. The addition of a small amount of acid--like phosphoric acid--and salts--like nitrates, phosphates and/or bichromates--to the fountain solution seems to overcome greasing and promote better wetting.
There are a great number and variety of fountain solution formulas. For some unknown reason, fountain solutions do not work well on aluminum plates unless they contain a nitrate salt. While bichromates are undesirable in fountain solutions because of their tendency to cause dermatitis, they are of help in preventing the stripping of steel rollers on the press. With the introduction of hard rubber and copper rollers and copperizing treatments for steel, this stripping tendency has decreased considerably and many plates now are operating successfully with solutions of the zinc nitrate, phosphoric acid and either gum arabic or cellulose gum type.
Typical fountain solution compositions for lithographic printing are described in the following U.S. patents:
______________________________________Wolfson et al 3,257,941 1966Uhlig 3,289,577 1966Griffith et al 3,354,824 1967Bondurant et al 3,398,002 1968Shimizu 3,522,062 1970Nasca 3,625,715 1971Van Dusen, Jr. 3,687,694 1972Harper 3,775,135 1973Suzuki 3,829,319 1974Leeds 3,877,374 1975______________________________________
Present day fountain solutions, however, are expensive and present disposal problems because of pollution laws. This is especially acute with respect to solutions containing acids, heavy metal salts and alcohols.
Another problem is paper waste and with ever-increasing costs, what used to be ignored, is now a prime area of concern. Each time a press is started, acceptable printing quality must wait until the press is in balance. In the case of newspapers, it is not uncommon to discard the first 200-500 newspapers on each start-up of the press. Such presses are often stopped for edition changes and web breaks. These interruptions substantially increase the day in day out paper waste.
The use of enzymes to remove portions of differentially hardened layers on lithographic plates is suggested by Etter in U.S. Pat. No. 3,620,737. This relates to preparing the plates and the enzyme action must be stopped before the plates are ready for printing. While Etter suggests a pre-printing treatment, Cooperman in U.S. Pat. Nos. 3,532, 599 and 3,813,342 suggests a post-printing treatment to remove accumulated gum deposits using specific enzymes. The use of a protein or a proteinaceous material during actual printing is not described or suggested in the prior art.
SUMMARY
The present invention improves lithographic printing, makes it possible to eliminate or reduce the amount of additives heretofore used in lithographic fountain solutions and reduces paper waste.
The invention provides an improvement in lithographic printing wherein a lithographic printing plate having oleophilic and hydrophilic areas on the printing surface of the plate is contacted with an aqueous fountain solution during printing. The improvement of the invention comprises using an aqueous solution containing a proteinaceous material as the fountain solution.
Proteins are made up of polypeptide chains which in turn are made up of amino acids linked head to tail in infinite variations. The utility of these materials in fountain solutions is believed to be due to their unusual chemical make-up. These materials are amphoteric and can be positively or negatively charged depending on the pH of the solution. Some are soluble under acid conditions, some at neutraility, and some under basic conditions. Because of their structure, they are very polar substances and, therefore, water loving. Their polarity also gives them the abilty to adhere to charged substances with extreme tenacity.
DESCRIPTION
Water soluble proteinaceous materials are suitable for use in the present invention. These include water soluble amino acids such as glycine, L-asparatic acid, L-glutamic acid, L-alanine, L-leucine, L-valine, and L-cystine, water soluble polypeptides such as polypeptide-LSN (Stepan Chem. Co.) Procote-180 (Ralston-Purina) and BAN (Novo Labs) and water soluble, active and inactive enzymes of the hydrolase type such as amylase, lipase, maltase, papain, pepsin, protease, sucrase, trypsin, diastase, rapidase, chymotrypsin A, acetyl-cholinesterase and the like.
The proteinaceous materials are used in an amount which is effective for obtaining the desired results. Generally an amount in the range of 0.05 to 5% by weight will be sufficient and optimum results are attained when using amount of less than 1% by weight, e.g. 0.1 to 0.5% by weight. The fountain solution can also contain other substances such as water soluble polymers such as polyox or polyvinyl alcohol (films of which can be used to package the proteinaceous materials in dry form) which improve the action of the proteinaceous materials.
EXAMPLE 1
An aqueous solution of 0.5% pepsin is used as the fountain solution in a conventional offset lithographic press. The printing quality is excellent and 30-50% less fountain solution is used in comparison to printing using a conventional fountain solution. It is also possible to change the type of plate without having to adjust the fountain solution/ink balance. Heretofor, each plate change meant having to adjust or replace the fountain solution.
Thus, according to the invention, the amount of fountain solution can be reduced by 30-50% and because less moisture is present the ink sets quicker and is more intense.
EXAMPLE 2
Example 1 is duplicated using 0.5% aqueous lipase with the same beneficial results.
EXAMPLE 3
Example 1 is duplicated using 0.5% aqueous protease with the same beneficial results.
EXAMPLE 4
Example 1 is duplicated using 0.5% aqueous amylase with the same beneficial results.
EXAMPLE 5
Example 1 is duplicated using 0.5% aqueous diastase with the same beneficial results.
EXAMPLE 6
Example 1 is duplicated using 0.5% aqueous papain with the same beneficial results.
EXAMPLE 7
Example 1 is duplicated using 0.5% aqueous rapidase with the same beneficial results.
EXAMPLE 8
Two enzymes, amylase (Aquazyme 120L-Novo Labs) and the protease (Alcalse 0.6L-Novo Labs) are used in active and inactive forms. The inactive forms are made by two methods: pH inactivation and heat inactivation. These protein materials are incorporated in a fountain solution at a concentration of approximately 0.1-0.2%. A test is run on a Harris sheet-fed press. Roll-ups and ink black-out tests are performed with these active and inactive proteins. No difference can be observed in the quality of the print or the quickness of roll-up both on start-up and after black-out. These tests demonstrate improvement with various proteins according to the invention.
The invention can also be used to advantage in a di-litho operation where letterpress machines are converted to lithographic printing with direct contact between the plate and the paper being printed.
EXAMPLE 9
A test is run with a protein material designated BAN (amylase) and supplied by Novo Labs, Denmark. A 120 grams of BAN are packed in film bags with Quik Sol-P supplied by Polymer Films, Inc., Rockville, Connecticut. These bags are water soluble and .ontain polyoxyethylene polymers (Polyox - Union Carbide). One bag containing BAN is placed into a 30-gallon (water) sump of a Goss Metro offset press. The bag and its entire contents dissolve quickly. A 50,000 edition newspaper is run using the fountain solution. High quality color and black and white prints of unusual clarity resulted.
EXAMPLE 10
A test is made similar to Example 9 except the Quik Sol-P bags were not used. Instead, one gram of Polyox WSR-205 and 120 grams of BAN were used with similar results.
EXAMPLE 11
Example 10 is repeated using Polyox WSR N-3000 with similar results.
EXAMPLE 12
A fountain solution is prepared using 2 grams per liter of L-lysine HCl provided by Ajinomoto Company, Inc., Tokyo, Japan. The fountain solution is used on a Harris sheet-fed press. Roll-up tests and black-out tests are run. The print quality and ease of clean-up were excellent.
EXAMPLE 13
Example 12 is repeated using other amino acids, namely, L-asparatic acid, glycine, L-glutamic acid, L-alanine, L-leucine, L-valine, L-cystine. All materials were obtained from Ajinomoto, Tokyo, Japan and results are similar to Example 12.
EXAMPLE 14
A fountain solution is prepared using Quik Sol-P bags containing 120 grams of polypeptide LSN anhydrous, which is hydrolyzed animal protein sold by Stepan Chemical Company, Northfield, Illinois. One bag containing polypeptide is added to 30 gallons of water in the sump of a Goss-Metro offset press. 50,000 copies of a daily newspaper are run. Quick roll-up, minimum paper waste, and good quality color and black and white images result.
EXAMPLE 15
A fountain solution similar to Example 9 is prepared using BAN and a water soluble Quik Sol "A" bag. Similar results were obtained on an offset press. Quik Sol "A" contains polyvinyl alcohol.
EXAMPLE 16
A 0.1% solution of a vegetable protein (Pro-cote polymers-Ralston Purina) is prepared. These materials are composed of amino acids, namely, the α-amino carboxylic acids whose polypeptide chains also function as fountain solution additives. The fountain solution is placed on a Harris sheet-fed press. Roll-up and black-out tests are made with results as in Example 9.
EXAMPLE 17
A fountain solution containing protease is tested under controlled conditions sanctioned by the ANPA. The tests are run under the following conditions:
Goss Perfecting Urbanite Press
Flint Fountain Solution (V2 0 2 0-control)
Flint Offset Black Ink
Standard Newspaper Print
New Molleton Socks on Dampening Rollers
Procedure for start-ups was as follows:
1. Folder disengaged
2. Infeed disengaged
3. Water feed on
4. Ink feed on
5. Water form roller down
6. Ink form roller down
7. Stop
8. Folder engaged
9. Infeed engaged
10. Print
11. Print speed 0 to 30 to 0 iph
Press runs are made using plates made from an ANPA test negative and a conventional negative, in this case, the front page of a newspaper. One of each plate is used with a protease solution of the invention and one each is used with the control solution.
__________________________________________________________________________EXPERIMENTAL FOUNTAIN SOLUTION - ANPADATA BASED ON NUMBER OF PRINTED COPIES FROM START-UP TO ACCEPTABLE IMAGE ANPA TEST NEGATIVE FRONT PAGE NEGATIVE% Protease % Fewer % Fewerin copies copiesFountain Differ- than Differ- thanSolution Conditions Example Control ence Control Example Control ence Control__________________________________________________________________________0.2 Start-up #1 13 19 6 32 11 17 6 350.2 Start-up #2 5 17 12 70 3 14 11 790.2 Start-up #3 21 23 2 9 14 13 -1 -80.2 Start-up #4 18 25 7 28 16 25 9 360.2 Black-out #1 25 53+ 28+ 53+ 25 34 9 26 Faded not acc. Faded at 530.2 Start-up #5 18 88+ 70+ 80+ 18 31 13 42 Following #1 not acc. Black-out at 880.2 Black-out #2 23 45+ 22+ 49+ 23 39 16 41 not acc. at 450.1 Start-up #6 43 41 -2 -5 41 27 -14 -52 Following #2 Black-out0.1 & pH 3.0 Start-up #7 15 33 18 55 17 25 8 30 Black-out 25 38 13 34 21 27 6 22 Start-up 17 36 19 53 17 23 6 26__________________________________________________________________________Total Averages Excluding Negative and Uncertain Values 11 40% 9.3 37%Average Deviation 47% 41% 28% 29%Average During Start-Ups Excluding Negative and Un-certain Values 10.6 41% 8.8 41%Average During Black-Outs Excluding Negative and Un-certain Values 13 34% 10 31%__________________________________________________________________________ | Method for lithographic printing wherein a lithographic printing plate having oleophilic and hydrophilic areas on the printing surface of the plate is contacted with ink and an aqueous fountain solution during printing. An aqueous solution comprising an enzyme is used as the fountain solution. | 1 |
CROSS REFERENCE TO RELATED APPLICATION
This is a Continuation-in-part of U.S. patent application Ser. No. 09/326,041 now U.S. Pat. No. 6,148,722 , Filed Jun. 4, 1999, for COMPACT DISC AND RECORDABLE COMPACT DISC THERMAL TRANSFER PRINTER, incorporated herein by reference, which in turn claims priority to Provisional Application Ser. No. 60/088,397, filed Jun. 8, 1998, and entitled COMPACT DISC (CD) AND RECORDABLE COMPACT DISC (CD-R) THERMAL TRANSFER PRINTER.
BACKGROUND OF THE INVENTION
The present invention relates to a printer that will print from a carrier ribbon, film or web to a substrate carried on a flexible support that is planar and is driven directly by rollers or drives. The substrate carrier can be removed from the printer to be changed, and/or for other manipulation, such as loading it into another device for a related operation on the substrate. A removed carrier can be driven back into the printer. A cartridge carrying the printhead is also provided.
Thermal printing technology for substrates, such as compact discs (CDs) and recordable compact discs (CD-Rs) and also identification cards incorporate pivotally mounted heads and linear platens with resilient surfaces and carriers that have clamping mechanisms for the substrate. The carriers are generally separately driven.
Current technology for printing onto plastic substrates uses expensive head actuating and force modifying mechanisms. The printhead is moved on pivotally mounted arms that extend substantially beyond the envelope of the printhead, with a linearly driven carriage that has to hold the disc over an expensive, flat resilient surface with a clamping device that moves with the carriage. Threading the ribbon through the printhead and mounting ports of the presently available printers is a tedious job which includes taping the ribbon to the carriage, then taping the ribbon after the carriage is driven into the printer. This leads to large, high-cost printers for plastic substrates such as CD's, CD-R's and digital videodiscs. It is desirable to substantially reduce the printer size in order to take less space for the CD printers, as well as reducing manufacturing costs and user interaction.
SUMMARY OF THE INVENTION
The present invention relates to a substrate carrier or tray and printhead cartridge that mount into a frame for reliably printing on flat substrates of various shapes, such as a rectangular ID card, CDs, CD-Rs, DVDs and irregular shapes. A substrate carrier or tray is substantially planar and is removable from the printer for loading. Friction drives that engage the planar carrier, such as one or more spring-loaded rollers are used. The substrate on the carrier is urged against stops by drive rollers, for positive positioning. The drive rollers shown act on a flexible or semi-flexible planar support that will move the substrate into the installed print cartridge.
A platen roller is mounted so that it and the carrier for the substrate can be moved against a printhead under a controlled spring force. The platen roller, in one form of the invention, can be slidably mounted, and can be urged toward the printhead with springs that can be varied in force. In another form of the invention, the platen, the substrate carrier and the substrate are mounted on a pivoting frame and urged up against the printhead where the force is reacted by the printhead for contact printing.
The pivoting frame mounts not only the platen, but also drive rollers for the substrate carrier. The force with which the platen, carrier and/or substrate are urged against the printhead during the loading and printing operation is controlled by a cam that acts on a cam follower connected to the platen frame by springs so that the frame pivots toward the printhead under spring load. One drive roller for the substrate tray or carrier is on the pivoting frame and rests against a spring-loaded pinch roller. The printhead cartridge also carries the printhead and a second pinch roller. The platen is spring-loaded and resilient to load the cartridge and the substrate against the printhead, which is held in a fixed position. A second drive roller is provided on the printer housing and cooperates with the second pinch roller, so the carrier is driven by rollers after it has passed through an inlet opening.
According to another aspect of the invention, a printhead cartridge contains the printhead, as well as the ribbon, film or web supply and take-up rollers. The cartridge permits easy loading of the ribbon since the ribbon does not have to be threaded through pairs of rollers or openings, and does not require special “lead-in” tapes or the like. Also, the printer provides easy front loading of both the printhead cartridge and the substrate carrier. The outer printer housing fits within a PC box or other container.
The flexible or semi-flexible planar substrate carrier or tray is moved in and out with motors or drives that are synchronized for printing and for insertion and removal. The carrier for the substrate can be adapted to a wide range of shapes, because the substrate is seated by being held against edges or stops on the carrier by the action of the five rollers. Alternatively, the carrier can have a recess formed to the peripheral shape of the substrate to provide for positioning the substrate.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of one form of the present invention;
FIG. 2 is a front view of the form of the invention shown in FIG. 1;
FIG. 3 is a schematic side-elevational view of the device of FIG. 1, again schematically illustrated;
FIG. 4 is a perspective view of a housing or cabinet showing a printhead cartridge on which the printhead is located about to be inserted into the cabinet;
FIG. 5 is a side elevational view of the form of the invention shown in FIG. 4;
FIG. 6 is a horizontal sectional view of the device shown in FIG. 5 taken generally along line 6 — 6 in FIG. 4;
FIG. 6A is a side view similar to FIG. 6 with the cartridge carrying the printhead and ribbons partially installed and about to be latched;
FIG. 6B is a view similar to FIG. 6A with the printhead fully in place and the cartridge carrying a substrate to be printed on the exterior of the main cabinet;
FIG. 7 is an enlarged sectional view of a portion circled in FIG. 6;
FIG. 7A is a sectional view similar to FIG. 7 with the portion enlarged circled in FIG. 6A;
FIG. 7B is an enlarged view of the portion of the circle in FIG. 6B;
FIG. 8 is a sectional view similar to that shown in FIG. 6 with the printhead and cartridge in working position, and printing about to start on a circular substrate or disc;
FIG. 9 is an enlarged fragmentary view of a portion of the assembly shown circled in FIG. 8;
FIG. 10 is an enlarged sectional view of the portion shown in FIG. 9 with printing about to commence;
FIG. 11 is a sectional view similar to that shown in FIG. 10, with the printing about a third of the way through, where a maximum chordal length of the print area on the circular substrate is encountered near the center opening of a CD;
FIG. 12 is a sectional view similar to FIG. 8, when the platen frame is lowered, after printing is done to allow the print ribbon to advance and the substrate and carrier to be moved back for another pass;
FIG. 13 is an enlarged sectional view of the circled portion in FIG. 12;
FIG. 14 is a top plan view of the printer with the platen frame in position in cross section, with the printhead cartridge removed for sake of clarity;
FIG. 15 is an enlarged sectional view of a portion circled in FIG. 14;
FIG. 16 is a sectional view taken generally along line 16 — 16 in FIG. 14;
FIG. 17 is an enlarged view of a printing shaft support and a cam follower plate with parts of a side wall of a platen frame broken away;
FIG. 18 is a top plan view similar to FIG. 14, illustrating a modified form of the substrate, in the form of an identification card carried on the carriers;
FIG. 19 is a sectional view of a typical character taken on line 19 — 19 in FIG. 18;
FIG. 20 is a top plan view of a further modified tray or carrier for carrying an irregularly shaped substrate on which printing is to be placed;
FIG. 21 is a sectional view taken on line 21 — 21 in FIG. 20;
FIG. 22 is a top view of a tray or carrier with a recess for holding a substrate; and
FIG. 23 is a sectional view taken on line 23 — 23 in FIG. 22 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 through 3 show a schematic view of a printer 10 embodying the principles of the present invention and in the illustrated embodiment includes a printhead 12 that has a series of very small heat elements (resistors) that transfer a base coating or an imaging compound, wax, resin or resin composites or sublimation dyes from a carrier ribbon, film or web 13 , to a substrate 14 . The substrate 14 may be an identification card of rectangular or irregular shape, a circular compact disc, a recordable compact disc, a DVD disc or other desired substrate that is to receive printing. The platen 15 is used to force the substrate 14 against the ribbon 13 and create intimate contact between the printhead, ribbon and substrate. The substrate is carried on a generally planar, flexible or semi-flexible support tray or carrier 17 . The carrier can be used with other types of printers such as ink jet printers, or with other devices that perform one of a series of operations in a process, such as a device that records data on CD's. The platen 15 will be controlled to push the carrier 17 and the substrate thereon toward the printhead so the substrate is urged against the printhead 12 with the desired amount of force for printing images.
Images are created in the form disclosed through control of the heat elements on the thermal transfer printhead to selectively apply imaging compound from the web or ribbon 13 to specific areas of the substrate. Colors can optionally be created with multiple passes using a panelled ribbon, combined with dithering techniques to create several perceived colors, as is known.
The platen roller 15 , which is driven by a stepper motor 15 A, can be controlled so as to control the speed of driving the carrier 17 and the substrate 14 , as it is held against the printhead 12 under a fixed spring load. The carrier is rigid enough so that it can support the weight of the substrate when it is fully extended out from the printer, as will be shown in subsequent drawings, in a position linearly horizontal to the plane of the tray or carrier as the substrate is being printed, and yet will have some “give” or flexibility as the platen roller 15 urges the carrier 17 and the disc 14 on the carrier against the printhead and as the rollers 16 feed the carrier through the printer. The force with which the platen roller engages the carrier 17 and thus the force with which the disc is urged against the printhead is controlled by springs 27 .
Brackets 18 are used for mounting the platen relative to the printhead as shown schematically, and the platen roller 15 can be moved out of the way, so that a frame that contains the printhead and ribbon can be removed from the printer easily.
Power supplies generally are those of a PC, and the printer can be driven from a personal computer. The platen roller is mounted in such a way that it is held against the carrier or support tray 17 in a floating manner without a pivotally mounted frame, such as by providing slots for guiding the carrier. The platen roller 15 is clamped to the printhead frame through intermediate brackets 18 and 19 A which can be unclamped and allow the platen roller to drop away from the printhead. By unclamping and moving the platen roller out of the way, the ribbon can be installed in a straightforward fashion.
The clamping brackets 18 and 19 A can be actuated fairly easily through a cam system mounted just above the printhead. This system saves space and allows for electronic control of the head force. The substrate and membrane or carrier are held by the pinch rollers 16 of the roller sets. The pinch rollers are the upper rollers and will first roll along the upper surface of the carrier 17 . When the leading edge of the substrate comes against the upper pinch roller it will slide along the surfaces of the carrier, the force of the pinch roller 16 will locate the substrate on the membrane by forcing or urging it up against a reference edge or stop 19 on the carrier when first being engaged. The reference edge or stop 19 and the squeezing action of the rollers 16 serve to position and then clamp and hold the substrate in a controlled, known position throughout the printing process. No separate clamping of the substrate is needed.
The chassis of the printer has a moveable portion 20 that allows the platen roller 15 to move vertically while maintaining the fixed horizontal position of the platen roller. The vertical movement is accomplished through a camshaft 21 mounted through the top portion of the chassis (which is fixed and non-moveable). The camshaft 21 is driven by a stepper motor 22 and has two springs 27 which are attached to a shaft or bracket 19 A which is driven by the camshaft on one end and pivotally attached to the moveable portion 20 of the chassis on the other so it tilts. By incrementally moving the camshaft 21 by actuating the stepper motor, 22 , the roller 15 can be raised or lowered under spring force, thus creating the pressure upon the support tray or carrier 17 . This allows the platen roller 15 to act as a pinch roller in the sense that as it is raised, it pinches the support tray or carrier 17 and the substrate between itself, the printhead and the ribbon. The pinching action creates pressure that is applied to the substrate as it passes under the printhead, depending on the position of the camshaft.
The springs 27 act on the platen to move it up in a desired manner, toward the planar carrier 17 to act against the printhead 12 .
In FIGS. 4 through 20, a further illustrative embodiment is shown. Referring first to FIG. 4, a main cabinet 30 forms a housing that has side walls 31 , and a top wall 32 as well as a bottom wall 34 , (see FIG. 6, and other Figures for example). A printhead cartridge assembly 36 that is a unitary assembly has a top wall 38 , and depending side walls 40 . The side walls 40 are made to fit between the side walls 31 of the main housing. The side walls 31 have an outer panel 31 A and an inner panel 31 B (FIGS. 6 and 16 ). It can be seen that the side walls 40 of the printer head cartridge include a latch recess 42 on each side that will be used for holding the printhead cartridge assembly 36 in position when it is fully inserted into the housing 30 . Also, as can be seen in FIG. 6, a cutout portion 29 of the inner panel 31 B of wall 31 has a support edge 29 A that will support the printhead cartridge 36 in proper position. As shown in FIG. 14, the ends of shafts 23 D and 24 D will slide on edges 29 A on each side of the housing.
The printhead cartridge 36 has a front wall 44 that includes a recess 46 that will permit the substrate support or carrier 17 and substrate 14 such as a CD, CD-R, DVD, ID card or the like to be on the exterior of the housing for loading, and then driven into the housing 30 for printing.
In FIG. 6, it can be seen that the supply roll 23 for the ribbon film or web 13 and the take-up roll 24 for the ribbon, film or web are mounted onto the side walls 40 of the printhead cartridge. The slots 23 A and 24 A shown in FIGS. 4 and 5 mount the shafts 23 D and 24 D for these supply and take-up rollers and hold the shafts in off-set notches. The thermal printhead 12 is mounted to the side walls 40 of the printhead cartridge assembly 36 , and is fixed in position. The print supply and take-up rollers 23 and 24 can be easily installed by moving the shafts 23 D and 24 D up from the bottom of the cartridge in slots 23 A and 24 A in the side walls 40 of the cartridge, without the need for threading the film or ribbon through particular rollers or slots. The ribbon will be passed over the printhead without threading it through any openings. The ribbon is thus simply laid over the exposed edge of the printhead when the rolls 23 and 24 are installed. Effortless loading of the ribbon is possible with the printhead cartridge removed from the housing.
A suitable sensor 12 A can be used for sensing the ribbon 13 for various controls. A motor 23 B can be used for driving the ribbon or web supply roll 23 . The ribbon take-up roller 24 will be driven from a motor 24 B through a gear train 24 C that includes a spur gear 24 F on a shaft on the housing side wall that will drivably mate with a spur gear 24 G when the printhead cartridge assembly is moved into position in the housing 30 . The gear 24 G is mounted on a pin or shaft 24 H.
A spring loaded pinch roller 48 is mounted on the printhead cartridge assembly 36 , and will cooperate with drive rollers, as will be explained, for driving the carrier 17 and the disc 14 across the printhead for printing.
In FIG. 6, the housing 30 is also shown in cross section. The carrier 17 is mounted for movement with a drive roller 50 at an input end of the housing that cooperates with a spring loaded pinch roller 52 to engage the tray or carrier 17 and drive it in direction as indicated by the arrow 54 (or in reverse). A platen and carrier support frame 56 has a top plate 60 and a pair of side walls or arms 58 , 58 to form an inverted channel. The drive roller 50 and pinch roller 52 are carried on shafts extending between the arms 58 . The carrier 17 moves over the top plate 60 , which is supported on the arms 58 that are pivotally mounted on the axis of a shaft 61 of a drive roller 62 . The arms 58 and top plate 60 extend toward the input end of the housing 30 . The frame 56 is in a lowered position in FIG. 6 .
The platen support top plate 60 joins the side arms or walls 58 . The drive roller 50 and platen roller carry and drive the carrier 17 and substrate 14 into printing position after the cartridge 36 is in place, as will be shown. The shaft 61 and roller 62 are suitably driven with stepper motor 61 A, and will drive the carrier 17 during the printing process. After the printhead cartridge has been moved into place, the drive roller 62 will also cooperate with the pinch roller 48 on the printhead cartridge for providing a driving force when the printing has commenced, and the tray or carrier 17 is being moved in direction indicated by arrow 54
As can be seen in FIG. 7, which is an enlarged cross section view, the side arms or walls 58 of the platen support frame 56 are to the side of triangular plates 69 that are pivoted on shaft 61 adjacent the housing side walls as well. There is a plate 69 on each side of the platen support frame 56 . Plates 69 rotatably mount a cross shaft 66 on which a pair of cam rollers 68 are mounted. The cam rollers 68 are also shown in FIG. 16 . The cam shaft 66 is driven by stepper motor 66 A under control from controller 96 and the platen roller stepper motor 15 A is also controlled by controller 96 so the platen drive motor and camshaft drive motor can be controlled under common control.
Upstanding ears 70 are part of plates 69 , which are independent of the side arms 58 , and these ears 70 hold a cross shaft 72 in position, (see FIG. 17 as well). The ends of the shaft 72 extend through slots 74 in the side walls 31 of the housing, so that there can be some movement of the shaft 72 to permit the printhead cartridge 36 to be inserted into the housing 30 and latched in place using shaft 72 . Shaft 72 has bearing hubs 76 at its ends, again as shown in FIGS. 15 and 16, and the receptacles 42 on the side walls 40 of the printhead cartridge are of size to receive these hubs 76 as the printhead cartridge assembly 36 is inserted into place. The receptacles 42 are formed with a guide edge or a lead-in edge 42 A that will slip under the hubs 76 and lift the shaft 72 so that the hubs 76 on the shaft 72 can slip into the receptacles 42 , and detent in place in recesses 42 B. When the printhead cartridge is moved into this position, the ends of shafts on the cartridge, including shaft 24 H mounting gear 24 G, protrude outwardly from the side walls 40 sufficiently to slide into open-ended slots 78 (see FIG. 6 for example) so that the printhead cartridge 36 is held from unwanted movement relative to the housing 30 , and the drive gear from gear train 24 C meshes with gear 24 G, the takeup rollers thus driven by the motor 24 B.
Cam rollers 68 carried on shaft 72 act against a pivoting cam follower plate 80 which has side arms 82 on opposite sides of the housing 30 pivoted on shaft 61 as well (see FIG. 17 ). When rotated, the cam rollers 68 will change the pivoted position of plate 80 . Springs 81 carried on the edge of plate 80 are used to apply a load to the frame 56 through a cross member 83 that mounts on walls 58 and on which end of springs 81 are hooked. When the printhead cartridge 36 is inserted, shaft 72 is lifted to enter the receptacles 42 , which lifts the frame 56 to its loaded and operating position as shown in FIG. 6 B. The frame 56 also can be moved a limited amount by moving cam rollers 18 to exert or remove lifting forces. When the substrate engages the printhead, the force by which the platen urges the substrate against the printhead can be increased by moving the cam rollers 68 to increase the tension in springs 81 . The cams can be moved to a lowered position to slightly space the platen, and substrate from the printhead for ribbon removal or fast ribbon feed.
The platen roller 15 is driven by stepper motor 15 A. The tray or carrier 17 and the substrate 14 are also driven through the printing cycle under the printhead 12 , and force from the springs 81 urges the platen roller 15 upwardly to act as a pinch roller that drives the carrier 17 and substrate 14 across the printhead. The platen 15 also has an outer resilient covering 86 as shown, and the tray or carrier is flexible so it will conform to some irregularities in the substrate or components.
Positioning the printhead cartridge assembly 36 for sliding into the housing 30 is illustrated schematically in FIG. 6, where the printhead cartridge is disengaged. The printhead cartridge assembly 36 is entering the provided opening in the front of the housing 30 for insertion. It can be seen in FIGS. 6A and 6B, that the side members 40 of the cartridge assembly 36 are approaching the shaft 72 that has the hubs 76 (FIG. 15) for retaining the cartridge when it latches in place. In the view in FIGS. 6A and 7A, it can be seen that the receptacles 42 and guide edge 42 A on each side are approaching the shaft 72 . This is also shown enlarged in FIG. 7 A. The print ribbon 13 from the supply roller 23 and take-up roller 24 is under the printhead 12 , and then the printhead cartridge assembly 36 will be slid into place as shown in FIG. 6B held by the shaft receptacles 42 , and the slots 78 at one end. When the printhead cartridge is fully inserted, as shown in FIG. 6B, the frame 56 and the tray or carrier 17 are lifted and the outer end is aligned with the end opening or recess 46 of the housing so the carrier can be moved out of the housing and loaded or it can be completely removed, and a carrier already loaded with a different shape substrate or the same shape inserted.
In FIG. 6B, the substrate carrier 17 is shown in its loading position, having been driven there by the drive rollers 50 and pinch roller 52 outwardly under control of a controller 96 . The signal to drive the carrier 17 out of the housing can be manual or programmed. The substrate 14 can be put onto the carrier and located against edge or stop 19 . This is also shown in FIG. 14 .
The drive roller 50 can then be driven from a suitable stepper motor 50 A under control of central controller 96 to move the carrier 17 and substrate 14 in the direction indicated by the arrow 54 and so that the leading end 14 A of the substrate 14 first engages the pinch roller 52 which is against the top surface of the carrier 17 and will exert a force moving the back edge of the substrate against stop 19 . The carrier and substrate are then moved by the drive under the printhead.
While, for simplicity, this description has shown individual stepper motors for platen roller 15 and rollers 50 and 62 , these rollers can be driven together with gears (or timing belts) using only one stepper motor, such as motor 61 A.
The start of the printing cycle is shown in FIG. 10, where the leading end 14 A of substrate or disc 14 is immediately under the printhead 12 , which has the resistors forming heating elements 12 B to provide print heat. The platen roller 15 is urged up by the cam rollers 68 acting through the plate 80 and springs 81 to provide a force to urge platen support frame 56 and the platen roller 15 about the pivot axis up against the carrier 17 . A standard, uniform force can be used to urge the substrate 14 against the printhead 12 .
FIG. 11 illustrates the positioning of the substrate 14 when it has been fed approximately ⅓ of the way through the printhead by the drive rollers 50 and 52 and by drive roller 62 .
The printhead opposes the force from platen 15 . The cartridge is held in position by slots 78 . Shaft 72 , which seats in receptacles 42 , and the cam shaft 66 , are both mounted on plates 69 , as can be seen in FIG. 17 . Thus the forces on the platen and printhead from spring 81 are contained within the plates 69 .
In FIGS. 12 and 13, the substrate has been moved from under the printhead 12 , and the print ribbon 13 is being advanced. The cams move so the platen support frame 56 pivots down slightly and platen roller 15 is permitted to move away from the printhead 12 , to permit the ribbon, film or web 13 to be advanced so that the next color can be printed. If multi colors are to be printed, the tray or carrier 17 and the substrate 14 would be reversed in direction and another layer printed over the same region. The substrate 14 is indexed appropriately using suitable sensors such as the sensor shown at 88 in FIG. 12 . The signal from the sensor will be used to coordinate the position of the substrate 14 with the ribbon, film or web 13 and a particular color panel that is on that film.
When printing is done, the tray or carrier 17 is lowered or released from the printhead by moving cam 68 and then the tray or carrier is backed out of the housing and the printed substrate 14 removed. A new substrate is put onto the carrier 17 and the printing is repeated anew. If desired, a new carrier 17 can be inserted, since the carrier 17 is held only by the drive and pinch rollers and can be moved completely out of the rollers 50 and 52 .
FIG. 18 illustrates the printer of the present invention, with the same designations on the printer as before, but a substrate carrier illustrated at 17 M is modified to carry a substrate 114 that is rectangularly shaped, and which is held in position on the upper surface 115 of the carrier 17 M with suitable stop members 116 , along the sides, and 118 along the trailing edge. The substrate 114 is thus positioned laterally, and will be urged against the stops 118 when the pinch roller and drive roller 50 and 52 that drive the leading end of the carrier and engage the end of the substrate.
The leading end of the carrier is positioned about to enter the roller set 50 and 52 , as previously described and because the pinch roller 52 will ride on the surface 115 initially, it will tend to slide the substrate 114 along the carrier when the leading end 114 A is engaged by the pinch roller. Before the pinch roller lifts to engage the substrate it will tend to push the substrate back against the stops 118 , to positively seat the substrate 114 in position for printing the same.
As illustrated in FIG. 19, the tray or carrier 17 M can be made of a suitable plastic material, such as a polycarbonate, or other plastics that can be molded, and will have wall 120 with I shaped edge flanges 122 to provide some rigidity along the edges. the frame 56 supports wall 120 as shown, and the flanges 122 fit outside of the arm 58 as shown schematically. The platen roller and the drive rollers fit up against the wall 120 . The carrier 17 M is sufficiently flexible so that slight irregularities would not cause gaps in the printing. The force from platen 15 makes the carrier wall 120 conform to slight irregularities because of the resilient platen roller and the spring mounting, and the flexibility in transverse direction of wall 120 .
Various other types of carriers 17 M can be advanced, but the carrier is generally planar so that it can be driven by a drive roller on one side and a pinch roller on the other side, or some other type of reaction member such as the fixed printhead, for moving it through the printer.
FIG. 20 illustrates a further modified carrier 17 N, which has an irregularly shaped substrate 130 mounted thereon using suitable side guides 132 , and at least one trailing end guide 134 . The carrier 17 N would be made as previously shown, except it has a wall 135 that has grooves 137 extending in longitudinal direction to provide lateral flexibility for bending or conforming to lateral irregularities, and the guide and pinch rollers would exert a force as indicated by the arrow 136 to seat the substrate against the rear guide 134 .
FIGS. 22 and 23 show a modified planar carrier or tray 150 made for carrying a recessed substrate such as a name tag or card 152 to be printed upon that is fed between the drive and pinch rollers 50 and 52 . The flat carrier 150 , and an irregular shaped substrate 152 , which as shown is a representation of Lake Michigan can be used for an identification badge or card for convention delegates.
The planar carrier or tray is of sufficient thickness so that the defining line 154 of the badge or substrate 152 can be milled as a recess 156 in the carrier or tray 150 . The substrate recess 156 is milled to leave a thickness of material of the carrier below the recess. The badge 152 can be cut out as separate items. The cut peripheral edge of the badge will fit within the defining line 154 on the carrier 150 , and fit down into the recess.
The planar carrier 150 can be made of two flat panels, including a base panel and an upper panel with the upper panel cut to form an opening of the shape desired. The opening could be closed on its bottom by bonding the base panel to the panel with the cut out.
The badges are held and located properly in the recess formed in the carrier. The carrier can have longitudinal grooves 160 to permit more lateral flexibility. The cutting of recesses of irregular shapes, or even rectangular shapes or ornamental designs, in the surface of a carrier or tray used with a printer increase the versatility of the printer.
It also can be seen in FIGS. 6A and 12 that electrical connections for the motors on the printhead cartridge assembly can be made with the connector shown at 90 , which includes a portion 90 A on the housing 30 , and a second portion 90 B on the printhead cartridge 36 . When the printhead cartridge 36 moves to its home position, as latched with the receptacle 42 , connection will be made for the power.
The controller shown at 96 will coordinate all functions, including the movement of the cam shaft 66 and the platen roller 15 , through the stepper motors 66 A and 15 A, and the position of cam shaft 66 can be changed so that the cam rollers 68 will move to lower the platen 15 as needed. The printing can be preprogrammed into the controller.
The term substrate is intended to include objects that have a surface which is to have printed material applied and which will fit onto a carrier or tray. In addition to the items previously described, the term substrate can include credit cards, playing cards, labels, name tags, sign of various types and similar flat surface objects.
Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. | A printer has a substrate carrier that is a planar membrane driven through the printer solely by friction drives. The planar membrane is completely removable from the printer, and can be adapted to support a substrate of desired configuration and held against locating surfaces while it is being driven through the printer by the friction drive. The friction drive comprises at least one set of rollers including a drive roller on one side of the carrier and a resiliently mounted roller on the other, and also includes a rotating resilient platen that is resiliently urged against a printhead for providing a reaction force for the friction drive while printing occurs. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
REFERENCE TO MICROFICHE APPENDIX
Not applicable.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the field of personal hygiene devices in general, and in particular to a device to allow the user to wipe their anal/rectum area.
2. Description of Related Art
As can be seen by reference to the following U.S. Pat. Nos. 4,099,289; 4,256,409; 4,615,066; and 5,127,127, the prior art is replete with myriad and diverse cleaning implements.
While all of the aforementioned prior art constructions are more than adequate for fulfilling their intended purpose and function, they are neither designed nor intended to fulfill the role played by the subject matter of the present invention.
While most able bodied individuals have never had to contend with this problem, a significant number of individuals experience a great deal of difficulty in applying normal hygienic techniques in the anal/rectum area due to physical handicaps or obesity.
As a consequence of the foregoing situation, there has existed a long standing need among physically challenged, and obese individuals, as well as with health care professionals assigned to their care, for a new type of personal hygiene device that can be employed in a quick, simple and clean manner by an individual to address their personal hygiene needs and the provision of such a construction is a stated objective of the present invention.
BRIEF SUMMARY OF THE INVENTION
Briefly stated, the personal hygiene device that forms the basis of the present invention comprises a handle unit, a spring loaded ejection unit and a sanitary wipe unit. The sanitary wipe unit is dimensioned to be received on one end of the spring loaded ejection unit.
As will be explained in greater detail further on in the specification, the handle unit has an elongated generally crescent shaped configuration to assist the user in both the placement and the back and forth movement of the sanitary wipe unit in the anal/rectum area to remove fecal matter in a well recognized fashion.
Furthermore, the spring loaded ejection unit is provided to forcibly remove the soiled sanitary wipe unit from the handle unit by the push of a button so that the used sanitary wipe unit can be discarded in the proper fashion.
BRIEF DESCRIPTION OF THE SEVERAL VIEW OF THE DRAWING
These and other attributes of the invention will become more clear upon a thorough study of the following description of the best mode for carrying out the invention, particularly when reviewed in conjunction with the drawings, wherein:
FIG. 1 is a perspective view of the personal hygiene device that forms the basis of the present invention in its assembled mode;
FIG. 2 is an isolated, detail view of the ejector ram;
FIG. 3 is an exploded view of the ejector ram and the sanitary wiper unit;
FIG. 4 is an exploded perspective view of the device; and
FIG. 5 is an isolated detail view of the ejector latch mechanism.
DETAILED DESCRIPTION OF THE INVENTION
As can be seen by reference to the drawings, and in particularly to FIG. 1, the personal hygiene device that forms the basis of the present invention is designated generally by the reference number 10. The device 10 comprises in general a handle unit 11, a spring loaded ejection unit 12, and a sanitary wipe unit 13. These units will now be described in seriatim fashion.
As shown in FIGS. 1 and 4, the handle unit 11 comprises an elongated contoured tubular handle member 20 preferably fabricated from stainless steel 21 or the like wherein the proximal end 22 of the handle member 20 is provided with a rubberized handle grip element 23. In addition, the intermediate portion 24 of the handle member 20 has a generally curved configuration and terminates in the distal end 25 of the handle member 20 which will be described presently.
As can best be seen by reference to FIGS. 3 through 5, the spring loaded ejection unit 12 comprises an ejection spring member 30 dimensioned to be received within the distal end 25 of the handle member 20. The distal end 25 of the handle member 20 is further provided with a peripheral collar element 26 disposed intermediate a push button aperture 27 and a detent aperture 28 whose purpose and function will be described presently.
In addition, the actuation of the ejection spring member 30 is controlled by a push button member 31 which is spring biased away from an interior portion of the handle collar element 26 by spring element 32 wherein the leading edge 33 of the push button member 31 is operatively engaged with the trailing edge 34 of a detent member 35 which is pivotally secured in the distal end 25 of the handle member 20. Furthermore, the push button member 31 and the detent member 35 normally project outwardly through the push button aperture 27 and the detent aperture 28 respectively, when the ejector spring member 30 is in its relaxed state.
Turning now to FIGS. 2 through 4, it can be seen that the sanitary wipe unit 13 comprises an inner generally tubular support member 40 provided with an interior, transverse spring bearing surface 41 and an interior peripheral recess 42, and an outer sanitary wipe member 43 fabricated from sterile cotton 44 or the like.
In operation, the user would insert the tubular support member 40 over the distal end 25 of the handle member 20 wherein the spring bearing surface 41 would compress the ejection spring member 30 until the detent 35 is received within the peripheral recess 42 in the support member 40. At this point, the sanitary wipe member 43 would be placed over the support member 40 and used in the manner as outlined herein to clean the user's anal/rectum areas of fecal matter or the like.
After the device 10 has been employed in its intended manner, the user would then dispose of the sanitary wipe member 43 and the tubular support member 40 by actuating the push button 31 to release the detent 35 from the recess 42 in the support member 40 to forcibly disengage the sanitary wipe unit 13 from the remainder of the device 10.
Although only an exemplary embodiment of the invention has been described in detail above, those skilled in the art will readily appreciate that many modifications are possible without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention as defined in the following claims.
In the claims, means-plus-function clauses are intended to cover the structures described herein as performing the recited function and not only structural equivalents, but also equivalent structures. Thus, although a nail and a screw may not be structural equivalents in that a nail employs a cylindrical surface to secure wooded parts together, whereas, a screw employs a helical surface, in the environment of fastening wooden parts, a nail and a screw may be equivalent structures.
Having thereby described the subject matter of the present invention, it should be apparent that many substitutions, modifications and variations of the invention are possible in light of the above teachings. It is therefore to be understood that the invention as taught and described herein is only to be limited to the extent of the breadth and scope of the appended claims. | A personal hygiene device 10 for cleaning waste material from the anal/rectum area of a person. The device 10 comprises a curved handle member 20 having a push button operated detent member 35 for releasably engaging a sanitary wiping member 43 relative to the distal end 25 of the handle member 20. | 0 |
BACKGROUND OF THE INVENTION
The present invention relates to medical therapy and appliances for post operative or post injury treatment of lower limbs.
Patients recovering from surgery involving the lower limbs or after treatment of injury to the lower limbs sometimes require an elevated position for the lower limb for proper positioning and to minimize potential edema or swelling. The weight of blankets and the like, bearing upon the foot of a patient can tend to rotate the patient's leg, causing distress to such patients. Further, the patient's condition might be that bedding laid over and contacting the patient can cause trauma or injury to a treated and recovering area of the lower limb. Thus, it is often desirable to use a blanket support with the foot elevator
Prior foot elevator devices have consisted of a foam block which is molded or cut to the desired contour and shape. Such foam block devices are bulky to handle and store. Alternatively, a wrap-style splint device has been used. However, such wrap-style devices are contraindicated where minimizing contact is desired.
Both prior devices restrict the circulation of air along the patient's skin where the device is used, causing irritation and general discomfort. Both prior devices are difficult to clean or sanitize for prolonged use or use by subsequent patients. Further, neither device provides satisfactory protection to the lower limb, especially the foot and toe area, from the weight and discomfort of blankets and other bedding bearing on the foot and toes.
SUMMARY OF THE INVENTION
The foot-elevator and blanket support of the present invention address the deficiencies of the prior devices. A collapsible device having an upper peripheral frame supporting a cradle is provided The upper frame is releasably connected to a base peripheral frame.
In one aspect of the invention, a peripheral frame blanket support is also releasably connected to the upper and base frames. In another aspect of the invention, the various peripheral frames are formed from stainless steel wire for enhanced durability and maintenance, including ease of sanitation. In another aspect of the invention, the cradle is a removable fabric covering which is stretched over the upper frame to form a hammock-like receiving area for the lower limb and enhances free air circulation to the body portion engaged thereby. The configuration of the wire frame is such that no body portion need contact the wire frame itself.
Further, the assembled device does not have the bulk of the prior devices. The three wire frame members can be disconnected from each other to further minimize the bulk of the present invention and enhance compact storage. When in its collapsed state, the-preferred embodiment constitutes a mere fraction of the bulk of prior devices.
These and other objects, 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 perspective view of the invention as used by a patient, with a portion of a lower limb and a portion of typical bedding shown in phantom.
FIG. 2 is an exploded perspective view of the invention.
FIG. 3 is an exploded perspective detail view of the connecting device at the distal end of the invention.
FIG. 4 is an exploded perspective detail view of the connecting device at the proximal end of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In a preferred embodiment, a foot elevator 10 of the present invention includes an upper peripheral frame 12, a cradle or hammock 14, a base peripheral frame 16 and a blanket support frame 18 (FIG. 1). Upper frame 12 and base frame 16 are releasably connected at the proximal and distal ends of foot elevator 10 by releasable connector mechanisms 20a and 20b. At the distal end of foot elevator 10, blanket support 18 releasably engages connecting mechanism 20b.
Base frame 16 comprises two frame members 22a and 22b and two connector disks 24a and 24b (FIG. 2). Each frame member 22 has a linear midportion 26, a pair of legs 28a and 28a, a pair of lateral portions 30a and 30b and terminal ends 32a and 32b. Each frame member 22 is preferably bent from approximately 0.187 inch (4.75 mm) diameter stainless steel wire. Legs 28 extend generally upwardly and inwardly, toward each other, from the ends of midportion 26. Legs 28 and midportion 26 lie substantially within a generally vertical reference plane. An approximately forty-five degree angle is defined between midportion 26 and each leg 28a and 28b. Lateral portions 30 extend generally horizontally and perpendicularly from legs 28. Terminal ends 32 extend approximately forty-five degrees upwardly and outwardly, away from midportion 26 at the end of lateral portions 30 and connect with connector disks 24.
Upper peripheral frame 12 is quite similar to base frame 16, having frame members 36a and 36b and connector disks 38a and 38b (FIG. 2). As with frame members 22 frame members 36 have a linear midportion 40, a pair of legs 42a and 42b, a pair of lateral portions 44a and 44b and terminal ends 46a and 46b. Each frame member 36 is also preferably bent from approximately 0.187 inch (4.75 mm) diameter stainless steel wire. Legs 42 extend generally downwardly and inwardly, toward each other, from each end of midportion 40. Legs 42 and midportion 40 lie substantially within a generally vertical reference plane. An approximately forty-five degree angle is defined between midportion 40 and each leg 42a and 42b. Lateral portions 44 extend generally horizontally and perpendicularly from legs 42. Terminal ends 46 extend approximately forty-five degrees outwardly and downwardly, away from midportion 40, from the end of lateral portions 44 and connect with connector disks 38. For manufacturing simplicity, each frame member 22 and 36 is preferably identical.
Blanket support 18 comprises a generally semicircular midportion 48, legs 50a and 50b, lateral portions 52a and 52b, terminal ends 54a and 54b and connector disk 56 (FIG. 2). Semicircular midportion 48 lies generally horizontally with legs 50 descending generally vertically from each end of midportion 48. Lateral portions 52 extend generally horizontally and perpendicularly toward each other from the lower end of legs 50. Terminal ends 54 extend approximately forty-five degrees downwardly and toward each other from the ends of lateral portions 52 and connect with connector disk 56.
Releasable connectors 20a and 20b comprise connector disks 24a and 24b, connector disks 38a and 38b, indexing pins 58a and 58b and handscrews 60a and 60b (FIGS. 3 and 4). Each disk 24 and 38 is preferably aluminum, approximately 1.375 inch (34.9 mm) in diameter and 0.25 inch (6.35 mm) thick. Each disk 24 and 38 also has a threaded aperture 62 for receiving the threaded shaft 64 of handscrew 60. By reference to the positions on a clockface, disk 24 is also provided with an indexing pin aperture 66 at the 5:30 position for forcibly receiving pin 58 and has a pair of frame apertures 68 penetrating the edge 70 of disk 24 at the 4:30 and 7:30 clock positions. Terminal ends 32 of base frame 16 are forcibly fit into frame apertures 68 (FIG. 2).
Disk 38 has an indexing pin aperture 72 at the 5:30 position (FIGS. 3 and 4). However, aperture 72 is sized for a slip fit with pin 58. Disk 38 also has a pair of frame apertures 74 at the 10:30 and 1:30 clock positions which penetrate the edge 76 of disk 38. Terminal ends 46 of upper frame 12 are forcibly fit into frame apertures 74 (FIG. 2).
Connector disk 56 is identical to disk 38 having an indexing pin aperture 78 for slip fit engagement with pin 58, a threaded aperture 80 for receiving threaded shaft 64 of handscrew 60 and a pair of frame apertures 82, positioned at the 10:30 and 1:30 clock positions and penetrating the edge 84 of disk 56 (FIG. 3). Terminal ends 54 of support frame 18 are forcibly fit into frame apertures 82 (FIG. 2).
Cradle 14 is constructed from a flexible material, preferably a knit-cotton blend as is commonly found in athletic socks and the like (FIG. 1). Cradle 14 is fabricated in a sock-like fashion to form a fabric tube with two open ends. The resulting "sock" is simply slid over upper frame 12 in a sock-like manner to assemble cradle 14 to upper frame 12 at midportion 40 of members 36. The "sock" breathes freely and allows free air circulation to the body part which is in contact with the "sock."
In use, upper frame 12 and base frame 16 are assembled as indicated in FIG. 2. Support frame 18 might or might not be included, depending upon the specific indications for treatment. Indexing pins 58 of disks 24 are aligned with pin apertures 72 of disks 38 and pin aperture 78 of disk 56, if support frame 18 is included (FIG. 3). Threaded shafts 64 of handscrews 60 are screwed into threaded apertures 62 and 80 to securely fasten frames 12, 16 and 18 together (FIGS. 1, 2, 3, and 4).
Foot elevator 10 can easily be cleaned and sanitized by removing cradle 14 from upper frame 12. Cradle 14 may be easily laundered or replaced and each frame 12, 16 and 18 and connector 20 can be sanitized using standard methods.
The above description is considered that of the preferred embodiment only. Modifications of the invention will occur to those who make or use the invention. Therefore, it is understood that the embodiment shown in the drawings and described above is merely for illustrative purposes and is not intended to limit the scope of the invention which is defined by the following claims as interpreted according to the principals of patent law. | A foot elevator having a peripheral wire base frame releasably connected with a peripheral wire upper frame. A peripheral wire blanket support frame releasably connectable to the base and upper frames is also provided. The base frame, the upper frame and the blanket support are releasably connected for disassembly and compact storage of the device. A cradle of flexible material is provided over a portion of the upper frame for support of a patient's lower limb. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to Japanese Patent Application No. 2011-272131 filed on Dec. 13, 2011. The entire disclosure of Japanese Patent Application No. 2011-272131 is hereby incorporated herein by reference.
BACKGROUND
[0002] 1. Technical Field
[0003] The present invention relates to a living body testing probe that conducts a test by contacting a living body.
[0004] 2. Related Art
[0005] As a living body testing probe for testing the inside of a living body, there are an ultrasonic probe in which a test is conducted by using reflection of ultrasonic waves inside a living body, a probe for testing a pulse wave in which a test of a pulse wave is conducted by using reflection of infrared light inside a living body, and the like. Among these living body testing probes, for example, in the ultrasonic probe, an ultrasonic element, an ultrasonic lens section, or the like is disposed in a living body contact part of the probe main body, and the test conditions in the ultrasonic probe are changed in a main testing device connected to the ultrasonic probe with a wire or wirelessly. For example, conventional living body testing probes are disclosed in Japanese Laid-Open Patent Publication No. 2011-72467 and Japanese Laid-Open Patent Publication No. 2003-164450.
SUMMARY
[0006] The conventional living body testing probes described in the above mentioned publications, however, have a disadvantage that the main testing device needs to be operated with one hand to change the test conditions while operating the living body testing probe with the other hand. Accordingly, if a dial switch, a lever switch, or the like for changing the test conditions is provided in the living body testing probe itself, the usability will be improved. However, since the living body testing probe needs to be cleaned frequently due to its nature, providing a mechanical switch such as a dial switch or a lever switch for changing the test conditions causes a problem that a space or opening created in a movable portion of the mechanical switch is difficult to clean, and water and the like used for cleaning enters the inside of the living body testing probe from the space or opening in the movable portion to the mechanical switch, which easily results in occurrence of a defect.
[0007] In terms of the above-described circumstances, an object of the present invention is to provide a living body testing probe suitable for cleaning in which the test conditions are easily changed.
[0008] In order to achieve the above-described object, a living body testing probe according to one aspect of the present invention includes a living body contact part, a grip part, a non-mechanical switch part and a notification part. The living body contact part is configured and arranged to contact a living body. The non-mechanical switch part is configured and arranged to receive an operation input for changing test conditions upon being touched or approached. The notification part is configured and arranged to output information indicative of a change in the test conditions based on the operation input received by the non-mechanical switch part.
[0009] According to the above described aspect of the present invention, since the non-mechanical switch part is provided in the living body testing probe itself, changing the test conditions can easily be conducted in the living body testing probe. Further, since the non-mechanical switch that receives operation input for changing test conditions upon being touched or approached is used as the switch, opening and the like will not be easily formed unlike in the case of using a mechanical switch. Therefore, a portion difficult to clean will not easily occur, and a situation in which water and the like used for cleaning enters the inside of the living body testing probe from the space can be avoided. Consequently, a living body testing probe suitable for cleaning in which the test conditions are easily changed can be achieved.
[0010] The living body testing probe preferably further includes a display part configured and arranged to display at least the test conditions. With this configuration, the usability of the living body testing probe is improved because the operation for changing the test conditions and confirmation of the test conditions can be conducted in the living body testing probe.
[0011] In the living body testing probe, the display part preferably serves as the non-mechanical switch part. Specifically, by using the display part as a touch panel (non-mechanical switch), the size of the living body testing probe can be reduced compared to a case in which the switch is provided separately from the display part.
[0012] In the living body testing probe, the notification part preferably includes a signal output section configured and arranged to output an operation signal via a wire. With this configuration, the living body testing probe may be connected to a main testing device via the wire, and the test conditions may be changed in the main testing device. Accordingly, since the living body testing probe does not need to have a drive circuit and the like necessary for driving in the living body testing probe, the size of the living body testing probe can be reduced.
[0013] In the living body testing probe, the non-mechanical switch part is preferably an optical switch. With this configuration, liquid-tight properties of the switch can easily be achieved.
[0014] The optical switch is preferably an infrared switch configured and arranged to be operated by light emission and light reception of infrared light. This configuration has an advantage that outside light will not easily affect an operation with the switch.
[0015] In the living body testing probe, the non-mechanical switch part is preferably provided in a protruded area protruding with respect to a region surrounding the non-mechanical switch part, or in a recessed area recessed with respect to the region surrounding the non-mechanical switch part. With this configuration, the position of the non-mechanical switch can easily be sensed by touch.
[0016] The living body testing probe according to the above described aspect of the present invention may be configured as an ultrasonic probe, for example. In such a case, the living body contact part is configured and arranged to generate and receive ultrasonic waves, for example. In the case of the ultrasonic probe, since the living body contact part is caused to contact a surface of a living body with application of gel, the ultrasonic probe is frequently cleaned. Therefore, the effect of the present invention configured to be suitable for cleaning becomes significant.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Referring now to the attached drawings which form a part of this original disclosure:
[0018] FIG. 1 is a simplified perspective view of an ultrasonic probe according to a first embodiment of the present invention.
[0019] FIG. 2 is a simplified perspective view of a testing device provided with an ultrasonic probe according to a second embodiment of the present invention.
[0020] FIGS. 3A and 3B are simplified top plan view and side elevational view the ultrasonic probe according to the second embodiment of the present invention.
[0021] FIGS. 4A and 4B are explanatory diagrams of an optical position detection device used as a switch in the ultrasonic probe according to the second embodiment of the present invention.
[0022] FIG. 5 is a simplified perspective view of a switch provided in the ultrasonic probe according to a modification example of the second embodiment of the present invention.
[0023] FIG. 6 is a simplified perspective view of an ultrasonic probe according to a third embodiment of the present invention.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0024] Next, embodiments of the present invention will be explained in detail with reference to the attached drawings. In the following explanations, an ultrasonic probe that tests (examines) a state inside a living body with ultrasonic waves will be described as an example of a living body testing probe.
First Embodiment
Overall Configuration
[0025] FIG. 1 is a simplified perspective view of an ultrasonic probe 1 A according to a first embodiment of the present invention. In the ultrasonic probe 1 A shown in FIG. 1 , a probe main body 20 has a generally flattened shape. The probe main body 20 has a living body contact part 21 for contacting the living body at the tip end thereof, and the rest of the probe main body 20 is used as a grip part 23 . The tip end of the living body contact part 21 is curved in an arc shape as shown in FIG. 1 . An ultrasonic transducer 24 , an acoustic lens (not shown in the drawings), and the like are embedded in the living body contact part 21 . The ultrasonic transducer 24 is provided with a plurality of elements configured such that an electrode is formed on both surfaces of a thick film of a piezoelectric body such as PZT (piezoelectric zirconate titanate) or polyvinylidene fluoride. When exciting pulses are applied to both the electrodes of this element, the piezoelectric body is caused to oscillate and generate ultrasonic waves, so that the inside of the living body is irradiated with the ultrasonic waves. When the ultrasonic transducer 24 receives reflected waves from the inside of the living body, the piezoelectric body is caused to oscillate and generate an electric signal, and this electric signal is converted into an ultrasound image.
[0026] In the present embodiment, a drive part 26 and a power supply part 27 are provided in the inside of the probe main body 20 . A monitor 4 (one example of a display part) constructed of a liquid crystal display device is provided in the grip part 23 in a completely liquid-tight state. The drive part 26 drives the ultrasonic transducer 24 . The drive part 26 also converts an electrical signal obtained via the ultrasonic transducer 24 into an ultrasound image (ultrasound image), and outputs it to the monitor 4 . The ultrasound image obtained by the ultrasonic probe 1 A is, therefore, displayed on the monitor 4 . In the present embodiment, the monitor 4 is provided in a recessed region that is recessed slightly with respect to the surrounding regions in the outer circumferential surface of the probe main body 20 .
[0027] In the ultrasonic probe 1 A with the above-described configuration, a power supply switch 29 is provided on a side surface of the probe main body 20 . The power supply switch 29 is a non-mechanical switch that uses a piezoelectric element, and is configured in a completely liquid-tight state.
[0028] Further, the ultrasonic probe 1 A has a switch 5 (one example of a non-mechanical switch part) for changing test conditions provided in the probe main body 20 . The ultrasonic probe 1 A also has a notification part 28 that outputs information indicative of a change in the test conditions to the drive part 26 based on an operation in the switch 5 . Examples of the test conditions include the intensity of ultrasonic waves, the scan mode (e.g., size of the scanning region, transmission frequency, focus depth, switching between different image modes such as B-mode and Doppler mode), and the like.
[0029] In the present embodiment, the switch 5 is a non-mechanical switch constructed of a resistive touch panel, a capacitance touch panel, or an optical touch panel, that is formed integrally with the monitor 4 . The resistive touch panel, the capacitance touch panel, and the optical touch panel are conventional components that are well known in the art. Since these non-mechanical switches are well known in the art, these structures will not be discussed or illustrated in detail herein. Rather, it will be apparent to those skilled in the art from this disclosure that the components can be any type of structure and/or programming that can be used to carry out the present invention.
[0030] A menu switching button for switching the display into the settings of the test conditions is displayed on the monitor 4 as well as the ultrasound image obtained by the ultrasonic probe 1 A. When a fingertip contacts or approaches the menu switching button, test condition selecting buttons are displayed. When a fingertip contacts or approaches a certain button among the test condition selecting buttons, the notification part 28 converts the results of selecting operation of the test conditions into a signal, and sends the signal to the drive part 26 . As a result, the drive part 26 controls operation of the ultrasonic transducer, such as the output of ultrasonic waves from the ultrasonic transducer 24 , according to the change in the test conditions. Accordingly, the optimum test conditions can be achieved depending on which part of the inside of a living body is tested. After the test conditions are changed in this manner, when a fingertip contacts or approaches the menu switching button, the display on the monitor 4 is switched into the display of an ultrasound image.
Effects of Present Embodiment
[0031] As explained above, in the ultrasonic probe 1 A of the present embodiment, since the living body testing probe itself has the switch 5 , the test conditions can easily be changed in the ultrasonic probe 1 A. Also, since a touch panel (non-mechanical switch) in which an operation for changing test conditions is conducted by contact or proximity is used as the switch 5 , a space and the like will not easily occur unlike in the case of using a mechanical switch that has a movable section. Therefore, a portion difficult to clean will not easily occur, and a situation in which water and the like used for cleaning enters the inside of the ultrasonic probe 1 A from the space can be avoided. Consequently, the present embodiment can achieve the ultrasonic probe 1 A suitable for cleaning in which the test conditions are easily changed.
[0032] In the ultrasonic probe 1 A of the present embodiment, the monitor 4 that displays at least the test conditions is provided. Consequently, the usability of the ultrasonic probe 1 A is improved because the operation for changing the test conditions and confirmation of the test conditions can be conducted in the ultrasonic probe 1 A.
[0033] Further, since the monitor 4 also serves as the non-mechanical switch 5 for changing test conditions, the size of the ultrasonic probe 1 A can be reduced compared to a case in which the switch 5 is provided separately from the monitor 4 .
[0034] Further, the monitor 4 (switch 5 ) is configured to be in a recessed region that is recessed slightly with respect to the surrounding regions in the outer circumferential surface of the probe main body 20 . Therefore, the position of the switch 5 can easily be sensed by touch.
[0035] In particular, in the case of the ultrasonic probe 1 A among living body testing probes, since the living body contact part 21 is caused to contact a surface of a living body with application of gel, the ultrasonic probe 1 A is frequently cleaned. Therefore, the effect of the ultrasonic probe 1 A according to the present embodiment configured to be suitable for cleaning becomes significant.
Second Embodiment
[0036] Referring now to FIGS. 2 to 5 , a living body testing probe in accordance with a second embodiment will now be explained. Since the basic configuration of the present embodiment is similar to that of the first embodiment, the components of the present embodiment that are identical or similar to the components of the first embodiment are indicated with a single prime (′). Moreover, in view of the similarity between the first and second embodiments, the descriptions of the parts of the second embodiment that are similar to the parts of the first embodiment may be omitted for the sake of brevity.
Overall Configuration
[0037] FIG. 2 is a simplified perspective view of a testing device provided with an ultrasonic probe 1 B according to a second embodiment of the present invention. FIGS. 3A and 3B are enlarged views of the ultrasonic probe 1 B according to the second embodiment of the present invention. Specifically, FIG. 3A is a top plan view of the ultrasonic probe 1 B, and FIG. 3 b is a side view of the ultrasonic probe 1 B.
[0038] In the first embodiment explained above, the drive circuit 26 and the monitor 4 are provided in the ultrasonic probe 1 A itself. In the present embodiment, however, an ultrasonic probe 1 B is connected to a main testing device 60 provided with a monitor 61 and the like via a cable 50 , as shown in a testing device 100 of FIG. 2 . The main testing device 60 is also provided with a drive part 66 and a power supply part 67 for the ultrasonic probe 1 B as well as the monitor 61 . Power feeding to the ultrasonic probe 1 B and driving the ultrasonic probe 1 B are conducted from the main testing device 60 by the cable 50 . Also, an electrical signal obtained in the ultrasonic probe 1 B is output to the main testing device 60 via the cable 50 , and an ultrasound image is displayed on the monitor 61 of the main testing device 60 .
[0039] In the present embodiment, similarly to the first embodiment, the ultrasonic probe 1 B has a switch 10 for easily changing test conditions, and the ultrasonic probe 1 B also has the notification part 28 ′ that output information indicative of a change in the test conditions based on an operation to the switch 10 .
[0040] More specifically, as shown in FIGS. 3A and 3B , in the ultrasonic probe 1 B of the present embodiment, the probe main body 20 ′ has a generally rod shape as a whole, and the probe main body 20 ′ has the living body contact part 21 ′ at the tip end thereof. The rest of the probe main body 20 ′ other than the living body contact part 21 ′ is used as the grip part 23 ′. The living body contact part 21 ′ is configured to be in a bulging area that bulges in a hemispherical shape as shown in FIG. 3A , and the ultrasonic transducer 24 ′, an acoustic lens (not shown in the drawings), and the like are embedded in the inside of the living body contact part 21 ′.
[0041] In the probe main body 20 ′, the switch 10 for changing test conditions such as the intensity of ultrasonic waves is provided in the grip part 23 ′, and the notification part 28 ′ that outputs information indicative of a change in the test conditions based on an operation in the switch 10 to the drive part 66 of the main testing device 60 by the cable 50 is provided in an end portion of the grip part 23 ′ on the opposite side of the living body contact part 21 ′. In the present embodiment, the notification part 28 ′ is a signal output section that outputs an operation signal in the switch 10 to the main testing device 60 via the cable 50 (one example of a wire). The notification part 28 ′ also has a function of sending an electrical signal obtained in the ultrasonic transducer 24 ′ to the drive part 66 of the main testing device 60 by the cable 50 .
[0042] Here, the switch 10 is an optical switch for changing test conditions based on a contact position or a proximity position of a fingertip, and such an optical switch is a type of a non-mechanical switch that does not have a movable portion. Various kinds of conventional non-mechanical switches can be used as the switch 10 . In the present embodiment, for example, the optical position detection device disclosed in Japanese Laid-open Patent Publication No. 2011-232191 and the like can be used.
Configuration of Switch 10
[0043] FIGS. 4A and 4B are explanatory diagrams of an optical position detection device used as the switch 10 in the ultrasonic probe 1 B according to the second embodiment of the present invention. Specifically, FIG. 4A is an explanatory diagram showing an overall configuration of the optical position detection device, and FIG. 4B is an explanatory diagram showing a positional relationship of a light source section and the like.
[0044] As shown in FIGS. 4A and 4B , the optical position detection device used as the switch 10 in the ultrasonic probe 1 B of the present embodiment has a translucent member 40 , a light source device 11 , a light receiving section 30 , and the like. More specifically, the light source device 11 of the switch 10 has a plurality of light source sections 12 that emit detection light L 2 toward a side Z 1 of a Z axis direction, and the light receiving section 30 of the switch 10 detects detection light L 3 reflected on a target object Ob such as a fingertip. In the switch 10 , the light source sections 12 emit the detection light L 2 from a rear surface 42 side of the translucent member 40 to a front surface 41 side of the translucent member 40 , and the light receiving section 30 detects the detection light L 3 reflected on the target object Ob and transmitted toward the rear surface 42 side of the translucent member 40 . For this purpose, a light receiving surface 31 of the light receiving section 30 faces the rear surface 42 of the translucent member 40 .
[0045] The light source device 11 has a first light source section 12 A, a second light source section 12 B, a third light source section 12 C, and a fourth light source section 12 D as the plurality of light source sections 12 on the rear surface 42 side of the translucent member 40 . These light source sections 12 have light emitting sections 120 a - 120 d directed toward the translucent member 40 , respectively. The detection light L 2 (detection light L 2 a -L 2 d ) emitted from the light source sections 12 is transmitted through the translucent member 40 and exits toward the visible front surface 41 side (detection light exit space of the detection light L 2 from the light source device 11 ). In the present embodiment, this detection light exit space (space on the visible front surface 41 side) forms a detection space in which the position of the target object Ob is detected.
[0046] The first light source section 12 A, the second light source section 12 B, the third light source section 12 C, and the fourth light source section 12 D are arranged in positions that correspond to corners of a rectangle respectively when seen from the detection space (Z axis direction). Each of the light source sections 12 (the first light source section 12 A, the second light source section 12 B, the third light source section 12 C, and the fourth light source section 12 D) is constructed of a light emitting element such as an LED (light emitting diode). In the present embodiment, each of the light source sections 12 emits the detection light L 2 (detection light L 2 a -L 2 d ) composed of infrared light whose peak wavelength is located in 840-1000 nm as diverging light. In the present embodiment, since the target object Ob is often a fingertip, infrared light (near infrared light of around 840-920 nm) having a wavelength range in which reflectivity with respect to the target object Ob (human body) is high is used as the detection light L 2 .
[0047] The light receiving section 30 is a photo diode, a photo transistor, or the like, in which the light receiving surface 31 faces the translucent member 40 . In the present embodiment, the light receiving section 30 is a photo diode that has a sensitivity peak in an infrared region.
[0048] In the switch 10 , the position of the target object Ob (fingertip) in the detection space is detected based on the light receiving results in the light receiving section 30 when the plurality of the light source sections 12 are sequentially lighted up. For example, based on the light receiving results in the light receiving section 30 when two of the light source sections 12 spaced apart in an X direction are sequentially lighted up, the ratio of the distance between one of the two light source sections 12 and the target object Ob and the distance between the other of the two light source sections 12 and the target object Ob is obtained. Also, based on the light receiving results in the light receiving section 30 when two of the light source sections 12 spaced apart in a Y direction are sequentially lighted up, the ratio of the distance between one of the two light source sections 12 and the target object Ob and the distance between the other of the two light source sections 12 and the target object Ob is obtained. Then, the X-Y coordinate position of the target object Ob is detected by combining the above results. Further, if a temporal change in the position of the target object Ob is detected, the movement of the target object Ob (movement of fingertip) as shown by arrows 15 of FIG. 3A can be detected. In the present embodiment, therefore, the position or movement of the target object Ob is related to the test conditions, and the test conditions are changed depending on a position of a fingertip in the switch 10 or depending on a movement direction of a fingertip.
[0049] In a case where the light receiving intensity in the light receiving section 30 is equal to or less than a predetermined value, it may be configured to determine that there is no operation for changing test conditions because a fingertip is away from the switch 10 . Consequently, an erroneous operation can be prevented.
Effects of Present Embodiment
[0050] As explained above, similarly to the above-described first embodiment, the ultrasonic probe 1 B of the present embodiment has the switch 10 provided in the living body testing probe itself. Thus, the test conditions can easily be changed in the ultrasonic probe 1 B. Also, since an optical position detection device (non-mechanical switch) in which an operation for changing test conditions is conducted by contact or proximity is used as the switch 10 , a space or opening will not easily formed in the ultrasonic probe 1 B unlike in the case of using a mechanical switch that has a movable section. Therefore, a portion difficult to clean will not easily occur, and a situation in which water and the like used for cleaning enters the inside of the ultrasonic probe 1 B from the space can be avoided. Consequently, the present embodiment has a similar effect as the first embodiment, and the ultrasonic probe 113 suitable for cleaning in which the test conditions are easily changed can be achieved, for example.
[0051] In the present invention, since the notification part 28 ′ is a signal output section that outputs an operation signal via the cable 50 , the test conditions can be changed from the main testing device 60 by the cable 50 . Accordingly, since the ultrasonic probe 1 B does not need to have a circuit and the like necessary for driving in the ultrasonic probe 1 B, the size of the ultrasonic probe 1 B can be reduced.
[0052] Further, since the switch 10 is an optical switch, liquid-tight properties of the switch 10 can easily be achieved. Furthermore, since the optical switch 10 is an infrared switch that uses light emission and light reception of infrared light, it has an advantage that outside light will not easily affect an operation with the switch 10 .
Modification Example of Second Embodiment
[0053] FIG. 5 is an explanatory diagram of the switch 10 ′ provided in the ultrasonic probe 1 B according to a modification example of the second embodiment of the present invention.
[0054] The switch 10 explained in the second embodiment may be configured to be in the same plane as an outer circumferential surface of the probe main body 20 . In this modification example, the switch 10 ′ is configured such that the translucent member 40 ′ is protruded with respect to the outer circumferential surface of the probe main body 20 ′ as shown in FIG. 5 . With this configuration, since the switch 10 ′ can be configured to be a protruded section, the position of the switch 10 ′ can easily be sensed by touch.
[0055] When the planar view shape of the translucent member 40 ′ is a cross shape protruded in an operation direction as shown by arrows 15 ′, it has an advantage that the operation direction can be sensed by touch. Further, a shallow recessed section 49 may be formed in the center of the translucent member 40 ′ such that the recessed section 49 indicates a reference position.
[0056] Alternatively, the translucent member 40 may be formed to be recessed with respect to the outer circumferential surface of the probe main body 20 . With this configuration, since the switch 10 can be configured to be a recessed region, the position of the switch 10 can easily be sensed by touch.
Third Embodiment
[0057] Referring now to FIG. 6 , a living body testing probe in accordance with a third embodiment will now be explained. Since the basic configuration of the present embodiment is similar to that of the first or second embodiment, the components of the present embodiment that are identical or similar to the components of the first or second embodiment will be given the same reference numerals as the parts of the first or second embodiment. Moreover, in view of the similarity between the first, second and third embodiments, the descriptions of the parts of the third embodiment that are similar to the parts of the first or second embodiment may be omitted for the sake of brevity.
[0058] FIG. 6 is a simplified perspective view of an ultrasonic probe according to a third embodiment of the present invention.
[0059] In the second embodiment, the monitor 4 is not provided in the ultrasonic probe 1 B that is connected to the main testing device 60 by the cable 50 . In the present embodiment, however, as shown in FIG. 6 , an ultrasonic probe 1 C provided with the monitor 4 is connected to the main testing device 60 via the cable 50 . The other configurations are substantially similar to the first embodiment.
[0060] Unlike the first embodiment, the ultrasonic probe 1 C does not have the drive part 26 and the power supply part 67 . Therefore, the monitor 4 displays the test conditions as the monitor 4 is mainly used as the switch 5 (touch panel).
Other Embodiment
[0061] In the first embodiment, the ultrasonic probe 1 A itself serves as the testing device. In a case where it is difficult to see test results with the small monitor 4 , however, it may be configured such that test results obtained by the ultrasonic probe 1 A are output to the main testing device 60 shown in FIG. 2 with a wire or wirelessly.
[0062] Although an ultrasonic probe is described as an example of the living body testing probe in the above described first to third embodiments, the present invention can be applied to other types of a testing probe such as a probe for testing a pulse wave in which a test of a pulse wave is conducted by using reflection of infrared light inside a living body.
General Interpretation of Terms
[0063] In understanding the scope of the present invention, the term “comprising” and its derivatives, as used herein, are intended to be open ended terms that specify the presence of the stated features, elements, components, groups, integers, and/or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers and/or steps. The foregoing also applies to words having similar meanings such as the terms, “including”, “having” and their derivatives. Also, the terms “part,” “section,” “portion,” “member” or “element” when used in the singular can have the dual meaning of a single part or a plurality of parts. Finally, terms of degree such as “substantially”, “about” and “approximately” as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. For example, these terms can be construed as including a deviation of at least ±5% of the modified term if this deviation would not negate the meaning of the word it modifies.
[0064] While only selected embodiments have been chosen to illustrate the present invention, it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made herein without departing from the scope of the invention as defined in the appended claims. Furthermore, the foregoing descriptions of the embodiments according to the present invention are provided for illustration only, and not for the purpose of limiting the invention as defined by the appended claims and their equivalents. | A living body testing probe includes a living body contact part, a grip part, a non-mechanical switch part and a notification part. The living body contact part is configured and arranged to contact a living body. The non-mechanical switch part is configured and arranged to receive an operation input for changing test conditions upon being touched or approached. The notification part is configured and arranged to output information indicative of a change in the test conditions based on the operation input received by the non-mechanical switch part. | 0 |
BACKGROUND OF THE INVENTION
(a) Field of the Invention
This invention generally relates to a pillow system which allows the user to adjust the height, or thickness, of the pillow by folding the components of the pillow. More specifically, but not by way of limitation, to a pillow formed from several sections. Each section being adapted for folding over the other section to allow the user to adjust the thickness of the pillow.
(b) Discussion of Known Art
Widely available pillows typically consist of a rectangular fabric casing that has been filled with some sort of cushion material, such as soft foam, feathers, cotton bunting and the like. While these pillows have been widely accepted for many years, they leave many important problems unresolved. One important problem is brought on by the fact that a person is likely to change positions while sleeping, and the appropriate distance for the support of the head from the surface of the mattress or sleeping surface varies with the person's position. The failure to properly support the head relative to the mattress or sleeping surface while sleeping results in problems such as strained muscles, shoulder pain, headaches, etcetera, as well as other problems associated with insufficient support.
To achieve the needed rest and skeletal support it is essential that the person's head be supported in a proper position relative to the rest of the body. The head, neck and shoulder girdle needs to remain in a relatively neutral position in order to avoid problems such as headaches, neck and shoulder problems due to muscular/skeletal malalignment. Specifically, when lying on one's side, it is very important to ensure that the head remains in-line with the spine. Moreover, if a person is lying on his side, it is also important to support the head in a position that allows the neck to remain along a line that is substantially normal to a line between the person's shoulders. Deviations from this posture will lead to disturbed sleep patterns, as well as problems associated with skeleton and muscle interaction.
Similarly, when a person sleeps on his back, the head should be supported at a position that allows the person's head to be supported at slight angle to the horizontal and at a small distance from the plane of the person's body. Again, support that allows the individual's posture to vary from this ideal positioning can lead to chronic problems.
The need for proper support of the person's head relative to the body while sleeping has long been recognized. However, known pillows and support devices have not been able to solve the problems associated with proper support of the head while sleeping. An example of known devices is shown in U.S. Pat. No. 395,043 to Doremus, where a pillow and multi-pocket slip are taught. The multi-pocket slip of the Doremus device includes pockets that have been attached to one another along a common line, so that the pockets extend from one another in a generally radial manner. The Doremus device allows the user to vary the thickness or height of the pillow below the user's head, and thus may support the user's head at a desired position relative to the plane on which the body rests. However, the Doremus device suffers from several important limitations. One important limitation is that the radial arrangement of the pockets of the case or slip permits the stacking of a limited number of pillow components. As the number of pillows or components being stacked increases, the greater the tendency that the uppermost component or pillow will remain at an angle relative to the point where the pockets are joined and the plane of support of the body. Additionally, the cushions or individual pillows used with the Doremus device can be combined in arrangements that use adjacent compartments. Therefore, if the user wishes to modify the stack combination, he would have to remove the individual pillows from the slip and rearrange them so that the desired pillows will be housed in adjacent pockets of the slip.
Additionally, the configuration of the Doremus invention is further disadvantaged in that the fill of the individual sections is likely to shift with use of the pillow. Once the fill of a particular pillow has shifted, the user must either rearrange the fill by pounding on the areas where the fill has settled or add another pillow from radial arrangement. The former solution is very disturbing to the ability to obtain proper night's sleep, while the latter offers a limited solution in that the second pillow will collapse into the cavity in the lower pillow, and the shifting of material will then begin on the second pillow.
In the art of mats, or coverings for chaise loungers and the like, artisans have approached the problems associated with the need to vary the thickness of a cushion has by attaching the cushions in series. The attachment of cushions in series has been popular in area of mats and cushions for chaise loungers due to the fact that these cushions must be capable of covering a long lounger or acting as a small mattress type pad to provide support under the entire body. Unfortunately, however, these devices provide little guidance to the artisan on how to solve the problems associated with varying the support of the head relative to the body when varying the position of the body over a planar surface such as a bed. For example U.S. Pat. No. 2,834,970 to Nappe teaches a sealed pad that includes several cushions attached in series. The Nappe invention is particularly well suited for solving the problems associated with the permanent compaction of the mat and the absorption of moisture by the mat, but giving little clue to the ordinary artisan as to how to use a set of cushions attached in series to vary the support of a person's head relative to the body.
Another cushioned mat is taught in U.S. Pat. No. 3,323,151 to Lerman. The Lerman device includes several foam pads connected in series. The Lerman pads are joined and sealed by means of a skin formed from the foam material by means of heated dies. Like the Nappe device, the Lerman device is particularly well suited for functioning as a seat cushion or a body support mat. However, the problems associated with the support of the head while sleeping are not addressed. This is probably due to the fact the field of mats or chaise cushions does not deal with the problems faced in the art of pillows, which involve orthotic considerations which are not necessarily dealt with in the field of mats or chaise cushions.
Still another known device is taught in U.S. Pat. No. 3,336,610 to Geddings. The Geddings device is yet another flat mat constructed of sections joined in series. The construction of the Geddings device is similar to the construction of the device taught in U.S. Pat. No. 5,491,851 to Alonso or U.S. Pat. No. 5,066,001 to Wilkinson. These devices are suitable for serving as mats for exercise or as cushions for chaises or the like, but, again, offer little guidance in solving the orthotic problems associated with supporting the head relative to the body during rest.
Still another device that uses cushions in series is taught in U.S. Pat. No. 4,606,087 to Alivizatos. The Alivizatos device includes several pockets that accept bead filled cushions. A significant feature of the Alivizatos device is that it combines the function of an infant support device with the functions of a carrying bag. The Alivizatos device, however, does not address the problems associated with providing proper support for the head while sleeping.
Thus, a review of known devices reveals that there remains a need for a pillow that allows variation of height of the support for the user's head relative to his body. Importantly, there remains a need for an adjustable pillow that allows the user to vary the height at which the head is supported relative to the user's body without having to dismantle the device during the night.
Still further, there remains a need for a stable pillow that allow for proper support and accommodates the natural contours of the user's anatomy to prevent muscolo/skeletal problems.
Importantly, known devices have not addressed the need for an orthotic pillow that provides proper orthopedic support and maintains alignment of the user's head, neck, and upper body shoulder and spine relationship.
SUMMARY
It has been discovered that the problems left unanswered by known art can be solved by providing a pillow system that includes the following elements:
a) a flexible support for holding a plurality of cushions in series; and
b) a plurality of pillow cushions having a body and a recessed area for receiving the user's head/ear.
A preferred embodiment of the invention the body of each pillow cushion includes a perimeter of sufficient structural rigidity so as to allow the formation of a stack of cushions. The center portion of these cushions, however, include a recessed area. Additionally, in a preferred embodiment of the invention, the mid portion of the cushions will be of a smaller cross-sectional area than the ends of the pillow cushions. It has been discovered that this configuration allows stable stacking of the pillow cushions that allows the user to maintain stable support and alignment of the user's head, neck, and upper body shoulder and spine, especially when using soft, easily deformable materials for the area of the cushion which receives the head.
It is contemplated that the body of the pillow cushions may be made from foam or similar material. Alternatively, it is contemplated that the perimeter of the body of the pillow may be formed from relatively densely packed cushion material, such as densely packed feathers, batting, matting material, or other known soft, deformable materials.
It has been discovered that by providing a pillow system that provides cushions that accept and support the contours of the body, and allows stacking of the individual cushions, one may solve problems left unsolved by the known devices. For example, by providing a recess in the pillow cushion, the disclosed invention maintains proper alignment of the head relative to the neck, spine and shoulders. Additionally, by allowing stable stacking of the individual cushions one also supports the head at the proper orientation relative to the neck, spine and shoulders. Conventional pillows are typically uniformly filled with a soft, deformable material to form a roll or tube having a generally uniform cross-section with the thickest section of the pillow being at its center. The generally rounded shape of the conventional pillow does not lend itself to stacking.
The disclosed invention allows stacking and provides cushions with a contoured section at approximately the mid portion of the cushions. The contoured portion includes a recess in the surface of the cushion and most preferably it produces new and useful results in support and adjustability that could not be achieved with known devices. In particular, the disclosed invention produces new and useful results in the support of the head relative to the neck, spine and shoulders.
Thus it will be appreciated that the disclosed invention solves the problems with known pillows and cushions by providing stable adjustability of the thickness of the pillow's support.
It will also be appreciated that the disclosed invention includes a flexible support for holding a plurality of cushions, each cushion having a body and a recessed area for receiving the user's head/ear allows, the multiple pillow cushions being held in an easily adjustable format during sleep. The format being provided in large part by the structure of the pillow case and cooperating cushions which allow the user to vary the thickness of the stack quickly and with little effort. Thus the instant invention allows the user to vary the thickness of the stack in the middle of the night, without causing significant disturbance to the user's sleep.
Still further, it will be appreciated that the instant invention allows the use of stable pillow cushions while providing the comfort of soft fill pillows.
Still further, it will be appreciated that the disclosed pillow system allows the user to vary the thickness of the support and vary the configuration of the system to allow use of the system as a seat and back rest. Thus the disclosed invention achieves new, synergistic, results that are not achievable with known configurations.
It should be understood that the disclosed invention also includes a method for treating problems associated with improper support of the head relative to the spine and shoulder girdle. The method including providing an adjustable a series of stackable pillow cushion for supporting a user's head in a desired relationship to the user's body, each pillow cushion including a body with a pair of substantially parallel surfaces, one of the surfaces having a first recessed area and at least two areas of firm support. Then placing the areas of firm support generally opposite to one another and next to the recessed areas, and stacking at least two pillow cushions over one another with the areas of firm support aligned over one another to adjust the height of the support of the stack of cushions and the height of the support of the head relative to the spine and shoulder girdle.
It should also be understood that while the above and other advantages and results of the present invention will become apparent to those skilled in the art from the following detailed description and accompanying drawings, showing the contemplated novel construction, combinations and elements as herein described, and more particularly defined by the appended claims, it is understood that changes in the precise embodiments of the herein disclosed invention are meant to be included within the scope of the claims, except insofar as they may be precluded by the prior art.
DRAWINGS
The accompanying drawings illustrate preferred embodiments of the present invention according to the best mode presently devised for making and using the instant invention, and in which:
FIG. 1 is a perspective view of an embodiment of the invention, the view illustrating the acceptance of a pillow cushion in a pillow case used with the invention.
FIG. 2 illustrates the use of a stack of pillow cushions and the accommodation of the user's head within the recess of the uppermost cushion.
FIG. 3 is a plan view illustrating the shape of a preferred embodiment of the invention.
FIG. 4 is a side elevational view of the embodiment shown on FIG. 3.
FIG. 5 is an end elevational view of a section the embodiment shown on FIG. 3.
FIG. 5A illustrates the instant invention and the alignment of the spine and shoulder blade area of the user.
FIG. 6 illustrates the stack of two pillow cushions with the balance of the cushions held away from the user's head
FIG. 7 illustrates yet another stack arrangement.
FIG. 8 illustrates the use of the invention as a seat cushion or back support.
FIG. 9 is a view looking at portions of two sides of a pair of separated cushions to be stacked together. The view illustrates the double stitching of the preferred embodiment of the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
While the invention will be described and disclosed here in connection with certain preferred embodiments, the description is not intended to limit the invention to the specific embodiments shown and described here, but rather the invention is intended to cover all alternative embodiments and modifications that fall within the spirit and scope of the invention as defined by the claims included herein as well as any equivalents of the disclosed and claimed invention.
Turning now to FIG. 1, where a perspective view of an orthopedic pillow system 10 made in accordance with the principles taught herein has been illustrated. From FIG. 1 it can be understood that the a preferred embodiment of the invention includes a plurality of pillow cushions 12 and means for flexibly securing one pillow cushion 12 relative to another pillow cushion 12. In a preferred embodiment of the invention which has been shown on FIG. 1, the means for flexibly attaching one pillow cushion to another pillow cushion includes a case 14.
Referring now to FIGS. 2 through 6 it will be understood that a preferred embodiment of the invention includes pillow cushions 12 with a body 16 of a desired thickness 18. The body 16 includes a first end 19 and a second end 21, each having a pair of surfaces, preferably an upper surface 20 and a lower surface 22, which are generally parallel to one another. As can be understood from FIG. 2, when a person lays on his side, along a support plane 23, a large proportion of the person's upper body weight is supported through the person's shoulders. This is due to the fact that the shoulders are the most prominent portions of the body, and thus bear against the support plane 23. Unfortunately, however, as the person's shoulder's are supported, the head and neck are left free to dangle from the upper torso area. Known pillow configurations support the head and neck by simply taking up the space between the support plane 23 and the person's head. This solution has been found to be inadequate due to the fact that known pillows do not provide a stable adjustment of the pillow's thickness. Pillows filled with bulk loose materials such as feathers will allow shifting of the fill material, so that the height of the support will fall during the night, leading to a compression of the neck/shoulder relationship and all anatomic structures between. This compression in turn leads to problems such as headaches, neck and shoulder pain, and sleep disturbance.
As shown on FIG. 3, a highly preferred embodiment of the invention solves the problems discussed above by including a first recessed area 24 in at least one of the surfaces of the pillow cushion. The first recessed area 24 preferably begins from a perimeter portion 26 on at least one of the surfaces as shown on FIG. 5. The recessed area 24 should be of a size that allows acceptance of the ear to allow proper blood flow through the ear, while accommodating portions of the head, and achieving other functions described below.
It is important to note that important new and useful results have been achieved by including the recessed area 24. In particular, it has been discovered that the recessed area 24 enhances the pillow system's ability to receive and support the user's head/ear. The narrowed section 28 of the cushion 12 provides the proper distance from the user's shoulder to the user's ear to allow the ear to be accepted into the recessed area 24.
As can be clearly understood from FIG. 3, the shape of the recess area 24 is particularly well suited for receiving the user's head/ear. It is important to note that the recess area 24 plays an important role in providing a balance of providing a structure with the desired rigidity that results in the proper support for the head relative to the rest of the body, while providing an area which does not inhibit blood circulation to the ear or portions of the head being supported.
It has also been discovered that the incorporation of the areas of firm support 34 near the ends of the body 16 of the pillow cushions 12 allows the user to adjust the height of the support with greater precision and stability. Thus, the disclosed system allows replacement and mixing of the individual cushions to establish a desired thickness. Moreover, the use of separate cushions allow the user to change only worn or matted down cushions instead of the entire pillow.
Furthermore, as can be understood by referring to FIG. 5, by placing a second recessed area 30, the second recessed area 30 being on the lower surface 22 of the body 16, one establishes an unsupported region 32 between the perimeter edges 26 of the pillow cushion 12. By providing an unsupported region 32 below the recessed area 24 or 30 one effectively reduces the stiffness of the pillow below the recessed areas. The reduction of the stiffness, coupled with the slopes due to deflection of the cushion around the recessed areas will function to keep the user's head and ear positioned over the recessed areas.
Therefore, it is to be understood that the lack of stability of known pillows is another important problem solved by the instant invention. As has been shown on FIGS. 3 and 4, the pillow cushion 12 will preferably include at least two areas of firm support 34 next to the recessed area 24 or 30. The areas of firm support 34 allow the stacking of several pillow cushions 12 in a stable manner. Specifically, when stacking several pillow cushions 12 over one another, the areas of firm support 34 should be aligned with one another. This alignment will provide stability to the stack as well as provide a load path for the transfer of the weight of the user's head and ear and neck down to the mattress or support plane 23.
The cooperation between the case 14 and the pillow cushions 12 has been illustrated in FIGS. 6 through 9. In FIG. 6 the pillow system 10 is shown supporting the user's head while the user sleeps on his back. It should be noted that while the preferred embodiment uses a case 14 with a plurality of pockets 38 a side opening 51 and at least one sown side edge 53 to hold the pillow cushions 12 in series with one another, it is also contemplated that one may vary the preferred structure by adding flexible tabs 15, strips or chord, to join one pillow cushion 12 to the next, as shown on FIG. 3. For example, it is contemplated that each pillow cushion 12 may be formed from a housing, from which extend tabs with hook and loop material. These tabs may then be used to attach one pillow cushion 12 to the next, allowing the user to mix or link any desired combination of pillow cushions 12.
As shown on FIG. 9, a preferred embodiment of the invention includes a case 14 in which the sown side edge 53 preferably includes sections of double stitching 39. The sections of double stitching define a section of material that allows for pivoting of one cushion 12 over the next, thus providing a neat, easy folding, structure that avoids bunching of the fabric of the case. The sections of double stitching 39 are preferably placed between the individual pockets 38, thus allowing the placement of one cushion 12 over the next, as indicated by arrow 41, with little effort during the night.
It is important to note that it is contemplated that the disclosed system may be modified without departing from the spirit and scope of the invention. For example, it is contemplated that the body 16 may be made from any of a variety of known soft materials. Thus, while it is contemplated that the body may be formed from foam material, it is also contemplated that the body may be formed by joining several fill-packed baffles next to one another. This would ensure the high density of the fill material at the areas of firm support 34. Additionally, it is contemplated that the recessed area 24 may be formed by placing smaller baffles between the areas of firm support 34.
Still further, while the preferred embodiment of the pillow cushions will include a pair of recessed areas, it is contemplated that the pillow system 10 may include a mixture of pillow cushions, some cushions with one recessed area 24, others with a pair of recessed areas 24 and 30, and still others without recessed areas. These combinations of pillows would allow variation of the stiffness of the stack. The stiffness could be varied, for example, by providing a pillow cushion without a recessed area to support a pillow cushion that includes a recessed area. The pillow cushion with a recessed area 24 being placed over the pillow cushion without a recessed area. This configuration would allow the recessed area to deflect under the weight of the user's head, and then inhibit the further deflection of the recessed area as the recessed area of the upper pillow cushion contacts the lower pillow cushion, which does not have a recessed area.
Additionally, the firmness of a stack of pillow cushions 12 could be varied by simply incorporating a recessed area 24 on a single surface of the body of the pillow cushion 12. The use of a single recessed area 24 produces a thicker, stiffer unsupported area 32.
Still further, as illustrated in FIG. 7, it will be appreciated that the above embodiments allow use of the pillow system 10 as a cushioning device for a chair or the like. Clearly, by combining pillow cushions with the desired stiffness, one may also customize the support offered by the pillow system 10 when the system is used as a cushioning device over a chair or as a back and head support when using the pillow system to lean against the headboard of a bed.
Thus it can be appreciated that the above described embodiments are illustrative of just a few of the numerous variations of arrangements of the disclosed elements used to carry out the disclosed invention. Moreover, while the invention has been particularly shown, described and illustrated in detail with reference to preferred embodiments and modifications thereof, it should be understood by that the foregoing and other modifications are exemplary only, and that equivalent changes in form and detail may be made without departing from the true spirit and scope of the invention as claimed, except as precluded by the prior art. | An apparatus and method for treating problems associated with improper support of the head relative to the spine and shoulder girdle. The apparatus and method including providing an adjustable a series of stackable pillow cushion for supporting a user's head in a desired relationship to the user's body, each pillow cushion including a body with a pair of substantially parallel surfaces, one of the surfaces having a first recessed area and at least two areas of firm support. Then placing the areas of firm support generally opposite to one another and next to the recessed areas, and stacking at least two pillow cushions over one another with the areas of firm support aligned over one another to adjust the height of the support of the stack of cushions and the height of the support of the head relative to the spine and shoulder girdle. | 0 |
This application corresponds to the U.S. national phase of Patent Cooperation Treaty application No. US97/01754, filed Jan. 31, 1997 under 35 U.S.C. §371, which claims priority of U.S. patent application Ser. No. 08/595,277, filed Feb. 1, 1996 now abandoned, the entire contents of both of which are incorporated herein by reference.
FIELD OF THE INVENTION
This invention relates generally to arthroplasty and, more particularly to devices and techniques for positioning a prosthesis prior to fixation through the injection of a bonding agent.
BACKGROUND OF THE INVENTION
In current human joint repair situations, it is common practice to prepare host bone stock to receive an implant then, if satisfied with the physical correspondence, apply cement to the host, install the prosthesis, and stabilize the arrangement until curing. This approach has several disadvantages. Foremost among them arises from the unpredictable process of ensuring that, although the prosthesis may have been ideally placed prior to cementation, once the cement is applied, orientation may shift, resulting in a final configuration which is less than optimal.
A few approaches have been attempted to assist in making the positioning of the final implant more predictable. As discussed further in the detailed description herein, one such approach utilizes a centralizing plug inserted distally within the medullary canal, and from which there extends a rod upon which a final implant including a corresponding central bore may be monorailed. The plug and rod are positioned in conjunction with a trial which also includes a central bore, which is then removed, the intramedullary cavity filled with cement and the final implant slid over the rod, displacing the cement as it is pushed down into position. Although this technique may assist in maintaining a side-to-side orientation prior to cementation, it does not address the simultaneous need for up-and-down and/or rotational stabilization. Additionally, as with current techniques, cement is applied to the host prior to the introduction of the final implant, leaving open the possibility that the final implant may be held in a position different from that associated with the trial, and may therefore result in an unacceptable misplacement as the cement cures.
Other approaches do reverse this order, and install the final implant prior to the injection of cement. The known approaches, however, utilize a highly specialized prosthetic device including centralizing protrusions and internal channels through which the cement is introduced. That is, in these systems, the prosthesis itself is used as the cement injector. Due to their requirement for a highly specialized final prosthetic element, such systems are incompatible with currently available implant devices, and therefore raise costs while reducing the options of the practitioner. In addition, they do not adequately address the need for simultaneously stabilizing multiple degrees of freedom prior and during cementation. As a further disadvantage, the systems which use the prosthesis as the cement injector tend to use the cement as a grout between the outer surface of the implant and the inner surface of the receiving cavity. It has been shown, however, that the changes of success are improved through the creation of a thicker cement “mantle,” as opposed to a thin grout-type layer. The need remains, then, for a system whereby the prosthesis may be stabilized relative to multiple degrees of freedom prior to cementation, and, ideally, remain compatible with existing prosthetic components while forming a strong and stable bond to the host.
SUMMARY OF THE INVENTION
The present invention resides in apparatus and methods for maintaining the proper positioning of a prosthetic implant having proximal and distal ends within a prepared bone cavity during cement injection and curing. In contrast to prior-art systems the invention provides first stabilization means, implantable within the bone cavity, for minimizing lateral movement of the distal end of the implant, and second stabilization means, physically separate from the means for minimizing lateral movement of the distal end of the implant, for minimizing both the lateral movement of the proximal end of the implant and the rotational movement of the implant overall. In the preferred embodiment, the second stabilization means includes an apertured cap removably securable to the end of a bone having the prepared cavity through which the implant is inserted and held in place. This cap, which may either be entirely rigid or include a pliable membrane in the vicinity of the aperture, preferably further includes a first port associated with cement injection and a second port associated with cement over-pressurization. In an alternative embodiment, the second stabilization means includes a manually operated mechanism enabling the implant to be temporarily yet rigidly secured thereto in accordance with a desired orientation, preferably affording adjustments along multiple degrees of freedom prior to the rigid securement thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A illustrates, in skeletal form, the first step of a prior-art implantation sequence involving host bed preparation;
FIG. 1B depicts an intermediate step in the prior-art sequence wherein the cavity prepared according to FIG. 1A is filled with cement;
FIG. 1C illustrates the final phase of this prior-art sequence wherein a femoral prosthesis is inserted into the injected cement prior to hardening;
FIG. 2A illustrates a prior-art improvement over the sequence shown in FIGS. 1A through 1C, wherein a distal plug is used for distal centering of the implant;
FIG. 2B illustrates yet another prior-art improvement over the approach of FIG. 2A wherein a vertically oriented rod is attached to the distal plug over which an implant may be slid after cement injection to further inhibit movement during curing;
FIG. 3 is an arrangement according to this invention showing the use of a proximal cap which may be used either with a specially prepared prosthetic device or commercially available unit;
FIG. 4 illustrates two independently usable alternative embodiments according to the invention, including a multiple degree-of-freedom proximal retainment structure and a distal plug including leaf springs;
FIG. 5 is a drawing which shows, from an oblique perspective, an alternative embodiment of the invention which clamps around the femur below the area of resection, and attaches to an elongated fastener oriented generally lengthwise with respect to the implant;
FIG. 6 is a drawing which shows how the invention could be applied to a humeral prosthesis; and
FIG. 7 is a drawing which shows how the invention may be applied to knee arthroplasty.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 of U.S. Pat. No. 5,340,362 shows an existing, prior-art procedure for inserting and cementing a prosthesis into a bone cavity, and this figure has been reproduced herein. In accordance with this technique, the canal is reamed or broached as shown in FIG. 1A, and a trial is typically inserted thereinto to ensure that the final prosthetic component will be properly received. After this trialing, cement is injected into the excavated area as shown in FIG. 1B, and the prosthesis is inserted as shown in FIG. 1C, and left in position while the cement hardens. As discussed in the background of the instant invention, the technique just described is deficient in that, although the prosthesis may be optimally oriented during the trial procedure, the position of the actual implant may shift upon insertion into the cemented host or thereafter, resulting in a misaligned final fixation.
Various improvements also exist in the prior art to minimize such adjustment problems. At the very least, as shown in FIG. 6 of U.S. Pat. No. 4,994,085, reproduced herein as FIG. 2A, a distal centralizer 16 is inserted beforehand into the intramedullary cavity 13 to which the distal tip 17 a of the implant 17 engages at point 16 a . This, at least, stabilizes the relative position of the distal tip 17 a , resulting in a narrower range of angles (A to B) through which the implant 17 may move within the cement-filled cavity prior to final curing. The teachings of this reference further improve upon post-cementation stabilization by incorporating a stabilizing rod 4 into the distal plug 6 over which a specially designed implant 2 having a centralized hole 4 is slidably installed, as shown in FIG. 2B herein (FIG. 4 of the issued patent). Assuming the various connections between rod 5 , plug 6 and the inner walls of the intermedullary canal are relatively rigid, and the various tolerances involved are substantially tight, movement of the implant 2 is further restricted until the cement finally cures.
Another approach taken according to the prior art involves the injection of cement after positioning of a specially designed implant into a prepared cavity. The '362 patent referenced above is directed toward such an approach. As with other arrangements of type, the final implant includes a cement canal along its longitudinal axis. A bone-cement injector is threaded onto the proximal portion of this cement canal, causing the cement to subsequently travel down and through the implant, eventually exiting through openings in and around its distal tip. A restrictor plug halts downward cement travel, thus initiating an upward, retrograde filling of the void in between the prosthesis and the cancellous bone wall. In addition to a single distal aperture through which the injected cement is introduced, side ports may also be included, as shown in U.S. Pat. No. 4,274,163 and various other prior-art references.
The methods and associated apparatus just described exhibit various shortcomings. In the technique described with reference to FIG. 2B herein, although movements within the curing cement bed are further restricted, the point of substantial stability remains at the distal tip of the implant, enabling a certain level of proximal misalignment to continue, as no true proximal stabilization is provided. Worse, perhaps, is that since the centering rod and bore through the specialized component are both circular, the final implant is still subject to up-and-down and/or rotational variation, resulting in potential misalignment upon fixation.
With respect to the techniques wherein cement is injected after installation, although the implant may be stabilized both proximally and distally as the cement is injected, as with the device of the '085 patent, a specially designed implant including the injector ports must be utilized, resulting in a specialized unit demanding significantly higher cost. Furthermore, regardless of the existing system utilized, attention to the pressure of the cement during injection and curing has not been adequately addressed. Although, for example, the system described in the '163 patent referenced above utilizes various components to maintain pressurization, numerous sophisticated articles are required, including a high pressure nitrogen gas source, disposable cylinder and various associated valves and tubing which may be difficult to assemble, require skilled operators, or create expensive waste and maintenance problems.
The present invention improves upon the prior art by providing a simplified apparatus and associated installation methods whereby an implant may be oriented both proximally and distally prior to the injection of cement, while, at the same time, providing means for guarding against rotational and up/down movement of the implant as well during such injection and subsequent curing. In addition, configurations according to the invention provide a simple means for expelling over-pressurized cement, thereby yielding a simple, but satisfactory indication that sufficient cement has been injected to an acceptable level. Although, in one embodiment, the invention makes advantageous use of a longitudinal bore through the implant, in another embodiment, all of the above improvements and advantages are realized in conjunction with standard, currently available prostheses, thus resulting in an approach which is both straightforward and economical.
FIG. 3 is an oblique drawing of an arrangement according to this invention depicting various independent embodiments. Overall, an implant 310 is shown inserted into a prepared cavity 312 , in this case the implant 310 being a femoral hip prosthesis and the cavity 312 being the intramedullary canal, though, as will be apparent to those of skill in the art of orthopaedics, the general principles disclosed herein are not restricted to this application, and may be used in other joint situations, including the knee (FIG. 7 ), shoulder (FIG. 8) and other situations. Certain features of the femur are shown such as the greater trochanter 313 and lesser trochanter 315 , and it is assumed that a resection not visible in this figure has been performed on at least a portion of the proximal end of the femur along with reaming and other preparation of the medullary canal itself to accept the implant 310 .
Broadly, according to the invention, an apertured proximal sealing cap is installed over the resection portion of the femoral shaft, the prosthesis 310 is inserted through the proximal opening 320 of the seal, and cement is injected through an injection port 322 . In a preferred embodiment, this proximal seal includes a horseshoe-shaped collar 330 having one or more means such as thumb screws 332 for releasably securing the collar 330 over the bone, and a preferably pliable gasket 334 made from rubber or other suitable polymeric materials through which the aperture 320 is formed. Also located on and through this gasket 334 is a flap valve 336 wherein the material forming the gasket 334 is adjusted to flap open or rupture at a predetermined pressure level, preferably on the order of 25 mm of mercury, which has shown to be advantageous for such orthopaedic purposes. Preferably, this flap valve 336 is formed either by scoring the material of the gasket 334 in a manner conducive to such rupture, or, alternatively, the material may be thinned in this area to break under load.
The embodiment of the proximal seal just described is that preferred for use in conjunction with standard, commercially available implants. That is, the aperture 320 formed in the gasket 334 may take the form of a slit, an oval, or another shape appropriate to the stem of the implant, enabling the device to be inserted therethrough and retained in place by the surrounding material of the gasket 334 against the stem, either through friction or high-tolerance. Alternatively, then, if a more precise geometry of the stem at the point where it emerges through the proximal seal is known, the material 334 may be of a more rigid composition, and may, in fact, be integrally formed to the collar 330 , in which case the injection port 322 and valve 336 may be more elaborate and substantial. For example, if the area 334 is metal, the port 322 may be threaded for a more solid connection to commercially available injector nozzles, and the valve 336 may take advantage of more sophisticated pressure-release techniques available in the art, including adjustability for a particular pressure or range of pressures.
Whether the implant is of a standard configuration or specialized for use in conjunction with the invention, a distal spacer 340 is preferably utilized for distal centering. A longitudinal rod 342 may optionally be added to, or installed on the plug 340 , requiring a specialized implant having a longitudinal bore 344 akin to that described in the '085 patent referred to above, the exception being that, according to this invention, the implant 310 would be monorailed onto the optional rod 342 prior to the injection of cement into the cavity formed between the walls of the implant and the prepared medullary canal. Thus, as discussed above, the present invention may either be used with a specially prepared implant having this longitudinal bore and/or convenient wall geometries or, alternatively, and unlike the prior art, a standard prosthesis may be used.
In the event that the prosthesis includes an arrangement to assist in installation or removal such as ring 350 , the alternative proximal stabilization configuration of FIG. 4 may be used. To further assist in proximal securement, a multiple degree-of-freedom clamp arrangement illustrated generally at 404 may be attached to a proximal cover 406 secured to femoral end or attached to a portion of available bone material by whatever means. In the embodiment shown, a first rod 408 securely affixed to the member 406 at point 409 , onto which there is disposed a slidable collar 412 which may be locked into position with a suitable device such as thumb screw 414 . A second rod 420 and collar 422 contains two thumb screws, one to lock the collar 422 in position along rod 420 , and a different thumb screw 430 for positive engagement with the prosthesis proper. It will be understood to those of skill that various other approaches may be utilized in accordance with the general principle contained herein to grasp and hold any portion or aperture of a standard implant without requiring its modification.
FIG. 4 also shows an alternative distal plug according to the invention which may be used in combination with any of the embodiments previously described. With such an inventive plug, it is first seated distally at an appropriate distance within the intermedullary canal, and includes a plurality of deformable upwardly oriented leaf springs 490 . Accordingly, with the plug 480 installed in place as shown, an even more generalized type of implant, and not requiring an actual, solid connection to such a distal spacer, may be inserted down and into the medullary canal and held in place while resisting distal side-to-side motion as the distal tip of the implant is retained within these leaf springs 490 . This also allows adjustments in a longitudinal direction enabling fine tuning at the effective length of the implant. Note in FIG. 4 that the aperture through which the implant is inserted is quite a bit larger than that shown in FIG. 4 and, in fact, does not include a seal per se. This is due to the fact that, in accordance with this embodiment, cement may, in fact, be injected prior to or after the implant is held in place both proximally and distally. Indeed, according to this particular embodiment, a standard distal plug may be used in conjunction with the mechanism shown generally at 404 even without a cap or collar as shown. For example, this mechanism 404 may simply attach to an existing bone surface or structure instead of the point 409 , thereby holding the implant in place proximally and distally while preventing motion in all dimensions as the cement cures, regardless of when it was injected. In accordance with an alternative methodology, the proximal and distal stabilizers may be used in conjunction with a trial then, upon achieving a desired orientation, a single manual fastener may be loosened, and the actual implant installed in the exact configuration of the trial to guarantee proper positioning.
FIG. 5 illustrates an alternative embodiment of the invention, seen generally at 502 from an oblique perspective. In this case, a prosthesis 504 , which may have a threaded bore along an axis 508 to receive a threaded fastener such as a bolt 506 , is physically coupled to a first structural element 520 which slidably engages with a collar 530 , and which may be tightened in place with a manual fastener such as thumb screw 532 . Other types of fasteners, including those requiring tools such as set screws, may alternatively be utilized for this purpose. In this embodiment, the prosthesis 504 may be rotated about the axis 508 with the bolt 506 in a slightly loosened condition, and then tightened when a desired angular rotation is achieved. A score mark 522 may be used in conjunction with score marks 524 to provide an indication of this desired angular rotation for future reference. Preferably, score marks are provided on the underside of member 520 as well in the vicinity of the attachment to the prosthesis, to assist in maintaining the desired rotational configuration once the bolt 506 is tightened. Prosthetic devices having a threaded bore along axis 508 are available from the Zimmer Company, though in the event that such a feature is not provided for, connection may be made to the prosthetic element itself as disclosed elsewhere herein, rendering this threaded bore convenient but not necessary to the invention.
Preferably in this embodiment a set of score marks 526 are also provided on the member 520 , such that with the member 520 being moved back and forth to adjust the lateral or transverse positioning of the implant, the fastener 532 may be used to lock the configuration in place, with the marks 526 being used to maintain a visual indication of the desired lateral configuration. Attached to collar 530 is a downwardly extending member 540 , which is received by a collar 544 having a manual adjustment device 546 . The member 540 may also include markings 542 , such that, as the element 540 is moved up and down to adjust for the axial length of the prosthesis, fastener 546 may be locked with the score marks 542 providing a visual indication.
The collar 544 is attached to a clamp 550 , which is rigidly attached to the outer surface of the femur through manual fasteners 552 and 554 . As a further optional convenience, the collar 544 may be rotationally variable, and locked into place along with member 540 with manual fastener 546 , with optional score marks 560 being used as a visual indication of this configuration, if so desired.
Although the various embodiments of this invention may be used to properly position a trial implant prior to the positioning of a final prosthetic element, it should be apparent that in all cases, the device such as 504 in FIG. 5 is assumed to be the final implant itself, thereby eliminating the need for a trial. Particularly if the various positioning elements of the invention are sufficiently low in profile, the entire assembly, including those shown in the figures, joint reduction may be carried out, with the various fasteners being adjustably and rigidly clamped, with the final implant positioned in place and rigidly connected thereto. Following this procedure, the properly positioned implant may be removed from its reduced configuration and cemented. According to the invention, depending upon the circumstances, the prosthesis may be cemented in situ , with the various positioning members according to the invention remaining locked in place, or, alternatively, one or more of the fasteners may be loosened, with the implant and, perhaps, other fasteners attached thereto, removed and repositioned once cement has been injected into the intramedullary canal.
For example, referring to the embodiment of FIG. 5, fastener 546 may be slightly loosened, with the prosthesis 504 and members 520 and 540 rigidly attached thereto being temporarily removed, the cavity filled with cement, and the prosthesis with members 520 and 540 reinserted, with member 540 being reinstalled into collar 544 , utilizing the score marks 542 to ensure that fixation will take place at a proper and desired orientation upon re-tightening of the fastener 546 . It will also be apparent that in the embodiment of FIG. 5 and others disclosed herein, that if the assembly attached to the femur and to the prosthetic element through using one or more structural elements according to the invention is sufficiently rigid, positioning of the final implant may be stabilized in three dimensions (for example, rotationally, transversely, and axially—i.e., with respect to the coronal, sagittal and transverse planes). | Apparatus and method are disclosed for maintaining the proper positioning of an implant ( 310, 504 ) within a prepared bone cavity ( 312 ) during cement injection and curing. First stabilization means ( 340, 480 ), implantable within the bone cavity, minimize lateral movement of the implant distal end, while second stabilization means ( 330, 334, 406, 404 ), physically separate from the first stabilization means ( 340, 480 ), minimize both the lateral movement of the implant proximal end and the rotational movement of the implant overall. In the preferred embodiment, the second stabilization means ( 330, 334 ) includes an aperture cap ( 334 ) removable securable to the end of a prepared bone. This cap ( 334 ), preferably further includes first and second ports ( 322, 336 ) associated, respectively, with cement injection and cement over-pressurization. In an alterative embodiment, the second stabilization means ( 406, 404 ) includes a manually operated mechanism enabling ( 404 ) the implant ( 504 ) to be temporarily, yet rigidly, secured thereto in accordance with a desired orientation, preferably affording adjustments along multiple degrees of freedom prior to the rigid securement thereof. | 0 |
[0001] The subject matter described herein was created during the performance of a cooperative research and development agreement with the Department of the Air Force (Contract No. F33615-03-2308 P00002). Therefore, the government of the United States may have certain rights to the claimed subject matter.
BACKGROUND
[0002] The present application is directed to control systems and, more particularly, to adaptive control systems for electric brake systems and the like.
[0003] Electric brake systems have been developed for use in the automotive, aerospace and aeronautical industries to control the speed, stability and operation of various vehicles and devices. Electric brake systems, commonly referred to as brake-by-wire systems, have be used in combination with, or in place of, conventional hydraulic brake systems.
[0004] A typical electric brake system includes an electric motor adapted to advance a piston into engagement with brake pads and/or a rotor, thereby generating a braking force. The amount of braking force generated typically is a function of the distal advancement of the piston. Therefore, the braking force may be controlled by controlling the operation of the electric motor.
[0005] The braking force applied by an electric brake system typically is controlled by monitoring the force exerted by the piston and/or the position of the piston and controlling the electric motor based upon the force and/or position signals to achieve the desired braking result. The force may be monitored directly using force gauges or the like, thereby providing a direct indication of the braking force. The position of the piston may be monitored using various sensors such that the displacement of the piston may be converted into a force signal by, for example, modeling the brake system as a spring and multiplying the piston displacement by a spring constant.
[0006] Using the direct force signal may be advantageous because it is the command typically generated by the system level control software. However, the force signal typically has a high signal to noise ratio and therefore may require significant filtering, resulting in a slower response time and reduced performance. Therefore, it may be preferable to used the position signal for controlling the brake system.
[0007] Attempts have been made to determine the braking force based upon the piston position input using a static look-up table that estimates the force based upon the position input. However, such systems do not account for the dynamics within the brake unit and the inevitable wear of the components of the systems (e.g., the brake pads) and therefore may provide inaccurate results.
[0008] Accordingly, there is a need for an adaptive control system for controlling the braking force in an electric brake system based upon a piston position signal.
SUMMARY
[0009] In one aspect, a method for controlling an electric brake system having a piston moveable by an electric motor is provided and includes the steps of storing data for correlating a position of the piston to a braking force applied by the piston, estimating a braking force associated with a specific position of the piston based upon the stored data, generating a control signal based upon the estimated braking force, determining a second braking force associated with the specific position and updating the stored data based upon a difference between the estimated braking force and the second braking force
[0010] In another aspect, a method for controlling an electric brake system having a piston moveable by an electric motor is provided and includes the steps of storing a look-up table in a database, the look-up table including at least two data points correlating a position of the piston to a braking force applied by the piston, determining a specific position of the piston, estimating a braking force associated with the specific position of the piston based upon the data points stored in the look-up table, generating a control signal based upon the estimated braking force, determining a second braking force associated with the specific position and updating at least one of the data points in the look-up table based upon a difference between the estimated braking force and the second braking force.
[0011] In another aspect, a control system for an electric brake system is provided and includes a piston, an electric motor operatively connected to the piston, wherein rotation of the motor is translated into advancement of the piston, a controller in communication with the motor, the controller including data values adapted to correlate a position of the piston into an associated braking force, a position sensor for monitoring the position of the piston, the position sensor being adapted to generate a position signal and communicate the position signal to the controller and a second sensor adapted to determine a second braking force value and communicate the second braking force value to the controller, wherein the controller is adapted to determine a first braking force value based upon the position signal and the stored data and generate a control signal based upon the first braking force value, and wherein the controller is adapted to update the stored data based upon a difference between the first braking force and the second braking force.
[0012] Other aspects will become apparent from the following description, the accompanying drawings and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a schematic illustration of an electric brake system including an adaptive control system;
[0014] FIG. 2 is a block diagram of the electric brake system of FIG. 1 ;
[0015] FIG. 3 is a block diagram of one aspect of the adaptive control system of FIG. 1 ;
[0016] FIG. 4 is a graphical illustration of a membership function according to one aspect of the adaptive control system of FIG. 3 ;
[0017] FIG. 5 is a graphical illustration of a membership function according to a second aspect of the adaptive control system of FIG. 3 ; and
[0018] FIG. 6 is a graphical illustration of the operation of the adaptive control system of FIG. 3 .
DETAILED DESCRIPTION
[0019] As shown in FIG. 1 , an electric brake system, generally designated 10 , may include a caliper housing 12 , an electric motor 14 , an actuator or piston 16 , two brake pads 18 , 20 and a rotor 22 . The brake system 10 may include a ball screw assembly and a gear train (not shown) that may translate the rotational force of the motor 14 into distal advancement of the piston 16 , thereby urging the piston 16 linearly into engagement with the brake pads 18 , 20 to apply a braking force to the rotor 22 .
[0020] As shown in FIGS. 1 and 2 , a controller 24 may be in communication with the brake system 10 for controlling the advancement and retraction of the piston 16 , thereby controlling the resulting braking force applied to the rotor 22 . In one aspect, the controller 24 may include a processor (not shown), such as a computer processor, and may be in communication with a force sensor 26 and a position sensor 28 .
[0021] The force sensor 26 may directly monitor the braking force applied to the rotor 22 (see line 27 ) and may communicate force signals to the controller 24 by, for example, communication line 30 . The position sensor 28 may monitor the position of the piston 16 relative to the housing 12 , the brake pads 18 , 20 and/or the rotor 22 (see line 29 ) and may communicate position signals to the controller 24 by, for example, communication line 32 .
[0022] In one aspect, the controller 24 may generate a control signal for controlling the operation of the motor 14 based upon the signals received from the sensors 26 , 28 and may communicate a control signal to the brake system 10 by way of communication line 34 . The control signal may be generated according to the adaptive control system described in greater detail below. The control signal may be communicated directly to the motor 14 or to any appropriate portion of the brake system 10 .
[0023] Those skilled in the art will appreciate that the communication of signals and commands, as described herein, may be performed over physical communication lines (e.g., wires) or wirelessly. Furthermore, the communication of signals may be performed within a single device or between multiple devices.
[0024] As shown in FIG. 3 , one aspect of the adaptive control system, generally designated 40 , may include a database or adaptive table 42 , an adaptation gain block 44 , a robustification deadzone block 46 and a summing block 48 . The system 40 additionally may include two inputs and one output: the position signal input 50 , the force signal input 52 and the estimated force output 54 . The estimated force output 54 may be used by the controller 24 for generating a control signal (see line 34 in FIG. 2 ) for controlling the brake system 10 .
[0025] The adaptive table 42 may receive the position signal input 50 from the position sensor 28 and may correlate the position signal, using a look-up table, equation or the like, into the estimated force output 54 . The adaptive table 42 may include a discrete number of data points such that output values may be obtained by interpolating between the data points.
[0026] The estimated force may be communicated to the summing block 48 by line 56 and the summing block 48 may determine a difference value (i.e., an error signal) between the estimated force output 54 and the force signal input 52 . For example, the error signal may be generally equal to the force signal input 52 minus the estimated force output 54 .
[0027] The force signal input 52 may be based upon signals received from the force sensor 26 . For example, the force sensor 26 may be piezo device or the like. However, those skilled in the art will appreciate that the force signal input 52 may be based upon any available force measurement or an estimate of force, such as a high precision force estimate. For example, the force signal input 52 may be derived from measurements of the motor speed or motor current, as described in U.S. Ser. No. 11/235,392 filed on Sep. 26, 2005, the entire contents of which are incorporated herein by reference.
[0028] The output of the summing block 48 may be passed to the deadzone block 46 by line 58 . The deadzone block 46 may be provided to filter error signals that are less then a predetermined minimum threshold value prior to communicating the error signals to the adaptation gain block 44 (e.g., by way of line 60 ) or directly to the adaptive table 42 . For example, if the absolute value of the error signal is less than N, wherein N is the predetermined minimum threshold value, then the output of the deadzone block 46 may be zero, or some other value. If the absolute value of the error signal is greater than or equal to N, then the error signal may be passed along unchanged.
[0029] The system 40 may include a gain block 44 which may apply a gain G to the error signal and may communicate the modified error signal (i.e., (Error Signal)*G) to the adaptive table 42 , by way of line 62 , as a second input to the adaptive table 42 . The gain G may be selected based upon the desired properties of the adaptive table 42 . Foe example, the gain G may be selected based upon the desired speed at with the adaptive table 42 is to be updated. In one aspect, the gain G may be a numeric value less than 1, such as, for example, 0.1 or 0.2.
[0030] In one aspect, the adaptive table 42 may update the data values (or other correlating values) based upon the error signal. In another aspect, the data values may be updated based upon the modified error signal.
[0031] Accordingly, in one aspect, the data values in the adaptive table 42 may be updated each time the error signal is greater than or equal to N. Alternatively, the data values may be updated each time the error signal is not zero.
[0032] For clarity, reference will be made to the data values provided at Table 1, which includes six discrete input values (i.e., position values), see block 50 , having six corresponding output values (i.e., estimated force values), see block 54 :
TABLE 1 Position Signal Input (units) Estimated Force Output (units) 0 5 0.1 10 0.2 15 0.3 20 0.4 25 0.5 30
[0033] The position values may be based upon the displacement of the piston and may have various units, such as inches, millimeters or the like. The estimated force values may be estimates of braking force that correspond to values of piston displace and may have various units, such as Newtons, dynes or the like. Furthermore, those skilled in the art will appreciate that the adaptive table 42 may have any number of data points and the data points may be scattered or organized in various ways.
[0034] In one aspect, as shown in FIGS. 4 and 5 , a plurality of membership functions (i.e., “f(input)”) may be provided, wherein each membership function may correspond to a discrete input value from the adaptive table 42 . The membership functions may be linear and/or finite, as shown in FIG. 4 , or non-linear and/or infinite, as shown in FIG. 5 . For example, functions 69 , 79 may correspond to input value 0, functions 70 , 80 may correspond to input value 0.1, functions 72 , 82 may correspond to input value 0.2, functions 74 , 84 may correspond to input value 0.3, functions 76 , 86 may correspond to input value 0.4 and functions 78 , 88 may correspond to input value 0.5. The membership functions may provide an indication of how each discrete data point in the adaptive table 42 is effected by the error signal.
[0035] Accordingly, in one aspect, for each non-zero signal passed from the deadzone block 46 , the output values in the adaptive table 42 may be updated by multiplying the membership function for the corresponding input value by the error signal or the modified error signal and adding the product to the previous (i.e., not updated) output value, as shown by Eq. 1:
Output(input)′=Output(input)+ f (input)*(Error Signal)*Gain (Eq. 1)
wherein Output(input) is the output value corresponding to a specific input value before the most recent update and Output(input)′ is the updated output value.
[0036] Applying Eq. 1 to the six data points in Table 1, the following Eqs. 2-7 may be obtained:
Output(0)′=Output(0)+ f (0)*(Error Signal)*Gain (Eq. 2)
Output(0.1)′=Output(0.1)+ f (0.1)*(Error Signal)*Gain (Eq. 3)
Output(0.2)′=Output(0.2)+ f (0.2)*(Error Signal)*Gain (Eq. 4)
Output(0.3)′=Output(0.3)+ f (0.3)*(Error Signal)*Gain (Eq. 5)
Output(0.4)′=Output(0.4)+ f (0.4)*(Error Signal)*Gain (Eq. 6)
Output(0.5)′=Output(0.5)+ f (0.5)*(Error Signal)*Gain (Eq. 7)
wherein Eqs. 2-7 accurately update the discrete table values based upon interpolated values between the discrete table values and the error signal.
EXAMPLE 1
[0037] Using the data values provided at Table 1, a position input value of 0.16 may correspond to an estimated force value of about 13. In one aspect, the estimated force value may be determined using an interpolation technique between input value 0.1 and input value 0.2.
[0038] Using the membership functions provided at FIG. 4 and assuming, for example, the actual force input value is 14, the gain G is 1, and the minimum threshold value N is 0.5, the updated output values may determined as follows:
Output(0)′=5+(0%)*(14−13)*(1)=5
Output(0.1)′=10+(40%)*(14−13)*(1)=10.4
Output(0.2)′=15+(60%)*(14−13)*(1)=15.6
Output(0.3)′=20+(0%)*(14−13)*(1)=20
Output(0.4)′=25+(0%)*(14−13)*(1)=25
Output(0.5)′=30+(0%)*(14−13)*(1)=30
FIG. 6 provides a graphical illustration of the original data values of Table 1 plotted against the updated data values.
EXAMPLE 2
[0039] Using the data values provided at Table 1, a position input value of 0.32 may correspond to an estimated force value of about 21. In one aspect, the estimated force value may be determined using an interpolation technique between input value 0.3 and input value 0.4.
[0040] Using the membership functions provided at FIG. 5 and assuming, for example, the actual force input value is 19, the gain G is 1, and the minimum threshold value N is 0.5, the updated output values may determined as follows:
Output(0)′=5+(0.5%)*(19−21)*(1)=4.99
Output(0.1)′=10+(3.5%)*(19−21)*(1)=9.93
Output(0.2)′=15+(5%)*(19−21)*(1)=14.90
Output(0.3)′=20+(81%)*(19−21)*(1)=18.38
Output(0.4)′=25+(6%)*(19−21)*(1)=24.88
Output(0.5)′=30+(4%)*(19−21)*(1)=29.92
[0041] Accordingly, a system, method and apparatus are provided for updating a look-up table such that position signals may be converted into force signals with more accuracy, thereby improving the control of the electric brake system 10 . In one aspect, the adaptive table may be updated repeatedly during a brake apply state of the brake system 10 .
[0042] Although various aspects have been shown and described, modifications may occur to those skilled in the art upon reading the specification. The public is hereby placed on notice that any patent that may issue on this application includes such modifications and is limited only by the scope of the claims. | A method for controlling an electric brake system having a piston moveable by an electric motor is provided. The method includes the steps of storing data for correlating a position of the piston to a braking force applied by the piston, estimating a braking force associated with a specific position of the piston based upon the stored data, generating a control signal based upon the estimated braking force, determining a second braking force associated with the specific position and updating the stored data based upon a difference between the estimated braking force and the second braking force. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
All of my prior patent applications are incorporated herein by reference, including my U.S. patent application Ser. No. 10/660,119, filed 11 Sep. 2003, my U.S. Provisional Patent Application Ser. No. 60/557,869, filed 31 Mar. 2004, my U.S. Provisional Patent Application Ser. No. 60/502,002, filed 11 Sep. 2003, and my U.S. Provisional Patent Application Ser. Nos. 60/409,383 and 60/409,386, both filed 11 Sep. 2002.
Priority of my U.S. Provisional Patent Application Ser. No. 60/557,869, filed 31 Mar. 2004, is hereby claimed.
In the US, this is a continuation-in-part of my U.S. patent application Ser. No. 10/660,119, filed 11 Sep. 2003, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the field of performance enhancing shoe components or inserts for use in conjunction with various types of foot-ware. More particularly, the present invention relates to the field of performance enhancing shoe components or inserts which absorb and store energy of local loads and forces, through elastic deformation, and then return the energy to the shoe wearer, or to an object struck by a shoe, in useful form as the load is removed.
2. General Background of the Invention
There is a high demand for athletic equipment which enhances the performance of athletes. At all levels of athletic competition, small improvements in performance can be the difference between success and failure. At the highest levels of athletics, the difference of a few tenths or hundredths of a second is all that separates the elite athlete from the ordinary. For this reason, equipment which improves performance even slightly, will be desired in high demand. The newer materials used in tennis racket construction or golf club shafts are examples of equipment which improves performance by absorbing and storing energy, then returns this energy in a useful form as the load is removed.
This high demand for performance enhancing athletic equipment includes the art of athletic shoes and shoe components. Most recent improvements in athletic shoes or athletic shoe components have been made for aesthetic reasons or for comfort or to reduce weight. Few changes in athletic shoes or their components have been for meaningful increases in athletic performance. Present athletic shoes and their components fail to provide an energy return to the wearer. Neither do they absorb energy and return energy to a ball or object struck by the shoe. Description of Prior Art
Athletic shoes typically comprise a fabric, leather or synthetic upper, an outsole including a treaded or cleated lower surface, and a midsole positioned between the outsole and the foot of the wearer. There may also be an insole positioned between the outsole and the foot of the wearer. If the shoe is not manufactured with an insole, a wearer may add an insole or replace the midsole with an insole.
The midsole of a conventional athletic shoe is generally formed from a flexible, resilient, relatively soft material in order to absorb shock that results from impact of the shoe with the ground. A typical outsole is made of a higher density, tougher, more rigid material in order to protect the shoe from degradation and to support the foot. The outsole must also be flexible in order to facilitate ease of movement of the foot during certain athletic motions.
The following US Patents are incorporated herein by reference:
U.S. Pat. Nos.:
4,454,662, 4,506,460, 4,858,338 5,025,573 5,052,130
5,179,791 5,203,793, 5,452,526, 5,572,804, 5,695,850
5,960,566, 6,120,880, 6,145,221 6,205,683, 6,485,661.
U.S. Pat. No. 5,572,804 discloses an inner sole for an athletic shoe that can have many degrees of stiffness, by the application of multiple inserts into the sole.
U.S. Pat. No. 5,452,526 discloses a soccer shoe with an outsole stiffener; the stiffening inserts are molded into the outer sole.
U.S. Pat. Nos. 6,120,880 and 5,694,850 disclose placing inserts into various portions of the insole of an athletic shoe to enhance performance.
U.S. Pat. No. 6,205,683 discloses placing a torsional insert within the inner sole of an athletic shoe.
U.S. Pat. No. 4,454,662 of 1984 issued to Stubblefield adds stiffening components to the arch and heel portions of the shoe. The present invention adds flexible components to just the front or to the front and outside edges of the shoe. The present invention may provide some measure of arch support, but little or no heel support. The shoe/sole/insert of an embodiment of the present invention will have a shape, location and function significantly different than the stiffening components in this patent.
There are numerous articles of footwear in the prior art in which inserts and shoe components are present in order to provide comfort, stability or support for the foot. For example, U.S. Pat. No. 4,506,460 of 1985 issued to Rudy describes moderators and stabilizers located under the forefoot and heel. The purpose of these moderators and stabilizers is to cushion shock forces, provide improved support, control and stability, store energy and return energy to the wearer. These moderators and stabilizers are located under and vertically alongside the forefoot and heel of the wearer. The present invention's primary location will be the toe of the shoe with little or nothing supporting the heel and forefoot. The shoe/sole/insert of embodiments of the present invention preferably have both horizontal and vertical components, with the vertical component only at the toe end of the shoe. The horizontal component of the shoe/sole/insert of embodiments of the present invention can differ in shape and location within the shoe.
U.S. Pat. No. 5,452,526 of 1995 issued to Collins describes a two-part stiffener, the first portion of which stiffens the waist or shank of the outsole; and the second portion both stiffens and provides resiliency to the forepart of the of the outsole. The purpose of this two-part stiffener is to provide physical properties which are selected for the appropriate use of the shoe and to provide comfort to the wearer. These stiffeners operate to stiffen the shank or waist of the outsole and a fore part of the outsole in response to transverse flexure of the user's foot at the ball of the foot. These stiffeners are relatively complex in shape and located in various places throughout the outsole and arranged in a manner to resist flexure about the longitudinal axis of the shoe. The shoe/sole/insert of embodiments of the present invention preferably provide resilience primarily in response to vertical flexure of the user's foot at the toe, or even in front of the toe, and to a lesser extent, in response to some transverse flexure only at the outside edge of the foot. The shoe/sole/insert of embodiments of the present invention preferably have relatively simple shapes with a location farther forward and whose function is not lateral support, but a vertical return to its original shape.
U.S. Pat. No. 5,572,804 issued to Skaja et al. in 1996 details method of construction of shoe midsole components from a flexible high polymer resin. These shoe sole components are formed from two sheets of thermoplastic resin, with each sheet consisting of different materials having different properties and containing varying shapes and sizes of support members. These support members comprise inwardly directed indentations in each sheet of the thermoplastic resin which must be precisely aligned with the matching indentation. The shoe/sole/insert of embodiments of the present invention will not be restricted to only the midsole, nor will it consist of a plurality of shaped protrusions scattered throughout the midsole component material. The horizontal component of the present invention can preferably be a thin, flat or slightly curved object consisting of a single or very few individual sizes and shapes extending to the front and side edges of the shoe outsole or midsole or inserted insole. Only if the present invention is hollow will it be important to more precisely match various protrusions or indentations.
U.S. Pat. No. 5,695,850 issued to Crow in 1997 is a performance shoe component consisting of 1,4-polybutadiene and a natural or synthetic rubber. This shoe component is most advantageously placed beneath the ball of the foot. The purpose of that location is to improve the wearer's ability to leap higher or run faster or provide cushioning. The horizontal component of the shoe/sole/insert of embodiments of the present invention will be most advantageously placed under and possibly beyond the front edges and outside edges of the shoe. The vertical component of the shoe/sole/insert of embodiments of the present invention are preferably most advantageously placed on top of, or directly above, the horizontal component. This location is intended to maximize the absorption of energy and to return a portion of this energy to the object struck.
U.S. Pat. No. 5,960,566 issued to Brown in 1999 and U.S. Pat. No. 6,485,661 issued to Brown in 2002 both consist of a composite material orthotic insert configured to enhance control over the motions of the foot within the shoe. The stated purpose of the insert is to control the movements of certain joints of the foot during walking and running. This orthotic insert is positioned under the heel and forefoot. The shape and position of the insert and its purpose in the aforementioned patent is clearly distinguishable from the shoe/sole/insert of embodiments of the present invention.
U.S. Pat. No. 6,120,880 issued to Crow in 2000 is a continuation of U.S. Pat. No. 5,695,850. The characteristics which distinguish the present invention from this patent are the same as those outlined above.
U.S. Pat. No. 6,205,683 issued to Clark et al. in 2001 is for an insole board which includes a shock diffusion plate located under the heel and midfoot. The location, shape and purpose of the shoe/sole/insert of embodiments of the present invention are clearly distinguishable.
U.S. Pat. No. 4,858,338 discloses an insert for a shoe sole, which includes an elastic strip, which absorbs and stores the energy of running and returns the energy to the wearer.
U.S. Pat. Nos. 5,025,573 and 5,179,791 disclose a composite shoe bottom with layers of firm and softer materials, which provide firm support and lateral stability.
U.S. Pat. No. 5,052,130 discloses a spring plate made of multiple layers of carbon fiber embedded in a polymer which stores and releases energy in a manner beneficial to a runner.
U.S. Pat. No. 6,145,221 discloses a cleated athletic shoe incorporating a cleat frame which supports the cleats in a manner which transfers upward forces from the cleat into the cleat frame when the shoe is weighted.
U.S. Pat. No. 5,720,118 issued to Mayer in 1998 provides an inlay for a shoe. The inlay comprises one piece of a hard material, preferably selected from metal, plastic, steel and spring steel. The stated purpose of this inlay is to reduce the risk of lateral snapping over of the foot, thus reducing the risk of ligament tears and strains. Another stated purpose is to protect the bottom of the foot from right angle pressures by distributing over the entire inlay pressures caused by small stones or uneven ground. This patent further describes a toe cap riveted to the inlay. This cap is made of spring steel; its stated function is to protect the toes and forefoot from falling objects.
The preferred embodiment of the present invention also consists of a horizontal and vertical component. An embodiment of the present invention has the vertical component forming a toe cap. Although the horizontal component may be made of metal, plastic or steel, the vertical component should be made of a softer, more energy absorbent material. The purpose of the vertical component in the present invention is not to protect the toes and forefoot from falling objects; rather, it is to transmit energy to the horizontal component so that both components working together will return more energy to the object struck by the wearer. The vertical component need not be riveted or otherwise attached to the horizontal component. It can fulfill its function merely by being placed directly above the horizontal component.
There are numerous articles of footware in the prior art in which inserts and shoe components are present in order to provide comfort, stability or support for the foot. The purpose of these moderators, stabilizers and orthotics is to cushion shock forces, provide improved support, control and stability, store energy and return energy to the wearer. An essential difference between the prior art and the preferred embodiments of the present invention is the vertical component. The vertical component is preferably located at the toe end of the shoe, and it will preferably rest upon the horizontal component, or be located directly above the horizontal component. The vertical component may be permanently attached to the horizontal component, or it may be manufactured as a separate piece and later attached to the horizontal component or placed above the horizontal component. The vertical component may be used without the horizontal component, it may be used an insert resting upon or located above the midsoles and/or outsoles of the prior art. The prior art primarily serves to provide comfort and stability to the wearer, or to increase the return of energy to the wearer. The primary purpose of embodiments of the present invention is to increase the return of energy to the object struck by the wearer.
The shoe/sole/insert of embodiments of the present invention preferably provide resilience primarily in response to vertical flexure at the toe, or in front of the toes of the foot of the wearer. To a lesser extent there may also be resilience in response to vertical flexure at the inside and outside edges of the forefoot. The shoe/sole/insert of embodiments of the present invention may have relatively simple shapes. The horizontal component can preferably be thin and flat or slightly curved objects consisting of individual sizes and shapes extending to the front and side edges of the shoe outsole or midsole or inserted insole.
A primary characteristic of the shoe/sole/insert of embodiments of the present invention, which distinguishes the present invention from most other patents incorporated by reference, is that of the vertical component. This vertical component preferably rests upon the horizontal component, or if not directly upon the horizontal component, the vertical component is located above the horizontal component. In order to increase the elastic deformation of the horizontal component of the shoe/sole/insert of embodiments of the present invention, in certain types of kicks or other uses of the shoe, the vertical component will be the first portion of the shoe/sole/insert to make contact with the object struck. In making contact with the object, this vertical component will absorb and transfer more energy to the horizontal component of embodiments of the present invention, which would return more energy to the object struck by the shoe, than would be possible without the vertical component. If the vertical component is not present, the foot inside of the shoe would make contact with the object struck before the horizontal component could make contact. The foot in such case would absorb some portion of the energy created in striking the object and could only transfer the unabsorbed energy to the horizontal component of embodiments of the present invention. The less energy transferred to the horizontal component, the less the horizontal component can be flexed, and the less the horizontal component is flexed, the less energy the horizontal component can transfer to the object struck, or to the wearer of the shoe.
The vertical component of the shoe/sole/insert of embodiments of the present invention will produce a more efficient transfer of the energy produced by the physical act of striking the object, back to the object struck. When a foot inside of a shoe without the shoe/sole/insert of embodiments of the present invention makes contact with the object struck, the foot acts as a type of energy sponge situated between the object struck and the horizontal component of embodiments of the present invention. The energy absorbed by the foot will be transferred to the bones, ligaments, tendons and muscles of the foot and leg. This absorbed energy will be felt in the foot and leg as heat. The more heat absorbed by the bones, ligaments, tendons and muscles of the foot and leg, the more fatigue and discomfort will be felt by the wearer of the shoe.
BRIEF SUMMARY OF THE INVENTION
The prior art does not anticipate the basic concepts of the present invention. The present invention will absorb and store energy from the foot at foot-strike and return some of this energy to the object being struck. The present invention, incidentally, may also cushion the foot, leg and body; provide foot stability and motion control; reduce fatigue; extend the float time of a runner and increase the jump height of the wearer. The present invention is intended to absorb, store and return energy to the object struck, which would otherwise be lost using the existing shoe components and inserts.
The horizontal component of embodiments of the present invention can comprise essentially a light-weight flat, or slightly curved, thin unitary object made of a flexible material or materials, which can be integrated into a shoe's outsole and/or midsole and/or insole. The object may extend from the heel or arch of the foot to or beyond the toes of the foot. The vertical component of the embodiments of the present invention will either rest upon, or be directly above the horizontal component; the vertical component of the object may even curve over the toe, producing a cap, which extends beyond and over the top of the toes. The horizontal and vertical components of the embodiments of the present invention may take various shapes dependent upon the wearer's preferences and intended use.
The shape of the vertical component of the shoe/sole/insert of embodiments of the present invention will be determined by the material or materials used in its manufacture, and the particular performance characteristics desired by the wearer of the shoe. The materials used, the shapes of the shoe/sole/inserts of embodiments of the present invention, and the location of the vertical components upon or above the horizontal components will also be dictated by concerns for safety. The Federation Internationale De Football Association (FIFA) in law 4 states that players must not use equipment or wear anything that is dangerous to himself or to other players. The vertical component should be made of a material or materials that are stiff enough to efficiently store the energy produced by the act of kicking an object and transfer that energy to the horizontal component. The material or materials making up the vertical component must also be flexible and soft enough to be used safely in the game played by the wearer. One example of a material which provides a high energy return is 1,4-polybutadiene. This material can be used in combination with other high energy return rubbers such as natural rubber, synthetic isoprene rubber, polyisoprene, butadiene acrylonitrile rubber and/or ethylenepropylene diene modified rubber.
The object of the present invention is to provide a vertical component of a soft, high energy return material which also provides shock absorption. It is a feature of the invention that the vertical component be compressible by the human foot to maximize energy return. Another feature of the present invention is that the vertical component transfer energy to a stiffer, and probably harder, horizontal component so that both components working together transfer energy to the object kicked by the wearer.
In order to accommodate this vertical component, the conventional soccer shoe may have to be modified. The location of the vertical component beyond the toes of the foot, rising vertically above the toes, and laterally back towards the heel on each side of the toes and forefoot would require a larger toe box than is now present in conventional soccer shoes. The length of the soccer shoe may also be a size or a number of sizes longer than the wearer customarily would wear. This additional length would also increase the size of the arc of the shoe through space as the foot is flexed before contacting the ball, and then extended through the ball in the follow through after contacting the ball.
The intent of the present invention is to provide shoe components which impart energy into the object struck. It is a feature of some embodiments of the present invention that it be placed as far forward and/or laterally as reasonable, in order that the ability to effectively use the shoe for purposes other than striking the object, is not significantly compromised.
The intent of the shoe component of the present invention is that a struck object travel faster and/or further than would be possible without this shoe component. Placing the present invention at the farthest end of the arc of the kicking leg and foot would consequently enable the maximum amount of absorption of energy by the component of the present invention. The more energy absorbed, the more energy would be available to transfer to the struck object.
The embodiments of the present invention may also provide more comfort to the wearer. Energy absorbed by the present invention will decrease the energy absorbed by the bones, muscles, joints, ligaments and tendons of the toes, leg and foot. This would reduce physical fatigue and/or pain. Using the present invention's energy return characteristics may also increase the ability of the wearer to jump higher, or to run faster by increasing the wearer's stride length. These shoe components may improve athletic performance in a variety of athletic endeavors.
The material or materials used in the manufacture and the shape or shapes of the present invention and the location of the present invention within the shoe may be varied depending upon the wearer's intended use. Specific applications may include increased comfort and foot stability, better motion control, an increase in energy efficiency, a decrease in fatigue and risk of injury and many other desired advantages.
The primary material for the horizontal components of embodiments of the present invention will preferably be a high tensile material such as graphite and carbon. A ratio of 10% carbon to 90% graphite will be stiffer than a ratio of 20% carbon to 80% graphite. The graphite fibers may be unidirectional, on a bias, or woven. The present invention may be 100% carbon or 100% graphite, or some combination of the two; this material or these materials may be laminated or combined with another material or other materials. There may be no graphite or carbon in the components of the present invention, but one or both of these are the primary materials used in the shafts of modern golf clubs and tennis rackets. The technology which has been recently been employed to increase the distance a golf ball travels when struck with the newer golf clubs; or the increase in velocity of a tennis ball struck by the newer tennis rackets, is a technology which can be used with the present invention. Other materials used in tennis rackets include kevlar, fiberglass and titanium. Golf club shafts are usually graphite or metal. The graphite, titanium and metal may be alloys. The components of the present invention can be made of the material or combinations of materials, whether in composite or laminate form, used in the construction of newer models of tennis rackets and golf club shafts.
The primary material or materials for the vertical component of embodiments of the present invention will preferably be a natural or synthetic rubber compound similar to that found in the outsole of tennis, basketball and cross training shoes. These compounds may include, but not limited to, combinations of 1,2-polybutadiene, 1,4-polybutadiene, synthetic isoprene rubber, natural rubber, polyisoprene, butadiene acrylonitrile rubber, ethylenepropylene diene modified rubber, styrene butadiene rubber, thermoplastic elastomers, and plastics such as polystyrene, ethylene vinyl acetate and polyvinyl chloride. The vertical component can be about as high as the front of the shoe in which it is to be inserted. It is preferably at least 50% as high as the front of the shoe in which it is to be inserted, more preferably at least 75%, even more preferably at least 90%, and most preferably at least 95% as high as the front of the shoe in which it is to be inserted. For example, for a relatively standard size soccer shoe (around US size 10, around European size 42, the vertical component is preferably at least 1 cm high, more preferably at least 1.5 cm high, even more preferably at least 2 cm high, and most preferably at least 2.5 cm high (all as measured from the inside of the sole of the soccer shoe). The vertical component can be about 0.10-2.0 cm thick, more preferably about 0.15-1.50 cm thick, even more preferably about 0.20-1.0 cm thick, and most preferably about 0.25-0.80 cm thick. For example, it can be about 0.50 cm thick.
The horizontal component can be about 0.01-2.0 cm thick, more preferably about 0.05-1.75 cm thick, even more preferably about 0.10-1.50 cm thick, and most preferably about 0.20-1.0 cm thick. For example, it can be about 0.50 cm thick.
The present invention includes a performance enhancing shoe components for a soccer shoe, the soccer shoe comprising a shoe upper and at least a sole secured to the upper such that a wearer's foot is positioned within the upper and above the sole, which incorporates one or more preformed objects embedded in an outsole body, or which constitutes the entire outsole; the horizontal and vertical components of embodiments of the present invention will operate to deflect, without permanent deformation, in response to an applied load creating a deflecting stress and then to return to its original shape upon removal of the applied load causing the deflecting stress, the horizontal and vertical components of the present invention operating to absorb, redistribute and store the energy of localized loads applied thereto through deflection and, by returning to its original shape, to return energy to the wearer and/or to an object struck by the shoe in such manner so as to impart to the struck object applying the load some portion of the energy produced by the applied load; the horizontal and vertical components can be made of one type of material or of a composite of one or more type of materials. For example, these components can be made of a laminate of one or more type of materials. The performance enhancing shoe components can have one or more shapes in one or more locations within the outsole shoe component depending upon the particular performance enhancing characteristics desired by the wearer. The vertical component of embodiments of the present invention may rest directly upon the horizontal component within the shoe outsole, or it may rest upon the shoe midsole or insole, so long as it is directly above the horizontal component of embodiments of the present invention.
The present invention includes a performance enhancing soccer shoe component for a soccer shoe which comprises a shoe upper and at least two soles, one of which is the outsole secured to the upper and a midsole which is located between the wearer's foot and the outsole. This midsole can incorporate one or more preformed objects, the horizontal components of embodiments of the present invention, embedded in the midsole material, or the horizontal component can constitute the entire midsole, and it also operates to deflect, without permanent deformation. This midsole can be added as part of the manufacturing process of the new shoe. This performance enhancing shoe component can include a midsole made of one type of material; alternatively, the midsole can be a composite of one or more type of materials—in such a case, it could be made of a laminate of one or more type of materials. The horizontal component can have one or more shapes in one or more locations within the midsole depending upon the particular performance enhancing characteristics desired by the wearer. The vertical component of embodiments of the present invention may rest directly upon the horizontal component within the midsole, or the vertical component may rest directly upon an insole, and directly above the horizontal component within the midsole.
The embodiments of the present invention include a performance enhancing soccer shoe insert which can be placed between the outsole and/or midsole and the wearer's foot. This inserted insole can contain one or more preformed objects, the horizontal components of embodiments of the present invention, embedded in the insole material, or the insert can constitute the entire insole, and it also operates in a manner consistent with previously described embodiments of the invention. This “after market” inserted insole can be added after the shoe has been manufactured and sold. The insole can be made of one type of material, or it can be made of a composite of one or more type of materials, in which case it could be made of a laminate of one or more type of materials. The components in the insole can have one or more shapes in one or more locations within the shoe insert depending upon the particular performance characteristics desired by the wearer. The vertical components of embodiments of the present invention will rest directly upon, or above the horizontal component of the insole.
Prototypes of the horizontal component were made and tested. The prototypes consisted of split fishing rods, made of combinations of fiberglass and graphite, then glued together. The glued together split fishing rods were shaped and inserted into soccer shoes for testing. The horizontal components alone increased the distance of soccer balls kicked when compared to the distance of soccer balls kicked without the horizontal insert.
The rubber toe outsole of a tennis shoe was then glued directly upon the horizontal split fishing rods component, and this was inserted into a soccer shoe. The addition of this vertical component not only increased the distance of a kicked soccer ball, it also felt dramatically different at the moment the shoe struck the ball. The wearer of the shoe felt less strain in the knee, ankle and foot than was felt with just the horizontal component inserted into the shoe. The kicked ball seemed to travel further and fly faster with less effort. The ease of effort and reduction of discomfort was more noticeable when the weather was colder. In cold weather, striking a soccer ball with the top of the shoe directly above the toes can be painful. The same kick in cold weather, with the vertical component inserted in the soccer shoe, is much more comfortable. The vertical component of the present invention makes contact with the ball, and absorbs some of the energy of the kick, before the kicked ball makes contact with the toes.
The vertical component will be located beyond and above the toes, then extend laterally back towards the heel and along both sides of the toes and forefoot. The portion of the vertical component along both the inside or outside of the foot, will also serve to transfer energy to a ball kicked by either the inside or the outside of the shoe. When a ball is struck with either the inside or the outside of the foot, the vertical component will cause the horizontal component to bend and twist to a greater extent than would be possible with just the horizontal component. The energy produced by the ball strike would be more efficiently transmitted to the ball than would be possible without the vertical component. Since the horizontal component is flat or slightly curved, it can be twisted by a force applied on the outside edges of the horizontal component. Upon release of the force applied on the outside edge, the horizontal component will untwist, and the energy produced by this untwisting motion can be transferred to the object struck.
During the course of a soccer game, there are instances where a player wishes to impart spin to a struck ball in order to curve the ball around or away from opponents. In order to impart spin to a ball, the ball must be struck off of its center and/or the ball must be struck by the side of the shoe. The greater the amount of spin the greater the ball will curve. The vertical element located along the outside of the of the toes and extending laterally towards the heel will allow ball strikers to impart more spin to the object struck than would be possible without the vertical component.
The present invention also includes a soccer shoe including the component or the insert of any embodiment of the present invention.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
For a further understanding of the nature, objects, and advantages of the present invention, reference should be had to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements and wherein:
FIG. 1 is a side view of a preferred embodiment of the apparatus of the present invention;
FIG. 2 is a top view of a preferred embodiment of the apparatus of the present invention;
FIG. 3 is a bottom view of a preferred embodiment of the apparatus of the present invention;
FIG. 4 is a top view of a preferred embodiment of the apparatus of the present invention;
FIG. 5 is a top or bottom view of a midsole or inserted insole illustrating an embodiment of the present invention as the entire outsole midsole or insole;
FIGS. 6 , 7 , 8 , 9 , 10 are top views of the outsole/midsole/insole insert illustrating alternative embodiments of the present invention;
FIG. 11 is a cross section of a toe of a soccer shoe showing the shoe and an embodiment of the present invention located within the shoe outsole;
FIG. 12 is a cross section of the heel of a shoe and an embodiment of the present invention located within the outsole;
FIG. 13 is a cross section of a toe of a shoe showing an embodiment of the present invention of the present invention located within the midsole of the shoe;
FIG. 14 is a cross section of the heel of a shoe showing an embodiment of the present invention located within the midsole of the shoe;
FIGS. 15 , 16 and 17 are top views of the outsole/midsole/insole insert illustrating alternative embodiments of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The athletic shoe shown for illustrative purposes is a soccer shoe even though the present invention may be used in other types of athletic or any other type of shoe. The soccer shoe shown in FIG. 1 is of generally conventional form. The shoe 1 has an upper 2 made of leather or similar material, with a tongue 3 and laces 4 . The shoe FIG. 1 has an outsole 5 and a midsole 6 either or both of which may incorporate the horizontal component of an embodiment of the present invention. The vertical component of an embodiment of the present invention will preferably be resting upon, or be immediately above, the horizontal component, regardless of whether the horizontal component is located in the midsole 6 or outsole 5 . The outsole 5 also incorporates molded or screw threaded studs or cleats 8 which come in contact with the ground when the shoe 1 is worn.
FIG. 2 is a top view of a shoe midsole 6 with an illustration of the horizontal component 7 illustrated by the striped lines, and the vertical component 76 illustrated by the cross hatched lines, of an embodiment of the present invention. This midsole 6 is worn between the foot and the outsole. The material 10 surrounding the shoe midsole of an embodiment of the present invention may consist of air, gas, foam rubber or other cushioning material.
FIG. 3 is a bottom view of a shoe outsole 5 illustrating the horizontal component 17 of an embodiment of the present invention embedded in the outsole 5 (outsole 5 can be made of the same material typically for soccer shoe outsoles).
FIG. 4 is a top view of a shoe insole insert 9 including the vertical component 27 , illustrated by the cross hatched lines, of an embodiment of the present invention resting directly upon or immediately above the horizontal component 37 of an embodiment of the present invention, illustrated by the striped lines. Insert 9 can be inserted in an otherwise standard soccer shoe after the shoe is manufactured and purchased.
FIG. 5 is a top view of an outsole 15 , a midsole 16 , or an inserted insole 19 illustrating an embodiment of the present invention where the entire outsole 15 , midsole 16 or insole 19 is the horizontal component and is illustrated by the striped lines, and the vertical component 29 , is illustrated by the cross hatched lines.
FIGS. 6 , 7 , 8 , 9 , 10 , 15 , 16 and 17 are top views of the outsole/midsole/insole insert illustrating the horizontal component 37 , 47 , 57 , 67 , 77 , 79 , 80 and 81 of alternative embodiments of the present invention, which are illustrated by the striped lines. The vertical component 38 , 48 , 58 , 68 , 78 , 82 , 83 and 85 of embodiments of the present invention will preferably rest upon or directly above the toe end of the horizontal components. The vertical components of embodiments of the present invention are illustrated by the cross-hatched lines. In FIG. 16 the vertical component 83 of alternative embodiments of the present invention forms a partial cap over the top of the fore foot within the shoe. In FIG. 17 the vertical component 84 of alternative embodiments of the present invention forms a full cap over the fore foot and toes within the shoe.
FIG. 11 is a cross section of the toe of shoe 1 showing the shoe upper 2 and the vertical component 87 of an embodiment of the present invention located at the extreme end of the toe of the shoe and located directly above the shoe outsole 5 , which contains the horizontal component 7 of the shoe.
FIG. 12 is a cross section of the heel of the shoe 1 and component 7 of an embodiment of the present invention (or any other component shown in FIGS. 2-10 ) located within the shoe outsole 5 .
FIG. 13 is a cross section of the toe of a shoe 1 showing the vertical component 97 of an embodiment of the present invention located at the extreme end of the toe of the shoe and resting upon the midsole 6 of the shoe, which contains the horizontal component 7 .
FIG. 14 is a cross section of the heel of the shoe 1 showing component 7 of an embodiment of the present invention (or any other component shown in FIGS. 2-10 ) within the midsole 6 of the shoe.
FIGS. 13 and 14 may also be used to illustrate a cross section of an embodiment of the present invention located within an insole inserted into the shoe.
FIG. 15 is a top view of the outsole/midsole/insole insert illustrating an alternative embodiment of the present invention showing a channel 99 located within the outsole/midsole/insole insert. This channel may be rectangular, as shown, or circular, semi-circular, round, triangular or oval. The number of these channels and their placement or alignment may vary. The purpose of this channel is to allow the wearer of the shoe to customize the performance characteristics of the horizontal component. Shaped bars or rods, etc. of material or materials in composite and/or laminate construction with varying flex, resilience and rebound characteristics may be put into these channels and easily removed or replaced. These materials may be chosen from those used to make the horizontal components of the present invention, though in a given shoe may be made of a different material from the horizontal components used in that shoe.
In the drawings the horizontal component of the shoe sole/insert of the present invention is shown in striped lines and the vertical component of the shoe/sole/insert of the present invention is shown in cross hatched lines, whether located in the outsole, midsole, or as part of an inserted insole. The horizontal and/or the vertical components of the present invention can be manufactured into the outsole and/or the midsole. If the component is manufactured into the outsole, the material may be a color different from the outsole. This different color would be desirable to distinguish the shoe from shoes without the components of the present invention in the outsole. The insert of an embodiment of the present invention may also be incorporated into an innersole, which is inserted into the shoe at some point after the manufacture of the other components of the shoe.
The shoe sole/insert of an embodiment of the present invention can be made of one material, or of a combination of natural and/or man-made materials. The choice of material or combination of materials, the shape of the materials, and the location of the component within the shoe can be determined by the wearer's desire to optimize specific performance enhancing characteristics of the shoe. The primary specific characteristic of the shoe sole/insert of the present invention is to efficiently return energy that would be wasted without the shoe sole/insert of the present invention. In response to an applied load, such as kicking a ball or striking the ground, the shoe sole/insert of the present invention will temporarily deform. Upon removal of the applied load, or a progressive reduction of the applied load, the shoe sole/insert of the present invention will return to its original shape. This absorption of energy and the return of otherwise wasted energy to the wearer and/or to the object struck by the shoe of the wearer is the essential performance enhancing characteristic of the present invention. Other applications of the present invention may include lighter weight, more comfort, less fatigue, more stability, less injury risk, better foot control, better foot support, or even better outward appearance of the shoe.
The shoe sole/insert of an embodiment of the present invention should have a relatively high tensile strength. The material or materials should also be elastic and have a strong tendency to return to an unstressed state once it is free from the stress of impact. The material or materials should also possess good fatigue resistance so that it will withstand repeated cycles of deforming when stressed and rebounding when the stress is removed. The material or materials may be a composite or be laminated in order to achieve desired combinations of the specific applications of the shoe. The material should have a modulus of elasticity of at least 250,000 psi. Typical materials are high modulus plastics such as polycarbonate materials (modulus of 300,000), ABS injected molded plastic, fiberglass composites (modulus of 3,000,000), graphite composites (modulus of 9,000,000), carbon composites, and various types of steel. The material or materials in the vertical component may have entirely different characteristics than the material or materials used in the horizontal components of embodiments of the present invention.
The shoe sole/insert of the present invention should be lightweight and thin. The thickness may be constant or may vary depending upon the desires and the intended use of the wearer. The cross sectional thickness of the present invention will vary, dependent upon the material used and the wearer's desires, but the thickness of the horizontal component is preferably in the range of 0.10-1.0 cm. The thickness of the vertical component is preferably in the range of 0.25 cm-0.80 cm. The shoe sole/insert of the present invention may also be hollow. The horizontal component of the shoe sole/insert of the present invention may extend the length of the foot, it may be shorter or longer than the foot, or extend beyond or over the heel and/or toes of the foot. The vertical component of the shoe/sole/insert of the present invention will rest upon or be placed directly above the horizontal component and will be located beyond and over the toes of the foot. The components of the shoe sole/insert of the present invention may be flat or round and/or any shape or combination of shapes, the surface may be flat, curved, grooved or corrugated. The shoe sole/insert of the present invention may consist of one or more parts, which may be connected or function independent of each other.
The shoe sole/insert of an embodiment of the present invention may be incorporated into the outsole and/or midsole and/or insole during the manufacturing process. The manufacturer may also leave a pocket or space in the outsole and/or midsole and/or insole for a separately manufactured component of the present invention. This would allow individual choice of a variety of materials or shapes in the wearer's discretion. The same shoe may then be able to accommodate a broad range of stiffer or more flexible shapes so that the wearer can snap the desired component into the pocket or space, then remove it at will, and snap in another variant of the component as desired.
While the foregoing description has referred particularly to soles for soccer shoes (and is preferably used with soccer shoes), the invention is also applicable to articles of footwear, whether athletic footwear or not, and both with and without studs. For example, the invention can be applied to casual or dress shoes, to tennis shoes and training shoes.
All measurements disclosed herein are at standard temperature and pressure, at sea level on Earth, unless indicated otherwise. All materials used, or intended to be used in a human being are biocompatible, unless indicated otherwise.
The foregoing embodiments are presented by way of example only; the scope of the present invention is to be limited only by the following claims. | An insert for soccer shoes absorbs and store energy from the foot at foot-strike and return some of this energy to the object being struck. The insert may also cushion the foot, leg and body; provide foot stability and motion control; reduce fatigue; extend the float time of a runner and increase the jump height of the wearer. The insert is intended to absorb, store and return energy to the object struck, which would otherwise lost using the existing shoe components and inserts. The insert preferably extends around the periphery of the front of the shoe and extends longitudinally as well from the front of the shoe towards the back of the shoe, at least to about the middle of the shoe, and preferably proximate the heel of the shoe. The insert preferably also extends vertically. | 0 |
FIELD OF THE INVENTION
The present invention relates to fluid dispensing devices and more particularly to pressurized tank sprayers.
BACKGROUND OF THE INVENTION
Pressurized tank sprayers are often utilized to dispense low viscosity liquids. The typical pressure sprayer consists of a tank or container for holding a solution, a hand pump, and a spray wand with a discharge valve. In operation, a person partially fills the tank with a solution leaving a portion of the tank unfilled. Next, the user attaches a hand pump to the tank. As the user strokes the hand pump, the pump mechanism forces air from outside the tank into the portion of the tank unoccupied by the solution, causing the air pressure in the tank to become greater than the atmospheric pressure outside of the tank. When a user triggers the discharge valve on the spray wand, the increased pressure within the tank propels the solution from the tank through a nozzle that terminates the spray wand. The pressure sprayer will continue to propel solution from the tank until the air pressure in the tank approximately equals the atmospheric pressure outside the tank. Then the user must again actuate the pump to redevelop the increased pressure within the tank.
Manufacturers commonly sell the liquids or solutes that a user may wish to dispense with a pressure sprayer in a concentrated form. Before distributing these solutes, users typically add a measured quantity of the concentrated solute to the pressure sprayer container. Additionally, users must dilute the concentrated solute with a solvent, usually by adding a quantity of water to the container before or after the solute is added to the container. While the measurement and dilution process effectively prepares the solute for distribution, some users may find the process inconvenient.
Some pressure sprayer containers include an opening that is insufficiently large to pour a liquid into easily. Often while pouring into these small openings, users may accidently spill some of the measured solute or solvent upon the ground, resulting in an incorrectly diluted product and wasted solute. In addition, when the opening to the tank is too small, it is difficult to see into the tank for cleaning or other purposes. Therefore, it would be desirable to provide a pressure sprayer that makes the task of adding liquids to the tank easier. It would also be desirable to provide a pressure sprayer that provides convenient access to the tank. In addition, it would be desirable if such pressure sprayer could be easily stabilized during assembly and disassembly of the tank components.
SUMMARY OF THE INVENTION
A tank sprayer includes a tank configured to receive fluid through an opening in the tank, a removable cap covering the opening in the tank, and a removable pump. The removable cap includes a first handle extending outwardly from a first side of the cap, a second handle extending outwardly from a second side of the cap opposite the first side, and a funnel provided between the first handle and the second handle. The funnel has a substantially conical sidewall and a drain leading to the opening in the tank. The removable pump engages the drain of the cap, wherein the pump is operable to advance air into the tank to pressurize the tank.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts a perspective view of a pressurized tank sprayer.
FIG. 2 depicts another perspective view of the pressurized tank sprayer of FIG. 1 .
FIG. 3 depicts a perspective view of the tank of the pressurized tank sprayer of FIG. 1 .
FIG. 4 depicts a side view of the pressurized tank sprayer of FIG. 1 .
FIG. 5A depicts a cross-sectional view of the cap for the pressurized tank sprayer of FIG. 1 .
FIG. 5B depicts a top view of the cap of FIG. 5A .
FIG. 5C depicts a perspective view of the cap of FIG. 5B .
FIG. 6 depicts a cross-sectional view of a double action hand pump of the pressurized tank sprayer of FIG. 1 .
FIG. 7 depicts a cross-sectional view of an upper portion of the double action hand pump of FIG. 6 .
FIG. 8 depicts a cross-sectional view of a lower portion of the double action hand pump of FIG. 6 .
FIG. 9A depicts a cross-sectional view of the lower portion of the double action hand pump in the downstroke configuration.
FIG. 9B depicts a cross-sectional view of the lower portion of the double action hand pump in the upstroke configuration.
FIG. 10A depicts a cross-sectional view of the upper portion of the double action hand pump in the downstroke configuration.
FIG. 10B depicts a cross-sectional view of the upper portion of the double action hand pump in the upstroke configuration.
DETAILED DESCRIPTION
Referring to FIGS. 1 and 2 , the pressurized tank sprayer 10 includes a tank 14 , cap 22 , measuring cup 26 , and double action pump 30 . The tank 14 includes a container 34 and a base 38 . The container 34 and base 38 may be distinct elements or the tank 14 may be constructed in one integral unit. The container 34 forms the portion of the tank 14 that holds the solution to be sprayed. As illustrated in FIGS. 1 and 2 , the container 34 has a generally substantially cylindrical shape which may also take the form of a slightly ellipsoidal shape to prevent the container 34 from becoming bowed or distorted when subject to air pressure. The container 34 is formed from a durable material that can withstand air pressure stress; including, polypropylene, polyethylene, and nylon. Embodiments of the container 34 formed from a generally opaque material may have measuring indicia on the interior surface of the container 34 visible from the opening 36 in the top of the container 34 . Embodiments of the container 34 formed from a generally translucent material may include measuring indicia on the exterior of the container 34 . The volume of the container 34 may vary depending on the embodiment and purpose of the sprayer.
As shown in FIG. 3 , the top portion of the container 34 includes a cylindrical rim 16 with an opening 36 . The cylindrical rim 16 may extend upward from the container 34 and included a threaded exterior surface, as illustrated in FIG. 3 . Alternatively, the cylindrical rim 16 may extend into the container 34 and include a threaded interior surface. The cylindrical rim 16 mates with an opposing threaded portion 24 of the cap 22 , illustrated in FIG. 5A . The opening 36 in the cylindrical rim 16 may have a diameter large enough for a user to insert his or her adult hand into the container 34 .
With reference to FIG. 2 , the container 34 includes a spray port 42 that accepts a spray wand outlet 46 . The spray wand outlet 46 may be secured to the spray port 42 with any suitable airtight and watertight sealing method, including a threaded engagement, epoxy, or an adhesive. As illustrated in FIG. 3 the spray port 42 includes an opening in fluid communication with the container 34 . With continued reference to FIG. 2 , the container 34 may contain an outlet 46 integral with the container 34 sidewalls. The outlet 46 includes a hose connection portion and a tube connection portion. The hose connection portion is on the exterior of the tank 14 and mates with the spray wand hose (not illustrated), of a typical spray wand as known in the art. The tube connection portion is on the interior of the tank 14 and mates with a pick-up tube within the container 34 that extends from the outlet 46 to the bottom of the container 34 .
The container 34 also includes an air pressure relief port 98 that accepts an air pressure relief valve 102 , as illustrated in FIGS. 1 and 4 . The air pressure relief port 98 is typically positioned on the container 34 above the maximum solution level. The air pressure relief valve 102 may be secured to the air pressure relief port 98 with any suitable airtight and watertight sealing method, including a threaded engagement, epoxy, or an adhesive. The air pressure relief valve 102 expels air when the air pressure in the container 34 exceeds a predetermined threshold. When the air pressure in the container 34 returns to a level below the threshold level the air pressure relief valve 102 automatically closes.
The base 38 portion of the tank 14 includes footholds 54 , 55 situated between footstands 50 , 51 as best illustrated in FIGS. 1 and 2 . The base 38 can be made from the same material as the container 34 ; including, polypropylene, polyethylene, and nylon. If the base 38 and the container 34 are made from different materials, the base 38 should be securely fastened to the bottom of the container 34 . Ideally, a user should be able to apply a strong upward force to the pump 30 without separating the base 38 from the container 34 .
The base 38 includes two footstands 50 , 51 that project laterally from opposite sides of the container 34 , and provide first and second lateral foot contact portions, as illustrated in FIGS. 1-4 . The footstands 50 , 51 have a convex periphery 57 . In one embodiment, the shape of the convex footstands 50 , 51 may approximately match the arch portion of a person's foot. The upper surface of each footstand 50 , 51 is suitable for a user to stand upon while stroking the pump 30 . In one embodiment, the upper surface of the footstands 50 , 51 includes a notched or ridged surface to grip the user's feet. The footstand 50 , 51 may include an inclined upper surface, with the highest portion of each foothold 50 , 51 proximate the container 34 and the lowest portion of each foothold 50 , 51 proximate the convex periphery 57 of each foothold 50 , 51 . In another embodiment, the diameter of the container 34 proximate the footholds 50 , 51 gradually decreases. The gradually decreasing container 34 diameter combined with the inclined upper surface of the foothold 50 , 51 , forms a concave region 52 that surrounds the inner portion of a user's shoe; thereby, enabling the user to stabilize the pressure sprayer while stroking the pump 30 . The side surfaces of the footstands 50 , 51 have a concave periphery 53 that smoothly transitions into the convex periphery 57 at a rounded corner 56 . Finally, the bottom of each footstand 50 , 51 includes a surface that engages the ground to support the tank sprayer 10 .
The two footholds 54 , 55 are positioned between the footstands 50 , 51 on the base 38 , as best illustrated in FIG. 1 . The footholds 54 , 55 are provided as recessed areas in the bottom portion of the container 34 . Specifically, distance A defines the length and distance B defines the width of the footholds 54 , 55 . In at least one embodiment, distance A is about three to twelve inches, and distance B is about one to six inches. Preferably, distance A is about four to six inches, and distance B is about two to three inches. The height of the footholds 54 , 55 is defined by the height of the footstands 50 , 51 as represented by distance C in FIG. 4 . In at least one embodiment, distance C is about one-half to four inches. Preferably, distance C is about one to two inches.
In the embodiment of FIGS. 1 to 4 , the footholds 54 , 55 are not configured to be stood upon; instead, the footholds 54 , 55 are recesses bordered by a concave sidewall 53 . The concave sidewalls 53 of the footholds 54 , 55 are configured to engage the sides of user's shoes, and provide rotational stability to the container 34 while the user rotates the cap 22 or the pump 30 . To provide a sufficient shoe contact surface, the footholds 54 , 55 include an area large enough to accept the inside forefoot portion of a man's foot or shoe. The height of the sidewalls 53 of the footholds 54 , 55 may be greater than the height of the sole portion of a man's shoe in order to provide a large area of engagement with the man's shoe and prevent the footstands 50 , 51 from sliding under or over the user's shoes while the user attempts to rotate the cap 22 or pump 30 .
Referring to FIGS. 1 and 2 the cap 22 is threadedly connected to the top portion of the container 34 to cover the opening 36 in the container. The cap 22 includes first and second handles 58 , 59 with a funnel 62 positioned between the handles 58 , 59 . The cap 22 is made from a rigid material, preferably plastic. The handles 58 , 59 and funnel 62 can be an integral unit, or each element can be individually formed and secured together. A sealing member 204 ensures that the cap 22 makes an airtight and watertight junction with the container 34 , even when the container 34 is subject to air pressure, as shown in FIG. 5 . Viable sealing members 204 include rubber or synthetic gaskets and o-rings.
The exterior periphery of the cap 22 includes a spray wand holder 66 , nozzle openings 68 , and strap connections 72 . The spray wand holder 66 supports the spray wand when the wand is not in use. As illustrated in FIGS. 2 , 5 A, and 5 C, the spray wand holder 66 is a circular opening in a projection extending from the cap 22 . Alternatively, the spray wand holder 66 can include a circular hole with a notch 70 slightly wider than the diameter of the rigid rod portion of the spray wand. The spray wand holder 66 can be formed at any portion along the periphery of the cap 22 , including in the handles 58 , 59 .
With continued reference to FIGS. 2 , 5 A, and 5 C, the nozzle openings 68 provide a storage area for spray wand nozzles. As illustrated, the nozzle openings 68 extend through the periphery of the cap 22 ; however in another embodiment the nozzle openings 68 are depressions in the cap 22 having a bottom surface that prevents a nozzle from falling through the opening 68 . The nozzle openings 68 have a conical interior surface that becomes narrower toward the bottom of the opening 68 . The interior surface grips the exterior of the nozzle to prevent the nozzle from becoming inadvertently jarred from the opening 68 . Furthermore, a portion of the nozzle remains above the surface of the cap 22 when the nozzle is inserted into the opening 68 . The portion of the nozzle remaining above the cap 22 can be grasped by the user when the user desires to remove the nozzle from the nozzle opening 68 .
The strap connections 72 provide a coupling point for the attachment members of a carrying strap. As shown in FIGS. 2 , 5 A, and 5 C, the strap connections 72 are laterally displaced upon the cap 22 to provide the user with a balanced lifting point. Each connection 72 includes an opening that extends therethrough. The opening is sized to couple with the attachment member of a carrying strap (not illustrated). The connections 72 are sufficiently rigid to permit a user to lift and carry the tank sprayer 10 without bending or deforming the connections 72 .
Also, on the exterior periphery of the cap 22 are the two laterally displaced handles 58 , 59 . A first handle 58 extends outwardly from a first side of the cap 22 , and a second handle 59 extends outwardly from a second side of the cap 22 opposite the first side. The left and right handles 58 , 59 assist the user in securing and removing the cap 22 from the container 34 . The handles 58 , 59 illustrated in FIGS. 1 and 2 include extension portions 116 and a horizontal connection portion 74 ; however, any handle 58 , 59 that permits a user to apply a rotational force to the cap 22 may be utilized. For example, in one embodiment, the handles 58 , 59 may include a curvature either toward or away from the base of the container 34 . Depending on the shape of the container 34 the curvature may simplify grasping the handles 58 , 59 . In another embodiment, the handles 58 , 59 extend outward in a substantially lateral direction relative to the funnel 62 such that a user's hands are positioned substantially to the sides of the funnel 62 when the tank 14 is in an upright position and the user's hands grasp the handles 58 , 59 . In still another embodiment, the handles 58 , 59 may exhibit vertical connection portions 74 . Handles 58 , 59 exhibiting a vertical connection portion 74 could have substantially the same shape as the illustrated handles 58 , 59 exhibiting a horizontal connection portion 74 ; however, each vertical connection portion 74 may include a single extension portion 116 .
As illustrated in FIGS. 1 and 2 , the handles 58 , 59 include an irregular gripping surface 74 . The gripping surface 76 reduces the likelihood that the user's gloves will slide along the surface of the handles 58 , 59 as the user attempts to rotate the cap 22 . As illustrated in FIG. 1 , the gripping surface 76 may simply include a series of ridges in the upper and/or lower portions of the horizontal connection portions 74 grasped by the user. In another embodiment, the handles 58 , 59 may include a rubberized coating instead of the series of ridges. Like the series of ridges, the rubberized coating surrounds the horizontal connection portions 74 .
The central portion of the cap 22 includes a funnel 62 and a drain 60 leading to the container 34 , as best illustrated FIGS. 5A to 5C . The funnel 62 can be formed integrally with the cap 22 , or the funnel 62 can be a distinct unit attached to the cap 22 . As shown in FIGS. 5A and 5C , the drain 60 is provided as a threaded opening which provides a passage to the opening 36 in the container 34 . The drain 60 is too small for a user to insert his or her adult hand. The substantially conical surface of the funnel 22 gradually becomes larger as the funnel 62 extends away from the drain 60 . The top edge of the funnel 62 is terminated with a ridge 78 . The depth of the funnel 62 depends on the embodiment, but in general the funnel 62 extends from the drain 60 to the top of the cap 22 . In another embodiment, the top of the funnel 62 includes a cylindrical rim that extends above the cap 22 to provide the user with an even larger pouring surface. In the disclosed embodiment, the conical surface of the funnel 62 is generally smooth, without cavities or irregularities in which the funneled solution may become isolated.
A measuring vessel 26 , provided in the form of a measuring cup 26 , is connected to the exterior periphery of the cap 22 , as shown in FIGS. 1 and 4 . The measuring cup 26 is made of a rigid and sturdy material such as plastic or metal, and is suitable to measure liquid, powdered, solid, or gelled solutions. In one embodiment, the measuring cup 26 includes multiple chambers 96 of a specified quantity. For instance, the measuring cup 26 may contain chambers 96 sized to hold a tablespoon, a liquid ounce, and twenty five milliliters. Furthermore, each chamber 96 may include additional indicia that further divide the chambers 96 into smaller quantities. In another embodiment, the measuring cup 26 simply includes one large chamber 96 with indicia marked on the inner surface. In either embodiment, the measuring cup 26 can be made from a translucent material and the measuring indicia can be formed into the outer surface of the chamber 96 or chambers 96 . The indicia indicate measured quantities in both Metric and United States Customary Units.
The measuring cup 26 includes arms 82 with tabs 86 that secure the first and second side of the measuring cup 26 to a pair of brackets 90 , as best illustrated in FIGS. 1 and 2 . The brackets 90 can be attached to, or integral with, the cap 22 or the handles 58 , 59 . In general, the measuring cup 26 is pivotably attached to the brackets 90 ; however, the measuring cup 26 can be removed and reattached by bending the resilient arms 82 , thereby pulling the tabs 86 out of the brackets 90 . When attached to the cap 22 , the measuring cup 26 pivots about the tabs 86 from an upright “fill” position to a tilted “pour” position. The bottom portion of the measuring cup 26 includes a post 92 that rests against the periphery of the cap 22 or the container 34 to maintain the measuring cup 26 in a level orientation while the measuring cup 26 is in the fill position. When the measuring cup 26 is pivoted, the contents of each chamber 96 are directed out of the measuring cup 26 and onto the conical surface of the funnel 62 , which is in fluid communication with the container 34 via the drain 60 . The measuring cup 26 includes a spout 94 into which the chambers 96 divert their contents when the measuring cup 26 becomes pivoted to the pour position. The spout 94 ensures the contents of the measuring chambers 96 are accurately directed onto the conical surface of the funnel 62 .
The upper periphery of the measuring cup 26 may include a ridge 80 , as most clearly illustrated in FIG. 5A . The ridge 80 extends from the body of the measuring cup 26 and can be used as a handle to pivot the measuring cup 26 . Additionally, in some embodiments, the ridge 80 may include measuring indicia corresponding to the capacity of the chambers 96 .
As previously mentioned, the spout 94 directs the contents of the chambers 96 on to the surface of the funnel 62 . Additionally, the spout 94 serves as an interlock device, as best illustrated in FIG. 4 . In particular, the pump housing 106 prevents the measuring cup 26 from pivoting to the pour position when the pump housing 106 is positioned in the drain 60 of the cap 22 . Motion is prevented because the spout 94 abuts the housing 106 of the pump 30 when the pump 30 is connected to the drain 60 in the cap 22 . The housing 106 prevents the measuring cup 26 from pivoting, because in order to pivot the spout 94 must move toward the center of the drain 60 ; however, with the pump housing 106 in the path of movement, the spout 94 cannot move toward the drain 60 . Of course, with the pump 30 removed from the drain 60 , the path of movement of the measuring cup 26 is unobstructed, permitting the measuring cup 26 to pivot to the tilted “pour” position.
The double action pump 30 includes an outer housing 106 , a pump mechanism, and a handle 110 , as illustrated in FIG. 6 . The housing 106 is made of a rigid material, usually plastic or metal. In one embodiment, the housing 106 has a cylindrical shape, with a diameter that abuts the spout 94 of the measuring cup 26 when the measuring cup 26 is in the fill position. In another embodiment, the housing 106 includes a spout receptor that engages the spout 94 once the housing 106 has been completely threaded into the drain 60 in the cap 22 . The spout receptor can be a spout 94 shaped indentation in the housing 106 that receives the spout 94 when the pump 30 is securely fastened to the cap 22 . In each embodiment, the housing 106 prevents the measuring cup 26 from pivoting when the pump 30 is attached to the cap 22 .
Referring now to FIGS. 6 to 8 , the housing 106 surrounds the pump mechanism and includes a threaded bottom portion 118 to secure the pump 30 to the threaded drain 60 in the cap 22 . An o-ring 114 prevents the pressure developed in the container 34 from escaping through the junction between the drain 60 and the outer housing 106 . The outer housing 106 , pump mechanism, and of course the handle 110 remain outside of the container 34 when the pump 30 is connected to the cap 22 . The length of the pump 30 combined with the height of the tank 14 enable a user to stroke the pump 30 without having to bend over excessively far on the downstroke, as compared to pressure sprayers that utilize a pump 30 submerged within the container 34 .
The pump handle 110 is threadedly connected to the top of the pump cylinder 138 , as illustrated in FIG. 7 . The handle 110 includes a horizontal contact bar 112 that a user may grasp while stroking the pump 30 . In one embodiment, the length of the contact bar 112 is slightly greater than the width of a man's hand, to permit a user to grasp the handle 110 and stroke pump 30 with a single hand. However, in another embodiment, the length of the contact bar 112 permits a man wearing work gloves to place his two hands side-by-side upon the contact bar 112 while stroking the pump. Additionally, the contact bar 112 includes a series of ridges that provide a gripping surface, and also make the handle 110 easier to hold, should the handle 110 become wet.
With continued reference to FIG. 7 , the handle 110 can be secured to the outer housing 106 enabling a user to carry the tank sprayer 10 by the pump handle 110 . The base of the handle 110 includes a tab 122 used to secure the handle 110 to the outer housing 106 . The tab 122 engages a slot 126 in the outer housing 106 when the handle 110 is fully depressed and rotated. In one embodiment, a pump cushioning spring 130 must also be depressed in order to slide the tab 122 into the slot 126 . The resistive force from the pump cushioning spring 130 presses the tab 122 against the top portion of the slot 126 ensuring the handle 110 remains in the locked position until the user desires to disengage the tab 122 from the slot 126 by rotating the handle 110 .
The pump mechanism injects air into the container 34 for compression. The pump mechanism includes a central connecting rod 134 , a pump cylinder 138 , a primary piston 142 , a secondary piston 146 , first and second check valves 150 , 154 , and a plurality of sealing members and gaskets, as illustrated in FIG. 6 . The interrelationship of each pump mechanism component is explained below.
With reference to FIG. 6 , the central connecting rod 134 is a hollow tube that includes a bottom end in fluid communication with the container 34 . The connecting rod 134 includes a top portion threadedly connected to the primary piston 142 , and a bottom portion threadedly connected to the outer housing 106 . O-ring 200 forms an air tight seal between the connecting rod 134 and the outer housing 106 . O-ring 194 forms an air tight seal between primary piston 142 and the connecting rod 134 . As explained within, the pump cylinder 138 forces air through the connecting rod 134 and into the container 34 for compression.
The pump cylinder 138 is a hollow tube that surrounds the central connecting rod 134 . The pump cylinder 138 is made from a rigid material, usually plastic. As illustrated in FIG. 7 , the pump cylinder 138 includes a top portion threadedly connected to the base of the handle 110 , and, as illustrated in FIGS. 8A and 8B , a bottom portion threadedly connected to the secondary piston 146 . An o-ring 190 ensures that the pump cylinder 138 makes an air tight junction with the secondary piston 146 .
The primary piston 142 and the second check valve 154 are threadedly engaged to the top of the connecting rod 134 , as illustrated in FIG. 7 . The primary piston 134 has an outside diameter slightly smaller than the inside diameter of the pump cylinder 138 . The primary piston 134 includes a groove 182 , which houses a “floating” o-ring 186 . The diameter of a cross section of the o-ring 186 is slightly smaller than the height of the groove 182 , such that the o-ring 186 is vertically displaceable within the groove 182 . As the pump 30 is stroked, the o-ring 186 moves to the top of the groove 182 on the upstroke, as illustrated by FIG. 10B , and moves to the bottom of the groove 182 on the downstroke, as illustrated by FIG. 10A .
With reference to FIG. 8 , the secondary piston 146 is a circular ring threadedly engaged to the bottom of the pump cylinder 138 . As the handle 110 is stroked, the pump cylinder 138 and the secondary piston 146 slide along the outer surface of the connecting rod 134 . The secondary piston 146 includes a groove 174 which houses a “floating” o-ring 178 . The diameter of a cross section of the o-ring 178 is slightly smaller than the height of the groove 174 , such that the o-ring 178 is vertically displaceable within the groove 174 . The o-ring 178 inside diameter is equal to the outside diameter of connecting rod 134 . As the pump 30 is stroked, the o-ring 178 slides up and down the outer surface of the connecting rod 134 , moving to the top of the groove 174 on the downstroke, as illustrated by FIG. 9A , and moving to the bottom of the groove 174 on the upstroke, as illustrated by FIG. 9B .
Check valves 150 , 154 include bases 152 , 156 with openings 158 , 162 and elastomeric diaphragms 166 , 170 , as illustrated in FIG. 7 . Each check valves 150 , 154 selectively seals a cavity of varying size formed by the motion of the pump cylinder 138 . When the air pressure above the check valves 150 , 154 exceeds the air pressure below the check valve 150 , 154 the edges of the diaphragm 166 , 170 flex away from the base 152 , 156 permitting air to travel to the area of lower pressure through the openings 158 , 162 . When the air pressure below the check valves 150 , 154 exceeds the air pressure above the check valves 150 , 154 , the air pressure forces the edges of the diaphragm 166 , 170 against the base 152 , 156 thereby sealing the openings 158 , 162 .
When a user initiates an upstroke, as illustrated in FIGS. 9B and 10B , by forcing the handle 110 and the pump cylinder 138 upward, the second check valve 154 opens allowing outside air to flow along direction A into the cavity defined at the top by the second check valve 154 and at the bottom by the primary piston 142 . Air continues to flow through the second check valve 154 into the aforementioned cavity throughout the entire upstroke motion. Additionally, the upstroke draws o-ring 186 against the top side of the groove 182 in the primary piston 142 , and o-ring 178 against the bottom side of the groove 174 in the secondary piston 146 . As the upward motion of the pump cylinder 138 causes the cavity between the pump cylinder 138 and the connecting rod 134 to become smaller, the air within the cavity is forced into groove 182 along directions P and B. After passing through the groove 182 the air flows along direction C, into the openings 158 in the first check valve 150 . Finally, the air flows into the connecting rod 134 , and ultimately into the container 34 for compression.
Alternatively, when a user initiates a downstroke, as illustrated in FIGS. 9A and 10A , by forcing the handle 110 and the pump cylinder 138 downward, the air trapped above the primary piston 142 forces the second check valve 154 closed, and o-ring 186 to the bottom of the groove 182 in the primary piston 142 . As the downward motion of the pump cylinder 138 causes the cavity above the primary piston 142 to become smaller, the air within the cavity is forced into groove 182 along direction G. Throughout the downstroke the air continues to flow, along direction H, through the openings 158 in the first check valve 150 , into the connecting rod 134 , and ultimately into the container 34 .
Also during the downstroke, the downward motion of the pump cylinder 138 forces o-ring 178 to the top of the groove 174 in the secondary piston 146 , permitting air to enter the cavity between the pump cylinder 138 and the connecting rod 134 , in the following manner. First, the downward motion develops a vacuum between the pump housing 106 and the pump cylinder 138 that draws in outside air along directions I and J. Next, the air is drawn around the pump cushioning spring 130 along direction L. Finally, the vacuum draws air between the secondary piston 146 and the connecting rod 134 , and through groove 174 , along direction M. In summary, the pump 30 includes two air chambers; during each pump 30 stroke one of the chambers is filled with outside air, while the air in the other chamber is evacuated into container 34 . Thereby, enabling the pump to deliver air to the container 34 during each pump 30 stroke.
After a series of pump 30 strokes, the user will have pumped a substantial volume of air into the container 34 . The air pressure generated by the increased volume of air forces the diaphragm 166 of the first check valve 150 to seat against the base 152 , thereby indefinitely maintaining the volume of air within the container 34 . When the user activates the valve on the spray wand the increased air pressure propels the solution from the container 34 .
To reduce the probability of the pump 30 becoming damaged due to vigorous downward stroking, the pump 30 includes a cushioning spring 130 . The bottom surface of the cushioning spring 130 contacts the bottom of the pump housing 106 , and the top of the spring 130 contacts the bottom portion of the secondary piston 146 . The spring 130 cushions the secondary piston 146 should the piston 146 become forcefully directed toward the bottom of the pump 30 . Additionally, the cushioning spring 130 provides tension upon the handle 110 when the handle 110 is in the locked position.
In operation, a user first obtains and utilizes appropriate safety attire, which may include safety glasses, gloves, apron, and face mask. Next, the user places his or her shoes in the footholds 54 , 55 , grasps the pump handle 110 , and slowly rotates the handle 110 until the pump 30 can be removed from the cap 22 . Then, with shoes remaining in the footholds 54 , 55 , the user grasps the cap handles 58 , 59 and rotates the cap 22 until it can be removed from the container 34 . Alternatively, the user may stand upon the footstands 50 , 51 when removing the cap 22 from the container 34 . With the cap 22 removed, the user can clean the inside of the container 34 or fill the container 34 with an appropriate amount of water or other solvent. Next, the user tightly secures the cap 22 to the container 34 , using the footholds 54 , 55 to stabilize the container 34 . If the user desires to add a solute to the solvent, the user can measure an appropriate quantity of solute in the measuring cup 26 . When the appropriate amount of solute has been measured, the user pivots the measuring cup 26 to the tilted “pour” position to direct the solute onto the surface of the funnel 62 through the drain 60 in the cap 22 and into the container 34 . Next, the user attaches the pump 30 to the threaded drain 60 . Finally, the user stands upon the footstands 50 , 51 and repeatedly strokes the pump 30 until a sufficient air pressure has been developed in the container 34 . Likewise, the user may stabilize the tank 14 with the footholds 54 , 55 while stroking the pump 30 . Finally, the user may the trigger the spray wand to distribute the product, following any and all directions provided by the manufacturer of the solvent or solute.
Those skilled in the art will recognize that numerous modifications can be made to the specific implementations described above. Therefore, the following claims are not to be limited to the specific embodiments illustrated and described above. The claims, as originally presented and as they may be amended, encompass variations, alternatives, modifications, improvements, equivalents, and substantial equivalents of the embodiments and teachings disclosed herein, including those that are presently unforeseen or unappreciated, and that, for example, may arise from applicants, patentees, and others. | A tank sprayer includes a tank configured to receive fluid through an opening in the tank, a removable cap covering the opening in the tank, and a removable pump. The removable cap includes a first handle extending outwardly from a first side of the cap, a second handle extending outwardly from a second side of the cap opposite the first side, and a funnel provided between the first handle and the second handle. The funnel has a substantially conical sidewall and a drain leading to the opening in the tank. The removable pump engages the drain of the cap, wherein the pump is operable to advance air into the tank to pressurize the tank. | 1 |
INCORPORATION BY REFERENCE TO ANY PRIORITY APPLICATIONS
[0001] Any and all applications for which a foreign or domestic priority claim is identified in the Application Data Sheet as filed with the present application are hereby incorporated by reference under 37 CFR 1.57.
TECHNICAL FIELD
[0002] The invention pertains to a mobile robot for cleaning a floor or other surface. In particular, the invention pertains to a robot configured to implement a class of trajectories designed to efficiently scrub or otherwise clean the floor.
[0003] BACKGROUND
[0004] From their inception, robots have been designed to perform tasks that people prefer not to do or cannot do safely. Cleaning and vacuuming, for example, are just the type of jobs that people would like to delegate to such mechanical helpers. The challenge, however, has been to design robots that can clean the floor of a home well enough to satisfy the exacting standards of the people the live in it. Although robots have been designed to vacuum floors, robots designed to perform mopping present unique challenges. In particular, such a robot should be able to dispense cleaning solution, scrub the floor with the solution, and then effectively remove the spent cleaning solution. Robots tend to perform unsatisfactorily, however, because hard deposits on the floor may require time for the cleaning solution to penetrate and removal of the dirty solution may leave streak marks on the floor. There is therefore a need for a cleaning robot able to implement a cleaning plan that enables the robot to apply cleaning solution, repeatedly scrub the floor with the solution, and leave the floor free of streak marks.
SUMMARY
[0005] The present invention pertains to a mobile robot configured to travel across a residential floor or other surface while cleaning the surface with a cleaning pad and cleaning solvent. The robot includes a controller for managing the movement of the robot as well as the treatment of the surface with a cleaning solvent. The movement of the robot can be characterized by a class of trajectories that achieve effective cleaning. These trajectories seek to: maximize usage of the cleaning solvent, reduce streaking, utilize absorption properties of the pad, and use as much of the surface of the pad as possible. In an exemplary embodiment, the trajectory may include an oscillatory motion with a bias in a forward direction by repeatedly moving forward a greater distance than backward. In the same exemplary embodiment, the cleaning pad is a disposable sheet impregnated with solvent that is then applied to and recovered from the surface by means of the trajectory.
[0006] In one embodiment, the cleaning robot includes a cleaning assembly; a path planner for generating a cleaning trajectory; and a drive system for moving the robot in accordance with the cleaning trajectory. The cleaning trajectory is a sequence of steps or motions that are repeated a plurality times in a prescribed order to effectively scrub the floor. Repetition of the sequence, in combination with the forward and back motion, causes the cleaning assembly to pass of areas of the floor a plurality of times while allowing time for the cleaning solution to penetrate dirt deposits.
[0007] The sequence repeated by the cleaning trajectory preferably comprises: (i) a first path for guiding the robot forward and to the left; (ii) a second path for guiding the robot backward and to the right; (iii) a third path for guiding the robot forward and to the right; and (iv) a fourth path for guiding the robot backward and to the left. The first path and third path result in a longitudinal displacement of the robot (movement parallel to the direction of progression) referred to as a first distance forward, and the second path and fourth path result in a longitudinal displacement referred to as a second distance backward. The first distance is greater than the second distance, preferably twice as large. In addition, the second path results in a lateral displacement (movement perpendicular to the direction of progression) which is referred to as the third distance, and the fourth path moves the robot laterally by a fourth distance that is equal in magnitude but opposite in direction from the third distance. In the preferred embodiment, the first through fourth paths are arcuate paths.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The present invention is illustrated by way of example and not limitation in the figures of the accompanying drawings, and in which:
[0009] FIG. 1A is an autonomous mobile robot, in accordance with a preferred embodiment;
[0010] FIG. 1B is the autonomous mobile robot moving in the forward direction, in accordance with a preferred embodiment;
[0011] FIG. 1C is the autonomous mobile robot moving in the backward direction, in accordance with a preferred embodiment;
[0012] FIG. 2 is a schematic diagram of a navigation system, in accordance with a preferred embodiment;
[0013] FIG. 3 is a cleaning trajectory for scrubbing a floor, in accordance with an exemplary embodiment;
[0014] FIGS. 4A-4D depict a sequence of steps that produce the trajectory of FIG. 3 ;
[0015] FIG. 5 is a cleaning trajectory for scrubbing a floor, in accordance with another exemplary embodiment;
[0016] FIGS. 6A-6D depict a sequence of steps that produce the trajectory of FIG. 5 ;
[0017] FIG. 7 is a cleaning trajectory for scrubbing a floor, in accordance with still another exemplary embodiment; and
[0018] FIGS. 8A-8B depict a sequence of steps that produce the trajectory of FIG. 7 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0019] Illustrated in FIG. 1A is an autonomous mobile robot 100 configured to clean or otherwise treat a floor or other surface using a trajectory designed to repeatedly scrub the floor. In the preferred embodiment, the mobile robot 100 includes a housing with a controller and navigation system (not shown) for generating a path to clean the entire floor, a drive system 110 configured to move the robot around a room or other space in a determined trajectory, and a cleaning assembly 120 A pivotably attached to the robot housing by means of a hinge 130 . The cleaning assembly 120 A preferably includes a curved bottom surface 122 configured to press a cleaning sheet to the floor. The mobile robot in the preferred embodiment is based on the cleaning robot taught in pending U.S. patent application Ser. No. 12/429,963 filed on Apr. 24, 2009, which is hereby incorporated by reference herein.
[0020] The cleaning component in the preferred embodiment is configured to scrub the floor with a disposable cleaning sheet, preferably a wet cleaning sheet impregnated with cleaning solution. In other embodiments, the cleaning assembly is configured to dispense cleaning solution directly on the floor and then scrub the floor with a dry cleaning sheet. In still other embodiments, the cleaning assembly is configured to employ cleaning components for brushing, dusting, polishing, mopping, or vacuuming the floor, which may be a wood, tile, or carpet, for example.
[0021] Illustrated in FIG. 2 is a schematic diagram of the navigation system in the preferred embodiment. The navigation system 200 includes a navigation module 210 configured to maintain an estimate of the robot's current pose while it navigates around its environment, preferably an interior room bounded by walls. The pose 212 , which includes both the position and orientation, is based on multiple sensor readings including wheel odometry 214 provided by encoders integrated into the wheels 110 , orientation readings 216 from a gyroscope (not shown) on board the robot, and position coordinates from an optical sensor configured to sense light reflected from the room's ceiling. The optical sensor may include one or more photo diodes, one or more position sensitive detectors (PSDs), or one or more laser range finders, for example. The optical sensor employed in the preferred embodiment is taught in U.S. Pat. No. 7,720,554, which is hereby incorporated by reference herein.
[0022] The navigation system further includes a path planner 220 for generating or executing logic to traverse a desired trajectory or path 222 to scrub the entire floor with no gaps. In path 222 designed by the path planner 220 is a combination of a first trajectory from a room coverage planner 222 and a second trajectory from a local scrub planner 226 , which are discussed in more detail below. Based on the current pose 212 and the desired path 222 , the motion controller generates motion commands 232 for the robot drive 240 . The commands in the preferred embodiment include the angular velocity for each of a pair of wheels 110 , which are sufficient to control the speed and direction of the mobile robot. As the robot navigates through its environment, the navigation module 210 continually generates a current robot pose estimate while the path planner 220 updates the desired robot path.
[0023] The first trajectory is designed to guide the robot throughout the entire room until each section of the floor has been traversed. The second trajectory is a pattern including a plurality of incremental steps that drive the cleaning assembly both forward and backward, and optionally left and right. The first trajectory ensures every section of the floor is traversed with the cleaning assembly while the second trajectory ensures each section of floor traversed is effectively treated with cleaning solution and scrubbed with multiple passes of the cleaning assembly.
[0024] The first trajectory may take the form of any of a number of space-filling patterns intended to efficiently traverse each part of the room. For example, the first trajectory may be a rectilinear pattern in which the robot traverses the entire width of the room multiple times, each traversal of the room covering a unique swath or row adjacent to the prior row traversed. The pattern in repeated until the entire room is covered. In another embodiment, the robot follows a path around the contour of the room to complete a loop, then advances to an interior path just inside the path traversed in the preceding loop. Successively smaller looping patterns are traversed until the center of the room is reached. In still another embodiment, the robot traverses the room in one or more spiral patterns, each spiral including a series of substantially concentric circular or substantially square paths of different diameter. These and other cleaning contours are taught in U.S. patent application Ser. No. 12/429,963 filed on Apr. 24, 2009.
[0025] The second trajectory scrubs the floor using a combination of forward and backward motion. The step in the forward direction is generally larger than the step in the backward direction to produce a net forward movement. If the second trajectory includes lateral movement, the steps to the left and right are generally equal. The repeated forward/backward motion, in combination with hinge 130 , causes the orientation of the cleaning assembly to oscillate between a small angle forward or a small angle backward as shown in FIGS. 1B and 1C , respectively. When driven in the forward direction, the cleaning assembly 120 B pivots forward which presses the front half of the cleaning pad against the floor while lifting the back half away from the floor. When driven in the reverse direction, the cleaning assembly 120 C pivots backward to press the back half of the cleaning pad against the floor while lifting the front half away from the floor. As a result, the front half of the cleaning sheet (1) scrubs the floor with the cleaning sheet impregnated with cleaning solution and (2) captures/collects dirt and debris as the robot advances in the forward direction (see FIG. 1B ). On the other hand, the back half of the cleaning sheet, which remains generally free of debris, scrubs the floor with cleaning solution released from the cleaning sheet. This serves to: (i) evenly apply cleaning solution, (ii) recover the cleaning solution mixed with dissolved dirt, (iii) produce an elapse time between application and recovery of the cleaning solution, (iv) mechanically agitate the cleaning solution on the floor, and (v) produce little or no visible streak marks on the floor. In the exemplary embodiment, the cleaning sheet is impregnated with a cleaning solution that is transferred to the floor by contact. In another embodiment the mobile robot includes a reservoir with at least one nozzle configured to either spray cleaning solution on the floor surface in front of the cleaning assembly or diffuse the cleaning solution directly into the upper surface of the sheet through capillary action.
[0026] Illustrated in FIG. 3 is an example of a second trajectory for scrubbing a floor. The trajectory is produced by repetition of the sequence of steps shown in FIGS. 4A-4D . The solid line 310 represents the path traced by the midpoint of the leading edge of the cleaning assembly 120 while the shaded region 320 represents the region of floor scrubbed by the cleaning assembly. When this sequence is employed, the robotic cleaner oscillates in the forward direction of motion as well as laterally. For each oscillation, the forward displacement (defined as the “fwd_height”) exceeds the backward displacement (defined as the “back_height”) so the robot advances in a generally forward direction (defined as the “direction of progression”). The robot also moves left and right equal amounts (defined as the fwd_width) which causes the robot to travel in a generally straight line.
[0027] The trajectory shown in trajectory in FIG. 3 is produced by repetition of the sequence of steps illustrated in FIG. 4A-4D in the prescribed order. Each step or leg comprises a motion with an arcuate path. The first leg 410 of the sequence shown in FIG. 4A advances the robot forward by fwd_height and to the left. In the second leg 420 shown in FIG. 4B , the robot moves backward by back_height and to the right. In the third leg 430 shown in FIG. 4C , the robot moves forward by fwd_height and to the right. In the fourth leg 440 shown in FIG. 4D , the robot moves backward by back_height and to the left. The forward arcing motions have a larger radius than the back motions such that the robot is oriented parallel to the direction of progression upon completion of the backward motion.
[0028] Trajectories that include arced or arcuate paths can provide several benefits over trajectories having only straight paths. For example, the trajectory shown in FIG. 3 , which consists of arcuate paths, causes the robot to continually turn or rotate while in motion. This rotation, in turn is detected by the on-board gyroscope and monitored by the navigation system for purposes of detecting slippage of the wheels 110 . When the detected rotation is different than the rotation associated with the curvature of the path, the robot can confirm slippage due to loss of traction, for example, and correct the robots course accordingly. In contrast, trajectories with straight paths make it difficult to detect slippage when, for example, both wheels slip at the same rate which cannot be detect with the gyro.
[0029] For the trajectory shown in FIGS. 3 and 4A-4D , the parameters are as follows:
[0030] (a) fwd_height: the distance traveled in the direction of progression on the forward legs or strokes has a value of approximately 1.5 times with width of the cleaning assembly 120 , the width being measured in the direction perpendicular to the direction of progression;
[0031] (b) back_height: the distance traveled in the direction opposite the direction of progression on the backward legs or strokes has a value of approximately 0.75 times the width of the cleaning assembly 120 ; and
[0032] (c) fwd_width: the distance traveled orthogonal to the direction of progression on the forward legs or strokes has a value of approximately 0.3 times the width of the cleaning assembly 120 .
[0033] In general, however, fwd_height may range between one and five times the width of the cleaning assembly 120 , the back_height may range between one third and four times the width of the cleaning assembly 120 , and the elapse time of a cleaning single sequence may range between five second and sixty seconds.
[0034] Where the cleaning sheet is a Swiffer® Wet Cleaning Pad, for example, each sequence of the trajectory is completed in a time between 15 to 30 seconds, which enables the cleaning solution to remain on the floor long enough to dissolve dirt but not so long that it first evaporates.
[0035] Illustrated in FIG. 5 is another example of a second trajectory for scrubbing a floor. The trajectory is produced by repetition of the sequence of steps shown in FIGS. 6A-6D . The solid line 510 represents the path traced by the midpoint of the leading edge of the cleaning assembly 120 while the shaded region 520 represents the region of floor scrubbed by the cleaning assembly. When this sequence is employed, the robotic cleaner oscillates in the forward direction of motion as well as laterally. For each oscillation, the forward displacement (“fwd_height”) exceeds the backward displacement (“back_height”) so the robot advances in a generally forward direction (“direction of progression”). The robot also moves left and right equal amounts (fwd width) which causes the robot to travel in a generally straight line.
[0036] The trajectory shown ion trajectory in FIG. 5 is produced by repetition of the sequence of steps illustrated in FIG. 6A-6D . Each step or leg comprises a motion with an arcuate path. The first leg 610 of the sequence shown in FIG. 6A advances the robot forward by fwd_height and to the left with a predetermined radius. In the second leg 620 shown in FIG. 4B , the robot moves backward by back_height and to the right along the same radius as leg 610 . In the third leg 630 shown in FIG. 6C , the robot moves forward by fwd_height and to the right with the same predetermined radius. In the fourth leg 640 shown in FIG. 6D , the robot moves backward by back_height and to the left with the same radius as above. The forward arcing motions progress a greater distance than the back motions so that the robot generally progresses in the forward direction.
[0037] For the trajectory shown in FIGS. 5 and 6A-6D , the parameters are as follows:
[0038] (a) fwd_height: the distance traveled in the direction of progression on the forward legs or strokes has a value of approximately 1.5 times with width of the cleaning assembly 120 , namely the direction perpendicular to the direction of progression;
[0039] (b) back_height: the distance traveled in the direction opposite the direction of progression on the backward legs or strokes has a value of approximately 0.75 times the width of the cleaning assembly 120 ; and
[0040] (c) radius: the radius of each arc is approximately equal to the diameter of the mobile robot, although the radius may range between 0.5 and 3 times the width of the cleaning assembly.
[0041] Illustrated in FIG. 7 is another example of a second trajectory for scrubbing a floor. The trajectory is produced by repetition of two legs that are both straight and parallel, as shown in FIGS. 7A-7B . The solid line 710 represents the path traced by the midpoint of the leading edge of the cleaning assembly 120 while the shaded region 720 represents the region of floor scrubbed by the cleaning assembly. When this sequence is employed, the robotic cleaner oscillates in the forward direction but not laterally. For each oscillation, the forward displacement (“fwd_height”) of the forward leg 810 exceeds the backward displacement (“back_height”) of the back leg 820 , so the robot advances in a generally forward direction.
[0042] In some embodiments, the robot further includes a bump sensor for detecting walls and other obstacles. When a wall is detected, the robot is configured to make a U-turn by completing a 180 degree rotation while moving the robot to one side, the distance moved being approximately equal to the width of the cleaning assembly. After completing the turn, the robot is then driven across the room along a row parallel with and adjacent to the preceding row traversed. By repeating this maneuver each time a wall is encountered, the robot is made to traverse a trajectory that takes the robot across each portion of the room.
[0043] The trajectory is preferably based, in part, on the pose of the robot which is tracked over time to ensure that the robot traverses a different section of the floor with each pass, thereby avoiding areas of the floor that have already been cleaned while there are areas still left to be cleaned.
[0044] One or more of the components of the mobile robot, including the navigation system, may be implemented in hardware, software, firmware, or any combination thereof. Software may be stored in memory as machine-readable instructions or code, or used to configure one or more processors, chips, or computers for purposes of executing the steps of the present invention. Memory includes hard drives, solid state memory, .optical storage means including compact discs, and all other forms of volatile and non-volatile memory.
[0045] Although the description above contains many specifications, these should not be construed as limiting the scope of the invention but as merely providing illustrations of some of the presently preferred embodiments of this invention.
[0046] Therefore, the invention has been disclosed by way of example and not limitation, and reference should be made to the following claims to determine the scope of the present invention. | A mobile robot configured to travel across a residential floor or other surface while cleaning the surface with a cleaning pad and cleaning solvent is disclosed. The robot includes a controller for managing the movement of the robot as well as the treatment of the surface with a cleaning solvent. The movement of the robot can be characterized by a class of trajectories that achieve effective cleaning. The trajectories include sequences of steps that are repeated, the sequences including forward and backward motion and optional left and right motion along arcuate paths. | 0 |
RELATED APPLICATIONS
This application claims priority from provisional application 60/578,178 filed on Jun. 8, 2004.
BACKGROUND OF THE INVENTION
The stimulation of the cochlea performed by a cochlear implant typically includes the reception of sound by a microphone placed near to a patient's ear and based on the analysis of this sound, the choice of a set of electrical injection contact points to be stimulated along the cochlea, the current levels to be injected at the injection electrical contact points and for each injection contact point a set of current return points and the current levels to be accepted at each one of these points, or alternatively, an opposite polarity voltage level to be placed at each current return contact point. A problem that has been encountered in cochlear stimulation is that of a fairly small dynamic range of stimulation. That is, the loudest sound comfortable to a patient (the “maximum comfort level” or MCL), is not as much greater than the softest sound detectable by the patient (the “threshold intensity”) as is the difference between softest sound and loudest sound in a natural hearing person.
U.S. Pat. No. 6,480,820, which is incorporated by reference as if fully set forth herein, discloses a method for recognizing sound events that may then form the basis for a scheme of cochlear stimulation. First a vector comprised of the instantaneous phase and magnitude of a sound signal time sample from one band pass filter, is computed. Then the moments when this vector passes the real axis are determined and the magnitude of the vector at these moments is determined. In the following text, these values are described as m t , the desired strength of stimulation. Other methods, however, may be used to find a set of values, m t .
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1A is an illustration of a dipole contact configuration.
FIG. 1B is an illustration of a monopole contact configuration.
FIG. 1C is an illustration of a tripole contact configuration.
FIG. 2 is a graph showing a comparison of the stimulatory effects of monopole and quadrupole stimulation, versus current.
FIG. 3A is an illustration of the response areas of the cochlea for a low-threshold, minimally localized area.
FIG. 3B is an illustration of the response areas of the cochlea for a mid-threshold, medium localized area.
FIG. 3C is an illustration of the response areas of the cochlea for a high-threshold, spatially restricted response area.
FIG. 4 is an illustration of a contact configuration used for quadrupole stimulation.
FIG. 5 is an illustration of the response areas of the cochlea for a low-threshold, minimally localized area, a mid-threshold, medium localized area, and a high-threshold, spatially restricted response area, also showing the cochlear stimulation perceived location.
FIG. 6 is an illustration of a contact configuration used for steered stimulation.
FIG. 7 is a graph showing response strength as a function of stimulus intensity for various values of α.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In one preferred embodiment, the present method is a method for electrically stimulating the cochlea, brain tissue or muscle tissue in order to lower the threshold intensity, to restrict the spread of neural excitation and thereby increase channel independence, and to extend the dynamic range of stimulation. The method is predicated on a base of technological developments making the approach feasible with support from a gathering body of empirical observations on the nature of neural population responses to electrical stimulation.
In one preferred embodiment the method makes use of a scalar electrode array positioned near the neurons of the spiral ganglion lying along the tonotopic continuum in the modiolus of the cochlea, in Rosenthal's canal. The array may have adjacent electrode contacts spaced less than 500 μm center-to-center. Currents from these contacts are taken as charge-balanced pulses to minimize contact erosion and cytotoxic byproducts. While the method does not restrict the stimulating waveforms beyond their being charge balanced to meet safety requirements, it may be used to substantially maximize effectiveness in evoking neural responses. Temporally symmetrical, biphasic pulses of a few tens to a few hundreds of microseconds in duration are practical approximations for these pulses. Temporally asymmetrical, but charge-balanced pulses may be used to meet other goals.
The preferred embodiment consists of determining for the frequency and magnitude of sound at each moment, a current delivery scheme through a specified set of contacts with specified intensities and polarities to achieve a desired spatial pattern of neural excitation in the auditory nerves of the cochlea. These contact patterns and intensities are determined from clinical measures of the implant wearer's psychophysical responses. A lookup table of contact patterns and intensities is stored in computer readable media in the cochlear implant system and referenced by the data processor of the system, which may also perform interpolation to find the exact desired pattern and intensity for a particular tone and loudness.
The relevant electrical, neurophysiological, and psychophysical parameters and measurements will be described in the next section. This will be followed by a review of known empirical evidence pertaining to neural responses to spatial contact patterns and intensities. The goals of the method and its implementation will then be detailed.
Relevant Parameters and Measurements
Physics of Electrical Stimulation. The electrical stimulation of tissue is constrained to have current conservation, i.e., the rate of charge sourcing must equal the rate of charge sinking since there are no appreciable capacitive effects. For safety reasons, the time-integrated charge at each contact must be zero (charge balancing). The effectiveness of electrical stimulation in neural and muscle tissue depends on the redistribution of charge across cellular membranes occurring over a few hundred microseconds at most, and this depends on rapidly varying potential gradients across portions of neurons or muscle cells.
In general, the larger the potential gradient across a cell is, the greater the effect on cell-membrane potential and subsequent changes in cell response. Quantitatively this maximizing of gradients near cells is equivalent to maximizing the second spatial derivative of the potential field. Given a fixed three-dimensional electroanatomy of the tissue this maximization is best achieved by placing small electrode contacts near neurons or muscle cells. Both of these conditions increase current density near the cells and, secondarily, potential gradients across the cell bodies as the currents disperse and converge around sources and sinks. Spatial positioning and surface areas of electrode contacts relative to the stimulated tissues thus determine the effects of electrical currents passed between the source and sink ensembles of electrode contacts. The method to be described is a dynamic manipulation of effective electrode-contact patterns, positions, and surface areas to effect optimal neural responses.
Spatial Contact and Intensity Patterns. FIG. 1 illustrates the terminology commonly used for spatial contact patterns and current intensities. A dipole 10 ( FIG. 1A ) is an ideal physical concept with two points sourcing and sinking current. In practice “bipolar” stimulation is through two contacts with significant metallic surface areas. Monopoles 12 ( FIG. 1B ) are small electrode contacts passing current to a distant, much larger “reference” or “extra cochlear” contact. For cochlear stimulation the monopolar contact is in the scala tympani, and the reference contact is external to the cochlea. Because of the large difference in surface areas the current densities and associated potential gradients near the monopole are much greater than near the reference. Another spatial configuration for contacts is the tripole 14 ( FIG. 1C ). If the tripole has the current values shown (−I/2, +I, −I/2) it can be referred to as a “quadrupole,” the additive combination of two dipoles (four contacts) with currents −I/2 and +I/2 from two sources combined in the center.
Note that one contact has been shown positive and one negative in these illustrations, but this relationship reverses when the phase of a biphasic pulse reverses. This is important because neurons near the cathode are more likely to be stimulated, so a temporal sequencing of stimulation may occur near each contact if they have similar surface areas. This is less likely to occur if one has a much larger surface area because it reduces local current densities and potential gradients.
Threshold. The minimum current intensity for evoking a neural response is defined as the threshold stimulus intensity (see FIG. 2 ). Since increasing current values are associated with undesirable electrochemical processes for metallic electrodes, a requirement of system design and a goal of this method is the minimization of threshold intensities. Monopolar stimulation of the cochlea has been observed to have lower thresholds than multipolar stimulation, an effect predictable from electric field theory. The method is designed to utilize the low-threshold characteristic of monopoles in combination with the advantages of multipolar stimulation to be described.
Dynamic Range. FIG. 2 shows the threshold and dynamic range for a typical response growth curve 20 with monopolar stimulation (curve A). Thresholds are usually 200 to 300 μA or less for monopoles with a rapid rise over a 4 to 6 decibels (dB) dynamic range to a level of response saturation. As suggested in the dashed curve 22 , bipolar stimulation usually has threshold values about 6 dB above monopoles with quadrupolar thresholds being 6 dB or more above monopolar thresholds. Bipolar and quadrupolar stimulation appear to have larger dynamic ranges than monopolar stimulation associated with a less rapid growth in response to saturation.
Response growth can be inferred from physiological and behavioral measures. Measures of neural spikes from individual neurons and the peak magnitudes of evoked potentials to electrical pulses provide an indication of response growth. For clinical measures the detection threshold, loudness estimates, comfort levels, and maximum tolerable levels can be estimated from patient responses.
Channel Independence and Minimizing Threshold. As with all information transmission, the number of independently variable information channels determines the potential number of alternatives that can be represented. The history of cochlear implants supports this dictum in that spatial and temporal resolution, in the form of more array contacts and higher pulse rates, appears correlated with better speech comprehension, that is, more information. Associating stimulation in one region of the cochlea with an information channel implies that achieving the maximum independence for its effect from stimulation at neighboring regions will enhance system performance. Low thresholds minimize the power needed to operate implantable stimulators, the size of the electrodes needed to support a given current or charge, and reduce the chance of producing harmful electrochemical byproducts and eroding electrode contacts. Monopolar stimulation produces low thresholds but great overlap in the neural regions activated, i.e., very poor channel independence, while high thresholds result from multipolar stimulation even though they have good channel independence. This is illustrated in FIG. 3 shown as the decreasing spatial spread of neural activity, measured as neural spike probability, in the transition from monopolar stimulation (panel A) to bipolar (panel B) and tripolar stimulation (panel C). The method to be described achieves the benefits of channel independence, characteristic of tripolar stimulation, and low thresholds, characteristic of monopolar stimulation.
The Method
Curve sets 30 and 34 in FIG. 3 characterize the response areas for the neural population activated by electrical stimulation of the cochlea with monopolar and quadrupolar stimulation, respectively. The transition from A to C is from a low-threshold, minimally localized response area to a high-threshold, spatially restricted response area. The method partially outlined in FIG. 4 provides the means for a continuous transition from these conditions through the use of active contacts 40 , 42 and 44 and passive reference contact 46 .
Quadrupolar stimulation spatially restricts the response area because the active lateral contacts 40 constrain the field divergence, and thereby the local field gradients and stimulated neural population, to a small area near the active contacts 40 . Controlling the current paths with monopolar stimulation (low-threshold, spatially extended response area) and quadrupolar stimulation (high-threshold, spatially restricted response) according to an intensity-dependent function will produce a low-threshold, spatially restricted response area. Current from the central scalar contact I is divided into monopolar current I m and quadrupolar current I q
I=I q +I m
based on the variable α (0≦α≦1.0) such that
I=αI +(1−α) I
The quadrupolar current
I q = α I = α I 2 + α I 2
is the sum of current to the scalar contacts 40 and 44 adjacent to the central 42 . The case of balanced currents for a quadrupole can be generalized to tripolar stimulation without the restriction of equal currents through the adjacent contacts.
The result of varying α is suggested for three curve sets 50 , 52 and 54 in FIG. 5 . The place of cochlear stimulation 56 remains the same, as does the site of activation in the neural population (vertical dashed lines). The extent of neural activation (horizontal dashed lines) would normally expand widely for low-threshold, monopolar stimulation (bottom panel), but using α to change to the quadrupolar stimulation mode restricts the spread of activation. Note that stimulus intensity and α vary together. It is necessary to define the nature and limits of the function relating α to the magnitude of sound determining the intensity of stimulus pulses.
The peak intensity for each electrical pulse is a function of a magnitude value m t in a series of discrete time-frequency-magnitude (TFM™) events indexed by t (described in referenced U.S. Pat. No. 6,480,820). Transforming the discrete time series m t to a series of pulse intensities s t is most directly based on two functions, one relating the loudness growth to electrical pulse intensity and the other electrical pulse intensity to sound magnitude. These two functions can be combined, and for discussion purposes a power function
S t =km t p
will be assumed where k is a scaling constant and p is an exponent whose values are determined from clinical measures. Psychophysical measures are used to estimate the threshold and MCL for s t with corresponding values for m t . Stimulation levels are restricted to be within these limits. The limits and function parameters must be estimated for each site of stimulation in the cochlea. The site of stimulation is mapped from instantaneous stimulus frequency f t and corresponds to the “central electrode contact” referred to here and will be indexed by i.
Implementation of the method requires that stimulus intensity be related to α so that the mapping
S t →α t
must be determined. This mapping is one-to-one, monotonic, and limited by threshold and MCL on s t . In summary, mappings are established for all stimulation sites indexed by i from instantaneous sound magnitude m t at time t to pulse intensity s t and the parameter α governing the stimulation mode:
m
t
->
i
(
s
t
,
α
t
)
In practice threshold and MCL would not be estimated on s t alone but on the full mapping function. Specifically threshold would be estimated with monopolar stimulation (α=0), and MCL would be estimated with quadrupolar stimulation (α=1.0). The form of the intervening map would meet the criteria of a smooth loudness growth and retention of channel independence over its range.
In generalizing to tripolar stimulation, three parameters represent how and where electrical current is passed for an elementary tripolar stimulation arrangement in cochlear implants:
1. the absolute current I[k] passed through a “central” electrode contact at position k along an array of contacts indexed from 1 to N. 2. the relative distribution of that current to adjacent, more apical (A) versus more basal (B) contacts to be represented by the parameter β defined below. 3. the relative distribution of that current to the adjacent contacts versus a distant return (or reference) contact (R) to be represented by the parameter α defined below.
The FIG. 6 shows the currents from contact 40 (IA), contact 42 (I[k]), contact 44 (IB), and contact 46 (IR) involved for one polarity. During a biphasic pulse the current directions would reverse to maintain charge balance over time, but this does not bear directly on the arguments. The steering parameter β determines the relative current distribution to the more apical and basal contacts, specifically,
β = I A - I B I A + I B
This parameter ranges from 1.0 (“hard apical steering”) to −1.0 (“hard basalward”). It is not defined for the condition where no current is passed to the adjacent contacts (I A +I B =0), the monopole condition where α=0 as described below. When β=0 the currents to the adjacent contacts are split evenly with I A =I B , and, assuming a homogeneous, isotropic tissue impedance, the field is concentrated symmetrically over the central contact. For β=1.0 current is passed only between the central and more apical contact shifting the field effect to its most apical position (excluding effects from α). The field is shifted most basalward when β=−1.0. If no current is passed to the return contact the β=1.0 and β=−1.0 conditions are dipole stimulations.
The total current is only indexed at the central contact as defined by the contact position along the array to avoid complexity in notation. All of the component currents I A , I B , and I R along with α and β are specific to cochlear position and can be position indexed. Multiple tripoles can coexist in an additive manner. While β specifies field steering, α is concerned with restriction of the field in a region near the central contact. Specifically, α determines the relative distribution of current between the adjacent contacts and the return contact as described previously. Using the notation introduced here:
I [ k ] = α I [ k ] + ( 1 - α ) I [ k ] = α I [ k ] + I [ k ] - ( I A + I B )
leading to the definition
α = I A + I B I [ k ] = I [ k ] - I R I [ k ]
a parameter ranging from 0.0 to 1.0 and representing the proportion of current in the tripole passing between the central contact and the adjacent contacts as opposed to the return contact. For α=0.0 no current passes to the adjacent contacts—the arrangement is a monopole. For α=1.0 all of the current passes to the adjacent contacts as generalized tripolar stimulation (β≠0), and for β=0 the arrangement is a quadrupole.
While β provides a means for steering fields, manipulating the ratio α of current to adjacent and return electrodes affects dynamic range and field spread. FIG. 7 summarizes the effect of varying α on dynamic range.
Each curve 60 in FIG. 7 represents the growth of a response measure with stimulus intensity from threshold to a maximum or saturated response level. The response strength can be taken as the probability of a neural spike, the number of neural spikes, or a measure of loudness; observations exist for all of these. The technique is to achieve low threshold and a large dynamic range by varying α as a function of stimulus intensity achieving the function indicated with the dashed line. The vertical axis for the dashed line is an absolute measure of response strength, as opposed to the response strength range for a particular α.
Clinical adjustment procedures must match individual variations in loudness perceptions to functions involving α and β. The interaction of these parameters in determining loudness is likely and will necessitate adaptive estimation of the dynamic range for these parameters. A general adjustment procedure might involve the following steps, initially under the β=0 condition for each cochlear position:
1. Estimation of the monopolar threshold (α=0) for the central contact. 2. Increase stimulus intensity to estimate the monopolar MCL. 3. Adjust α from 0 upward with associated increases in stimulus intensity to approximate successive MCLs at higher a levels to estimate the MCL characterized by a stimulus current and α max . 4. Establish the function between threshold with α=0 and MCL and α max . 5. Determine if this function varies appreciably with changes in β.
In summary, α and β parameterize two useful manipulations of tripolar stimulation: morphing between a monopole and a quadrupole to gain low thresholds and increased dynamic range with a spatially narrow field, the method introduced here, and field steering from apical to basal directions to achieve potentially continuous spatial mapping in the vicinity of the central electrode. In practice stimulus intensity would be mapped into α and stimulus frequency into β. A two-dimensional parameter space is defined by α and β. They are mathematically independent, although this does not necessarily imply that their physiological effects are independent.
The preceding Detailed Description section is all to be taken by way of example, rather than limitation. In particular skilled persons will readily recognize that many of the concepts presented could find application either directly or by way of analogous concepts to the stimulation of muscle or brain or other nervous system tissue. | A method of stimulating neurons in a patient's cochlea. The method uses a plurality of cochlear electrodes, substantially arranged in a linear array within the cochlea and a relatively distant electrode. Charge is injected through a first one of the cochlear electrodes and an opposite charge is injected on either the relatively distant electrode; or a set of adjacent cochlear electrodes, being adjacent to the first one of the cochlear electrodes; or on a combination of the relatively distant electrode and the set of adjacent electrodes; and choosing the electrode or electrodes on which to inject charge in dependency on sound volume to be represented. | 0 |
This application claims the benefit to U.S. Provisional Application No. 60/154,882 filed Sep. 20, 1999.
FIELD OF THE INVENTION
The invention relates to certain multidentate phosphite ligands, the catalyst compositions made therefrom and a catalytic hydrocyanation process which employs such multidentate phosphite ligands. In particular, the ligands have phenyl containing substituents attached to the ortho position of the terminal phenol group and/or attached to the ortho position of the backbone.
TECHNICAL BACKGROUND OF THE INVENTION
Phosphorus ligands are ubiquitous in catalysis and are used for a number of commercially important chemical transformations. Phosphorus ligands commonly encountered in catalysis include phosphines (A), and phosphites (B), shown below. In these representations, R can be virtually any organic group. Monophosphine and monophosphite ligands are compounds which contain a single phosphorus atom which serves as a donor to a metal. Bisphosphine, bisphosphite, and bis(phosphorus) ligands in general, contain two phosphorus donor atoms and normally form cyclic chelate structures with transition metals.
There are several industrially important catalytic processes employing phosphorus ligands. For example, U.S. Pat. No. 5,910,600 to Urata, et al. discloses that bisphosphite compounds can be used as a constituting element of a homogeneous metal catalyst for various reactions such as hydrogenation, hydroformylation, hydrocyanation, hydrocarboxylation, hydroamidation, hydroesterification and aldol condensation.
Some of these catalytic processes are used in the commercial production of polymers, solvents, plasticizers and other commodity chemicals. Consequently, due to the extremely large worldwide chemical commodity market, even small incremental advances in yield or selectivity in any of these commercially important reactions are highly desirable. Furthermore, the discovery of certain ligands that may be useful for applications across a range of these commercially important reactions is also highly desirable not only for the commercial benefit, but also to enable consolidation and focusing of research and development efforts to a particular group of compounds.
U.S. Pat. No. 5,512,696 to Kreutzer, et al. discloses a hydrocyanation process using a multidentate phosphite ligand, and the patents and publications referenced therein describe hydrocyanation catalyst systems pertaining to the hydrocyanation of ethylenically unsaturated compounds. U.S. Pat. Nos. 5,723,641, 5,663,369, 5,688,986 and 5,847,191 disclose processes and catalyst compositions for the hydrocyanation of monoethylenically unsaturated compounds using zero-valent nickel and multidentate phosphite ligands, and Lewis acid promoters.
U.S. Pat. No. 5,821,378 to Foo, et al. discloses a liquid phase process for the hydrocyanation of diolefinic compounds to produce nonconjugated acyclic nitrites as well as a liquid phase process for the isomerization of those nitrites to 3- and/or 4-monoalkene linear nitriles where the reactions are carried out in the presence of zero-valent nickel and a multidentate phosphite ligand. Other catalytic processes for the hydrocyanation of olefins and the isomerization of monoalkene nitriles are described in the patents and publications referenced therein. Commonly assigned, published PCT Application WO99/06357 discloses multidentate phosphite ligands having alkyl ether substituents on the carbon attached to the ortho position of the terminal phenol group for use in a liquid phase process for the hydrocyanation of diolefinic compounds to produce nonconjugated acyclic nitrites as well as a liquid phase process for the isomerization of those nitrites to 3- and/or 4-monoalkene linear nitrites.
The use of multidentate phosphate ligands having binaphthalene and/or biphenyl bridging groups for hydroformylation reactions is disclosed in U.S. Pat. Nos. 5,235,113, 5,874,641, 5,710,344 and published PCT Application WO 97/33854
While the catalyst systems described above may represent commercially viable catalysts, it always remains desirable to provide even more effective, higher performing catalyst precursor compositions, catalytic compositions and catalytic processes to achieve full commercial potential for a desired reaction. The effectiveness and/or performance may be achieved in any or all of rapidity, selectivity, efficiency or stability, depending on the reaction performed. It is also desirable to provide such improved catalyst systems and/or processes which may be optimized for a commercially important reaction such hydrocyanation or isomerazation. Other objects and advantages of the present invention will become apparent to those skilled in the art upon reference to the detailed description which hereinafter follows.
SUMMARY OF THE INVENTION
The invention provides for a hydrocyanation process comprising reacting an acyclic, aliphatic, monoethylenicaly unsaturated compound in which the ethylenic double bond is not conjugated to any other olefinic group in the molecule with a source of HCN in the presence of a catalyst composition comprising a Lewis acid, a zero-valent nickel and at least one multidentate phosphite ligand selected from the group represented by the following formulae I II or III, in which all like reference characters have the same meaning, except as further explicitly limited.
wherein
R 1 is independently C 1 to C 18 primary or secondary alkyl;
R 2 is independently aryl or substituted aryl;
R 3 is independently aryl or substituted aryl;
R 4 is independently C 1 to C 18 primary alkyl;
R 5 is hydrogen;
R 6 is independently aryl or substituted aryl;
R 7 is independently C 1 to C 18 primary or secondary alkyl;
R 8 is independently C 1 to C 18 primary or secondary alkyl; and
R 9 is independently C 1 to C 18 primary or secondary alkyl;
wherein other positions on the aromatic rings may also be substituted with alkyl, ether or ester groups, or combinations of two or more thereof.
The invention also provides for a multidentate phosphite ligand having the structure represented by the following Formula I, II or III in which all like reference characters have the same meaning, except as further explicitly limited.
wherein
R 1 is independently C 1 to C 18 primary or secondary alkyl;
R 2 is independently aryl or substituted aryl;
R 3 is independently aryl or substituted aryl;
R 4 is independently C 1 to C 18 primary alkyl;
R 5 is hydrogen;
R 6 is independently aryl or substituted aryl;
R 7 is independently C 1 to C 18 primary or secondary alkyl;
R 8 is independently C 1 to C 18 primary or secondary alkyl; and
R 9 is independently C 1 to C 18 primary or secondary alkyl;
wherein other positions on the aromatic rings may also be substituted with alkyl, ether or ester groups, or combinations of two or more thereof.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention provides for certain multidentate phosphite ligands, improved catalyst systems employing such ligands, and the use of such multidentate phosphite ligands in hydrocyanation reactions.
The catalyst compositions useful in the invention preferably are comprised of a multidentate phosphite ligand of formula I, II and III and a transition metal.
wherein
R 1 is independently C 1 to C 18 primary alkyl;
R 2 is independently aryl or substituted aryl;
R 3 is independently aryl or substituted aryl;
R 4 is independently C 1 to C 18 primary alkyl;
R 5 is hydrogen;
R 6 is independently aryl or substituted aryl;
R 7 is independently C 1 to C 18 primary or secondary alkyl;
R 8 is independently C 1 to C 18 primary or secondary alkyl; and
R 9 is independently C 1 to C 18 primary or secondary alkyl;
wherein other positions on the aromatic rings may also be substituted with alkyl, ether or ester groups, or combinations of two or more thereof.
The divalent bridging compounds used in the ligands described in formulae I, II, and III may be prepared by a variety of methods known in the art. For example, 3,3′,5,5′-tetramethyl-2,2′-biphenol can be prepared according to J. Org. Chem., 1963, 28, 1063 and 3,3′,5,5′,6,6′-Hexamethyl-2,2′-biphenol can be prepared according to JP 85-216749. The3,3′-diaryl-substituted 1,1′-2-naphthols can be obtained according to J. Org. Chem., 1998, 63, 7536.
Phosphorochloridite may be prepared by a variety of methods known in the art, for example, see descriptions in Polymer, 1992, 33, 161; Inorganic Synthesis, 1966, 8, 68; U.S. Pat. No. 5,210,260; Z. Anorg. Allg. Chem., 1986, 535, 221. With ortho-substituted phenols, phosphorochloridites can be prepared in situ from PCl 3 and the phenol. Also, phosphorochloridites of 1-naphthols can be prepared in situ from PCl 3 and 1-naphthols in the presence of a base like triethylamine. Another process for preparing the phosphochlorodite comprises treatment of N,N-dialkyl diarylphosphoramidite with HCl. ClP(OMe) 2 has been prepared in this manner, see Z. Naturforsch, 1972, 27B, 1429. Phosphorochloridites derived from substituted phenols have been prepared using this procedure as described in commonly assigned U.S. Pat. No. 5,821,378.
By contacting the thus obtained (OAr) 2 PCl, wherein Ar is a substituted aryl, with a divalent bridging compound, for example by the method described in U.S. Pat. No. 5,235,113, a bidentate phosphite ligand is obtained which can be used in the process according to the invention.
The transition metal may be any transition metal capable of carrying out catalytic transformations and may additionally contain labile ligands which are either displaced during the catalytic reaction, or take an active part in the catalytic transformation. Any of the transition metals may be considered in this regard. The preferred metals are those comprising group VIII of the Periodic Table. The preferred metals for hydroformylation are rhodium, cobalt, iridium, ruthenium, palladium and platinum. The preferred metals for hydrocyanation and/or isomerization are nickel, cobalt, and palladium, and nickel is especially preferred for hydrocyanation.
The catalyst compositions of the invention are comprised of at least one multidentate phosphite ligand according to any one of formulae I, II and III and a transition metal. In embodiments of the invention, catalyst compositions useful for processes such as hydroformylation may have Group VIII compounds such as can be prepared or generated according to techniques well known in the art, as described, for example, WO 95 30680, U.S. Pat. No. 3,907,847, and J. Amer. Chem. Soc., 1993, 115, 2066. Examples of such suitable Group VIII metals are ruthenium, rhodium, and iridium. Suitable Group VIII metal compounds are hydrides, halides, organic acid salts, acetylacetonates, inorganic acid salts, oxides, carbonyl compounds and amine compounds of these metals. Examples of suitable Group VIII metal compounds are, for example, Ru 3 (CO) 12 , Ru(NO 3 ) 2 , RuCl 3 (Ph 3 P) 3 , Ru(acac) 3 , Ir 4 (CO) 12 , IrSO 4 , RhCl 3 , Rh(NO 3 ) 3 , Rh(OAc) 3 , Rh 2 O 3 , Rh(acac)(CO) 2 , [Rh(OAc)(COD)] 2 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , RhH(CO)(Ph 3 P) 3 , [Rh(OAc)(CO) 2 ] 2 , and [RhCl(COD)] 2 (wherein “acac” is an acetylacetonate group; “OAc” is an acetyl group; “COD” is 1,5-cyclooctadiene; and “Ph” is a phenyl group). However, it should be noted that the Group VIII metal compounds are not necessarily limited to the above listed compounds. The Group VIII metal is preferably rhodium. Rhodium compounds that contain ligands which can be displaced by the multidentate phosphites are a preferred source of rhodium. Examples of such preferred rhodium compounds are Rh(CO) 2 (acetylacetonate), Rh(CO) 2 (C 4 H 9 COCHCO-t-C 4 H 9 ), Rh 2 O 3 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , Rh(O 2 CCH 3 ) 2 , and Rh(2-ethylhexanoate). Rhodium supported on carbon may also be used in this respect.
Nickel compounds can be prepared or generated according to techniques well known in the art, as described, for example, in U.S. Pat. Nos. 3,496,217; 3,631,191; 3,846,461; 3,847,959; and 3,903,120, which are incorporated herein by reference. Zero-valent nickel compounds that contain ligands which can be displaced by the organophosphorus ligand are a preferred source of nickel. Two such preferred zero-valent nickel compounds are Ni(COD) 2 (COD is 1,5-cyclooctadiene) and Ni{P(O-o-C 6 H 4 CH 3 ) 3 } 2 (C 2 H 4 ), both of which are known in the art. Alternatively, divalent nickel compounds may be combined with a reducing agent, to serve as a source of nickel in the reaction. Suitable divalent nickel compounds include compounds of the formula NiY 2 where Y is halide, carboxylate, or acetylacetonate. Suitable reducing agents include metal borohydrides, metal aluminum hydrides, metal alkyls, Zn, Fe, Al, Na, or H 2 . Elemental nickel, preferably nickel powder, when combined with a halogenated catalyst, as described in U.S. Pat. No. 3,903,120, is also a suitable source of zero-valent nickel.
Depending upon the desired reaction to be performed, the catalyst composition of this invention may also include the presence of one or more Lewis acid promoters, which affect both the activity and the selectivity of the catalyst system. The promoter may be an inorganic or organometallic compound in which the at least one of the elements of said inorganic or organometallic compound is selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium and tin. Examples include ZnBr 2 , ZnI 2 , ZnCl 2 , ZnSO 4 , CuCl 2 , CuCl, Cu(O 3 SCF 3 ) 2 , CoCl 2 , CoI 2 , FeI 2 , FeCl 3 , FeCl 2 , FeCl 2 (TBF) 2 , TiCl 4 (THF) 2 , TiCl 4 , TiCl 3 , ClTi(OiPr) 3 , MnCl 2 , ScCl 3 , AlCl 3 , (C 8 H 17 )AlCl 2 , (C 8 H 17 ) 2 AlCl, (iso-C 4 H 9 ) 2 AlCl, Ph 2 AlCl, PhAlC 2 , ReCl 5 , ZrCl 4 , NbCl 5 , VCl 3 , CrCl 2 , MoCl 5 , YCl 3 , CdCl 2 , LaCl 3 , Er(O 3 SCF 3 ) 3 , Yb(O 2 CCF 3 ) 3 , SmCl 3 , B(C 6 H 5 ) 3 , TaCl 5 . Suitable promoters are further described in U.S. Pat. Nos. 3,496,217; 3,496,218; and 4,774,353. These include metal salts (such as ZnCl 2 , CoI 2 , and SnCl 2 ), and organometallic compounds (such as RAlCl 2 , R 3 SnO 3 SCF 3 , and R 3 B, where R is an alkyl or aryl group). U.S. Pat. No. 4,874,884 describes how synergistic combinations of promoters can be chosen to increase the catalytic activity of the catalyst system. Preferred promoters include CdCl 2 , FeCl 2 , ZnCl 2 , B(C 6 H 5 ) 3 , and (C 6 H 5 ) 3 SnX, where X═CF 3 SO 3 , CH 3 C 6 H 5 SO 3 , or (C 6 H 5 ) 3 BCN. The mole ratio of promoter to nickel present in the reaction can be within the range of about 1:16to about 50:1.
HYDROCYANATION OF MONOOLEFINIC COMPOUNDS
The present invention provides for a process of hydrocyanation, comprising reacting an unsaturated compound with a source of hydrogen cyanide in the presence of a catalyst composition comprising a transition metal selected from Ni, Co, and Pd, and a Lewis acid compound, and at least one ligand selected from the group represented by formulae I, II, or III. Representative ethylenically unsaturated compounds which are useful in the hydrocyanation process of this invention are shown in Formulae IV or V, and the corresponding terminal nitrile compounds produced are illustrated by Formulae IV or VI, respectively, wherein like reference characters have same meaning.
wherein
R 22 is H, CN, CO 2 R 23 , or perfluoroalkyl;
y is an integer of 0 to 12;
x is an integer of 0 to 12 when R 22 is H, CO 2 R 23 or perfluoroalkyl;
x is an integer of 1 to 12 when R 22 is CN; and
R 23 is C 1 to C 12 alkyl, or aryl.
The nonconjugated acyclic, aliphatic, monoethylenically unsaturated starting materials useful in this invention include unsaturated organic compounds containing from 2 to approximnately 30 carbon atoms. Suitable unsaturated compounds include unsubstituted hydrocarbons as well as hydrocarbons substituted with groups which do not attack the catalyst, such as cyano. Examples of these monoethylenically unsaturated compounds include ethylene, propylene, 1-butene, 2-pentene, 2-hexene, etc., nonconjugated diethylenically unsaturated compounds such as allene, substituted compounds such as 3-pentenenitrile, 4-pentenenitrile, methyl pent-3-enoate, and ethylenically unsaturated compounds having perfluoroalyl substituents such as, for example, C z F 2z+1 , where z is an integer of up to 20. The monoethylenically unsaturated compounds may also be conjugated to an ester group such as methyl pent-2-enoate. Preferred are nonconjugated linear alkenes, nonconjugated linear Allen-nitriles, nonconjugated linear alkenoates, linear alk-2-enoates and perfluoroalkyl ethylenes. Most preferred substrates include 3- and 4-pentenenitrile, alkyl 2-, 3-, and 4-pentenoates, and C z F 2z+1 CH═CH 2 (where z is 1 to 12).
3-Pentenenitrile and 4-pentenenitrile are especially preferred. As a practical matter, when the nonconjugated acyclic aliphatic monoethylenically unsaturated compounds are used in accordance with this invention, up to about 10% by weight of the monoethylenically unsaturated compound may be present in the form of a conjugated isomer, which itself may undergo hydrocyanation. For example, when 3-pentenenitrile is used, as much as 10% by weight thereof may be 2-pentenenitrile. (As used herein, the term “pentenenitrile” is intended to be identical with “cyanobutene”).
The preferred products are terminal alkanenitriles, linear dicyanoalkylenes, linear aliphatic cyanoesters, and 3-(perfluoroalkyl) propionitrile. Most preferred products are adiponitrile, alkyl 5-cyanovalerate, and C z F 2z+1 CH 2 CH 2 CN, where z is 1 to 12.
The present hydrocyanation process may be carried out, for example, by charging a reactor with the reactants, catalyst composition, and solvent, if any; but preferably, the hydrogen cyanide is added slowly to the mixture of the other components of the reaction. Hydrogen cyanide may be delivered as a liquid or as a vapor to the reaction. Another suitable technique is to charge the reactor with the catalyst and the solvent to be used, and feed both the unsaturated compound and the HCN slowly to the reaction mixture. The molar ratio of unsaturated compound to catalyst can be varied from about 10:1 to about 2000:1.
Preferably, the reaction medium is agitated, for example, by stirring or shaking. The reaction product can be recovered by conventional techniques such as, for example, by distillation. The reaction may be run either batchwise or in a continuous manner.
The hydrocyanation reaction can be carried out with or without a solvent. The solvent, if used, should be liquid at the reaction temperature and pressure and inert towards the unsaturated compound and the catalyst. Suitable solvents include hydrocarbons, such as benzene or xylene, and nitrites, such as acetonitrile or benzonitrile. In some cases, the unsaturated compound to be hydrocyanated may itself serve as the solvent.
The exact temperature is dependent to a certain extent on the particular catalyst being used, the particular unsaturated compound being used and the desired rate. Normally, temperatures of from −25° C. to 200° C. can be used, the range of 0° C. to 150° C. being preferred.
Atmospheric pressure is satisfactory for carrying out the present invention and hence pressures of from about 0.05 to 10 atmospheres (50.6 to 1013 kPa) are preferred. Higher pressures, up to 10,000 kPa or more, can be used, if desired, but any benefit that may be obtained thereby would probably not justify the increased cost of such operations.
HCN can be introduced to the reaction as a vapor or liquid. As an alternative, a cyanohydrin can be used as the source of HCN. See, for example, U.S. Pat. No. 3,655,723.
The process of this invention is carried out in the presence of one or more Lewis acid promoters which affect both the activity and the selectivity of the catalyst system. The promoter may be an inorganic or organometallic compound in which the in which the at least one of the elements of said inorganic or organometallic compound is selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobiumn, molybdenum, cadmium, rhenium and tin. Examples include ZnBr 2 , ZnI 2 , ZnCl 2 , ZnSO 4 , CuCl 2 , CuCl, CU(O 3 SCF 3 ) 2 , CoCl 2 , CoI 2 , FeI 2 , FeCl 3 , FeCl 2 , FeCl 2 (THF) 2 , TiCl 4 (THF) 2 , TiCl 4 , TiCl 3 , ClTi(OiPr) 3 , MnCl 2 , ScCl 3 , AlCl 3 , (C 8 H 17 )AlCl 2 , (C 8 H 17 ) 2 AlCl, (iso-C 4 H 9 ) 2 AlCl, Ph 2 AlCl, PhAlCl 2 , ReCl 5 , ZrCl 4 , NbCl 5 , VCl 3 , CrCl 2 , MoCl 5 , YCl 3 , CdCl 2 , LaCl 3 , Er(O 3 SCF 3 ) 3 , Yb(O 2 CCF 3 ) 3 , SmCl 3 , B(C 6 H 5 ) 3 , TaCl 5 . Suitable promoters are further described in U.S. Pat. Nos. 3,496,217; 3,496,218; and 4,774,353. These include metal salts (such as ZnCl 2 , CoI 2 , and SnCl 2 ), and organometallic compounds (such as RAlCl 2 , R 3 SnO 3 SCF 3 , and R 3 B, where R is an alkyl or aryl group). U.S. Pat. No. 4,874,884 describes how synergistic combinations of promoters can be chosen to increase the catalytic activity of the catalyst system. Preferred promoters include CdCl 2 , FeCl 2 , ZnCl 2 , B(C 6 H 5 ) 3 , and (C 6 H 5 ) 3 SnX where X═CF 3 SO 3 , CH 3 C 6 H 5 SO 3 , or (C 6 H 5 ) 3 BCN. The mole ratio of promoter to nickel present in the reaction can be within the range of about 1:16 to about 50:1.
The invention will now be illustrated by the following non-limiting examples of certain embodiments thereof, wherein all parts, proportions, and percentages are by weight, unless otherwise indicated.
The following definitions are applicable wherever the defined terms appear in this specification:
The term “hydrocarbyl” designates a hydrocarbon molecule from which one hydrogen atom has been removed. Such molecules can contain single, double or triple bonds.
3PN: 3-pentenenitrile
2PN: 2-pentenenitrile
4PN: 4-pentenenitrile
2M3: 2-methyl-3-butenenitrile
VN: valeronitrile
ESN: ethylsuccinonitrile
MGN: 2-methylglutaronitrile
5FVN: 5-formylvaleronitrile
M3P: methyl 3-pentenoate
BD: 1,3-butadiene
COD: 1,5-cyclooctadiene
Et 3 N: triethylamine
PCl 3 : phosphorus trichloride
THF: tetrahydrofuran
The protocol for calculating certain reaction results for hydrocyanation reactions and isomerization reactions follows:
For step 1 hydrocyanation reactions the % useful pentenenitriles (PN's) and the 3PN/2M3 ratio is reported. The product distribution is analyzed by gas chromatograph using valeronitrile as an internal standard. The % usefil PN's is the molar ratio of the sum of 3PN(cis and trans) and 2M3 divided by the amount of HCN. The 3PN/2M3 ratio is the ratio of cis and trans 3PN to 2M3.
For step 2 hydrocyanation reactions the selectivity to adiponitrile (ADN) is ADN/(ESN+MGN+ADN). The 3PN and 4PN conversion is calculated using 2-ethoxyethylether (EEE) as an internal standard. The total conversion of pentenenitriles (PN's) to dinitriles (DN's), based on the assumption that all material is accounted for, is calculated as (sum (mol DN's)/sum (PN's+BN's+DN's)). (BN's are butenenitriles). The conversion based on HCN is calculated by dividing the total conversion of PN's to DN's by the HCN/PN ratio in the original feed, i.e., (mol DN/mol PN at sart)/(mol HCN/mol PN at start).
EXAMPLE 1
2′-Ethoxyl-1,1′-biphenyl-2-ol was prepared by modifying the procedure reported in J. Org. Chem. 1981, 46, 4988. In 50 mL of acetone was added 10 g of 2,2′-biphenol and 9.4 g of potassium carbonate. After stirring at room temperature for one hour, a solution of iodoethane (9.2 g in 10 mL of acetone) was added slowly dropwise. The mixture was filtered, washed with acetone, and solvent removed by rotary evaporation. The residue was flashed chromatographed to give 5.1 g of the2′-ethoxyl-1,1′-biphenyl-2-ol as a colorless oil. 1 H NMR (C 6 D 6 ): 7.20 (m, 3H), 7.10 (m, 1H), 7.05 (m, 1H), 6.85 (m, 2H), 6.55 (m, 1H), 3.38 (q, 2H), 0.81 (t, 3H).
In a nitrogen purged glove box, the above phenol (0.73 g, 3.40 mmol) was dissolved in 10 mL ether, and cooled to −30° C. To this was added cold (−30° C.) 1M phosphorous trichloride solution (1.7 mL), followed by dropwise addition of 1M triethylamine solution (4.0 mL). The solution was stirred at room temperature for 5 minutes, then kept at −30° C. for two hours. The reaction mixture was filtered through a pad of Celite® and concentrated to yield 0.67 g of the corresponding phosphorous chloridite. 31 P NMR (toluene): 160.4 (78%), 126 (22%). The phosphorous chlorodite was reacted with 1,1′-bi-2-naphthol in the presence of triethylamine to yield ligand II. 31 P NMR (toluene): 131.3 (major), 130.2.
EXAMPLE 2
2,2′-dihydroxy-1,1′-binaphthalene-3,3′-bis(diphenylether) was prepared according to literature procedure reported in J. Org. Chem. 1998, 63, 7536). Under an atmosphere of nitrogen, a 250 mL two-necked Schlenk flask equipped with a reflux condenser was charged with 3,3′-bis(dihydroxyborane)-2,2′-dimethoxy-1,1′-binaphthyl (2.250 g, 5.60 mmol), Pd(PPh 2 ) 4 (0.360 g, 0.42 mmol), Ba(OH) 2 (5.25 g, 30.6 nunol), 4-bromo-diphenylether (4.47 g, 17.9 mmol), 1,4-dioxane (36 mL) and H 2 O (12 mL). The reaction mixture was refluxed for 24 hours. Upon cooling to room temperature, the mixture was diluted with CH 2 Cl 2 (150 mL) and washed with 1 N HCl (2×75 mL) and brine (2×75 mL). The solution was dried over MgSO 4 . Removal of the solvent gave a brown oil, which was diluted in dry CH 2 Cl 2 (125 mL) and cooled −40° C. Over a period of 10 min, BBr 3 (3 mL) was slowly added and the reaction mixture was stirred at room temperature overnight. The resulting red-brown solution was cooled to 0° C., and H 2 O (300 mL) was carefully added. The organic layer was separated and then washed with H 2 O (2×300 mL), 1 N HCl (300 mL) and brine (300 mL). The resulting solution was dried over MgSO 4 and concentrated. The resulting red oil was chromatographed on silica to give 2,2′-dihydroxy-1,1′-binaphthalene-3,3′-bis(diphenylether) as a white crystalline solid (0.80 g, 23%). 1 H (C 6 D 6 ): 7.80 (s, 2H), 7.64 (d, J=8.2 Hz, 2H), 7.53 (d, J=8.7 Hz, 4H), 7.22 (d, J=8.3 Hz, 2H), 7.12 (m, 4H) 7.05-6.96 (m, 14H), 5.03 (s, 2H).
Under an atmosphere of nitrogen, a cold (−35° C.) anhydrous diethyl ether solution (20 mL) of 2,2′-dihydroxy-1,1′-binaphthalene-3,3′-bis(diphenylether) (0.405 g, 0.65 mmol) was added to the phosphochlorodite of 5,6,7,8-tetrahydro-1-naphthol (0.588 g, 1.63 mmol) dissolved in diethyl ether (10 mL). While maintaining this temperature, triethylamine (0.23 mL, 1.63 mmol) was added dropwise to the above mixture resulting in the formation of a white precipitate. After stirring at room temperature for three hours, the reaction mixture was filtered through a pad of basic alumina and Celite®. The filtrate was evaporated to yield the desired diphosphite as a white powder (0.537 g, 65%). 31 P { 1 H} NMR (202.4 MHz, C 6 D 6 ): 132.75 ppm.
EXAMPLE 3
Under an atmosphere of nitrogen, a cold (−35° C.) anhydrous diethyl ether solution (5 mL) of 2,2′-dihydroxy-1,1′-binaphthalene-3,3′-bis(diphenyl) (0.050 g, 0.08 mmol) was added to the phosphochlorodite of 5,6,7,8-tetrahydro-1-naphthol (0.076 g, 0.21 mmol) dissolved in diethyl ether (5 mL). While maintaining this temperature, triethylamine (0.03 mL, 0.21 mmol) was added dropwise to the above mixture resulting in the formation of a white precipitate. After stirring at room temperature for three hours, the reaction mixture was filtered through a pad of basic alumina and Celite®. The filtrate was evaporated to yield the desired diphosphite as a white powder (0.043 g, 58%). 31 P { 1 H} NMR (202.4 MHz, C 6 D 6 ): 127.83, 132.14, 132.60 (major), 133.66, 141.51, 143.99 ppm.
Hydrocyanation Results for the Ligand of Example 2
Preparation of catalyst: A catalyst solution was prepared by adding 0.0039 g of Ni(COD) 2 (0.014 mmol) in 0.320 ml toluene to 0.062 g of the ligand of Example 2 (0.049 mmol) in 0.200 mL toluene
Hydrocyanation of 3,4 Pentenenitrile (3,4 PN): 116 μl of the above catalyst solution (0.0031 mmol Ni), and 13 μl of a solution of ZnCl 2 in 3PN (0.0067 mmol ZnCl 2 ) were added to a vial fitted with a septum cap. The vial was cooled to −20° C. and 125 μl of a solution of HCN, t-3PN, and 2-ethoxyethyl ether (0.396 mmol HCN, 0.99 mmol t-3PN) was added. The vial was sealed and set aside for 24 hours at room temperature. The reaction mixture was diluted with ethyl ether and the product distribution analyzed by GC using 2-ethoxyethyl ether as an internal standard. Analysis showed that 22.7% of the starting pentenenitriles had been converted to dinitrile product (62.8% yield based on HCN.) The selectivity to the linear ADN isomer was 97.4%.
Hydrocyanation Results for the Ligand of Example 3
Preparation of catalyst: A catalyst solution was prepared by adding 0.0039 g of Ni(COD) 2 (0.014 mmol) in 0.320 ml toluene to 0.025 g of the ligand of Example 3 (0.020 mmol) in 0.200 mL toluene
Hydrocyanation of 3,4 Pentenenitrile (3,4 PN): 116 μl of the above catalyst solution (0.0031 mmol Ni), and 13 μl of a solution of ZnCl 2 in 3PN (0.0067 mmol ZnCl 2 ) were added to a vial fitted with a septum cap. The vial was cooled to −20° C. and 125 μl of a solution of HCN, t-3PN, and 2-ethoxyethyl ether (0.396 mmol HCN, 0.99 mmol t-3PN) was added. The vial was sealed and set aside for 24 hours at room temperature. The reaction mixture was diluted with ethyl ether and the product distribution analyzed by GC using 2-ethoxyethyl ether as an internal standard. Analysis showed that 9.2% of the starting pentenenitriles had been converted to dinitrile product (25.4% yield based on HCN.) The selectivity to the linear ADN isomer was 97.5%.
Example #
Step 2 conv
Step 2 dist
1
10.4
94.6
2
22.7
97.4
3
9.2
97.5 | Hydrocyanation reactions employing multidentate phosphite ligands and multidentate phosphite ligands are disclosed. The ligands have phenyl containing substituents attached to the ortho position of the terminal phenol group and/or attached to the ortho position of the bridging group. Catalyst compositions havng such ligands achieve 97% or greater distribution in hydrocyanation. | 2 |
This is a continuation of co-pending application Ser. No. 643,550 filed on Aug. 23, 1984, now abandoned.
THE BACKGROUND OF THE INVENTION
The pigment suspension of the present invention is used for producing a film coating of such items as pharmaceutical tablets, confectionary pieces, and the like. The pigment suspension is typically stirred into a larger volume of polymer solution. The resulting film-forming suspension is used in the coating process. The film coating, in the form of a very thin film, must be uniform and consistent from one batch of tablets to the next.
The technique of film coating is generally known in the prior art. U.S. Pat. No. 2,954,323 to Endicott et al. discloses the increased efficiency and superior coating properties obtained with film coating in general as compared to other processes of coating.
The present invention relates to a pigment suspension which comprises, as pigment, titanium dioxide. Such pigment suspensions for use in film coating are preferably sold having a concentration of titanium dioxide as high as possible. However, as the concentration of titanium dioxide increases, the suspension tends to become more viscous and may reach a point where it becomes difficult to pour from its container. Upon aging, a thick suspension of titanium dioxide may harden to the extent of becoming unusable.
In developing a high concentration pigment suspension, it is desirable to obtain a product in which the titanium dioxide particles form a stable suspension and will not settle for a prolonged period of time. The need is for a pigment suspension which will readily pour from its container and will maintain its uniform properties, during both transportation and storage, until ready for application in film coating.
U.S. Pat. No. 3,981,984 to Signorino discloses a pigment suspension which claims to achieve a high concentration of titanium dioxides in a non-aqueous solvent. This pigment suspension consists of titanium dioxide particles, a protective colloid such as hydroxypropyl cellulose, and a non-aqueous solvent such as ethanol. Signorino teaches that as the titanium dioxide particles are added to the solvent, the mixture becomes too viscous, and the further addition of the protective colloid serves to suspend the particles and reduce the viscosity.
In view of the increasingly strict requirements of governmental regulating agencies in regard to the use of organic solvents, it has become desirable to obtain aqueous pigment suspensions. However, a high content of titanium dioxide in water is not normally possible for use in film-coating. Although titanium dioxide suspensions in an aqueous sugar syrup are known, such suspensions are not generally suitable for use in a film-forming polymer solution.
The present invention involved a search for a combination of ingredients which would permit a high content of titanium dioxide particles in an aqueous suspension useful in film coating. Due to the fact that the composition may comprise merely water and a very small amount of xanthan gum, not requiring the presence of organic solvents, the composition is very simple, safe and inexpensive to make.
THE OBJECTS OF THE INVENTION
One object of the present invention is to achieve a pigment suspension which contains a high titanium dioxide content.
Another object of the present invention is to achieve a high concentration pigment suspension in a solvent comprising a substantial amount of water, for use in film coating.
A further object of the invention is to obtain a high concentration pigment suspension which pours readily from containers.
A further object of the invention is to obtain a high concentration pigment suspension which does not settle upon aging.
A further object of the present invention is to obtain a pigment suspension with a high titanium dioxide concentration which is capable of being transported to customers in containers, and which may readily be combined with a film-forming polymer solution by stirring.
A further object of the present invention is to produce an aqueous pigment dispension which is inflammable and non-hazardous during handling and safe for use in edible products intended for human consumption.
The above and other objects of the present invention will become apparent from a reading of the following detailed description of the invention and the preferred embodiments thereof.
DETAILED DESCRIPTION OF THE INVENTION
The pigment suspension of the present invention comprises a mixture of titanium dioxide, xanthan gum, and water.
The titanium dioxide pigment employed in the present invention is preferably water dispersable titanium dioxide 3328, sold by Whitaker, Clarke and Daniels in South Plainfield, N.J. The pigment is suitable present in an amount by weight of about 20 to 75 percent, and most preferably in an amount by weight of about 30 to 60 percent.
Titanium dioxide is a relatively heavy pigment which, when mixed in a solvent, tends to settle out and form a thick non-pourable layer of pigment on the bottom of the container. It has now been found that an excellent aqueous pigment dispersion can be obtained by the addition of a very small amount of xanthan gum.
Xanthan gum is a high molecular weight polysaccharride produced in a fermentation process by the microorganism Xanthomonas campestris. The gum, which is produced as an exocellular coating surrounding the cell wall of the microorganism, is unique and very specific, and the properties thereof are constant and reproducable under given conditions.
Xanthan gum is known as a suspending or dispersing agent in various applications. For example, xanthan gum has been used to suspend solids in ceramic glazes, paints, and textile print pastes.
The use of xanthan gum to create a high concentration titanium dioxide pigment suspension for use in a film-forming process in the food and drug industry is believed to be entirely new.
A commercially available xanthan gum, suitable in the present invention, is KELTROL, and especially Keltrol F, a finely meshed xanthan gum, manufactured by Kelco, a division of Merk and Co., Incorporated.
The suspension of the present invention differs from other suspensions in that it can exhibit gel like behavior or very fluid behavior. Typically, the suspension actually sets up and only breaks down into a liquid by shearing action, such as produced by merely shaking the container of the pigment suspension, resulting in a readily pourable pigment suspension.
The xanthan gum is present in the invention in amounts, by weight, ranging from 0.005 to 5.0 percent. As is evident, typically only relatively very small quantities of the xanthan gum need be present in the suspension. A preferred range is 0.05 to 0.50 percent.
Compositions of the present invention were tested by what is referred to as an oven test. An oven test is an accelerated method of assessing the long-term properties of a pigment suspension. The oven test typically involved heating the pigment suspension at 104° F. for a period, initially, of 96 hours. This accelerated test is believed to be equivalent to 3 to 4 months at 85° F. Compositions of the present invention have withstood heating at 104° F. for one month. The oven test results were evaluated according to the following rating system.
RATING SYSTEM
1.0: A rock hard or very hard settle is obtained. The suspension fails to redisperse.
2.0: A paste or semi-hard solid is obtained. The suspension fails to pour from its container without force or requires the use of a spatula.
3.0: A threshold suspension, with some supernatant, but stable. After agitation, the suspension is still thick, but pourable.
4.0: A suspension with or without supernatant but no settle is obtained. The consistency is like thick yogurt. On agitation the suspension becomes fluid.
5.0: A soft, fluid dispersion with no settle is obtained. It pours from its container with no agitation and flows freely.
5.5: The suspension has no settle, but is very watery.
6.0: The suspension is too watery, and is not acceptable.
EXAMPLE 1
In a blender, the following components were weighed out and mixed:
______________________________________Component Percent by Weight______________________________________Water 69.80%Xanthan Gum 0.20%TiO.sub.2 30.00%______________________________________
The xanthan gum was added to the water while mixing at a moderate speed. Mixing was maintained for about 3 minutes or until all of the gum had dissolved. The titanium dioxide was added slowly while the blender was mixing. The speed was adjusted to maintain a vortex in the mixture.
An oven test was performed at 104° F. for 96 hours. A rating of 5.5 was obtained. After a further period of 21 days at 104° F., a rating of 5.5 was obtained, indicating that the properties of the pigment suspension remained stable.
Xanthan gum has unique properties which permit the creation of a stable and pourable titanium dioxide pigment suspension. Other gums or colloids, natural and synthetic, do not produce a satisfactory product. The following table illustrates other gums which were tried, but found unacceptable.
TABLE A______________________________________ Percent WeightComponent Trial/1 2 3______________________________________Distilled water 49.80 49.80 49.80Titanium dioxide 50.00 50.00 50.00Guar gum 0.20Polyvinylpyrrolidone 0.20KLUCEL 0.20Rating 1.0 1.0 1.0______________________________________
As shown in Table A, guar gum, polyvinylpyrrolidone, and KLUCEL, a brand of hydroxypropyl cellulose manufactured by Hercules Co. in Wilmington, Del., were unacceptable, resulting in a suspension that was immediately unusable. Gum arabic was satisfactory only at high levels such as 15 percent, too high for commercial practicability.
Conventional additives may be included in the present composition, as will be understood by those skilled in the art. For example, about 0.1 percent of an antimicrobial agent such as methylpropyl paraben or potassium sorbate is suitable.
It is to be understood that the foregoing detailed description and preferred embodiment are merely given by way of illustration, and modifications may be made, within the skill of the art, without departing from the scope and spirit of the invention. | The invention is directed to a pigment suspension, for use in film coating, comprising titanium dioxide, xanthan gum, and an aqueous solvent. It was found that a pigment suspension comprising 30 percent titanium dioxide was obtainable that did not settle or harden for an extended period of time. | 2 |
BACKGROUND OF THE INVENTION
This invention relates to apparatus for transporting compressed air cylinders to a given site and more particularly to dispensing a continuous air supply to emergency rescue sites or confined spaces, as defined by OSHA, that are frequently impossible to reach except with portable equipment.
DESCRIPTION OF THE PRIOR ART
Remote air supply carts or trucks of various types are employed by firefighters and other emergency rescue personnel in search and rescue operations requiring entry into confined spaces where the air supply is inadequate or contaminated as well as industrial application where workers operate in confined spaces. Various forms of equipment are used to supply air to such individuals as well as providing a compressed air source for the operation of various cutting tools, air hammers etc. used for breaking through barriers and freeing trapped victims of cave-ins or collapsed structures.
Currently available equipment of this type has saved many lives. In numerous emergency situations, rescue operations could not have succeeded without it. There are, however, a number of deficiencies and limitations in the present equipment that need to be corrected.
A first and very important deficiency is the lack of protection of the equipment against damage to exposed gauges, valves and other critical parts of the apparatus that can readily be incurred as the result of impact with surrounding obstacles. The cart or truck when being moved through confined spaces with limited lighting and visibility is susceptible to damage. This poses a very serious hazard and risk that the equipment may not be operable by the time it reaches the victim.
A second deficiency that is generally present in such equipment is the lack of separate air manifolds for breathing air and for tool operation. As a source for breathing air the pressure should be regulated to 120 psi or less; for tool operation higher pressures (12-250 psi) are preferred. Because both air sources are commonly required at the same time, it is not always possible to adjust pressure for the instant application, and with simultaneous use a compromise between the two preferred pressures means less than ideal conditions for one or both uses. Excessive pressure to a face mask can also rupture its diaphragm.
Some prior art equipments also fail to give attention to the importance of guarding against accidental ignition of combustible atmospheres. If the truck is constructed of steel it can produce sparks when it strikes a rock or other hard surface during transport. Using such a truck in a combustible atmosphere can therefore be quite hazardous.
Another deficiency of the prior art equipment is that the remote air system is limited to the amount of compressed air contained in the cylinders and the size of the cylinders is limited to the conventional wheels that are used on the truck. With conventional wheels, the cart is difficult to maneuver over the rough and irregular surfaces that are frequently encountered in rescue operations.
SUMMARY OF THE INVENTION
In accordance with the invention claimed, a remote air transport cart or truck is provided in a novel construction that overcomes the deficiencies and limitations of prior art equipment.
It is, therefore, one object of this invention to provide an improved remote air transport truck for use in emergency rescue operations and for various industrial application.
Another object of this invention is to provide such a remote air transport truck with protective shields that guard against damage to critical parts of the equipment during transport through constricted passageways to the emergency destination or work area for industrial application.
A further object of this invention is to provide in such an air transport truck separate manifolds for breathing air and for tool operation with the pressures separately regulated to the proper levels for each application.
A still further object of this invention is to provide such an air transport truck with improved maneuverability by virtue of its use of a solid rubber roller resistant to corrosives in place of conventional wheels for rolling support.
A still further object of this invention is to provide such an air transport truck incorporating all of the aforementioned improved characteristics while maintaining dimensions that allow passage through manholes and other restricted openings.
Still another object of this invention is to provide an air transport truck to be used as a filling station by fire fighters who may hook up their tanks to outlets provided on the front of the truck for transfilling their air bottles.
A further object of this invention is to provide a continuous and uninterrupted air supply from a remote/supply or source i.e., compressor or high volume cylinders. This is accomplished through the state of the art quick connections engineered into the air circuit.
Yet another object of this invention is the capability to supply additional trucks with a continuous air source. A series connection of trucks allows multiple teams/tools to operate in unison.
Yet another modification is the use of air filled gauges instead of oil filled. This safety feature will prevent chemical reactions that may be caused if gauge breakage were to occur in certain atmospheric conditions.
A further object of this invention is to provide a continuous and uninterrupted air supply from a remote air supply or source, i.e. compressor or high volume cylinders.
Further objects and advantages of the invention will become apparent as the following description proceeds and the features of novelty which characterize this invention will be pointed out with particularity in the claims annexed to and forming a part of this specification.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention may be more readily described with reference to the accompanying drawings in which:
FIG. 1 is a perspective view of the remote air supply truck of the invention, with the truck shown in position for being moved from one location to another.
FIG. 2 is a perspective view showing the rear and one side of the air supply truck with the truck standing in an upright position;
FIG. 3 is a perspective view of the air supply truck with the truck resting on its rollers and hand grips, this constituting its preferred operational position in cramped quarters that afford limited headroom;
FIG. 4 is a perspective view of the air supply truck taken from the front of the truck with both side doors open and showing the air canisters mounted on the doors;
FIG. 5 is a cross-sectional view taken along line 5--5 of FIG. 4 and illustrating the means employed to secure the air canisters within the door-mounted protective canister containers;
FIG. 6 is a plan view of the control and instrument panel as organized for a first embodiment of the invention;
FIG. 7 is a plan view of the control and instrument panel as organized for a second embodiment of the invention;
FIG. 8 is a perspective view of the air supply truck of the invention as seen from one side of the truck with the door open;
FIG. 9 is a schematic illustrating the interconnections of the gauges, controls and fittings comprising the air control system of the remote air transport truck for the first embodiment of the invention; and
FIG. 10 is a schematic of the air control system for the second embodiment of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring more particularly to the drawings by characters of reference, FIGS. 1-4 and FIG. 8 disclose the mechanical construction of the remote air supply cart or truck 10 of the invention.
As shown in the drawings, truck 10 provides a protective enclosure comprising a fixed front panel 11, a fixed rear panel 12, a bottom panel 13, hinged side doors 14 and 15, and a double-hinged top cover 16. The individual parts of the enclosure are made of sheet aluminum or other relatively soft material which does not produce sparks when impacted by rocks or other hard surfaces, all hardware fasteners are stainless steel or brass.
The front, rear and bottom panels, 11, 12 and 13, are secured to an aluminum frame 17 which is partially exposed in FIGS. 1, 2, 3 and 8. The side doors 14 and 15 are secured along their rear edges to the adjoining edges of rear panel 12 by piano hinges 18 and 19.
As shown more clearly in FIG. 8, the upper end of the enclosure is inclined to provide a sloping surface 21 on which are mounted air pressure controls, air pressure gauges and fittings for the attachment of air hoses. Rigidly attached to frame 17 is a lifting bar 22 which rises from a lower frame attachment near the base of the frame and passes through an opening in the center of surface 21. The protruding upper end of bar 22 has an opening 23 for attachment to a hoisting cable by means of which the truck may be lowered through a vertical passageway.
The double-hinged cover 16 when in its closed position as shown in FIGS. 1 and 2 provides a protective covering for the controls, gauges and fittings mounted on surface 21. To facilitate this function, cover 16 is formed by two parts including a narrow parallel extending panel 24 and a laterally extending panel 25 with respect to the longitudinally axis of the truck. These two panels are attached to each other at their adjoining edges by a piano hinge 26. Panel 24 is attached at its edge opposite hinge 26 to the upper edge of front panel 11 by another piano hinge 27. Hinge 27 also lies along the lower front edge of sloping surface 21. When cover 16 is closed, as shown in FIG. 1, and truck 10 is sitting upright as shown in FIG. 2, panel 24 rises from the front edge of surface 21 thereto to a height level with the higher rear edge of surface 21. From the upper edge of panel 24, panel 25 extends perpendicularly across the top of surface 21. As cover 16 is being moved to its closed position, the upper end of bar 22 passes through a slotted opening 28 in the center of panel 25. Bar 22 and the mating opening 28 serve as a latching mechanism that secures cover 16 in its closed position. In its open position, cover 16 hangs down over front panel 11 as shown in FIGS. 3, 4 and 8.
To facilitate moving the truck over rough or rocky surfaces, cart 10 is equipped with solid rubber rollers 29 and handles 30 with the rollers being resistive to acids and corrosive gases.
As shown in FIG. 2, the three-section roller 29 is positioned below the lower edge of rear panel 12. Two handles 30 extend perpendicularly rearward from the upper corners of panel 12 so that a person moving the truck can grasp the two handles and push or pull truck 10 as one would push a wheelbarrow. The rollers are found to provide easier passage over bumps and crevices that are difficult to negotiate with conventional wheels.
Handles 30 have rubber grips and are attached to the truck by means of threaded studs that extend from the attached ends into threaded holes in frame 17. The handles are thus readily removable when it becomes necessary for passage through a small opening.
The rear panel 12 is protected against damage while the truck is being moved over sharp edges by three runners 31. As shown in FIG. 2, two of the runners 31 are positioned lengthwise along the outer vertical edges and one at the center of panel 12.
In use at the emergency location, truck 10 may be accessed or operated in an upright position as shown in FIGS. 2 and 4 or in the lowered horizontal position shown in FIG. 3. In the horizontal position, truck 10 rests on roller 29 and on handles 30. In this position, sloping surface 21 of the control panel provides improved visibility of gauges and controls for the operation.
Two air cylinders comprising canisters 32 are mounted inside protective containers 33 that are secured by means of brackets 34 shown in FIG. 5 to the inside surfaces of side doors 14 and 15. The cylinders and their containers swing out for easy access when the doors are opened as shown in FIG. 4. Containers 33 are made of a tough synthetic material that protects the cylinders against damage while the doors are open.
Cylinders 32 are secured within the containers by means of two elastic bands 35, one near the top and one near the bottom of the cylinders. The elastic bands 35 encircle cylinder 32, as shown in FIG. 5, their ends secured to mounting brackets 34 by plastic attachment members 36. During installation and removal of the cylinders from the containers, the elastic bands 35 are pulled away from the cylinders by means of nylon straps 37 that are looped around bands 35 and extend through slotted openings 38 in the walls of containers 33.
Side doors 14 and 15 are held closed by latches 39, two located on each door.
Control panel 41 on surface 21 is shown in FIG. 6 as seen by the operator when truck 10 is resting in the horizontal position shown in FIG. 3. Incorporated in control panel 41 are six breathing air outlets 42, one tool air outlet 43, three pressure gauges including a high pressure gauge 44 for the primary air supplied from the air cylinders, a low pressure gauge 45 for breathing air pressure, and an intermediate pressure gauge 46 for tool air pressure, a breathing air pressure control 47, and a tool air pressure control 48. Controls 47 and 48 may be adjusted to set breathing air and tool air, respectively to the appropriate levels up to 120 psi maximum for breathing and between 120 to 250 psi maximum for tool operation. PSI means pounds per square inch of pressure.
For certain applications a greater number of tool outlets will be found appropriate. In such cases a modified control panel 41' may be employed as shown in FIG. 7. In this case three breathing air outlets 42 and three tool air outlets 43 are provided.
FIG. 9 is a schematic showing the elements of the pressure control and delivery system 49. Included in system 49 are the gauges, controls and outlets already described in connection with control panel 41. In FIG. 9, air pressure controls 47 and 48 are more specifically identified as regulators (REG), but they are actually one and the same.
Air is supplied to system 49 from one or both of the air cylinders 51 or from an external high pressure line via intake port 52. Conventional couplings or disconnects 53 connect the cylinders to the high pressure lines of system 49. Immediately downstream from disconnects 53 are bleeder valves 54, incorporated for the purpose of bleeding off pressure prior to a disconnection from the cylinder. Because the connections to the cylinders are made via flexible air hoses 55 (see also FIG. 4) to permit mounting the cylinders on the side doors, swivel joints 56 are incorporated in series.
Downstream from the swivel joints, air from the cylinders enter the high pressure distribution lines 57 via check valves 58. The check valves 58 are one-way valves that prevent momentary loss of pressure in the distribution system during the disconnection of one of the air cylinders. Air pressure in the high pressure distribution lines is displayed by air filled gauges 44. A low pressure condition in these lines indicative of impending problems due to depletion of the air supply is signaled by an audio alarm 59.
From the high pressure lines 57 high pressure air enters the controls or regulators 47 and 48, each of which is equipped with a low pressure relief valve 61. The relief valves relieve pressure on the low pressure side of the regulators in the event of a regulator malfunction that produces hazardous pressure levels in the low pressure lines.
From the low pressure side of regulator 47 air is delivered, at up to 120 psi maximum, via low pressure lines 62 to breathing air manifolds 63 and 64 which feed the six breathing air outlets 42. The pressure in these lines is adjustable by means of regulator 47 and the instant pressure is displayed by gauge 45.
From the low pressure side of regulator 48, tool air is delivered via high pressure line 65 to tool air outlet 43 at a variable 120 to 250 psi. Tool air pressure is adjustable by means of regulator 48 and is displayed by gauge 46.
As mentioned earlier, system 49 may also be supplied from an external high pressure line. Intake port 52 is incorporated for this purpose. Port 52 and two quick fill ports 66 and 67 are located in a recessed connector panel 68 in the front panel 11 of truck 10 as shown in FIGS. 1 and 3. Air from the external high pressure line entering at port 52 passes through a check valve 69 into the high pressure lines 58.
Quick fill ports may be used to supply air for other users from air cylinders 51, or they may be used to introduce air into system 49 from another source in an emergency situation.
An alternate distribution and control system 49' corresponding to control panel 49 is shown in FIG. 10. Control system 49' is the same as control system 49 except that control system 49' has only one breathing air manifold 63 with three breathing air outlets 42 and it has a tool air manifold 69 with three tool air outlets 43. As in the case of system 49, breathing air pressure and tooling air pressure are separately regulated and controlled.
It should be noted that truck 10 is covered by a metallic housing comprising fixed front panel 11, fixed rear panel 12, bottom panel 13, hinged side doors 14 and 15 and a double-hinged top cover 16. Any exposed opening in the enclosure are covered by a panel 70 as shown in FIG. 2.
Although but two embodiments of the invention have been illustrated and described, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the spirit of the invention or from the scope of the appended claims. | A truck containing air cylinders and associated pressure control and delivery apparatus for use in supplying breathing air and air for tool operation in remote rescue operations. The truck is shielded for protection of its equipment against damage due to impact. Separate breathing air and tool air regulation and delivery channels are incorporated. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] In one of its aspects, the present invention generally relates to repair processes that the technician may invoke in order to optimize the repair of damage such as that sustained by a vehicle under collision. More specifically, in this aspect, the present invention relates to the process of identification of the correct steps after the implementation of which corrective forces can be applied to correct collision damage.
[0003] In another of its aspects, the present invention relates to automobile repair systems and more directly to those requiring the elevation, mobility and anchoring of automobiles under repair.
[0004] In another of its aspects, the present invention relates to methods and apparatus for the attachment of devices to a pliable medium where force must be applied, often to correct damage or deformity, and which are then removable without significant secondary damage sustained by the medium.
[0005] In yet another of its aspects, the present invention generally relates to repair apparatus that may be used by an operator to correct damage or distortion in a medium. More specifically, in this aspect, the present invention relates tools required to the correct damage or distortion in a medium, such as a vehicle body or frame, where force is to be applied but where the site of the work presents obstacles, such as vehicle bumpers, to the direct application of corrective force.
[0006] In another of its aspects, the present invention generally relates to repair processes that the mechanic may invoke in order to optimize the repair of a damaged or distorted medium, such as a metal medium. More specifically, in this aspect, the invention relates to the process of establishing an anchor point, to which corrective forces can be applied, on a medium in order to repair damage to the medium. Said damage would be that suffered by the body and/or frame of a vehicle due to collision.
[0007] In another of its aspects, the present invention generally relates to apparatuses designed to aid in the correction of damage to a medium in the establishment of an anchor point, the drilling of holes, or the installation of a rivet. More specifically, in this aspect, the present invention relates to the repair of damage where the work may be obstructed or where the application of force to repair damage requires reinforcement at the site of the work and where drilling or rivet installation is desired to be performed.
[0008] In another of its aspects, the present invention relates to methods and apparatus for the installation of rivets into a medium for the purposes of anchoring and particularly for the installation of rivets provided with internal threads to be installed from one side of the work.
[0009] In another of its aspects, the present invention generally relates to work to be performed utilizing an installed rivet. More specifically, in this aspect, the present invention relates to the utilization of an installed rivet where the installed rivet is deemed to be insufficient to withstand the stresses to be applied thereon.
[0010] In another of its aspects, the present invention relates to methods and apparatuses for drilling into a medium where the medium may be difficult to access, the work requires the drilling of holes relatively spaced at distances according to tight tolerances, the operator may only have unpowered or low rotation driving devices at his disposal, the axis of drilling must be perpendicular to the face of the work, or where any combination of the above situations is present.
[0011] In another of its aspects, the present invention relates to apparatuses designed to guide a drill bit in the drilling of holes into a medium. More specifically, the present invention relates to the drilling of holes into a medium where the work may be obstructed by surface irregularities, where magnetic mounting is desirable, or where there is insufficient access at the site of the work by means of conventional drill guides.
[0012] 2. Description of the Prior Art
[0013] Existing repair methodologies lack standardization in both process and apparatus in the correction of damage. The technician is often burdened with customization of the methods and tools used to repair damage on a per job basis increasing the duration of the process and necessitating the use of tools both costly and cumbersome to operate.
SUMMARY OF THE INVENTION
[0014] In one of its aspects, the present invention provides a process for the technician to be able to perform collision repair, and offers the technician a standardized process which may be applied to the maximum number of problems with a minimum of effort, to recommend the tools, from a standardized kit, which the technician will require in order to carry out the steps in this process, to thereby reduce the time and/or cost of repair, and/or to minimize secondary damage that may be caused by the implementation of inappropriate methods and/or tools.
[0015] In another of its aspects the present invention provides a universal system and comprehensive mechanism for the repair of automobiles which is free from one or more of the defects of the prior art repair methodologies. In accordance with the present invention, a universal system of repair is provided that will elevate the vehicle from any level surface and allow its transport to any predefined repair zone. In this aspect, the present invention provides the facility to elevate, secure onto apparatus and move any passenger automobile without refitting for width and length variation. Once in the repair zone, the vehicle can be anchored to conventional, repair industry standard, floor mounted anchor points integrating into the base clamp and/or can be independently stabilized by locking the repair apparatus into position. Rotation of the vehicle can be then achieved by unlocking three of the four locking points and then rotating about the axis of the remaining locked point. Further, this aspect provides facility for additional high resolution spot anchoring to the damaged regions of the automobile reducing unnecessary stresses to undamaged regions during the repair process thereby minimizing secondary damage to an unperceivable level.
[0016] In yet another aspect, the present invention is to provide a standardized method and complimentary apparatus for the mounting of a threaded shaft onto a medium such as the metal structure of a vehicle to provide a sturdy attachment means for the purposes of applying force to correct structural damage. Further, this aspect of the invention provides a versatile and adaptive means of attachment in regions otherwise inaccessible or difficult to access thereby limiting the subsequently applied forces to the damaged region. This method provides the mechanic with an economic and/or time saving method in the selection and application of the appropriate apparatus herein.
[0017] In another of its aspects, the present invention is to provide a tool to correct damage or distortion in a medium, such as a vehicle body or frame, where the work is inaccessible or only partly accessible. Further, this aspect of the invention provides the facility within said tool for proper anchoring at the site of the work, to offer the operator at least two axes of rotation about the site of the work in order to efficiently apply forces as required, to provide adaptable means to clear obstructions to the work, and/or to reduce the potential of secondary damage caused by the use of inappropriate tools. Another aspect of the invention is to increase safety in the immediate environment of the apparatus by allowing the operator to rigidly mount said apparatus before the application of force thereby eliminating the possibility of the device being disengaged when unattended. A further aspect of the invention aims to standardize the apparatus required to perform said tasks.
[0018] In another of its aspects, the present invention is to provide a process for the mechanic to create an anchor point on a damaged medium in order to apply corrective forces to said anchor point. A further aspect of this invention is to offer the mechanic a standardized process which may be applied to the maximum number of problems with a minimum of effort, to recommend the tools, from a standardized kit, which the mechanic will require in order to carry out the steps in this process, to thereby reduce the time and/or cost of repair, and/or to minimize secondary damage that may be caused by the implementation of inappropriate methods and/or tools.
[0019] In another of its aspects, the present invention is to provide a tool which is versatile in scope, effective in clearing obstructions to its application, and sufficiently sturdy to withstand forces applied to correct damage a the site of the work. Further, this aspect of the invention is to provide a single platform that may be used to guide a drill or to establish a rivet in a medium without having to resort to the use of several tools exclusive to each task. In another of its aspects, this invention aims to reduce the cost of repair, in both time requirements and/or tool requirements. The aim of the present invention is to reduce the occurrence of secondary damage that may be caused by improperly applied forces by providing the operator the facility to mount the apparatus, and to thereby apply forces, as close to the desired point of application as possible.
[0020] In another of its aspects, the present invention is to provide a method and apparatus for the installation of threaded rivets into a medium which is inexpensive, simple in design, allows the operator versatility in application, allows the operator freedom of one hand, and permits the installation of said rivets from one side of the work.
[0021] In another of its aspects, the present invention is to provide a facility to reinforce an existing, installed rivet. An additional aspect of this invention is to allow the technician to select a level of reinforcement as required by the work thereby increasing the stress bearing facility of the system of the washer and the rivet to levels unattainable by the rivet alone. In the absence of a suitable site for a rivet but where a washer may be installed, the technician is provided the facility to use the washer as a stand alone device to bear the stresses of the work that would otherwise be borne by a rivet. It is the aim of this invention to provide the technician with a tool that is economical and simple to implement in the event that a rivet requires reinforcement or in the absence of a rivet.
[0022] In yet another of its aspects, the present invention is to provide a method and complimentary apparatus for drilling into a medium under conditions unsuitable for existing systems and apparatus, is inexpensive, compact in design, versatile in application, is capable of performing its intended function under tight tolerance and at the site of the work such as that required for the installation of brackets, allows the operator to concentrate applied forces to rotation and not against the face of the work thereby reducing fouling of the drill bit and resulting in a hole perpendicular to the face of the work. Further aspects of this invention are to provide a method and apparatus for the drilling of holes into a medium which may be performed at low rotation speeds reducing the generation of heat at the site of the work without lubrication and/or at high rotation speeds where a localized air cooling facility may be engaged.
[0023] In another of its aspects, this invention is to provide a tool which is effective in clearing obstructions to its application, compact, simply applied, and sufficiently sturdy to withstand forces applied in the drilling of holes at the site of the work and to allow the drilling to be performed at an angle to the plane of the work desirable to the operator. Further to this aspect of the invention, a means to reduce heat resulting from the action of drilling and to safely remove drilling exhaust in the form of fragments which can otherwise obstruct the drilling action or injure the operator is provided. In another aspect, this invention is to reduce the cost of drilling in both setup time and tool requirements. In this aspect, it is the aim of the present invention to provide a means for the operator to accurately define the location of the intended hole(s).
BRIEF DESCRIPTION OF DRAWINGS
[0024] FIG. 1 is a flowchart diagram of the collision repair process.
[0025] FIG. 2 is a flowchart diagram of the hook-up process.
[0026] FIG. 3 is an illustration of a pinch clamp.
[0027] FIG. 4 is an illustration of a bracket.
[0028] FIG. 5 is an illustration of a drill cartridge.
[0029] FIG. 6 is an illustration of locking pliers.
[0030] FIG. 7 is an illustration of a piercing punch.
[0031] FIG. 8 is an illustration of a mobile, 4 point anchoring apparatus.
[0032] FIG. 9 is an illustration of a vector transfer apparatus.
[0033] FIG. 10 is a diagram of the repair zone equipped with floor anchors.
[0034] FIG. 11 is a detailed diagram of the elevation and mobility apparatus.
[0035] FIG. 12 is a diagram of the anchored base clamp.
[0036] FIG. 13 is a diagram of the adjustable clamp on a section of crossbeam.
[0037] FIG. 14 is a diagram of an anchor facility affixed to a section of crossbeam.
[0038] FIG. 15 is a detailed diagram of the crossbeam fitted for apparatus integration.
[0039] FIG. 16 is a side elevation of a threaded shaft configured for use with a nut.
[0040] FIG. 17 is a bottom view of a threaded shaft.
[0041] FIG. 18 is a side elevation of a threaded shaft configured for use with a threaded rivet.
[0042] FIG. 19 is a side elevation of a threaded shaft configured for use with a forming nut.
[0043] FIG. 20 is an isometric view of a threaded shaft configured for use with a twist and lock attachment.
[0044] FIG. 21 is a side elevation of a threaded shaft configured for use with a threaded bracket.
[0045] FIG. 22 is a side elevation of a threaded shaft and a sectional view of a right angle bracket with which it is engaged.
[0046] FIG. 23 is an isometric view of a threaded shaft and a one-point vise clamp bracket.
[0047] FIG. 24 is an isometric view of a threaded shaft and a two-point vise clamp bracket.
[0048] FIG. 25 is an isometric view of a threaded shaft and MacPherson strut housing bracket.
[0049] FIG. 26 is an isometric view of a vector transfer apparatus with a straight arm attachment.
[0050] FIG. 27 is a side elevation of a vector transfer apparatus with a straight arm attachment.
[0051] FIG. 28 is a side elevation of a vector transfer apparatus with a straight arm attached perpendicular to the axis of the locked, internally threaded cylinder.
[0052] FIG. 29 is an isometric view of a vector transfer apparatus with an adjustable right angle arm attachment.
[0053] FIG. 30 is an isometric view of a vector transfer apparatus with a chain tightener attachment.
[0054] FIG. 31 is an isometric view of the vector lock mechanism.
[0055] FIG. 32 is an isometric view of the vector lock mechanism with locking bolt fixture exposed.
[0056] FIG. 33 is a side elevation of a vector transfer apparatus with a high resolution vector lock mechanism.
[0057] FIG. 34 is an isometric view of a vector transfer apparatus with a high resolution vector lock mechanism.
[0058] FIG. 35 is a flowchart diagram of the hook up process.
[0059] FIG. 36 is an illustration of a pinch clamp.
[0060] FIG. 37 is an illustration of the front and side of a universal bracket.
[0061] FIG. 38 is an illustration of a drill cartridge.
[0062] FIG. 39 is an illustration of locking pliers.
[0063] FIG. 40 is an illustration of a piercing punch.
[0064] FIG. 41 is an isometric view of a right angle repair bracket.
[0065] FIG. 42 is a side elevation of the length of a right angle repair bracket.
[0066] FIG. 43 is a side elevation along the width of a right angle repair bracket.
[0067] FIG. 44 is a side elevation of a flat repair bracket.
[0068] FIG. 45 is a top view of a flat repair bracket.
[0069] FIG. 46 is a side elevation of a flat repair bracket mounted on a medium and reinforced by a washer.
[0070] FIG. 47 is an isometric view of an adjustable mount flat repair bracket equipped with an anchor attachment.
[0071] FIG. 48 is a top view of an adjustable mount flat repair bracket equipped with an anchor attachment.
[0072] FIG. 49 is a side elevation of an adjustable mount flat repair bracket equipped with an anchor attachment and installed on a medium to be repaired.
[0073] FIG. 50 is a side elevation of a right angle repair bracket installed on a medium by locking pliers means.
[0074] FIG. 51 is a side elevation of a right angle repair bracket installed on a medium with the aid of locking pliers and engaged with two drill guide attachments.
[0075] FIG. 52 is a top view of a flat or right angle repair bracket installed on a medium and engaged by an anchor plug attachment and a drill guide attachment.
[0076] FIG. 53 is a side elevation of two wall thickness gauges.
[0077] FIG. 54 is a side elevation of a rivet and a rivet installed in a medium.
[0078] FIG. 55 is a sectional view of an hollow anvil body.
[0079] FIG. 56 is a side elevation of a mandrel.
[0080] FIG. 57 is a sectional view of a mandrel installed in an hollow anvil body.
[0081] FIG. 58 is a sectional view of an assembled anvil apparatus.
[0082] FIG. 59 is a sectional view of an assembled anvil apparatus where the mandrel has been drawn upward along the axis of rotation.
[0083] FIG. 60 is a side elevation of an anvil assembly with a pin passing through it.
[0084] FIG. 61 is a top view of an anvil assembly with a pin passing through it.
[0085] FIG. 62 is a top view of an anvil wrench.
[0086] FIG. 63 is a side elevation of an anvil wrench.
[0087] FIG. 64 is a side elevation of an anvil apparatus with the ring portion of an anvil wrench engaged therein.
[0088] FIG. 65 is a top view of a rivet reinforcement washer.
[0089] FIG. 66 is a side elevation of a rivet reinforcement washer.
[0090] FIG. 67 is a side elevation of a rivet reinforcement washer installed on a medium with a rivet.
[0091] FIG. 68 is a top view of a rivet reinforcement washer installed on a medium.
[0092] FIG. 69 is a side elevation of a rivet reinforcement washer installed on a medium with a rivet and engaged by a bracket attachment.
[0093] FIG. 70 is a side elevation of a rivet reinforcement washer installed on a medium with a rivet and engaged by a tool attachment.
[0094] FIG. 71 is a sectional view of a drill cartridge apparatus.
[0095] FIG. 72 is a side view of a drill cartridge housing.
[0096] FIG. 73 is a top view of a drill cartridge housing.
[0097] FIG. 74 is a sectional view of a disassembled drill cartridge apparatus.
[0098] FIG. 75 is a sectional view of a drill cartridge apparatus and a drill plug engaged with a drill bracket and medium.
[0099] FIG. 76 is a top view of a drill cartridge apparatus and a drill plug engaged with a drill bracket and medium.
[0100] FIG. 77 is a side elevation of a magnetic drill guide with raised magnets.
[0101] FIG. 78 is a bottom view of a magnetic drill guide with raised magnets.
[0102] FIG. 79 is a side elevation of a magnetic drill guide with raised magnets and attached air cooling apparatus.
[0103] FIG. 80 is a bottom view of a magnetic drill guide with raised magnets and attached air cooling apparatus.
[0104] FIG. 81 is a bottom view of a magnetic drill guide with attached air cooling apparatus engaged with a center line positioning apparatus.
[0105] FIG. 82 is a side elevation of a magnetic drill guide with countersunk magnets, mounting eyelets, and attached air cooling apparatus.
[0106] FIG. 83 is a bottom view of a magnetic drill guide with countersunk magnets, mounting eyelets, and attached air cooling apparatus.
[0107] FIG. 84 is a side elevation of an unthreaded mounting shaft with facility for eyelet attachment.
[0108] FIG. 85 is an isometric view of a vehicle elevation apparatus with a mounting bracket attachment for the engagement of a mounting shaft.
[0109] FIG. 86 is a side elevation of a bracket engaged with a medium under repair with a chain attachment.
[0110] FIG. 87 is a side elevation of two brackets engaged on opposing sides of a medium under repair with a chain attachment.
[0111] FIG. 88 is a side elevation of an inverted vector transfer apparatus engaged with a medium under repair.
[0112] FIG. 89 is a side elevation of a push jack subtended by brackets engaged with a medium under repair.
[0113] FIG. 90 is a side elevation of push jack bracket.
[0114] FIG. 91 is an isometric view of an unthreaded mounting shaft with threaded stud mounting facility.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0115] In accordance with an embodiment of the present invention, a process is provided for collision repair where the following steps summarize the effort:
damage assessment is performed to inform further steps; the collision repair process is invoked where the technician is to follow the instructions outlined in the proposed process and make decisions based on the requirements of the work as part of the process; and upon completion of this process, the technician is ready to apply forces at appropriate points as required by the work.
[0119] The collision repair process noted in the above steps will be better understood with reference to the drawings as listed in the description of drawings above.
[0120] The description of the collision repair process will be discussed in detail with reference to FIGS. 1 to 9 . A collision repair process is provided as in FIG. 1 wherein a flowchart format is used to best illustrate the steps involved. The collision repair process flowchart is comprised of several steps which take the form of either an action to be taken or an action preceded by a decision to be made by the technician. Arrows are used to indicate the direction of flow.
[0121] The start terminal 1 is the initialization of the collision repair process. The technician must identify the damage that is to be repaired using the process.
[0122] The decision 2 offers the technician the option of utilizing a mobile, 4 point anchor apparatus whereby the vehicle under repair is raised onto beams and is anchored thereto while said apparatus may be moved on the work floor as required. This determination is dependent on the location of the damage on the vehicle where undercarriage damage would strongly suggest an affirmative response.
[0123] The action 3 is invoked if the technician has determined that the mobile, 4 point anchor apparatus, such as that in FIG. 8 , is required for the work. The anchor apparatus allows the technician to raise the vehicle to the desired height and to anchor appropriately. After completion of the anchoring, the technician may proceed to implement the hook-up process 4 as described in detail with reference to FIG. 2 below.
[0124] If the anchor apparatus is determined to be unnecessary in decision 2 , the technician may directly proceed to implement the hook-up process 4 as described in detail with reference to FIG. 2 below.
[0125] Decision 5 is offered after the successful implementation of the hook-up process 4 . Stress relief is offered where it is not desirable to directly apply forces of great magnitude, where anchoring may not be as sturdy as desired, or where the ability to apply forces of great magnitude is hindered.
[0126] If stress relief is determined to be necessary in decision 5 , the action 6 is to be implemented whereby stress relief is attained by means of vibration of the medium under repair or impact such as that provided by a hammer, during the application of force, or additional anchoring is performed at the site of the work.
[0127] After the completion of action 6 or if stress relief is determined to be unnecessary in decision 5 , the technician is given the option of proceeding with either action 7 or action 8 . Action 7 requires the implementation of the apparatus of FIG. 9 wherein a device is provided which allows the technician to clear obstacles, such as the bumper of a vehicle, and to accurately set and lock the vector at which force is to be applied. The technician may choose to proceed with action 8 wherein force may be directly applied to the site of the work by means of a chain or other pulling or pushing device.
[0128] After the completion of either of the actions of 7 or 8 , the process may be concluded with the application of force at a magnitude and vector appropriate to the work.
[0129] A hook-up process is provided as in FIG. 2 wherein a flowchart format is used to best illustrate its intended usage. The hook-up process flowchart is comprised of several steps which take the form of either an action to be taken or an action preceded by a decision to be made by the technician as in FIG. 1 . Arrows are used to indicate the direction of flow.
[0130] The start terminal 10 is the initialization stage of the process. At this stage, a point on the medium to be repaired must be appropriately chosen to be able to correct damage if force is applied at the correct vector through this location.
[0131] The decision 11 offers the technician the option of proceeding with or without the use of mounting holes. This determination is dependent on the site of the work, the magnitude of the force to be applied in respect of the sustaining ability of the mounting spot, and whether a mounting hole is a practical means of attachment of an anchoring device.
[0132] The action 12 is invoked if the technician has chosen to proceed without a hole or holes and is therefore satisfied that a clamping method is sufficient to sustain the forces to be applied in correcting the damage. In this case, a pinch clamp may be used as that illustrated in FIG. 3 . Once the clamp is attached, the technician may move to the end terminal 21 where a device to sustain the application of force may be attached, such as a threaded hook-up shaft, secured chain, etc., and thus the process is complete.
[0133] The decision 13 is invoked if the technician has determined that the use of a mounting hole or holes is appropriate to the work. In this decision, the technician must respond to the question as to whether mounting holes are present and if so, whether these mounting holes are appropriately located.
[0134] The action 14 is invoked if the technician determines that a mounting hole or holes must be produced. In order to produce a mounting hole, a bracket, as in FIG. 4 , must be attached with which a drill cartridge, as in FIG. 5 , is engaged in order to produce a hole. The mounting of said bracket may be achieved by one of three methods from which the technician is to choose the most practical given the work. The methods of mounting the bracket offered to the technician are the use of locking pliers, as in FIG. 6 , a threaded stud welded to the medium, or a piercing punch, as in FIG. 7 , in order to create a small diameter hole where a self-tapping screw is engaged to mount said bracket.
[0135] Upon completion of action 14 , the technician is offered the option of using a bracket in decision 15 with which to engage devices which will sustain the application of force or to directly attach said devices. If the technician chooses to waive the bracket option then the process is again completed at end terminal 21 in the attachment of said device(s).
[0136] If the requirement of the bracket is established in decision 15 , then the technician is instructed to mount said bracket in action 20 by means of a threaded rivet, which is to engage a bolt, or a conventional nut and bolt configuration through the newly produced hole(s) in action 14 . Once the bracket is secured, the process may again be completed at end terminal 21 as before.
[0137] Returning to decision 13 , if the technician is able to utilize any existing holes then decision 16 may be invoked. Here, the technician must decide whether to proceed with the aid of a bracket or to directly mount any devices which will sustain the application of force. If the technician chooses to waive the bracket option then the process is completed at end terminal 21 as before. If the technician does require a bracket for the purposes of mounting any devices which will sustain the application of force, then action 17 is to be invoked where the bracket is secured to the medium by means of either a threaded rivet or a nut and bolt configuration as in action 20 above.
[0138] The technician may proceed to decision 18 where the requirement of any additional hole(s), in order to provide additional mounting strength, is to be determined. If additional holes are not required, the technician may proceed to end terminal 21 to complete the process as before. In the event of additional holes required, the technician may proceed to action 19 in order to engage the drill cartridge to produce said hole(s).
[0139] Once the requisite hole requirement is satisfied in action 19 , the technician need only to secure the bracket, by means of threaded rivet or nut and bolt configuration as before, utilizing new mounting hole. The process is then completed at end terminal 21 once any devices which will sustain the application of force have been attached.
[0140] In an embodiment of the present invention a repair zone will be described with reference to FIG. 10 . The vehicle under repair 28 is intended to be brought within a perimeter described by floor anchor points 24 which are illustrated in their relative positions in the industry defined configuration and further situated in the perimeter described by additional floor anchor points 26 .
[0141] Precise positioning and elevation of the vehicle is attained with the aid of the apparatus which will be described with reference to FIG. 11 . The elevation and mobility apparatus 46 is secured to crossbeam 30 and a wheel assembly 48 is attached to said crossbeam 30 . The combined elevation and mobility apparatus 46 and the crossbeam 30 is now moved into position such that the unsecured end of the crossbeam 30 is brought under the vehicle 28 , perpendicular to its length, and allowed to extend on the other side of the vehicle 28 . An additional elevation and mobility apparatus 46 is then secured to the unsecured end of the crossbeam 30 after the removal of the wheel assembly 48 which is adjustable and removable by screw clamps 42 . The elevation of the crossbeam 30 relative to the elevation and mobility apparatuses 46 is then configured by the height adjustment bolt 32 which passes through a threaded hole in the crossbeam 30 and then said crossbeam 30 is locked at desired elevation by lock pins 40 providing perpendicularity once tightly secured relative to the height of the elevation and mobility apparatus. The elevation of the elevation and mobility apparatuses 46 relative to the floor is then adjustable by means of bolt 34 and locked by means of screw lever 36 .
[0142] Final positioning of the vehicle 28 is achieved by maintaining the elevation of the elevation and mobility apparatuses 46 above the floor such that the attached wheels 38 are free to move. Immobility is attained by lowering the elevation and mobility apparatuses 46 to the floor thereby rendering the attached wheels 38 incapable of providing movement. Should partial immobility be desired, for rotation, said elevation and mobility apparatuses 46 can be maintained above the floor and said attached wheels 38 can be locked as desired and thus rotation axis defined.
[0143] A second pair of elevation and mobility apparatuses 46 and a crossbeam 30 can then be put into position at the other end of the vehicle 28 as required by the repair.
[0144] The mechanism by which the elevation and mobility apparatus 46 is attached to the crossbeam 30 will be described in detail with reference to FIG. 15 . The height adjustment bolt 68 passes through a self aligning nut 70 of cylindrical shape contained within the hollow end region of the crossbeam 72 . The axis of rotation of the self aligning nut 70 is defined by the insertion of the set screw 74 through axis hole 78 in the hollow end region of the crossbeam 72 and into the appropriately threaded end of the self aligning nut 70 . Thus the necessary maneuverability of the assembled system, as indicated by the range of angles through which the height adjustment bolt 80 may pass relative to the crossbeam 72 , is afforded until the requisite height is determined and the height adjustment bolt 68 is tightened such that crossbeam 72 is brought perpendicular to the height of the elevation and mobility apparatus 46 with the aid of lock pins 40 .
[0145] Securing the final position of the elevation and mobility apparatus 46 , before repair, will be described with reference to FIG. 12 . Base clamps 50 are brought into contact with the elevation and mobility apparatuses 46 at those points on the floor deemed critical under stress and said base clamps are secured to floor anchor points 24 or 26 as convenient. Securing to floor anchor points 24 or 26 is achieved by passing the floor anchor bolt 52 through the saw-toothed washer 54 and then passing said assembly through the base clamp 50 , and potentially through appropriately provided anchoring holes 44 on the elevation and mobility apparatus 46 , into the threaded floor anchor points 24 or 26 such that the teeth of said saw-toothed washer 54 come into contact with the saw-toothed edges of the base clamp 50 thereby eliminating movement under stress.
[0146] Securing of the vehicle 28 to the combined apparatus will be described with reference to FIG. 13 . Two adjustable clamps 56 are attached to a section of crossbeam 58 between the elevation and mobility apparatuses 46 and are spaced according to the distance between the lower sills on the undercarriage of the vehicle 28 and are locked into position by means of bolts 60 . Said distance varies by brand and model of vehicle 28 however the present invention provides universal accommodation for this distance by means of said adjustability. The adjustable clamps 56 are then tightened to the lower sills on the undercarriage of the vehicle 28 by means of clamp bolts 62 thus completing the preparation process for repair.
[0147] Further, spot anchoring is achieved with higher resolution than conventional systems which are typically floor anchored. Such anchoring means will be described with reference to FIG. 14 . A chain anchor point 66 is affixed to a section of crossbeam 64 at a point outside the perimeter of the vehicle 28 thereby providing anchoring means. Similarly, chain anchor points 66 may be affixed to the elevation and mobility apparatuses 46 providing additional anchoring points. Such high resolution anchoring in the present invention allows the stress of repair to be localized to the damaged region thereby reducing secondary damage which is prevalent in conventional systems.
[0148] In accordance with an embodiment of the present invention, a method is provided for the attachment of an appropriate threaded shaft in preparation for the further attachment of devices enabling the application of force. The attachment of the threaded shaft is performed according to the following steps:
selection of mounting method according to material thickness, accessibility, and the distribution of forces required by the work; selection of threaded shaft appropriate to the choice of mounting method; and engagement of the threaded shaft with the medium, either directly or by means of bracket, and this finalization of preparation for the attachment of further devices to provide means for the application of force to the affected region.
[0152] The apparatus required to perform the steps outlined above will be better understood with reference to the figures listed in the description of drawings above.
[0153] The description of the directly mountable threaded shafts will be discussed with reference to FIGS. 16 through 20 . A threaded shaft is provided as in FIG. 16 such that it has a threaded outer cylinder 78 , a smaller diameter threaded bolt 82 for engagement with a nut 80 through a medium 76 . The threaded shaft is also provided with a square socket 84 to facilitate engagement with a wrench, such as an impact wrench, commonly available to the mechanic. This threaded shaft is further illustrated in FIG. 17 having square a socket 86 .
[0154] A threaded shaft is provided as in FIG. 18 for applications where the medium 94 with which the threaded shaft is to be engaged is provided with an installed threaded rivet 92 . Similar to the threaded shaft of FIG. 16 , the threaded shaft of FIG. 18 is provided with a threaded outer cylinder 90 , a square socket 98 , and a smaller diameter threaded bolt 96 to engage the installed threaded rivet 92 . This threaded shaft is further provided with an annular cavity 88 to eliminate the obstruction posed by the head of the installed threaded rivet 92 when the threaded shaft is in full abutment of the medium.
[0155] A threaded shaft is provided as in FIG. 19 for applications where the medium 106 with which the threaded shaft is to be engaged is of reduced material rigidity requiring the additional rigidity afforded by the deformation of said medium 106 . Similar to the threaded shaft of FIG. 18 , the threaded shaft of FIG. 19 is provided with a threaded outer cylinder 102 , a square socket 110 , and a smaller diameter threaded bolt 108 to engage the forming nut 104 through the medium 106 . The forming nut 104 is provided with an annular depression which forms the negative of the positive forming shape 100 allowing the deformation of the medium 106 when the threaded shaft is fully engaged with said medium 106 and forming nut 104 .
[0156] A threaded shaft is provided as in FIG. 20 for specific automotive applications where portions of the undercarriage of a vehicle are suitably designed, such as the undercarriage of a BMW automobile, to engage the twist and lock mechanism comprised of key 112 and lock 114 . Similar to the threaded shaft of FIG. 19 , the threaded shaft of FIG. 20 is provided with a threaded outer cylinder 116 and further may be provided with a square socket 110 .
[0157] The description of the bracket mountable threaded shaft will be better understood with reference to FIGS. 21 through 25 . A bracket mountable threaded shaft is provided as in FIG. 21 for applications where a bracket is first engaged with a medium and subsequently a threaded shaft is required to be engaged with said bracket. Similar to the threaded shafts of FIGS. 16 through 20 , the threaded shaft of FIG. 21 is provided with a threaded outer cylinder 124 , a square socket 118 to facilitate engagement with a wrench, and a smaller diameter threaded bolt 122 not exceeding the length of the threaded region of the intended bracket. This threaded shaft is further provided with a barrier form 120 intended for fitting the format of the bracket providing additional mating strength with said bracket.
[0158] A right angle bracket and threaded shaft are engaged as in FIG. 22 . Once the bracket 126 is mounted to a medium, an engaged threaded shaft has a free threaded outer cylinder 128 for the purposes of further attachments. A threaded shaft may be engaged at either or both planes of the right angle bracket 126 and it is understood that flat brackets or brackets of other configurations may be used to engage a threaded shaft.
[0159] A vise equipped with one tightening point and a threaded shaft are provided as in FIG. 23 . The single point vise 130 is configured similar to the bracket of FIG. 22 in that it may be engaged with the threaded shaft 132 . Said vise configuration is intended for applications where a suitable anchoring point is available such as the pinch well along the undercarriage of a vehicle.
[0160] A vise equipped with two tightening points and a threaded shaft are provided as in FIG. 24 . The double point vise 134 is similar to the bracket of FIG. 22 and the single point vise of FIG. 23 in that it may be engaged with the threaded shaft 136 . The use of a double point vise 134 facilitates the distribution of force among its points of contact. It is understood that vises equipped with multiple tightening points may be used without departing from the scope of the invention.
[0161] A MacPherson strut housing mountable bracket and threaded shaft are provided as in FIG. 25 . The MacPherson strut housing bracket 144 is equipped with swivel arms 146 in order to accommodate varying housing dimensions. The swivel arms 146 are further provided with plugs 142 which are intended to engage holes at the three points common to MacPherson strut housings. A threaded shaft 142 may be engaged by the MacPherson strut housing bracket 144 by means of the threaded receptacle 140 .
[0162] A description of an unthreaded mounting shaft with an eyelet attachment facility will be discussed with reference to FIG. 84 . A mounting shaft 692 is provided with an internal thread to engage an appropriately threaded eyelet 690 which may then be used to engage a chain or hook for the application of force according to the requirements of the operator. It is understood that said mounting shaft 692 may be equipped with any of the mounting configurations as described above with reference to FIGS. 16 to 25 . It is further understood that the threaded shafts, as described above with reference to FIGS. 16 to 25 , may be of a configuration lacking external threads along the axis of the shaft whilst retaining mounting and attachment facilities.
[0163] A description of an unthreaded mounting shaft with threaded stud mounting platform will be discussed with reference to FIG. 91 . A mounting shaft 760 is provided with an internal thread to engage a threaded eyelet as above. The mounting shaft 760 is equipped with an additional internal thread on its opposing end to engage a threaded stud on mounting platform 762 . Said mounting platform 762 may be magnetically held to the work surface in preparation for welding to said surface. A clearance recess 764 is provided in order to facilitate removal of said mounting platform 762 by means of prying away from the work surface after the completion of the action of repair. The mounting shaft 760 is shown provided with wrench tightening facility 766 which is configured to allow the engagement of a wrench which would be commonly available in the shop of the operator. It is understood that said wrench tightening facility 766 may be incorporated into any of the above mentioned mounting shafts. It is also understood that said clearance recess 764 may be of varying configurations allowing clearance of obstacles to mounting in addition to providing above mentioned facility for prying said mounting platform 762 away from the surface of the work.
[0164] A description of a mounting bracket to engage the above described threaded and unthreaded mounting shafts will be discussed with reference to FIG. 85 . A mounting shaft bracket 696 is provided with a receptacle 694 to engage mounting shafts as those discussed with reference to FIGS. 16 through 25 and FIG. 84 . Said mounting shaft bracket 696 is shown to be readily mounted to a vehicle elevation apparatus but may additionally be configured to mount to surfaces as required by the work. A tightening screw facility 695 is provided such that the elevation of the engaged mounting shaft within the hollow of said bracket 696 may be adjusted and secured by the operator.
[0165] In accordance with an embodiment of the present invention, the following steps are provided in order to effectively implement the apparatus herein:
an anchor point is established at the site, such as a point on a vehicle body or frame, at which force is desired to be introduced in order correct material damage or distortion; the vector transfer apparatus, and appropriately chosen attachment engaged therewith, is engaged at said anchor point and appropriately configured as to the direction of desired force application; and force is applied at the accessible end of the vector transfer apparatus in order to effectively transfer corrective forces to said anchor point.
[0169] The apparatus required to perform the above steps will be better understood with reference to the drawings as listed in the description of drawings above.
[0170] The description of the vector transfer apparatus will be discussed with reference to FIGS. 26 to 30 and FIG. 88 . A vector transfer apparatus is provided as in FIG. 26 comprised of an internally threaded cylinder 150 with which to engage an appropriately gauged threaded shaft at the anchor point, a vector lock mechanism 152 enabling the operator to adjust the angle of engagement through a range of approximately 120 degrees at approximately fifteen degree increments, a straight arm 154 affixed to said vector lock mechanism 152 at an angle allowing the operator to clear obstructions to the work between the anchor point and the free end of the straight arm 154 , a chain 156 affixed to the free end of the straight arm 154 as an example of a point on which force may be exerted in a direction away from the body of the vector lock mechanism 152 . The chain 156 may be substituted with an assortment of means functioning to facilitate the application of force by engaging the free end of said straight arm 154 .
[0171] The structure of the vector transfer apparatus of FIG. 26 is further illuminated in the side view illustration of FIG. 27 . The apparatus is comprised of an internally threaded cylinder 158 , a vector lock mechanism 160 , a straight arm 162 , and a chain 164 as that in FIG. 26 .
[0172] A modified configuration of the vector transfer apparatus is provided as in FIG. 28 . The apparatus is similarly comprised of an internally threaded cylinder 166 and a vector lock mechanism 168 as in FIGS. 26 and 27 . The straight arm 170 is affixed parallel to the lower edge of the vector lock mechanism 168 in contrast to the previous figures facilitating the clearing of obstructions which may differ from those addressed in the previous configurations. The apparatus is provided with a chain attachment 172 as before.
[0173] A vector transfer apparatus with an adjustable arm attachment is provided as in FIG. 29 . This apparatus comprises an internally threaded cylinder 176 and a vector lock mechanism 178 as before. The apparatus is shown engaged with a threaded shaft 174 as that which would be present at the anchor site. A straight arm connector 180 , affixed to the vector lock mechanism 178 , is provided equipped with a facility to mate with a further arm attachment 182 configured to slide within the hollow of said straight arm connector 180 . The arm attachment 182 is secured to the apparatus by means of length locking bolt 190 passing through a guide hole in the straight arm connector 180 and then through the operator selected hole, chosen from spaced holes provided on the arm attachment 182 , and engaged with a nut on the opposing side to hold said length locking bolt 190 , and thus the arm attachment 182 , firmly in place. The arm attachment 182 is further provided with height adjustment of end piece 188 , allowed mobility within the lower chamber, by means of screw 184 which at full engagement of appropriately provided thread will lock end piece 188 at required position relative to lower chamber. A chain 186 is shown attached to said end piece 188 as in previously described configurations.
[0174] A vector transfer apparatus with an attached chain tightening mechanism is provided as in FIG. 30 . This apparatus comprises an internally threaded cylinder 194 and a vector lock mechanism 190 as before and is shown engaged with a threaded shaft 192 as that which would be present at the anchor site. The vector lock mechanism 190 is provided such that it may be engaged with a chain tightening mechanism 196 , commonly available to the collision repair technician, as shown. The chain tightening mechanism 196 has a chain 198 attached similar to the configurations previously described.
[0175] An inverted vector transfer apparatus is provided as in FIG. 88 . The inverted vector transfer apparatus 724 is provided with facility to engage a mounted shaft 722 which is further mounted to the medium under repair 720 . The vector transfer apparatus 724 is supported against the medium 720 by support 728 of material sufficient to withstand distortion under the stresses applied to the chain attachment 726 and serves to distribute forces applied and prevent rotation about the mounting point of mounted shaft 722 where the desired application of force is along the longitudinal axis of the medium 720 . Any of the vector transfer apparatuses may be used in said inverted fashion as required by the work where the operator may find the non-inverted usage impractical or where the forces needed to be applied are better aligned with the inverted vector apparatus 724 .
[0176] A detailed description of the vector lock mechanism will be discussed with reference to FIGS. 31 and 32 . A vector lock mechanism is provided as in FIG. 31 comprising an internally threaded cylinder 202 , upper lock bolt 196 , lower lock bolt 200 , mounting panel 194 , and angle setting holes such as hole 198 bored on said mounting panel 194 . The lower lock bolt 200 may be removed to allow the operator to rotate the internally threaded cylinder 202 about the axis of the installed upper locking bolt 196 . Said internally threaded cylinder 202 may be rotated, relative to mounting panel 194 , to the desired angle and then set at said angle by means of reinserting and securing said lower locking bolt 200 at the appropriate hole passing through mounting plate 194 , locking bolt fixture of the internally threaded cylinder 202 , and the opposing mounting plate. A threaded shaft 192 is shown to be engaged with the vector lock mechanism illustrating the facility of the unit to be rotated about the axis of the threaded shaft 192 , maintaining the engagement, allowing the operator to position the vector lock mechanism according to the requirements of the work in this plane.
[0177] A vector lock mechanism is provided as in FIG. 32 wherein the locking bolt fixtures are exposed. Similar to FIG. 31 , this vector lock mechanism comprises an internally threaded cylinder 214 , upper lock bolt 208 , lower lock bolt 212 , mounting panel 206 , and angle setting holes such as hole 210 bored on said mounting panel 206 . Said internally threaded cylinder 214 is shown with locking bolt fixtures configured such that when abutted with mounting panel 206 , the upper locking bolt may pass through upper fixture and lower fixture may be aligned with each of the holes in mounting panel 206 such as hole 210 allowing the engagement of lower locking bolt 212 at the desired angle. Holes in the mounting panel 206 are provided, along the abutment path of said lower fixture, allowing a rotation range about the axis of the installed upper locking bolt 208 of approximately 120 degrees at approximately fifteen degree setting increments. It is understood that holes may be provided in this path for varying rotation ranges at varying setting increments without departing from the spirit of the present invention. A threaded shaft 204 is illustrated to be engaged with the vector lock mechanism as in FIG. 31 and similarly this configuration allows rotation of the unit about said threaded shaft 204 .
[0178] A vector transfer apparatus is provided as in FIG. 33 where a pulling hook 218 is used to provide corrective forces. The arm attachment 222 is provided as before to clear obstacles to the work. A high resolution vector lock mechanism comprised of an internally threaded cylinder 224 , a rotation window 226 , and an adjustment bolt 228 provides adjustability of the vector transfer apparatus through the full range of angles defined by the rotation window 226 . The rotation of the adjustment bolt 228 about its axis provides the means to set the angle of the arm attachment 222 relative to the static angle adopted by the internally threaded cylinder 224 . The adjustment bolt 228 is prevented from motion parallel to its axis by means of bushings. The high resolution vector lock mechanism is anchored to the site of the work by means of the internally threaded cylinder 224 engaged with a bracket 220 which is further engaged with the medium 216 on which work is to be performed. Anchoring at the site of the work includes but is not limited to the implementation of the bracket 220 .
[0179] A vector transfer apparatus is provided as in FIG. 34 where a pulling hook 236 is used to provide corrective forces as before. This vector transfer apparatus comprises the same components as those of FIG. 33 and is shown engaged with a bracket 234 . The head of the adjustment bolt 230 is shown to be accessible and operable by tools readily available to the technician. Removable locking pin 244 is used to engage the adjustment bolt 230 with the internally threaded cylinder 240 and removable locking pin 232 , which additionally provides an axis of rotation for said vector transfer apparatus, is used to engage arm attachment 242 with said internally threaded cylinder 240 .
[0180] In accordance with an embodiment of the present invention, a process is provided for the establishment of an anchor point, a hook-up spot, on a medium in preparation for the application of corrective forces where the following steps summarize the effort:
a point on a damaged or distorted contiguous medium, such as the body or frame of a vehicle having been involved in a collision, is chosen as the best suited for force to be applied to correct said damage; the hook-up process is invoked where the mechanic is to follow the instructions outlined in the proposed process and make decisions based on the requirements of the work as part of the process; and upon completion of this process, the mechanic is provided the facility to attach those devices which will sustain the application of force, such as a threaded hook-up shaft, bolted chain, etc., while achieving the desired repair.
[0184] The hook-up process noted in the above steps will be better understood with reference to the drawings as listed in the description of drawings above.
[0185] The description of the hook-up process will be discussed in detail with reference to FIGS. 35 to 40 . A hook-up process is provided as in FIG. 35 wherein a flowchart format is used to best illustrate its intended usage. The hook-up process flowchart is comprised of several steps which take the form of either an action to be taken or an action preceded by a decision to be made by the mechanic. Arrows are used to indicate the direction of flow.
[0186] The start terminal 248 is the initialization stage of the process. At this stage, a point on the medium to be repaired must be chosen appropriate to be able to correct damage if force is applied at the correct vector through this location.
[0187] The decision 250 offers the mechanic the option of proceeding with or without the use of mounting holes. This determination is dependent on the site of the work, the magnitude of the force to be applied in respect of the sustaining ability of the mounting spot, and whether a mounting hole is a practical means of attachment of an anchoring device.
[0188] The action 252 is invoked if the mechanic has chosen to proceed without a hole or holes and is therefore satisfied that a clamping method is sufficient to sustain the forces to be applied in correcting the damage. In this case, a pinch clamp may be used as that illustrated in FIG. 36 . Once the clamp is attached, the mechanic may move to the end terminal 270 where a device to sustain the application of force may be attached, such as a threaded hook-up shaft, bolted chain, etc., and thus the process is complete.
[0189] The decision 254 is invoked if the mechanic has determined that the use of a mounting hole or holes is appropriate to the work. In this decision, the mechanic must respond to the question as to whether mounting holes are present and if so, whether these mounting holes are appropriately located.
[0190] The action 256 is invoked if the mechanic determines that a mounting hole or holes must be produced. In order to produce a mounting hole, a universal bracket, as in FIG. 37 , must be attached with which a drill cartridge, as in FIG. 38 , is engaged in order to produce a hole. The mounting of said bracket may be achieved by one of three methods from which the mechanic is to choose the most practical given the work. The methods of mounting the bracket offered to the mechanic are the use of locking pliers, as in FIG. 39 , a threaded stud welded to the medium, or a piercing punch, as in FIG. 40 , in order to create a small diameter hole where a self-tapping screw is engaged to mount said bracket.
[0191] Upon completion of action 256 , the mechanic is offered the option of using a universal bracket in decision 258 with which to engage devices which will sustain the application of force or to directly attach said devices. If the mechanic chooses to waive the bracket option then the process is again completed at end terminal 270 in the attachment of said device(s).
[0192] If the requirement of the universal bracket is established in decision 258 , then the mechanic is instructed to mount said bracket in action 268 by means of a threaded rivet, which is to engage a bolt, or a conventional nut and bolt configuration through the newly produced hole(s) in action 256 . Once the bracket is secured, the process may again be completed at end terminal 270 as before.
[0193] Returning to decision 254 , if the mechanic is able to utilize any existing holes then decision 260 may be invoked. Here, the mechanic must decide whether to proceed with the aid of a bracket or to directly mount any devices which will sustain the application of force. If the mechanic chooses to waive the bracket option then the process is completed at end terminal 270 as before. If the mechanic does require a bracket for the purposes of mounting any devices which will sustain the application of force, then action 262 is to be invoked where the bracket is secured to the medium by means of either a threaded rivet or a nut and bolt configuration as in action 268 above.
[0194] The mechanic may proceed to decision 264 where the requirement of any additional hole(s), in order to provide additional mounting strength, is to be determined. If additional holes are not required, the mechanic may proceed to end terminal 270 to complete the process as before. In the event of additional holes required, the mechanic may proceed to action 266 in order to engage the drill cartridge to produce said hole(s).
[0195] Once the requisite hole requirement is satisfied in action 266 , the mechanic need only to secure the universal bracket, by means of threaded rivet or nut and bolt configuration as before, utilizing new mounting hole. The process is then completed at end terminal 270 once any devices which will sustain the application of force have been attached.
[0196] In another embodiment, a method is provided for the installation of a repair bracket at the site of the work in order to facilitate drilling, rivet installation, anchor establishment on the medium. The installation process is performed according to the following steps:
selection of the repair bracket according to the intended action or actions to be performed; affixation of the repair bracket to the medium by a means in accordance with the accessibility of the work, the requirements of the work, and the characteristics of the medium; engagement of an attachment such as a drill guide, rivet press, anchor, etc., with the affixed repair bracket; performance of the action of repair; and removal of the affixed repair bracket after completion of the repair process.
[0201] The apparatus required to perform the above steps will be better understood with reference to the drawings below as listed in the description of drawings above.
[0202] The description of the universal repair bracket will be discussed in detail with reference to FIGS. 41 through 48 . A right angle repair bracket is provided as in FIG. 41 comprised of platform walls such as wall 274 , attachment receptacles such as receptacle 276 which may or may not be threaded or tapered dependent on the configuration of the intended attachment, exhaust paths such as exhaust path 278 which allow the removal of debris at the surface of the medium at the site of the work, and mounting holes such as mounting hole 280 which allow the bracket to be affixed to the medium by various means. A right angle repair bracket is provided as in FIG. 42 where the configuration of the platform wall 282 , the attachment receptacle 284 , and the mounting hole 286 are further illustrated from a work side view. FIG. 43 provides an additional view of the right angle bracket highlighting the relative scaling of the platform wall 290 and the attachment receptacle 292 .
[0203] A flat repair bracket is provided as in FIG. 44 where a single plane platform wall 298 has attachment receptacles such as attachment receptacle 294 and a centrally located mounting hole 296 . A work side view of the flat repair bracket of FIG. 44 is provided in FIG. 45 showing attachment receptacle 304 equipped with exhaust paths as in FIG. 41 , the centrally located mounting hole 302 , and the platform wall 300 .
[0204] A flat repair bracket is provided as in FIG. 46 mounted to a medium 308 where the attachment receptacle is shown to be tapered unlike those of FIGS. 41 through 45 facilitating engagement with like attachments. A washer 310 is shown engaged with the work end of the attachment receptacle where said washer may be mounted to the medium 308 by means of weld and when fitted with the repair bracket, provides additional load bearing capacity for the entire repair bracket system should additional load bearing capacity be required by the work.
[0205] An adjustable mount repair bracket is provided as in FIG. 47 where said bracket is equipped with an anchor 318 should load be desired to be applied thereto. This repair bracket has movable attachment receptacles such as receptacle 322 tightened into position by bolts such as bolts 314 and 316 and further locked into position by the serrated side 320 of the repair bracket. Said attachment receptacles can additionally be tightened or held in their desired positions by a nut with a handle such as devices 312 and 324 . The movement of said attachment receptacles offers the technician the ability to define the relative distance between mounting points as desired thereby providing greater flexibility in avoiding obstacles, utilizing existing holes, or in drilling new holes.
[0206] An adjustable mount repair bracket is provided as in FIG. 48 where the work side of the bracket is illustrated with attachment receptacles 326 and 328 . The anchor 330 is drawn with dashed lines to indicate its position to be on the opposing side and the serrated surface 332 is shown to be on the work side in order to engage said attachment receptacles 326 and 328 once tightened into position.
[0207] Implementation of an adjustable mount repair bracket is shown as in FIG. 49 where the repair bracket is affixed to medium 334 which has damage requiring correction 336 . The medium 334 pictured here is similar to that of a automobile frame where a rectangular hollow pipe is common. The repair bracket may be mounted as shown utilizing existing holes to mount attachment receptacles such as 338 that may be tightened from the interior of the pipelike frame by wrench 346 . Three such attachment receptacles are shown where the rightmost receptacle is used as a guide for drill bit 340 rotated by power tool 342 in order that further holes may be produced in order to secure the repair bracket to said medium as required by the work. The anchor 344 is shown to be free to bear the force required to correct damage 336 at the appropriate vector as chosen by the operator. The number and functionality of attachment receptacles engaged on such a repair bracket are only limited by the length of the body of said repair bracket.
[0208] A variation on the mounting technique used to affix a right angle repair bracket is provided as in FIG. 50 where locking pliers 354 has adjustability along adjustment shaft 356 with arm 348 forcing right angle bracket 350 against medium 352 . The centrally located hole of the bracket as shown in FIGS. 41, 42 , 44 , and 45 may be used as an interface to force the right angle bracket 350 against the medium with said locking pliers.
[0209] The locking pliers method of affixing the right angle bracket to a medium is provided as before in FIG. 51 where attachments are shown to be engaged with said right angle bracket. A drill guide 358 is engaged with said right angle repair bracket on the plane of the medium facing west whereas an additional attachment 360 is simultaneously engaged with the plane of the medium facing south thereby illustrating the facility of the repair bracket in allowing dual plane simultaneous functionality.
[0210] A repair bracket is provided as in FIG. 52 in order to illustrate the functionality of the repair bracket in allowing the operator to use said bracket in conjunction with a drill guide 368 in order to produce evenly spaced holes, distance between said holes being defined by the relative distances of the attachment receptacles of the repair bracket 366 , through the wall of a medium 364 having a similar configuration as those of FIGS. 50 and 51 . A plug attachment 370 is used to affix the repair bracket 366 to the work face of the medium while a drill guide 368 is engaged with the free attachment receptacle of the bracket and drilling action is performed. Once a hole is produced, the plug attachment 370 may be used to affix the repair bracket 366 to the medium at the site of the newly produced hole thereby again freeing the other attachment receptacle to produce an additional hole with the aid of said drill guide. Additional holes may be produced by repeating this method as desired resulting in evenly spaced holes such as holes 362 .
[0211] A description of a chain equipped bracket will be discussed with reference to FIG. 86 and FIG. 87 . A chain equipped bracket 702 is provided as in FIG. 86 having an extended chain 704 facilitating the application of force. Said bracket 702 may be mounted to medium 700 at location 706 by welding or nut-and-bolt configuration as shown.
[0212] Two chain equipped brackets 710 and 716 having extended chains 712 and 714 , respectively, are provided as in FIG. 87 mounted at locations 708 and 718 on opposing sides of a medium under repair providing the operator additional facility to apply force as may be required by the work and where access to the work area may allow.
[0213] A description of the push jack bracket will be discussed with reference to FIGS. 89 and 90 . Push jack brackets 734 and 730 of male and female configurations, respectively, are provided as in FIG. 89 . A push jack 732 , commonly available to the technician, is shown engaged with said brackets 734 and 730 which are further engaged with medium 736 subtending the region of damage 736 to be repaired. Said configuration allows the application of force, provided by said push jack 732 , along the longitudinal axis of the medium 738 as required in order to correct the region of damage 736 . It is understood that either the male push jack bracket 734 or female push jack bracket 730 may be used to engage the push jack 732 without the aid of the other as required by the work.
[0214] A male push jack bracket is provided as in FIG. 90 . Said push jack bracket is provided with a male element 740 in order to engage the female end of a push jack such as push jack 732 of FIG. 89 . Engagement of & said push jack may be accomplished at any point between positions 746 and 754 through a range of angles 742 greater than ninety degrees. Said push jack bracket is mounted to medium 752 by means of bolt 750 or is welded at points such as 748 or both means may be used to mount said push jack bracket. Said apparatus is provided with a bolt clearance recess 744 in order to allow the free rotation of the push jack through the range of angles 742 as described above without being obstructed by bolt 750 . The range of angles 742 allows force to be applied at various points as required by the work. It is understood that the female push jack bracket is similarly configured with the exception that it has a female element as opposed to the male element 740 as described above.
[0215] In yet another embodiment, a method is provided for the installation of a threaded blind rivet. The process of installation is performed according to the following steps:
measurement of medium wall thickness into which threaded blind rivet is to be installed; selection of the length of threaded blind rivet to be used according to information provided by wall thickness gauge which may be correspondingly coded by colour or otherwise; engagement of the threaded blind rivet with the threaded lower portion of a mandrel which is inserted into the bore of an appropriately sized anvil; and deforming of the shank of the rivet, and thus installation within the medium, with the aid of the composite device consisting of the mandrel, anvil, a custom wrench and rotation force applied thereon.
[0220] The apparatus required to perform the above steps will be better understood with reference to the drawings as listed above.
[0221] The measurement of medium wall thickness will be discussed with reference to FIG. 53 . A wall thickness gauge 374 is provided having a width less than the diameter of the hole intended to house the rivet. Preferably, the length of wall thickness gauge 374 is suitable for fitting into the palm of the hand of the operator and its material is of a minimum thickness and rigidity allowing operation in the intended environment without deformation. Said wall thickness gauge 374 is provided such that is has slots 376 and 380 and the hole 378 provided for attachment to a chain or otherwise for simple portability. Said slots 376 and 380 are of equal dimension perpendicular to the length of wall thickness gauge 374 sufficient to engage the medium wall and provide the operator with a relative reading of thickness and are of differing dimensions parallel to the length of the wall thickness gauge 374 offering depths corresponding to the lower range of medium wall thickness for which the method and apparatus for the installation of threaded blind rivets is to be utilized.
[0222] A wall thickness gauge 382 is provided which is similarly equipped with slots 384 and 388 and the hole 386 through its geometric center as those of wall thickness gauge 374 and is of equal length, width, material and material thickness to said wall thickness gauge 374 . Slots 384 and 388 are provided such that their dimensions perpendicular to the length of wall thickness gauge 382 are equal to those of slots 376 and 380 of wall thickness gauge 374 . Slot 384 is provided such that its dimension parallel to the length of wall thickness gauge 382 is marginally greater than that of slot 376 . Slot 388 is provided such that its dimension parallel to the length of wall thickness gauge 382 represents the upper limit of medium wall thickness for which the method and apparatus for the installation of threaded blind rivets is to be utilized.
[0223] Said wall thickness gauges are employed by insertion of the head into the hole intended for the installation of the rivet into the medium and engaging of the slot with the thickness of said medium. The wall thickness gauge which allows the engagement of the thickness of the medium of one slot and does not allow the engagement of the thickness of the medium with the other slot provides the operator with the range for which a corresponding length of rivet is assigned. The assignment of said rivet lengths is environment dependent and it is understood that any number of gauges with appropriate slot dimensions may be used with assignments to any number of rivet lengths, if resolution of lengths should need to increase, without departing from the scope of the invention.
[0224] The threaded blind rivet and the desired installation outcome of said rivet will be discussed with reference to FIG. 54 . A rivet 390 is provided such that it is of length previously selected, of diameter appropriate to the hole of intended installation, is internally threaded, and is provided with an annular flange 392 . Said rivet 390 may be provided with a coating of commercially available retaining compound to coat the outer surface of said rivet 390 including the under surface of said flange 392 . Said retaining compound is chosen such that its retaining capability is only activated under application of pressure which the rivet 390 will endure during the installation process and will cure under anaerobic conditions provided by the compressed rivet 394 after installation in the medium 398 . The compressed rivet 394 , if coated, will adhere to any surface of the medium 398 to which it is installed with the aid of said retaining compound at any point of contact with said medium 398 between the under surface of the flange of said compressed rivet 394 and the ring 396 formed during the compression and thus distortion of said rivet. Once cured at the site of installation, said retaining compound further prevents movement of said compressed rivet 394 within the allotted hole thus increasing its ability to function under stress beyond that provided by mechanical coupling.
[0225] Further, an anvil assembly is provided in accordance with the present invention and will be discussed with reference to FIGS. 55 to 61 .
[0226] An hollow anvil body 400 is provided as in the cross-section of said anvil body 400 shown in FIG. 55 having an hollow bore through its center consisting of an upper chamber 402 and a lower chamber 404 . Said hollow anvil body 400 is equipped with two rounded slots 406 on opposing sides at equal elevation.
[0227] A mandrel 408 is provided as shown in FIG. 56 such that it has a larger top portion thread 410 suitable to engage a large nut, a smaller lower portion thread 414 suitable to engage a rivet and the hole 412 through its center. Said mandrel 408 is of a length allowing said threads 410 and 414 to be spaced at a distance greater than the length of the lower chamber 404 within the hollow anvil body 400 .
[0228] Assembly of said mandrel and said hollow anvil body is shown in FIG. 57 where the inserted mandrel 418 passes through the anvil body 416 . Said lower thread 414 of said mandrel 418 will emerge through the bottom portion of said hollow anvil body 416 at a length sufficient to fully engage a threaded rivet. Said upper thread 410 of said mandrel 418 will emerge into upper chamber 402 of said hollow anvil body 416 at a length sufficient to engage a nut.
[0229] A nut 422 is provided as in FIG. 58 such that it will engage the upper thread 410 of a mandrel 430 . A washer 424 and a thrust bearing 426 are provided within the upper chamber 402 of an hollow anvil body 420 to create a reactionary force when said nut 422 is caused to be threaded upon said mandrel 430 and to maintain applied forces parallel to the axis of rotation thereby reducing the possibility of friction between said mandrel 430 and said hollow anvil body 420 .
[0230] A pin 428 is provided such that it will pass through the hollow anvil body 420 , at the rounded slots 406 provided for this purpose, and through the body of the mandrel 430 , at the hole 412 provided for this purpose, thus restricting the relative rotation of said hollow anvil body 420 and said mandrel 430 . The pin 428 is additionally restricted to movement along the length axis of the anvil assembly by the rounded slots 406 thereby providing a means of limiting the movement of said mandrel 430 along this axis thus limiting deformation of the compressed rivet 394 . For further clarification, the side view of a pin 444 passing through an hollow anvil body 440 and a mandrel 442 is shown in FIG. 60 and the top view of a pin 448 passing through an anvil and mandrel assembly 446 is shown in FIG. 61 .
[0231] Upon the application of force to a nut 434 , as shown in FIG. 59 , against the upper thread 408 of a mandrel 438 , said mandrel 438 will be drawn upward through the hollow anvil body 432 along the length axis of the rounded slots 406 where the rotation of said mandrel 438 is restricted by means of the inserted pin 436 . A rivet engaged with the lower thread 412 of said mandrel 438 will be forced against the hollow anvil body 432 at its lower end thereby generating the force required to compress said rivet thereby fixing it within the medium as indicated in FIG. 54 .
[0232] An anvil wrench will be discussed with reference to FIGS. 62 to 64 . An anvil wrench 454 , as shown from the top in FIG. 62 , is provided to engage a pin 476 passing through the assembly of FIG. 64 . Once engaged, the anvil wrench 454 is used to control the rotation of said assembly. The anvil wrench 454 provided thus is equipped with a ring 450 of diameter sufficient to pass freely over the hollow anvil body 470 . Two slots 456 are positioned on said ring 450 such that a line joining said slots would be perpendicular to the shaft of the anvil wrench 454 in the same plane and such that said slots 456 will freely engage said pin 476 . The anvil wrench 454 is fitted with a first attachment 452 perpendicular to the plane of the shaft of said anvil wrench 454 .
[0233] A first attachment 460 , as shown in the side view of an anvil wrench in FIG. 63 , is provided such that it can support a second attachment 462 thereto in a plane parallel to that of the anvil wrench 464 . Two slots 468 , positioned on the ring portion 458 of anvil wrench 464 , are shown in the shape desired for engagement with a pin 476 of FIG. 64 and thus rotational manipulation of said assembly of FIG. 64 is afforded.
[0234] The ring portion 472 of an anvil wrench 470 is shown in engagement of a pin 476 in FIG. 64 . The geometry of slots 468 allows rotation along the length axis of said assembly of FIG. 64 to be restricted to that desired by manipulation of the anvil wrench 474 .
[0235] During the installation of a threaded rivet, the anvil wrench 474 is engaged with the assembly of FIG. 64 such that when force is applied to a nut 434 against the upper thread 410 of mandrel 438 , only movement along the length axis of the assembly of FIG. 64 is permitted. One handed operation of the apparatus for the installation of threaded blind rivets is permitted when a powered tool, commonly available to the mechanic, is used to engage the nut 434 such that said powered tool is pressed against said second attachment 462 of anvil wrench 464 and is allowed to rest against said first attachment 460 .
[0236] In another aspect of the present invention, the device provided is to be installed at the site of the work where a rivet has been previously installed in a medium. The implementation of the present invention will be better understood with reference to the drawings as listed in the description of drawings above.
[0237] The description of the rivet reinforcement washer will be discussed with reference to FIGS. 65 to 68 . A rivet reinforcement washer 480 is provided as in FIG. 65 comprised of an raised annular support channel to abut and distribute the load, weld holes 482 , 486 , and 490 to facilitate mounting the washer, a central hole 488 to clear the intended rivet path, and a moisture exhaust path 484 should moisture or debris collect under rivet reinforcement washer 480 .
[0238] A rivet reinforcement washer is shown as in FIG. 66 having a central hole 492 and a raised annular support channel 494 illustrating the geometry of said channel 494 . This geometry is chosen such that the inner ring is to be closely matched as a negative to the attachment providing the greatest surface area of contact and such that the outer ring is wedge shaped to provide the greatest possible support under stress.
[0239] A rivet reinforcement washer is provided as in FIG. 67 where the washer 496 is mounted to a medium 498 and where said washer 496 is positioned such that there is full access to the internally threaded rivet 500 already installed, thereby not interfering with the utility of the internally threaded rivet.
[0240] A rivet reinforcement washer is provided as in FIG. 68 mounted on a medium 502 . The washer 504 is mounted to said medium by means of welds 506 , 508 , and 510 along the outer flange of said washer. Due to the low profile of washer 504 , it may be acceptable to allow it to remain attached after its utility has been exhausted. The washer 504 can be easily removed after use by sanding at said weld points or by various other means familiar to the technician should the washer become an obstruction or present cosmetic incongruity after use.
[0241] Applications of the rivet reinforcement washer will be discussed with reference to FIGS. 69 and 70 . An installed rivet reinforcement washer is shown in FIG. 69 providing load support for a bracket attachment 512 and offering access to the rivet 516 installed in medium 518 . The inner ring of the raised channel of washer 514 is shown fully abutting the lower portion of the bracket attachment thereby providing the greatest possible load support. The washer 514 is shown without the extended outer flange of those washers illustrated in FIGS. 65 to 68 . The embodiment relating to the presence of the outer flange is to be selected according to the requirements of the work where increasing the diameter of the outer flange increases the load bearing facility of the system but may need to be restricted in order to avoid obstructions at the site of the work.
[0242] A second rivet reinforcement washer is shown in FIG. 70 providing load support for attachment 520 illustrating the versatility of said washer in its ability to accommodate various attachments as required by the work. The washer 522 is mounted on a medium 524 at a site where a rivet 523 is previously installed as in FIG. 69 . Attachment 520 is equipped with a bolt to engage rivet 523 after passing through the central hole of washer 522 and medium 524 .
[0243] In another embodiment, a method is provided for drilling into a medium. The drilling process is performed according to the following steps:
selection of the drill bit according to material and size appropriate for the medium to be drilled; selection of drill bracket, either right-angled or flat, dependent on accessibility of work; affixation of the angled bracket or the flat bracket to the medium; engagement of the drill cartridge apparatus with the bracket; application of rotation force thereon, at the appropriate point, to compress internal spring forcing drill bit against medium; application of rotation force thereon, at the appropriate point, to produce intended hole; and drilling, at predefined distances relative to first hole, may be performed using a plug to hold the drill bracket in place and engaging further holes on this drill bracket as above.
[0251] The apparatus required to perform the above steps will be better understood with reference to the drawings as listed in the description of drawings above.
[0252] The description of the drill cartridge apparatus will be discussed in detail with reference to FIGS. 71 to 74 . A drill cartridge apparatus is provided as in FIG. 71 such that it comprises a drive nut 528 to which driving force is to be applied, a drill cartridge housing 530 , a compressed air inlet 536 for cooling, a drill bit 538 engaged with lower threaded portion of drill shaft 540 , a compression spring 542 to force drilling end of apparatus against medium, and an adjustment nut 546 in order to compress said compression spring 542 upon application of appropriate rotation force. Said drill cartridge apparatus of FIG. 71 is further equipped with thrust bearing 532 and bushings 534 and 544 to maintain applied forces parallel to the axis of rotation when such force is applied to drive nut 528 causing the drill shaft 540 and attached drill bit 538 to engage the medium intended to be drilled.
[0253] The drill cartridge housing 548 is provided as in FIG. 72 having a compressed air inlet 550 and a radial mounting flange 552 equipped with mounting hole 554 . The drill cartridge housing is shown in FIG. 73 including the radial mounting flange 556 and mounting hole 558 where an industry standard NPT connector 560 is engaged with said compressed air inlet.
[0254] The drill cartridge apparatus is provided as in FIG. 74 , illustrating its components in greater detail. The drill cartridge apparatus comprises the drive nut 562 , an upper bushing 564 , an adjustment nut 566 equipped with threads to engage the threads of the drill cartridge housing 580 .
[0255] A compression spring 568 is provided producing the required downward force on the drill shaft 574 once support collar 572 and thrust bearing 570 are made to pass over said shaft to the point fixed by the spring pin 576 and adjustment nut 566 is engaged with drill cartridge housing 580 . The drill shaft 574 is separately threaded in its upper and lower regions to engage drive nut 562 and drill bit 584 respectively. The engagement of the drill shaft 574 by the drive nut 562 allows the independent rotation of the drill shaft 574 and hence said drill bit 584 within the housing as a downward force is maintained on said shaft by means of the compressed spring 568 . A lower bushing 578 is provided to maintain applied forces parallel to the axis of rotation as in the cases of the upper bushing 564 and the thrust bearing 570 . Drill bit 584 is to be selected as to the requirements of the work.
[0256] The drill cartridge housing 580 is provided with a compressed air inlet 582 which allows attachment of an industry standard NPT connector and associated devices thereby delivering, through provided channel, air cooling at the site of drilling should such cooling be required.
[0257] Implementation of the drill cartridge apparatus will be discussed with reference to FIGS. 75 and 76 . A drill cartridge apparatus is engaged with an appropriate bracket as in FIG. 75 where a plug 594 is used to set the position of a drill bracket 596 with the aid of an existing hole, in the medium 592 , where possible for the purpose of drilling at relative distance as defined by the configuration of said bracket. The drill cartridge apparatus 586 is engaged with said bracket by means of nut 590 and compressed air inlet 588 remains accessible to provide cooling, if necessary at the site of the work.
[0258] The implementation of FIG. 75 is further illustrated in the top view of FIG. 76 . The drill cartridge apparatus 598 is engaged with the drill bracket by means of nut 600 passing through a hole in the drill bracket similar to that provided at hole 602 . The drilling position is again set by means of plug 604 securing the drill bracket against the face of the medium.
[0259] In another embodiment, a method is provided for the implementation of the drill guide at the site of the work in order to facilitate drilling into the medium. The implementation process is performed according to the following steps:
choice of a drill guide with either raised or countersunk magnets, magnetic engagement of the drill guide with the surface of the medium at the site of the work, accurate adjustment of drill guide to suit the required location of the work, engagement of the drill guide with drill bit and accompanying apparatuses required to perform the drilling, performance of the action of drilling while supplying air through intake provided to reduce heat and to remove exhaust at the site of the work, and removal of the magnetic drill guide after completion of the drilling.
[0266] The apparatus required to perform the above steps will be better understood with reference to the drawings below as listed in the description of drawings above.
[0267] The description of the magnetic drill guide will be discussed in detail with reference to FIGS. 77 through 83 . A magnetic drill guide is provided as in FIG. 77 comprised of drill shaft opening 610 to allow the drill bit to pass through the body of the guide to engage the medium, a guide platform 612 elevated from the surface of the medium in order to clear obstructions to the work and to allow an exhaust path for the fragments produced by the action of drilling. Magnetic standoffs such as 614 and 616 elevate said platform 612 and affix the apparatus to a ferrous medium with force sufficient to maintain its position under the stress of the work. Guide housing 618 maintains the structure of the guide at the intended angle relative to the plane of the work face of the medium.
[0268] A magnetic drill guide is provided as in FIG. 78 shown from the work side in order to illustrate the configuration of magnetic standoffs 622 , 624 , 626 , and 628 as they are attached to the underside of the guide platform 620 which is equipped with drill shaft opening 630 . Said configuration allows the apparatus to clear surface obstructions, maintains a symmetrical radial distribution, from said drill shaft opening 630 , of said magnetic standoffs 622 , 624 , 626 , and 628 such that the apparatus remains mechanically balanced at the site of the work, and provides sufficient paths for the exhaust of the work.
[0269] A magnetic drill guide with affixed compressed air receptacle and intake path is provided as in FIG. 79 comprised of drill shaft opening 632 , guide platform 634 , magnetic standoffs such as 636 , intake path 638 to provide cooling at the site of the work as well as forcing drill exhaust away from the site of the work, and conventional compressed air receptacle 642 configured to be attached to compressed air facilities commonly available to the technician.
[0270] A magnetic drill guide is provided as in FIG. 80 shown from the work side as in FIG. 78 with the addition of conventional compressed air receptacle 648 and further comprised of guide platform 644 , magnetic standoffs such as 646 , and drill shaft opening 650 as before.
[0271] A magnetic drill guide equipped with a compressed air receptacle and engaged with a center line positioning apparatus is provided as in FIG. 81 shown from the work side. Said magnetic drill guide 658 is accurately positioned at the site of the work with the aid of the positioning apparatus 652 . Said positioning apparatus 652 may be mounted on the medium by means of mounting holes such as 654 utilizing existing holes where the aperture of 656 may be used to establish the center line of intended drilling. Due to the “V” configuration of the working end of the positioning apparatus 652 , it may be used to engage said magnetic drill guide 658 at any of the four corners of the guide platform 644 as described in FIG. 80 . Such positioning allows the operator to drill along a center line which is established and passes through mounting hole 654 and aperture 656 .
[0272] A magnetic drill guide with countersunk magnets and mounting eyelets is provided as in FIG. 82 comprised of drill shaft opening 660 to allow the drill bit to pass through the body of the guide to engage the medium, a guide platform 662 designed to abut the medium on the work side, magnets embedded within said platform, eyelets for mounting with screws such as 664 and 668 , exhaust path 666 , and conventional compressed air receptacle 670 . Said screws may be self tapping and mounting by said means allows reinforcement of magnetic mounting or may be used as the sole mounting means on a non-ferrous medium. Guide housing 672 maintains the structure of the guide at the intended angle relative to the plane of the work face of the medium.
[0273] A magnetic drill guide is provided as in FIG. 83 shown from the work side and illustrating mounting eyelets 678 and 682 . Magnets such as 676 are countersunk to allow the entire platform to abut the work face. An exhaust path 674 is provided with arrows indicating the intended direction of air flow. The guide is equipped with conventional compressed air receptacle 680 as before. It is understood that the relative sizes of the magnetic standoffs, countersunk magnets, the number of magnets, the number and distribution of mounting eyelets, the angle of the guide housing relative to the plane of the face of the work, and the relative size of the drill shaft opening are shown thus in FIGS. 77 through 83 in order to simply communicate the functionality of an embodiment of the present invention and any alteration of said parameters does not depart from the scope of this embodiment of the present invention. | A process is provided to facilitate the repair of damage, such as that sustained by the body or frame of a vehicle during collision. The present invention provides a standardized process for vehicle body repair and offers the technician a standardized and practical toolkit to be implemented into said process. The present invention allows the technician to reduce the costs both in time and equipment required to perform the repair. Further, the possibility of secondary damage arising from inappropriate application of methodologies and tools is significantly reduced with the implementation of the present invention. | 1 |
RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application Ser. No. 61/558,775, filed Nov. 11, 2011, the disclosure of which is hereby incorporated in its entirety herein by reference
FIELD OF THE INVENTION
[0002] The present invention relates to novel 4-pregenen-11β-17-21-triol-3,20-dione derivatives, processes for preparing them, pharmaceutical compositions containing them and their use as pharmaceuticals, as modulators of glucocorticoid or mineralocorticoid receptors. The invention relates specifically to the use of these compounds and their pharmaceutical compositions to treat disorders associated with glucocorticoid or mineralocorticoid receptor modulation.
BACKGROUND OF THE INVENTION
[0003] Glucocorticoid (GC) agonists represent a class of anti-inflammatory compounds that are useful in treating multiple ocular conditions including elevated intraocular pressure, glaucoma, uveitis, retinal vein occlusions, macular degeneration, diabetic retinopathy, various forms of macular edema, post-surgical inflammation, inflammatory conditions of the palpebral and bulbar conjunctiva, cornea, and anterior segment of the globe, such as allergic conjunctivitis, ocular rosacea, dry eye, blepharitis, retinal detachment, meibomian gland dysfunction (MGD), superficial punctate keratitis, herpes zoster keratitis, iritis, cyclitis, selected infective conjunctivitis, corneal injury from chemical, radiation, or thermal burns, penetration of foreign bodies, allergy, or combinations thereof.
[0004] A potential use limiting and sight-threatening side-effect of traditional GC agonist therapies (e.g. fluocinolone acetonide) is ocular hypertension that is likely generated by an increased resistance of aqueous humor flow through the trabecular meshwork. The mechanism of GC agonist-induced outflow resistance and subsequent ocular hypertension is not well understood.
[0005] As such, GC modulation through agonist or antagonist activity of GC receptors that does not result in increased intraocular pressure or other side effects is needed in the art and is described herein.
SUMMARY OF THE INVENTION
[0006] The present invention relates to novel 4-pregenen-11β-17-21-triol-3,20-dione derivatives useful in treating one or more ocular conditions. Methods of treating one or more ocular conditions are also disclosed. Ocular conditions treated using compounds and/or formulations described herein include, but are not limited to, elevated intraocular pressure, glaucoma, uveitis, retinal vein occlusions, macular degeneration, diabetic retinopathy, various forms of macular edema, post-surgical inflammation, inflammatory conditions of the palpebral and bulbar conjunctiva, cornea, and anterior segment of the globe, such as allergic conjunctivitis, ocular rosacea, dry eye, blepharitis, retinal detachment, meibomian gland dysfunction (MGD), superficial punctate keratitis, herpes zoster keratitis, iritis, cyclitis, selected infective conjunctivitis, corneal injury from chemical, radiation, or thermal burns, penetration of foreign bodies, allergy, or combinations thereof.
[0007] In one aspect, the invention therefore provides a compound of Formula I, its enantiomers, diastereoisomers, hydrates, solvates, crystal forms and individual isomers, tautomers or a pharmaceutically acceptable salt thereof,
[0000]
[0000] wherein:
R 1 is optionally substituted C 7 -C 11 alkyl, optionally substituted C 2 -C 8 alkenyl, optionally substituted C 2 -C 8 alkynyl optionally substituted C 4 or C 6-8 cycloalkyl, optionally substituted aryl, substituted benzyl, optionally substituted heterocycle, optionally substituted C 3 -C 10 cycloalkenyl, optionally substituted C 5 -C 10 cyclodiene, optionally substituted O(C 3 -C 6 ) alkyl, amino groups, sulfonamide groups, amide groups, except phenyl.
[0008] In another embodiment, the invention therefore provides a compound of Formula I, wherein R 1 is selected from:
[0000]
[0009] The term “alkyl”, as used herein, refers to saturated, monovalent or divalent hydrocarbon moieties having linear or branched moieties or combinations thereof and containing 7 to 11 carbon atoms. One methylene (—CH 2 —) group, of the alkyl group can be replaced by oxygen, sulfur, sulfoxide, nitrogen, carbonyl, carboxyl, sulfonyl, sulfate, sulfonate, amide, sulfonamide, by a divalent C 3-8 cycloalkyl, by a divalent heterocycle, or by a divalent aryl group. Alkyl groups can be independently substituted by halogen atoms, hydroxyl groups, cycloalkyl groups, amino groups, heterocyclic groups, aryl groups, carboxylic acid groups, ester groups, ketone groups, phosphonic acid groups, sulphonic acid groups, phosphoric acid groups, nitro groups, amide groups, sulfonamide groups.
[0010] The term “cycloalkyl”, as used herein, refers to a monovalent or divalent group of 4, and 6 to 8 carbon atoms derived from a saturated cyclic hydrocarbon. Cycloalkyl groups can be monocyclic or polycyclic. Cycloalkyl can be independently substituted by halogen atoms, sulfonyl C 1-8 alkyl groups, sulfoxide C 1-8 alkyl groups, sulfonamide groups, nitro groups, cyano groups, —OC 1-8 alkyl groups, —SC 1-8 alkyl groups, —C 1-8 alkyl groups, —C 2-6 alkenyl groups, —C 2-6 alkynyl groups, ketone groups, alkylamino groups, amino groups, aryl groups, C 3-8 cycloalkyl groups or hydroxyl groups.
[0011] The term “cycloalkenyl”, as used herein, refers to a monovalent or divalent group of 3 to 10 carbon atoms derived from a saturated cycloalkyl having at least one double bond. Cycloalkenyl groups can be monocyclic or polycyclic. Cycloalkenyl groups can be independently substituted by halogen atoms, sulfonyl groups, sulfoxide groups, nitro groups, cyano groups, —OC 1-6 alkyl groups, —SC 1-6 alkyl groups, —C 1-6 alkyl groups, —C 2-6 alkenyl groups, —C 2-6 alkynyl groups, ketone groups, alkylamino groups, amino groups, aryl groups, C 3-8 cycloalkyl groups or hydroxyl groups.
[0012] The term “cyclodiene”, as used herein, refers to a monovalent or divalent group of 5 to 10 carbon atoms derived from a saturated cycloalkyl having two double bonds. Cyclodiene groups can be monocyclic or polycyclic. Cyclodiene groups can be independently substituted by halogen atoms, sulfonyl groups, sulfoxide groups, nitro groups, cyano groups, —OC 1-6 alkyl groups, —SC 1-6 alkyl groups, —C 1-6 alkyl groups, —C 2-6 alkenyl groups, —C 2-6 alkynyl groups, ketone groups, alkylamino groups, amino groups, aryl groups, C 3-8 cycloalkyl groups or hydroxyl groups.
[0013] The term “halogen”, as used herein, refers to an atom of chlorine, bromine, fluorine, iodine.
[0014] The term “alkenyl”, as used herein, refers to a monovalent or divalent hydrocarbon radical having 2 to 8 carbon atoms, derived from a saturated alkyl, having at least one double bond. One methylene (—CH 2 —) group, of the alkenyl can be replaced by oxygen, sulfur, sulfoxide, nitrogen, carbonyl, carboxyl, sulfonyl, sulfate, sulfonate, amide, sulfonamide, by a divalent C 3-8 cycloalkyl, by a divalent heterocycle, or by a divalent aryl group. C 2-8 alkenyl can be in the E or Z configuration. Alkenyl groups can be substituted by alkyl groups, as defined above or by halogen atoms.
[0015] The term “alkynyl”, as used herein, refers to a monovalent or divalent hydrocarbon radical having 2 to 8 carbon atoms, derived from a saturated alkyl, having at least one triple bond. One methylene (—CH 2 —) group, of the alkynyl can be replaced by oxygen, sulfur, sulfoxide, nitrogen, carbonyl, carboxyl, sulfonyl, sulfate, sulfonate, amide, sulfonamide, by a divalent C 3-8 cycloalkyl, by a divalent heterocycle, or by a divalent aryl group. Alkynyl groups can be substituted by alkyl groups, as defined above, or by halogen atoms.
[0016] The term “heterocycle” as used herein, refers to a 3 to 10 member ring, which can be aromatic or non-aromatic, saturated or unsaturated, containing at least one heteroatom selected form oxygen, nitrogen, sulfur, or combinations of at least two thereof, interrupting the carbocyclic ring structure. The heterocyclic ring can be interrupted by a C═O; the S and N heteroatoms can be oxidized. Heterocycles can be monocyclic or polycyclic. Heterocyclic ring moieties can be substituted by halogen atoms, sulfonyl groups, sulfoxide groups, nitro groups, cyano groups, —OC 1-6 alkyl groups, —SC 1-6 alkyl groups, —C 1-8 alkyl groups, —C 2-6 alkenyl groups, —C 2-6 alkynyl groups, ketone groups, alkylamino groups, amino groups, aryl groups, C 3-8 cycloalkyl groups or hydroxyl groups.
[0017] The term “aryl” as used herein, refers to an organic moiety derived from an aromatic hydrocarbon consisting of a ring containing 6 to 10 carbon atoms, by removal of one hydrogen atom. Aryl can be substituted by halogen atoms, sulfonyl C 1-6 alkyl groups, sulfoxide C 1-6 alkyl groups, sulfonamide groups, carboxcyclic acid groups, C 1-6 alkyl carboxylates (ester) groups, amide groups, nitro groups, cyano groups, —OC 1-6 alkyl groups, —SC 1-6 alkyl groups, —C 1-6 alkyl groups, —C 2-6 alkenyl groups, —C 2-6 alkynyl groups, ketone groups, aldehydes, alkylamino groups, amino groups, aryl groups, C 3-8 cycloalkyl groups or hydroxyl groups. Aryls can be monocyclic or polycyclic.
[0018] The term “hydroxyl” as used herein, represents a group of formula “—OH”.
[0019] The term “carbonyl” as used herein, represents a group of formula “—C(O)—”.
[0020] The term “ketone” as used herein, represents an organic compound having a carbonyl group linked to a carbon atom such as —(CO)R x wherein R x can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
[0021] The term “amine” as used herein, represents a group of formula “—NR x R y ”, wherein R x and R y can be the same or independently hydrogen, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
[0022] The term “carboxyl” as used herein, represents a group of formula “—C(O)O—”.
[0023] The term “sulfonyl” as used herein, represents a group of formula “—SO 2 —”.
[0024] The term “sulfate” as used herein, represents a group of formula “—O—S(O) 2 —O—”.
[0025] The term “sulfonate” as used herein, represents a group of the formula “—S(O) 2 —O—”.
[0026] The term “carboxylic acid” as used herein, represents a group of formula “—C(O)OH”.
[0027] The term “nitro” as used herein, represents a group of formula “—NO 2 ”.
[0028] The term “cyano” as used herein, represents a group of formula “—CN”.
[0029] The term “amide” as used herein, represents a group of formula “—C(O)NR x R y ,” wherein R x and R y can be the same or independently hydrogen, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
[0030] The term “ester” as used herein, represents a group of formula “—C(O)OR x ,” wherein R x is alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
[0031] The term “sulfonamide” as used herein, represents a group of formula “—S(O) 2 NR x R y ” wherein R x and R y can be the same or independently hydrogen, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
[0032] The term “sulfoxide” as used herein, represents a group of formula “—S(O)—”.
[0033] The term “phosphonic acid” as used herein, represents a group of formula “—P(O)(OH) 2 ”.
[0034] The term “phosphoric acid” as used herein, represents a group of formula “—OP(O)(OH) 2 ”.
[0035] The term “sulphonic acid” as used herein, represents a group of formula “—S(O) 2 OH”.
The formula “H”, as used herein, represents a hydrogen atom. The formula “O”, as used herein, represents an oxygen atom. The formula “N”, as used herein, represents a nitrogen atom. The formula “S”, as used herein, represents a sulfur atom.
[0040] Compounds of the invention are:
(8S,9S,10R,11S,13S,14S,17R)-17-glycoloyl-11-hydroxy-10,13-dimethyl-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl (4-bromophenyl)acetate; (8S,9S,10R,11S,13S,14S,17R)-17-glycoloyl-11-hydroxy-10,13-dimethyl-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl 3-(phenylsulfonyl)propanoate; (8S,9S,10R,11S,13S,14S,17R)-17-glycoloyl-11-hydroxy-10,13-dimethyl-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl 2-furoate.
[0044] Some compounds of Formula I and some of their intermediates have at least one stereogenic center in their structure. This stereogenic center may be present in an R or S configuration, said R and S notation is used in correspondence with the rules described in Pure Appli. Chem. (1976), 45, 11-13.
[0045] The term “pharmaceutically acceptable salts” refers to salts or complexes that retain the desired biological activity of the above identified compounds and exhibit minimal or no undesired toxicological effects. The “pharmaceutically acceptable salts” according to the invention include therapeutically active, non-toxic base or acid salt forms, which the compounds of Formula I are able to form.
[0046] The acid addition salt form of a compound of Formula I that occurs in its free form as a base can be obtained by treating the free base with an appropriate acid such as an inorganic acid, such as for example, hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid and the like; or an organic acid such as for example, acetic, hydroxyacetic, propanoic, lactic, pyruvic, malonic, fumaric acid, maleic acid, oxalic acid, tartaric acid, succinic acid, malic acid, ascorbic acid, benzoic acid, tannic acid, pamoic acid, citric, methylsulfonic, ethanesulfonic, benzenesulfonic, formic and the like (Handbook of Pharmaceutical Salts, P. Heinrich Stahal & Camille G. Wermuth (Eds), Verlag Helvetica Chemica Acta-Zürich, 2002, 329-345).
[0047] The base addition salt form of a compound of Formula I that occurs in its acid form can be obtained by treating the acid with an appropriate base such as an inorganic base, for example, sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, ammonia and the like; or an organic base such as for example, L-Arginine, ethanolamine, betaine, benzathine, morpholine and the like. (Handbook of Pharmaceutical Salts, P. Heinrich Stahal & Camille G. Wermuth (Eds), Verlag Helvetica Chemica Acta-Zürich, 2002, 329-345).
[0048] Compounds of Formula I and their salts can be in the form of a solvate, which is included within the scope of the present invention. Such solvates include for example hydrates, alcoholates and the like.
[0049] With respect to the present invention reference to a compound or compounds, is intended to encompass that compound in each of its possible isomeric forms and mixtures thereof unless the particular isomeric form is referred to specifically. Compounds according to the present invention may exist in different polymorphic forms. Although not explicitly indicated in the above formula, such forms are intended to be included within the scope of the present invention.
[0050] The compounds described herein are useful in treating a variety of ocular conditions including, but not limited to elevated intraocular pressure, glaucoma, uveitis, retinal vein occlusions, macular degeneration, diabetic retinopathy, various forms of macular edema, post-surgical inflammation, inflammatory conditions of the palpebral and bulbar conjunctiva, cornea, and anterior segment of the globe, such as allergic conjunctivitis, ocular rosacea, dry eye, blepharitis, retinal detachment, meibomian gland dysfunction (MGD), superficial punctate keratitis, herpes zoster keratitis, iritis, cyclitis, selected infective conjunctivitis, corneal injury from chemical, radiation, or thermal burns, penetration of foreign bodies, allergy, or combinations thereof.
[0051] In still another embodiment of the invention, there are provided methods for treating disorders associated with modulation of the glucocorticoid receptors (GR) and/or the mineralocorticoid receptors (MR). receptors. Such methods can be performed, for example, by administering to a subject in need thereof a therapeutically effective amount of at least one compound of the invention, or any combination thereof, or pharmaceutically acceptable salts, hydrates, solvates, crystal forms and individual isomers, enantiomers, and diastereomers thereof.
[0052] In another embodiment, there are provided pharmaceutical compositions including at least one compound of the invention in a pharmaceutically acceptable carrier.
[0053] The compounds described herein may be administered at pharmaceutically effective dosages. Such dosages are normally the minimum dose necessary to achieve the desired therapeutic effect. Generally, such doses will be in the range of about 1 mg/day to about 1000 mg/day; more preferably in the range of about 10 mg/day to about 500 mg/day. In another example embodiment, the compound or compounds may be present in a composition or formulation in a range of about 0.5 mg/kg/day to about 100 mg/kg/day or about 1 mg/kg/day to about 100 mg/kg/day. However, the actual amount of the compound to be administered in any given case will be determined by a physician taking into account the relevant circumstances, such as the age and weight of the patient, the patient's general physical condition, the severity of ocular condition, and the route of administration. In some instances, dosing is evaluated on a case-by-case basis.
[0054] In another example embodiment, provided are pharmaceutical compositions including at least one compound in a pharmaceutically acceptable carrier. Pharmaceutical compositions can be used in the form of a solid, a solution, an emulsion, a dispersion, a micelle, a liposome, and the like, wherein the resulting composition contains one or more compounds described herein, as an active ingredient, in admixture with an organic or inorganic carrier or excipient suitable for enteral or parenteral applications. One or more compounds may be combined, for example, with the usual non-toxic, pharmaceutically acceptable carriers for tablets, pellets, capsules, suppositories, solutions, emulsions, suspensions, and any other form suitable for use. The carriers which can be used include glucose, lactose, gum acacia, gelatin, mannitol, starch paste, magnesium trisilicate, talc, corn starch, keratin, colloidal silica, potato starch, urea, medium chain length triglycerides, dextrans, and other carriers suitable for use in manufacturing preparations, in solid, semisolid, or liquid form. In addition auxiliary, stabilizing, thickening and coloring agents and perfumes may be used. Compounds described herein are included in pharmaceutical compositions in an amount sufficient to produce the desired effect upon the process or disease condition.
[0055] In another embodiment, the compounds described herein can be administered orally in any acceptable form, such as a tablet, liquid, capsule, powder and the like. However, other routes may be desirable or necessary, particularly if the patient suffers from nausea. Such other routes may include, without exception, transdermal, parenteral, subcutaneous, intranasal, intrathecal, intramuscular, intravenous, and intrarectal modes of delivery. Additionally, formulations may be designed to delay release of the active compound over a given period of time, or to carefully control the amount of drug released at a given time during the course of therapy.
[0056] Pharmaceutical compositions in a form suitable for oral use, for example, are administered as tablets, troches, lozenges, aqueous or oily suspensions, dispersible powders or granules, emulsions, hard or soft capsules, or syrups or elixirs. Compositions intended for oral use may be prepared according to any method known to the art for the manufacture of pharmaceutical compositions and such compositions may contain one or more agents selected from the group consisting of a sweetening agent such as sucrose, lactose, or saccharin, flavoring agents such as peppermint, oil of wintergreen or cherry, coloring agents and preserving agents in order to provide pharmaceutically elegant and palatable preparations. Tablets containing compounds described herein in admixture with non-toxic pharmaceutically acceptable excipients may also be manufactured by known methods.
[0057] The pharmaceutical compositions may be in the form of a sterile injectable suspension. This suspension may be formulated according to known methods using suitable dispersing or wetting agents and suspending agents. The sterile injectable preparation may also be a sterile injectable solution or suspension in a non-toxic parenterally-acceptable diluent or solvent, for example, as a solution in 1,3-butanediol. Sterile, fixed oils are conventionally employed as a solvent or suspending medium. For this purpose any bland fixed oil may be employed including synthetic mono- or diglycerides, fatty acids (including oleic acid), naturally occurring vegetable oils like sesame oil, coconut oil, peanut oil, cottonseed oil, etc., or synthetic fatty vehicles like ethyl oleate or the like. Buffers, preservatives, antioxidants, and the like can be incorporated as required.
[0058] Invention compounds may also be administered in the form of suppositories for rectal administration of the drug. These compositions may be prepared by mixing the invention compounds with a suitable non-irritating excipient, such as cocoa butter, synthetic glyceride esters of polyethylene glycols, which are solid at ordinary temperatures, but liquefy and/or dissolve in the rectal cavity to release the drug.
[0059] The actual amount of the compound to be administered in any given case will be determined by a physician taking into account the relevant circumstances, such as the severity of the condition, the age and weight of the patient, the patient's general physical condition, the cause of the condition, and the route of administration. Described herein are compounds capable of modulating glucocorticoid receptors (GR) and/or mineralocorticoid receptors (MR). The compounds described can have greater GR activation and/or binding potency compared to a compound such as cortisol. As such, the compounds can efficiently treat ocular indications. The compounds can further be metabolized by esterase enzymes within the eye to form the natural agonist cortisol, thereby reducing the risk of ocular hypertension. The cortisol remaining within the eye and body is further metabolized to inactive compounds via naturally occurring dehydroxylases and other enzymes making this a safe therapeutic approach.
[0060] In patients, the naturally occurring endogenous GC agonist cortisol (hydrocortisone) has a minimal effect on intraocular pressure when applied locally via eye drops compared to synthetic GCs such as dexamethasone, prednisolone, and fluorometholone (Cantrill et al., 1975). Further support of the overall superior safety of cortisol as a therapeutic is the fact that various topical hydrocortisone formulations are currently sold over the counter directly to consumers.
[0061] Without wishing the bound to any particular theory, it was surprisingly discovered that the presently described compounds can have more glucocorticoid receptor modulation than cortisol because of the modification to the 17-position of the cortisol molecule.
[0062] As used herein, the term “therapeutically effective amount” means the amount of the pharmaceutical composition that will elicit the biological or medical response of a subject in need thereof that is being sought by the researcher, veterinarian, medical doctor or other clinician. In some embodiments, the subject in need thereof is a mammal. In some embodiments, the mammal is human.
[0063] The excipients used may be, for example, (1) inert diluents such as calcium carbonate, lactose, calcium phosphate or sodium phosphate; (2) granulating and disintegrating agents such as corn starch, potato starch or alginic acid; (3) binding agents such as gum tragacanth, corn starch, gelatin or acacia, and (4) lubricating agents such as magnesium stearate, stearic acid or talc. The tablets may be uncoated or they may be coated by known techniques to delay disintegration and absorption in the gastrointestinal tract and thereby provide a sustained action over a longer period. For example, a time delay material such as glyceryl monostearate or glyceryl distearate may be employed.
[0064] In some cases, formulations for oral use may be in the form of hard gelatin capsules wherein the compounds are mixed with an inert solid diluent, for example, calcium carbonate, calcium phosphate or kaolin. They may also be in the form of soft gelatin capsules wherein the compounds are mixed with water or an oil medium, for example, peanut oil, liquid paraffin, or olive oil.
[0065] The compounds described herein can also be administered as an ophthalmically acceptable formulation or composition. A liquid which is ophthalmically acceptable is formulated such that it can be administered topically to the eye. The comfort should be maximized as much as possible, although sometimes formulation considerations (e.g. stability) may necessitate less than optimal comfort. In the case that comfort cannot be maximized, the liquid should be formulated such that the liquid is tolerable to the patient for topical ophthalmic use. Additionally, an ophthalmically acceptable liquid should either be packaged for single use, or contain a preservative to prevent contamination over multiple uses.
[0066] For ophthalmic application, solutions or medicaments are often prepared using a physiological saline solution as a major vehicle. Ophthalmic solutions should preferably be maintained at a comfortable pH with an appropriate buffer system. The formulations may also contain conventional, pharmaceutically acceptable preservatives, stabilizers and surfactants.
[0067] Preservatives that may be used in ophthalmic compositions described herein include, but are not limited to, benzalkonium chloride, chlorobutanol, thimerosal, phenylmercuric acetate and phenylmercuric nitrate. A useful surfactant is, for example, Tween 80. Likewise, various useful vehicles may be used in the ophthalmic preparations described herein. These vehicles include, but are not limited to, polyvinyl alcohol, povidone, hydroxypropyl methyl cellulose, poloxamers, carboxymethyl cellulose, hydroxyethyl cellulose and purified water.
[0068] Tonicity adjustors may be added as needed or convenient. They include, but are not limited to, salts, particularly sodium chloride, potassium chloride, mannitol and glycerin, or any other suitable ophthalmically acceptable tonicity adjustor.
[0069] Various buffers and means for adjusting pH may be used so long as the resulting preparation is ophthalmically acceptable. Accordingly, buffers include acetate buffers, citrate buffers, phosphate buffers and borate buffers. Acids or bases may be used to adjust the pH of these formulations as needed.
[0070] In one example embodiment, an ophthalmic composition as described herein may have ingredients used in the following amounts listed in Table 1.
[0000]
TABLE 1
Ingredient
Amount (% w/v)
active ingredient
about 0.001-5
preservative
0-0.10
vehicle
0-40
tonicity adjustor
1-10
buffer
0.01-10
pH adjustor
q.s. pH 4.5-7.5
antioxidant
as needed
surfactant
as needed
purified water
as needed to make 100%
[0071] In other embodiments, the ophthalmically acceptable liquid can be formulated for intraocular injection. The compounds described herein can be formulated as a liquid, gel paste, or the like for intraocular injection. Further, the compounds can be formulated into sustained release or controlled release intraocular implants comprising biodegradable polymers such as polylactic acid, poly glycolic acid, combinations thereof and the like.
[0072] Some exemplary compositions can include a combination of two or more compounds as described herein. Different ratios of compounds can be formulated depending on a particular ocular condition or set of conditions being treated.
[0073] Since individual subjects may present a wide variation in severity of symptoms and each composition has its unique therapeutic characteristics, the precise mode of administration and dosage employed for each subject is left to the discretion of the practitioner.
[0074] The present invention concerns also processes for preparing the compounds of Formula I. The compounds of Formula I according to the invention can be prepared analogously to conventional methods as understood by the person skilled in the art of synthetic organic chemistry. The synthetic scheme set forth below, illustrate how compounds according to the invention can be made.
[0000]
R′ is C 1 -C 4 alkyl, or the like, preferably CH 3
DETAILED DESCRIPTION
[0076] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention claimed. As used herein, the use of the singular includes the plural unless specifically stated otherwise.
[0077] It will be readily apparent to those skilled in the art that some of the compounds of the invention may contain one or more asymmetric centers, such that the compounds may exist in enantiomeric as well as in diastereomeric forms. Unless it is specifically noted otherwise, the scope of the present invention includes all enantiomers, diastereomers and racemic mixtures. Some of the compounds of the invention may form salts with pharmaceutically acceptable acids or bases, and such pharmaceutically acceptable salts of the compounds described herein are also within the scope of the invention.
[0078] The present invention includes all pharmaceutically acceptable isotopically enriched compounds. Any compound of the invention may contain one or more isotopic atoms enriched or different than the natural ratio such as deuterium 2 H (or D) in place of protium 1 H (or H) or use of 13 C enriched material in place of 12 C and the like. Similar substitutions can be employed for N, O and S. The use of isotopes may assist in analytical as well as therapeutic aspects of the invention. For example, use of deuterium may increase the in vivo half-life by altering the metabolism (rate) of the compounds of the invention. These compounds can be prepared in accord with the preparations described by use of isotopically enriched reagents.
[0079] The following examples are for illustrative purposes only and are not intended, nor should they be construed as limiting the invention in any manner. Those skilled in the art will appreciate that variations and modifications of the following examples can be made without exceeding the spirit or scope of the invention.
[0080] As will be evident to those skilled in the art, individual isomeric forms can be obtained by separation of mixtures thereof in conventional manner. For example, in the case of diasteroisomeric isomers, chromatographic separation may be employed.
[0081] Compound names were generated with ACD version 12.0; and Intermediates and reagent names used in the examples were generated with software such as Chem Bio Draw Ultra version 12.0 or Auto Nom 2000 from MDL ISIS Draw 2.5 SP1.
[0082] In general, characterization of the compounds is performed according to the following methods:
[0083] NMR spectra are recorded on 300 and/or 600 MHz Varian and acquired at room temperature. Chemical shifts are given in ppm referenced either to internal TMS or to the solvent signal.
[0084] All the reagents, solvents, catalysts for which the synthesis is not described are purchased from chemical vendors such as Sigma Aldrich, Fluka, Bio-Blocks, Combi-blocks, TCI, VWR, Lancaster, Oakwood, Trans World Chemical, Alfa, Fisher, AK Scientific, AmFine Com, Carbocore, Maybridge, Frontier, Matrix, Ukrorgsynth, Toronto, Ryan Scientific, SiliCycle, Anaspec, Syn Chem, Chem-Impex, MIC-scientific, Ltd; however some known intermediates, were prepared according to published procedures.
[0085] Usually the compounds of the invention were purified by column chromatography (Auto-column) on an Teledyne-ISCO CombiFlash with a silica column, unless noted otherwise.
Example 1
Intermediate 1
2-(Trimethoxymethyl)furan
[0086]
[0087] An anhydrous solution of HCl in methanol was prepared by slowly adding acetyl chloride (10.5 mL) to methanol (20 mL) at room temperature. The solution was stirred 2 h. After cooling in an ice bath under nitrogen, 2-furonitrile (12 mL, 137 mM) was added by syringe. The reaction was stirred in a dry atmosphere at 0° C. overnight. After warming to room temperature the intermediate was precipitated by the addition of dry ether (50 mL). It was filtered out in a dry scintered glass funnel in a dry box and washed with dry ether. After ether evaporation the solid was treated with dry methanol and stirred at 50° C. for 70 h. The mixture was treated with dry ether (60 mL) and ammonium chloride was removed by filtration through a dry scintered glass funnel. Concentration of the filtrate gave the title compound (6 g) as a colorless oil.
Example 2
Intermediate 2
rel-(8R,9R,10S,11R,13R,14R,17S)-2′-(2-furyl)-11-hydroxy-2′-methoxy-10,13-dimethyl-1,6,7,8,9,10,11,12,13,14,15,16-dodecahydro-5′H-spiro[cyclopenta[a]phenanthrene-17,4′-[1,3]dioxane]-3,5′(2H)-dione
[0088]
[0089] A solution of cortisol (10.4 g, approximately 28 mM), dried by evaporation from ethanol-butanol) in dry tetrahydrofuran (40 mL) was treated with crude Intermediate 1 (5.4 g, 32 mM) and 0.5 mL of a solution of anhydrous p-toluenesulfonic acid in toluene (approximately 0.7 M). The reaction was stirred at room temperature 48 h. Additional dry THF was added (100 mL) and anhydrous p-TSA solution (2 mL), and the reaction was stirred 48 h. The reaction was partially concentrated and stirred another night. The reaction was partitioned between ethyl acetate and aqueous dibasic sodium phosphate. The organic layer was washed with brine, dried, and evaporated. The residue was purified by chromatography (silica gel, 30-70 ethyl acetate-dichloromethane) and gave Intermediate 2 (0.9 g).
Example 3
Compound 1
(8S,9S,10R,11S,13S,14S,17R)-17-glycoloyl-11-hydroxy-10,13-dimethyl-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl 2-furoate
[0090]
[0091] Intermediate 1 was dissolved in tetrahydrofuran (20 mL) and cooled in and ice/salt water bath under an inert atmosphere. The solution was treated with 0.37 mL of a 1M aqueous sulfuric acid solution. The reaction was stirred cold for 2 h. The reaction worked up with dibasic sodium phosphate solution and ethyl acetate. The ethyl acetate solution was washed with brined, dried and evaporated. The product was purified by chromatography (silica gel 60, 50-50 ethyl acetate-dichloromethane) and concentrated. The residue was crystallized from dichloromethane-hexane to give Compound 1 (1.9 g, 82%).
[0092] NMR (CDCl 3 , TMS): δ 1.00 (s, 3H), 1.13 (m, 3H), 1.47 (s, 3H), 1.51 (m, 1H), 2.54-1.74 (m's, 13H), 2.90 (m, 1H), 3.08 (m, 1H), 4.37 (m, 2H), 4.56 (m, 1H), 5.71 (s, 1H), 6.54 (m, 1H), 7.20 (m, 1H), 7.61 (m, 1H).
Example 4
Intermediate 3
Methyl 2-(4bromophenyl)acetimidate hydrochloride
[0093]
[0094] In a manner similar to that described in Example 1, 2-(4-bromophenyl)acetonitrile is converted to Intermediate 3. The residue that was obtained was not treated with methanol but isolated to give Intermediate 3.
Example 5
Intermediate 4
rel-(8R,9R,10S,11R,13R,14R,17S)-2′-(4-bromobenzyl)-11-hydroxy-2′-methoxy-10,13-dimethyl-1,6,7,8,9,10,11,12,13,14,15,16-dodecahydro-5′H-spiro[cyclopenta[a]phenanthrene-17,4′-[1,3]dioxane]-3,5′(2H)-dione
[0095]
[0096] In a manner similar as described in Example 2, cortisol and Intermediate 3 were converted to Intermediate 4. Purification by silica gel flash chromatography (20% ethyl acetate in CH 2 Cl 2 elution) provided the 24.8 mg of Intermediate 4: ICMS-ESI (m/z): calculated for, C 30 H 37 BrO 6 , 572, 574; [M+H] + found 573, 575.
Example 6
Compound 2
(8S,9S,10R,11S,13S,14S,17R)-17-glycoloyl-11-hydroxy-10,13-dimethyl-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl (4-bromophenyl)acetate
[0097]
[0098] In a manner similar as described in Example 3, Intermediate 4 was converted to Compound 2. Purification of the crude reaction mixture by silica gel chromatography (20% ethyl acetate, methylene chloride) provided the 57.7 mg of Compound 2. ICMS-ESI (m/z): calculated for, C 29 H 35 BrO 6 , 558, 560; [M+H] + found 559, 561.
Example 7
Intermediate 5
rel-(8R,9R,10S,11R,13R,14R,17S)-2′-ethoxy-11-hydroxy-10,13-dimethyl-2′-[2-(phenylsulfonyl)ethyl]-1,6,7,8,9,10,11,12,13,14,15,16-dodecahydro-5′H-spiro[cyclopenta[a]phenanthrene-17,4′-[1,3]dioxane]-3,5′(2H)-dione
[0099]
[0100] In a manner similar as described in Example 2, cortisol and ((3,3,3-trimethoxypropyl)sulfonyl)benzene were converted to Intermediate 5. Purification of the crude reaction mixture by silica gel chromatography (20% ethyl acetate, methylene chloride) provided the 13.1 mg of Intermediate 5. ICMS-ESI (m/z): calculated for, C 32 H 42 O 8 S, 586; [M+H] + found 587.
Example 8
Compound 3
(8S,9S,10R,11S,13S,14S,17R)-17-glycoloyl-11-hydroxy-10,13-dimethyl-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl 3-(phenylsulfonyl)propanoate
[0101]
[0102] In a manner similar to experiment described in Example 3, Intermediate 5 was converted to the title compound. Purification of the crude reaction mixture by silica gel chromatography (20% ethyl acetate, methylene chloride) provided the 96.9 mg of Compound 3. ICMS-ESI (m/z): calculated for C 30 H 38 O 6 S, 558; [M+H] + found 559.
Example 9
Glucocorticoid Receptor Transactivation Potencies for Cortisol and 17-Ester Derivatives
[0103] Glucocorticoid receptor (GR) activation potency was assessed using a HeLa cell line containing the MMTV-bla reporter (MMTV-bla HeLa CELLSENSOR®, Invitrogen Corp., Carlsbad, Calif.). This cell line was stably transfected with an expression construct containing β-lactamase cDNA under control of the MMTV response element previously identified as a glucocorticoid receptor response element. Results from one experiment performed in duplicate for the compounds and the control compound, dexamethasone, are summarized in Table 2. All assays were performed as 10-point dose responses using a half log-fold dilution series starting with a maximum compound concentration of 100 nM. The compounds were incubated for 5 hours. The activation of endogenous GR leads to expression of the reporter β-lactamase which is detected by the conversion of a FRET substrate in a ratiometric assay format. This functional assay allows for measurement of receptor agonism by compounds and can be used to determine compound potency and selectivity. Assay reproducibility was determined by calculating Z′ values for untreated versus maximum stimulation. The Z′ value was greater than 0.6, indicating good reproducibility of the assay format.
[0104] Several compounds showed dose-dependent stimulation of the GR signaling pathway (Table 2). Two compounds, cortisol 17-cyclopentanoate and cortisol 17-benzoate, showed about 30-fold greater potency compared to the parent molecule cortisol.
[0000]
TABLE 2
Glucocorticoid receptor potency. Shown are the EC 50 (nM) and Z′ values for
the control compound, dexamethasone, and the compounds tested in agonist mode.
EC50
% Activation
Compound
(nM) GR
at 100 nM
Z′
1.05
Control Compound
0.87
41.6
43
0.87
>100
17
0.87
—
0
0.87
Example 10
Mineralocorticoid Receptor Transactivation Potencies for Cortisol and 17-Ester Derivatives
[0105] Mineralocorticoid receptor (MR) activation potency was assessed using a HEK 293T cell line containing the UAS-bla reporter (UAS-bla HEK 293T CELLSENSOR®). This cell line was stably cotransfected with an expression construct containing β-lactamase cDNA under control of the GAL4 Upstream Activator Sequence (UAS) and another expression construct encoding for the fusion protein GAL4(DBD)-MR(LBD). Results for one experiment performed in duplicate for the novel compounds and the control compound, aldosterone, in agonist mode are summarized in Table 2. All assays were performed as 10-point dose responses using a half log-fold dilution series starting with a maximum compound concentration of 100 nM. The compounds were incubated for 16 hours. The activation of the fusion protein GAL4(DBD)-MR(LBD) leads to expression of the reporter β-lactamase which is detected by the conversion of a FRET substrate in a ratiometric assay format. This functional assay allows for measurement of receptor agonism by compounds and can be used to determine compound potency and selectivity. Assay reproducibility was determined by calculating Z′ values for untreated versus maximum stimulation. The Z′ value was greater than 0.6, indicating good reproducibility of the assay format. Several compounds showed dose-dependent stimulation of the MR signaling pathway (Table 3).
[0000]
TABLE 2
Mineralocorticoid receptor potency. Shown are the EC 50 (nM) and Z′ values
for the control compound, aldosterone, and the compounds tested in agonist mode.
%
EC50 (nM)
Activation
Compound
GR
at 100 nM
Z′
0.47
Control Compound
0.77
2.90
75
0.77
3.48
79
0.77
5.53
77
0.77
Example 11
Treating Elevated Intraocular Pressure
[0106] A 58 year old male visits his ophthalmologist for a routine check-up. The physician discovers that the patient exhibits an elevated intraocular pressure and is at high risk for future complications. The patient is instructed to apply a topical liquid formulation containing one of the compounds in Table 1 once daily to each eye.
[0107] The patient returns for a follow-up visit three months later. Upon measuring intraocular pressure, it is noted that the patient now exhibits a reduced intraocular pressure.
Example 12
Treating Ocular Irritation
[0108] A 38 year old male visits his ophthalmologist complaining of irritation in his right eye. The physician discovers that the patient's right eye is inflamed and red. The patient is instructed to apply a topical liquid formulation containing one of the compounds in Table 1 twice daily to the right eye.
[0109] The patient returns for a follow-up visit a week later. Upon inspection of the right eye, it is noted that the patient's eye is no longer red and the patient indicates that the irritation is gone.
[0110] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
[0111] The terms “a,” “an,” “the” and similar referents used in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.
[0112] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.
[0113] Certain embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
[0114] In closing, it is to be understood that the embodiments of the invention disclosed herein are illustrative of the principles of the present invention. Other modifications that may be employed are within the scope of the invention. Thus, by way of example, but not of limitation, alternative configurations of the present invention may be utilized in accordance with the teachings herein. Accordingly, the present invention is not limited to that precisely as shown and described. | The present invention relates to novel 4-pregenen-11β-17-21-triol-3,20-dione derivatives, processes for preparing them, pharmaceutical compositions containing them and their use as pharmaceuticals, as modulators of glucocorticoid or mineralocorticoid receptors. The invention relates specifically to the use of these compounds and their pharmaceutical compositions to treat disorders associated with glucocorticoid or mineralocorticoid receptor modulation. | 0 |
CROSS REFERENCES TO RELATED APPLICATIONS
[0001] This is a U.S. National Stage Application which claims the benefit of priority, under 35 U.S.C. §371, to International Application No. PCT/CN2005/001903, filed Nov. 11, 2005, which claims priority to Chinese Application No. 200420086385.X, filed on Dec. 16, 2004; Chinese Application No. 200520078247.1, filed on Jan. 17, 2005; and Chinese Application No. 200520078680.5, filed on Apr. 27, 2005.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a drug mixing and delivery device, particularly to a drug mixing and delivery device having at least one pressurized vial. The drug mixing and delivery device can be automatically repositioned and can inject the contents of a solvent vial into a plurality of solute vials containing powdered drugs for reconstitution.
[0004] 2. Description of the Related Art
[0005] Conventional methods for mixing at least two drugs or reconstituting a drug utilizing a syringe are cumbersome and inefficient. For example, when reconstituting a powdered drug, a nurse or medical personnel will first draw some water or solvent using an ordinary syringe to be injected into a vial containing a powdered drug. Once the drug is fully dissolved in solution, the mixture may then be withdrawn and injected into a separate vial for storage. This process is complicated, inefficient and risks contamination of the resulting drug mixture.
[0006] Conventional drug mixing and delivery devices that incorporate pre-sealed vials and/or cartridges have a complex structure that require the usage of customized vials and/or cartridges. These prior art devices are disadvantageous because they are not compatible with existing commercial vials commonly found in the market and are expensive to manufacture.
SUMMARY OF THE INVENTION
[0007] Accordingly, it is an objection of the present invention to provide an efficient and effective drug mixing and delivery device that has a simplified structure is compatible with conventional commercial vials.
[0008] In order to achieve the above objectives and other objectives, a drug mixing and delivery device of the present invention includes an outer sleeve, an inner sleeve, a hollow needle and a pressurized solvent vial. The inner sleeve is inserted into the outer sleeve, wherein the inner sleeve and outer sleeve are movable relative to one another along the central axis of the sleeves. The needle extends through the center of the outer sleeve and inner sleeve along a center axis. A collar that engages with the mouth of the solvent vial is formed on a distal end of the inner wall of the outer sleeve. A flange is formed on a middle portion of the inner wall of the outer sleeve. A circular bulging portion is formed on a distal end of the inner wall of the outer sleeve. One end of the inner sleeve is sealed and a collar, having an inward bias, is formed on the inner wall of the inner sleeve near the open end. The inner sleeve is positioned between the flange and the circular bulging portion, with its open end pointing outward. The hollow needle extends through the inner sleeve along its center axis and is fixed to the inner sleeve in the center of the sealed end of the inner sleeve.
[0009] Preferably, the drug mixing and delivery device includes a collar having a cross-section shaped like a triangle and wherein an inner diameter of the flange is smaller than that of the collar and the circular bulging portion. Expansion joints are formed in the outer sleeve on the side engaging with the inner sleeve.
[0010] When the drug mixing or reconstitution is completed, the solute vial or the outer sleeve may be removed so that the needle withdraws from the rubber stopper of the solute vial.
[0011] The invention may further include an automatic repositioning means that would enable the needle to withdraw from the rubber stopper of a solute vial by itself. An automatic repositioning drug mixing and delivery device comprises an outer sleeve, an inner sleeve, a hollow needle, a elastic member and a pressurized solvent vial, in which the inner sleeve is inserted into the outer sleeve and is movable relative to the outer sleeve along a longitudinal central axis of the sleeves. The hollow needle pierces through the center portion of the outer sleeve and the inner sleeve along the central axis. A distance plate having a center hole is provided inside the outer sleeve and a distance piece is provided on the inner sleeve coupled to the solvent vial. One end of the hollow needle extends out of the distance piece of the inner sleeve and is fixed to the distance piece. An elastic member is provided between the distance plate of the outer sleeve and the distance piece of the inner sleeve; the outer sleeve and the inner sleeve are respectively provided with retaining members that engage with each other.
[0012] In a preferred embodiment, the end of the hollow, needle which extends out the distance piece of the inner sleeve, is provided with a protective sheath, while the other end of the hollow needle is positioned inside a thorough hole formed on the distance plate. Furthermore, the elastic member may be a spring or an elastic rubber sheath.
[0013] In a preferred embodiment, the distance piece is positioned inside the inner sleeve. A round bulge is formed on the inner wall of the inner sleeve at one end of the inner sleeve. The round bulge and the mouth of the solvent vial are tightly fitted or interference fitted with each other.
[0014] In a preferred embodiment, the distance piece is positioned at the top portion of the inner sleeve and the diameter of the distance plate is greater than that of the outer sleeve.
[0015] In a preferred embodiment, a round bulge is formed on the inner wall of the outer sleeve at one side. The round bulge and the mouth of the solute vial are tightly fitter or interference fitted with each other.
[0016] In a preferred embodiment, one side of the outer sleeve is provided with expansion joints along the axial direction, and a collar is formed on the inner wall of the outer sleeve. The distance between the outer sleeve and the distance plate is equals to or slightly greater than the thickness of the outer edges of the mouth of the solute vial.
[0017] In a preferred embodiment, the retaining members are sliding channels or open grooves having locking notches formed in opposite direction on the inner wall of the outer sleeve; clippers, formed on the outer wall of the inner sleeve, engage with the sliding channels or open grooves and the locking notches.
[0018] In clinical practice, to satisfy a standard dosage requirement, it is usually necessary to mix and transfer multiple vials worth of drugs, typically 3-5 vials, to a transfusion bottle. Because of this significant volume requirement, conventional methods require the usage of multiple drug mixing and delivery devices, which is wasteful and expensive.
[0019] Therefore, a drug mixing and delivery device for reconstituting powdered drugs contained in a plurality of solute vials is proposed. The device comprises an outer sleeve, a bush, an inner support, an inner sleeve, a hollow needle, elastic members and a pressurized solvent vial. The inner sleeve is inserted in the outer sleeve and movable relative to the outer sleeve along a longitudinal central axis of the sleeves. The hollow needle pierces through the central portion of the outer sleeve and the inner sleeve along the central axis. The outer sleeve is connected to the bush provided with a movable plate. The elastic members are provided above and below the movable plate respectively. The movable plate is confined within the bush by a collar. The inner support is positioned within the outer sleeve. The hollow needle is fixed to the movable plate and is positioned inside a thorough hole formed in the inner support and a thorough hole formed in the bush. An end cap is connected to the outer sleeve via a ripping ring. The inner sleeve is inserted into the end cap.
[0020] Preferably, in the drug mixing and delivery device for reconstituting powdered drugs contained in a plurality of solute vials of the invention, the upper portion of the inner sleeve engages with the mouth of the solvent vial and the lower portion of the bush engages with the mouth of the solute vial. An annular step or a bulge is formed on the upper portion of the inner sleeve. The maximum traveling distance of the inner support is defined by an annular step formed inside the outer sleeve. The elastic member can be a a spring or an elastic rubber sheath.
[0021] The drug mixing and delivery device of any embodiment of the present invention for reconstituting powdered drugs contained in a plurality of solute vials can distribute the contents of a pressurized large volume solvent vial to a plurality of solute vials containing powdered drugs. Then the pressurized drug mixture contained in these vials can be delivered to a transfusion bottle one by one utilizing the same drug mixing and delivery device. Therefore, due to the simple operation of this inexpensive device, the drug mixing and delivery device of the present invention is suitable for clinical use.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIG. 1 is a vertical cross-section view of the drug mixing and delivery device of the present invention;
[0023] FIG. 2 is a planar view of FIG. 1 ;
[0024] FIG. 3 is a vertical cross-section view of the drug mixing and delivery device of the present invention in which the contents of a solvent vial and a solute vial are being mixed.
[0025] FIG. 4 is a vertical cross-section view of a solvent vial and a solute vial mounted on the drug mixing and delivery device of the present invention prior to initiating mixing.
[0026] FIG. 5 is a vertical cross-section view of the drug mixing and delivery device of the present invention showing the solute vial and the inner sleeve without the outer sleeve.
[0027] FIG. 6 is a vertical cross-section view showing the drug mixing and delivery device of the present invention delivering a mixed drug solution to a bottle.
[0028] FIG. 7 is a vertical cross-section view of a solvent vial and a solute vial mounted on the automatic repositioning drug mixing and delivery device of the present invention prior to initiating mixing.
[0029] FIG. 8 is a vertical cross-section view showing the automatic repositioning drug mixing and delivery device of the present invention in which the contents of a solvent vial and a solute vial are being mixed.
[0030] FIG. 9 is a vertical cross-section view showing the automatic repositioning drug mixing and delivery device of the present invention without a solvent vial.
[0031] FIG. 10 is a partial perspective view showing a sleeve of the automatic repositioning drug mixing and delivery device of the present invention.
[0032] FIG. 11 is a planar view showing the inner sleeve of the automatic repositioning drug mixing and delivery device of the present invention.
[0033] FIG. 12 is a vertical cross-section view showing a variation of the inner sleeve of the automatic repositioning drug mixing and delivery device of the present invention.
[0034] FIG. 13 is a is a vertical cross-section view showing a variation of the inner sleeve of the automatic repositioning drug mixing and delivery device of the present invention.
[0035] FIG. 14 is a is a vertical cross-section view showing a variation of the inner sleeve of the automatic repositioning drug mixing and delivery device of the present invention.
[0036] FIG. 15 is a is a vertical cross-section view showing a variation of the inner sleeve of the automatic repositioning drug mixing and delivery device of the present invention.
[0037] FIG. 16 is a vertical cross-section view showing a variations of the inner sleeve of the automatic repositioning drug mixing and delivery device of the present invention.
[0038] FIG. 17 is a vertical cross-section view showing the automatic repositioning drug mixing and delivery device of the present invention with a solvent and solute vial.
[0039] FIG. 18 is a vertical cross-section view showing the automatic repositioning drug mixing and delivery device of the present invention without the solute vial.
[0040] FIG. 19 is a vertical cross-section view of one of many solute vials and a solvent vial that can be mounted on the drug mixing and delivery device for reconstituting powdered drugs prior to initiating mixing;
[0041] FIG. 20 is a vertical cross-section view of the drug mixing and delivery device for reconstituting powdered drugs in which the contents of one of may solute vials is being mixed with the contents of a solvent vial.
[0042] FIG. 21 is a vertical cross-section view of the drug mixing and delivery device for reconstituting powdered drugs in which a mixed drug solution is being transferred to a transfusion bottle.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0043] The present invention is directed to a drug mixing and delivery device and a method for using said device that enables simplified and efficient mixing and delivery of a drug composition. The drug mixing and delivery device utilizes the internal pressure differential between two vials to transfer the contents of one vial into a second vial, wherein the vials may be any standard commercial drug vials or drug ampoules.
[0044] As shown in FIG. 3 and FIG. 4 , the drug mixing and delivery device of the present invention generally comprises a solvent vial 12 and a solute vial 11 connected by a sleeve portion. Solvent vial 12 is inverted such that its mouth 13 is inserted into an upper distal end of an outer sleeve, 2 and a mouth 14 of solute vial 11 is inserted into a lower distal end of outer sleeve 2 .
[0045] As shown in FIG. 1 and FIG. 2 , a collar 1 , which has a triangle-shaped cross-section, flange 4 , which has a rectangle-shaped cross-section, and a circular bulging portion 8 are respectively formed on an upper, middle and lower portion of the inner wall of outer sleeve 2 of the drug mixing and delivery device of the present invention. A plurality of expansion joints 7 are formed longitudinally between flange 4 and the bottom edge of outer sleeve 2 . Inner sleeve 5 , which is positioned in the lower portion of an inner wall of outer sleeve 2 , is similar to a bottle cap in its structure. A rounded collar 6 , which is inwardly biased so as to securely engage a vial is formed along a bottom edge of inner sleeve 5 to engage with the bottom edge of mouth 14 of solute vial 11 . A hollow needle 3 is fixed at the center of the inner sleeve along the central axis.
[0046] When using the drug mixing and delivery device of the present invention, first mouth 14 of solute vial 11 is inserted into collar 6 , which is formed on inner sleeve 5 , so that the hollow needle 3 pierces through a rubber stopper 10 of solute vial. Mouth 13 of solvent vial 12 may then be inserted into collar 1 , which is formed on an inner wall of outer sleeve 2 , so that the needle 3 pierces through rubber stopper 9 of solvent vial 12 , thus initiating the drug mixing operation, as shown in FIG. 3 .
[0047] Alternatively, solvent vial 12 may be previously assembled with the sleeve portion as part of a whole assembly. Similar to the previously disclosed method, needle 3 may either consecutively or simultaneously pierce stoppers 9 and 10 of solute vial 11 and solvent vial 12 . During the manufacturing process, mouth 13 of solvent vial 12 may engage outer sleeve 2 until mouth 13 is wedged between the protrusion of collar 1 , as shown in FIG. 4 . Collar 1 functions as a positioning point that prevents needle 3 from penetrating stopper 9 . Solvent vial 12 and outer sleeve 2 may be fixedly positioned relative to one another such that mouth 13 is wedged between the protrusion of collar 1 , as shown in FIG. 4 , and can be packed as an assembly for clinical applications. When in use, a nurse or medical personnel need only apply a slight force to insert solute vial 11 into the other side of outer sleeve 2 so that mouth 14 of solute vial 11 is properly engaged with inner sleeve 5 so as to be positioned to initiate drug mixing, as shown in FIG. 4 .
[0048] Mixing may begin by applying force to inverted solvent vial 12 , such as by pushing down in solvent vial 12 . It will be appreciated that the force applied to solvent vial 12 will also be transferred to collar 1 . Because flange 4 and outer sleeve 2 are formed as an integral structure and because flange 4 also engages with an upper portion of inner sleeve 5 , the force applied to solvent vial 12 will also force outer sleeve 2 and inner sleeve 5 to move downward, and thereby force mouth 14 of solute vial 11 to be fully inserted within collar 6 of inner sleeve 5 .
[0049] When the mouth 14 of solute vial 11 contacts the portion of inner sleeve 5 adjacent to flange 4 , a lower end of needle 3 will pierce through rubber stopper 10 , such that solute vial 11 becomes directly connected to needle 3 , and such that collar 6 of inner sleeve 5 is positioned beneath mouth 14 of solute vial 11 . A downward force may then be applied to solvent vial 12 until an upper end of needle 3 pierces through rubber stopper 9 of solvent vial 12 , such that solvent vial 12 also directly connects to needle 3 . Then the content of solvent vial 12 may be immediately injected into solute vial 11 through needle 3 since the internal pressure of solvent vial 12 is greater than that of solute vial 11 . Therefore, the powdered drugs inside solute vial 11 may be dissolved in or fully mixed with the contents of solvent vial 12 . Solvent vial 12 has already been pre-pressurized during the manufacturing process, so when it is connected to solute vial 11 through needle 3 , the pressure differential between the vials will force the contents of solvent 12 into solute vial 11 until the pressure within the two vials reaches equilibrium, as shown in FIG. 3 .
[0050] Because the distance between collar 1 and flange 4 is approximately equal to or slightly greater than the thickness of mouth 13 of solvent vial 12 , mouth 13 may be tightly snapped into and secured between collar 1 and flange 4 . After the contents of vials 11 and 12 are properly mixed, the outer sleeve of solvent vial 12 may be removed. As the solvent vial 12 is pulled upward from the sleeve, outer sleeve 2 will also move upward because mouth 13 of solvent vial 12 remains engaged with collar 1 . At the same time, inner sleeve 5 will also move upward because circular bulging portion 8 , formed on outer sleeve 2 , engages with the collar 6 , formed on a bottom portion of inner sleeve 5 , until collar 6 of inner sleeve 5 engages with the bottom face of mouth 14 of solute vial 11 . At this point inner sleeve 5 is in its highest position but does not disengages with solute vial 11 , and a lower end of needle 3 is pulled out of rubber stopper 10 . by continuously pulling solvent vial 12 upward, circular bulging portion 8 will move upward along the outer wall of inner sleeve 5 because of expansion joint 7 until outer sleeve 2 disengages with inner sleeve 5 completely. At this point needle 3 is positioned above mouth 14 of solute vial 11 because collar 6 formed on a lower portion of inner sleeve 5 tightly retains the lower edges of mouth 14 of solute vial 11 , forming a pressurized automatic syringe, as shown in FIG. 5 .
[0051] Alternatively, the above procedure can be performed by holding and pulling outer sleeve 2 in an upward direction to achieve the same effect and result.
[0052] Solute vial 11 may then be turned upside down to transfer the mixed drug of solute vial 11 to transfusion bottle 15 . As shown in FIG. 6 , when one end of needle 3 pierces stopper 16 of transfusion bottle 15 , a counteractive force will push needle 3 through rubber stopper 10 of solute vial 11 . Because the pressure within solute vial 11 is greater than that of transfusion bottle 15 , the contents of solute vial 11 will be injected into transfusion bottle 15 to complete a one-time drug delivery operation.
[0053] In addition, in order to better engage the mouths of solvent vial 12 and solute vial 11 , outer sleeve 2 can have different customized inner diameters by forming a step in the middle of outer sleeve 2 .
[0054] The drug mixing and delivery device of the present invention has many advantages. Not only can the drug mixing and delivery procedure be quickly executed, it also avoids possible contamination of the mixture by eliminating the need for multiple transfers of the drug solution and by eliminating usage of a conventional syringe.
[0055] Additionally, a portion of needle 3 located within the inner sleeve can be provided with an elastic rubber sheath to protect needle 3 from being contaminated. The rubber sheath will extend automatically to cover the needle end after the drug is delivered to protect the operator from accidental injury.
[0056] Additionally, because a special manufacturing means are necessary to pressurize solvent vial 12 , the drug mixing and delivery device of the present invention is desirably constructed to be an environment friendly and disposable one time use appliance.
[0057] Another feature of the drug mixing and delivery device of the present invention is that the three sections, solute vial 11 , solvent vial 12 and the connecting sleeve, can either be individually packaged in aseptic packages, or solvent vial 12 and the sleeve portion can be assembled and packed together. Alternatively, all three sections can be assembled together in the factory and packed in one aseptic package to facilitate the operation of the device and eliminate the possibility of mixing the wrong drugs.
[0058] As shown in FIG. 7 , the drug mixing and delivery device of the present invention may further include a means for automatically returning or automatically repositioning the device to an original state. An automatic repositioning drug mixing and delivery device of the present invention generally comprises an outer sleeve 22 , an inner sleeve 25 , a needle 23 , a elastic member 210 , a solvent vial 12 and a solute vial 11 . A distance piece 29 is formed inside inner sleeve 25 and is transversely oriented with respect to inner sleeve 25 . A plurality of spaced round bulges 215 are formed on an inner wall of inner sleeve 25 above distance piece 29 . Two clippers 21 , formed at a lower end portion of an outer wall of inner sleeve 25 , are symmetrically situated and protrude outward from inner sleeve 25 . A distance plate 20 is formed inside outer sleeve 22 and is transversely oriented with respect to outer sleeve 22 . A plurality of spaced round bulges 28 are formed on an inner wall of the outer sleeve 22 below the distance plate 20 . As shown in FIG. 10 , a pair of channels 24 is symmetrically formed in an inner wall of outer sleeve 22 . Two locking notches 26 are formed at the distal ends of the pair of channels 24 , facing in opposite directions with respect to each other, as shown in FIG. 10 . The two clippers 21 , formed at a lower end portion on the outer wall of inner sleeve 25 , can be inserted into and moved along channels 24 and engaged with locking notches 26 . Needle 23 having two piercing ends, is fixed to distance piece 29 of inner sleeve 25 . One end of needle 23 extends out of the distance piece 29 , and the other end of the needle 23 is positioned inside a through hole 212 , formed in the center of distance plate 20 of outer sleeve 22 . In a preferred embodiment, elastic member 210 is a spring which is positioned around needle 23 and extends between distance piece 29 and distance plate 20 . The outer edge of mouth 13 of pressurized solvent vial 12 is tightly fitted and secured between round bulges 215 , formed on the inner wall of inner sleeve 25 , and the outer edge of mouth 14 of solute vial 11 is tightly fitted and secured between round bulges 28 formed on an inner wall of outer sleeve 22 . FIG. 7 shows the placement of solvent vial 12 and solute vial 11 prior to mixing.
[0059] To initiate mixing the contents of the two vials, solvent vial 12 is pressed downward; inner sleeve 25 will then correspondingly move downward against spring 210 . Clippers 21 will slide downward along channel 24 until they reach locking notches 26 , while an upper end of needle 23 will pierce through rubber stopper 9 of solvent vial 12 . When clippers 21 reach locking notches 26 , the lower end of needle 23 will pierce through rubber stopper 10 of solute vial 11 so that needle 3 operatively connects the two vials and initiates mixing. The pressurized content of solvent vial 12 will then flow into the solute vial 11 through needle 23 , as shown in FIG. 8 . Solute vial 11 will then contain the pressurized mixed drug solution.
[0060] When mixing is complete, inner sleeve 25 may be loosened and returned to its original position; the elastic member 210 , which is preferably a spring, will push against inner sleeve 25 when an initial external downward force to solvent vial 12 has been removed, as shown in FIG. 9 . At the same time, the lower end of needle 23 will retract from rubber stopper 10 of solute vial 11 . Solvent vial 12 may then be removed, and solute vial 11 may be turned upside down. Then an end of needle 23 that extends through distance piece 29 may be used in turn to pierce a rubber stopper of a transfusion bottle. Applying an external force against solute vial 11 , clippers 21 of inner sleeve 25 will again slide along working channels 24 to locking notches 26 . Due to a resultant counterforce, needle 23 will again pierce through rubber stopper 10 of solute vial 11 . When needle 23 has pierced both stoppers, the mixed drug solution will be injected into the transfusion bottle due to the higher internal pressure within solute bottle 11 , thereby completing a one-time delivery to the transfusion bottle, wherein the drug mixing and delivery operation are performed under aseptic condition.
[0061] Locking notches 26 retain the connection between solvent vial 12 and solute vial 11 by slightly rotating inner sleeve 2 clockwise so that clippers 21 latch with locking notches 26 . Of course, locking notches 26 are an optional feature of the invention since the connection between solvent vial 12 and solute vial 11 can be retained simply by applying and maintaining pressure to solvent vial 12 or inner sleeve 25 , i.e. by applying pressure with one's hand. Needle 23 will disengage with rubber stopper 10 once the pressure is released. Of course, other means can be used for retaining the connection between the two vials, such as a retaining ring, a protruding ring or a positioning step, etc. Elastic member 210 can also be a sleeve made of elastic rubber instead of a spring.
[0062] FIG. 12-FIG . 16 show various possible structural configurations of a distal end of inner sleeve 25 for mating with a solvent vial.
[0063] FIG. 17 and FIG. 18 show another embodiment of the automatic repositioning drug mixing and delivery device of the present invention. The difference between the embodiments of FIGS. 17-18 and FIGS. 7-8 is that the structural element above distance piece 29 of FIGS. 7-8 has been removed so that the mating ends of an inner sleeve 205 for receiving a solvent vial 12 is shaped like a flat plane, similar to the inner sleeve of FIG. 12 . Two open grooves 204 and two open locking holes 206 engage with the two clippers 201 , which are formed on inner sleeve 205 . The mating ends of the outer sleeve 202 for receiving mouth 14 of solute vial 11 is shaped like a socket. The round bulge formed on the outer sleeve 202 is located at an edge of the socket, forming collar 208 . The side wall of the socket is formed with a plurality of vertical, symmetrically spaced expansion joints 207 . When solvent vial 12 is disengaged with inner sleeve 205 , the protruding end of the needle 203 can be covered with a protective sheath 213 made of a hard material. A distal end of sheath 213 , having an opening, is inserted into a recess portion 214 , which is formed in the center of distance piece 209 , to protect needle 203 from contamination or damage and to prevent accidental needle related injuries.
[0064] As shown in FIG. 19 , a drug mixing and delivery device for a plurality of powdered drug vials of the present invention generally comprises an outer sleeve 318 , a bush 33 , an inner support 313 , an inner sleeve 310 , a hollow needle 37 , a spring 314 , a spring 34 and a large solvent vial 39 . Bush 33 is fixed to a distal end of the outer sleeve 318 , and an end of bush 33 includes a movable plate 35 through which extends needle 37 . Spring 34 is set between movable plate 35 and a bottom portion of bush 33 . The maximum travel distance of movable plate 35 within bush 33 is defined by collar 316 , which is formed on an inside wall of an upper portion of bush 33 . The inside of outer sleeve 318 is also provided with an inner support 313 having a needle hole. Spring 314 is set between an inner support 313 and a movable plate 35 . The maximum travel distance of inner support 313 , which is located inside outer sleeve 318 , is defined by an annular step 36 . An upper distal end of outer sleeve 318 is provided with an end cap 311 coupled to outer sleeve 318 through ripping ring 312 . An annular step 317 formed on the inside of inner sleeve 310 forms the receiving socket for solvent vial 39 . The end cap 311 engages with a step 32 formed on a lower portion of inner sleeve 310 so that inner sleeve 310 cannot be separated from outer sleeve 318 by pulling inner sleeve 310 in an upward direction.
[0065] When the two vials are not directly connected by needle 37 , spring 34 pushes movable plate 35 upward until it reaches collar 316 , and spring 314 pushes inner support 313 upward until it reaches annular step 36 , which is located inside outer sleeve 318 . This configuration represents an initial position of the device prior to an application of external force on the device or after releasing an external force from the device.
[0066] During drug mixing, solvent vial 39 may be pushed downward with a little force. Stopper 38 of solvent vial 39 will press against annular step 317 so that inner sleeve 310 presses against inner support 313 accordingly. Movable plate 35 will then be pressed by compressed spring 314 , which in turn is pressed by inner support 313 . Meanwhile, needle 37 will pierce through stopper 14 of solute vial 11 through a thorough hole 315 , and at the same time, needle 37 will pierce stopper 38 of solvent vial 39 , so that the two vials are directly connected via needle 37 , as shown in FIG. 20 . Because graduated solvent vial 39 , which may have a plurality of marks indicating volume, is pressurized, the contents of solvent vial 39 will flow into solute vial 11 via needle 37 . Solvent vial 39 may be released when a predetermined amount of the content in solvent vial 39 is delivered to a solute vial 11 .
[0067] The above operation can be repeated so that the content of solvent vial 39 can be introduced to several solute vials 11 that may contain the same or different drugs and thereby pressurize multiple solute vials 11 . Only one drug mixing and deliver device is necessary to deliver the drug solution from solute vials 11 to a transfusion bottle.
[0068] During the drug delivery operation for delivering the mixed drug solution in solute vials 11 to transfusion bottles, ripping ring 312 may be removed by hand so that end cap 311 , inner sleeve 310 , solvent vial 39 and outer sleeve 318 are separated. Then, as shown in FIG. 21 , outer sleeve 318 and solute vial 11 are inverted so that outer sleeve 318 covers a mouth of transfusion bottle 320 . Pressure is then applied to solute vial 11 so that the parts comprising outer sleeve 318 assume the positions depicted in FIG. 20 . At this time, needle 37 pierces through stopper 319 of transfusion bottle 320 and the contents of solute vial 11 is injected into transfusion bottle 320 . Solute vial 11 may be replaced with another solute vial 11 to repeat the above operation so that the contents of several solute vials are delivered to one transfusion bottle 320 .
[0069] Only one drug mixing and delivery device is necessary to distribute the contents of a solvent vial into several solute vials, which contain powdered drugs, thereby pressurizing said solute vials so that it is possible to deliver the mixed drug solutions from multiple solute vials to a transfusion bottle. This will reduce the number of the drug mixing and delivery device required in a large scale operation and facilitate operation as well as reduce cost.
INDUSTRIAL APPLICABILITY
[0070] To operate the drug mixing and delivery device of the present invention, one need only insert the mouth of a solvent vial into a corresponding mating portion of the device and insert a solute vial into a corresponding opening in an inner sleeve of the device. By applying an external pressure to the solvent vial, the ends of a hollow needle pierce through the rubber stoppers of said vials. Because the solvent vial is pressurized, its contents will flow into the solute vial to mix with the contents of the solute vial. After mixing, the solvent vial may be separated from the outer sleeve of the device by pulling on the solvent vial. The remaining solute vial, engaged with the inner sleeve of the device, essentially functions as a pressurized syringe. The mixed drug solution may then be transferred from the solute vial to a transfusion bottle by allowing the hollow needle to pierce through the rubber stopper of the transfusion bottle and solute vial. The simple drug mixing and delivery device of the present invention significantly reduces the possibility of contamination and improves work efficiency.
[0071] In addition to the features mentioned above, the drug mixing and delivery device can be automatically repositioned. After the drug mixing operation is completed, the hollow needle will move out from the rubber stopper of the solute vial and the solute vial will be automatically reverted to its original sealed condition upon releasing the force applied by an elastic member. When the volume of the solvent vial and the solute vial is large, requiring a long period of time for drug mixing, it is possible to maintain the connection between the two vials by engaging a pair of clippers, located on the outer wall of the inner sleeve, with the locking notches of the device by applying pressure to the solvent vial until the needle pierces the stopper of the solvent vial and then rotating the inner sleeve so that the clippers lock with the locking notches. When the drug mixing operation is completed, the clippers may be disengaged from the locking notches by rotating the inner sleeve in a reverse direction; the hollow needle will then retract from the rubber stopper of the solute vial.
[0072] The drug mixing and delivery device may also be used to reconstituting drugs contained in several solute vials drugs and can be used to distribute the pressurized contents of a large solvent vial to several solute vials. The contents of the multiple solute vials can be delivered to a transfusion bottle one by one by using the same drug mixing and delivery device. This eliminates the need for using a drug mixing and delivery device for each solute vial, thereby simplifying operation and reducing cost. | A medicine mixer for applying drug comprises a menstruum vial ( 12 ), an outer cannula ( 2 ) and a solute vial ( 11 ) (powdered drug ampoule) which are in one. Retaining ring ( 1 ), chuck ring ( 4 ) and convex ring ( 8 ) are disposed respectively at up portion, middle portion and nether portion of the inner wall of the outer cannula ( 2 ). An inner cannula ( 5 ) with a ducting needle ( 3 ) is disposed between the chuck ring ( 4 ) and the convex ring ( 8 ). In use the lower end of the outer cannula ( 2 ) is inserted to the opening ( 14 ) of the solute vial ( 11 ), and the opening ( 13 ) of the menstruum vial ( 12 ) is inserted into the retaining ring ( 1 ) of the outer cannula ( 2 ), so that rubber plugs ( 10,9 ) are pierced successively by the ducting needle ( 3 ) to connect two vials and thus mix drug. Then the outer cannula ( 2 ) is unfixed and the drug is applied to an infusion bottle ( 15 ). A medicine mixer for applying drug which can be repositioned automatically and a medicine mixer for applying drug which can delivery drug to many ampoules are also provided. The structure of the device is simple and cost is low. It is suitable to be combined with commercial ampoules. It is used conveniently and simply, and applied broadly. | 0 |
TECHNICAL FIELD
This invention relates to the restoration of teeth to their normal, anatomical form and function, particularly to a device for facilitating restoration with the use of conventional matrix bands, and more particularly, to the repair of interproximal caries using light cured composite materials.
BACKGROUND OF THE INVENTION
Anatomically, teeth are aligned to and with each other in an arch form contacting each other on a mesial and distal side. The size, shape and tightness of these contacts is vital to the health of the teeth and supporting periodontal structures. As caries develop in the interproximal surfaces, there is a need to restore the surfaces to the proper anatomical form and to reestablish the appropriate contact points.
The typical practice, following cavity preparation, is to place a dental matrix band circumferentially around a tooth for filling and holding restorative material to achieve the proper contour. Dentists commonly use the dental matrix band with a matrix band retainer instrument which helps to position the band and to tighten it securely about the tooth. To adjust the fit of the band and to maintain it in a suitable position during restoration, other dental instruments, such as the triangular shaped wedge, are commonly used. The wedge may be inserted, just above the gumline, between the tooth being restored and an adjacent tooth. The wedge slightly separates the teeth to accommodate the thickness of the band and to create a seal at the end of the band to keep the filling material in place. It is also known in the art to use a sectional matrix ring system which fits between two teeth for applying contoured bands and establishing a tight contact.
Over the years, various types of devices have been developed to help distend the band during an initial composite curing period. While the conventional devices have added many advances to the field, they retain significant limitations. Perhaps the most common limitation of conventional devices is that the restoration tends to result with a narrow contact area at the marginal ridge. When the contact area is smaller in size than ideal, the restoration is weak and subject to fracture. It can leave a gap between the contact point, gum and neighboring teeth for food entrapment and infection. Devices designed to overcome contact weakness have been shown to be cumbersome in use and to provide inconsistent results. The wedge, for instance, is operated by hand and thus depends upon a variant level of torque which can be subject to human error. Once in position, the wedge can shift out of place. If made of wood, or similar porous material, it is prone to moisten with saliva and lose its effectiveness. The matrix ring instrument requires an ideal preparation to function correctly and tends to be cumbersome due to the need to engage multiple components. These devices can be cumbersome, time consuming and may even hinder the practitioners' view of the restoration.
In the past, the most common restorative material has been silver amalgam, a metal putty. Due to its strength, amalgam material maintains its shape. In this way, the amalgam filling material also functions to assist with the displacement of the dental matrix band into tight contact with the adjacent tooth. Today, with the advancements in dental materials, compactable composite resins are increasingly used. Unlike amalgams, composite resins do not have the condenseability necessary to displace the matrix band in position during restoration. As a result, the elastic memory of the band pulls away from the adjacent tooth thereby leaving a gap or space. The elastic memory exhibits a very flat proximal surface which, following restoration, yields a thin contact area at the marginal ridge. This result is clinically undesirable. The band is not well deformed to appropriate contour by composite material alone.
SUMMARY OF THE INVENTION
This invention facilitates the restoration of teeth by providing for deformation of the interproximal segments(s) of a matrix band, or other dental aid, to the natural tooth contours through a predictable tight contact area with an easy-to-use self-supporting tool. It can be easily and optimally used in conjunction with conventional devices, such as wedges. This invention adapts for use on many types of preparations. It further allows for the use of cured composite resin materials, and is designed to provide maximal visibility and access for quick deposition and curing of the materials.
The invention is a dental tool for assisting the restoration of a tooth, comprising, as a preferred embodiment, an elongated frame, having a first member at one end of the elongated frame, the first member having a channel for receiving a strut component; a second member movably attached to the elongated frame parallel to the first member, the second member also having a channel for receiving a strut component; a means for adjusting the second member relative to the first member connected with the second member and attached to the elongated frame opposite to the first member; and strut components removably disposed through the channels of the first and second members. The strut components can include struts extending perpendicularly therefrom and a means for removably attaching the strut components to the members. Optionally, one strut is symmetrically conical in shape with a curved base and a flattened part for optimal contact with the tooth, and another strut is shorter, cylindrical in shape and has a flattened end to provide counter pressure.
The invention accommodates variations in tooth sizes by providing a means for adjusting the members to alter the distance between the struts. Depending upon the type of restoration desired, struts of varied length and size can be used. They can be removed and reattached in an inverted position for use of the invention on a tooth in the opposite side of the mouth.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view illustrating a preferred embodiment of the dental tool.
FIG. 2 is a top view of the dental tool showing channels to receive strut components.
FIG. 3 shows an embodiment of a strut component with a cylindrical strut.
FIG. 4 shows an embodiment of a strut component with a symmetrical conical strut.
FIG. 5 shows a preferred embodiment of attaching a strut component to the first member.
FIG. 6 shows an embodiment of the invention with struts of variant lengths.
FIG. 7 shows an embodiment of the invention with struts of the same length.
FIGS. 8A, 8 B, 8 C, and 8 D show a use of the dental tool to aid in tooth restoration.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings, and particularly to FIGS. 1 and 2, an embodiment of the dental tool invention is shown generally 1 and includes an elongated frame 2 , a first member 5 , a second member 6 that is parallel to the first member 5 , and a means for adjusting the first 5 and second 6 members relative to one another in order to tighten a matrix band or other dental aid about a tooth. Each of said first member 5 and second member 6 has a strut extending therefrom for making contact with the tooth. In a preferred embodiment of the invention, each of said first member 5 and second member 6 has a channel 14 and 15 , respectively, disposed through it for receiving a strut component, as shown in FIG. 2 . Elongated frame 2 preferably has the first member 5 nonmovably fixed to one end of elongated frame 2 and has second member 6 movably attached to elongated frame 2 , as depicted in FIGS. 1 and 2. However, it is possible to nonmovably affix second member 6 to elongated frame 2 and to movably attach first member 5 to elongated frame 2 , or to movably attach both first member 5 and second member 6 to elongated frame 2 , and still attain the same result with the invention. The means for adjusting second member 6 relative to first member 5 preferably is a handle 4 with a helical thread stem 7 extending therefrom that is attached to elongated frame 2 at its end opposite first member 5 and that is disposed through second member 6 and into first member 5 . The practitioner may turn handle 4 with his or her fingers, thereby advancing or retreating second member 6 along helical thread 7 toward or away from first member 5 . This allows the tool to tighten or release a matrix band or other dental aid as desired.
In a preferred embodiment, as shown in FIG. 2, the first member 5 and second member 6 have channels 14 and 15 , respectively, disposed through them for receiving strut components 20 or 30 . However, it is possible to have the first member 5 and second member 6 formed into struts, rather than using strut components 20 and 30 , and still attain the same result with the invention. As shown in FIG. 3, strut component 20 is comprised of strut 21 extending perpendicularly from strut component 20 , of ridge 22 , of body 23 adapted to be received by channel 14 or 15 , and of a means for removably attaching strut component 21 to first member 5 or second member 6 as desired. In a preferred embodiment, the means for removably attaching strut component 20 includes threaded portion 24 and a removable cap 25 designed to receive said portion 24 as shown in FIG. 3 . Strut 21 is generally cylindrical in shape in proportion to a tooth and has a flattened end to provide a point of counter pressure on the tooth. Ridge 22 is slightly raised relative to the body 23 of the strut component. Body 23 fits within channel 14 or 15 of first member 5 and/or second member 6 , as desired, and ridge 22 serves to position strut component 20 within channel 14 or 15 and to align strut 21 properly with respect to dental tool 1 . FIG. 5 shows how strut component 20 removably attaches to either first member 5 or second member 6 .
As shown in FIG. 4, strut component 30 is comprised of strut 31 extending perpendicularly from strut component 30 , of ridge 32 , of body 33 adapted to be received by channel 14 or 15 , and of a means for removably attaching strut component 31 to first member 5 or second member 6 as desired. In a preferred embodiment, the means for removably attaching strut component 30 includes threaded portion 34 and a removable cap 35 designed to receive said portion as shown in FIG. 4 . Strut 31 is generally conical. It is generally symmetrically conical in shape in proportion to a tooth, with a flat part to contact the area being restored, and a curvature toward the gingival margin. Strut 31 is longer than strut 21 in order to properly distend a matrix band, which is fitted around the treated tooth, snugly against a neighboring tooth. Ridge 32 is slightly raised relative to the body 33 of the strut component. Body 33 fits within channel 14 or 15 of first member 5 and/or second member 6 , as desired, and ridge 32 serves to position strut component 30 within channel 14 or 15 and to align strut 31 properly with respect to dental tool 1 .
In this way, struts are easily adjusted or exchanged to suit the restoration by simply attaching or removing the strut component from the first member 5 and second member 6 . Strut components 20 and 30 can be used interchangeably when placed on first member 5 and second member 6 for adapting the dental tool for use with a tooth on the opposite side of the mouth. The strut components 20 and 30 may be comprised of various materials including, for example, metal, nylon, polytetraflouride, polyethylene or quartz, among other materials.
It should be noted that the dental tool can utilize strut component 30 on first member 5 and second member 6 so that a practitioner can use struts of the same size and shape, as shown in FIG. 7 . Likewise, strut component 20 can be used on first member 5 and second member 6 at the same time. Alternatively, the practitioner can use the tool with strut components 30 and 20 when struts of unlike size and shape are desired, as shown in FIG. 6 . Additionally, in this way, the struts 21 and 31 are offset in order to maximize vision. They are interchangeable and can be used in any combination to best advantage.
During use of the invention, the practitioner prepares the cavity by conventional or other means, extending to one or more interproximal surfaces, and removing all carious dentin. Unlike most other contact instruments, an intact axial wall is not needed to secure a tight contact. And, cavo-surface margins need not be in ideal positions. The matrix band is then placed, tightened and secured with a wedging device, and proper etching and bonding steps are begun. As this procedure sets, a small amount of composite is placed at the gingival floor(s) and this dental tool invention 1 is inserted. The dental tool 1 will distend and maintain proper band conformation by placing the strut components 20 and 30 in position relative to the preparation and by adjusting the strut components 20 and 30 as desired using the means for adjusting first member 5 and second member 6 relative to one another. Additional material, such as composite resin, is placed and cured to achieve a secure hold. Once cured, the dental tool invention 1 is removed and the remainder of the cavity is filled. The band and wedge are removed and the restoration, if desired, is adjusted and polished.
For a mesial occlusal or a distal occlusal, one strut, preferably conical strut 31 , is placed into the proximal box and another strut, preferably short cylindrical strut 21 , is placed at the pulpal floor in the dovetail section of the prepared cavity for counter pressure. For optimal advantage, the flattened portion of conical strut 31 is placed against the dental matrix band at the position of desired contact. Then, the handle 4 is adjusted to distend and shape the dental matrix band simultaneously achieving separation between the adjacent teeth, to account for the thickness of the matrix band. At this point, additional composite material can be placed and light cured. When sufficient material has been applied to maintain the generated tooth shape, form and contact area, the dental tool instrument is removed. Any residual voids are quickly filled, shaped, and cured. The wedge and band are removed and the restoration is adjusted, contoured and polished accordingly. FIGS. 8A through 8D show an illustration of how the invention can be used to improve tooth restoration, in contrast to a restoration done without the invention. The final filling is ideal in all aspects of anatomy, function, and contact—all with the use of readily available, recognizable, existing materials and supplies.
When the restoration involves both interproximal areas, or a mesial occlusal distal, another embodiment of the invention is shown to use a conical strut 31 on both first member 5 and second member 6 . As described in the above embodiment, a small amount of restorative is placed at the gingival floor and, then, both struts are placed at ideal levels and tightened to conform the matrix band appropriately. Composite resin material is placed and cured until sufficient filling exists to hold the proper share without the apparatus. The invention is removed, voids filled, and the restoration is finished. With the extended depth of cure of the compactable resins now available, this procedure is very quick as well as predictably functional. | jIn restoration of teeth, the use of conventional matrix bands and wedges tends to leave gaps or spaces which can through inefficient restoration lead to fracture or infection, and also prove to be time consuming and inefficient. This invention addresses shortcomings of conventional restorative devices by providing an easy to use dental tool that has a first member and a second member with struts that adjust to fit into the proximal box, and that provides a predictably tight contact area for optimal tooth restoration. | 0 |
CROSS-REFERENCE TO RELATED PATENTS
This application is related to U.S. Pat. No. 4,143,652, granted Mar. 13, 1979, entitled "Surgical Retaining Device", and U.S. Pat. No. 4,491,435, granted Jan. 1, 1985, and entitled "Jointed Stand".
BACKGROUND OF THE INVENTION
The present invention broadly relates to a retaining device or apparatus and, more specifically, pertains to a new and improved construction of a retaining device for holding a surgical instrument.
Generally speaking, the surgical retaining or holding device of the present invention comprises a holder block which is displaceably and selectively securable along and at a guide member, such as a guide rail. The holder block is provided with clamping elements for engagement with the guide rail. Furthermore, the retaining device is provided with a support rod for holding the surgical instrument or the like. This support rod is displaceable and positionally securable with respect to the holder block.
Wound hooks are a particular example of surgical instruments which, by means of the retaining device which expediently incorporates a number of articulatedly or hingedly coupled link members, are fixed or secured to a guide rail positioned along an operating table. It should be understood that instead of using wound hooks with such retaining devices other surgical instruments, such as speculars, wound spreaders, magnifying lenses, spatulas, holders for X-ray plates or X-ray cassettes and similar instruments that the surgeon deems necessary to perform the operation or his or her work may be mounted at the retaining device.
In the aforementioned U.S. Pat. No. 4,143,652, granted Mar. 13, 1979, there have been disclosed to the art such type of surgical retaining or holding devices for which there exists an increasing demand. They have been improved to such an extent that they are capable of arresting or positionally fixing larger wound hooks with adequate retention or holding force as, for instance, is necessary when performing more complicated surgical operations such as at the thorax and during abdominal surgery in order to positionally retain the edges of the surgical wound or incision with the requisite reliability.
In the course of development work these retaining or holding devices could be further improved such that the end of the articulated or link arm which carries the surgical instrument can now be positively or immovably held in position and is incapable of positionally shifting during the surgical operation.
A serious disadvantage or shortcoming of all of the heretofore known retaining or holding devices resides in the fact that these retaining devices comprise several mutually independent and different facilities or means, each serving for performing a specific function. One such facility or means may serve to displace and arrest the retaining device along the guide rail, whereas another may serve to adjust the elevational position of the surgical instrument by allowing for appropriate sliding of the support rod in the holder block and its retention thereat. Thus, the known retaining devices have a separate arrangement in order to clamp the holder block at the guide rail and which is accomplished with the aid of a tensioning or tightening lever, whereas a second clamping arrangement serves to fixedly clamp the support rod which is provided with the surgical instrument. A hand wheel serves to actuate the second clamping arrangement. This disadvantage is a considerable one, since during an operation it is usually required to move or displace the holder block along the guide rail as well as to re-position the elevational level or location of the wound hook. Additionally, the support rod of the known retaining devices can only be turned or rotated about its own lengthwise axis and can not be rotated and fixed with respect to an axis transverse thereto. Thus, the clamped portion of the support rod of the known retaining devices always extends perpendicular with respect to the guide rail located at the operating table.
SUMMARY OF THE INVENTION
Therefore with the foregoing in mind it is a primary object of the present invention to provide a new and improved construction of a retaining or holding device, especially a surgical retaining or holding device, which does not exhibit the aforementioned drawbacks and shortcomings of the prior art constructions.
Another and more specific object of the present invention aims at providing a new and improved construction of a retaining device or the like for surgical instruments in which the displaceable securing or clamping action of the retaining device along the stationary guide rail as well as the angular and translatory positioning and securing of the support rod is substantially simplified.
Still another important object of the present invention aims at the provision of a new and improved construction of a retaining device for surgical instruments which allows for a simplified yet highly reliable selective spatial positioning of the surgical instrument in a desired site for accomplishing a surgical operation and secure retention of the thus spatially positioned surgical instrument with a minimum of effort.
Yet a still further noteworthy object of the present invention aims at the provision of a new and improved construction of a retaining device for surgical instruments which contains relatively few structural parts for accomplishing a reliable and positive spatial positioning of the surgical instrument in a desired locality for the operating surgeon and by virtue of the simplified construction of the retaining device requires fewer parts to undergo a sterilization operation so that such sterilization operation is effectively simplified.
Yet a further significant object of the present invention aims at providing a new and improved construction of a retaining or holding device for surgical instructions and which is relatively simple in construction and design, extremely economical to manufacture, highly reliable in operation, not readily subject to breakdown and malfunction and requires a minimum of maintenance and servicing.
Now in order to implement these and still further objects of the present invention which will become more readily apparent as the description proceeds the surgical retaining device of the present invention is manifested by the features that clamping or gripping means are provided for displaceably securing the support rod. These clamping or gripping means, defining a clamping mechanism, are rotatable and arrestable in position with respect to the clamping elements of the holder block. The clamping or gripping means simultaneously actuate the clamping elements of the holder block when positionally arresting the support rod.
In this manner a substantial simplification is attained, since only one single actuating or activating means is necessary for actuating the clamping or gripping means for the support rod as well as the clamping elements of the holder block. In addition, an angular displacement of the support rod is now possible in a vertical plane extending substantially perpendicular to the lengthwise axis of the holder block. A still further advantage may be seen in the small number of parts or components as compared to the prior art devices. This affords a simpler and more efficient sterilization of such parts or components without the need for dismantling the same.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein throughout the various figures of the drawings there have been generally used the same reference characters to denote the same or analogous components and wherein:
FIG. 1 shows a perspective view of a preferred embodiment of surgical instrument retaining or holding device constructed according to the present invention;
FIG. 1a illustrates on a somewhat enlarged scale and partially in cross-sectional view the retaining or holding device depicted in FIG. 1;
FIG. 2 shows a perspective view of a portion of the holder block and the clamping mechanism of the retaining or holding device depicted in FIG. 1 and illustrating the same in a dismantled and exploded view;
FIG. 3 shows in a perspective and exploded view certain details of the arrangement depicted in FIG. 2;
FIG. 4 shows a front view of the thrust sleeve of the arrangement of FIG. 2.
FIG. 5 shows a side view of part of the holder block of the retaining device; and
FIG. 6 shows a plan view of FIG. 5.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Describing now the drawings, it is to be understood that to simplify the showing thereof only enough of the structure of the surgical instrument retaining or holding device has been illustrated therein as is needed to enable one skilled in the art to readily understand the underlying principles and concepts of the present invention. Turning now specifically to FIGS. 1 and 1a of the drawings, the retaining or holding device 6 illustrated therein by way of example and not limitation will be seen to comprise a holder block 8 and a clamping or gripping mechanism 39. The holder block 8 is selectively displaceably fixed to an operating table 1 by means of a guide or clamp rail 2 which extends along a longitudinal edge or side 1' of the operating table 1. The guide rail 2 may, for example, possess a substantially T-shaped cross-section having a narrow horizontal face or surface 3 and a broader vertical face or surface 4. The guide rail 2 is fixedly connected or attached to the longitudinal edge or side 1' of the operating table 1 by means of, for example, screws 5 or equivalent fastening expedients appropriately spaced along the length of the guide rail 2.
The retaining or holding device 6 is, on the one hand, selectively displaceable along and fixable in desired position at the guide rail 2 and, on the other hand, serves to receive and positively hold an instrument support means here shown in the form of a support rod or supporting member 7. The support rod 7 can be positionally adjusted and positively locked in different elevational and angular positions in the retaining or holder device 6. The support rod 7 serves to hold an only schematically indicated surgical instrument 51 which may be constituted, for instance, by a wound hook. This support rod 7 is composed of individual mutually interlinked or articulated members of known construction.
The retaining or holder device 6 is attachable to and slidable along the guide rail 2 by means of the holder block 8 serving primarily as a guide element and position fixation element for the retaining device 6. The holder block 8 comprises as its guide element a substantially ring-shaped guide body 9 for the clamping or gripping mechanism 39 as will be discussed hereinafter. As will be recognized from FIG. 5, an inwardly projecting shoulder or collar 10 at one end of the guide body 9 forms an inner guiding bore or ring 11 in which there is guided a thrust sleeve or sleeve member 12 (FIG. 2) as will be further described hereinafter. FIG. 2 shows an end position of the thrust sleeve or sleeve member 12 in the guiding bore or ring 11. This end or terminal position of the thrust sleeve or sleeve member 12 depicted in FIG. 2 is that position where an outer shoulder 13 at one end of the thrust sleeve 12 abuts against the inwardly projecting shoulder or collar 10 of the guide body 9 during displacement of the thrust sleeve 12 in the guiding bore or ring 11. The shoulder or collar 13 thus serves to limit the stroke or displacement motion of the thrust sleeve 12.
The substantially ring-shaped or cylindrical guide body 9, at the side or end opposite the inwardly projecting shoulder 10, has merging therewith a substantially horseshoe-shaped or bifurcated body or part 14 which is advantageously integrally formed with the ring-shaped guide body 9. The horseshoe-shaped body or part 14 has an opening 15 possessing a substantially wedge-shaped projection 15' (see FIG. 5) and the ring-shaped or cylindrical guide body 9 is open-ended so that the thrust sleeve 12 can be appropriately inserted into the ring-shaped or cylindrical guide body 9. The horse-shoe shaped or bifurcated body or part 14 has an angular or cornered outer contour or configuration and is provided at a side surface 16 thereof with an inwardly extending fixed clamping jaw or jaw member 17 which, in conjunction with a pivotable clamping jaw or jaw member 18, constitute the clamping elements or means for clamping the retaining or holding device 6 to the guide rail 2. The pivotable clamping jaw 18 is pivotably journalled about a pivot pin 20 whose oppositely situated ends are mounted in two horn-like parts or protrusions 19 of the horseshoe-shaped or bifurcated body or part 14.
As shown in FIG. 3 the pivotable clamping jaw 18 comprises two mutually offset substantially parallel extensions or arms or arm members 21 and 22 which are interconnected to one another by a connection piece or body portion 23 which extends approximately perpendicular to both of these arms 21 and 22. The entire pivotable clamping jaw 18 is constructed as a massive single integral unit and is provided in the longitudinal central plane or middle thereof with a recess 24. A bore 25 extends transversely through the connecting piece or body portion 23. Furthermore, there is provided a spring or hairpin spring 26 having a spiraled body or coiled portion 27 and tensioning or biasing arms 28 and 29. The pivot pin 20 is inserted into the bore 25 and the spring 26 is located in the recess 24 such that the pivot pin 20 extends through the spiraled body or coiled portion 27 of the spring 26. Furthermore, there is provided another bore 30, terminating in the bottom portion or base of the recess 24, which serves to receive the tensioning or biasing arm 29 of the spring 26 (see FIG. 1a). The other, bent or angled biasing or tensioning arm 28 of the spring 26 contacts a bottom surface 31 of the thrust sleeve or sleeve member 12, thereby bounding or delimiting the one terminal or end position of the thrust sleeve or sleeve member 12. A clamping or set screw 32 secures the pivot pin 20 from dropping out of the bore 25. The set screw 32 is screwed into a corresponding threaded bore of one of the horn-like parts or protrusions 19 and projects into a corresponding transverse bore or borehole provided in the pivot pin 20.
By virtue of the construction as described hereinbefore there is obtained the result that the pivotable clamping jaw 18 can only be swiveled or pivoted in a clockwise direction as indicated by the arrow B in FIG. 1a against the force of the spring 26. This pivotable or swivelable motion is caused by an axial force A acting upon the extension or arm 21 of the pivotable clamping jaw 18 as will still be described more fully hereinafter. This axial force A causes the pivotable clamping jaw 18 to swivel in the clockwise direction B thereby clamping, in conjunction with the fixed clamping jaw 17, the holder block 8 of the retaining device 6 at the guide rail 2 located between these clamping jaws 17 and 18.
This cooperation or coaction of the fixed clamping jaw 17 with the pivotable clamping jaw 18 may be compared to a human hand, and the action of the pivotable clamping jaw 18 can be considered as resembling that of the thumb. Because of the inclined faces at the inside of both clamping jaws 17 and 18 the holder block 8 is pressed against the outer vertical face or surface 4 of the guide rail 2 during tensioning or tightening of the retaining device 6. Additionally, the special shape or configuration of the inner surfaces of the clamping jaws 17 and 18 enables the usage of an identical holder block 8 for all kinds of operating table guide rails 2. Such guide rails 2 may be standardized differently in different countries. It bears mentioning that the fixed clamping jaw 17 is substantially hook-shaped, enabling it to hook over or engage behind the horizontal face or surface 3 of the guide rail 2. Consequently, the retaining device 6 as a whole remains hangingly suspended on the guide rail 2 even when the pivotable clamping jaw 18 is not clampingly engaging the guide rail 2, thus avoiding an unintentional dropping of the retaining device onto the floor.
As best recognized by referring to FIGS. 1a, 2 and 4, the thrust sleeve or sleeve member 12 has a substantially cylindrical portion 33 provided with an elongated hole or opening 34. The cylindrical portion 33 further possesses a longitudinal groove 35. On a top surface 36 of the thrust sleeve or sleeve member 12 located opposite the bottom surface 31 thereof, a threaded bolt or threaded spindle 37 is axially attached to the thrust sleeve or sleeve member 12. Screwed onto the bolt 37 is a tightening nut or butterfly or wing nut 38 which serves as the actuating or activating means of the retaining device 6. A cap screw 38' or the like engaging with the threaded bolt 37 prevents a disengagement of the tightening nut 38 from the threaded bolt 37.
The thrust sleeve or sleeve member 12 coacts with a clamping or gripping mechanism 39. This clamping or gripping mechanism 39 comprises an inner or lower clamping or gripping part or head 40 and an outer or cover-like clamping or gripping head or part 41. The inner sleeve-shaped clamping or gripping head or part 40 has a cylindrical or ring-shaped portion 42 terminating in an outwardly projecting flange portion or rim 43 at one end thereof, whereas the other end is provided with an inwardly projecting flange portion or inner flange 44, the inside diameter of which corresponds to the outside diameter of the cylindrical portion 33 of the thrust sleeve or sleeve member 12. The inwardly projecting flange portion 44 is further provided with a guide pin or projection 45 which radially extends inwardly, projecting into the longitudinal groove 35 of the thrust sleeve or sleeve member 12. The inner or inside diameter of the cylindrical portion 42 corresponds to the outside diameter of the cylindrical guide body 9. With reference to FIG. 1a the inwardly projecting flange portion 44 has on its outer or right-hand side thereof two diametrically opposed and coaxially arranged recesses 46 and 47, each having a substantially semi-cylindrical or semi-circular cross-section. Together with correspondingly shaped semi-cylindrical or semi-circular recesses 48 and 49 provided in the outer or right-hand located cover-like clamping or gripping head 41 they constitute a passageway for the support rod 7. The recesses 46, 47, 48 and 49 serve as contact surfaces for gripping the support rod 7. The aforementioned passageway extends perpendicular to and intersects the lengthwise axis 60 of the holder block 8. The support rod 7, also extending through the elongated hole or opening 34 of the thrust sleeve or sleeve member 12, possesses a longitudinal groove 54 into which projects a key or pin 61 or the like which is provided at an externally toothed arresting sleeve 50 so that the latter may be displaceably but non-rotatably guided upon the support rod 7. The tooth gaps or spaces between the teeth 52 of the externally toothed arresting sleeve 50 cooperate with a pin 53 provided in the outer or cover-like clamping or gripping head or part 41 for adjustingly fixing the rotational position of the support rod 7.
In operation, as shown in FIG. 1, the holder block 8 is positioned onto the guide rail 2 such that this guide rail 2 is located between the fixed clamping jaw or jaw member 17 and the pivotable clamping jaw or jaw member 18. The support rod 7, directly or indirectly supporting the surgical instrument 51, extends through the passageway formed by the semi-circular or semi-cylindrical recesses 46, 47, 48 and 49 of the clamping or gripping mechanism 39 and through the elongated hole or opening 34 of the thrust sleeve or sleeve member 12. This thrust sleeve or sleeve member 12 is subjected to the action or force of the bent tensioning arm 28 of the spring or spring member 26. The outwardly projecting flange portion or rim 43 of the inner gripping head 40 is in abutting relationship with the extension or arm 21 of the pivotable clamping jaw 18. This is the open or unclamped position of the retaining device 6, i.e. of the holder block 8 as well as of the clamping or gripping mechanism 39, enabling the holder block 8 to slide or move along the guide rail 2 while the support rod 7 can elevationally slide in the clamping or gripping mechanism 39, and specifically within the inner or lower clamping part or head 40 and the outer cover-like clamping part or head 41. Both clamping or gripping heads or parts 40 and 41 bear against the inclined protruding arm 21 of the pivotable clamping jaw 18. This pivotable clamping jaw 18 is retained in its open position under the action of the spring 26. The clamping or gripping mechanism 39 together with the support rod 7 can be rotated or angularly displaced around or with respect to the ring-shaped guide body 9 such that the support rod 7 can be selectively angularly displaced in the direction of the double-headed arrow C in FIG. 1 within a vertical plane parallel to the guide rail 2 and substantially perpendicular to the threaded bolt or screw 37.
When the butterfly or wing nut 38 is now tightened, the inner or left-hand clamping part or gripping head 40 and the outer or right-hand clamping part or gripping head 41 shown in FIG. 1a, which are guided to be non-rotatable, are pressed against one another thus fixedly gripping and retaining the support rod 7 by means of their semi-circular recesses or bores 46, 47, 48 and 49. Simultaneously, both clamping parts or gripping heads 40 and 41 are conjointly slidingly moved along the thrust sleeve or sleeve member 12. The movement of the clamping parts or gripping heads 40 and 41 is rendered possible by virtue of the provision of the elongate hole or opening 34. This movement causes the flange portion or rim 43 of the inner clamping part or gripping head 40 to move in the direction of the arrow A (FIG. 1a), thereby exerting a force upon the extension or arm 21 which results in a rotational clockwise movement in the direction of the arrow B against the action of the spring 26. The pivoting motion of this pivotable clamping jaw 18 in relation to the fixed clamping jaw 17 causes the retaining or holder device 6 to be firmly clamped onto the guide rail 2. In this manner the entire retaining device 6 is fixed in a position determined by the user. Only the butterfly or wing nut 38 needs to be tighted in order to simultaneously grip and fix the support rod 7 in its desired position and to clamp the holder block 8 onto the guide rail 2. Loosening the wing nut 38 would result in simultaneously loosening or releasing these parts.
Loosening or release of the retaining device 6 is accomplished by turning the wing nut 38 in the opposite direction causing the pivotable clamping jaw 18 to swivel or pivot in the counterclockwise direction under the action of the spring 26. Conjointly therewith the counterclockwise pivotal or swivel movement of the arm 21 of the pivotable clamping jaw 18 causes the clamping parts or gripping heads 40 and 41 to be pushed outwardly or to the right in FIG. 1a along the cylindrical portion 33 of the thrust sleeve or sleeve member 12. In order to facilitate this outward movement the flange portion or rim 43 may be rounded. In continuing the loosening or release of the wing nut 38 the clamping parts or gripping heads 40 and 41 mutually separate, i.e. they are no longer tightly pressed together so that the support rod 7 is released and free to move in relation to the holder block 8.
Finally, it is deemed worthwhile mentioning that without in any way impeding the manipulation of the retaining device 6 a sterilized hood or the like may be clamped by the pivotable clamping jaw 18. By simply turning the wing nut 38 the surgical instrument can be selectively positioned in any desired position.
The entire retaining device can be sterilized without the need to disassemble the same in a simple manner in an autoclave or other appropriate sterilizing facility or piece of equipment, particularly since all parts or components are advantageously formed of stainless steel.
While there are shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims. | The retaining device comprises a holder block operatively associated with a clamping mechanism. The retaining device is displaceably and selectively securable along a guide rail by means of the holder block. A surgical instrument is carried by a support rod which is axially movable up and down and positionally securable in the clamping mechanism. The arresting of the holder block at the guide rail and the support rod in the clamping mechanism is effected by a tensioning or tightening member, such as a tensioning nut or spider acting upon both the holder block and the support rod. | 0 |
BACKGROUND OF THE INVENTION
The present invention relates to a combination hydraulic and mechanical steering system, and more particularly to such a steering system for a vehicle having multiple independently steerable wheel sets, and most particularly, to a cam assembly for translating the motion of an operator manipulated steering wheel into linear motion for controlling a servomechanism that angularly positions each of the wheel sets in a plurality of different steering modes.
Vehicles used for transporting large loads over relatively small distances, such as from a fabricating section of a shipyard to the assembly section of a shipyard, normally have a plurality of wheel sets supporting a load-bearing platform. Since the loads imposed upon such transporting vehicles are relatively large, the vehicles require a large number of wheels to distribute the load to the ground. The wheel sets are usually differentially steerable to provide adequate maneuvering capability and to eliminate tire scuffing when the vehicle is turned. Prior art transporting vehicles employ steerable wheel sets that provide the capability to turn in a circle whose center is centrally and laterally offset relative to the longitudinal dimension of the transporting vehicle. This mode of steering is normally referred to as the conventional mode. Since the plurality of wheel sets are distributed longitudinally and laterally under the load platform, each of the wheel sets must have a different turning radius relative to the other so that the turning circles for the wheel sets of the entire vehicle will have a common center. One prior art device for differentially steering the wheel sets of a transporting vehicle employs only mechanical linkages between the various wheel sets. The wheel sets are interconnected by a plurality of tie rods of varying lengths coupled to radius arms affixed to the wheel sets, providing the capability to differentially turn each of the independent wheel sets so that for a given steering command, the turning radius of each of the wheel sets coincides with the common center of the desired turning circle.
In many applications it is desirable to be able to change from the conventional steering mode, wherein the transporting vehicle turns about a common center, to what is known as oblique or "crab" steering, wherein each of the wheel sets is turned to an identical angular position so that the entire vehicle can move transversely to its normally longitudinal direction of travel. With the conventional mechanical linkage used in the prior art, it is impossible to change from the conventional mode of steering to the crab mode of steering without a complete changeover of the mechanical tie rod and turning arm linkages. Because replacement of the mechanical steering linkage in this manner is not economically feasible, present transporting vehicles employing a mechanical steering system are offered with only the conventional steering mode. Some vehicles with mechanical steering linkage can be modified to provide oblique steering; however, all wheels are steered at different angles resulting in unacceptable tire scuffing and mechanical stress on the steering system.
In order to provide the capability of changing from a conventional steering mode to a crab steering mode, each of the wheel sets on the transporting vehicle must have the capability of being steered independently while different means for programming the turning angle of each individual wheel set for a given mode of steering must be provided. In U.S. Pat. No. 3,572,458, issued to Hans Tax, a dual mode steering system for individually steering a plurality of wheel sets is disclosed. This dual mode steering system provides the capability of changing between a conventional steering mode and a crab steering mode, as well as other capabilities. In this system a steering wheel is employed to rotate a shaft carrying a set of cams. Each cam corresponds to a given wheel set on a vehicle and has a follower cam that is coupled to an arm of a potentiometer. A variable voltage, depending upon the position of the arm connected to the cam follower, is transmitted through an electronic control circuit to a servomotor, which in turn drives a rotatable shaft on which a wheel is mounted. Feedback from the shaft to the electronic control circuit is provided via a rotational to rectilinear motion transducer, which in turn drives an arm of a second potentiometer. The variable voltage provided to the electronic control circuit from the second potentiometer is conditioned by the circuit to stop the servomotor at the position predetermined by the position of the arm of the first potentiometer. For the conventional steering mode, a first set of cams is employed that have varying cam surfaces, which are related to the desired turn radius for a given wheel set. A second set of cams, each of which is identical to the other, can be interchanged with the first set of cams to angularly position each of the wheel sets to provide the crab mode of steering. Although the system disclosed by Tax employs a workable means by which the steering mode can be changed, it has the drawback of being electronically controlled. The environment in which many transporting vehicles employing multiple wheel sets are used is not conducive to longevity of the electronic circuitry. For example, a transporting vehicle used in a shipyard is constantly subjected to an influx of dirt and saline water that cause corrosion, which results in maladjustment in or inoperability of the electronic steering circuitry. Thus such systems require constant maintenance and because of their electronic complexity require special repair skills not normally found in vehicle maintenance personnel. Moreover, although the system disclosed by Tax employs a means by which the mode of steering can be changed, that system does not provide a means by which the mode of steering can be quickly changed by an operator from his control station.
It is therefore a broad object of the present invention to provide a steering system for a transporting vehicle having a plurality of steerable wheel sets: that provides the capability to independently steer each of the wheel sets according to a predetermined program; that provides the capability to change quickly among several steering modes, including the conventional steering mode, the crab steering mode, and other modes; that eliminates electronics from the steering control system; that is relatively easy to maintain, that can withstand the adverse environmental conditions, that can be maintained and repaired by one of ordinary skill in vehicle maintenance; that provides a plurality of cam sets, each set corresponding to a given steering mode; and that employs protective devices by which injury to the cam sets or the actuating mechanism can be prevented should part of the overall mechanism become inoperative.
SUMMARY OF THE INVENTION
In accordance with the foregoing objects, and other objects that will become apparent to one of ordinary skill in the art upon reading the following specification, the present invention provides an improvement in a multiple mode steering system for a wheeled vehicle. The steering system includes a vehicle frame, a steerable wheel supporting member mounted for rotation about an axis on the frame, a reversible motor means for varying the angular position of the steerable member relative to the frame, and a servomechanism operably coupled to the motor means and having a control member for controlling the motor means. The improvement comprises a first cam and a second cam, each of which has a predetermined shape and rotational axis, interconnected by a coupling means. The coupling means is mounted to rotate the cams about their respective rotational axes. An operator controlled steering means is operably connected to rotate the cams responsive to operator command. A follower means contacts the first cam and converts the rotational movement of the first cam into linear movement in the follower. The follower means is operably coupled to actuate the control member of the servomechanism to control the motor means, and in turn steer the wheel supporting member. Means is provided for relatively axially shifting the first and second cams and the follower means so that the follower means can be disengaged from the first cam and shifted to contact the second cam, thereby enabling it to convert the rotary movement of the second cam into linear movement to actuate the control member of the servomechanism. The invention further provides a unique mounting system and shift mechanism for a plurality of cam sets mounted on a single rotatable shaft. The shaft is axially shiftable by a fluid motor to at least three different positions. The cam sets are so arranged on the shaft relative to a plurality of followers so that the followers simultaneously disengage from a first set of cams and re-engage a second set of cams after the cam mounting shaft has been shifted. In addition, the present invention provides a combination steering system for a transporting vehicle that allows each of the wheel sets to be independently steered and which enables the steering mode of the transporting vehicle to be quickly changed from a conventional steering mode, to a crab steering mode, to an altered conventional steering mode wherein two transporting vehicles are interconnected in end-to-end relationship, and a fourth steering mode that allows the rear wheels of the vehicle to track or follow the remaining wheels, i.e. the rear wheels of the vehicle are held in a forwardly directed steering position as the remaining wheels are angularly positioned to turn the forward portion of the transporting vehicle.
BRIEF DESCRIPTION OF THE DRAWINGS
A better understanding of the present invention can be derived by reading the ensuing specification in conjunction with the accompanying drawings wherein:
FIGS. 1 and 2 are plan and side elevation views of a transporter employing the hydraulic steering system according to the present invention;
FIG. 3 is a schematic representation of the steering system showing various operator locations, a steerable wheel set, a control cable for controlling the hydraulic power means, and a means for positioning the control cable responsive to the operator's command from the steering location;
FIGS. 4, 5, 6 and 7 are schematic plan views of the wheel positions of the transporter as controlled by the steering system of the present invention in the conventional steering mode, the crab steering mode, the end-to-end coupled conventional steering mode, and the tracking steering mode, respectively;
FIG. 8 is an elevation view in partial cross section of the cam housing and programmed cam assembly of the present invention;
FIG. 9 is a cross-sectional view of the cam housing and assembly of FIG. 8 taken along section line 9--9;
FIGS. 10, 11 and 12 are plan views, in partial cross section and partially broken away, of the shifting mechanism associated with the cam assembly illustrated in FIGS. 8 and 9 showing, respectively, first, second and third positions of the shift mechanism;
FIG. 13 is an enlarged cross-sectional view similar to that of FIG. 9 showing the construction of the cam follower and the follower lifting mechanism as operated when the cam assembly is being shifted;
FIG. 14 is a typical cam employed with the cam assembly of the present invention; and
FIGS. 15a, 15b, 15c, 15d, and 15e are schematic views of the wheel positions as related to the typical cam illustrated in FIG. 14.
DESCRIPTION OF PREFERRED EMBODIMENT
Referring first to FIGS. 1 and 2 a load transporting vehicle or transporter, generally designated 10, has operator's cabs 12 and 14 mounted at the longitudinal ends of a platform supporting, frame assembly 16. The platform 18 is broken away in the plan view to expose the frame assembly 16 and the location of the multiple wheel sets 20, which support the transporter for traverse over the ground. Each of the wheel sets comprises a turntable 22 to which is affixed a downwardly extending wheel supporting arm 24. A wheel suspension arm 26 is pivotally attached at its one end to the bottom of the downwardly extending wheel supporting arm 24. A dual set of wheels 28 is rotatably mounted at the other end of the trailing arm 26. Each of the turntables 22 is mounted for rotation relative to the frame 16 about a vertically oriented axis, i.e., an axis perpendicular to or transverse to the rotational axis of the wheels 28. A hydraulic piston and cylinder assembly having an integral shock absorber (not shown) is interconnected between the trailing arm 26 and the main wheel supporting arm 24 or the turntable 22 to fix the trailing arm in a predetermined position. By supplying fluid to or exhausting fluid from this piston and cylinder assembly, the trailing arm 26 can be swung about its pivotal connection to the main support arm 24 to raise and lower the platform of the transporter relative to the ground. Thus, the transporter when in its lowered position can be driven under a load statically supported above the ground and can then be raised to elevate the load above its static support so that the load can be transported to a desired location. In this embodiment, ten wheel sets are employed, with three transversely or laterally spaced wheel sets being positioned adjacent each of the longitudinal ends of the frame 16 and two wheel sets being spaced longitudinally inwardly from the three endmost wheel sets. It is to be understood by one of ordinary skill in the art that any number of wheel sets, preferably from four to 10 or more can be used, dependent upon the physical size of the transporter and the gross vehicle weight for which it is designed.
Referring now to FIG. 3 in conjunction with FIGS. 1 and 2, the steering system for the transporter includes operator controlled steering stations 34 and 36 in each of the operator cabs 12 and 14, which can individually control a cam assembly 38 enclosed by a housing 39 shown in dotted outline, an actuating cable 40, which in turn actuates a hydraulic control valve 42 for the hydraulic power means 44 that rotates the turntable of the wheel set 20. Each of the steering stations 34 and 36 comprises a steering wheel 34a coupled to a conventional hydraulic power steering servomechanism 34b, which is coupled to a servomotor 46 in the cam assembly 38 via hydraulic conduits 48. When the steering wheel is turned, a shaft 50, coupled to the hydraulic servomotor 46, is rotated a predetermined amount dependent upon the operator's angular movement of the steering wheel. Likewise, the steering station 36 is coupled via hydraulic conduits 52 to the hydraulic servomotor 46. In addition, a third set of hydraulic lines 54 are provided so that a third steering station 56 on a second transporter can be coupled to the servomotor 46 in the event that more than two transporters are coupled in end to end relationship to carry loads larger than that for which a single transporter is designed. A plurality of cams 58, 60, 62 and 64, each of which has a cam surface of predetermined shape, is affixed to the shaft 50 in the cam assembly housing 39. Four cams are provided for each of the wheel sets on the transporter. Only one sub-set is shown in FIG. 3; however, it is to be understood that a sub-set of four cams is provided for each of the ten steerable wheel sets in the transporting vehicle shown in FIGS. 1 and 2. Cam 58 is a corresponding one of an interrelated set of cams that moves the cable 40 to actuate the control valve 42 to correctly position the turntable 40 according to a first desired mode of steering, for example, the conventional steering mode. The second cam 60 is a corresponding one of a second set of cams that actuates the control valve 42 according to a second mode of steering, for example the crab steering mode. Additional modes of steering are provided by third and fourth sets of cams of which cam 62 and 64 are respectively corresponding ones for the wheel set 20 shown in FIG. 3. The third mode of steering can be one that is provided for steering an end-to-end coupling of two transporters in a conventional mode. The fourth mode of steering can be provided to steer the transporter in a tracking mode, i.e, a mode wherein the rear wheels are not repositioned angularly when the wheels forward of the rear wheels are steered, thus requiring the rear wheels to track or follow the turning wheels to prevent the rear of the vehicle from swinging outwardly as the vehicle turns. In the tracking mode of steering the center of the turning circle for all wheel sets resides on a transverse line through the axles of the rear wheel sets.
As shown in FIG. 3, a cam follower 66 is positioned to contact and follow the cam surface of cam 58. The follower 66 is attached to the cable of the sheathed cable assembly 40, commonly known as a boden cable. One end of the sheath of the boden cable 40 is affixed to the cam assembly housing 39 while the other end of the cable travels to its corresponding wheel assembly where the other end of the sheath is fixed relative to the turntable as will be described in greater detail below. The cam follower 66 is coupled to the cable that reciprocates within the sheath. The end of the cable opposite that attached to the follower 66 is affixed to the control member, such as the control spool, within the control valve 42. Thus, as the steering wheel in a given one of the steering stations 34, 36 or 56 is rotated, the shaft 50 is rotated via the hydraulic servomotor 46 in turn rotating the cam 58. As the cam 58 rotates the movement of the follower 66 will reposition the cable relative to its sheath and in turn actuate the control member of the hydraulic control valve 42. Thus a given setting of the steering wheel as manipulated by an operator will cause the end of the cable coupled to the control member of the hydraulic control valve 42 to move to a new position corresponding to the degree of rotation of the cam 58. As disclosed in the copending application to Weyer filed on an even date herewith and expressly incorporated herein by reference, Ser. No. 588,422, filed June 19, 1975 the entire assembly of four sets of cams is mounted on a single shaft 50 that can be axially shifted. In this manner the mode of steering can quickly be changed at the operator's command and by relatively repositioning the follower 66 coupled to the cable 40 over the appropriate cam for each wheel set.
Referring now to FIG. 4, the transporter 10 is shown with its wheel sets 20 being steered in the conventional steering mode. In the conventional steering mode, the rotational axes of each of the wheel sets intersect at a common center. As the transporter is steered in a smaller turning circle, the center moves closer to the vehicle. The common center 70 is representative of the minimum turning circle of the transporter in the conventional steering mode. In the conventional steering mode, each of the wheel sets is positioned at a different angle for a given turning circle. The angular positioning of each of the wheel sets is programmed into a cam set having an appropriately shaped cam for each of the wheel sets for actuating the hydraulic servomechanism to position the respective wheel set.
FIG. 5 schematically illustrates the crab or oblique steering mode in which each of the wheel sets 20 is rotated to the same relative angle in response to a steering command by the operator. In this manner, the transporter 10 can move obliquely from its normally longitudinal direction of travel. The cam set for the crab mode of steering can be so configured as to allow the transporter to move perpendicularly to its normal longitudinal direction of travel as well as all in directions intermediate the forward and perpendicular directions. As shown in FIG. 5, each of the wheel sets have been rotated through 45° so that the orientation of the transporter itself remains parallel to its original direction of travel, but can move obliquely in a direction 45° from its longitudinal direction of travel.
FIG. 6 schematically illustrates a first transporter 10 and a second transporter 10' connected in end-to-end relationship by suitable coupling means 72. As coupled, the transporters can be controlled from either a cab 12 on the transporter 10 or a cab 14' on the transporter 10'. A third cam set can be provided in the cam assembly of the present invention so that the transporters 10 and 10' can be steered in a conventional manner about a minimum turning circle having its center located at point 74, which lies on a line perpendicular to the longitudinal direction of travel and centered between the coupled ends of the transporters 10 and 10'. As can be seen, the rotational axes of the wheels of each of the wheel sets pass through the center point 74, defining the minimum turning radius of the coupled transporters. It is to be understood that in the conventional steering modes in FIGS. 4 and 6 that a greater turning radius is achieved by moving the center of the common turning circle transversely outwardly away from the side of the transporters. When the transporters are moving straight ahead, i.e., in a longitudinal direction, the rotational axes of all the wheel sets are parallel and the center of the turning circle lies at infinity.
FIG. 7 is a schematic illustration of the transporter 10 in what is referred to as the tracking mode of steering. In this mode of steering, the center of the turning circle when at its minimum is located at point 76 along the longitudinal side of the transporter. The center of the turning circle in the tracking mode lies on the coincident rotational axes of the wheels on the rear wheel sets 20a, 20b and 20c. The remaining wheel sets 20 are controlled by a fourth cam set provided in the cam assembly so that the rotational axes of the wheels of each wheel set intersect at the common center lying along the rear wheel rotational axes. In this manner, the transporter can be steered in a manner similar to that of an ordinary vehicle wherein the rear wheel sets do not rotate responsive to an operator command but only the wheel sets forwardly of the rear wheel sets. In this manner, the rear portion of the transporter 10 does not swing outwardly when the vehicle is turned, but the forward end of the vehicle turns at a greater rate than in the conventional steering mode.
The cam group or subset illustrated in FIG. 3, including cams 58, 60, 62 and 64, are representative of the cam subset for one of the rear wheel sets 20a, 20b or 20c of the transporter 10. As illustrated, the cam 58 is one cam of the set for the conventional steering mode to steer the vehicle as shown in FIG. 4. The cam 60 is one cam of the crab steering set to steer the transporter 10 in the manner illustrated in FIG. 5. Likewise, the cam 62 is one cam of the end-to-end coupled, conventional steering mode set for steering the end-to-end coupled transporters 10 and 10' in a manner similar to that illustrated in FIG. 6. The cam 64 is a corresponding one of the cam set for steering the transporter 10 in the tracking mode of steering as illustrated in FIG. 7.
Referring now to FIGS. 8 and 9 illustrating the preferred embodiment of the cam assembly of the present invention, the cam assembly is the mechanism into which the angular positioning of each of the wheel sets is programmed for a given steering mode. The cam assembly, generally designated 38, resides in a structure serving both as a frame and a housing. The housing consists of a lower box-like portion 39a and an upper box-like portion 39b. The cam shaft 50 is mounted in suitable bearings 80 and 82 affixed to the lateral end walls of the lower portion 39a of the housing. The shaft 50 extends longitudinally through the housing 39 and protrudes through the bearings 80 and 82 beyond each of the end walls 84 and 86. A steering servomotor 46 is mounted on a bracket 88 that is fixed to the one end wall 86 and extends longitudinally outwardly therefrom. The rotary drive shaft 90 of the steering servomotor 46 is coupled to the shaft 50 by a rotary coupling 92. In this embodiment, the steering servomotor 46 is a rotary hydraulic motor coupled to the power steering assembly 34 (shown in FIG. 3) via conduits 48.
Still referring to FIGS. 8 and 9, a plurality of cams 58, 60 and 62 are affixed to the shaft 50 so that their rotational axes are coincident with the rotational axis of the shaft 50. A first set of cams 58a through 58j, for example, for a conventional steering mode, are mounted in spaced relationship along the shaft. A second set of cams 60a through 60j and a third set of cams 62a through 62j are interleaved between each other and the first set of cams 58a through 58j so that a first grouping or subset comprises cams 58a, 60a and 62a. A second grouping of cams comprises cams 58b, 60b and 62b on down to a final grouping of cams comprising 58j, 60j and 62j. Each subset or group of cams corresponds to a given wheel set.
A shifting mechanism, generally designated 94, is coupled to the end of the shaft 50 opposite to the steering servomotor 46. The shifting mechanism 94 is mounted on a longitudinally outwardly extending bracket 96 affixed to the end wall 84 of the lower portion 39a of the cam assembly housing. The shift mechanism 94, which will be described in greater detail below, can axially shift and position the shaft 50 in any one of three positions, corresponding to first, second and third steering modes. It will be understood by one of ordinary skill in the art that two or more steering modes can be provided by increasing or decreasing the number of cam sets, and correspondingly the number of cams in each subset from the three cams as illustrated in the preferred embodiment and by providing the shifting mechanism 94 with the capability to shift the shaft to an increased number of axial positions corresponding to the number of cams in each subset.
A guideblock 98 is mounted in an aperture provided in the top wall 100 of the lower portion 93a of the cam assembly housing. The guideblock 98 carries a plurality of bores, equaling the number of cam subsets. The bores are parallel to each other and aligned radially relative to the shaft 50 and to the cams 58, 60 and 62. Cam followers generally designated 102, are mounted for reciprocating movement in each of the bores. The cam followers are respectively positioned over the location of each of the cam subsets 58, 60 and 62. For example, the cam follower 102a is positioned relative to the cam subset comprising cams 58a, 60a and 62a so that when the shift mechanism 94 positions the shaft 50 in a first position, the follower will reside on and follow the cam surface of cam 58a. When the shift mechanism 94 shifts the shaft 50 to its second position axially offset from its first position, the cam follower 102a will engage and follow the cam surface of cam 60a as illustrated. Likewise, when the shift mechanism shifts the shaft 50 to its third position axially offset from the first and second positions, the cam follower 102a will disengage from the surface of cam 60a and be re-engaged upon the cam surface of cam 62a. Each of the cam followers 102a through 102j are respectively coupled to a cable 40 mounted for linear movement within its corresponding sheath. Such cables are commonly available and conventionally referred to as boden cables. Each of the boden cables 40a through 40j has its respective sheath affixed to the top wall 104 of the upper portion 39b of the housing 39. The upper portion 39b of the housing is mounted on the top wall 100 of the lower portion 39a of the housing and encloses the upper portion of each of the followers 102 as well as the terminus of the boden cables. Each of the cables 40 are coupled by appropriate connectors 106 to the upper ends of the followers 102 that project upwardly from the top of the guideblock 98. Thus, as the shaft 50 is rotated via the steering servomotor 46, each of the followers 102 will rest upon and follow the surface of its respective cam. As the shaft 50 is rotated, the followers 102 will reciprocate within their respective bores in the guide block 98, thus providing linear bidirectional movement to the cable portion of the boden cables 40, which in turn actuates the hydraulic control valve 42 of its corresponding wheel set.
As best seen by referring to FIGS. 9 and 13, a lift bar 110 is affixed to the lower portion of each one of the followers 102. The lift bar 110 is oriented transversely relative to the reciprocation direction of the followers 102 as well as being oriented transversely to the rotational axis of the cam shaft 50. The lift bar 110 extends in a mutually opposite direction from the followers 102 and terminates at each end at a location within the lower portion 39a of the housing and at a location spaced outwardly from the periphery of the cams 58 through 62. Springs 112 are coupled to the ends of the bar 110 and are strung in tension downwardly from the ends of the bar 110 and affixed to the floor 114 of the lower portion 39a of the housing. In this manner, the follower 102 is biased in a downward direction so that it is held securely on the peripheral cam surface of the particular cam that it is contacting. Thus, as the cam shaft 50 is rotated and the radius of a given cam upon which one of the followers 102 resides decreases, the cam follower will be biased downwardly so as to accurately follow the surface of the cam. Likewise, the springs 112 have sufficient elasticity so that as the radius of a given cam increases, the cam follower 102 will reciprocate in its bore in the guide block 98 upwardly against the tension of the springs 112.
Referring now to FIGS. 10, 11 and 12, the preferred embodiment of the shift mechanism 94 comprises a pair of fluid actuated, linearly acting piston and cylinder assemblies 120 and 122 coupled to an extension 50a of the cam shaft 50 by a link 124. The cam shaft extension 50a is axially aligned with the cam shaft 50. Each of the piston and cylinder assemblies 120 and 122 are positioned on mutually opposite sides of the shaft extension 50a and are pivotally attached respectively to yokes 126 and 128, which are in turn affixed to and extend outwardly from the side wall 84 of the lower portion of the cam assembly housing. A cam shaft extension arm 50a is affixed to the cam shaft 50 by conventional means (not shown) that allows the cam shaft 50 to rotate relative to the extension 50a but which fixes the cam shaft extension 50a to the cam shaft so that no relative axial movement can occur between the two. The piston arm 120a of the piston and cylinder assembly 120 is pivotally attached by a pin 130 to one end of the link 124. The piston arm 122a of the piston and cylinder assembly 122 is pivotally attached via pin 132 to the opposite end of the link 124. The link in turn is pivotally attached at a location intermediate the pivot pins 130 and 132 to the cam shaft extension 50a via pin 134. The pivotal axes of all of the connections to the link 124 are mutually parallel. The pivotal axis of the connection between the cam shaft extension 50a and link 124 is oriented diametrically to the longitudinal axis of the cam shaft extension 50a and diametrically to the axis of rotation of the cam shaft 50.
Each of the piston and cylinder assemblies 120 and 122 can be of the two position, single acting, pneumatic or hydraulic type wherein the piston and corresponding piston rod are biased in a first direction by means of an internal spring (not shown). Upon application of fluid pressure within the cylinder, the piston and corresponding piston arm moves rectilinearly to its maximum extension. Upon relief of pressure within the cylinder the internal spring returns the piston and corresponding piston arm to its first position.
In operation, the piston and cylinder assemblies are both biased toward their respective first positions as shown in FIG. 10. In this embodiment the piston arms 122a and 120a are biased outwardly from the housing. The corresponding cam followers 102 reside over and contact the surfaces of cam set 58 corresponding, for example, to the conventional steering mode. When fluid pressure is applied to one of the cylinders via an operator control (not shown) one of the piston arms, for example piston arm 122 of assembly 122, will retract to its maximum extent causing the link 124 to angulate relative to the extension 50a and move inwardly toward the cam assembly. This movement of the link 124 will cause a corresponding axial displacement of the cam shaft extension 50a and consequently of the cam shaft 50. In this manner, the followers are positioned over the second set of cams 60 corresponding to the crab steering mode (as specifically illustrated in FIG. 11). To shift the cam assembly so that the followers 102 reside over and contact the surface of the third set of cams 62, fluid pressure is applied to the second piston and cylinder assembly 120 causing the piston arm 120a to retract against its internal biasing spring. The other end of the link 124 is thus moved toward the cam assembly housing (as shown in FIG. 12) and is realigned in an orientation parallel to its original orientation. In this manner, the movement of the link 124 is translated to the cam shaft extension 50a, causing the cam shaft 50 to again axially shift so that the set of cams 62, for example corresponding to the end-to-end coupled steering mode, resides under the followers 102. When it is desired to return to the first steering mode, the fluid pressure is relieved from the cylinders, causing the link 124 to reassume its original position and to axially shift the cam shaft 50 so that the followers reside over the cam set 58.
As best seen in FIG. 9, each of the cams of all of the cam sets has a common and equal radius that is related to the straight ahead positioning of each of the wheel sets for travel in the straight ahead longitudinal direction. This is the position at which the cams are shown in FIG. 9. On either side of this position the cam surfaces begin to vary relative to one another. It is most desirable that shifting between modes of steering, i.e., shifting the cam sets so that a different set will reside under the followers 102, be accomplished only when the cams are angularly positioned so that all of the followers are at an equal height, i.e., linearly aligned parallel to the rotational axis of the cam shaft 50. If, however, the cam shaft 50 is axially shifted at this location the biasing force of the springs 112 will cause the cam follower to move downwardly into the space between adjacent cams as the cam shaft is shifted. This would result in an undesirable lateral force being placed on the cams as the next adjacent cam bears against it. Moreover, the operator would have to manually reset the followers on the cams upon shifting. To solve this problem, a means for lifting the cam followers a small distance above the respective cam surfaces is provided.
Referring to FIG. 13 in conjunction with FIGS. 8 and 9, each of the followers 102 is provided with a transversely extending arm 148 attached to its upper end. The transversally extending arm terminates short of the sidewall of the upper portion 39b of the housing. A pair of fluid actuated piston and cylinder assemblies, generally designated 140 and 142, are mounted on the inner surface of the end walls of the lower portion 39a of the housing 39. The assemblies are oriented so that the respective piston arms 140a and 140b are mounted for reciprocating movement in a direction generally parallel to the reciprocation direction of the followers 102. A bar 144, oriented generally parallel to the rotational axis of the cam shaft 50 and transversely to the direction of reciprocation of the followers, is connected between the upper ends of the piston arms 140a and 140b. The travel of the piston arms 140a and 140b is chosen such that at the lower extent of their travel the bar 144 resides below the bottom surface of the transversely extending arms 148 on the upper ends of each of the cam followers. The upper limit of travel of the piston arms 140a and 140b is chosen such that the bar 144 is raised upon simultaneous actuation of the assemblies 140 and 142 a sufficient distance to contact the lower edge of the transverse arms 148 and to lift the arms 148 and consequently the followers 102 a very small distance, on the order of an eighth of an inch or less. In this manner, the bottom end of the followers normally residing on the cams is lifted above the cam surface so that the cam shaft 50 and the corresponding cams can be axially shifted without interference from the cam followers. The piston and cylinder assemblies 140 and 142 can be of conventional hydraulic or pneumatic type. Preferably they are of the single acting type that are biased in a downward direction by an internal spring or other biasing means (not shown). In this manner, the piston arms 140a and 140b will normally reside at the bottom end of their respective strokes, thus preventing interference between the lift arm 144 and the transverse arms 148 on the cam followers as the followers 102 ride upon the respective cam surfaces.
The cam followers 102 are also provided with means for preventing damage to the cams and/or to the boden cable and corresponding control valves. Referring to FIGS. 8, 9 and 13 each of the cam followers comprises a tube 150 in which is reciprocally mounted a bar or rod 152. The tube 150 contains a diametrically oriented and longitudinally extending slot 154 that terminates short of the bottom end of the tube. A spring 156 is mounted in the tube 150 and bears against the closed upper end of the tube 150 and against the top end of the rod 152. A pin inserted through a diametrical bore in the rod 152 and through the slot 154 in the tube 150 retains the rod 152 within the tube. The lower end of the rod 152 carries a cam following wheel 156 mounted for rotation on the lower end of the rod 152. If the control valve or boden cable or other mechanism is damaged to an extent that the tube 150 cannot move in an upward direction when the radius of a cam increases, the rod 152 can move upwardly within the tube 150 against the compression of spring 156. In this manner, further damage to the remaining portion of the mechanism is prevented.
As can be seen by reference to the aforementioned copending patent application, expressly incorporated herein by reference, and by reference to FIG. 3 hereof, the rotational drive mechanism of the present invention for steering the individual wheel sets is responsive to linear movement of a boden cable or other linear actuating device that is coupled between the cam assembly and a control member of a servomechanism for angularly positioning a given wheel set. As disclosed in the aforementioned patent application, the servomechanism can be a hydraulic control valve incorporating a unique feedback mechanism for stopping the rotation of the wheel set at a location responsive to the position of the actuating end of the boden cable or other linear actuator relative to the servomechanism. In the preferred embodiment of the servomechanism, the control member, the control spool of the hydraulic valve, is responsive to linear movement. The feedback to the control spool is also linear in nature. Thus, for a given linear movement of the boden cable, a corresponding angular repositioning of the wheel set will occur. That is, if the actuating member moves 1/4 of 1 inch in a given direction from a centered location, the wheel set will rotate through a predetermined angle in a first rotational direction. The wheel set will likewise move through the same angle in the opposite direction when the actuating member is moved through the same distance in an opposite direction.
Referring now to FIG. 14, a typical cam 58 is incorporated in the cam assembly has a central rotational axis corresponding to the rotational axis of the shaft 50 to which the cam is affixed. The cam 58 has an ever-increasing radius from a point 168 of minimum radius in a counterclockwise direction to a point 176 of maximum radius. Both points 168 and 176 on the surface of the cam lie on a common radial line directed outwardly from the rotational axis of the cam. One of ordinary skill in the art will recognize that for a given turning circle for the transporter, each of the wheel sets must be rotated through a predetermined angle so that the turning circles of each of the wheel sets lies at a common center (for the conventional mode of steering). Thus, each corresponding cam in the conventional steering mode set must be designed so as to move the boden cable 102 through a predetermined distance to actuate the servomechanism to angularly position the corresponding wheel set. Dependent upon the chosen steering mode, each cam in a set corresponding to a given steering mode, will have a predetermined surface curvature. For example, all the cams of the cam set designed for the crab mode of steering will be identical. For the conventional mode of steering both for a single transporter and for end-to-end coupled transporters, each of the cams in the set will be different from each of the other cams. For a tracking steering mode as described above the tracking wheels (the rear wheels) will all have cams identical to each other and in the case of the tracking mode will be circular, as it is not desired for the rear wheels to turn in the tracking mode. However, all wheels forwardly of the tracking wheels will have turning angles programmed by cams each of which have a different cam surface shape.
Again referring to FIG. 14 a typical simplified cam is illustrated wherein, the radius r 1 of the cam lying on a common diameter with the minimum and maximum radius locations but on the diametric side of the rotational axis is chosen as the centering point for the wheel set 20 shown in FIG. 15a. Thus, when the cam follower 102 is positioned at point 172 lying on radius r 1 , the wheel set 20 is adjusted to direct the vehicle in its straight ahead, longitudinal direction of travel indicated by arrow 178. In other words the radius r 1 of the cam 58 corresponds to an infinitely long turning radius R 1 for the wheel set 20. When the cam of 58 is rotated 90° in a clockwise direction the follower will rise from the point 172 to the point 174 on the cam surface 58. For purposes of representation, the radius r 3 between the axis of rotation and point 174 is equal to the radius r 1 minus x, x being some fixed quantity depending upon the actuation distance required for the control member of the servomechanism. With this cam relationship as the cam is rotated 90° from its centered position at point 172 so that the follower resides at point 174, the wheel set 20 will rotate as illustrated in FIG. 15b through 45° so that its turning radius will be R 2 . Likewise, when the cam 58 is rotated 90° in the counterclockwise direction the cam follower 102 will drop to the point 170 on the cam surface. For purposes of illustration, the radius r 2 between the point 170 on the cam surface and the axis of rotation 166 is equal to r 1 minus x. When the cam 58 is rotated in the clockwise direction so that the cam follower 102 resides at point 174 on the cam surface, the wheel set 20 will be rotated 45° in the counterclockwise direction so that its turning radius will be R 3 .
In a similar manner, the length of the radius r 5 of the cam between the rotational axis 166 and the point 176 on the cam surface is equal to the radius r 1 plus some quantity y greater than x. In a similar manner, the length of radius r 4 between the rotational axis 166 and the lowest point 168 on the cam surface is chosen to be equal to r 1 minus y. As illustrated in FIG. 15d when the cam 58 is rotated in a counterclockwise direction through approximately 180° so that the cam follower 102 resides substantially at point 168 on the cam surface, the wheel set will rotate through 95° in a clockwise direction so that the wheel set 20 will have a turning radius of R 4 . In a similar manner, when the cam 58 is rotated in a clockwise direction so that the follower 102 resides substantially at point 176 on the cam surface, the wheel set 20 will rotate through approximately 95° in the counterclockwise direction giving the wheel set 20 a turning radius of R 4 .
The representative cam illustrated in the FIG. 14 is representative of cams in the oblique steering mode cam set. It will be understood by one of ordinary skill in the art that the varying radiuses of the cam can be chosen as desired to position the corresponding wheel set at any given angular position desired dependent upon the angular position of the cam itself. In this manner, the several cams in a set can be designed so that they program the turning of several independently steerable wheel sets so that each resides in a desired position for a given rotation of the cam set relative to the location of the followers.
The present invention has been described in relation to a preferred embodiment. After reading the foregoing specification, one of ordinary skill in the art will be able to effect various changes, substitutions of equivalents, and other alterations without departing from the scope and intent of the invention as disclosed herein. It is therefore intended that the scope of protection granted by patent be limited only by the definition contained in the appended claims. | A load transporting vehicle has a plurality of independently steerable wheel sets, each of which incorporates a turntable having a downwardly extending strut and a pivotally mounted trailing arm that carries a pair of wheels. The turntable is rotatably mounted on the vehicle frame. A pair of double acting piston and cylinder assemblies are coupled to rotate the turntable via a rack and pinion. A hydraulic control valve, having a control spool actuated by a boden type cable, controls the flow of hydraulic fluid to the piston and cylinder assemblies.
The linear movement of the boden cable is programmed and controlled by rotatable cams. Three or four sets of cams, each set of which controls a different mode of steering, are mounted on a rotatable shaft. Each set of cams has a single cam to a given boden cable and associated wheel set. The sets of cams are interleaved to form groups corresponding to each wheel set. By axially shifting the shaft, a cam follower connected to the boden cable disengages from one cam and engages a next adjacent cam to change from one mode of steering to another. A cam follower lifting mechanism is provided to raise the followers from the cam surfaces during the shifting procedure. | 1 |
This is a continuation of U.S. patent application Ser. No. 08/349,523, filed 5 Dec. 1994, now U.S. Pat. No. 5,565,111.
BACKGROUND OF THE INVENTION
Hunting wild animals, and especially deer, is an art requiring the proper mix of intelligence, patience, endurance and the fight equipment. Because deer rely heavily on their highly developed sense of smell to alert them to a multitude of factors, such as danger, food, the presence of other animals, it is necessary for the hunter to blend into the environment, without alerting the deer to his presence. It is also very helpful to provide some means to attract the animal to the hunter's vicinity.
With respect to deer, and especially the male of the species or the buck, a buck lure is often used to tempt the buck. Buck lures have application not only for deer hunters, but for photographers and other wildlife enthusiasts.
The predominant type of deer lure used today is in the form of a liquid which is generally prepared by fermenting tarsal glands of several deer in urine. The urine is usually a combination of buck, doe and fawn urine. The urine is generally collected by bringing a herd of deer into a building with grates on the floor. The deer urinate onto the grates, and the urine falls through the grates for collection.
A major problem with this method of collection of urine is, however, that the deer also defecate onto the grates and the urine thus becomes contaminated with feces. Deer feces is approximately 35% composed of bacteria (dry weight).
The bacteria which may be found in the contaminated urine include, but are not limited, to the following, all of which are pathogenic to human beings: Listeria, Shigella, Escherichia Coli, Salmonella, Clostridium perfringens, and Giardia Lamblia. Symptoms of infection by these organisms include: chills, fever, diarrhea, dehydration, hemorrhagic colitis, hemolytic uremic syndrome (kidney failure), brain damage, and death. The contaminated urine also may contain a variety of viruses, which are also pathogenic. Thus, the hunter who applies an untreated deer lure to the ground risks infection by any of these pathogens.
Furthermore, the presence of these organisms in the urine shortens the shelf life of the deer lure preparation because of degradation. The deer lure preparation changes to a darker or black color, which is considered to be unsellable. The store must therefore rotate its stock of deer lure preparation fairly frequently.
There is a need for a method of processing big game scent, such as deer lure preparations, which kills or removes pathogenic bacteria without destroying or denaturing the aromatic character of the lure which causes deer to be attracted to the lure.
SUMMARY OF THE INVENTION
A method of processing big game scent, such as deer lures, comprising the steps of filtering a mixture of urine and feces through a series of successively finer filters in order to remove contaminants and pathogenic bacteria from the scent without destroying or denaturing the aromatic attractants. In a second embodiment, the mixture is heated to a temperature to destroy pathogens. A third embodiment is a combination of filtering followed by heating.
A principal object and advantage of the present invention is that it kills or removes pathogenic organisms such as bacteria which may cause diseases in human beings.
A second object and advantage of the present invention is that it prolongs the shelf life of the scent by removing the organisms which cause degradation of the scent.
A third object and advantage of the present invention is that the aromatic compounds which cause deer to be attracted to the scent are not substantially destroyed or denatured by the process.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a first method of carrying out the present invention.
FIG. 2 is a schematic diagram of a second method of carrying out the present invention.
FIG. 3 is a schematic diagram of a third method of carrying out the present invention.
FIG. 4 is a chart of the output of a gas chromatograph run on a sample of untreated deer urine.
FIG. 5a is table showing a chemical analysis of the gas chromatograph run of FIG. 4.
FIG. 5b is a continuation of the table beginning in FIG. 5a, showing a chemical analysis of the gas chromatograph run of FIG. 4.
FIG. 6 is a chart of the output of a gas chromatograph run on a sample of deer urine treated vacuum-sealed heating and cooling.
FIG. 7 is table showing a chemical analysis of the gas chromatograph run of FIG. 6.
FIG. 8 is a table showing the results of bacterial cultures performed on urine treated by the methods of this invention.
FIG. 9 is a chart of the output of a head-space gas chromatograph run on a sample of untreated deer urine.
FIG. 10 is a chart of the output of a head-space gas chromatograph run on a sample of deer urine treated by vacuum-sealed heating and cooling.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows the steps involved in a first method of carrying out the present invention. In the first step (not shown), urine is collected from an animal. Urine is generally collected by bringing the animal into an enclosure with a floor consisting of a grate with openings. As the animal urinates, urine falls through the grate and is collected in containers placed under the grate, as is well known in the art. As the animal defecates, feces also falls through the grate openings and becomes mixed with the urine. The fecal matter must be removed from the urine, because feces contains approximately 35% (dry weight) of bacteria.
The first method of carrying out the present invention involves filtering the feces/urine mixture through a series of successively finer filters.
The first filter in the series must be coarse enough to remove particulate fecal matter (greater than 30 microns) without clogging. If too coarse a filter is used, the fecal matter will not be removed. If too fine a filter is used, the fecal matter will quickly clog the filter and inhibit filtration. In the preferred embodiment, the first filter comprises a filter with pores of 30 microns in diameter. The urine is filtered through the first filter to produce a first filtrate.
Next, a second coarse filter is employed to remove particulate matter not removed by the first filter. In the preferred embodiment, a filter with pores 5 microns in diameter is used. The first filtrate is filtered through the second filter to produce a second filtrate.
In the third step, a filter with pores small enough to prevent the passage of bacteria is used. In the preferred embodiment, the third filter has pores 0.45 microns in diameter. The second filtrate is filtered through the third filter to produce a third filtrate.
In the fourth step, another filter with smaller pores is used to remove any bacteria passed through the third filter. In the preferred embodiment a filter with pores 0.40 microns in diameter is used. The third filtrate is filtered through the fourth filter, producing a fourth filtrate.
In contrast to an untreated specimen of deer urine/feces, which may contain millions of CFU/ml., FIG. 8 shows that the first method has removed essentially all bacteria from the sample.
FIG. 8 shows the results of a bacterial culture run on the fourth filtrate. Sample 1 was filtered according to the first method described above, put into an unsanitized bottle, and sampled for bacteria by known standard methods. Sample 2 was treated identically, except that a musk scent was added to the urine. FIG. 8 shows that Sample 1 and Sample 2 contain, respectively, 1400 and 10 colony-forming units/ml. (CFU/ml.).
FIG. 2 shows the steps involved in a second method of carrying out the present invention. The mixture of feces in urine is collected as described above. Then the mixture is placed in a container. The container may be vacuum-sealed, or the bottles used for selling the final product may be used.
After placing the mixture in the container, the container and the mixture therein are heated to a temperature sufficient to kill pathogenic organisms such as bacteria and viruses. The critical temperature for killing such organisms is 161 degrees Fahrenheit. However, use of a temperature significantly higher than the critical temperature may cause the aromatic attractant compounds in the scent to denature or be destroyed.
In one preferred embodiment, the container is vacuum-sealed and the container and the mixture are heated to a temperature of 163 degrees Fahrenheit and held at that temperature for 45 seconds. It has been found that this temperature and time period kill all bacteria without significantly altering the aromatic attractant compounds in the scent, as will be discussed below.
After the heating step, the container and the mixture are cooled to approximately room temperature. In the preferred embodiment, the cooling step is carded out by circulating cold water around the container for approximately 10 minutes.
In another embodiment, the container comprises the bottle that will be used in selling the final product, and is not vacuum-sealed. Without vacuum-sealing, the method is modified so that the heating step comprises heating the container and mixture to 145 degrees Fahrenheit for 30 minutes. It has been found that vacuum-sealed heating and cooling are not necessary at this lower temperature in order to avoid altering the aromatic attractant compounds in the scent.
FIG. 4 shows the results of a gas chromatography analysis of a sample of untreated deer urine, and FIGS. 5a and 5b display tabular results showing the chemical composition found by gas chromatography. FIGS. 6 and 7 are corresponding figures showing the results of a gas chromatography run on a sample of deer urine treated by vacuum-sealed heating and cooling.
It will be clear to the observer that FIG. 6 and FIG. 4 are very similar. That is, the major chemical compounds of the urine, responsible for the scent are left untouched by the vacuum-sealed healing and cooling. FIGS. 5 and 7 confirm that the major chemical compounds of the urine responsible for the scent are left untouched by the method.
To confirm that the major volatile compounds of the urine are not removed by the heating and cooling of the urine, a head-space gas chromatography run was performed. In head-space gas chromatography, a sample of the air above the urine in a sealed container is removed and analyzed. This "head-space" air will contain mainly volatile compounds. FIG. 9 shows a head-space gas chromatography run on untreated urine. FIG. 10 shows a head-space gas chromatography run on urine treated by heating and cooling as described above. There is very little difference in the two runs, indicating that the volatile compounds have not been destroyed or denatured by the heating and cooling process.
To confirm that essentially all bacteria were killed by heating and cooling as described, a bacteria culture was performed on the product after heating and cooling as described above. FIG. 8, Sample 3, shows the results. It will be seen that the treated sample contains less than 10 CFU/ml., showing that essentially all bacteria have been removed.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore desired that the present embodiment be considered in all respects as illustrative and not restrictive, reference being made to the appended claims rather than to the foregoing description to indicate the scope of the invention. | A method of processing big game scent, such as deer lures, comprising the steps of filtering a mixture of urine and feces through a series of successively finer filters in order to remove contaminants and pathogenic bacteria from the scent without destroying or denaturing the aromatic attractants. In a second embodiment, the mixture is heated to a temperature to destroy pathogens. A third embodiment is a combination of filtering followed by heating. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an improved lung graft preservative composition and an improved method for viable preservation of the lung graft for transplantation. More particularly, this invention relates to a lung graft preservative composition comprising an ascorbyl tocopheryl phosphate compound or a pharmacologically acceptable salt thereof and a method for viable preservation of a lung graft which comprises using said compound or salt.
2. Description of the Prior Art
For a successful organ transplantation, the organ resected from a donor must be kept functionally intact for a certain time period. Each kind of organ has its own characteristics and, hence, demands a unique protocol for viable storage. However, the preservation principles applicable to all organs in common are metabolic inhibition or metabolic maintenance.
For the viable preservation of the lung isolated For transplantation, (1) the donor core cooling method employing an extracorporeal circuit, (2) the method comprising flushing the pulmonary vascular bed with a perfusate from the pulmonary artery and, then preserving the lung under cooling, (3) the simple topical cooling method, and (4) the heart-lung autoperfusion method are known. Generally, however, for an effective cooling of the lung prior to resection, the method comprising flushing the lung from the pulmonary artery, immediately resecting the lung and immersing It in a preservative solution such as Euro-Collins solution is frequently employed.
However, it has been pointed out that these techniques have the drawback that on warm blood reperfusion of the lung after storage, pulmonary edema develops for some reasons or others so that the depression of the gas exchange function of the lung cannot be adequately prevented. Therefore, a more improved preservative for use in lung transplantation has been demanded and earnest research and development are in progress.
In the course of their ceaseless research into the pharmacology of ascorbyl tocopheryl phosphate compounds, the inventors of this invention discovered that these compounds are useful for the viable preservation of the lung isolated for transplantation. This discovery was followed by further studies which have resulted in the development of this invention.
SUMMARY OF THE INVENTION
This invention is, therefore, directed to: (1) A lung graft preservative composition comprising a phosphoric acid diester compound of the following formula or a pharmacologically acceptable salt thereof (hereinafter referred to briefly as the compound) ##STR2## (wherein R 1 and R 2 are the same or different and each represents a hydrogen atom or a methyl group) and (2) a lung graft preserving protocol employing said composition.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 represents arterial blood oxygen partial pressure after lung transplantation. The ordinate represents arterial blood oxygen partial pressure (PaO 2 ) (unit: mmHg) and the abscissa represents the time (unit: hr.) after lung transplantation,
FIG. 2 represents arterial blood carbon dioxide partial pressure after lung transplantation. The ordinate represents arterial blood carbon dioxide partial pressure (PaCO 2 ) (unit: mmHg) and the abscissa represents the time (unit: hr.) after lung transplantation.
FIG. 3 represents extravascular lung water after lung transplantation. The ordinate represents extravascular lung water (EVLW) (unit: ml/kg) and the abscissa represents the time (unit: hr.) after lung transplantation.
FIG. 4 represents blood shunt fraction after lung transplantation. The ordinate represents blood shunt fraction (unit: %) and the abscissa represents the time (unit: hr.) after lung transplantation.
FIG. 5 represents pulmonary vascular resistance after lung transplantation. The ordinate represents pulmonary vascular resistance (PVR) (unit: dyne/sec/cm 5 ) and the abscissa represents the time (unit: hr.) after lung transplantation.
FIG. 6 represents pulmonary arterial pressure after lung transplantation. The ordinate represents pulmonary arterial pressure (PAP) (unit: mmHg) and the abscissa represents the time (unit: hr.) after lung transplantation.
FIG. 7 represents cardiac output after lung transplantation. The ordinate represents cardiac output (CO) (unit: 1/min.) and the abscissa represents the time (unit: hr.) after lung transplantation.
The symbols used in FIGS. 1-7 represent:
The group treated with the lung preservative composition of this invention
▪ The group treated with Euro-Collins solution (control)
* p<0.05
Each plot on the ordinate is a mean value.
DETAILED DESCRIPTION OF THE INVENTION
The compound for use in the lung graft preservative composition and lung graft preserving method of this invention can be synthesized by inter alia the process in Japanese Patent Publication H-2-44478 or Japanese Patent Application Kokai S-62-205091, or any improvement thereof.
The compound for use in the lung graft preservative composition and lung graft preserving method of this invention is already known to be useful as an anticataract agent, a prophylactic and therapeutic agent for crimacteric disturbance, a skin care cosmetic ingredient (Japanese Patent Publication H-2-44478), art antiinflammatory agent (Japanese Patent Publication H-1-27044), an antiulcer agent (Japanese Patent Application Kokai S-63-270626), and a prophylactic and therapeutic agent for ischemic organic impairment (Japanese Patent Application Kokai H-2-111722), among others. However, it is not known that this compound is useful for the preservation of the lung to be transplanted.
The compound for use in the lung graft preservative composition and lung graft preserving method of this invention may be whichever of its free form and in the form of a pharmacologically acceptable salt thereof and these substances can be selectively used according to the intended mode of use. The pharmacologically acceptable salt mentioned above includes, among others, salts with alkali metals such as sodium, potassium, etc. and salts with alkaline earth metals such as calcium, magnesium, etc. Other kinds of salts, if pharmacologically acceptable, can also be used likewise.
According to the clinical objective and need, more than one species of the compound can be incorporated, in an appropriate combination, in the lung graft preservative composition and preserving method of this invention.
The compound for use as the active ingredient in the lung graft preservative composition and preserving method of this; invention is a very safe substance with an extremely low toxic potential and, as such, can be used with advantage for the purposes of this invention. [e.g. the LD 50 values of L-ascorbyl DL-α-tocopheryl phosphate potassium (hereinafter referred to briefly as EPC-K)≧5 g/kg p.o. (rats) and ≧100 mg/kg i.v. (rats)].
The lung graft preservative composition of this invention can be provided in a liquid form or supplied in a solid form for extemporaneous reconstitution. The solid form can be advantageously used as dissolved, suspended or emulsified in purified water, physiological saline or like medium. The solid form includes tablets, granules and powders, among others, which can be respectively manufactured by the known techniques. These preparations are preferably sterilized by known techniques such as membrane filtration or heat sterilization. Preparations may contain conventional additives such as an excipient, binder, buffer, isotonizing agent, stabilizer, pH control agent, preservative, solubilizer, thickening agent and so on.
Unless contrary to the object of this invention, the lung graft preservative composition of this invention may contain other organ-preserving ingredients which are generally used for the viable preservation of lung grafts. Among such ingredients are antibiotics, insulin, carbohydrates (mannitol, etc.), vitamins (vitamin C, vitamin E, etc.), organic acids (lactic acid, citric acid, etc.), nucleic acid bases (adenosine triphosphate etc.), antihypertensive agents (calcium-channel blockers, β-adrenergic antagonists, angiotensin-converting enzyme inhibitors, etc.), antiplatelet factor, antidiuretic hormone, anticoagulant (e.g. heparin) and so on.
Furthermore, the compound can be dissolved in the known organ preservative solution, such as Euro-Collins (EC) solution and University of Wisconsin solution [ViaSpan (registered trademark) produced by DuPont], to provide a lung graft preservative solution.
The lung graft preservative composition of this invention can be used in the known manner in which lung preservatives in general are employed in lung transplantation. For example, It can be used as follows. A sterilized cassette is filled with the lung graft preservative solution previously cooled to a predetermined temperature and the lung graft is placed in the preservative solution for cooling at a constant temperature. Then, a catheter is inserted into the pulmonary artery and the lung is perfused with the cooled preservative composition through the catheter to wash out the blood from within the organ. In the transplantation of a cadaver lung, the pulmonary vein is cut and the lung is perfused with the cooled preservative composition of this invention from the pulmonary artery, followed by resection of the lung. The thus-treated and resected lung is preserved at a constant low temperature in a sterile cassette filled with the preservative of this invention.
The proper concentration of the compound in the lung graft preservative composition of this invention is dependent on the species of compound, condition of the lung, and the necessary duration of preservation but the recommended final concentration in a liquid preparation is generally about 5×10 -9 g/ml to 5×10 -3 g/ml and preferably about 5×10 -8 g/ml to 5×10 -5 g/ml.
The osmolarity of such a liquid lung graft preservative composition of this invention is adjusted, by known means, to about 260 mOsm to about 360 mOsm, preferably about 275 mOsm to about 320 mOsm. The pH of the liquid preparation should also be adjusted, by known means, to about 3 to 10, preferably about 4 to 9.
The temperature suited for the lung graft preservation employing the preservative composition of this invention is dependent on the species and concentration of compound, condition of the lung and the desired duration of preservation but is generally about -5° C. to 20° and preferably about 0° C. to about 15° C.
In preserving the lung with the lung graft preservative composition of this invention, the known organ cassette, module and other hardware can be utilized.
EXAMPLES
The following test example and formulation examples are intended to illustrate this invention in further detail.
Example 1
Lung Preserving Effect of the Lung Graft Preservative Composition of this Invention in the Transplantation of Cardiac Arrest Donor Lungs
The lung preserving effect of the lung graft preservative composition of this invention in the transplantation of cardiac arrest donor lungs was experimentally evaluated.
[Test substance] L-Ascorbyl DL-α-tocopheryl phosphate potassium (abbreviation: EPC-K) dissolved in modified Euro-Collins solution 1 )
[Method] The left-lung transplantation model was constructed in adult mongrel dogs and used. The donor was brought to cardiac standstill by intravenous administration of potassium chloride solution and allowed to stand at room temperature for 2 hours. Then, while Group I (n=3) was perfused with Euro-Collins solution, an organ preservative which is commonly used in lung transplantation, Group II (n=3) was perfused with the lung graft preservative composition of this invention, followed by preservation at 4° C. for 12 hours. After the lung was transplanted into the recipient, the right pulmonary artery and right main branchus were ligated and the pulmonary function parameters were determined over a period of 6 hours. The results are shown in FIGS. 1-7.
Results
As shown in FIG. 1, the arterial blood oxygen partial pressure (PaO 2 ) was 108±38 mmHg in Group I vs. 460±94 mmHg in Group II after 6 hours. Results in Favor of Group II were obtained at other time-points, too.
As shown in FIG. 2, the arterial blood carbon dioxide partial pressure (PaCO 2 ) after 5 hours was 71.4±11.2 mmHg in Group I vs. 32.4±20.9 mmHg in Group II, indicating that the lung graft preservative composition of this invention is remarkably effective.
As shown in FIG. 3, the value of extravascular lung water (EVLW) which is an indicator of pulmonary edema, indicates that the lung graft preservative composition of this invention is effective in inhibiting edema.
The value of pulmonary blood shunt fraction, shown in FIG. 4, indicates that the lung graft preservative composition of this invention exerts a pulmonary blood shunt inhibitory effect which is significant after 1 and 2 hours. This inhibitory effect was also noted at other time-points.
It is also apparent from the pulmonary vascular resistance (PVR) value given in FIG. 5 that the lung graft preservative composition of this invention inhibits the increase of pulmonary vascular resistance.
The pulmonary arterial pressure (PAP) value shown in FIG. 6 indicates that the lung graft preservative composition of this invention inhibits pulmonary edema without increasing pulmonary vascular resistance.
The cardiac output (CO) data shown in FIG. 7 indicates that the lung graft preservative composition of this invention exerts no adverse influence on the heart.
Thus, the lung graft preservative composition of this invention showed very favorable effects on various parameters of pulmonary function after blood reperfussion, suggesting that this preservative composition is useful for the viable preservation of cardiac arrest cadaver lungs.
______________________________________1) Composition of Modified Euro-Collins Solution______________________________________K.sub.2 HPO.sub.4 7.40 g/lNaHCO.sub.3 0.84 g/lKH.sub.2 PO.sub.4 2.04 g/lKCl 1.12 g/lMgSO.sub.4 0.48 g/lD50W 50 ml/lHeparin 5,000 units/lOsmolarity 326 mOsm/kg______________________________________
Formulation Example 1
______________________________________EPC-K 0.01 gK.sub.2 HPO.sub.4 7.40 gNaHCO.sub.3 0.84 gKH.sub.2 PO.sub.4 2.04 gKCl 0.6 gMgSO.sub.4 0.48 gWater for injection q.s.Hydrochloride acid q.s.Sodium hydroxide q.s.Total 1000 mlpH 7.3______________________________________
The above ingredients are mixed in the conventional manner and scaled in a one-liter PVC bag to provide a lung graft preservative solution.
Formulation Example 2
______________________________________EPC-K 0.1 gMannitol 5 gWater for injection q.s.Sodium hydroxide q.s.Total 100 mlpH 7.3______________________________________
The above ingredients are mixed in the conventional manner and sealed in 2 ml glass amplues to provide an injectable solution.
This solution is extemporaneously mixed with an appropriate amount of an organ preservative, such as Euro-Collins or ViaSpan solution, to provide a lung preservative solution.
Example 3
______________________________________Solid preparation______________________________________ EPC-K 10 mg Sucrose 500 mg______________________________________
The above solid preparation is dissolved in water for injection in the conventional manner and filled in 5 ml-glass vials to provide a lung graft preservative.
This preservative is extemporaneously mixed with an appropriate amount of an organ preservative solution, such as Euro-Collins or ViaSpan solution, to provide a lung graft preservative solution.
The lung graft preservative composition and preserving method of this invention produce excellent effects on various parameters of pulmonary function and can be used with advantage for the viable preservation of lung grafts. | This invention provides a lung graft preservative composition comprising a phosphoric acid diester compound of the formula: ##STR1## (wherein R 1 and R 2 are the same or different and each represents a hydrogen atom or a methyl group) or a pharmaceutically acceptable salt thereof and a method for the preservation of the lung graft using the compound. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority from U.S. Provisional Patent Application Serial No. 60/257,427, filed Dec. 21, 2000, now pending.
BACKGROUND OF THE INVENTION
[0002] 1. Field of Invention
[0003] This invention relates to gasification systems for the production of electricity from biomass, such as shredded bark, wood chips, sawdust, sludges and other carbonaceous fuels or feedstocks. More particularly, the present invention relates to an improved method of operating a parallel entrained bed pyrolysis unit with improved circulation and reduced erosion of system components.
[0004] 2. Description of Related Art
[0005] Biomass gasification systems have been developed which are useful for the production of electrical power in remote areas or in areas wherein a large amount of agricultural biomass waste is produced. Current biomass gasification systems generally rely on combustion of a portion of the biomass feedstock to provide the heat required for gasification of the remainder of the biomass feedstock. However, the combustion of a portion of the raw biomass stream for heat production can significantly reduce the overall efficiency of the gasifier system. It has also proven advantageous to utilize the waste carbonaceous char produced in the gasification as a fuel source for generating heat in a combustor. Since the char is basically a waste product from the gasifier, its consumption in the combustor has less of an adverse effect on the system efficiency than is seen in systems wherein a portion of the raw biomass is used as a combustor fuel source.
[0006] U.S. Pat. No. 4,828,581 to Feldmann et al, describes an exemplary gasifier system for the production of fuel grade gas from carbonaceous fuels using very high biomass throughputs in a fluidized bed gasifier operating at low inlet gas velocities. The process described in Feldmann et al. uses a combustor to heat a bed of fluidized sand, which is directed to a gasifier wherein the heated sand serves as a heat source for the pyrolysis of the biomass material. Unlike prior systems, the system of Feldmann et al. relies on the entrainment of char in a flow of sand from the gasifier outlet to allow operation at an advantageously low inlet velocity of as low as 0.5 ft/sec but with a biomass throughput from 500 to 4400 lbs/ft 2 -hr. The Feldman et al. system is suited to the production of a medium BTU gas which may be used as a fuel source for the production of electricity in a standard gas fired boiler/turbine system.
[0007] One of the problems commonly associated with the use of such fluidized bed gasifier systems is the erosion of the piping comprising the systems by the circulating sand used to transfer heat within the gasifier system. This problem has been found to be especially severe at bends in the system piping, wherein the circulating sand can severely erode the piping. In severe cases, this erosion can shorten the lifetime of the gasifier system and may lead to catastrophic failure of the piping.
[0008] In fluidized bed systems wherein sand is used as a heat transfer medium from a combustor to a gasifier, it is necessary to minimize or eliminate the leakage of oxygen containing gases from the combustor into the gasifier. Contamination of the gasifier with oxygen results in the undesirable formation of carbon dioxide and water from the CO and H 2 end products of the gasification reaction, lowering the efficiency of gasification. However, it has proven difficult in prior systems to develop a method whereby the sand may be transported from the combustor to the gasifier and back while maintaining an air tight seal to prevent entry of oxygen into the gasifier.
[0009] In some instances, depending upon the nature of the feedstock used, these prior systems have also experienced problems resulting from the agglomeration of the ash, sand, and char mixture, and subsequent blockage of flow through the system. At the high operating temperatures of gasifier systems, at least a portion of the agglomeration of ash is the result of the partial melting of the ash constituents. It would clearly be desirable to develop a method of reducing or eliminating the agglomeration of the ash, sand and char mixture.
[0010] Accordingly, it is an object of the present invention to provide an improved method of directing the flow of sand through a parallel entrained bed pyrolysis system whereby erosion of system components is minimized.
[0011] It is another object of the present invention to provide an improved method of allowing the flow of sand and char in a fluidized bed pyrolysis system while maintaining and air tight seal between the gasifier and the combustor components of the system.
[0012] It is yet another object of the present invention to provide an improved method of reducing or preventing the agglomeration of ash, sand and char in a fluidized bed pyrolysis system.
SUMMARY OF THE INVENTION
[0013] The process system according to this invention relates to improvements to a parallel entrainment fluidized bed gasifier system. A first aspect of the present invention relates to a method for reducing ash agglomeration in a parallel entrainment fluidized bed gasifier/combustor system. A carbonaceous feedstock is provided and supplemented with a quantity of MgO prior to introduction into the gasifier combustor system. Upon gasification and combustion, the MgO alters the eutectic of the resultant ash to raise the melting point and substantially reduce the agglomeration of ash and sand which results from partial ash melting at high temperatures.
[0014] A second aspect of the present invention relates to an apparatus and method for reducing erosion at piping bends in fluidized particulate piping systems which utilizes sand retention cavities positioned at the piping bends to receive and retain a portion of the fluidized particulate. The retained fluidized particulate serves as an ablatable buffer to protect the surface of the piping bends from erosion by the flow of particulate impacting the wall.
[0015] A third aspect of the present invention relates to an apparatus and method for facilitating the flow of sand and char fragments from a first compartment to a second compartment while minimizing the flow of gases between the first and second compartments. A surger chamber is provided for receiving a flow of sand and char fragments from the first compartment. The surger chamber includes an inlet nozzle disposed to deposit the sand and char mixture into the lower portion of the surger chamber. An outlet is disposed above the point at which the nozzle deposits sand and char mixture into the surger chamber, such that the outlet is disposed to allow the gravitationally driven flow of sand and char from the surger chamber to the second compartment. Thus, when operating, the surger chamber maintains a quantity non-fluidized sand and char disposed between then inlet nozzle and the outlet, which acts to maintain a substantially gas resistant seal between the first and second compartments.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] [0016]FIG. 1 is a block diagram illustrating a gasifier system useful in the process according to a preferred embodiment of the present invention.
[0017] [0017]FIG. 2 illustrates a gas distributor in accordance with a preferred embodiment of the present invention.
[0018] [0018]FIG. 3 illustrates a surger pot for allowing the transfer of sand and char between the gasifier and combustor components of the gasifier system of FIG. 1 while maintaining a substantially gas tight seal between the gasifier and combustor.
[0019] [0019]FIG. 4 illustrates a sand retention cavity for reducing piping erosion in accordance with a preferred embodiment of the present invention.
[0020] [0020]FIG. 5 is a graph of Differential Thermal Analyzer (DTA) data for wood ash only.
[0021] [0021]FIG. 6 is a graph of Differential Thermal Analyzer (DTA) data for a 50/50 mixture of sand and wood ash.
[0022] [0022]FIG. 7 is a graph of Differential Thermal Analyzer (DTA) data for a mixture of sand and wood ash supplemented with kaolin.
[0023] [0023]FIG. 8 is a graph of Differential Thermal Analyzer (DTA) data for a mixture of sand and wood ash supplemented with MgO.
[0024] [0024]FIG. 9 is a graph of Differential Thermal Analyzer (DTA) data for pine ash only.
[0025] [0025]FIG. 10 is a phase diagram for K 2 O—MgO—SiO 2 .
[0026] [0026]FIG. 11 is a graph of K 2 O and MgO content of bed ash components in a system fed with poplar.
[0027] [0027]FIG. 12 is a graph of K 2 O and MgO content of bed ash components in a system fed with switch grass.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The basic method of operating a parallel entrained bed pyrolysis unit is similar to 30 that disclosed in U.S. Pat. No. 4,828,581 to Feldmann et al., incorporated fully herein by reference as if fully set forth. As illustrated in FIG. 1, the gasifier system A of the present invention generally includes a gasifier 20 and a combustor 22 which operate cooperatively to convert biomass into heat and a useful medium BTU product gas. Combustor 22 operates to convert residual char left over after gasification of biomass in gasifier 20 into heat. The heat produced in combustor 22 is then transferred to gasifier 20 to drive the gasification reaction. This allows for an increase in system efficiency by eliminating the need for consumption of a separate fuel source to provide heat to drive the gasification reaction.
[0029] In gasifier system A, feedstock material AA is first passed through a dryer 30 wherein any entrained water is evaporated to produce dried feedstock BB, which is routed into a storage bin 32 for storage prior to introduction into gasifier 10 .
[0030] Gasifier 20 may be a standard fluidized bed gasifier which receives dried feedstock BB and subjects it to heat in an oxygen-free environment, partially volatilizing the feedstock to release a mixture of H 2 , CO, CH 4 and C 02 . Gasifier 20 is heated by a sand stream DD or other inert fluidized material which is received from combustor 22 . Sand stream DD is fluidized by blowing a flow of steam CC through the sand from the lower portion of gasifier 20 through a gas distributor 24 . Feedstock stream BB and sand stream DD are both introduced into gasifier 20 in proximity to gas distributor 24 .
[0031] Gas distributor 24 can be of any conventional type, such as the perforated plate-type gas distributors most commonly used in fluidized bed systems. However, as illustrated in FIG. 2, in the preferred embodiment, an improved gas distributor 24 includes a plurality of pipes disposed in the bottom portion of gasifier 20 , each having downwardly disposed injection holes 26 for injecting air into the sand bed to fluidize it. The downward orientation of the injection holes 26 ensures that any tramp material is blown back up into the fluidized section of the bed. Thus, the entirety of the bed is fluidized, preventing the accumulation of the tramp material in the base of the vessel and ensuring that the sand is continually circulated, preventing the formation of cold spots in the gasifier vessel. This is advantageous over the more traditional perforated plate-type gas distributors which can allow dead spots and incomplete circulation in the gasifier 20 .
[0032] Gasifier 20 operates as a circulating bed gasifier in that the char formed during gasification of feedstock BB retains the general size and shape of the feedstock and is circulated out the exit port of gasifier 20 and into a cyclone separator 36 . Cyclone separator 36 separates the entrained sand and char which is circulated from gasifier 20 to form a sand and char stream EE and a product gas stream FF. Product gas stream FF comprises at least CO and H 2 , but may include a variety of other gases depending upon the characteristics of input feed stream BB. Product gas stream FF may be directed through a heat recovery unit 38 and a scrubber 40 to remove any residual particulates or char. Gasifier 20 is essentially a hybrid having an entrained zone for transfer above a fluidized bed gasifier.
[0033] Leakage of oxygen into gasifier 20 would decrease the efficiency of the gasification reaction and increase the undesirable combustion of the product gas to C 0 2 and H 2 O. In order prevent such oxygen leakage into the gasifier it is desirable to maintain a substantially air-tight seal between the combustor 22 and the gasifier 20 . This may be accomplished in part through use of a surger pot 56 which allows movement of the sand and char accumulated from gasifier cyclone 36 to combustor 22 . As illustrated in FIG. 3, surger pot 56 works by directing sand and char downward from gasifier cyclone 36 through a nozzle 60 into surger a chamber 62 . As sand accumulates, it fills surger chamber 62 to a level above the outlet of nozzle 60 whereupon a portion of the sand flows via the force of gravity through an outlet 64 and into combustor 22 . A similar second surger pot 58 is positioned below combustor a cyclone separator 52 for allowing flow of heated sand back to gasifier 20 . Use of these surger pots allows for transfer of sand and char between the gasifer 20 and combustor 22 with a minimum of gas exchange therebetween.
[0034] Sand and char stream EE is directed from gasifier cyclone 36 to combustor 22 wherein the sand is again fluidized and the char is combusted to ash to provide heat to reheat the sand before recycling the sand to gasifier 20 . In general, the sand in combustor 22 is fluidized by the injection of air GG from below, again circulating the sand and ash mixture so that it passes out an exit port 50 in the top region of combustor 22 to combustor cyclone separator 52 which separates out the sand for recirculation to gasifier 20 . A mixture of flue gas and ash HH exits the top of combustor separator 52 and is directed to ash recovery cyclone 54 . Ash recovery cyclone 54 separates the ash stream JJ from the flue gas stream KK. In the preferred embodiment, the ash is then collected as waste and the flue gas stream KK is directed to dryer 30 as a heat source for drying raw feedstock AA.
[0035] Gasifier system A operates with a recirculating particulate phase and at inlet gas velocities in the range required to fluidize the sand or other recirculating particulate phase. For example, a velocity of 0.8 to 2 ft/sec with a 20×50 mesh sand has allowed smooth stable operation. Velocities of 0.5 to 7 ft/sec can be used. Gasifier system A can operate at wood feed rates that exceed 3000 lbs/hr of dry biomass per square foot of reactor cross sectional area. Throughputs of 4400 lbs-ft 2 /hr are achievable and possibly even higher.
[0036] In a preferred low inlet gas velocity high throughput embodiment, biomass gasifier system A can operate with biomass throughputs of from 100 and preferably 500-4400 lb/ft 2 -hr but with inlet gas velocities of 0.5-7 ft/sec. These low gas inlet velocities also serve to reduce the erosion caused by circulation of the mixed bed material, which can be a problem in systems having a high gas inlet velocity.
[0037] As shown in FIG. 4 erosion of the piping of gasifier system A which is utilized to transfer sand can be minimized through the use primarily straight piping interconnected via sharp bends having sand retention cavities 70 . For example, in the currently preferred embodiment, sand retention cavities 70 are utilized at the piping at sharp 90 degree piping bends 72 located adjacent the top of both gasifier 20 and combustor 22 . In operation, sand collects within the sand retention cavity and serves as an ablatable buffer 74 to deflect moving abrasive flows of sand away from the piping surface. Since the sand is being deflected by a stationary sand buffer rather than the piping surface, erosion of the piping surface is minimized. Generally, the sand retention cavities 70 should have a depth of approximately one half of the diameter of the piping. If a sand retention cavity 70 is too shallow, sand will not accumulate within the sand retention cavity 70 and erosion will not be adequately reduced.
[0038] The method of operating a gasifier according to this invention comprises introducing inlet gas at a gas velocity generally less than 7 ft/sec to fluidize a high average density bed in gasifier 20 . The high average density bed is formed into a dense fluidized bed in a first space region by means of the inlet gas CC. The dense fluidized bed contains a circulating first heated relatively fine and inert solid bed particle component. Carbonaceous material is inputted into the first space region with dense fluidized bed at a rate from 100-4400 lbs/ft 2 -hr and more preferably 500-4400 lbs/ft 2 -hr and endothermic pyrolysis of the carbonaceous material is accomplished by means of the circulating heated inert material so as to form a product gas. Contiguous to and above the dense fluidized bed a lower average density entrained space region is formed containing an entrained mixture of inert solid particles, char and carbonaceous material and the product gas. Surprisingly, the char maintains relatively the same size and shape as the input feedstock material. This results in an approximate 1:1 ratio of char to sand due the differing densities of the char and sand density.
[0039] The entrained mixture is then removed from the entrained space region of the gasifier 20 to a separator 36 such as a cyclone wherein the entrained mixture of inert solid particles, char and carbonaceous material is separated from the product gas. Residence time of the carbonaceous material in the gasifier 20 typically does not exceed 3 minutes on average. Finally, at least the inert solid particles are returned to the first space region after passage through an exothermic reaction zone such as a combustor 22 to first heat the inert particles. To facilitate the exothermic reaction, it can be advantageous to route the entire entrained mixture absent product gas through the combustor 22 so that the char can be combusted as a heat source.
[0040] In the system of the preferred embodiment of the present invention, the fluidized bed of heated sand or other relatively inert material at the lower end of the gasifier 20 forms a region of relatively high density. Inputted wood or other carbonaceous material, being lighter than the sand, floats on the fluidized sand. As the wood is gasified by the hot sand, an entrained region of sand, char and carbonaceous particles forms in the upper end of the gasifier 20 .
[0041] The highest concentration of entrained wood and is be found at the top of the densely fluidized zone within the gasifier 20 . Entrained hot sand circulates through the entrained wood and char. As the carbonaceous particles pyrolyze, they generate gas forming a high velocity region above the fluidized bed. Despite a low gas inlet velocity below the bed the gas velocity above the fluidized bed becomes high enough to actually remove particles from the bed. By operating at low inlet gas velocity, high residence time (up to 3 minutes on average) in the reaction vessel can be achieved while still allowing high throughputs of carbonaceous material generating gas to form the entrained region above the fluidized region.
[0042] In this system, solids are removed from the top of the vessel, and removed from the system by entrainment despite the low inlet gas velocities below the bed. This is made possible by the design of using a fluidized region, above which is an entrained region from which all bed particles including inerts and char are removed. Entrainment occurs in part because of the gas generated in situ contributing significantly to the volume of gas moving through the reaction vessel, while avoiding destructive slugging.
[0043] The carbonaceous material fed to the gasifier 20 can have greater than 60% of the available carbon converted upon a single pass through the gasifier system A. The remainder of the carbon is burned in the combustor 22 to generate heat for the pyrolysis reaction. If other fuel is used in the combustor 22 , then additional carbon can be converted in the gasifier 20 . With wet fuels, such as municipal waste, carbon conversions might vary upward or downward depending on the operating temperature of the gasifier 20 .
[0044] The inlet gas fed to the gasifier 20 typically can be steam, recycled-product-gas, combustion by-product gas, inert gases such as nitrogen, and mixtures thereof. Preferred gases for the invention are steam and recycled-product-gas. Addition of other gases such as inert gases or combustion by-product gases will reduce the efficiency and advantages of the invention. Likewise, the addition of air or oxygen reduces the efficiency and advantages of the invention and, thus, is not preferred.
[0045] Steam is a convenient gas because it is relatively cheap and can be condensed from the product gas prior to distribution. Nitrogen, on the other hand, while allowing the same carbon conversion and the same product gas distribution remains in the product gas as diluent thereby reducing its utilization value. Air or oxygen are generally not used because the heat required to gasify the feed is introduced by the hot circulating inert solids whereas in some prior art systems the oxygen bums a portion of the char and product gases to provide heat. Use of air or oxygen would tend to reduce the utilization value of the product gas.
[0046] In this invention entrained material exits the vessel near the top of the gasifier 20 to a cyclone or other inertial settling device 36 for separating the product gas from the char, carbonaceous material and inert material. All system solids are entrained except for unwanted tramp material such as scrap metal inadvertently introduced with the fuel feedstock, for which a separate cleanout provision may be needed.
[0047] The system of the present invention is versatile and could be combined with any type of combustor, fluidized, entrained, or non-fluidized, for heating the inert material. The inert material is heated by passage through an exothermic reaction zone of a combustor to add heat. The inert material is understood to mean relatively inert as compared to the carbonaceous material and could include sand, limestone, and other calcites or oxides such as iron oxide. Some of these “relatively inert materials” actually could participate as reactants or catalytic agents, thus “relatively inert” is used as a comparison to the carbonaceous materials and is not used herein in a strict or pure qualitative chemical sense as commonly applied to the noble gases. For example, in coal gasification, limestone is useful as a means for capturing sulfur to reduce sulfate emissions. Limestone might also be useful in catalytic cracking of tar in the gasifier 20 .
[0048] Other useful materials may also be added to the gasifier feedstock to improve system operation. For example, it has been found that the agglomeration of ash, sand, and char in gasifier system A can be reduced by adding of magnesium oxide (MgO) to the feedstock material. This agglomeration is generally a result of the partial melting of the ash at the high temperatures present in combustor 20 , and consequential agglomeration of the ash, sand and any residual char into a non-fluidizable mass which may potentially disrupt flow in the fluidized system. In prior systems, calcium oxide (CaO) and alumina (Al 2 O 3 ) have been added in an attempt to reduce agglomeration of ash by diluting the ash. However, it has been found that the addition of MgO is even more effective to reduce agglomeration. The presence of MgO chemically alters the low temperature eutectic of the ash mixture, raising the melting point to effectively reduce agglomeration of ash via melting. One of ordinary skill in the art should recognize that other materials which alter the low temperature eutectic of the ash mixture to raise its melting point may also be useful in the present invention. Preferably MgO is added to the feedstock of the present invention at a weight percent or between 1% and 25% of the feedstock weight. More preferably at least 2% and even more preferably between 2% and 10% MgO is added to the feedstock to reduce aggregation in accordance with the present invention.
EXAMPLE 1
[0049] Hybrid poplar and the switch grass were tested as high growth species feedstocks for use in the gasification system of the present invention. These high-growth species feedstocks result in ash components that can cause difficulty in operation of the gasification system. It is hypothesized that high growth species generally concentrate certain elements in their ash. These are represented by the more soluble alkali and alkaline earth elements which are found as alkali and alkaline earth oxides in the ash analysis. When the ashes of the hybrid poplar and switch grass were analyzed, high levels of potassium and phosphorous and both higher and lower levels of silica relative to previous wood feedstocks tested were found as shown in Table 1.
[0050] During two of the initial tests with the hybrid poplar feed material, some Stability was noticed in sand circulation in the gasifier system. This Stability was determined to be the result of agglomeration in the combustor sand bed to form ash agglomerates caused by low melting ash constituents or by reaction of the ash oxides on the surface of sand particles. The ash agglomerates were loose agglomerates that easily disintegrated at
TABLE 1 % BY WEIGHT % BY WEIGHT % BY WEIGHT MINERAL COMPONENT PINE ASH SWITCH GRASS ASH HYBRID POPLAR ASH SiO 2 32.46 69.92 2.59 Al 2 O 3 4.50 0.45 0.94 TiO 2 0.40 0.12 0.26 Fe 2 O 3 3.53 0.45 0.50 CaO 49.20 4.80 47.20 MgO 0.44 2.60 4.40 K 2 O 2.55 15.00 20.00 Na 2 O 0.44 0.10 0.18 SO 3 2.47 1.90 2.74 P 2 O 5 0.31 2.60 5.00 SrO — 0.04 0.13 BaO — 0.22 0.70 Mn 2 O 4 — 0.15 0.14 Total Oxides 96.30 98.35 84.78 Carbon Dioxide, CO 2 14.00
[0051] room temperature when touched. An examination of the hybrid poplar ash analysis showed the ash to be 95.0 percent basic oxides. Hence, one likely agglomeration mechanism would be the fluxing of the acidic bed material (SiO 2 ) by the basic ash. However, agglomeration of ash-CaO mixtures in DTA tests (discussed below) have discounted ash fluxing of the sand bed as the likely cause of the agglomeration.
[0052] The presence of low-melting species initially was thought to be inconsistent with the reported ash fusion temperatures, all above 2700 F. However, it was realized that some species, such as those containing potassium, may have been volatilized during the analytical ashing process so that the reported ash fusion values may represent potassium-free ash.
[0053] The ash agglomerates formed during the gasifier system tests were submitted for scanning electron microscopic examination. The microscopic examination revealed that the sand particles had been glued together with a low melting material. These samples then were analyzed by electron microprobe in an attempt to identify the troublesome material. This analysis showed that the “glue” between the sand particles consisted of 67.74 percent SiO 2 , 16.1 percent K 2 O, 0.6 percent CaO, 5.47 percent TiO 2 , and 10.1 percent Fe 2 O 3 . Similarly, analysis of the surface coating on the particle showed the same species in the same general ratio. The results of these analyses showed that the fused material did not contain sulfur or chlorine. Most of the previous work on ash agglomeration from biomass species has focused on the presence of sulfur and on the resulting formation of low melting sulfates as the primary cause of agglomeration of a sand bed. The agglomeration found in the combustor of the system of the present invention, based on the microprobe analysis, was not caused by the formation of sulfates, but appears to result from the formation of compounds such as alkali-silicates.
[0054] To evaluate the behavior of the ash, additional tests were run in a Differential Thermal Analyzer (DTA). The DTA was used to identify endotherms caused by melting of compounds formed by the reacting of the ash constituents with the bed material and/or within the ash itself. Typical DTA curves are shown in FIGS. 5 through 9. These show that two primary endothermic peaks are present in each of the samples suggesting fusion occurred at approximately 500 C. and 770 C. for wood ash alone or a 50/50 mixture of sand and wood ash (FIGS. 5 and 6 respectively).
[0055] The strong endotherm at about 770 C. suggests that the material could be a single well defined compound or it could be a eutectic formed in a binary and/or ternary system of compounds. Compounds with melting points near 770 C. consistent with the ash analysis would be compounds containing potassium, phosphorus, calcium, and silica and perhaps, sulfur. The electron probe results rule out sulfur, but suggest that titanium and iron could be involved. The melting point of KCl is 776 C. and it sublimes. However, the ultimate analysis (Table 1) reports low levels of chlorine (0.01 percent) in the wood. If KCI were present in the ash, it would have had an impact on the ash fusion temperature (which remained above 2700 F.). Potassium metaphosphate (KPO 3 ) has a melting point of 807 C. and potassium tetrasilicate (anhydrous) has a melting point of 770 C. Both could contribute to the agglomeration.
[0056] Compounding this simplistic approach is the greater probability that eutectics exist between binary and ternary oxide systems such as K 2 O, SiO 2 and one of the other oxides. A review of the phase diagram for the system SiO 2 —K 2 O5iO 2 (FIG. 10) suggests that beside the well defined melting point of 770 C. for the compound anhydrous potassium tetrasilicate (K 2 O 4SIO 2 or K 2 SiO 9 , 78% SiO 2 —22% K 2 O) a eutectic exists at about 68 percent SiO 2 32 percent K 2 O which has a melting point of about 750 C. A eutectic can exist in the system KPO 3 K 4 P 2 O 5 with a melting point at 613 C.
[0057] With the large reservoir of potassium as oxide in the combustion fluidized sand bed, especially with the hybrid poplar ash, localized reaction between K 2 O and SiO 2 can occur to form compounds leading to eutectic mixtures on the surface of the sand (SiO 2 ) particles. Gradient concentrations of K 2 O in SiO 2 are possible in the layer surrounding the sand particle.
[0058] If potassium tetra-silicate or related eutectics are the problem, the formation of potassium silicate must then be prevented or the silicate must be modified after forming in order to prevent agglomeration in the bed. As a direct comparison with other types of wood ash, a DTA test was run with pine ash. This curve, as shown in FIG. 7, shows much less severe endotherms than the poplar ash probably due to the low levels of K 2 O in the pine ash. Additionally, this material was not agglomerated when removed from the sample cup.
[0059] Prior studies have indicated that the tendency of ash to agglomerate the sand bed could be reduced by the addition of additives such as kaolin clay, and CaO. Thus, these substances were tested in the DTA either with wood ash alone or with a 1:1 mixture of wood ash and bed sand. These tests and their results are listed in Table 2. The kaolin clay was ineffective in preventing agglomeration as shown by the continued presence of
TABLE 2 Sample Description* Atmosphere Max Temp./Scan Rate Observations Hybrid Poplar Ash Air 1000 C./50° C./min Peaks at 493 and 772 C., sample agglomerated when removed Poplar Ash + silica sand Air 1000 C./50° C./min Peaks at 492 and 785 C., sample agglomerated when removed Poplar ash + silica sand + Air 1000 C./50° C./min Peaks at 436 and 785 C., sample CaO lightly agglomerated when removed Poplar ash + silica sand + Air 1000 C./50° C./min Peaks at 495 and 778 C., sample kaolin agglomerated when removed Poplar ash + silica sand + Air 1000 C./50° C./min Peaks at 367, slight peaks at 506 MgO and 749 C., sample only slightly agglomerated when removed Poplar ash + CaO Air 1000 C./50° C./min Peaks at 420, 493, and 782 C., sample agglomerated when removed Poplar ash from twigs Air 1000 C./50° C./min Peaks at 792 and 889 C., sample agglomerated when removed Poplar ash from stem Air 1000 C./50° C./min Small peaks at ˜500 C., peaks at 789 and 898 C., sample agglomerated when removed Pine ash Air 1000 C./50° C./min Slight peaks at 740 C., no agglomeration present
[0060] peaks at 780 C. in FIG. 8 and the formation of agglomerates. Therefore, it was concluded that the reaction rates for the formation of potassium silicate are sufficiently high to effectively prevent the potassium from combining with another acidic oxide (such as alumina) as a means of preventing the agglomeration. Substituting a basic oxide for the sand as the bed material would then provide the means to limit the formation of the low melting silicates to that which can be formed by the components of the ash itself. In the case of the hybrid poplar ash, the low concentration of silica in the ash will limit the quantity of silicate that can form in the ash. However, because of the bed sand, the level of silicates that can form may still be troublesome.
[0061] In the DTA tests summarized in Table 2, the CaO had little effect on the endothermic peaks, but physical examination of the sample after the test showed that the agglomeration was less severe than with the ash alone or with the ash and sand mixture. Surprisingly, it was found that the addition of Magnesia (MgO) provided substantially reduced agglomeration and reduced endothermic peaks shown in FIG. 9 in comparison to ash and sand with or without CaO. All of the remaining tests during this program phase utilized a co-feed of MgO to control the agglomeration in the combustor bed.
[0062] MgO was added at a rate approximately equal to the ash composition in the feed material or about 2 percent of the wood feed rate. Although a parametric evaluation of the minimum MgO addition rate was not conducted, qualitatively the 2 percent addition level was adequate to control agglomeration. With MgO added to the combustor bed, the combustion temperature was not restricted during testing.
[0063] An extended length was performed to examine the effectiveness of MgO to minimize agglomeration problems as they occur during operation. At the start of the extended length test, MgO feed was held at 25 lb/hr, a level slightly lower than during previous tests. After 4 hours of feeding at this lower MgO level, however, a reduction in performance was noticed indicating some agglomeration had occurred. By increasing the MgO feed back to the previous level of 35 lb/hr agglomeration ceased and smooth operation was restored. Near the end of the test, the MgO feeder motor stalled for a short period which again led to some agglomeration in the bed. When MgO feed was restored, the symptoms of agglomeration were eliminated and smooth operation continued.
[0064] There is supporting information in the literature on the effect MgO has on the melting points in the K 2 O SiO 2 system. Examination of the ternary diagram for the system K 2 O MgO SiO 2 (FIG. 10) at the 5 mole percent level suggests increases in the 770 C. and lower melting of the K 2 O—SiO 2 system points to 900 to 1000 C.
[0065] The potassium content in the circulating sand bed was measured at the end of each of the tests with hybrid poplar and switch grass. The results of these individual analyses are presented graphically in FIGS. 11 and 12. The curves show cumulative quantities of feedstock on the X-axis versus bed constituents. As is shown, the potassium content stabilizes in the combustor bed at approximately 0 . 6 percent with the hybrid poplar and 0.5 percent with switch grass. The stabilization is caused by a combination of MgO elutriation and sand makeup in the combustor bed. In both cases, the maximum concentration of MgO at the end of the tests was about 3.5 percent. Such a level of MgO in the bed would provide a reasonable target concentration for control of agglomeration in a commercial gasification facility. Previous testing with other varieties of wood feed material indicate that only the high growth materials require such an addition of MgO due to their much lower potassium in the ash. The “dip” shown in FIG. 15 reflects a large sand makeup during the test procedure.
[0066] It thus will be appreciated that the objects of this invention have been fully and effectively accomplished. It will be realized, however, that the foregoing preferred specific embodiment has been shown and described for the purpose of this invention and is subject to change without departure from such principles. Therefore, this invention includes all modifications encompassed within the spirit and scope of the following claims. | An improved system and method is provided for operating a parallel entrainment fluidized bed gasifier system. A first aspect of the present invention relates to a method for reducing ash agglomeration in a parallel entrainment fluidized bed gasifier/combustor system by adding a quantity of MgO to the feedstock used in the gasifier/combustor system. A second aspect of the present invention relates to an apparatus and method for reducing erosion at piping bends in fluidized particulate piping systems which utilizes sand retention cavities positioned to receive and retain a portion of the fluidized particulate. A third aspect of the present invention relates to an apparatus and method for facilitating the flow of sand and char fragments from a first compartment to a second compartment while minimizing the flow of gases between the first and second compartments. | 2 |
FIELD OF THE INVENTION
The present invention relates to structures and synthesis of creatine-fatty acid compounds bound via an anhydride linkage. Another aspect of the present invention relates to a compound comprising a creatine molecule bound to a fatty acid, wherein the fatty acid is preferably a saturated fatty acid and bound to the creatine via an anhydride linkage.
BACKGROUND OF THE INVENTION
Creatine is a naturally occurring amino acid derived from the amino acids glycine, arginine, and methionine. Although it is found in meat and fish, it is also synthesized by humans. Creatine is predominantly used as a fuel source in muscle. About 65% of creatine is stored in the musculature of mammals as phosphocreatine (creatine bound to a phosphate molecule).
Muscular contractions are fueled by the dephosphorylation of adenosine triphosphate (ATP) to produce adenosine diphosphate (ADP). In the absence of a mechanism to replenish ATP stores, the supply of ATP would be totally consumed in 1-2 seconds. Phosphocreatine serves as a major source of phosphate from which ADP is regenerated to ATP. Within six seconds following the commencement of exercise, muscular concentrations of phosphocreatine drop by almost 50%. Creatine supplementation has been shown to increase the concentration of creatine in the muscle (Harris R C, Soderlund K, Hultman E. Elevation of creatine in resting and exercised muscle of normal subjects by creatine supplementation. Clin Sci (Lond). 1992 September; 83(3):367-74) and further, the supplementation enables an increase in the resynthesis of phosphocreatine (Greenhaff P L, Bodin K, Soderlund K, Hultman E. Effect of oral creatine supplementation on skeletal muscle phosphocreatine resynthesis. Am J. Physiol. 1994 May; 266(5 Pt 1):E725-30) leading to a rapid replenishment of ATP within the first two minutes following the commencement of exercise. Through this mechanism, creatine is able to improve strength and reduce fatigue (Greenhaff P L, Casey A, Short A H, Harris R, Soderlund K, Hultman E. Influence of oral creatine supplementation of muscle torque during repeated bouts of maximal voluntary exercise in man. Clin Sci (Lond). 1993 May; 84(5):565-71).
The beneficial effects of creatine supplementation with regard to skeletal muscle are apparently not restricted to the role of creatine in energy metabolism. It has been shown that creatine supplementation in combination with strength training results in specific, measurable physiological changes in skeletal muscle compared to strength training alone. For example, creatine supplementation amplifies the strength training-induced increase of human skeletal satellite cells as well as the number of myonuclei in human skeletal muscle fibres (Olsen S, Aagaard P, Kadi F, Tufekovic G, Verney J, Olesen J L, Suetta C, Kjaer M. Creatine supplementation augments the increase in satellite cell and myonuclei number in human skeletal muscle induced by strength training. J. Physiol. 2006 June 1; 573(Pt 2):525-34). Satellite cells are the stem cells of adult muscle. They are normally maintained in a quiescent state and become activated to fulfill roles of routine maintenance, repair and hypertrophy (Zammit P S, Partridge T A, Yablonka-Reuveni Z. The Skeletal Muscle Satellite Cell: The Stem Cell That Came In From the Cold. J Histochem Cytochem. 2006 Aug. 9). ‘True’ muscle hypertrophy can be defined as “as an increase in fiber diameter without an apparent increase in the number of muscle fibers, accompanied by enhanced protein synthesis and augmented contractile force” (Sartorelli V, Fulco M. Molecular and cellular determinants of skeletal muscle atrophy and hypertrophy. Sci STKE. 2004 July. 27; 2004(244):re11). Postnatal muscle growth involves both myofiber hypertrophy and increased numbers of myonuclei—the source of which are satellite cells (Olsen S, Aagaard P, Kadi F, Tufekovic G, Verney J, Olesen J L, Suetta C, Kjaer M. Creatine supplementation augments the increase in satellite cell and myonuclei number in human skeletal muscle induced by strength training. J. Physiol. 2006 June 1; 573(Pt 2):525-34).
Although creatine is used predominantly in muscle cells and most of the total creatine pool is found in muscle, creatine is actually synthesized in the liver and pancreas. Thus, the musculature's creatine concentration is maintained by the uptake of creatine from the blood stream regardless of whether the source of creatine is endogenous, i.e. synthesized by the liver or pancreas, or dietary, i.e. natural food sources or supplemental sources. The creatine content of an average 70 kg male is approximately 120 g with about 2 g being excreted as creatinine per day (Williams M H, Branch J D. Creatine supplementation and exercise performance: an update. J Am Coll Nutr. 1998 June; 17(3):216-34). A typical omnivorous diet supplies approximately 1 g of creatine daily, while diets higher in meat and fish will supply more creatine. As a point of reference, a 500 g uncooked steak contains about 2 g of creatine which equates to more than two 8 oz. steaks per day. Since most studies examining creatine supplementation employ dosages ranging from 2-20 g per day it is unrealistic to significantly increase muscle creatine stores through merely food sources alone. Therefore, supplemental sources of creatine are an integral component of increasing, and subsequently maintaining supraphysiological, muscular creatine levels.
Creatine supplementation, thus results in positive physiological effects on skeletal muscle, such as: performance improvements during brief high-intensity anaerobic exercise, increased strength and enhanced muscle growth.
Creatine monohydrate is a commonly used supplement. Creatine monohydrate is soluble in water at a rate of 75 ml of water per gram of creatine. Ingestion of creatine monohydrate, therefore, requires large amounts of water to be co-ingested. Additionally, in aqueous solutions creatine is known to convert to creatinine via an irreversible, pH-dependent, non-enzymatic reaction. Aqueous and alkaline solutions contain an equilibrium mixture of creatine and creatinine. In acidic solutions, on the other hand, the formation of creatinine is complete. Creatinine is devoid of the ergogenic beneficial effects of creatine. It is therefore desirable to provide, for use in individuals, e.g. animals and humans, forms and derivatives of creatine with improved characteristics such as stability and solubility. Furthermore, it would be advantageous to do so in a manner that provides additional functionality as compared to creatine monohydrate alone.
The manufacture of hydrosoluble creatine salts with various organic acids have been described. U.S. Pat. No. 5,886,040, purports to describe a creatine pyruvate salt with enhanced palatability which is resistant to acid hydrolysis.
U.S. Pat. No. 5,973,199, purports to describe hydrosoluble organic salts of creatine as single combination of one mole of creatine monohydrate with one mole of the following organic acids: citrate, malate, fumarate and tartarate individually. The resultant salts described therein are claimed to be from 3 to 15 times more soluble, in aqueous solution, than creatine itself.
U.S. Pat. No. 6,166,249, purports to describe a creatine pyruvic acid salt that is highly stable and soluble. It is further purported that the pyruvate included in the salt may be useful to treat obesity, prevent the formation of free radicals and enhance long-term performance.
U.S. Pat. No. 6,211,407 purports to describe dicreatine and tricreatine citrates and a method of making the same. These dicreatine and tricreatine salts are claimed to be stable in acidic solutions, thus hampering the undesirable conversion of creatine to creatinine.
U.S. Pat. No. 6,838,562, purports to describe a process for the synthesis of mono, di, or tricreatine orotic acid, thioorotic acid, and dihydroorotic acid salts which are claimed to have increased oral absorption and bioavailability due to an inherent stability in aqueous solution. It is further claimed that the heterocyclic acid portion of the salt acts synergistically with creatine.
U.S. Pat. No. 7,109,373, incorporated herein in its entirety by reference, purports to describe creatine salts of dicarboxylic acids with enhanced aqueous solubility.
The above disclosed patents recite creatine salts, methods of synthesis of the salts, and uses thereof. However, nothing in any of the disclosed patents teaches, suggests or discloses a compound comprising a creatine molecule bound to a fatty acid.
In addition to salts, creatine esters have also been described. U.S. Pat. No. 6,897,334 describes method for producing creatine esters with lower alcohols i.e. one to four carbon atoms, using acid catalysts. It is stated that creatine esters are more soluble than creatine. It is further stated that the protection of the carboxylic acid moiety of the creatine molecule by ester-formation stabilizes the compound by preventing its conversion to creatinine. The creatine esters are said to be converted into creatine by esterases i.e. enzymes that cleave ester bonds, found in a variety of cells and biological fluids.
Fatty acids are carboxylic acids, often containing a long, unbranched chain of carbon atoms and are either saturated or unsaturated. Saturated fatty acids do not contain double bonds or other functional groups, but contain the maximum number of hydrogen atoms, with the exception of the carboxylic acid group. In contrast, unsaturated fatty acids contain one or more double bonds between adjacent carbon atoms, of the chains, in cis or trans configuration
The human body can produce all but two of the fatty acids it requires, thus, essential fatty acids are fatty acids that must be obtained from food sources due to an inability of the body to synthesize them, yet are required for normal biological function. The essential fatty acids being linoleic acid and α-linolenic acid.
Examples of saturated fatty acids include, but are not limited to myristic or tetradecanoic acid, palmitic or hexadecanoic acid, stearic or octadecanoic acid, arachidic or eicosanoic acid, behenic or docosanoic acid, butyric or butanoic acid, caproic or hexanoic acid, caprylic or octanoic acid, capric or decanoic acid, and lauric or dodecanoic acid, wherein the aforementioned comprise from at least 4 carbons to 22 carbons in the chain.
Examples of unsaturated fatty acids include, but are not limited to oleic acid, linoleic acid, linolenic acid, arachidonic acid, palmitoleic acid, eicosapentaenoic acid, docosahexaenoic acid and erucic acid, wherein the aforementioned comprise from at least 4 carbons to 22 carbons in the chain.
Fatty acids are capable of undergoing chemical reactions common to carboxylic acids. Of particular relevance to the present invention are the formation of salts and the formation of esters. The majority of the above referenced patents are creatine salts. These salts, esterification via carboxylate reactivity, may essentially be formed, as disclosed in U.S. Pat. No. 7,109,373, through a relatively simple reaction by mixing a molar excess of creatine or derivative thereof with an aqueous dicarboxylic acid and heating from room temperature to about 50° C.
Alternatively, a creatine-fatty acid may be synthesized through ester formation. The formation of creatine esters has been described (Dox A W, Yoder L. Esterification of Creatine. J. Biol. Chem. 1922, 67, 671-673). These are typically formed by reacting creatine with an alcohol in the presence of an acid catalyst at temperatures from 35° C. to 50° C. as disclosed in U.S. Pat. No. 6,897,334.
While the above referenced creatine compounds have attempted to address issues such as stability and solubility in addition to, and in some cases, to add increased functionality as compared to creatine alone, no description has yet been made of any creatine-fatty acid compound, particularly that comprising a saturated fatty acid.
SUMMARY OF THE INVENTION
In the present invention, compounds are disclosed, where the compounds comprise a molecule of creatine bound to a fatty acid, via an anhydride linkage, and having a structure of Formula 1:
where:
R is an alkyl group, preferably saturated, and containing from about 3 to a maximum of 21 carbons.
Another aspect of the invention comprises the use of a saturated fatty acid in the production of compounds disclosed herein.
A further aspect of the present invention comprises the use of an unsaturated fatty in the production of compounds disclosed herein.
DETAILED DESCRIPTION OF THE INVENTION
In the following description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without these specific details.
The present invention relates to structures and synthesis of creatine-fatty acid compounds bound via an anhydride linkage. In addition, specific benefits are conferred by the particular fatty acid used to form the compounds in addition to, and separate from, the creatine substituent.
As used herein, the term ‘fatty acid’ includes both saturated, i.e. an alkane chain as known in the art, having no double bonds between carbons of the chain and having the maximum number of hydrogen atoms, and unsaturated, i.e. an alkene or alkyne chain, having at least one double or alternatively triple bond between carbons of the chain, respectively, and further terminating the chain in a carboxylic acid as is commonly known in the art, wherein the hydrocarbon chain is not less then four carbon atoms. Furthermore, essential fatty acids are herein understood to be included by the term ‘fatty acid’.
As used herein, “creatine” refers to the chemical N-methyl-N-guanyl Glycine, (CAS Registry No. 57-00-1), also known as, (alpha-methyl guanido) acetic acid, N-(aminoiminomethyl)-N-glycine, Methylglycocyamine, Methylguanidoacetic Acid, or N-Methyl-N-guanylglycine. Additionally, as used herein, “creatine” also includes derivatives of creatine such as esters, and amides, and salts, as well as other derivatives, including derivatives having pharmacoproperties upon metabolism to an active form.
According to the present invention, the compounds disclosed herein comprise a creatine molecule bound to a fatty acid, wherein the fatty acid is preferably a saturated fatty acid. Furthermore, the creatine and fatty acid being bound by an anhydride linkage and having a structure according to Formula 1. The aforementioned compound being prepared according to the reaction as set forth for the purposes of the description in Scheme 1:
With reference to Scheme 1, in Step 1 an acyl halide (4) is produced via reaction of a fatty acid (2) with a thionyl halide (3).
In various embodiments of the present invention, the fatty acid of (2) is selected from the saturated fatty acid group comprising butyric or butanoic acid, caproic or hexanoic acid, caprylic or octanoic acid, capric or decanoic acid, lauric or dodecanoic acid, myristic or tetradecanoic acid, palmitic or hexadecanoic acid, stearic or octadecanoic acid, arachidic or eicosanoic acid, and behenic or docosanoic acid.
In alternative embodiments, of the present invention, the fatty acid of (2) is selected from the unsaturated fatty acid group comprising oleic acid, linoleic acid, linolenic acid, arachidonic acid, palmitoleic acid, eicosapentaenoic acid, docosahexaenoic acid, and erucic acid.
Furthermore, the thionyl halide of (3) is selected from the group consisting of fluorine, chlorine, bromine, and iodine, the preferred method using chlorine or bromine.
The above reaction proceeds under conditions of heat ranging between from about 35° C. to about 50° C. and stirring over a period from about 0.5 hours to about 2 hours during which time the gases sulfur dioxide and acidic gas, wherein the acidic gas species is dependent on the species of thionyl halide employed, are evolved. Preferably, the reaction proceeds at 45° C. for 1.5 hours.
Step 2 of Scheme 1 entails the neutralization of the carboxylic acid of the creatine portion through the addition of an inorganic base. The inorganic base is selected from the group comprising sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, sodium carbonate. Preferred inorganic bases for the purposes of the present invention are sodium hydroxide and potassium hydroxide.
Neutralization, as described above, is followed by the evaporation of water, resulting in the isolation of the corresponding salt. For example, potassium hydroxide, when used as the inorganic base, results in the production of the potassium creatine salt.
Step 3 of Scheme 1 involves the drop wise addition of the prepared acyl halide (4) to the creatine salt (6) in a cooled flask and subsequent purification by two rounds of distillation to yield the desired anhydride compound (1), the anhydride compound being a creatine fatty acid compound of the present invention.
In various embodiments, according to aforementioned, using the saturated fatty acids, the following compounds are produced produced: butyric 2-(1-methylguanidino)acetic anhydride, hexanoic 2-(1-methylguanidino)acetic anhydride, 2-(1-methylguanidino)acetic octanoic anhydride, decanoic 2-(1-methylguanidino)acetic anhydride, 2-(1-methylguanidino)acetic tetradecanoic anhydride, 2-(1-methylguanidino)acetic palmitic anhydride, icosanoic 2-(1-methylguanidino)acetic anhydride, and docosanoic 2-(1-methylguanidino)acetic anhydride.
In additional embodiments, according to aforementioned, using the unsaturated fatty acids, the following compounds are produced produced: (Z)-hexadec-9-enoic 2-(1-methylguanidino)acetic anhydride, 2-(1-methylguanidino)acetic oleic anhydride, (Z)-docos-13-enoic 2(1-methylguanidino)acetic anhydride, 2-(1-methylguanidino)acetic (9Z, 12Z)-octadeca-9,12-dienoic anhydride, 2-(1-methylguanidino)acetic (9Z,12Z,15Z)-octadeca-9,12,15-trienoic anhydride, 2-(1-methylguanidino)acetic (6Z,9Z,12Z)-octadeca-6,9,12-trienoic anhydride, (5Z,8Z,11Z,14Z)-icosa-5,8,11,14-tetraenoic 2(1-methylguanidino)acetic anhydride, (5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11,14,17-pentaenoic 2(1-methylguanidino)acetic anhydride, 2(1-methylguanidino)acetic (8Z,11Z,14Z,17Z,20Z)-tricosa-5,8,11,14,17,20-hexaenoic anhydride.
The following examples illustrate specific creatine-fatty acids and routes of synthesis thereof. One of skill in the art may envision various other combinations within the scope of the present invention, considering examples with reference to the specification herein provided.
EXAMPLE 1
Butyric 2-(1-methylguanidino)acetic anhydride
In a dry 2-necked, round bottomed flask, equipped with a magnetic stirrer and fixed with a separatory funnel, containing 8.75 ml (120 mmol) of thionyl chloride, and a water condenser, is placed 9.05 ml (100 mmol) of butanoic acid. Addition of the thionyl chloride is completed with heating to about 40° C. over the course of about 30 minutes. When addition of the thionyl chloride is complete the mixture is heated and stirred for an additional 30 minutes. The water condenser is then replaced with a distillation side arm condenser and the crude mixture is distilled. The crude distillate in the receiving flask is then fractionally distilled to obtain the acyl chloride, butyryl chloride.
Separately, in a single-necked, round bottomed flask, equipped with a magnetic stirrer, 6.56 g (50 mmol) of creatine is dissolved in 500 ml of water. To this is added 55 ml of 1M sodium hydroxide with vigorous stirring, until heat production ceases. At this point the water is removed by evaporation to yield the carboxylate salt, sodium 2-(1-methylguanidino)acetate, shown below.
Finally, in a dry 2-necked, round bottomed flask, fixed with a separatory funnel, containing 6.39 g (60 mmol) of the prepared butyryl chloride, and side arm water condenser fixed with a dry receiving flask, is placed 12.08 g (66 mmol) of sodium 2-(1-methylguanidino)acetate. The round bottomed flask is placed in an ice bath and the butyryl chloride is added drop wise. After addition is completed the mixture is shaken and the ice bath is replaced by a heating mantle. The flask is then heated until no more solution is dropping into the receiving flask. This crude distillate is then further fractionally distilled to yield butyric 2-(1-methylguanidino)acetic anhydride.
EXAMPLE 2
Hexanoic 2-(1-methylguanidino)acetic anhydride
In a dry 2-necked, round bottomed flask, equipped with a magnetic stirrer and fixed with a separatory funnel, containing 6.97 ml (90 mmol) of thionyl bromide, and a water condenser, is placed 5.68 ml (45 mmol) of hexanoic acid. Addition of the thionyl bromide is completed with heating to about 50° C. over the course of about 50 minutes. When addition of the thionyl bromide is complete the mixture is heated and stirred for an additional hour. The water condenser is then replaced with a distillation side arm condenser and the crude mixture is distilled. The crude distillate in the receiving flask is then fractionally distilled to obtain the acyl bromide, hexanoyl bromide.
Separately, in a single-necked, round bottomed flask, equipped with a magnetic stirrer, 6.56 g (50 mmol) of creatine is dissolved in 500 ml of water. To this is added 55 ml of 1M sodium hydroxide with vigorous stirring, until heat production ceases. At this point the water is removed by evaporation to yield the carboxylate salt, sodium 2-(1-methylguanidino)acetate, shown below.
Finally, in a dry 2-necked, round bottomed flask, fixed with a separatory funnel, containing 10.81 g (60 mmol) of the prepared hexanoyl bromide, and side arm water condenser fixed with a dry receiving flask, is placed 13.18 g (72 mmol) of sodium 2-(1-methylguanidino)acetate. The round bottomed flask is placed in an ice bath and the hexanoyl bromide is added drop wise. After addition is completed the mixture is shaken and the ice bath is replaced by a heating mantle. The flask is then heated until no more solution is dropping into the receiving flask. This crude distillate is then further fractionally distilled to yield hexanoic 2-(1-methylguanidino)acetic anhydride.
EXAMPLE 3
Dodecanoic 2-(1-methylguanidino)acetic anhydride
In a dry 2-necked, round bottomed flask, equipped with a magnetic stirrer and fixed with a separatory funnel, containing 5.85 ml (80 mmol) of thionyl chloride, and a water condenser, is placed 10.02 g (50 mmol) of dodecanoic acid. Addition of the thionyl chloride is completed with heating to about 45° C. over the course of about 40 minutes. When addition of the thionyl chloride is complete the mixture is heated and stirred for an additional 50 minutes. The water condenser is then replaced with a distillation side arm condenser and the crude mixture is distilled. The crude distillate in the receiving flask is then fractionally distilled to obtain the acyl chloride, dodecanoyl chloride.
Separately, in a single-necked, round bottomed flask, equipped with a magnetic stirrer, 7.87 g (60 mmol) of creatine is dissolved in 600 ml of water. To this is added 78 ml of 1M ammonium hydroxide with vigorous stirring, until heat production ceases. At this point the water is removed by evaporation to yield the carboxylate salt, ammonium 2-(1-methylguanidino)acetate, shown below.
Finally, in a dry 2-necked, round bottomed flask, fixed with a separatory funnel, containing 15.31 g (70 mmol) of the prepared dodecanoyl chloride, and side arm water condenser fixed with a dry receiving flask, is placed 12.44 g (84 mmol) of ammonium 2-(1-methylguanidino)acetate. The round bottomed flask is placed in an ice bath and the dodecanoyl chloride is added drop wise. After addition is completed the mixture is shaken and the ice bath is replaced by a heating mantle. The flask is then heated until no more solution is dropping into the receiving flask. This crude distillate is then further fractionally distilled to yield dodecanoic 2-(1-methylguanidino)acetic anhydride.
EXAMPLE 4
2-(1-methylguanidino)acetic stearic anhydride
In a dry 2-necked, round bottomed flask, equipped with a magnetic stirrer and fixed with a separatory funnel, containing 4.81 ml (66 mmol) of thionyl chloride, and a water condenser, is placed 15.65 g (55 mmol) of stearic acid. Addition of the thionyl chloride is completed with heating to about 45° C. over the course of about 40 minutes. When addition of the thionyl chloride is complete the mixture is heated and stirred for an additional 45 minutes. The water condenser is then replaced with a distillation side arm condenser and the crude mixture is distilled. The crude distillate in the receiving flask is then fractionally distilled to obtain the acyl chloride, stearoyl chloride.
Separately, in a single-necked, round bottomed flask, equipped with a magnetic stirrer, 7.87 g (60 mmol) of creatine is dissolved in 600 ml of water. To this is added 72 ml of 1M potassium hydroxide with vigorous stirring, until heat production ceases. At this point the water is removed by evaporation to yield the carboxylate salt, potassium 2-(1-methylguanidino)acetate, shown below.
Finally, in a dry 2-necked, round bottomed flask, fixed with a separatory funnel, containing 21.27 g (70 mmol) of the prepared stearoyl chloride, and side arm water condenser fixed with a dry receiving flask, is placed 23.40 g (77 mmol) of potassium 2-(1-methylguanidino)acetate. The round bottomed flask is placed in an ice bath and the stearoyl chloride is added drop wise. After addition is completed the mixture is shaken and the ice bath is replaced by a heating mantle. The flask is then heated until no more solution is dropping into the receiving flask. This crude distillate is then further fractionally distilled to yield 2-(1-methylguanidino)acetic stearic anhydride.
EXAMPLE 5
2-(1-methylguanidino)acetic (9Z,12Z)-octadeca-9,12-dienoic anhydride
In a dry 2-necked, round bottomed flask, equipped with a magnetic stirrer and fixed with a separatory funnel, containing 9.35 ml (128 mmol) of thionyl chloride, and a water condenser, is placed 24.90 ml (80 mmol) of linoleic acid. Addition of the thionyl chloride is completed with heating to about 40° C. over the course of about 40 minutes. When addition of the thionyl chloride is complete the mixture is heated and stirred for an additional 50 minutes. The water condenser is then replaced with a distillation side arm condenser and the crude mixture is distilled. The crude distillate in the receiving flask is then fractionally distilled to obtain the acyl chloride, (9Z,12Z)-octadeca-9,12-dienoyl chloride.
Separately, in a single-necked, round bottomed flask, equipped with a magnetic stirrer, 7.87 g (60 mmol) of creatine is dissolved in 600 ml of water. To this is added 78 ml of 1M ammonium hydroxide with vigorous stirring, until heat production ceases. At this point the water is removed by evaporation to yield the carboxylate salt, ammonium 2-(1-methylguanidino)acetate, shown below.
Finally, in a dry 2-necked, round bottomed flask, fixed with a separatory funnel, containing 17.93 g (60 mmol) of the prepared (9Z,12Z)-octadeca-9,12-dienoyl chloride, and side arm water condenser fixed with a dry receiving flask, is placed 10.66 g (72 mmol) of ammonium 2-(1-methylguanidino)acetate. The round bottomed flask is placed in an ice bath and the (9Z,12Z)-octadeca-9,12-dienoyl chloride is added drop wise. After addition is completed the mixture is shaken and the ice bath is replaced by a heating mantle. The flask is then heated until no more solution is dropping into the receiving flask. This crude distillate is then further fractionally distilled to yield 2-(1-methylguanidino)acetic(9Z,12Z)-octadeca-9,12-dienoic anhydride.
Thus while not wishing to be bound by theory, it is understood that reacting a creatine or derivative thereof with a fatty acid or derivative thereof to form an anhydride can be used enhance the bioavailability of the creatine or derivative thereof by improving stability of the creatine moiety in terms of resistance to hydrolysis in the stomach and blood and by increasing solubility and absorption. Furthermore, it is understood that, dependent upon the specific fatty acid, for example, saturated fatty acids form straight chains allowing mammals to store chemical energy densely, or derivative thereof employed in the foregoing synthesis, additional fatty acid-specific benefits, separate from the creatine substituent, will be conferred.
EXTENSIONS AND ALTERNATIVES
In the foregoing specification, the invention has been described with a specific embodiment thereof; however, it will be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. | The present invention describes compounds produced from a creatine molecule and a fatty acid molecule. The compounds being in the form of creatine-fatty acid compounds being bound by an anhydride linkage, or mixtures thereof made by reacting creatine or derivatives thereof with an appropriate fatty acid previously reacted with a thionyl halide. The administration of such molecules provides supplemental creatine with enhanced bioavailability and the additional benefits conferred by the specific fatty acid. | 2 |
BACKGROUND OF THE INVENTION
This invention relates in general to suspension systems of motor vehicles, of the type automatically providing hydraulic adjustment of the vehicle height or ground clearance, and wherein the spring proper may be of pneumatic or metallic construction.
In many countries traffic regulations require that vehicle bumpers be kept at a minimum height above the road surface. Now, with a suspension system of the type broadly defined here-inabove and after prolonged standing of the vehicle, the unavoidable hydraulic leakages cause the suspension to yield or collapse and therefore the bumpers to assume a position below the minimum prescribed level.
A known proposition for solving this problem consisted in providing means for blocking up the suspension system, which comprised a special insert adapted to be locked, notably in the form of a pawl and ratchet device, but this may be regarded as scarcely suited for the purpose, due to the considerable stress implemented, not to mention manufacturing cost and reliability factors.
SUMMARY OF THE INVENTION
It is the primary object of the present invention to provide an improved solution to the above-defined problem which is characterised in that the means for blocking up the supension system under parking or similar conditions include buffer members each adapted to be retracted and engaged in the fashion of a lock-bolt or chock between a movable suspension member and a fixed portion of the vehicle body or chassis.
According to a preferred embodiment of this invention the control means associated with the buffer members comprise for each buffer member a hydraulic actuator incorporating spring means for urging the buffer member to its retracted position, and a hydraulic chamber communicating with the hydraulic actuators of the system and adapted, when the vehicle hand brake control lever is moved to its braking position, to force hydraulic fluid into the actuators as to move the buffer members to their operative position.
BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the suspension system with the hydraulic height adjustment feature according to this invention will appear as the following description proceeds with reference to the attached drawings, in which:
FIG. 1 is a diagrammatic view illustrating with parts broken away a typical arrangement for controlling the blocking up of the suspension members of hydro-pneumatic wheels of a motor vehicle;
FIG. 2 is a detail view showing in axial section the control device, the hydraulic chamber and a solenoid valve associated therewith;
FIG. 3 is another detail and fragmentary view showing a part-section taken along the line III--III of FIG. 2;
FIG. 4 is a side elevational and sectional view, as seen in the direction of the arrow 4 of FIG. 5, of one end of a wheel suspension arm which is adapted to be engaged by a retractable buffer member, the section being taken along the line IV--IV of FIG. 5;
FIG. 5 is a section taken along the line V--V of FIG. 4;
FIG. 6 is a plan view from above of the components shown in FIG. 5, and
FIG. 7 is a detail view showing in cross section taken along the line VII--VII of FIG. 5 a detail of the same assembly.
DETAILED DESCRIPTION OF THE INVENTION
The vehicle suspension system shown diagrammatically in FIG. 1 for illustrating the principles of the present invention is intended for a well-known type of train of independent wheels which comprises hydropneumatic blocks 1.
Each road wheel 2 is carried by a wheel arm 3 pivoted at 4 to the body of chassis of the vehicle, and this wheel arm 3 is connected to the piston rod 5 of a hydraulic suspension cylinder 6 constituting one of the components of the system for adjusting the height or trim of the body, the hydraulic fluid chamber of this cylinder 6 being separated by means of a flexible membrane 7 from a gas-filled chamber 8 constituting the suspension sphere substituted for the conventional spring, it being understood that the body of each hydropneumatic block 1 is rigidly secured to the vehicle body or chassis. The hydraulic cylinders 6 of this train of wheels are usually supplied with hydraulic fluid in the well-known manner via a correcting device (not shown) consisting of a valve responsive to the ground clearance of the vehicle body, in order to keep the height at a constant value in the static condition of the vehicle.
To prevent the collapsing of the vehicle suspension system under prolonged parking conditions, as a consequence of unavoidable leakages in the hydraulic system, there is provided in the above-described assembly, for each wheel suspension assembly, a retractable buffer member 9 adapted to be interposed, when the vehicle is brought to a standstill, between a buffer arm 3a rigid with the wheel carrier arm 3 and a rigid bearing portion 10 of the vehicle body or chassis, buffer arm 3a consisting in this example of the member usually provided for co-acting with the conventional rubber buffers B limiting the permissible beats of the suspension arms.
Each retractable buffer member 9 is rigid with a push-rod 11 slidably mounted in a cylinder 12 secured to the body or chassis. This push-rod 11 is responsive to the opposed actions of a hydraulic receiver 13 incorporating a flexible diaphragm and a return spring 14 constantly urging the retractable buffer member 9 to its retracted position.
The hydraulic receivers 13 are interconnected by a pipe line connected in turn via a line 15 to chamber 16 in which the hydraulic fluid is adapted to be forced towards the receivers 13 when the hand brake control lever 17 is moved to its braking position.
In this example the pair of receivers 13 of the train of wheels are connected in parallel, but it is clear that a series connection therebetween could be provided as well, the same arrangement being contemplated for the other train of wheels of the vehicle if this other train of wheels is also equipped with hydropneumatic blocks or the like.
Disposed between the hydraulic chamber 16 and pipe line 15 is a solenoid poppet valve 18. This valve 18 comprises a core formed with an axial passage 19 adapted to be isolated by a poppet 20 urged to its passage opening position by a coil spring 21, poppet 20 closing passage 19 when the solenoid coil 22 is energized.
This coil 22 is adapted to be supplied with energizing current from the storage battery 23 of the vehicle via a conventional engine ignition switch 24.
The poppet 20 is also formed with an axial passage 25 and comprises a seat-forming portion 26 adapted to be closed by a spring 27 engaging another poppet valve 28, the force of spring 27 being such that, under certain conditions, as will be explained presently, the hydraulic fluid is allowed to return in the direction from receiver 13 to chamber 16.
When valve 20 is open a normal communication is established between chamber 16 and the passage 19 connected to pipe line 15, this communication being provided (see FIG. 1) via a passage 29 parallel to the cavity guiding the poppet valve 20.
The chamber 16 is closed by a flexible diaphragm 30 responsive to a piston 31 slidably mounted in a body 32 secured to the chassis or body of the vehicle and also rigid with the solenoid valve body. Slidably mounted in turn in piston 31 is a push-rod 33 co-acting piston 31 through the medium of a coil compression spring 34 disposed therebetween.
The push-rod 33 carries at its outer end a roller follower 35 engaging a control actuator or cam 36 consisting of a suitably shaped rod slidably mounted in a bore of body 32 and coupled to the hand brake control lever 17 shown in its brake-release position in FIG. 1. The aforesaid cam 36 is formed with an inclined face 37 adapted to force the roller follower 35 inward and thus compress the spring 34 when the hand-brake control lever 17 is pulled to its brake-applying position as shown in FIG. 1, i.e. in the direction of the arrow F.
The control means for blocking up the suspension system according to this invention operates as follows:
When the vehicle is driven and subsequently brought to a standstill, the driver cuts off the ignition switch 24 before applying the hand brake and the assembly is in the position shown in FIG. 1, i.e. with, inter alia, the movable buffer members 9 retracted by the force of their corresponding return springs.
When the hand brake control lever 17 is pulled in the direction of the arrow F to apply the brakes, the cam face 37 forces the roller follower 35 of push-rod 33 inwards and this push-rod 33, via spring 34, moves the piston 31 and diaphragm 30 to force the liquid out from chamber 16 through the parallel passage 29 and axial passage 19 of the open solenoid poppet valve 18 into the pipe line 15 and eventually the hydraulic receivers 13.
Therefore, actuating the hand brake will tend to move the buffer members 9 on the bearing surface of member 10 to a position interfering with the path of the corresponding buffer arm 3a of the wheel carrier arm assembly 3. This engagement between each buffer member 9 and the relevant bearing surface 10 takes place freely in the position of the suspension system which corresponds to the normal height or ground clearance of the vehicle, as obtained when the vehicle is driven or has just been driven, for it is only after a certain time after the vehicle has been brought to a standstill and as a consequence of hydraulic leakages as mentioned hereinabove that the buffer arms 3a will engage the corresponding buffer members 9 and thus prevent any undesired further collapsing or yielding of the vehicle suspension. It will be seen that the order in which the hand brake is actuated and the ignition switch 24 is cut off is immaterial, for if the switch is not turned off before applying the hand brake the solenoid valve 18 remains closed but the spring 34 is compressed during the brake application and the chamber 16 constitutes a hydraulic pressure accumulator and will become operative as described hereinabove to set the buffer members 9 in position when the switch 24 is actuated and thus caused to open the solenoid valve 18.
Should at least one buffer member 9 be prevented from being engaged as a consequence of the momentary position of the buffer arm 3a, for example when the vehicle is stopped along a considerably canted road (i.e. a road inclined in the transverse direction), it will be seen that this condition can by no means prevent the other buffer members from positioning themselves since in this arrangement they are controlled hydraulically, and that if as a consequence of the unloading of the vehicle, for instance, the aforesaid buffer member clears the buffer arm engagement passage, this buffer arm will also assume the proper position as a consequence of the accumulating action of chamber 16.
When re-starting the vehicle engine, closing the ignition switch 24 will close the solenoid valve 18 by energizing the coil thereof, but on the other hand releasing the hand brake brake will release the spring 34. Under these circumstances, if the buffer members 9 are not urged against their bearing members 10 by the relevant buffer arm 3a, or when they are no longer urged by the relevant buffer arm 3a as a consequence of the recharging of the cylinders 6 by means of the hydraulic correcting device provided in the suspension system for restoring the normal height of the vehicle, their return springs 14 will restore them to the retracted position, as illustrated in FIG. 1, by forcing the hydraulic fluid from the corresponding receiver 13 towards the chamber 16, thus opening the calibrated poppet 28 therein to permit the ingress of the corresponding volume of fluid into this chamber and allowing the components 31, 33, 34 and 35 to resume their initial positions shown in FIG. 1. Also in this case the order in which the hand brake control lever 17 and the ignition switch 24 are actuated is immaterial.
It will be noted that during the operation of the vehicle, while the engine is running, the hand brake control 17 can be actuated both when the vehicle is stationary and when it is being driven, without inasmuch inserting the buffer member 9 inbetween the arm 3a and bearing member 10, for under these conditions the solenoid coil 22 is energized and the poppet valve 20 is seated, the only consequence of a hand brake control actuation being the compression of spring 34 and the building up of liquid pressure in chamber 16.
It will be seen that should hydraulic leakages occur in the circuit controlling the buffer members 9 these members could not be actuated untimely since they are normally urged by their springs to their retracted position.
Likewise, an electric failure cannot cause by itself the actuation of buffer members 9, since such actuation can only take place when, in addition, the hand brake control 17 has been pulled intentionally.
FIGS. 2 and 3 illustrate a typical embodiment of an assembly incorporating the solenoid valve, the hydraulic chamber and the brake control means. In these Figures, the components identical with or similar to those of FIGS. 1 are designated by the same reference numerals to which the index "a" is added. The fluid passage 29 is embodiment as an equivalent passage 20b provided in the outer periphery of the bore guiding the poppet 20a in its cavity.
Moreover, the piston 31a and push-rod 33a are now prevented from rotating by the presence of lateral studs 38 having integral heads engaging axial internal grooves formed in the body 32a, studs 38 engaging on the one hand, without play, apertures formed to this end through the wall of piston 31a and on the other hand elongated holes 33b formed in push-rod 33a to enable this push-rod to compress the spring 34a.
It is also apparent from FIGS. 2 and 3 that cam member 36a is guided in the body 32a and has a contour engaging or wrapping about one-third of the periphery of roller follower 35a urged thereagainst by spring 34a.
FIGS. 4 to 7 inclusive illustrate likewise a practical embodiment of a hydraulic receiver with the corresponding retractable buffer member, these two last-mentioned components being secured to a support 40 for the fixed suspension buffers B in which a buffer member 3'a rigid with the wheel carrier arm 3' is adapted to move. The other members corresponding to those of FIG. 1 are designated by the same reference numerals with in addition the index letter a. The cylinder 12a on the diaphragm-type hydraulic receiver 13a is detachably mounted on a support 41 welded to a mounting platform 42 welded in turn to support 40.
This support 41 has a lug 41a in which notches 41b are formed to permit the axial locking of the cylinder 12a by means of a spring clip 43 engaging notches 41b and also bosses 12b formed on cylinder 12a.
The support 41 also has a bore for guiding the buffer member 9a as clearly shown in FIG. 4, this buffer member 9a being shown in its operative position in FIGS. 5 and 6.
Although specific embodiments of this invention have been described hereinabove and illustrated in the attached drawings, it will readily occur to those skilled in the art that various modifications and changes may be made thereto without departing from the scope of the invention as set forth in the appended claims. | Hydraulic height-adjustment vehicle suspension system includes an arrangment for blocking up the suspension and adapted to prevent the collapsing thereof when the vehicle is kept stationary for a prolonged time period. The blocking arrangement includes a buffer member retractable and engageable in the fashion of a chock or the like, between a movable member of the suspension system and a fixed portion of the body or chassis of the vehicle. Preferably, a control for each buffer member includes a hydraulic receiver operating against the force of a return spring urging the buffer member to its retracted position, and a hydraulic chamber is provided which communicates with the receivers and is urged to its hydraulic fluid delivering condition by the actuation of the hand brake control of the vehicle to its brake applying position. | 1 |
RELATED APPLICATIONS
This application is a divisional application of U.S. Ser. No. 10/160,579 filed May 31, 2002 now abandoned entitled THERMAL QUENCHING OF TISSUE, which is a continuation in part of U.S. Ser. No. 09/364,275 filed Jul. 29, 1999, now U.S. Pat. No. 6,451,007, entitled THERMAL QUENCHING OF TISSUE.
FIELD OF THE INVENTION
This invention is related to the delivery of laser or other source of thermal energy to biological or other tissue for treatment therein.
BACKGROUND OF THE INVENTION
It is sometimes desirable to cause heat affected changes in a selected structure in tissue, such as a vein or hair follicle without causing heat affected changes in tissue adjacent to the selected structure. Selective photothermalysis is a method of irradiating with a laser or pulsed light source that is preferentially absorbed by a pre-selected target. The amount of energy or fluence delivered to the target is chosen such that the temperature rise in the targeted region results in an intended thermal treatment of the target.
Heating of the epidermis may occur during treatment of the target and several methods have been described for cooling the surface of skin during and prior to treatment to minimize the risk of thermal injury to tissue adjacent to the targeted veins. One early method included pre-cooling with ice for several minute prior to treatment. U.S. Pat. No. 5,282,797 issued Feb. 1, 1994 to Chess describes a method of circulating cooling fluid over a transparent plate in contact with the treatment area to cool the epidermis during treatment. U.S. Pat. No. 5,344,418 issued Sep. 6, 1994 to Ghaffari describes a method whereby a coolant is used for a predetermined time interval in coordination with the delivery of laser energy to optimize the cooling of the epidermis and minimize cooling of the targeted vessel. U.S. Pat. No. 5,814,040 issued Sep. 29, 1998 to Nelson et al. describes a cooling method whereby a cryogenic spurt is applied for a predetermined short time directly onto the skin in the target region. The time period for cooling is confined only to the epidermis while leaving the temperature of deeper port wine stains substantially unchanged. Many of the cooling methods may limit the amount of significant thermal damage to the epidermis during treatment.
It may be desirable to shrink collagen in order to reduce the appearance of undesirable conditions of the skin such as acne scars and wrinkles. The following U.S. patents to Sand teach controlled thermal shrinkage of collagen fibers in the cornea using light at wavelengths between 1.8 and 2.55 microns: U.S. Pat. No. 4,976,709, Class No. 606/5, issued Dec. 11, 1990; U.S. Pat. No. 5,137,530; U.S. Pat. No. 5,304,169; U.S. Pat. No. 5,374,265; and U.S. Pat. No. 5,484,432.
U.S. Pat. No. 5,810,801, class no. 606/9 issued Sep. 22, 1998 to Anderson et al. teaches a method and apparatus for treating wrinkles in skin by targeting tissue at a level between 100 microns and 1.2 millimeters below the surface, to thermally injure collagen without causing erythema, by using light at wavelengths between 1.3 and 1.8 microns. Because of the high scattering and absorption coefficients, precooling is utilized to prevent excess heat build up in the epidermis when targeting the region of 100 microns to 1.2 mm below the surface. Specific laser and cooling parameters are selected so as to avoid erythema and achieve improvement in wrinkles as the long term result of a treatment.
ADVANTAGES AND SUMMARY OF THE INVENTION
The present invention provides a system for achieving erythema and/or mild edema in an upper layer of skin, without causing blisters, and without the risk of high fluence levels or critical need for cooling.
The invention uses a source of thermal energy, which may be infrared in the wavelength range of 1100 nm to 2.9 nm, to cause thermally mediated effects in skin. The systems and methods are directed toward heating the skin with a source of energy which is uniformly attenuated with depth in skin for a predetermined time period and predetermined fluence so that the exposure time of the epidermis and the peak temperature reached by the epidermis are such that the epidermis does not blister but the thermally mediated injury in the skin below the epidermis causes a transient erythema to initiate a healing response. By achieving erythema and/or mild edema in an upper layer of skin, the system precludes the risk of high fluence levels or critical need for cooling. The dosage and time period of application are adjusted to prevent excess accumulation of heat in the epidermis, which would cause tissue damage. Thermal quenching is used to remove latent heat from the treatment site to prevent thermal damage to the tissue. Collagen remodeling is induced by distributing the laser energy over a series of more benign treatments spaced weeks apart.
It is therefore an advantage and an object of the present invention to provide an improved system for selectively cooling tissue during photothermal treatment.
It is a further advantage of the present invention to provide such a system which uses dynamic cooling to quench heat build up during and after photothermal treatment.
It is a further advantage of the present invention to provide such a system which selectively heats a subsurface structure in tissue and subsequently quenches heat build up in non-target tissue.
It is a further advantage of the present invention to reduce the level of pulsed energy needed for treatment by minimizing precooling of the tissue.
It is a further advantage of the present invention to provide such a system which selectively heats a subsurface structure in skin to cause thermal affected changes in said subsurface structure without significant epithelial damage due to subsequent heating from the target region.
It is a further advantage of the present invention to provide such a system which selectively heats vascular lesions in tissue and quenches subsequent heat build up in epithelial tissue.
It is a further advantage of the present invention to provide such a system which selectively heats hair follicles in tissue and quenches subsequent heat build up in epithelial tissue.
It is a further advantage of the present invention to require less cooling of the target area than is typically required, resulting in more efficient heating of the selected target and less thermal damage to surrounding tissue.
In a preferred embodiment, the system for generating light energy is a laser system such as but not limited to a solid-state laser, including but not limited to a neodymium-doped yttrium-aluminum-garnet (Nd:YAG) laser.
In additional preferred embodiments, the system for generating light energy is a gas discharge flashlamp or an incandescent-type filament lamp.
The energy from the generating system may be directed into or coupled to a delivery device such as but not limited to a fiber optic or articulated arm for transmitting the light energy to the target tissue.
The light energy may be focused on tissue with a focusing lens or system of lenses.
The surface of the tissue may be cooled with a cooling device including but not limited to an irrigating solution, a spray or flow of refrigerant or other cryogenic material, or a transparent window cooled by other active means, or other dynamic or passive cooling means.
The tissue may be preheated with a heating device such as, but not limited to an intense light source, a flashlamp, a filament lamp, laser diode, other laser source, electrical current, or other electromagnetic or mechanical energy which penetrates into layers of tissue beneath the surface. The preheating can occur simultaneously or just prior to the surface cooling of tissue from the cooling device such that the tissue preheating results in a temperature rise in underlying layers of tissue, and a temperature profile results. The pulsed application of energy from the energy delivery device results in a temperature profile that preferentially heats a selected structure or target in tissue, and the post cooling prevents thermal damage to tissue adjacent to that structure. This also reduces the overall pulse energy level needed of the pulsed treatment device due to the fact that a desirable temperature profile exists prior to delivery of the pulsed treatment energy.
The tissue may be post cooled with a dynamic cooling device such as, but not limited to a pulse, spray or other flow of refrigerant such that the post cooling occurs after a temperature rise in an underlying targeted structure and a temperature profile results such that the pulsed application of energy from the energy delivery device results in a temperature profile that preferential heats a selected structure in tissue without subsequent undesirable heating to tissue adjacent to that structure from thermal conduction.
Numerous other advantages and features of the present invention will become readily apparent from the following detailed description of the invention and the embodiments thereof, from the claims and from the accompanying drawings.
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.
Further objects and advantages of the present invention will be come apparent through the following descriptions, and will be included and incorporated herein.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a representative schematic block diagram of a preferred embodiment of a system for thermal quenching of tissue of the present invention.
FIG. 2 is a more detailed representative schematic block diagram of a preferred embodiment of the delivery device shown in FIG. 1 of the present invention.
FIG. 3 is a representative sample data plot of the temperature of surface tissue and target tissue achieved by methods and systems of the prior art having precooling.
FIG. 4 is a representative sample data plot of the temperature of surface tissue and target tissue achieved by a preferred embodiment of the method and system of the present invention such as shown in FIGS. 1 and 2 having precooling.
FIG. 5 is a representative sample data plot of the temperature of surface tissue and target tissue achieved by a preferred embodiment of the method and system of the present invention such as shown in FIGS. 1 and 2 without precooling.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The description that follows is presented to enable one skilled in the art to make and use the present invention, and is provided in the context of a particular application and its requirements. Various modifications to the disclosed embodiments will be apparent to those skilled in the art, and the general principals discussed below may be applied to other embodiments and applications without departing from the scope and spirit of the invention. Therefore, the invention is not intended to be limited to the embodiments disclosed, but the invention is to be given the largest possible scope which is consistent with the principals and features described herein.
It will be understood that in the event parts of different embodiments have similar functions or uses, they may have been given similar or identical reference numerals and descriptions. It will be understood that such duplication of reference numerals is intended solely for efficiency and ease of understanding the present invention, and are not to be construed as limiting in any way, or as implying that the various embodiments themselves are identical.
The description that follows is presented to enable one skilled in the art to make and use the present invention, and is provided in the context of a particular application and its requirements. Various modifications to the disclosed embodiments will be apparent to those skilled in the art, and the general principals discussed below may be applied to other embodiments and applications without departing from the scope and spirit of the invention. Therefore, the invention is not intended to be limited to the embodiments disclosed, but the invention is to be given the largest possible scope which is consistent with the principals and features described herein.
FIG. 1 is a representative schematic block diagram of a preferred embodiment of a system 100 for thermal quenching of tissue of the present invention. Operation of energy source 102 to produce energy for delivery by the system 100 is controlled according to control signal 104 from control system 106 . Control system 106 includes a physician interface 108 for operating the system. Said interface 108 optionally includes a footswitch for energy delivery, display and interactive and/or menu driven operation utilizing operator input, prompts, etc. Additional energy delivery control interface means shall be known to those skilled in the art.
In a preferred embodiment, energy source 102 is a neodymium doped yttrium-aluminum-garnet (Nd:YAG) laser, energized by a flash-lamp or laser diode. Energy source 102 is controlled by control system 106 which comprises the software and electronics to monitor and control the laser system, and interface 108 . The beam of laser energy I 10 from the energy source 102 is directed into a delivery device 112 which may be an optical fiber, a fiber bundle or articulated arm, etc.
Modern instruments to provide dynamic cooling of the surface layers of tissue or other materials are well suited to these applications. A coolant spray can be provided through a handpiece or it could be provided with another separate device. Finally, a connection to a computer and the control system 106 of the energy source 102 will allow the system 100 to utilize electronic or other thermal sensing means and obtain feedback control signals for the handpiece. An optimum cooling strategy might be one that uses a post-irradiation cooling spurt that provides cooling or dissipation of the epidermal heat generated by absorption of energy in the non-isotropic skin, optionally containing various pigmentation levels. An appropriate cryogen spray would be liquid nitrogen or tetrafluoroethane, C.sub.2H.sub.2F.sub.4, an environmentally compatible, non-toxic, non-flammable freon substitute. In clinical application the distance between the aperture of the spray valve and the skin surface should be maintained at about 20 millimeters.
In a preferred embodiment of the present invention, upon delivery of laser energy onto the surface and therethrough, the target tissue will be raised to the optimal treatment temperature and generally not any higher, in an adequately rapid process, with the surface temperature of the skin remaining at a temperature below the threshold for damage temperature. It will be understood that the threshold for damage temperature is the temperature below which the skin or other tissue can be elevated without causing temporary or permanent thermal damage, and above which the tissue may undergo either transient or long term thermally induced physiological change. As described, the wavelength of irradiated light energy is selectively absorbed by hemoglobin or hair follicles, or other tissue with pigmentation or chromophores of a certain type, but passes through the surface and overlying/adjacent tissue to the target tissue with minimal absorption. However, once the target tissue or structure becomes elevated in temperature, surrounding and adjacent tissue will become hot due to conduction of heat from the target tissue or structures. Post-irradiation cooling can then be initiated, and tissue other than the target tissue is prevented from increasing in temperature beyond the threshold of damage or adverse effect. Adverse effects of elevated tissue surface temperature include discomfort or pain, thermal denaturing of proteins and necrosis of individual cells at the surface only, or deeper tissue ablation potentially leading to hyperplasia, scarring, or hyperpigmentation, a proliferation of cells formed in response to the induced trauma. In a preferred embodiment of the method of the present invention, heating and subsequent post-cooling are performed in a predetermined timing sequence, optionally with the use of timer circuits and/or other controller means.
Thus, it will be obvious to those skilled in the art that a passive heat sink includes glass or sapphire tip probes, and other types of devices to lay on the surface of the skin. It will also be obvious that a dynamic type of heat sink will refer to those actively cooled by flowing gas or liquid, jets or spurts of coolant such as freon, and other active types of heat exchangers suitable for surface cooling while irradiating sub-surface portions of collagen tissue. U.S. Pat. No. 5,820,626 issued Oct. 13, 1998 to Baumgardner and U.S. application Ser. No. 08/938,923 filed Sep. 26, 1997 by Baumgardner et al., both incorporated herein by reference in their entireties, teach a cooling laser handpiece with refillable coolant reservoir, and can be utilized as a handpiece for delivery device 112 and heat sink 114 .
FIG. 2 is a more detailed representative schematic block diagram of a preferred embodiment of the delivery device 112 shown in FIG. 1 of the present invention. The energy from the energy source 102 is directed into delivery device 112 via a delivery channel 130 which may be a fiber optic, articulated arm, or an electrical cable etc. At the distal end of delivery device 112 is a energy directing means 131 for directing the pulsed energy toward the surface tissue 116 and overlaying tissue 118 overlaying the target tissue or structure 120 . A nozzle 134 is useful for directing coolant from reservoir 135 to the tissue 118 , and a valve 136 for controlling the coolant interval. A temperature sensor 137 may be used to monitor the temperature rise of the target tissue 118 . Control system 106 monitors the temperature signal from sensor 137 and controls valve 136 and energy source 102 . Reservoir 135 may be in the delivery device 112 or elsewhere, and contains a refrigerant which may be applied to surface tissue 120 by spraying said refrigerant from cooling nozzle 124 in conjunction with delivery of pulsed treatment energy to the patient.
FIG. 3 is a representative sample data plot of the temperature of surface tissue 116 and target tissue 120 achieved by methods and systems of the prior art having precooling. The waveforms are representative of oscilloscope-type traces which reproduce signals generated by one or more thermal detectors. In general, with precooling the coolant is applied just prior to the delivery to the pulsed energy. Waveform 240 indicates the periods of time and associated temperatures of the target tissue and the surface tissue during the processes of the prior art. Initially, as indicated by time period 241 , the temperature of the surface tissue 116 as well as the target tissue 120 , as shown in FIGS. 1 and 2 , are at T.sub.s and T.sub.t respectively. It will be understood that typically the skin surface is at a temperature somewhat below actual body temperature. Typically, this range might be between about 28 and about 34 degrees Celsius. Furthermore, a target vein, hair follicle or other structure can be assumed to be at about or somewhat just below 37 degrees Celsius, or actual body temperature. Once the refrigerant is applied to surface tissue 116 by opening valve 136 during a subsequent time period 244 , the temperature T.sub.s drops to a level determined by the length of time 244 for which the surface tissue 120 is exposed to the coolant. By way of example, for time periods of about 30 milliseconds, T.sub.s may drop from a typical temperature of about 32 degrees Celsius to just above 0 degrees Celsius. However, as the target tissues 120 is deeper than the surface 116 , initially T.sub.t is not significantly affected and may drop by only a few degrees. A short delay 245 following delivery of refrigerant may be used, and is typically between 0 and 100 milliseconds. This allows time for cooling of at least a layer of epidermis to a depth of 50 to 250 micrometers. Following time periods 244 and optional period 245 , the pulsed energy is applied over predetermined or other time period 246 . The time period 246 depends on the size of the target and the fluence delivered, as indicated by principles of selective photothermalysis. For example, in experiments with an Nd:YAG laser operating at 1064 nanometers, one application of a 10 millisecond period and a fluence of 50 joules per square centimeter was sufficient to treat small blood vessels, and fluences of up to 150 joules per square centimeter and time periods of up to 200 milliseconds are useful for treating larger vessels of 1 to 3 millimeters in cross-section. During period 246 T.sub.t increases to a therapeutically effective value, whereas T.sub.s remains below the threshold indicated as 250 for patient discomfort or tissue damage.
Subsequent to treatment, the target tissue 116 cools by conduction of thermal energy to adjacent overlaying tissue 118 including the surface tissue 116 , with a resultant temperature rise in the target tissue 120 dependant on the size and depth of the target tissue 120 . As T.sub.t equalizes with surrounding tissue, the T.sub.s may rise above the level of patient discomfort and even cause damage to surface tissue 116 .
FIG. 4 is a representative sample data plot of the temperature of surface tissue 116 and target tissue 120 achieved by a preferred embodiment of the method and system of the present invention such as shown in FIGS. 1 and 2 having precooling. The method of the present invention includes the process of precooling surface tissue 116 and target tissue 120 slightly, followed by a short time period 245 and subsequent delivery of thermal energy to the body during time period 246 such as shown in FIG. 3 . In the present invention, however, refrigerant is also applied subsequent to the energy pulse by opening valve 136 as desired or as indicated, thus keeping T.sub.s below the threshold for damage temperature 250 . FIG. 4 shows a pulse of coolant applied during time period 248 which is subsequent to the application of pulsed energy during period 246 . This results in thermal quenching of the surface tissue 116 . The thermal quenching pulse or other flow of refrigerant or other means for cooling is applied after the beginning of treatment period 246 and may be initiated before or after the end of time period 246 . It is important that the peak or highest temperature of the surface tissue 116 never rise above the threshold for damage temperature 250 . The time point at which the peak temperature in the surface tissue 116 is achieved is dependant on the size and depth of the target 120 .
In one experimental example, cryogenic fluid was applied to the surface tissue 116 within 10 milliseconds of the end of the energy pulse of time period 246 and for a duration 248 of 20 milliseconds. For vascular treatment with an Nd:YAG laser with pulse widths of 5 milliseconds to 200 milliseconds, the period of thermal quenching 248 preferably 10 milliseconds to 30 milliseconds immediately after the treatment energy. This sequence significantly reduced patient discomfort compared to treatment with out thermal quenching. The effect of thermal quenching is not dependant on pre-cooling and may be used as the only method of cooling in many cases.
FIG. 5 is a representative sample data plot of the temperature of surface tissue and target tissue achieved by a preferred embodiment of the method and system of the present invention such as shown in FIGS. 1 and 2 without precooling. As in the method shown in FIG. 4 , the thermal quenching pulse or other flow of refrigerant or other means for cooling over time period 248 is applied after the beginning of treatment period 246 and may be initiated before or after the end of time period 246 . It is important that the peak or highest temperature of the surface tissue 116 never rise above the threshold for damage temperature 250.
The present invention requires less cooling of the target tissue, structure or area during the treatment phase than is typically required, resulting in more efficient heating of the selected target and less thermal damage to surrounding tissue.
It will be understood that while numerous preferred embodiments of the present invention are presented herein, numerous of the individual elements and functional aspects of the embodiments are similar. Therefore, it will be understood that structural elements of the numerous apparatus disclosed herein having similar or identical function may have like reference numerals associated therewith.
In a preferred embodiment of the present invention, re-heating of tissue, especially target or subsurface tissue can be useful. U.S. application Ser. No. 09/185,490 filed Nov. 3, 1998 by Koop et al. entitled Subsurface Heating of Tissue teaches methods and systems for performing subsurface heating of material and tissue, and is incorporated herein by reference in its entirety. With these methods and apparatus, target or subsurface tissue is preheated to an elevated, non-destructive temperature which is somewhat below that of treatment. Thereafter, the temperature of the target tissue or structures is raised to treatment temperature. Once this second increase in temperature is achieved, the target tissue or structures will conduct heat into the body, especially to adjacent tissue and surface tissue, at which time the post-cooling of the present invention can be initiated so as to prevent damage to adjacent tissue or dermis or other surface tissue.
In one embodiment the invention utilizes an Nd:YAG laser at 1320 nm wavelength, (such as the CoolTouch 130, CoolTouch Corp., Auburn Calif.) as the source of treatment energy. At 1320 nm the absorption depth in tissue is such that energy is deposited throughout the upper dermis, with most absorption in the epidermis and upper dermis, a region including the top 200 to 400 microns of tissue. The energy falls off approximately exponentially with the highest level of absorbed energy in the epidermis. Optical heating of skin follows exposure to the laser energy. If the time of exposure to the laser is very short compared to the time required for heat to diffuse out of the area exposed, the thermal relaxation time, than the temperature rise at any depth in the exposed tissue will be proportional to the energy absorbed at that depth. However, if the pulse width is comparable or longer to the thermal relaxation time of the exposed tissue than profile of temperature rise will not be as steep. Conduction of thermal energy occurs at a rate proportional to the temperature gradient in the exposed tissue. Lengthening the exposure time will reduce the maximum temperature rise in exposed tissue.
For instance, at 1.3 microns the laser pulse width may be set to 30 milliseconds and fluence to less than 30 joules per square centimeter. This prevents excessive heat build up in the epidermis, which is approximately the top 100 microns in skin. The papillary dermis can then be heated to a therapeutic level without damage to the epidermis. The epidermis will reach a temperature higher than but close to that of the papillary dermis.
The epidermis is more resilient in handling extremes of temperature than most other tissue in the human body. It is therefore possible to treat the papillary dermis in conjunction with the epidermis without scarring or blistering, by treating both layers with laser energy and allowing a long enough exposure time such that the thermal gradient between the epidermis and underlying layers remains low. In this way the underlying layers can be treated without thermal damage to the epidermis.
It is known that thermal damage in tissue is time dependant and brief exposures to high temperature levels may be tolerated in situations where long exposures are lethal or injurious. Terminating the exposure of the epidermis to elevated temperatures will decrease the risk of damage to the epidermis. In this invention thermal quenching is used to terminate the exposure of the epidermis to elevated temperatures. In this embodiment cryogen spray cooling is use to reduce the epidermal temperature following the exposure to laser radiation. The laser heats the epidermis and lower layers simultaneously because of penetration of the laser energy into tissue. The cryogen cooling works from the top surface and heat flows out of the lower layers by conduction over a time period equivalent to the thermal relaxation time at each depth of tissue. As a result the epidermis is heated for a shorter time period than the papillary dermis or other deeper layers.
In this invention a top layer of tissue can be protected by limiting the time of exposure to elevated temperatures, and deeper layers are protected by the attenuation of light energy in tissue water.
The depth of protection due to cooling is determined by the degree of cooling and the time delay after laser exposure. In the embodiment described here 30 milliseconds of cooling spray is applied without delay, (within 5 milliseconds), after the termination of the laser exposure. The cooling may be delayed to cause longer thermal exposures of the surface. The amount of cooling is enough to reduce the temperature of the surface to non-therapeutic levels. Higher cooling levels will terminate heat build up deeper in tissue.
A wavelength of 1.3 microns is used in this embodiment to treat the middle layers of skin. Other wavelengths such as 1.45 or 2.1 microns may by used to treat more superficial layers of skin by this method. It is important that the wavelength is chosen such that there is absorption in tissue water such that the energy attenuation versus depth is fairly uniform over an area of skin. The range of wavelengths longer than 1100 nm in the infrared have this property. It is important that the energy source used for this invention is uniformly attenuated with depth in tissue. Ultrasound, microwaves, and RF electrical current are examples.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Although any methods and materials similar or equivalent to those described can be used in the practice or testing of the present invention, the preferred methods and materials are now described. All publications and patent documents referenced in the present invention are incorporated herein by reference.
While the principles of the invention have been made clear in illustrative embodiments, there will be immediately obvious to those skilled in the art many modifications of structure, arrangement, proportions, the elements, materials, and components used in the practice of the invention, and otherwise, which are particularly adapted to specific environments and operative requirements without departing from those principles. The appended claims are intended to cover and embrace any and all such modifications, with the limits only of the true purview, spirit and scope of the invention.
The description that follows is presented to enable one skilled in the art to make and use the present invention, and is provided in the context of a particular application and its requirements. Various modifications to the disclosed embodiments will be apparent to those skilled in the art, and the general principals discussed below may be applied to other embodiments and applications without departing from the scope and spirit of the invention. Therefore, the invention is not intended to be limited to the embodiments disclosed, but the invention is to be given the largest possible scope which is consistent with the principals and features described herein.
In a preferred embodiment of the present invention, re-heating of tissue, especially target or subsurface tissue can be useful. U.S. application Ser. No. 09/185,490 filed Nov. 3, 1998 by Koop et al. teaches methods and systems for performing subsurface heating of material and in incorporated herein by reference in its entirety. In these methods, target or subsurface tissue is preheated to an elevated, non-destructive temperature which is somewhat below that of treatment. Thereafter, the temperature of the target tissue or structures is raised to treatment temperature. Once this second increase in temperature is achieved, the target tissue or structures will conduct heat into the body, especially to adjacent tissue and surface tissue, at which time the post-cooling of the present invention can be initiated so as to prevent damage to adjacent tissue or dermis or other surface tissue.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Although any methods and materials similar or equivalent to those described can be used in the practice or testing of the present invention, the preferred methods and materials are now described. All publications and patent documents referenced in the present invention are incorporated herein by reference.
While the principles of the invention have been made clear in illustrative embodiments, there will be immediately obvious to those skilled in the art many modifications of structure, arrangement, proportions, the elements, materials, and components used in the practice of the invention, and otherwise, which are particularly adapted to specific environments and operative requirements without departing from those principles. The appended claims are intended to cover and embrace any and all such modifications, with the limits only of the true purview, spirit and scope of the invention.P
Thus, specific embodiments and applications of thermal quenching of tissue 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. | The present invention provides a system for achieving erythema and/or mild edema in an upper layer of skin, without causing blisters, and without the risk of high fluence levels or critical need for cooling. | 0 |
BACKGROUND OF THE INVENTION
This invention relates to an extrusion forging method particularly suitable for extrusion forging long products.
The extrusion forging method generally comprises placing a billet in a container and exerting pressure on the billet as held in the container with a punch, for example, thereby extruding the billet through a die. Since this method can be easily performed even on billets of hard metal, it has come to find extensive utility in the fabrication of various parts including automobile parts. Heretofore, the extrusion forging method has been mainly utilized for the fabrication of relatively short rods of circular and complex sections. The reason for the small length of the products is that the production of long rods not merely necessitates application of high pressure during the extrusion forging but also entails a possibility that the fabricated products, when being removed from the die, will be malformed and accordingly lacking in dimensional precision.
SUMMARY OF THE INVENTION
An object of this invention is to provide an extrusion forging method which permits the extrusion forged products to be removed from the die without any malformation.
The present invention attains this object using a double action hydraulic press to support a punch on the inner ram and a container on the outer ram respectively of the press. First, the container is set in position on a die which is fixed in advance, a given billet is placed in the container, and the inner ram is driven to lower the punch to a prescribed depth within the container to effect required extrusion forging. After the extrusion forging, the punch is elevated to a prescribed level and left standing at that level and the outer ram is subsequently driven to raise the container. In this case, since the upper part of the billet still remains undeformed within the container, the extruded part is raised together with the container. Thus, the extruded part is again passed through the die. The container is further raised until the leading end of the extruded part completely departs from the die. In the meantime, the further rise of the container, in effect, allows the punch which is left standing at the elevated level to be inserted therein, with the result that the punch will push the extruded product out of the container. If the extruded part sustains a bend in the course of the extrusion, for example, it will be freed of the bend because it is passed again through the die and because tensile stress is exerted upon the material of the extruded part while the extruded part is being extracted from the die by the container. Further, during the extraction of the extruded product from the container, the extruded part does not sustain any malformation because this extraction proceeds while the undeformed part of the billet is kept in contact with the punch. The extrusion forging performed by this invention, therefore, assures high precision forging even for products of great length.
The other objects and characteristics of the present invention will become apparent from the further disclosure of the invention to be made hereinbelow with reference to the accompanying drawing.
BRIEF EXPLANATION OF THE DRAWING
FIG. 1 is an explanatory diagram illustrating the conventional extrusion forging method.
FIG. 2 is a longitudinal cross section illustrating one preferred embodiment of the extrusion forging apparatus according to the present invention.
FIGS. 3(A), 3(B), 3(C), 3(D) and 3(E) are explanatory diagrams illustrating a process in which the extrusion forging is carried out by use of the apparatus of FIG. 2.
FIG. 4 is an explanatory diagram illustrating the condition of pressure being exerted upon a billet undergoing extrusion forging.
FIG. 5 is a graph showing a typical relation between the adhering force and the length/diameter ratio of an aluminum billet in the container after the extrusion has been carried out by use of the extrusion apparatus of this invention.
FIG. 6 is a graph showing a typical relation between the adhering force and the length/diameter ratio of a mild steel billet in the container after the extrusion has been carried out by use of the extrusion apparatus of this invention.
DESCRIPTION OF PREFERRED EMBODIMENT
The extrusion forging heretofore practiced in the art will be described with reference to FIG. 1.
A billet 2 to be fabricated is placed in a container 1 and a punch 3 is worked to apply pressure downwardly to the upper part of the billet 2 in the container 1. Consequently, the billet 2 is extruded through a die 4 as shaped in a cross section conforming to the cross section of the die 4. In the extrusion of the billet 2 under the pressure of the punch 3, the upper terminal part 5 of the billet 2 remains undeformed within the container 1 even after the thrust of the punch for the extrusion has reached its end. Consequently, the extrusion forged product cannot be removed from the apparatus through the die 4. In the conventional apparatus, therefore, it has been customary for the extrusion forged product to be removed from the apparatus by causing the leading end of the extruded part 7 to be pushed upwardly by a knockout punch 6 thereby permitting the product to be withdrawn in the direction of the undeformed end thereof. In the extrusion forging method, the forging pressure applied by the punch 3 to bear upon the billet 2 is extremely high and, consequently, the extruded part remains partially in tight contact with the die 4. The frictional resistance offered between their surfaces in such tight contact is fairly high. The force with which the knockout punch 6 pushes the leading end of the extruded part therefore is fairly high. Thus, the length of the extruded part 7 has to be limited to the range in which the knockout operation can be effectively performed without inducing the phenomenon of buckling.
This invention has been perfected with a view to solving the aforementioned various faults found with the conventional extrusion forging method. It permits the extrusion forged product to be removed from the apparatus without causing the extruded part of the billet to sustain any buckling and, therefore, enables long billets to be effectively extrusion forged to yield forged products of high precision. This invention will be described with reference to FIG. 2.
An extrusion forging apparatus 10 of the present invention is provided with a container 11, a punch 13, and a die 14. It is further provided with a double action hydraulic press 16 which has an inner ram 18 and an outer ram 19 concentrically disposed thereon.
The die 14 is fixed in position and reinforced with a stress ring 22. For the purpose of this positioning, the die 14 is mounted on a cylindrical pressure pad 23 and kept pressed down by a die fixing plate 25, with the periphery thereof restrained with a die holder 24. The die fixing plate 25 is fastened to the die holder 24. The cylindrical pressure pad 23 and the die holder 24 are mounted on the pressure base 26. All these components are held fast to each other by the cooperation of the die holder retainer 27 and the retainer 20. The retainer 20 is fixed on the bolster 21.
The container 11 is positioned above the die 14. The container consists of a hollow cylindrical wall and has the outer surface of the hollow wall kept squeezed with a stress ring 28. By virtue of its slightly converged cross section 29, the stress ring 28 is pressed against the upper case 31 by a fixing plate 30. The fixing plate 30 is fixed to the upper case 31, while the upper case 31 is fastened to the outer ram 19 which is capable of vertical motion. Thus, the container 11 is made to move in the vertical direction above the die 14 by the outer ram 19 of the press 16.
To the upper opening of the container 11 is opposed the leading end of the punch 13. The rear end of the punch 13 is fixed through a load cell 32 to the inner ram 18 which is adapted to be moved in the vertical direction independently of the outer ram 19. When the inner ram 18 is lowered, the punch 13 fits into the container 11 and descends in conjunction therewith.
Now, the operation of extrusion forging to be carried out by use of the extrusion forging apparatus of the construction described above will be described below.
First, the outer ram 19 of the double action hydraulic press 16 is operated to lower the container 11 and set it in position on the die 14 (FIG. 3(A)).
Then, a billet 12 to be extrusion forged is inserted and set in position within the container 11 (FIG. 3(B)). After the billet 12 has been set right, the inner ram 18 of the double action press 16 is operated to lower the punch 13 and allow it to enter the container 11 and apply pressure to bear upon the billet 12. As a result, the billet 12 is forced through the die 14, and extruded in the shape of the die into the cylindrical pressure pad 23 (FIG. 3(C)). By the time that the descent of the punch 13 is terminated, the greater part of the billet 12 has been converted by extrusion forging into an extruded part 17 and the remaining part 15 remains in its original undeformed shape within the container 11. After the punch 13 has been lowered and the extruded part 17 has been formed to a prescribed length, the inner ram 18 is operated to start the punch 13 moving upwardly and allow it to depart from the container 11, reach a prescribed level where it stands by (FIG. 3(D)). Then, the outer ram 19 is operated to raise the container 11. Since the undeformed part 17 of the billet is attached fast to the inner surface of the container 11, the extruded part 17 is lifted together with the container 11 and drawn out of the die (FIG. 3(E)). while the extruded part 17 is being extracted from the die, it is subject to the large tensile force produced by the container 11 and the die 14. If the extruded part 17 happens to have sustained a bend during the extrusion forging, this great tensile force serves to mend the bend. The continued ascent of the container 11 has an effect of enabling the punch 13 left standing by to enter the container 11. When the height of the punch 13 is fixed in advance so that the leading end of the punch 13 comes into contact with the undeformed part 15 of the billet after the time that the leading end of the extruded part 17 has completely departed from the die 14, the punch is enabled to give a push to the upper end surface of the undeformed part of the billet enough for the extrusion forged product to be forced out of the container 11. Consequently, the extrusion forged product can be removed from the extrusion forging apparatus 10 without sustaining any malformation in the extruded portion.
In the extrusion forging method described above, the fact that, during the ascent of the container 11, the undeformed part of the billet remains attached to the container 11 with a fastness greater than the frictional force offered by the die 14 so that the undeformed part is raised in conjunction with the container and the extruded part is consequently drawn out of the die 14. This aspect of the present invention will be described below with reference to FIG. 4.
Let "D" stand for the bore of the container (the outside diameter of the billet to be extrusion forged), "l c " for the length of the undeformed part of the billet remaining in the container, "P c " for the surface pressure exerted at the interface between the undeformed part of the billet and the container, "μ c " for the frictional coefficient between the undeformed part of the billet and the container, "d" for the inside diameter of the die (the outside diameter of the extruded part), "l d " for the die land length, "P d " for the surface pressure between the extruded part of the billet and die land, and "μ d " for the frictional coefficient between the extruded part of the billet and the die land, and the following formula (1) will define the requirement for the adhering force produced between the container and the undeformed part of the billet to be greater than the frictional force produced between the die and the extruded part of the billet in order for the extruded part of the billet to be drawn out of the die because of the fastness of the attachment of the undeformed part of the billet to the inner surface of the container.
μ.sub.c ·P.sub.c ·πD·l.sub.c ≧μ.sub.d ·P.sub.d ·π.sub.d l.sub.d (1)
More specifically, because the adhering force of the undeformed part of the billet to the container is determined by the length of the undeformed part of the billet to the diameter of the billet, satisfaction of the formula (2) derived from the aforementioned formula (1) will suffice for the fulfilment of the requirement mentioned above. ##EQU1##
The surface pressure P c between the undeformed part of the billet and the container and the surface pressure P d between the extruded part of the billet and the die can be determined only by actual measurement. It can be safely inferred, however, that the ratio of the two surface pressures P c and P d is proportional to the flow stress of the materials involved. In case where the extrusion forging is performed under the conditions of 19.8 mm as the diameter of the billet, 20 mm as the bore of the container, and 50 percent as the reduction in area, for example, the equivalent strain of the billet within the container is about 0.02 and the equivalent strain of the extruded part is about 2.0. It can, therefore, be assumed that the mean flow stress exerted on a billet of pure aluminum within the container is about 3 kgf/mm 2 and that exerted on the extruded part of the billet is about 11.5 kgf/mm 2 . The ratio between the surface pressure "P c " to the surface pressure "P d ", therefore, is found to be about 3:11.5. On the assumption that the frictional coefficient "μ 2 " on the surface of the die is about twice the frictional coefficient "μ c " on the inner surface of the container and that the die land length is 2 mm, the formula (2) may be developed by using the numerical value mentioned above, as follows: ##EQU2##
This means that when an aluminum billet 20 mm in diameter is extrusion forged into a round bar at 50 percent of reduction in area, with the other conditions ignored for the convenience of discussion here, the fast attachment of the undeformed part of the billet to the container and the safe removal of the extruded part from the die can be obtained by allowing the undeformed part remaining inside the container to have a length of not less than about 11 mm.
To verify these numerical values, billets of aluminum and mild steel were actually subjected to extrusion forging to yield products of circular and complex cross sections.
First, billets made of annealed pure aluminum in dimensions of 20 mm of diameter and 60 mm of length were extrusion forged, with Jonhnson's wax No. 111 as the lubricant, through a die having the shape of a cone with an inlet angle of 60° and involving a die land length of 2 mm, to produce round bars, bars with keyways, and bars with splined ways. The reduction in area was in all cases fixed at about 50 percent (with the extrusion ratio of 2).
These billets were extrusion forged to give undeformed parts of varying length and the extrusion forged products were tested to determine whether or not their undeformed parts would adhere to the container so fast as to permit safe removal of the products from the die. The results were as shown in the graph of FIG. 5. In this graph, the vertical axis shows the adhering force between the undeformed part of the billet and the container and the horizontal axis shows the ratio of the length of the undeformed part of the billet within the container to the diameter thereof. The solid circle () represents an extruded bar of a circular section, the solid triangle () an extruded rod of a keyway section, and the solid square () an extruded rod of a splined section, while the corresponding blank marks indicate the cases in which the extrusion forged rods remained in the die.
It is noted from the graph that in the case of rods of circular sections, the borderline between adhesion of the extruded products to the container and to the die occurs at a ratio of the length of the undeformed part of the billet in the container to the diameter of the billet of about 0.8. This value is slightly greater than the value 0.54 found by calculation. The reason for this difference is that in the formula of the calculation, the possible increase in the force of extraction due to the slight expansion of the diameter at the leading end of the extruded part and the bend formed in the extruded part were not taken into consideration. In the case of rods of complex sections, safe removal of the extruded part from the die could be obtained without fail so far as the ratio of the length of the undeformed part of the billet remaining within the container to the diameter of the billet was not less than 1.5.
The procedure described above was repeated faithfully for extrusion forged rods of a circular section and rods of the same two complex sections as described above, except that mild steel billets (C: 0.17 percent) were used in the place of aluminum billets and a zinc phosphate coating with Bonderlube 235 was used as a lubricant in the place of Johnson's wax. The results were as shown in the graph of FIG. 6. It is noted from the graph that the adhering force of the undeformed part of the billet to the container was about five times that obtained in the case of aluminum billets and that adhesion of the extrusion forged product to the container sufficient to permit safe removal of the product from the die could be obtained without fail when the ratio of the length of the undeformed part of the billet remaining within the container to the diameter of the billet was not less than 0.9 in the case of rods of a circular section and not less than 1.5 in the case of rods of complex sections such as shafts with keyway sections or splined sections.
The adhering force of the extrusion forged product to the die is affected by the material of the billet, the die angle, the die land length, the reduction in area, the type of lubricant, the speed of extrusion forging, the shape of the product, the swell in the diameter of the extruded part, the bend formed, etc. The experiments conducted by the inventors so far have ascertained that the extrusion forged product adheres to the container fast enough to permit safe removal of the product from the die without reference to the manner of extrusion forging and regardless of cross-sectional complexity whenever the length of the undeformed part of the billet remaining within the container is at least about 1.5 times the diameter of the billet.
The value mentioned above represents the minimum limit. This length may be increased when the undeformed part of the billet is intended for some specific use. The appropriate length of the billet to be extrusion forged and the length of the billet to be left undeformed within the container can easily be fixed when the length of the extruded part and the reduction in area are known in advance. Further, the undeformed part of the billet to be left within the container can be given an ample length by having the downward thrust of the punch properly fixed in advance.
As is clear from the description given above, the extrusion forged product obtained by this invention is not required to be struck at one end thereof with a knockout punch so as to be pushed in the reverse direction. Thus, the extruded part of the billet has no possibility of sustaining any malformation during its removal from the die. This invention, accordingly, enables billets of greater length to be advantageously extrusion forged without being malformed. Generally, the extruded product sustains a slight bend during the extrusion forging. Since the present invention provides for extraction of the product from the die under tensile stress, the bend is mended during the forced extraction. The product, therefore, enjoys improved dimensional accuracy. | Apparatus for extrusion forging essentially comprises a double action hydraulic press composed of an inner ram. Extrusion forging of a billet is accomplished by placing the billet in a container and inserting a punch into the container thereby forcing the billet through the die. After the extrusion forging, the punch is raised to a prescribed level and held there and the container is subsequently raised. Since the undeformed part of the billet is attached fast to the container, the rising container drags the extruded part of the billet out of the die and, at the same time, brings the undeformed part of the billet into powerful collision with the punch and consequently knocks the extrusion forged product out of the container. | 1 |
BACKGROUND OF THE INVENTION
Storage racks for small articles, ranging from pencils and pens to other items such as paint brushes, cassettes, computer floppy discs and small containers are available in many sizes, styles, constructions and configurations. Previously known storage racks do not effectively maintain a uniform holding pressure against articles inserted between a pair of loops, especially when the supported articles vary in thickness or weight or if a large number of articles are supported on the rack at one time. Previously used plastic loops lost their gripping strength due to the type of flow usually referred to as "creep" and were subject to unintentional removal due to twisting.
SUMMARY OF THE INVENTION
It is a principal object of the present invention, therefore, to provide a new and improved storage rack for small articles and things utilizing plastic loops which provide a uniform holding pressure against an article or thing being supported regardless of its weight or thickness and independently of the number of articles being held in the storage rack.
Another object of this invention is a storage rack having supporting loops which maintain a sufficiently constant pressure on the articles and things being held that the rack may be used as a wire guide.
An additional object of this invention is a storage rack which provides for the easy installation of supporting loops but resists the unintentional pull out of these loops.
Yet another object of this invention are article-supporting loops which are mounted in a manner which permits their legs to slide along the length of the storage rack but resist pullout of the loops during such sliding movement.
Still another object of this invention are article-supporting loops formed of strips of tough, resilient, abrasion-resistant resin having legs which are free to slide along the length of the rack to accommodate supported articles and things of varying weights and cross sections while maintaining a substantially uniform holding pressure against the articles and things being supported.
Yet an additional object of this invention is a retaining loop for a storage rack that is highly resistant to the type of flow usually referred to as "creep".
Still an additional object of this invention is a storage rack that is formed so that it may be supported by fasteners, suction cups or adhesive, including but not limited to stick wax blocks of adhesive.
Accordingly, the invention relates to a storage rack for small articles and things comprising an elongated housing having a rear wall adapted to be positioned against a supporting surface, a front wall including upper and lower portions separated by a narrow opening extending substantially the entire length of the housing and a rib extending forwardly of the rear wall in alignment with the narrow opening. A multiplicity of retainer loops are mounted side by side on the elongated housing. Each retainer loop is formed of a strip of a tough, resilient, abrasion-resistant resin. Each retainer loop has a bight portion, two legs, a tail formed at the end of each leg and a notch formed in each tail. The retaining loops are installed in the elongated housing with their legs extending through the narrow opening in the front wall of the housing and with the bight portions of the loops positioned outwardly of the front wall. The tails of the legs of the loops engage the upper and lower portions of the front wall and the notches of the legs of the loops receive the rib. The legs of adjacent loops will slide along the length of the rib when elongated articles are inserted between pairs of retaining loops to thereby accommodate articles or things of varying cross sections while maintaining essentially uniform pressure against the articles or things being held in the storage rack.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is illustrated more or less diagrammatically in the following drawings wherein:
FIG. 1 is a front elevational view of a first embodiment of a storage rack for small articles constructed in accordance with the teachings of the present invention;
FIG. 2 is a top plan view of the storage rack of FIG. 1;
FIG. 3 is a cross sectional view taken along line 3--3 of FIG. 1;
FIG. 4 is a plan view of a first embodiment of a loop in its flattened outstretched condition;
FIG. 5 is a front elevational view of a second embodiment of a storage rack for small articles constructed in accordance with the teachings of the present invention with some hidden parts shown in dashed lines;
FIG. 6 is a top view of an end wall of the storage rack of FIG. 5;
FIG. 7 is a side elevational view of the end wall of FIG. 6;
FIG. 8 is a side elevational view of the storage rack of FIG. 5 with some hidden parts shown in dashed lines;
FIG. 9 is a side elevational view of the storage rack of FIG. 5 with some parts removed and shown supported on a horizontal surface;
FIG. 10 is a partial side elevational view of a modified form of a mounting base; and
FIG. 11 is a plan view of a loop of the modified storage rack shown in its flattened, outstretched condition.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 to 4 of the drawings illustrate a first embodiment of the invention shown as an elongated rack 11 which is intended to be used for the storage of a variety of small articles of varying sizes, shapes and weights. Specifically, for purposes of illustration, and not by way of limitation, a pen 13 and a computer floppy disc 15 are shown supported on the rack. It should be understood and appreciated that other articles such as measuring tapes, chalk, putty knives, erasers, paint brushes, cassettes, etc., may be stored on such a rack and the rack, either alone, or in association with other similar racks may be used as a wire guide.
The storage rack 11 includes an elongated housing 21 which may be formed of plastic or wood or other suitable material and includes a rear wall 23 which may be provided with openings for receiving screws or other fasteners to attach the rear wall to a supporting wall with neither the openings or the supporting wall shown in the drawings for clarity of illustration. Completing the housing are a front wall 25, a top wall 27, a bottom wall 29 and end walls 31. The end walls 31 extend forwardly of the front wall. 25 of the elongated housing 21 and the portions of the end walls located forwardly of the front wall are enlarged laterally with lugs 32. A narrow opening or passage 33 is formed in the front wall 25 and divides the front wall into upper and lower portions 35 and 37, respectively. A retainer loop insertion slot 38 extends through the upper and lower portions 35 and 37 of the front wall 25. Abutments 39 are formed in the housing adjacent the end walls 31. A rib 41, which may be formed integrally with the rear wall 23, extends forwardly of the rear wall terminating adjacent the inner surface of the front wall 25.
The storage rack 11 further includes a multiplicity of retainer loops 51. The retainer loops are each formed of a strip of a tough, resilient, abrasion-resistant resin, preferably a polyester resin or a laminate. The preferred resin for the retainer loops is two layers of oriented polyethylene terephthalate laminated with a central layer of polyethylene, the same basic construction as is used in commercial identification cards and similar articles. The strip of resin should be formed having a width equal to the width of the narrow opening 33 in the front wall 25 of the housing 21.
Each retainer loop 51 is formed with a bight portion 53 joining a pair of legs 55. A laterally extending tail 57 is formed at the distal end of each leg. A longitudinally notch 59 is formed in the tail at the end of each leg.
Each retainer loop 51 is supported on the storage rack 21 by inserting the tails 57 of its legs 55 into the loop insertion slot 38 so that the notches 59 receive and fit over the rib 41. When the legs of the retainer loops are so installed, the tails 57 of the legs 55 engage the rear surfaces of the upper and lower portions 35 and 37 of the front wall 25 of the elongated housing 21. Also, the bight portions 53 of the retainer loops will extend outwardly of the front wall 25 of the housing and will be supported by both the lower portion 37 of the front wall and the rib 41.
The number of retainer loops 51 inserted into the narrow opening 33 will depend on the average size of the articles expected to be supported on the rack. Because the tails 57 of each of the legs of the loops are free to slide along the rib 41, it is possible to accommodate articles placed between a pair of loops, even though the articles vary considerably in their cross sections, while maintaining the pressure by the legs of the loops against the object or article being supported at a generally uniform level. The provision of the tails 57 of the legs 55 of the loops 51 to engage the inner surfaces of the upper and lower portions 35 and 37 of the front wall 25 in combination with the engagement of the rib 41 with the portions of the tails around the notches 59 prevents a pull-out of the loops 51 even under relatively heavy loads provided by the articles being held. The end walls 31 of the housing also function to hold the retainer loops in position and maintain a uniform pressure against the articles being held. The lug portions 32 of the end walls which extend outwardly of the front wall 35 engage the end retainer loops near the bight portions thereof while the abutments 39 engage the loops near their tails 57.
Although the storage rack 11 of the first embodiment of the invention is shown with a single elongated housing 21, it should be understood and appreciated that the housing 21 may be made in sections attached to one another to create a storage rack of a desired capacity. Further, it is within the teachings of this invention to make an elongated housing with several discrete openings or passages 33 located end to end for receiving groups of retainer loops 51 rather than one extremely long opening 33 since a more uniform pressure is obtained against the objects being held by limiting the number of retainer loops in each grouping.
A second embodiment of the invention is shown in FIGS. 5-11 of the drawings. The storage rack 101 shown in these drawings is suitable for attachment to either a vertical or a horizontal supporting surface. The storage rack 101 is preferably injection molded of a suitable plastic and includes a base l03 and an upright wall portion 105 formed integrally. The base 163 is offset from the bottom edge 107 of the upright wall portion 105 and can be seen most clearly in FIGS. 8, 9 and 10 of the drawings. Downwardly opening channels 109, 111 and 113 are formed below the base 103 and these channels extend across the width of the storage rack. Ribs 115 are provided in channels 109 and 111 to dig into blocks of adhesive wax 117 which are inserted into the channels in the manner shown in FIG. 10 of the drawings to adhere the storage rack to a horizontal supporting surface which is not shown in FIG. 10 of the drawings. The center and wider channel 113 receives and supports suction cups 119 to adhere the storage rack to the horizontal supporting surface 121 as shown in FIG. 9 of the drawings.
To permit the mounting of the storage rack 101 on uneven or slightly rough surfaces such as the horizontal surface 121, a thin sheet 123 of a plastic having a layer of a pressure sensitive adhesive on the side facing the supporting surface, which adhesive is not shown in the drawings, is provided. This mounting arrangement works especially well when the suction cups 119 engage the adhered plastic sheet 123 attached to the surface 121 as shown in FIG. 9 of the drawings.
An elongated housing 131 is formed integrally with the upright wall portion 105 of the storage rack 101 at the upper end of the upright wall portion. The upright wall portion 105 forms the rear wall of the housing. Completing the housing 131 are a front wall 133, a top wall 135 and a bottom wall 137 all formed integrally with the upright wall portion 105 of the storage rack 101. A narrow opening or passage 141 is formed in the front wall 133 and this opening divides the front wall into upper and lower portions 143 and 145, respectively.
A rib 151 shown in FIG. 9, which may be formed integrally with the upright wall portion 105, extends forwardly of the rear wall of the housing 131 terminating in an enlarged semi-cylindrical nose 153 positioned adjacent the inner surface of the front wall 133 of the housing 131. The nose 153 is molded with a hole 155 at each end and an elongated slot 157 extending into each hole to allow expansion of the nose to receive screws 159 to fasten the end walls 161 to the elongated housing 131 as shown in FIG. 8 of the drawings.
The end walls 161 as shown in FIGS. 6 and 7 are each molded in one integral piece having a planer portion 163 of somewhat rectangular shape with an arcuate end 165 and an irregularly shaped wall 167 projecting from the planer portion 163. The irregular wall includes ribs 169 defining a somewhat rectangular plug 171 which snugly fits into the open ends of the housing 131. The ribs 169 also define a recess 173 which receives the rib 151 and nose 153 of the wall portion 105. A passage 175 is formed through the planer portion 163 of the end wall 161 to receive the screw 159 to fasten the end wall to the housing as shown in FIGS. 5 and 8 of the drawings.
The storage rack 101 further includes a multiplicity of retainer loops 181. The retainer loops are each formed of a strip of a tough, resilient, abrasion-resistant resin, preferably a polyester resin or a laminate. The preferred resin for the retainer loops is two layers of oriented polyethylene terephthalate laminated with a central layer of polyethylene, the same basic construction as is used in commercial identification cards and similar articles. The strip of resin should be formed having a width equal to the width of the narrow opening 141 in the front wall 133 of the elongated housing 131.
Each retainer loop 181 as shown most clearly in FIG. 11 is formed with a bight portion 183 joined by a pair of legs 185. A laterally extending tail 187 is formed at the distal end of each leg. A longitudinally extending notch 189 is formed in the tail at the end of each leg and at its inner end the notch expands to a circular configuration 191.
Each retainer loop 181 is installed on the storage rack 101 by removing an end wall 161 and inserting the tails 187 of the legs 185 of the loop into the housing 131 so that the circular opening 191 of the notch 189 of each tail fits over the semi-cylindrical nose 153 of the rib 151 as can be viewed in FIG. 9 of the drawings. When the retainer loops are so installed, the tails 187 of the legs 185 engage the rear surfaces of the upper and lower portions 143 and 145 of the front wall 133 of the elongated housing 131. Also, the bight portions 183 of the retainer loops 181 will extending outwardly of the front wall 133 of the housing through the passage 141 and the retainer loops 181 will be supported by both the lower portion 145 of the housing and the rib 151 and its nose 153.
The number of retainer loops 181 inserted into the narrow passage 141 of the storage rack 101 will depend on the average size of the articles expected to be supported in the rack. Because the tails 187 of each of the legs of the loops are free to slide along the nose 153 and the rib 151, it is possible to accommodate articles placed between a pair of ribs even though the articles may vary considerably in their cross sections while maintaining the pressure exerted by the legs of the loop against the object or article at a generally uniform level. The provision of the tails 187 of the legs 185 of the loops 181 to engage the inner surfaces of the upper and lower portions 143 and 145 of the front wall 133 in combination with the engagement of the rib nose 153 with the portions of the tail around the notches and circular cut out portion 191 prevents a pull out of the loops 181 even under relatively heavy loads provided by the articles being held.
The end walls 161 of the housing 101 also function to hold the retainer loops 181 in position on the storage rack 101 and maintain a uniform pressure against the articles being held in the rack. The planer portions 163 of the end walls engage the retainer loops at opposite ends of the rack near the bight portions 183 thereof. The plug portions 171 of the end walls engage the retainer loops near their tails 187.
The storage rack 101 may also be supported on a vertical surface, which is not shown, in the manner depicted in FIG. 8 of the drawings in which suction cups 201 are anchored in keyhole openings 203 in the upright wall portion 105 of the rack. Additionally, it is apparent that instead of suction cups, screws 159 may be installed through the keyholes 203 to support the rack on a vertical surface or under appropriate circumstances, adhesives, including but not limited to stick wax blocks or double sided adhesive tape may be used. | A rack for supporting small articles or aligning wires. The rack may either be hung on a vertical surface or seated on a horizontal surface. The rack includes an elongated housing with an elongated entrance slot formed in its front wall. A multiplicity of retainer loops are supported side-by-side on the elongated housing with their bight portions in front of the housing to receive and support the small articles and to align the wires. The retainer loops are formed with tails which hold them in the elongated housing and have slots which fit over a rib in the housing to prevent twisting of the loops. The end of the rib may be enlarged to be received in complementary shaped slots in the loops to increase pull out resistance of the retainer loops. When small articles or wires are inserted between pairs of retainer loops, the tails of the loops will slide along the rib to accommodate articles of varying cross sections while maintaining essentially uniform pressure against the articles being held. The rack is formed so that it may be supported by fasteners, suction cups or adhesive, including stick wax blocks of adhesive. | 0 |
TECHNICAL FIELD
The present invention relates to exercise devices in general and, more particularly, to devices which permit exercise of the quadriceps muscle.
BACKGROUND OF THE INVENTION
It is widely known that the stability of the knee joint depends primarily on the strength of the quadriceps muscle. It is widely recognized that strengthening and rehabilitation of the quadriceps muscle is best achieved by having a patient straighten his or her knee joint in opposition to a resistive force applied at the patient's instep. Such devices for exercising a quadriceps muscle are found, for example, in U.S. Pat. No. 3,120,954 (Apostol), U.S. Pat. No. 3,558,131 (Dragon), U.S. Pat. No. 4,254,949 (Brentham) and U.S. Pat. No. 4,304,401 (Goodman). The Apostol, Dragon and Brentham devices are relatively large and not readily moved from place to place. Thus, the Apostol and Dragon devices, which are used for exercising muscles other than the quadriceps, are practical only for use in the office of a physical therapist or in such other public exercise facility. The Brentham device, which takes the form of a chair with built in exercising apparatus, is practical for home use but is not sufficiently portable to permit it to be taken with the patient on a trip, or the like. The Goodman device is relatively portable in that it can be readily lifted in one hand and transported by a patient. However, in achieving the desirable portability feature Goodman has sacrificed tension adjustability and other considerations. Specifically, Goodman employs a planar surface supported at approximately chair height in front of a suitable chair. The patient sits in the chair with his leg extending over the planar surface so that the knee bends and the lower part of the leg is suspended. An elastomeric strap is secured to the patient's instep so that the patient may straighten his or her leg against the tension in the strap to exercise the quadriceps muscle. The tension in the strap is not adjustable so that the Goodman arrangement has limited use in view of the varying degrees of muscle strengthening and rehabilitation needs of a user. Moreover, the Goodman apparatus, in use, places relatively high stress on the patient's knee since the greatest tensile stress in the strap occurs when the gravitational force acting on the patient's leg is at a maximum (i.e., as the leg approaches its straightened position). Additional stress is placed on the knee by virtue of the fact that the effective pivot axis of the apparatus is considerably below the bending axis of the knee, resulting in strain on the knee rather than on the quadriceps muscle during the use of this device. In this regard, it should be noted that the only prior art known to me wherein the effective pivot axis of the exercise device is aligned with the bending axis of the knee is the Brentham device. However, in Brentham, as noted above, the apparatus is not sufficiently portable to permit it to be carried from place to place in one hand. In addition, the Brentham device lacks sufficient adjustability in the resistive force against which the patient is exercising. Still further, the Brentham device is designed to exercise both the quadriceps muscle and the hamstring muscle. This is achieved by utilizing an hydraulic element to resist both upward and downward movement of the lower portion of the leg. While a device for exercising both the quadriceps and hamstring muscles is desirable, the use of a single resistive element for both muscles in a single exercise routine presents severe calibration problems. More particularly, it is difficult to find a common resistive force which is suitable for exercising both the hamstring and quadriceps muscles.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a portable quadriceps exercising device which places minimal strain on the knee joint.
It is another object of the present invention to provide a portable quadriceps muscle exerciser in which the exercise force which must be exerted by the user is readily adjustable to a specific calibration.
It is yet another object of the present invention to provide a portable quadriceps exerciser device which can be readily carried about by a patient and deployed quickly and simply.
It is still another object of the present invention to provide a portable quadriceps exercising device in which the carrying case is an integral part of the device and is capable of storing all of the exercise components therein.
In accordance with the present invention, a portable quadriceps exerciser includes a frame member on which a user sits with one buttock and thigh so that the knee is disposed just forward of the frame member and the lower leg dangles therefrom. The frame member may be a flatboard or the top wall of a box used to store the exerciser components when they are not in use. A pair of brackets project forwardly of the frame member and pivotally support a pair of arm members for pivotal movement about an axis which is substantially coaxial with the bending axis of the user's knee. The distal ends of the arm members are joined by a cross-piece which is aligned with the instep of the user so that the user may rotate the arm members upward and away from the frame member as the user straightens his or her leg. One or more rubber straps are connected between the frame member and the distal ends of the arm members to provide a tension force against movement which opposes straightening of the user's leg. The point of attachment of the rubber straps to the frame member is adjustable so that the tension force is adjustable for different needs. In the preferred embodiment, the front wall of the box is secured to the straps and is mountable at different longitudinal locations to provide the tension adjustability. The height of the box is selected so that, when placed on a conventional chair, it permits the dangling leg of a user to be raised above the floor.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and still further objects, features and advantages of the present invention will become apparent upon consideration of the following details and description of specific embodiments thereof, especially when taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a view in perspective of a preferred embodiment of the present invention illustrated in its closed or stored position;
FIG. 2 is a longitudinal sectional view of the embodiment of FIG. 1 shown in its stored or closed condition;
FIG. 3 is a longitudinal sectional view similar to FIG. 2 but wherein the device is shown in its deployed condition;
FIG. 4 is a view in section taken along lines 4--4 of FIG. 3;
FIG. 5 is a top view of the embodiment of FIG. 1 shown with its cover removed;
FIG. 6 is a top view in plan of a second embodiment of the present invention;
FIG. 7 is a side view of the embodiment of FIG. 6.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring specifically to FIGS. 1-5 of the accompanying drawings, a portable quadriceps muscle exerciser 10 is housed in an enclosed box having a top wall 11, bottom wall 13, side walls 15 and 17, front end wall 19 and rear end wall 21. The box is illustrated as having rectangular cross-sections in each of its length, width and depth dimensions; however, this is not an important aspect of the invention and cross-sectional variations from rectangular can be employed within the scope of the invention. Bottom wall 13 serves as a cover for the box and is hinged to the bottom portion of side wall 17 by means of hinges 23. A pair of conventional snap-closure latch member 25 are provided at the opposite side of the box to permit the bottom wall cover to be latched closed to side wall 15.
Front wall 19 has an outer surface from which a handle member 27 projects. The handle member 27 permits the box to be easily lifted and carried about in one hand. To this end, the box may be made of rigid lightweight wood, plastic or other composition. A pair of hooks, 29, 30 project upwardly from the interior surface of front wall 19 and are threaded so as to engage respective ends of handle 27 through suitably provided holes in front wall 19. Front wall 19 is removably mounted in the front end position of the box by means of a pair of transversely-aligned channels 31, 33 extending-vertically in side walls 15, 17 respectively. The channels 31, 33 mate with corresponding flanges 35, 37 (see FIG. 5) which project from the front wall 19. Flanges 35, 37 are slidably received in grooves 31, 33 so that front wall 19 can be removed when the cover or bottom wall 13 is open. A plurality of aligned pairs of similar channels 39, 41 are defined in side walls 15, 17, respectively, and are also sized to slidably receive flanges 35, 37 of front wall 19. Each channel pair 39, 41 is disposed at a different distance from the front end of the box so that front wall 19 can be positioned at different distances from the front end, as desired. When positioned in a channel pair 39, 41, front wall 19 faces the opposite direction from its end position in channel 31, 33 so that its interior surface and hooks 29, 30 face the forward direction in the box.
A pair of transversely-spaced elongated bracket members 43, 45 are pivotally mounted at their proximal ends on the interior sides of respective side walls 15, 17 about a common pivot axis A. Pivot axis A may represent an elongated rod extending transversely of the box and secured to the sidewalls 15, 17 in journaled relation with bracket members 43, 45. The bracket members are broadened in the width dimension at their distal ends and pivotally support respective arm members 49, 51 by means of pivot pins 53 or the like. The two pivot pins define a common transverse pivot axis for the arm members 49, 51. Bracket members 43, 45 and arm members 49, 51 are preferably made of steel, aluminum or other similarly strong and relatively lightweight material.
A first strap 55 of rubber or other elastomeric material is secured between the distal end of arm member 49 and hook 29. A second such strap 57 is secured between the distal end of arm member 51 and hook 30. A cross-piece 59 is secured between the distal ends of the two arm members 49, 51 and takes the form of a cushioned roller of the type conventionally employed in prior art exercise devices. The threaded ends of a shaft for roller 59 extend through suitable provided apertures in the distal ends of arm members 49, 51 and straps 55, 57 to be engaged by nuts 61 which secure these elements in place while permitting roller 59 to rotate in a conventional manner.
A strut member includes a cross-bar 63, of rectangular cross-section, journaled at its ends in respective frame members 43, 45. A support rod 65 is threadedly engaged at one of cross-bar 63 and has its other end free.
Bracket members 43, 45 are pivotable about axis A between a stowed or stored position (illustrated in FIG. 2) and a deployed position (illustrated in FIGS. 3 and 5). In the stowed position the bracket members are disposed entirely within the box and arm members 49, 51 are pivoted about pins 53 so that the arm members and roller 59 are likewise disposed entirely within the box. If, as illustrated in FIG. 3, front wall 19 is disposed in channels 31, 33 with the handle 27 facing outward, straps 55 and 57 are also disposed entirely within the box.
In order to rotate the bracket members to the deployed position, cover or bottom wall 13 is unlatched at 25 and opened. Front wall 19 is then removed from channels 31, 33 and the bracket members 43, 45 are pivoted about axis A until their distal ends project out through the front end of the box vacated by front wall 19. This results in arm members 49, 51 and roller 59 being disposed outside the box. Front wall 19 is then disposed in whichever channel pair 39, 41 provides the desired tension on the elastomeric straps 55 and 57 which thereby project out through the open front end of the box.
In order to use the unit for exercising the quadriceps muscle, a patient or user first places the box on a chair or similar flat surface. The patient then sits on the top wall 11 with the buttock and thigh of the leg having the muscle to be exercised. The thigh is longitudinally positioned with respect to the box such that the axis of bending of the knee is substantially co-axially aligned with pivot axis 53 as illustrated in FIG. 3. In this regard, it should be noted that the top or outer surface of top wall 11 is preferably flat, as shown, but may be otherwise contoured so long as it readily accommodates the thigh and buttock of the patient. Likewise, the bottom or outer surface of bottom wall 13 is illustrated as being flat so that it may properly rest without tilt on the seating surface of a chair, bench, or the like; however, variation from flatness may be accommodated as long as the box can be stably supported on a seat. With the patient thusly positioned, the lower part of the leg is placed between arm members 49, 51, so that roller 59 resides at or near the patient's instep, as illustrated in FIG. 3. The patient can then perform a quadriceps muscle strengthening exercise by straightening his or her leg against the tension force applied thereto by elastomeric straps 55, 57 via roller 59. In other words, the patient rotates roller 59 and arm member 49, 51 upward and away from the box (clockwise as viewed in FIG. 3).
As the roller is rotated approximately 90° during the exercise, the opposing tension force effected by straps 55, 57 varies. This is because the direction of the force exerted on the roller 59 by straps 55, 57 varies as the arm members 49, 51 are rotated. More specifically, the direction of the resistant force of the straps is initially considerably displaced from the length dimension arm members 49, 51 so that a relatively large component of the resistant force acts perpendicular to the arm members and in opposition to the patient's upward leg rotation. As the arm members are pivoted upward, the direction of the resultant resistant force of the straps becomes closer to parallel to arm members 49, 51, thereby significantly reducing the perpendicular force component against which the patient is exerting force. Thus, as the patient's leg approaches the straightened position, which is the position of maximum stress on the knee joint, the effect of the resistant force of the straps becomes minimal and the patient's effort is exerted substantially against gravity only. It can be seen, therefore, that where gravity is minimal (i.e., in the 90° bent position of the leg), the effective resistant force of the straps is maximum, and where the effect of gravity is maximum (i.e., the straightened leg position), the effective strap force is minimum. The total force (gravity plus the straps) acting against the patient's efforts is therefore very nearly uniform throughout the 90° straightening of the knee. This desirable feature is not considered or achieved in portable prior art devices for exercising quadriceps muscles.
It should be noted that, when the unit is deployed in the manner illustrated in FIG. 3, a portion of the patient's weight is applied against top wall 11. With front wall 19 moved from the front end of the box to the desired channel pair 39, 41, the patient's weight could cause collapse of the front end of the box. In order to prevent this, the strut member 63, 65 is provided and is positioned along the length of bracket members 43, 45 so as to be located proximate the front end of the box in the deployed position of the unit. In addition, the strut member prevents bracket members 43, 45 from moving vertically when the apparatus is in use.
In addition to serving as self-contained storage compartment for the brackets, arms and straps, the box serves another practical function for the portable exerciser unit. Specifically, the box raises the patient's knee sufficiently above the floor so that the patient's foot is above the floor. The patient can therefore swing his or her leg through a full 90° path without scraping the floor. The typical chair or bench seat is raised eighteen to twenty inches above the floor. Such seats are designed to permit the average adult to sit in the seat with his or her feet touching the floor. The height of the exerciser box is therefore made sufficient to permit the foot of the average sized adult to dangle above the floor when that adult is seated on the box placed on a chair or bench seat. Typically, the height of the box for this purpose is four to five inches.
The arm members 49, 51, as described above, are sized to permit roller 59 to contact the instep of the average sized person. The unit may be provided with alternative pairs of arm members of different lengths to accommodate unusually tall or short people.
In a working embodiment which I have constructed, the following dimensions, materials and parameters were employed. The box was made of finished oak, three-eights of an inch thick, with outside dimensions of twenty inches by seven and three-quarter inches by four and three-quarter inches. Front wall 19 was also finished oak and was one-quarter inch by four inches by seven and three-eighths inches. Eight pairs of channels 39, 41 were three-eighths inch wide, three-sixteenth inch deep and are spaced at successive one inch intervals beginning eleven inches from end wall 21 and extending rearward therefrom. The axial length of bracket members 43, 45 from pivot axis A to pivot axis 53 was eleven and one-quarter inches, and pivot axis 53 is displaced off that axis a distance of two and one-half inches. Arm members 49, 51 are typically fifteen inches long but may be provided in lengths of thirteen and seventeen inches. Straps 55 and 57 were twenty-two inches long. Pivot axis A was disposed fourteen inches from end wall 21. It is understood that those dimensions are pounded by way of example only and are not to be construed as limiting the scope of the present invention.
An alternative embodiment of the present invention is illustrated in FIGS. 6 and 7 to which express reference is now made. A flat board member 70 is of generally rectangular configuration and similar in size and shape to the top wall 11 of the embodiment of FIGS. 1-5. A pair of bracket members 71, 73 are fixedly secured to the side edges of board 70 by means of screws 75, or the like. The bracket members 71, 73 project beyond the forward edge 77 of the board and terminate in respective right angle flange portions 79, 81 which project upwardly when the apparatus is in use. Arm members 83, 85 are pivotally secured to respective bracket member flange portions 79, 81 so as to pivot about a common axis 80 which is disposed horizontally when the device is in use. A roller 86 is journaled between the distal ends of arm members 83, 85. A rubber strap 87 is secured at its ends to the distal ends of arm members 81, 83 by means of nuts 89 which engage threaded ends of the shaft 88 of roller 86.
A plurality of recesses 90 are spaced in longitudinal alignment along the top surface of board 70. Recesses 90 are each configured to receive a peg member 91. When the peg member is inserted in any of the recesses, a sufficient portion of the peg member projects upwardly from the board member to be engaged by the strap 87. Specifically, the strap 87 extends from the distal end of arm member 81, around peg 91 and back to the distal end of arm 83. The tension in strap 87 can be adjusted by placing the peg 91 in the appropriate recess 90.
In use, board 70 is placed on the seat of a board or bench with the top surface of the board, containing recesses 90, facing upward. The user sits on the board with one buttock and thigh so that the bending axis of his or her knee joint is co-axially aligned with pivot axis 80. In this regard, the upward projection of flange members 79, 81 permits this alignment of axes. Operation then proceeds in the same manner described above for the embodiment of FIGS. 1-5.
The embodiment of FIGS. 6 and 7 may, in some cases, not raise the patient's knee high enough so that the foot of the patient is not raised above the floor when the board is placed on the seat of a chair or bench. To overcome this, any suitable means of elevating the board on the chair, such as telephone books, etc., may be employed. Alternatively, the board may be provided with legs, such as telescopically retractable legs, which are capable of raising the board sufficiently.
While I have described and illustrated various specific embodiments of my invention, it will be clear that variations from the details of construction which are specifically illustrated and described may be resorted to without departing from the true spirit and scope of the invention as defined in the appended claims. | A portable quadriceps muscle exerciser includes a frame member on which a user sits with one buttock and thigh so that the lower leg dangles from the knee joint at the forward end of the device. Spaced bracket members project on opposite sides of the knee and pivotally support a pair of spaced arm members about a pivot axis which is substantially coaxial with the bending axis of the knee joint. The distal ends of the arm members are connected by a cross-piece which engages the patient's instep. One or more elastic straps extend between the frame member and the distal arm ends to resist rotation of the arms as the patient's leg is straightened. The location of the attachment of the straps to the frame member is adjustable to adjust the strap tension. In a preferred embodiment the frame member is a box into which all of the components can be pivoted for storage and which raises the patient's foot above the floor. The front wall of the box is secured to the straps and re-positionable to adjust the strap tension. | 0 |
This is a division of application Ser. No. 08/286,054, filed on Aug. 4, 1994, now abandoned, which, in turn, is a continuation-in-part of application Ser. No. 08/120,706, filed on Sep. 13, 1993, now abandoned, which, in turn, is a continuation of application Ser. No. 07/747,770, filed Aug. 20, 1991, now abandoned, which, in turn, is a divisional application of application Ser. No. 07/504,493, filed Apr. 4, 1990, now U.S. Pat. No. 5,166,406.
FIELD OF THE INVENTION
This invention relates to a process for the preparation of glutaric acid derivatives.
BACKGROUND OF THE INVENTION
The invention relates to a process for the preparation of 1- 2-(alkoxycarbonyl)ethyl!-1-cyclopentane-carboxylic acid derivatives, the use of which has previously been disclosed in EP-A-0274334 as intermediates for the preparation of certain substituted glutaramide diuretic agents having utility in the treatment of hypertension, heart failure, renal insufficiency and in other disorders.
EP-A-0274234 describes two methods for the preparation of 1- 2-(alkoxycarbonyl)ethyl!-1-cyclopentanecarboxylic acid derivatives by which the dianion derived from cyclopentanecarboxylic acid by treatment with a strong base, e.g. lithium diisopropylamide, is treated with either (i) an acrylate derivative, or (ii) an ester of 3-bromopropanoic acid followed by optional further alkylation as required, to provide the desired products. However, the favored route, involving use of an acrylate derivative, can not be used for certain preferred embodiments of the present invention due to competing elimination reactions.
It has now been discovered that 1- 2-(alkoxycarbonyl)-ethyl!-1-cyclopentanecarboxylic acid derivatives may be unexpectedly prepared by the oxidative rearrangement of 2-acyl- or 2-alkoxycarbonyl-cyclohexanone derivatives, offering further commercially important improvements over the existing processes such as ease and lower cost of operation.
SUMMARY OF THE INVENTION
The present invention provides a process for preparing a compound of the formula: ##STR3## or a base salt thereof, wherein R 2 is hydrogen or C 1 -C 6 alkyl optionally substituted by up to 3 substituents each independently selected from C 1 -C 6 alkoxy and C 1 -C 6 alkoxy (C 1 -C 6 alkoxy)-; and R 3 is C 1 -C 6 alkyl or benzyl, said benzyl group being optionally ring-substituted by up to 2 nitro or C 1 -C 4 alkoxy substituents, comprising reacting a compound of the formula: ##STR4## wherein R 1 is C 1 -C 4 alkyl, phenyl, benzyl or C 1 -C 4 alkoxy; and R 2 and R 3 are as previously defined for a compound of the formula (I), with hydrogen peroxide or a source of peroxide ions. The process can followed by conversion of the compound of the formula (I) to a base salt thereof.
Preferably, R 1 is C 1 -C 4 alkyl, phenyl or C 1 -C 4 alkoxy. More preferably, R 1 is methyl, phenyl or ethoxy. Most preferably, R 1 is methyl or ethoxy.
Preferably, R 2 is hydrogen or C 1 -C 6 alkyl optionally substituted by one C 1 -C 6 alkoxy or C 1 -C 6 alkoxy (C 1 -C 6 alkoxy)- substituent.
More preferably, R 2 is hydrogen, 2-methoxyethoxymethyl, 2-methoxyethyl or methoxymethyl.
Most preferably, R 2 is hydrogen or 2-methoxyethoxymethyl.
Preferably, R 3 is C 1 -C 6 alkyl or benzyl, said benzyl group being optionally ring-substituted by one nitro or C 1 -C 4 alkoxy substituent.
More preferably, R 3 is ethyl, tert-butyl, benzyl, 4-nitrobenzyl or 4-methoxybenzyl.
Most preferably, R 3 is tert-butyl.
Examples of base salts of the compounds of the formula (I) include alkali metal, alkaline earth metal, ammonium and mono-, di- or tri(C 1 -C 4 alkyl)ammonium salts.
Preferably the base salt of a compound of the formula (I) is the isopropylammonium salt.
The present invention also relates to novel compounds of the formula (II) which are useful as intermediates in the preparation of certain substituted glutaride diuretic agents having utility in the treatment of hypertension, heart failure, renal insufficiency, and in other disorders.
DETAILED DESCRIPTION OF THE INVENTION
The source of peroxide ions includes reagents such as hydrogen peroxide, peroxy acids (e.g. peroxy(C 1 -C 4 )-alkanoic acids), sodium perborate or a hydrate thereof, and sodium percarbonate, which are used in the presence of water. Preferably hydrogen peroxide, sodium perborate tetrahydrate or sodium percarbonate is used. Most preferably hydrogen peroxide is used.
The skilled man will appreciate that a certain amount of water must be present in the reaction mixture so that peroxide ions may be generated from the reagent.
The reaction is preferably carried out using hydrogen peroxide in the presence of water.
The reaction is preferably carried out in a suitable solvent in the presence of acid or base. Although the reaction does proceed slowly under neutral conditions, it has been found that acidic or basic reaction conditions accelerate the rate.
Suitable solvents for the reaction include C 1 -C 6 alkanols and toluene.
Preferably the solvent is methanol, tert-butanol or toluene.
Most preferably the solvent is tert-butanol.
When the reaction is carried out in the presence of acid, preferred acids include mineral acids and C 1 -C 4 alkanoic acids.
Preferably the acid is sulphuric acid or acetic acid. The reaction may also be carried out using a C 1 -C 4 alkanoic acid as the solvent in the absence of an additional acid. Acetic acid is preferred.
When the reaction is carried out in the presence of base, preferred bases include sodium or potassium hydroxide, carbonate or bicarbonate.
Preferably the base is sodium hydroxide or sodium or potassium bicarbonate.
Sodium percarbonate is a basic reagent per se and is typically not used in the presence of acid or a further base.
The reaction conditions and, in particular, the solvent and the nature and/or concentration of the acid or base used in the process provided by the present invention are chosen such that the reaction proceeds safely and at a favorable rate, without hydrolysis or transesterification of the ester functionality in the starting material (II) or product (I) occurring.
A preferred embodiment of the present invention provides a process for preparing a compound of the formula (I), or a base salt thereof, comprising reaction of a compound of the formula (II) with
(a) aqueous hydrogen peroxide in
(i) a suitable organic solvent in the presence of an acid,
(ii) a suitable organic solvent in the presence of a base, or
(iii) a C 1 -C 4 alkanoic acid;
(b) sodium perborate, or a hydrate thereof, in a C 1 -C 4 alkanoic acid; or
(c) sodium percarbonate in a suitable organic solvent in the presence of water: said process being optionally followed by a conversion of the compound of the formula (I) to a base salt thereof,
wherein R 1 , R 2 and R 3 are as previously defined for compounds of the formulae (I) and (II).
A most preferred embodiment of the present invention provides a process for preparing a compound of the formula (I), or a base salt thereof, comprising reaction of a compound of the formula (II) with
(a) aqueous hydrogen peroxide in
(i) tert-butanol or toluene in the presence of a catalytic amount of sulphuric acid,
(ii) either tert-butanol in the presence of sodium or potassium bicarbonate, or methanol in the presence of sodium hydroxide, or
(iii) acetic acid;
(b) sodium perborate tetrahydrate in acetic acid; or
(c) sodium percarbonate in tert-butanol in the presence of water: said process being optionally followed by conversion of the compound of the formula (I) to a base salt thereof, wherein R 1 , R 2 and R 3 are as previously defined for compounds of the formulae (I) and (II).
Sodium perborate is commercially available in several different hydrate forms, although the tetrahydrate (e.g. available from the Aldrich Chemical Company Ltd.) is preferred for the purpose of the present invention. Sodium perborate tetrahydrate may be formulated as either NABO 3 .4H 2 O or NaBO 2 .H 2 O 2 .3H 2 O and provides a source of peroxide ions in aqueous solution:
B(OH).sub.3 (O.sub.2 H)!.sup.- +H.sub.2 ⊙→ B(OH).sub.4 !.sup.3- +H.sub.2 O.sub.2
(see F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 5th Edition, page 172).
Sodium percarbonate is a commercially available (e.g. from Fluka Chemicals Ltd.) bleaching agent and provides a source of peroxide ions in the presence of water. The molecular formula is generally represented as Na 2 CO 3 . 3/2 H 2 O 2 (see Chem. Lett., 1986, 665-6).
Alkyl and alkoxy groups containing 3 or more carbon atoms and C 4 -alkanoic acids may be straight or branched chain.
The process provided by the present invention may be carried out according to the following methods:
1. In a typical procedure, a stirred solution of a compound of the formula (II) in a suitable organic solvent, e.g. t-butanol or toluene, is cautiously treated with an aqueous (typically about 30 weight %) solution of hydrogen peroxide and a catalytic amount of a suitable acid, e.g. sulphuric acid, preferably maintaing the reaction temperature at below 50° C., most preferably at about room temperature, throughout the addition. The reaction is further stirred at room temperature for up to 24 hours although longer reaction times may be necessary. The product of the formula (I) is isolated and purified using conventional techniues.
2. In a typical procedure, a stirred solution of compound of the formula (II) in a suitable organic solvent, e.g. C 1 -C 4 alkanol such as tert-butanol or methanol, is cautiously treated with a suitable base, e.g. sodium or potassium hydroxide or bicarbonate, and an aqueous (typically about 30 weight %) solution of hydrogen peroxide, maintaining the reaction temperature at from 0° C. to 50° C. throughout the additions. The reaction is further stirred at from room temperature to 50° C. for up to 24 hours, or longer if necessary. The product of the formula (I) is isolated and purified by conventional techniues.
3. In a typical procedure, a stirred solution of a compound of the formula (II) in a C 1 -C 4 alkanoic acid, e.g. acetic acid, is cautiously treated with an aqueous (typically about 30 weight %) solution of hydrogen peroxide, maintaining the reaction temperature at below 40° C. throughout the addition to avoid hydrolysis of the ester functionalility. The reaction is further stirred at room temperature for up to 24 hours. The product of the formula (I) is isolated and purified using conventional techniques.
4. In a typical procedure, a stirred solution of a compound of the formula (II) in a C 1 -C 4 alkanoic acid, e.g. acetic acid, is treated portionwise with sodium perborate tetrahydrate maintaining the reaction temperature at below 20° C. during the addition. The mixture is further stirred at room temperature for up to 48 hours. The product of the formula (I) is isolated and purified using conventional techniques.
5. In a typical procedure, a stirred solution of a compound of the formula (II) in a suitable organic solvent., e.g. a C 1 -C 4 alkanol such as tert-butanol, is treated with sodium percarbonate at about room temperature. The reaction is stirred at from room temperature to 60° C. for about 24 hours. The product of the formula (I) is isolated and purified by conventional techniques.
It will be appreciated by the skilled man that the reaction time will vary in each individual case dependent on several factors, such as the nature of the substituents and the reaction temperature employed.
The course of the reaction may be monitored using conventional methods, e.g. thin-layer chromatography.
The starting materials of the formula (II) may be prepared by a Michael addition reaction as illustrated in Scheme 1, using comparable reaction conditions to those described by Kryshtal et al, Synthesis, 1979!, 107. ##STR5## wherein R 1 , R 2 and R 3 are as previously defined for a compound of the formula (I).
In a typical procedure, an acrylate derivative of the formula (IV) is added to a stirred mixture of a compound of the formula (III), potassium carbonate and a catalytic amount of benzyltriethylammonium chloride in toluene at about room temperature, and the reaction further stirred at from room temperature to 50° C., preferably at about 40° C., for up to 24 hours. The product of the formula (II) is isolated and purified using conventional techniqques.
The reaction may also be performed in the absence of benzyltriethylammonium chloride by reacting a compound of the formula (III) with an acrylate derivative of the formula (IV) in the presence of a suitable base, e.g. potassium carbonate or potassium tert-botoxide, in a suitable organic solvent, e.g. a C 1 -C 4 alkanol (preferably tert-butanol) or acetonitrile, at about room temperature. When R 2 is other than hydrogen in this reaction and potassium tert-butoxide is used as the base, it is preferably added to the reaction mixture at about -10° C. and this is followed by a period of stirring of the reaction at from 0° C. to room temperature. The product of the formula (II) is isolated and purified by conventional techniques.
The compounds of the formula (III) and the acrylate derivatives of the formula (IV) are either known compounds which may also be commercially available, or are prepared by conventional methods in accordance with literature precedents.
A base salt of a compound of the formula (I) may be prepared by mixing together solutions containing approximately equimolar amounts of a compound of the formula (I) and a suitable base. The base salt is recovered by filtration or by filtration or by evaporation of the solvent.
The process provided by the invention is illustrated by the following Examples:
EXAMPLE 1
1- 2-(tert-Butoxycarbonyl)ethyl!-1-cyclopentanecarboxylic acid
To a solution of crude 2-acetyl-2- 2-(tert-butoxycarbonyl)-ethyl!cyclohexanone (see Preparations 1 and 2) (42 g, 0.15 mol) in t-butanol (84 ml) was cautiously added a 30% aqueous hydrogen peroxide solution (21 ml, 0.187 mol) and conc. sulphuric acid (0.25 ml, 98% w/w) at room temperature, maintaining the reaction temperature below 50° C. during the addition. The mixture was stirred at room temperature for 18 hours, partitioned between dichloromethane (100 ml) and water (100 ml), and the layers separated. The dichloromethane layer was washed with 5% aqueous sodium sulphite solution (50 ml), dried over magnesium sulphate, filtered and concentrated under reduced pressure to give a pale yellow solid, (43 g). The solid partially crystallized on standing overnight to provide, after collecting and washing with pentane, the title compound, (15.5 g).
The mother liquors were concentrated and purified by column chromatography on silica gel by eluting with ethyl acetate/hexane (1:10) to provide, after combination and evaporation of appropriate fractions, a further 14.47 g of the title compound (combined yield=29.97 g, 78%). 1H-NMR (300 MHz, CDCl 3 ):=1.45 (s, 9H), 1.45-1.60 (m, 2H), 1.62-1.78 (m, 4H), 1.92-1.99 (m, 2H), 2.11-2.21 (m, 2H), 2.21-2.33 (m, 2H) ppm.
EXAMPLE 2
1- 2-(tert-Butoxycarbonyl)ethyl!-1-cyclopentanecarboxylic acid
To a solution of 2-acetyl-2- 2-(tert-butoxycarbonyl)-ethyl!-cyclohexanone (see Preparations 1 and 2) (2.0 g, 7.45 mmol) and concentrated sulphuric acid (98% w/w, one drop) in toluene (6.0 ml) was added, dropwise, a 30% aqueous solution of hydrogen peroxide (1.05 ml, 9.31 mmol) at room temperature. The mixture was stirred for 68 hours at room temperature, treated with a further quantity of a 30% aqueous solution of hydrogen peroxide (0.4 ml, 3.72 mmol) and stirred for a further 16 hours at room temperature. The mixture was partitioned between toluene (25 ml) and 5% aqueous sodium sulphite solution and the layers separated. The toluene layer was washed with dilute aqueous ammonia solution (25 ml of 0.880 ammonia in 200 ml of distilled water, 4×25 ml). The combined aqueous extracts were washed with toluene (25 ml), acidified to pH 2-3 with 5.0N aqueous hydrochloric acid solution and extracted with toluene (3×25 ml). The combined toluene extracts were dried over magnesium sulphate, filtered and concentrated under reduced pressure to give an oil, (1.11 g, 61%). The crude product was crystallized from pentane (7.5 ml/g) to give the title compound as a colorless solid. Rf. 0.28 (silica, hexane/ethyl acetate 2:1). 1 H-NMR (300 MHz, CDCl 3 ):=1.45 (s, 9H). 1.45-1.60 (m, 2H), 1.62-1.78 (m, 4H), 1.92-1.99 (m, 2H), 2.11-2.21 (m, 2H), 2.21-2.33 (m, 2H) ppm. Analysis %: Found: C, 64.26; H, 9.27; C 13 H 22 O 4 requires: C, 64.44; H, 9.15.
EXAMPLE 3
1- 2-Benzyloxycarbonyl)ethyl!-1-cyclopentanecarboxylic acid
To a solution of crude 2-acetyl-2- 2-(benzyloxycarbonyl)-ethyl!cyclohexanone (see Preparation 3) (19.7 g, 0.065 mol) in tert-butanol (35 ml) at room temperature was cautiously added, over a period of 30 minutes, a 30% aqueous hydrogen peroxide solution (8.8 ml, 0.078 mol) and concentrated sulphuric acid (0.25 ml, 98% w/w). The mixture was stirred at room temperature for 20 hours, partitioned between dichloromethane (100 ml) and water (100 ml) and the layers separated. The dichloromethane layer was washed with a 5% aqueous sodium sulphite solution (50 ml), dried over magnesium sulphate, filtered and concentrated under reduced pressure. Purification of the residue by chromatography on silica gel by initially eluting with ethyl acetate/hexane (1:2 changing to 1:1), followed by neat ethyl acetate in the latter stages, gave, after combination and evaporation of appropriate fractions, the title compound as a yellow oil, (12.17 g, 72%). RF. 0.17 (silica, hexane/ethyl acetate/acetic acid, 74:25:1). IR (thin film): v=3800-2400, 1735, 1695, 1450 cm -1 . Analysis %: Found: C, 69.70; H, 7.18; C 16 H 20 O 4 requires: C, 69.55; H, 7.29.
EXAMPLE 4
1- 2-(Ethoxycarbonyl)ethyl!-1-cyclopentanecarboxylic acid
To a solution of 2-acetyl-2- 2-(ethoxycarbonyl)-ethyl!-cyclohexanone (see Preparation 4) (40 g, 0.16 mol) in tert-butanol (85 ml) was added, dropwise, a 30% aqueous solution of hydrogen peroxide (21.7 ml, 0.19 mol) and concentrated sulfuric acid (0.25 ml, 98% w/w) at room temperature. The mixture was further stirred for 24 hours, partitioned between dichloromethane (100 ml) and distilled water (100 ml) and the layers separated. The dichloromethane layer was washed with 5% aqueous sodium sulphite solution, dried over magnesium sulphate, filtered and concentrated under reduced pressure to give a yellow oil, (34.35 g). Purification of this material by chromatography on silica by eluting with ethyl acetate/hexane (1:2 changing to 1:1), followed by neat ethyl acetate in the latter stages, gave, after combination and evaporation of appropriate fractions, the title compound as a yellow oil, (22.96 g, 67%). RF. 0.28 (silica, ethyl acetate/hexane, 1:1). 1 H-NMR (300 MHz, CDCl 3 ):=1.31 (t, 3H), 1.47-1.62 (m, 2H), 1.62-1.82 (m, 4H), 1.92-2.08 (m, 2H), 2.10-2.27 (m, 2H), 2.32-2.46 (m, 2H), 4.19 (q, 2H) ppm. 13 C-NMR (75.5 MHz, CDCl 3 ):=14.26, 25.15, 31.21, 33.56, 36.15, 53.21, 60.49, 173.38, 183.52 ppm.
EXAMPLE 5
1- 2-(tert-Butoxycarbonyl)-3-(2-methoxyethoxy)propyl!-1-cyclopentanecarboxylic acid
To a solution of 2-acetyl-2- 2-(tert-butoxycarbonyl)-3-(2-methoxyethoxy)propyl!cyclohexanone (see Preparations 5 and 11) (50 mg, 0.14 mmol) in tert-butanol (0.5 ml) was added a 30% aqueous hydrogen peroxide solution (0.02 ml, 0.168 mmol and concentrated sulphuric acid (one drop) at room temperature. The mixture was stirred at room temperature for 4 hours, partitioned between dichloromethane (10 ml) and water (10 ml), and the layers separated. The aqueous layer was extracted with dichloromethane (2×10 ml), the combined organic extracts dried over magnesium sulphate, filtered and concentrated under reduced pressure to give the title compound, (49 mg). Rf. 0.36 (silica, ethyl acetate). 1 H-NMR (300 MHz, CDCl 3 ):=1.43 (s, 9H), 1.43-1.60 (m, 2H), 1.61-1.65 (m, 4H), 1.78 (dd, 1H), 2.0 (dd, 1H), 2.08-2.20 (m, 2H), 2.59-2.70 (m, 1H), 3.38 (s, 3H), 3.48-3.65 (m, 6H) ppm.
EXAMPLE 6
1- 2-(tert-butoxycarbonyl)-3-(2-methoxyethoxy)propyl!-1-cyclopentanecarboxylic acid isopropylamine salt (1:1)
To a solution of 2-acetyl-2- 2-tert-butoxycarbonyl)-3-(2-methoxyethoxy)propyl!cyclohexanone (see Preparations 5 and 11)) (5.45 g, 0.015 mol) in tert-butanol (10.9 ml) and concentrated sulphuric acid (one drop) was added a 30% aqueous hydrogen peroxide solution (2.1 ml, 0.018 mol) at room temperature. The mixture was stirred at room temperature for 24 hours, partitioned between dichloromethane (20 ml) and 2.0M aqueous sodium hydroxide solution (20 ml) and the layers separated. The dichloromethane layer was washed with water (10 ml), the combined aqueous extracts acidified to pH 2 with 5.0M aqueous hydrochloric acid solution and extracted with n-hexane (2×20 ml). The combined n-hexane extracts were washed with water (5 ml), concentrated under reduced pressure and azeotropically dried with ethyl acetate to give the title acid, (3.99 g, 96% by GC normalization). Rf. 0.44 (silica, ethyl acetate, 1% acetic acid). 13 C-NMR (75.5 MHz, CDCl 3 ):=24.44, 24.80, 27.82, 34.97, 36.51, 37.29, 44.43, 53.35, 58.84, 70.06, 71.72, 73.20, 80.44, 173.88, 183.33 ppm.
The crude product (3.4 g, 0.01 mol) was dissolved in 34 ml of n-hexane and isopropylamine (0.61 g, 0.01 mol) added at room temperature. The precipitated salt was cooled to 0° C. granulated for 2 hours and collected to give the title compound (3.57 g, 72.1% overall yield; HPLC main band assay 98.7%), m.p. 84°-87° C. 1 H-NMR (300 MHz, CDCl 3 ):=1.23 (d, 6H), 1.45 (s, 9H), 1.35-1.50 (m, 2H), 1.58-1.70 (m, 4H), 1.78 (dd, 1H), 1.88 (dd, 1H), 2.05-2.19 (m, 2H), 2.60-2.69 (m, 1H), 3.28 (heptet, 1H), 3.36 (s, 3H), 3.48-3.62 (m, 6H), 5.98 (brs, 3H) ppm. 13 C-NMR (75 MHz, CDCl 3 ):=21.99, 24.51, 24.97, 27.86 34.64, 37.14, 37.98, 43.05, 44.94, 54.57, 58.78, 69.91, 71.68, 73.48, 79.98, 174.79, 183.22 ppm. Analysis %: Found: C, 61.64; H, 10.30; N, 3.46; C 20 H 39 NO 6 requires: C, 61.67; H, 10.09; N, 3.60.
EXAMPLE 7
1- 2-(4-Nitrobenzyloxycarbonyl)ethyl!-1-cyclopentanecarboxylic acid
To a solution of 2-acetyl-2- 2-(4-nitrobenzyloxycarbonyl)-ethyl!cyclohexanone (see Preparation 8) (1.68 g, 4.85 mmol) in tert-butanol (3.3 ml) was added, dropwise, a 30% aqueous solution of hydrogen peroxide (0.65 ml, 5.82 mmol) and concentrated sulphuric acid (98% w/w, one drop) at room temperature. The mixture was stirred for 48 hours, partitioned between toluene (25 ml) and 5% aqueous sodium sulphite solution and the layers separated. The toluene layer was washed with dilute aqueous ammonia solution (25 ml of 0.880 ammonia in 200 ml of distilled water, 4×25 ml). The combined aqueous extracts were washed with toluene (25 ml), acidified to pH 2-3 with 5.ON aqueous hydrochloric acid solution and extracted with toluene (3×25 ml). The combined toluene extracts were dried over magnesium sulphate, filtered and concentrated under reduced pressure to give an oil which solidified on standing, (0.96 g, 61.9%). The crude product was recrystallized from ethyl acetate/hexane 1:1 (3 ml/g) to give the title acid, m.p. 78°-80° C. Rf. 0.27 (silica, hexane/ethyl acetate 2:1+1% acetic acid). 1 H-NMR (300 MHz, CDCl 3 ):=1.49-1.61 (m, 2H), 1.63-1.78 (m, 4H), 1.97-2.06 (m, 2H), 2.11-2.22 (m, 2H), 2.42-2.50 (m, 2H), 5.22 (s, 2H), 7.55 (d, 2H), 8.23 (d, 2H) ppm. 13 C-NMR (75 MHz, CDCl 3 ):=24.98, 30.80, 33.12, 36.03, 52.86, 64.71, 123.68, 128.30, 143.03, 147.61, 172.71, 183.79 ppm. Analysis %: Found: C, 59.71; H, 5.86; N, 4.44; C 16 H 19 NO 6 requires: C, 59.81; H, 5.96; N, 4.36.
EXAMPLE 8
1- 2-(4-Methoxybenzyloxycarbonyl)ethyl!1-cyclopentane-carboxylic acid
To a solution of 2-benzoyl-2- 2-(4-methoxybenzyloxycarbonyl)-ethyl!cyclohexanone (see Preparation 9) (2.16 g, 5.47 mmol) in tert-butanol (4.3 ml) was added, dropwise, a 30% aqueous solution of hydrogen peroxide (0.74 ml, 6.56 mmol) and concentrated sulphuric acid (98% w/w, one drop) at room temperature. The mixture was stirred for 48 hours, partitioned between toluene (25 ml) and 5% aqueous sodium sulphite solution and the layers separated. The toluene layer was washed with dilute aqueous ammonia solution (25 ml of 0.880 ammonia in 200 ml of distilled water, 4×25 ml). The combined aqueous extracts were washed with toluene (25 ml), acidified to pH 2-3 with 5.ON aqueous hydrochloric acid solution and extracted with toluene (3×25 ml). The combined toluene extracts were dried over magnesium sulphate, filtered and concentrated under reduced pressure to give the title compound as an oil, (0.746 g, 44.6%). RF. 0.16 silica, hexane/ethyl acetate 2:1). 1 H-NMR (300 MHz, CDCl 3 ):=1.45-1.59 (m, 2H), 1.65-1.78 (m, 4H), 1.98-2.06 (m, 2H), 2.12-2.22 (m, 2H), 2.34-2.46 (m, 2H), 3.84 (s, 3H), 5.06 (s, 2H), 6.91 (d, 2H), 7.31 (d, 2H) ppm. Analysis %: Found: C, 67.05; H, 7.18; C 17 H 22 O 5 requires: C, 66.65; H, 7.24.
EXAMPLE 9
1- 2-(tert-Butoxycarbonyl)ethyl!-1-cyclopentanecarboxylic acid
To a solution of 2-acetyl-2- 2-(tert-butoxycarbonyl)-ethyl!cyclohexanone (see Preparations 1 and 2) (2.06 g, 7.67 mmol) in methanol (8.0 ml) was added, dropwise, a 30% aqueous solution of hydrogen peroxide (1.04 ml, 9.21 mmol) at room temperature. The mixture was cooled to 0° C. and a 20% aqueous solution of sodium hydroxide (1.0 ml) added dropwise. The mixture was stirred for 24 hours at room temperature, partitioned between toluene (25 ml) and 5% aqueous sodium sulphite solution and the layers separated. The toluene layer was washed with dilute aqueous ammonia solution (25 ml of 0.880 ammonia in 200 ml of distilled water, 4×25 ml). The combined aqueous extracts were acidified to pH 2-3 with 5.ON aqueous hydrochloric acid solution and extracted with toluene (3×25 ml). The combined toluene extracts were dried over magnesium sulphate, filtered and concentrated under reduced pressure to give the title acid as a colorless oil, (0.816 g, 44%). Rf. 0.24 (silica, hexane/ethyl acetate 2:1). 1 H-NMR (300 MHz, CDCl 3 ):=1.45 (s, 9H), 1.45-1.60 (m, 2H), 1.62-1.78 (m, 4H), 1.92-1.99 (m, 2H), 2.11-2.21 (m, 2H), 2.21-2.33 (m, 2H) ppm.
EXAMPLE 10
1- 2-(tert-Butoxycarbonyl)ethyl!-1-cyclopentanecarboxylic acid
To a solution of 2-acetyl-2- 2-(tert-butoxycarbonyl)-ethyl!cyclohexanone (see Preparations 1 and 2) (2.0 g, 7.45 mmol) in tert-butanol (4.0 ml) was added, in one portion, sodium percarbonate (0.935 g, 5.96 mmol) at room temperature. The mixture was heated to 50°-55° C. for 8 hours, stirred at room temperature for 16 hours, partitioned between toluene (25 ml) and 5% aqueous sodium sulphite solution and the layers separated. The toluene layer was washed with dilute aqueous ammonia solution (25 ml of 0.880 ammonia in 200 ml of distilled water, 4×25 ml). The combined aqueous extracts were acidified to pH 2-3 with 5.ON aqueous hydrochloric acid solution and extracted with toluene (3×25 ml). The combined toluene extracts were dried over magnesium sulphate, filtered and concentrated under reduced pressure to give the title acid as a colorless oil which solidified on standing, (1.119 g, 62%). Rf. 0.25 (silica, hexane/ethyl acetate 2:1). 1 H-NMR (300 MHz, CDCl 3 ):=1.45 (s, 9H), 1.45-1.60 (m, 2H), 162-1.78 (m, 4H), 1.92-1.99 (m, 2H), 2.11-2.21 (m, 2H), 2.21-2.33 (m, 2H) ppm.
EXAMPLE 11
1- 2-(tert-Butoxycarbonyl)ethyl!-1-cyclopentanecarboxylic acid
To a solution of 2-acetyl-2- 2-(tert-butoxycarbonyl)-ethyl!cyclohexanone (see Preparations 1 and 2) (1.0 g, 3.72 mmol) in acetic acid (10 ml) was added sodium perborate tetrahydrate (0.57 g, 3.72 mmol) in one portion at 15° C. The mixture was mechanically stirred for 1 hour during which time the internal temperature rose to 18° C. A further portion of sodium perborate tetrahydrate (0.57 g, 3.72 mmol) was then added and the mixture stirred for a further 1 hour. After this time a final portion of sodium perborate tetrahydrate (0.57 g, 3.72 mmol) was added and the mixture stirred at room temperature for 48 hours. The reaction was filtered to remove solids and the filter pad washed with ethyl acetate (2×25 ml). The combined filtrate and washings were washed with 5% aqueous sodium sulphite solution (2×50 ml), dried over magnesium sulphate, filtered and concentrated under reduced pressure to give a colourless oil, (0.92 g). The crude product was crystallized from pentane (4 ml/g) to give the title acid as a colorless solid, (0.617 g, 68.5%). Rf. 0.3 (silica, hexane/ethyl acetate, 2:1). 1 H-NMR (300 MHz, CDCl 3 ):=1.45 (s, 9H), 1.45-1.60 (m, 2H), 1.62-1.78 (m, 4H), 1.92-1.99 (m, 2H), 2.11-2.21 (m, 2H), 2.21-2.33 (m, 2H) ppm. Analysis %: Found: C, 64.32; H, 9.03; C 13 H 22 O 4 requires: C, 64.44; H, 9.15.
EXAMPLE 12
1- 2-(tert-butoxycarbonyl)ethyl!-1-cyclopentanecarboxylic acid
To a suspension of 2- 2-(tert-butoxycarbonyl)ethyl!-2-ethoxycarbonylcyclohexanone (see Preparation 10) (1.0 g, 3.35 mmol) and sodium hydrogen carbonate (0.281 g, 3.35 mmol) in tert-butanol (2.0 ml) was added, in four portions over a period of 1.5 hours, a 30% aqueous solution of hydrogen peroxide (4×0.11 ml, 4.0 mmol) at 40° C. The mixture was stirred at 40° C. for 20 hours. A fifth charge of a 30% aqueous solution of hydrogen peroxide (0.11 ml) and a further quantity of sodium hydrogen carbonate (0.281 g, 33.5 mmol) was added, and the mixture stirred at 40° C. for 8 hours. The mixture was partitioned between hexane (40 ml) and 5% aqueous sodium sulphite solution (25 ml) and the layers separated. The hexane layer was washed with dilute aqueous ammonia solution (25 ml of 0.880 ammonia in 200 ml of distilled water, 5×40 ml). The combined aqueous extracts were acidified to pH 2-3 with 5.ON aqueous hydrochloric acid solution and extracted with dichloromethane (3×25 ml). The combined dichloromethane extracts were washed with distilled water (25 ml), dried over magnesium sulphate, filtered and concentrated under reduced pressure to give the title compound as an oil, (0.362 g, 44.6%). Rf. 0.29 (silica, hexane/ethyl acetate 2:1). Analysis %: Found: C, 64.78; H, 9.39; C 1 H 22 O 4 requires: C, 64.44; H, 9.15.
The following Preparations illustrates the preparation of certain intermediates used the preceeding Examples:
PREPARATION 1
2-Acetyl-2- 2-(tert-butoxycarbonyl)ethyl!cyclohexanone
To a suspension of 2-acetylcyclohexanone (100 g, 0.71 mol), potassium carbonate (118.3 g, 0.85 mol) and benzyltriethylammonium chloride (3.18 g, 0.014 mol) in toluene (280 ml), was added, in one portion, tert-butyl acrylate (137.1 g, 155.2 ml, 1.07 mol) at room temperature. The suspension was stirred at 40° C. for 18 hours, diluted with distilled water (1 L) and toluene (500 ml), and the layers separated. The aqueous layer was extracted with toluene (3×500 ml), the combined toluene extracts dried over magnesium sulphate, filtered and concentrated under reduced pressure to give a brown oil, (197.8 g). Rf. 0.41 (silica, hexane/ethyl acetate, 3:1). The crude product was used without further purification.
An analytical sample was prepared from the crude reaction product by chromatography on silica gel by eluting with ethyl acetate/hexane (1:4) to provide, after combination and evaporation of appropriate fractions, the title compound as a colorless oil. IR (thin film): v=2980, 2940, 2870, 1725, 1695, 1500, 1365 cm 1 . Analysis %: Found: C, 67.22; H, 8.64; C 15 H 24 O 4 requires: C, 67.14; H, 9.01.
PREPARATION 2
2-Acetyl-2- 2-(tert-butoxycarbonyl)ethyl!cyclohexanone
To a suspension of 2-acetylcyclohexanone (2.8 g, 0.02 mol) and potassium carbonate (2.8 g, 0.02 mol) in tert-butanol (16.8 ml) was added tert-butyl acrylate (3.33 g, 0.026 mol) over a period of 10 minutes at room temperature. The suspension was stirred at room temperature for 48 hours, diluted with distilled water (16.8 ml) and dichloromethane (16.8 ml) and the layers separated. The aqueous layer was extracted with dichloromethane (16.8 ml) and the combined dichloromethane extracts concentrated under reduced pressure to give a brown oil (5.05 g). The crude product was crystallized from n-pentane (50 ml) to give the title compound as a colorless solid, (3.02 g, 56.2%), m.p. 47°-53° C. Rf. 0.41 (silica, hexane/ethyl acetate 2:1). 1 H-NMR (300 MHz, CDCl 3 ):=1.41-1.55 (m, 2H), 1.47 (s, 9H), 1.62-1.84 (m, 4H), 1.96-2.04 (m, 2H), 2.10-2.21 (m, 2H), 2.17 (s, 3H), 2.26-2.53 (m, 2H) ppm. Analysis %: Found: C, 66.89; H, 9.04; C 15 H 24 O 4 requires: C, 67.14; H, 9.01.
PREPARATION 3
2-Acetyl-2- 2-(benzyloxycarbonyl)ethyl!cyclohexanone
To a solution of 2-acetylcyclohexanone (9.6 g, 0.068 mol), potassium carbonate (11.3 g, 0.082 mol) and benzyltriethylammonium chloride (0.3 g, 0.0013 mol) in toluene (26 ml), was added benzyl acrylate (16.72 g, 0.103 mol) at room temperature. The mixture was heated at 40° C. for 20 hours, cooled, partitioned between water (200 ml) and toluene (200 ml) and toluene (200 ml) and the layers separated. The aqueous layer was extracted with toluene (2×200 ml), the combined organic extracts dried over magnesium sulphate, filtered and concentrated under reduced pressure to provide the title compound as a pale yellow oil, (20.7 g), Rf. 0.2 (silica, hexane/diethyl ether, 2:1). The crude product was used without further purification.
An analytical sample was prepared from the crude reaction product by chromatography on silica gel by eluting with hexane/ether (2:1) to provide, after combination and evaporation of appropriate fractions, the product as a colorless oil. IR (thin film): v=2940, 2870, 1735, 1715, 1695, 1450 cm -1 . Analysis %: Found: C, 71.57; H, 7.45; C 18 H 22 O 4 requires: C, 71.50; H, 7.33%.
PREPARATION 4
2-Acetyl-2- 2-(ethoxycarbonyl)ethyl!cyclohexanone
To a solution of 2-acetylcyclohexanone (25 g, 0.18 mol), potassium carbonate (29.5 g, 0.21 mol) and benzyltriethylammonium chloride (0.8 g, 0.0035 mol) in toluene (70 ml) was added ethyl acrylate (29 ml, 27 g, 0.27 mol) at room temperature. The mixture was heated at 40° C. for 20 hours, filtered and partitioned between distilled water (200 ml) and toluene (200 ml). The organic layer was dried over magnesium sulphate, filtered and concentrated under reduced pressure to give the title compound as a brown oil, (41.7 g, 97%).
The crude product was used in Example 4 without further purification.
PREPARATION 5
2-Acetyl-2- 2-tert-butoxycarbonyl)-3-(2-methoxyethoxy)-propyl!cyclohexanone
To a suspension of 2-acetylcyclohexanone (103 mg, 0.88 mmol), potassium carbonate (121 mg, 0.88 mmol) and benzyltriethylammonium chloride (3 mg, 0.015 mmol) in toluene (0.5 ml) was added, in one portion, tert-butyl 2-(2-methoxyethoxymethyl)acrylate (see Preparations 6 and 7) (191 mg, 0.88 mmol) at room temperature. The suspension was stirred at room temperature for 18 hours, at 40° C. for 8 hours, colled and diluted with water (10 ml) and extracted with ethyl acetate (3×10 ml). The combined organic extracts were dried over magnesium sulphate and concentrated to dryness under reduced pressure. The crude product was purified by flash column chromatography on silica gel by eluting with hexane/ethyl acetate (2:1) to provide, after combination and evaporation of appropriate fractions, the desired product as a colorless oil, (86 mg). Rf. 0.2 (silica, hexane/ethyl acetate, 2:1). IR (thin film: v=2980, 2935, 2870, 1720, 1695, 1450 cm -1 . Analysis %: Found: C, 64.22; H, 9.03; C 19 H 32 O 6 requires: C, 64.02; H, 9.03.
PREPARATION 6
tert-Butyl 2-(2-methoxyethoxymethyl)acrylate
To a solution of tert-butyl 2-(bromomethyl)acrylate (2.0 g, 9.0 mmol) in 2-methoxyethanol (30 ml) at 0° C. was added, in one portion, potassium carbonate (2.5 g, 18 mmol) and the mixture stirred at 0° C. for 1 hour. The reaction was diluted with distilled water (100 ml) and extracted with dichloromethane (100 ml). The layers were separated and the aqueous layer further extracted with dichloromethane (2×50 ml). The combined organic extracts were dried over magnesium sulphate, filtered and concentrated under reduced pressure. The residue was purified by chromatography on silica by eluting with hexane/ethyl acetate (2:1) to give, after combination and evaporation of appropiate fractions, the title compound as a yellow oil, (1.6 g, 82%). Rf. 0.32 (silica, hexane/ethyl acetate, 2:1). 1 H-NMR (300 MHz, CDCl 3 ):=1.50 (s, 9H), 3.42 (s, 3H), 3.56-3.63 (m, 2H), 3.65-3.74 (m, 2H), 4.25 (s, 2H), 5.84 (s, 1H), 6.25 (s, 1H) ppm.
PREPARATION 7
tert-Butyl 2-(2-methoxyethoxymethyl)acrylate
a. tert-Butyl 2-(4-methylphenylsulphonylmethyl) acrylate
To a solution of tert-butyl methacrylate (10 g, 70.3 mmol) in dichloromethane (44 ml) was added, in one portion, p-toluenesulphinic acid, sodium salt, dihydrate (15 g, 70.3 mmol) followed by iodine (17.8 g, 70.3 mmol) and the mixture stirred at room temperature for 24 hours. The reaction was cooled to 0° C. and triethylamine (10.6 g, 105.4 mmol) was added over a period of 10 minutes. The mixture was stirred at 0° C. for 15 minutes and at room temperature for 3 hours, diluted with dichloromethane (100 ml) and distilled water (100 ml). The layers were separated and the aqueous layer further extracted with dichloromethane (50 ml). The combined organic extracts were washed with 1.ON aqueous hydrochloric acid solution (50 ml), saturated aqueous sodium hydrogen carbonate solution (50 ml), distilled water (50 ml) and concentrated under reduced pressure to give a yellow-brown oil, (19.63 g). The material was dissolved in ethyl acetate (40 ml) and triethylamine (7.1 g, 70.3 mmol) added. The mixture was heated at reflux for 8 hours and stirred at room temperature for 16 hours, washed with distilled water (100 ml), 1.ON aqueous hydrochloric acid soluton (100 ml), saturated aqueous sodium hydrogen carbonate solution (100 ml) and the organic layer concentrated under reduced pressure to give a yellow-brown oil (17 g). The crude product was crystallized from hexane/ethyl acetate 4:1 (5 ml/g) to give the title compound as a yellow solid, (13.09 g, 62.8%; 98.64% pure by GC normalization). Rf. 0.31 (silica, hexane/ethyl acetate, 3:1). 1 H-NMR (300 MHz, CDCl 3 ):=1.35 (s, 9H), 2.48 (s, 3H), 4.12 (s, 2H), 5.91 (s, 1H), 6.47 (s, 1H), 7.34 (d, 2H), 7.75 (d, 2H) ppm. 13 C-NMR (75 MHz, CDCl 3 ):=21.67, 27.81, 57.54, 81.73, 128.91, 129.70, 130.55, 132.53, 135.63, 144.83, 163.80 ppm. Analysis %: Found: C, 60.76; H, 6.80; C 15 H 20 O 4 S requires: C, 60.79; H, 6.80.
b. tert-Butyl 2-(2-methoxyethoxymethyl)acrylate
To a suspension of the product of part (a) (14 g, 0.047 mmol) in 2-methoxyethanol (70 ml) at )° C. was added, in one portion, potassium carbonate (13.06 g, 0.094 mol) and the mixture stirred at 0° C. for 3 hours. The reaction was diluted with distilled water (100 ml) and extracted with dichloromethane (100 ml). The layers were separated and the aqueous layer further extracted with dichloromethane (50 ml) and the combined organic extracts concentrated under reduced pressure. The residue was purified by chromatography on silica eluting with hexane/ethyl acetate (6:1) to give, after combination and evaporation of appropriate fractions, the title compound as a colorless oil, (8.62 g, 84%). Rf. 0.32 (silica, hexane/ethyl acetate, 2:1. 1 H-NMR (300 MHz, CDCl 3 ):=1.50 (s, 9H), 3.42 (s, 3H), 3.56-3.63 (m, 2H), 3.65-3.74 (m, 2H), 4.25 (s, 2H), 5.84 (s, 1H), 6.25 (s, 1H) ppm.
PREPARATION 8
2-Acetyl-2- 2-(4-nitrobenzyloxycarbonyl)ethyl!cyclohexanone
The title compound was prepared in 69% yield after chromatography (silica gel, gradient elution with hexane/ethyl acetate) from 2-acetylcyclohexanone and p-nitrobenzyl acrylate using a similar method to that used in Preparation 2. Rf. 0.2 (silica, hexane/ethyl acetate, 2:1). 1 H-NMR (300 MHz, CDCl 3 ):=1.40-1.78 (m, 4H), 1.89-2.47 (m, 8H), 2.07 (s, 3H), 5.13 (s, 2H), 7.45 (d, 2H), 8.17 (d, 2H) ppm. Analysis %: Found: C, 62.75; H, 5.90; N, 3.87; C 18 H 21 NO 6 requires: C, 62.24; H, 6.09; N, 4.03.
PREPARATION 9
2-Benzoyl-2- 2-(4-methoxybenzyloxycarbonyl)ethyl!cyclohexanone
The title compound was prepared in 65.5% yield after chromatography (silica gel, hexane/ethyl acetate 4:1) from 2-benzoylcyclohexanone and p-methoxybenzyl acrylate using a similar method to that used in Preparation 2. (M + 394.13, 53%). Rf. 0.39 (silica, hexane/ethyl acetate 2:1). 1 H-NMR (300 MHz, CDCl 3 ):=1.38-1.49 (m, 1H), 1.68-1.82 (m, 3H), 1.98-2.57 (m, 7H), 2.82-2.91 (m, 1H), 3.82 (s, 3H), 5.03 (s, 2H), 6.87 (d, 2H), 7.26 (d, 2H), 7.42 (t, 2H), 7.56 (t, 1H), 7.88 (d, 2H) ppm. Analysis %: Found: C, 73.05; H, 6.74; C 24 H 26 O 5 requires: C, 73.08; H, 6.64.
PREPARATION 10
2- 2-(tert-Butoxycarbonyl)ethyl!-2-ethoxycarbonylcyclohexanone
To a solution of 2-ethoxycarbonylcyclohexanone (5.0 g, 0.029 mol) and tert-butyl acrylate (4.83 g, 0.037 mol) in tert-butanol (30 ml) was added, in one portion, potassium carbonate (4.0 g, 0.029 mol). The suspension was stirred at room temperature for 22 hours, diluted with dichloromethane (100 ml) and distilled water (100 ml) and the layers separated. The aqueous layer was extracted with dichloromethane (2×100 ml) and the combined dichloromethane extracts dried over magnesium sulphate, filtered and concentrated under reduced pressure. The residue was purified by chromatography on silica by eluting with hexane/ethyl acetate (4:1) to give, after combination and evaporation of appropriate fractions, the title compound as a colorless oil, (7.99 g, 92.3%; 98.92% by GC normalization) (MH + 299.03, 8.53%). Rf. 0.15 (silica, hexane/ethyl acetate 4:1). 1 H-NMR (300 MHz, CDCl 3 ):=1.20 (t, 3H), 1.37 (s, 9H), 1.52-2.46 (m, 12H), 4.08-4.21 (m, 2H) ppm. 13 C-NMR (62 MHz, CDCl 3 ):=13.97, 22.38, 27.36, 27.91, 29.52, 30.49, 36.06, 40.85, 59.87, 61.19, 80.10, 171.61, 172.22, 207.39 ppm. Analysis %: Found: C, 64.19; H, 8.80; C 16 H 26 O 5 requires: C, 64.41; H, 8.78.
PREPARATION 11
2-Acetyl-2- 2-(tert-butoxycarbonyl)-3-(2-methoxyethoxy)-propyl!cyclohexanone
To a suspension of 2-acetylcyclohexanone (3.5 g, 0.025 mol) and tert-butyl 2-(2-methoxyethoxymethyl)-acrylate (see Preparations 6 and 7) (5.41 g, 0.025 mol) in acetonitrile (20 ml) was added, in one portion, potassium tert-butoxide (0.14 g, 0.0012 mol) at -10° C. The mixture was stirred at -10° C. for 24 hours, at 0° C. for 6 hours and at room temperature for 18 hours. The mixture was partitioned between ethyl acetate (15 ml) and distilled water (30 ml) and the layers separated. The aqueous layer was extracted with eithyl acetate (2×15 ml) and the combined ethyl acetate extracts concentrated under reduced pressure to give a brown oil (7.52 g). The residue was purified by chromatography on silica by eluting with hexane/ethyl acetate (4:1) to give, after combination and evaporation of appropriate fractions, the title compound as a colorless oil, (4.98 g, 55.8%). Rf. 0.23 (silica, hexane/ethyl acetate, 2:1). Analysis %: Found: C, 64.44; H, 9.02; C 19 H 32 O 6 requies: C, 64.02; H, 9.05. | The invention provides a process for preparing a compound of the formula: ##STR1## or a base salt thereof, wherein R 2 is hydrogen or C 1 -C 6 alkyl optionally substituted by up to 3 substituents each independently selected from the group consisting of C 1 -C 6 alkoxy and C 1 -C 6 alkoxy(C 1 -C 6 alkoxy)-; and R 3 is C 1 -C 6 alkyl or benzyl, said benzyl group being optionally ring-substituted by up to 2 nitro or C 1 -C 4 alkoxy substituents. comprising reacting a compound of the formula: ##STR2## wherein R 1 is C 1 -C 4 alkyl, phenyl or benzyl or C 1 -C 4 alkoxy; and R 2 and R 3 are as previously defined for a compound of the formula (I), with hydrogen peroxide or a source of peroxide ions: said process being optionally followed by conversion of the compound of the formula (I) to a base salt thereof. The present invention also relates to novel compounds of the formula (II). | 2 |
FIELD OF THE INVENTION
[0001] This invention relates to paint can lids. More particularly, it relates to a removable port assembly allowing easy access to the contents of the can while maintaining a good seal around the rim.
BACKGROUND OF THE INVENTION
[0002] Paint is commonly tinted by opening the metal lid of a can containing a coating base, which may already have some tint in it, and adding concentrated colorant to match a color specified by a customer. One problem with this system is that the lids on cans do not close properly, in many instances. A paint spill may therefore occur when the container is subsequently agitated, typically by shaking, due to the force of the liquid pushing against the lid. If a tint/stain system is used, wherein the colorant is added to a low-viscosity coating base for applications such as for example stains for wooden decks, the problem is more pronounced, particularly since paint cans and lids are not manufactured to tight tolerances, thus allowing the potential for leakage.
[0003] Additionally, the above-mentioned procedure requires that the paint can then be opened so that the customer can check the color of the paint for accuracy, usually by painting a swatch on top of the lid, and may require a further addition of concentrated colorant and resealing, followed by additional shaking of the can. All of this is time-consuming and potentially messy.
[0004] Beyond these issues, paint cans are then opened by the user once the painting task begins, with the paint being typically poured out of the can, during which the paint tends to run into the gutter in the rim of the can. The result is that dried paint builds up in this location, preventing proper sealing of the can thereafter. Due to this, air gets into the can, causing deterioration of the paint in storage, and the presence of paint in the gutter may also cause rusting, which may contaminate the paint. As well, depending on the toxicity of the materials present in the can, issues of environmental exposure may be created by the poor seal, including the risk of accidental opening of the can during the disposal process.
[0005] Although the discussion herein concentrates on the structure of paint cans, it will be appreciated that a number of materials can be stored in such cans, with some of the same problems noted above. Therefore use of the term “paint can” herein means the kind of can traditionally known for storing paint, but not limited to any particular contents of the can, as it is known in the art that such cans may contain paint, stain, varnish, etc.
[0006] There continues to be a need for improved ways of accessing the contents of paint cans for viewing and/or dispensing, while maintaining a good seal around the rim of the lid.
SUMMARY OF THE INVENTION
[0007] In one aspect, the invention is a port assembly for a can with a removable lid, the port assembly allowing inspection of and access to the interior of the can without removal of the lid. The port assembly comprises a port in the lid and a port stopper adapted to close the port in the lid to prevent contents of the can from escaping. When opened, the port assembly provides access to the contents of the can. The port stopper has at least one portion that is substantially transparent and substantially colorless, allowing visual inspection of the contents of the can when the port assembly is closed.
[0008] In another aspect, the invention is a pouring spout adapted to interface with a port assembly in a removable lid of a can, the port assembly comprising a port in the lid; and a port stopper adapted to interface with the port to create a closed configuration in which contents of the can cannot escape and an open configuration that provides access to the contents of the can, the pouring spout having means for interfacing with the port.
[0009] In yet another aspect, the invention is a removable lid for a can, the lid comprising a port assembly for allowing inspection of and access to the interior of the can without removal of the lid, as described above.
[0010] In a further aspect, the invention comprises a can including a lid and a port assembly in the lid, as described above.
[0011] In a still further aspect, the invention is a method of adding a material to a can. The can has a removable lid with a port that is adapted to interface with a port stopper to create a closed configuration in which contents of the can cannot escape, and an open configuration that provides access to contents of the can. The port stopper has at least one portion that is substantially transparent and substantially colorless, to allow visual inspection of the contents of the can in the closed configuration. The method comprises introducing the material into the can through the port without removing the lid; and engaging the port with the port stopper.
BRIEF DESCRIPTION OF DRAWINGS
[0012] [0012]FIG. 1 is a side cross-sectional view of a prior art paint can lid.
[0013] [0013]FIG. 2 is an exploded side view of a paint can lid equipped with a port assembly comprising a port stopper and a port collar, according to one aspect of the invention.
[0014] [0014]FIG. 3 is a top view of the paint can lid of FIG. 2, showing the port collar in place.
[0015] [0015]FIG. 4 is a top view of the port stopper of FIG. 2.
[0016] [0016]FIG. 5 is a side cross-sectional view of the port stopper of FIG. 2 and FIG. 4.
[0017] [0017]FIG. 6 is an exploded cross-sectional view of a paint can lid equipped with a port assembly comprising a port stopper and matching port collar configured to minimize contamination by paint of threads designed to join the two, according to another aspect of the invention.
[0018] [0018]FIG. 7 is an exploded cross-sectional view of a paint can lid similar to that of FIG. 6, with the threads on the port stopper and port collar reversed, according to yet another aspect of the invention.
[0019] [0019]FIG. 8 is an exploded cross-sectional view of a paint can lid similar to that of FIG. 7, showing additional space where the port stopper screws into the port collar, according to still another aspect of the invention.
[0020] [0020]FIG. 9 is an exploded cross-sectional view of a paint can lid similar to that of FIG. 7, showing a lip around the top of the port stopper, according to a further aspect of the invention.
[0021] [0021]FIG. 10 is a top view of a lid with a port assembly in place, showing positioning of the port assembly relative to the rim, according to a still further aspect of the invention.
[0022] [0022]FIG. 11 is a perspective view of a pouring spout designed to fit into a lid equipped with a port collar, according to yet a further aspect of the invention.
[0023] [0023]FIG. 12 is a perspective view of a can equipped with a lid comprising a port assembly, according to an even further aspect of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0024] The invention will next be illustrated with reference to the figures, wherein the same numbers indicate the same elements in all figures. Such figures are intended to be illustrative rather than limiting and are included herewith to facilitate the explanation of the present invention. The figures are not to scale, and not intended as engineering drawings.
[0025] Referring now to FIG. 1, there is shown a side cross-sectional view of a prior art lid 10 comprising a main lid body 12 and a raised rim 14 . The main lid body has an upper surface 11 and a lower surface 13 , which is inside a can when the lid is in use. Such a lid is commonly used in sealing cans such as might be used for paints, varnishes, stains, laquers, and a variety of other liquid or solid materials. The lid may be made of a metal, typically steel, but may be made of any of a number of materials including other metals and a variety of plastics. The rim 14 of the lid is pressed into a receiving V-shaped notch in the open top of a can (not shown), thereby sealing the can.
[0026] [0026]FIG. 2 shows, according to one embodiment of the invention, a lid 20 equipped with a port assembly, useful for accessing the interior of a can on which the lid is mounted, without a need to remove the lid. The figure shows the port assembly comprising a port stopper 22 (shown in side view) in position to be screwed into a port collar 30 (shown in side cross-section view), to close port 32 in the main lid body 12 . Materials of construction for the main lid body 12 and rim 14 may be any convenient material known in the art, and may as nonlimiting examples comprise a metal, glass, or a polymeric material. Typically the lid will comprise steel for the main lid body and the rim.
[0027] Port stopper 22 has a top 24 comprising an optional lip 26 , and top 24 is integral with first threaded cylinder 28 , which has a bottom 29 . Optional lip 26 extends beyond the diameter of first threaded cylinder 28 , and may serve to reduce contamination of the contents of the can to which the lid is attached. Although first threaded cylinder 28 is shown as threaded along most of its length, it need only be threaded on the end section adjacent bottom 29 . In addition, although the threads are shown in FIG. 2 as straight, they may have a taper. The threads may be of any convenient pitch and threads/unit length.
[0028] Materials of construction for port stopper 22 may be any convenient material including, as nonlimiting examples, a metal, wood, glass, ceramic, or a polymeric material. Preferred is a substantially transparent and substantially colorless material, with nonlimiting examples being polymethyl methacrylate, polycarbonate, and polyethylene terephthalate. In addition, it may be advantageous to use materials of construction for port stopper 22 , or coatings thereon, that cause the contents of the can to wet and/or adhere to the surface of the stopper. Conversely, for some applications it may be advantageous for the materials or construction or coatings to resist wetting by the contents of the can.
[0029] Port collar 30 comprises a hollow cylinder, threaded on the inside surface, and open at both ends. In the embodiment of FIG. 2, port collar 30 comprises upper and lower collars 30 a and 30 b , which are attached to the upper an lower surfaces 11 and 13 , respectively, of main lid body 12 . The upper and lower collars may be separate as shown, or may be integral with each other, for example by means of connecting portions going through holes in main lid body 12 (holes not shown). In addition, upper collar 30 a is optional, and may be dispensed with entirely. Port collar 30 may be made from any convenient material known in the art, including as nonlimiting examples a metal, wood, glass, ceramic, or a polymeric material. Most typically, port collar 30 will comprise steel.
[0030] [0030]FIG. 3 shows a top view of one embodiment of an upper collar 30 a such as was seen in FIG. 2. Upper collar 30 a overlies and is coextensive with an opening in main lid body 12 , forming port 32 of diameter D. In this embodiment, upper collar 30 a is attached to main lid body 12 and lower collar 30 b (not shown) by means of fasteners 34 , such as screws or rivets. Although fasteners are shown in FIG. 3, adhesives such as epoxy or polyisocyanate resins, or other attachment means may also be used.
[0031] [0031]FIGS. 4 and 5 show, respectively, a top view and a side cross-section view of one embodiment of a port stopper 22 such as was seen in FIG. 2, showing additional detail, according to the invention. FIG. 4 shows a depression 34 in the top of port stopper 22 , with the bottom 29 underlying depression 34 being attached to (or integral with) a raised grip 36 , suitable for being grasped when opening the port. An optional slot 38 is shown on grip 36 , suitable for engaging with a spatulate tool, for example a screwdriver, or coin, or the like in opening the port.
[0032] In the embodiment shown in FIG. 4, grip 36 is a straight bar of approximately rectangular cross-section extending across and integral with (or affixed to) bottom 29 within the depression 34 , on a diameter thereof. Other shapes are however possible for grip 36 , including but not limited to bars with curved sides, multiple bars, bars arranged in a spokelike manner, bars with a non-rectangular cross section, and a plurality of pegs instead of bars. Alternatively, grip 36 may be configured such that port stopper 22 can be removed by a common tool such as a wrench, or configured to match the shape of a custom-made tool. Other configurations of grip 36 may be contemplated, and are intended to be considered within the scope of this invention.
[0033] In general, instead of or in addition to grip 36 , there may be provided one or more means for engagement of and transfer of torque to the port stopper for unscrewing the port stopper from the port collar. Such means might include, but are not limited to, slots, multiple holes for engagement of special tools, depressions with geometric shapes for engagement by screwdrivers (Phillips head, hex, star head, etc.) or other tools (such as but not limited to a bung wrench), or any geometry suitable for engagement by the human hand.
[0034] [0034]FIG. 5 shows the port stopper 22 of FIG. 4 in cross-sectional view. In this embodiment of the invention, the top of grip 36 is recessed relative to the top 24 of the port stopper. The top of grip 36 may however be even with top 24 , or above it. Preferably however, grip 36 is not so high as to extend above the rim 14 of lid 10 (reference FIG. 2). Such an arrangement is conducive to cans having lids equipped with port assemblies.
[0035] In a preferred embodiment of the invention, at least a portion of bottom 29 and/or grip 36 of port stopper 22 is substantially transparent and substantially colorless, allowing the user to see the color of the contents of a can employing a lid 20 equipped with a port assembly according to the invention, without the need to remove the port stopper 22 . By substantially transparent and substantially colorless, it is meant that a user can visually inspect the contents of the can through the port stopper without having to remove the stopper, and that the view so obtained is a good representation of what the contents would look like without the stopper in place. Thus, for example, the port may somewhat hazy, as long as sufficient light is transmitted to allow an accurate view of the contents.
[0036] [0036]FIG. 6 shows another embodiment of the invention, showing in cross-sectional view a lid 120 with a port assembly. The port assembly comprises port stopper 122 , shown here in position for screwing into port collar 130 , to close port 132 in main lid body 112 . Port stopper 122 has a top 124 that is integral with a first threaded cylinder 128 , which is open at the bottom end 129 . Although first threaded cylinder 128 is shown as threaded along most of its length, it need only be threaded on the end section adjacent bottom end 129 . As well, threaded cylinder 128 may be longer than annular space 140 into which it screws, leaving a portion of threaded cylinder 128 protruding from annular space 140 . Or, threaded cylinder 128 may be so short in length that, when screwed into annular region 140 , it does not reach the bottom. In addition, although the threads are shown in FIG. 6 as straight, they may have a taper. The threads may be of any convenient pitch and threads/unit length.
[0037] In the embodiment shown in FIG. 6, grip 136 (seen in an end-view) is a straight bar of approximately rectangular cross-section extending across and within a depression 134 in top 124 , on a diameter thereof. Although grip 136 may be a hollow raised structure, as shown in FIG. 6, it may instead be solid. Other shapes are however possible for grip 136 , including but not limited to means of engagement such as have been described above in relation to grip 36 , in relation to FIGS. 4 and 5. Even further configurations of grip 136 may be contemplated, and are intended to be considered within the scope of this invention.
[0038] In a preferred embodiment of the invention, and as discussed above in relation to FIG. 5, at least a portion of top 124 , including grip 136 and/or the part of top 124 under depression 134 , of port stopper 122 is substantially transparent and substantially colorless.
[0039] Port collar 130 comprises a threaded well comprising an inner tube 160 having an outer surface 162 , an outer tube 164 having an inner surface 166 , a connecting ring 168 between the inner tube and the outer tube, and an annular region 140 between the inner surface of the outer tube and the outer surface of the inner tube, with threads being located on the inner surface 166 of the outer tube 164 .
[0040] Port collar 130 is affixed on its outer surface 137 to main lid body 112 at joint 142 , forming port 132 . The top end 131 of port collar 130 may lie flush with the upper surface 111 of main lid body 112 , or may extend a distance K above it. Distance K may be between about 0 inch about ⅜ inch, preferably about ⅛ inch. The distance, if any, that joint 142 rises above upper surface 111 of main lid body 112 will depend upon distance K, and will be determined by considerations of convenience and mechanical strength. The bottom end 133 of port collar 130 extends a distance P below the lower surface 113 of main lid body 112 . Distance P is typically between about ¼ inch and about 1 inch, preferably about ½ inch. By virtue of the presence of the protrusion of the bottom end 133 below the lower surface 113 , there may be additional mixing action created when a can fitted with such a port collar is agitated, thus providing improved homogeneity of the liquid being mixed.
[0041] Joint 142 may be provided by for example press-fitting port collar 130 into main lid body 412 , by welding or soldering it in place. Alternatively, port collar 130 and main lid body 112 may both be part of a single piece, obtained for example by molding, in which case joint 142 may be automatically incorporated during the preparation of lid 120 . As another alternative, port collar 130 and main lid body 112 may be affixed together with a polymeric material. Useful materials include, inter alia, cross-linked polyethylene, poly(ethylene-vinyl acetate), polyvinyl chloride, polystyrene, polyurea, or polyurethane. Preferred are resilient materials such as synthetic and natural latex rubbers, neoprene, acrylonitrile-butadienestyrene or styrene-butadiene-styrene block copolymers, thermoplastic elastomers, ethylene-propylene rubbers, and silicone elastomers. The exact dimensions of joint 142 are not critical, but may typically be a band about ⅜ inch wide and about ⅛ inch thick. The term “thick” here means in a direction outward from port collar 130 along main body lid 112 .
[0042] [0042]FIG. 7 shows, as provided by the invention, an embodiment in which the threaded portions of port stopper 228 and port collar 230 are reversed, relative to the configuration shown in FIG. 6. Thus in FIG. 7 the threads in port collar 230 are on the outer surface 262 of inner tube 260 , and the threaded portion of port stopper 222 is arranged to match this configuration.
[0043] [0043]FIG. 8 shows an embodiment of the invention similar to that of FIG. 7, in which annular region 340 has a width (w) that is wider than the thickness (t) of threaded cylinder 328 , thereby affording an empty space (w-t) within annular region 340 even when threaded cylinder 328 is screwed into port collar 330 . Such an empty space may facilitate screwing port stopper 322 and port collar 330 together by allowing outflow of air or liquid from annular region 340 . An example of liquid that might be present in annular region 340 may for example be paint or varnish or other contents spilled or overflowed from a can to which a lid 320 having a port assembly is attached.
[0044] [0044]FIG. 9 shows another embodiment of the invention, similar to that shown in FIG. 6, in which top 424 of port stopper 422 additionally comprises a lip 426 , which may serve to reduce contamination of annular region 440 by any of a variety of materials that might tend to find their way into it, for example dust and dirt, or spilled can contents. Lip 426 may extend any convenient distance from threaded cylinder 428 , and will typically be wide enough to extend at least to cover substantially all of port collar 430 when the port stopper 422 has been screwed into it. Also, as shown in FIG. 9, grip 436 may optionally be solid rather than hollow.
[0045] [0045]FIG. 10 shows yet another exemplary embodiment of a lid 520 according to the invention, comprising a rim 514 and a main lid body 512 fitted with a port assembly consisting of a port stopper 522 and a port collar (hidden from view beneath port stopper 522 ). The port stopper 522 is located at a distance C from rim 514 . Distance C may be from about 0 inch to a distance that would put port stopper 522 in about the center of main lid body 512 ; this distance may vary with the size and shape of the lid, and will typically be chosen for convenience in manufacturing and/or use of the lid 520 . In particular, distance C may be chosen to correspond to a location that facilitates use of colorant dispensers typically used for tinting paints or other coatings. Note that although a circular lid 520 is shown in FIG. 10, the lid may be square, or rectangular, or any other shape as may be convenient. Note also that rim 514 may be of a similar shape as shown at rim 14 in FIG. 2, but may be any convenient form of closure, for example bendable metal flanges or an adhesive. Alternatively, lid 520 may be integral with a can or other container, in which case no rim or equivalent closure means may be needed.
[0046] The diameter of port assemblies according to the invention may vary according to the type and size of can on which the lid with port assembly is to be used, the nature of the contents contained in the can, and/or other factors. A lid for use with a paint can may typically have a port assembly affording a port size of between about 1½ inches and about 4 inches, to allow the entry of paintbrushes. Typically, the port diameter will be between about 2 inches and about 3 inches. Such a size will tend to facilitate the addition of paint pigment by automated paint color matching equipment such as is widely used in the art to prepare custom color paints.
[0047] [0047]FIG. 11 shows, in another embodiment of the invention, a pouring spout 650 adapted to screw into a port collar such as has been described and illustrated in FIGS. 2 and 6. Pouring spout 650 comprises a hollow body with an optionally threaded cylindrical section 652 at one end, and may optionally have an angled opening 654 along part of the wall 656 and across part of the top end 658 of the spout. Use of such a spout may afford a convenient means of discharging the contents of a can that has been equipped with a port collar, without the need to remove the lid. The lid may then be closed with a port stopper such has been described in relation to the drawings. Pouring spout 650 may be made of any convenient material, including as nonlimiting examples a metal, wood, glass, ceramic, or a polymeric material. If a resilient material such as a rubber or other polymeric material is used for its construction, pouring spout 650 may optionally be made without threads, but rather be press-fit into a port collar prior to use.
[0048] [0048]FIG. 12 is a perspective view of a can 721 comprising a body 723 upon which is mounted a lid 720 fitted with a port stopper 722 , according to another aspect of the invention. Such a can may be used to contain a variety of materials, including but not limited to paint, varnish, stain, lacquer, drying oil. It may also be used for storing foodstuffs such as honey, maple syrup, and other edibles. It may also be used for holding motor oil or other lubricants, solvents, or other industrial materials. Other uses are possible, and are contemplated by this invention.
[0049] A port assembly according the invention makes it possible to easily open the can, for access to the contents for the purposes of dispensing or for adding colorant or other additives, for example when a custom color is being prepared, or when biocides such as fungicides, algaecides, and/or bactericides are to be added. These are to be construed as non-limiting examples, since the benefits of the present invention are not limited to a particular type of material contained in, or added to, the can. It is also contemplated that the present invention may be used to introduce any or all of any number of ingredients into the can, in any sequence.
[0050] Such additions may be done without the customer ever needing to open the can at the rim, as is currently done, thereby risking contamination of the joint where the rim attaches to the can. Thus air leakage may be minimized, potentially improving the shelf life of the contents of the can. Use of the port assembly may also reduce time and effort involved in the process of adding colorant, and the process of neatly dispensing liquids from the can, using the optional spout described above.
[0051] Having described the invention, we now claim the following and their equivalents. | A port assembly for a paint or similar can, in which a port in the lid is fitted with a threaded collar and a threaded stopper that fits into it. The port assembly allows easy access to the contents of the can while maintaining a good seal around the rim. If the threaded stopper is transparent and colorless, a user may view the contents of the can. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the separation of cereal hydrocolloidal compositions from the crude fiber components of oat, barley, or combinations of grain products. The cereal hydrocolloidal compositions are useful as texturizers and nutrients for improving the health benefits of foods.
Dietary fibers are the soluble and insoluble components of cell walls that are resistant to endogenous digestion in the human upper digestive tract [Am. J. Clin. Nutr. 25: 464-465 (1972)]. Such fibers consist primarily of cellulose, hemicellulose, pectic substances, oligosaccharides, lignin, gums and mucilages.
Dietary fiber has been an important food component since early times. Diets containing significant amounts of dietary fiber are known to assist in the digestive process. Burkitt et al. [Lancet 2: 1408-1411 (1972)] teach that dietary fiber has a role in the prevention of certain large-intestine diseases, including cancer of the colon and diverticulitis. Burkitt et al. also indicate that serum cholesterol rises when dietary fiber is removed from the diet, and that eating a fiber-rich diet lowers serum cholesterol. Trowell [Am. J. Clin. Nutr. 25: 464-465 (1972)] and Dreher [Handbook of Dietary Fiber, An Applied Approach, Marcel Dekker, Inc., New York, N.Y. (1987)] have reported on similar conclusions regarding the relationship between fiber and health benefits.
It is now known that soluble and insoluble fibers provide different health benefits. For example, wheat bran is very rich in insoluble crude fiber (mainly cellulose and hemicelluloses) and is excellent for decreasing the transit time of food through the digestive tract [Anderson et al., Am. J. Clin. Nutr. 32: 346-363 (1979)]. Some soluble fibers, especially beta-glucan, are reported to reduce total plasma cholesterol [Behall et al., J. Am. Coll. Nutr. 16: 46-51 (1997)].
2. Description of the Prior Art
Dietary fiber typically consists of morphologically intact cellular tissues of various seed brans, hulls, and other agricultural by-products that have a high content of crude fiber [Dintzis et al., Cereal Chem. 56:123-127 (1979)]. When added to foods, these fibers impart a gritty texture to the final product. One solution to this problem has been to grind the fibers to give finer powders, but these powders still retain their high crude fiber contents. Likewise, the alkaline or alkaline/peroxide treatment of agricultural byproducts as reported by Gould (U.S. Pat. Nos. 4,649,113 and 4,806,475), Gould et al. (U.S. Pat. No. 4,774,098), Ramaswamy (U.S. Pat. No. 5,023,103); and Antrim (U.S. Pat. No. 4,038,481) does not remove the crude fiber. Morley et al. (U.S. Pat. No. 4,565,702) and Sharma (U.S. Pat. No. 4,619,831) teach enrobing the high crude fiber insoluble dietary fibers with soluble fibers (gums) for providing better texture and mouthfeel.
Soluble fibers are water-soluble polysaccharides such as pectin-like fruit and beet by-products (Thibault et al., U.S. Pat. No. 5,275,834). There have been a number of reports of alkaline extraction of agricultural materials, including hulls and brans, for obtaining their soluble hemicellulose components (Wolf, U.S. Pat. No. 2,709,699; Rutenberg et al., U.S. Pat. No. 2,801,955; and Gerrish et al., U.S. Pat. No. 3,879,373).
Gould et al., U.S. Pat. No. 4,497,840, describe foods made from oat bran which contain at least 150% more crude fiber than the whole oat flour. Also, Murtaugh et al., U.S. Pat. No. 4,908,223, show grinding oat bran and rice products to make frozen desserts without any separation of crude fiber components. Rudel, U.S. Pat. No. 4,961,937, also used non-separated oat products in baked products.
The oat soluble fiber, also called oat gum or beta-glucan, of the oat groat was fractionated as a separate component by an extensive series of separation described by Hohner and Hyldon, U.S. Pat. No. 4,028,468. Another wet-milling of oats to give various fractions including oat proteins was described by Cluskey et al., Cereal Chem., 50, 475(1973). Also beta-glucan enriched cellulose-containing fiber with little starch was described by Lehtomaki et al., U.S. Pat. No. 5,183,677. Oat beta-glucan was water extracted from oat groat in U.S. Pat. No. 5,512,287 by Wang et al. Also, barley beta-glucan was purified by an alkaline extraction procedure of Bhatty (U.S. Pat. No. 5,518,710).
Inglett (U.S. Pat. No. 4,996,063) teaches that water-soluble dietary fiber compositions are prepared by treatment of milled oat products with α-amylase and removal of insoluble components by centrifugation. In a related development, Inglett (U.S. Pat. No. 5,082,673) teaches that a soluble dietary fiber and maltodextrin-containing product is prepared by hydrolyzing a cereal flour or a blend of cereal flour and starch with an α-amylase. This soluble fiber composition has been described for use in ready-to-eat cereal (Smith and Meschewski, U.S. Pat. No. 5,275,831) and low fat comminuted meat products (Jenkins and Wild, U.S. Pat. Nos. 5,294,457 and 5,585,131).
The use of mechanical shear to reduce the viscosity of cereal flours has been described by Gantwerker and Leong, U.S. Pat. Nos. 4,438,150 and 4,485,120, to prepare instant cereal porridges. There is no teaching or suggestion in these patents that involve separating any component of the cooked flours.
SUMMARY OF THE INVENTION
I have now discovered a novel class of hydrocolloidal compositions recovered from the liquid fraction obtained by subjecting oat or barley substrates to a heat-shearing treatment. These compositions are rich in soluble fiber, principally β-glucan, and are substantially free of insoluble fiber particles. The hydrocolloidal products are smooth in texture and display the properties of a dairy cream, coconut cream, or fat imitation on rehydration. They are recovered in about 70-95% yields.
In accordance with this discovery, it is an object of the invention to provide hydrocolloid gels that are smooth in texture, are rich in β-glucans, and have sensory properties that render them suitable for a wide-range of food applications.
It is also an object of the invention to provide a method for the isolation of the aforementioned hydrocolloids from oat and barley substrates.
It is also an object of the invention to extend the sensory properties of the subject hydrocolloids by coprocessing the oat or barley starting substrates with other cereal substrates.
A further object of the invention is to enhance the soluble β-glucan content of foods without adding the coarseness of crude insoluble fiber.
Other objects and advantages of the invention will become readily apparent from the ensuing description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 presents the results of flavor evaluation of muffins prepared with various levels of the oat bran hydrocolloid of the invention.
FIG. 2 presents the results of texture evaluation of muffins prepared with various levels of the oat bran hydrocolloid of the invention.
FIG. 3 is a series of viscograms comparing the pasting properties of oat bran hydrocolloid prepared in accordance with the invention with hydrolyzed oat bran and unprocessed oat bran.
DETAILED DESCRIPTION OF THE INVENTION
The starting materials for use in the invention include any source of oat or barley bran or flour. Optionally, these materials may be coprocessed as described herein with other substrates including cereal bran, cereal flour, soybean flour, cereal starch, and tuber starch. Without limitation thereto, examples of such optional substrates include rice bran, corn germ, wheat germ, cereal flours, soybean flour, and cereal or tuber starches. "Flours" are defined herein to include any wet-milled or dry-milled fraction derived from the endosperm of the indicated cereal or legume or from a starchy tuber.
In general, the process of the invention involves a heat-shearing of the oat or barley substrate (optionally in combination with other grain substrates) in aqueous slurry in a series of treatments resulting in substantial disruption of the cellular structures to yield reductions in slurry viscosity greater than 90%. These treatments include heat and shear at a level to render the slurry sufficiently flowable that it will pass through pores of a filter, such as a sieve, or for insoluble crude fiber particles to be separated from the slurry by centrifugal forces. The specific conditions of treatments will vary depending on the nature of the starting substrate, other conditions employed in the overall treatment process, and the specific method of drying. Preferably, the substrate is subjected to conditions of elevated temperatures during application of both mechanical and hydraulic shear. The mechanical and hydraulic forces may be applied simultaneously with one another or sequentially. After the crude fiber solids are removed from the slurry, the recovered hydrocolloid-containing liquid is dried by conventional means.
The specific conditions for carrying out the process of the invention are as set forth below. Oat or barley substrate is slurried with water at concentrations in the range of about 5-25% (pH 4-9), and preferably in the concentration range of about 8 to 18% range. The pH of the slurry should be kept approximately neutral, e.g. pH 4-8, and preferably pH 5-7, in order to prevent significant solubilization of components in the starting substrate that would discolor the recovered hydrocolloid product or otherwise interfere with the desired hydrocolloid properties.
The forces for mechanically shearing the flour or bran during or after cooking are provided by a variety of shearing devices, such as dispersator, colloid mill, Waring™ blender, extruder, homogenizer, or the like. In most cases, it is preferred that the device applies mechanical shear to the cooking or cooked cereal materials. After the cooking with mechanical shear, it is then preferred to treat the slurried substrate with a hydraulic heat-shear such as excess steam jet-cooking [see R. E. Klem and D. A. Brogley, Pulp & Paper. Vol. 55, pages 98-103 (May 1981)]. A steam jet cooker can be used for providing adequate heat-shear without prior mechanical heat-shear, provided the slurry is recycled two or more times. Alternatively, the slurry can be passed through a continuous jet-cooker for 5 to 30 min.
The critical element of the process of the invention is providing adequate physical disruptive forces to the cereal substrate to break down the cellular structures into a flowable hydrocolloidal liquid slurry capable of being separated into liquid and solid portions. It is desirable to conduct the treatment under conditions of elevated temperatures in the range of about 75-190° C., and preferably in the range of about 90-150° C. The requisite time period of treatment will, of course, vary with the starting substrate and the other conditions of treatment, but will typically be on the order of about 1-60 minutes. Longer periods of time at high temperatures will cause browning and other degradation of the product. Lower temperatures will decrease the flow character of the slurry, making it unsuitable for the insoluble fibrous particles to be separated. It is preferred to have a viscosity less than 20 poise (P) at temperatures greater than 90° C. with solids contents between about 5 and 25%.
The viscosity of the cooked cereal slurry prepared under the aforementioned conditions of heat-shear is reduced to less than 90% of the initial slurry prior to treatment. The non-heat sheared cooked products are thick gelatinous nonflowable materials that are not amenable to separations as described below. Moreover, fiber particles will not separate from a thick gelatinous slurry greater than about 20 to 50 P in any reasonable time period to be considered practical. If it is desired to reduce slurry viscosity after the initial heat-shearing, either the heat-shearing may be repeated or the solids content of the slurry may be adjusted to improve the flowability.
The hydrocolloidal flowable products of the invention are contained in the hot liquid fraction after separation of the crude fiber particles from the heat-sheared-cooked slurry. This separation is carried out by centrifugation or filtration including sized opening such as sieves with washing of the fiber solids as necessary. The most suitable centrifugation forces (RCF) are between about 50 and 15,000×g. The results of Examples 2 and 8 suggest, there is a relationship between relative centrifugal force (RCF) and quantity of recovered insoluble materials after shearing. The most suitable pore opening for separating the crude fiber particles on sieves are between about 0.4 mm and 0.04 mm. If desired, multiple sieves can be used to stagger the particle loading for sieve separation. A vibrating separator is an efficient method of separating the insoluble particles. Product yield is improved by combining the hydrocolloid liquid from the separator with the hot water washings of the fiber particles. The concentration of the liquid can vary between about 5 to 25% solids content.
The hydrocolloid liquid recovered from centrifugation or filtration is dried by conventional methods, including drum drying, spray drying, freeze drying, hot-air, and the like. The dried products are readily dispersible in water to give a high viscosity creamy fluid.
The products of the invention are thermo-shear-thinning gels, or hydrocolloids. The term "thermo-shear-thinning" is used herein to mean that aqueous dispersions of the gels demonstrate significantly reduced viscosities (at least about 50% reduction) at elevated temperatures (at least up to about 95° C.), as compared to the viscosities at ambient temperatures. For example, when dispersed in water at 10% solids, the hydrocolloids of the invention yield a viscosity greater than 5 poises at 25° C. and on heating to 95° C., exhibit a decrease in viscosity greater than 50%, preferably greater than 75%, and in some cases, 95% or greater. Starting substrates that have not been subjected to the heat-shear process described herein do not demonstrate this property. Typically, the hydrocolloid products are characterized by low crude fiber levels and by β-glucan levels in the range of about 1-15%, depending on the starting substrate and the specific conditions of treatment. For instance, with barley flour as the starting substrate, the β-glucan level in the final product may be as high as 15% dry weight basis, and preferably in the range of about 5-15%. With oat flour, the β-glucan level is typically in the range of 1-6%, preferably 2-6%. Oat bran will usually yield hydrocolloids having a β-glucan level in the range of 6-12%, and preferably 7-12%. The β-glucan component is completely solubilized by virtue of being in the soluble fraction. Crude fiber contents will typically be in the range of about 0.1-1%, and preferably in the range of 0.1-0.5%.
The smooth textured hydrocolloids are suitable as ingredients in preparing β-glucan-rich foods without imparting undesirable cotton-like or dry mouthfeel, or a sandy, bulky, chalky, or gritty texture characteristic of crude fiber. The hydrocolloids of the invention can be used as ingredients in a variety of food products, particularly in baked goods and desserts. They are especially suitable as substitutes for dairy or coconut creams. In baked goods, a replacement of a portion of the fat and/or replacement of a portion of the flour with the hydrocolloid product results in an enhancement of the soluble β-glucan content and the textural qualities, including moistness. Total replacement for dairy or coconut creams in ice cream and other desserts are possible using the invention materials, especially when the hydrocolloid is derived from oat bran.
The following examples are presented only to further illustrate the invention and are not intended to limit the scope of the invention which is defined by the claims.
EXAMPLE 1
Oat Bran Hydrocolloid
To 5100 ml deionized water in a 5-gal (19 l) container, 900 g of oat bran concentrate (Quaker Oats®) was added and mixed with a dispersator (PMC® Model 90, high viscosity head, about 10,000 rpm) to generate a temperature in the range of 80-95° C. Continuous shear force was applied to maintain this temperature for 30 min before adding 6 l of boiling water. The slurry was steam jet-cooked at 138-141° C. and 40-45 psi. The hot slurry from the cooker was immediately passed into a Sweco® separator with 50 and 80 steel mesh sieves to recover the hydrocolloid liquid. The wet fiber solids from the sieves were collected, reslurried with boiling water, and recollected on the sieves. The liquid wash is combined with the hydrocolloid liquid before drum drying the liquid to give oat bran hydrocolloid, 536 g. The combined wet fiber solids were oven dried to give 175 g. The analyses of the products are listed below:
__________________________________________________________________________ Yield Water Crude Soluble Protein Crude Starch by Material % % Fiber % β-Glucan % % Fat % Ash % diff. %__________________________________________________________________________Oat Bran Invention 76 6.8 0.4 9.0 23.4 5.7 3.1 51.6 Product Fiber Particles 24 3.8 13.9 7.7 23.1 4.0 8.2 39.3 Control Oat Bran 100 6.9 2.8 8.6 23.4 8.1 4.2 46.0__________________________________________________________________________
EXAMPLE 2
Oat Bran Hydrocolloid
A 4 l plastic container was placed in a 10 l plastic bucket and insulated as a steam heated bath. A Polytron® homogenizer with a PT-DA-6060/2WEC aggregate was used to mix 270 g of oat bran (Grain Millers) and 1.8 l boiling water (13% solids) with steam heat. The Polytron® was adjusted to give 5000 RPM agitation for 30 minutes before 1.5 l boiling water was added to give a 7.6% solids content. The slurry was heated to boil in a microwave oven before measuring the viscosity with a Cannon® LV2000 Viscometer at 82° C. using spindle # 2.
______________________________________ RPM 6 12 30 60______________________________________Viscosity, P 2.5 2.2 2.0 1.8______________________________________
The liquid was placed into centrifuge bottles, heated in a microwave to near 90° C., centrifuged at 4 different relative centrifugal force (RCF) values at near 45° C. for 20 min in a Beckman® centrifuge, Model J2-21. Top liquid layer was decanted and recovered as the hydrocolloid liquid and freeze-dried. The lower solids were discarded.
______________________________________ Recovered Crude Hydrocolloid Centrifuge Fiber Sample %.sup.a RCF, xg %______________________________________2A 59 44 0.74 2B 58 707 0.49 2C 52 2830 0.49 2D 49 11300 0.33______________________________________ .sup.a Yields were low because of losses in the small runs.
EXAMPLE 3
Oat Bran Hydrocolloid
To 5.1 l deionized water in a 5-gal (19 l)container, 900 g of oat bran concentrate (Quaker Oats®) was added using a dispersator (PMC® Model 90, high viscosity head, 10,000 rpm) to obtain a smooth textured slurry. To the slurry, 6 l of cool water was added before pumping into a recycling jet-cooker. The slurry was recycled for 10-15 min at a temperature of 138-141° C. and a pressure of 40-45 psi. After decreasing the steam pressure in the recycling tank, the slurry was pumped into basket centrifuge (Alpha deLaval®, B.B. EOM, Clarifier). The liquid was collected and drum dried to give oat bran hydrocolloid, 2000 g (73% yield). The solids from the centrifuge were oven dried to give 743 g. The oat bran hydrocolloid had the following composition:
__________________________________________________________________________ Yield Water Crude Soluble Protein Crude Starch by Material % % Fiber % β-Glucan % % Fat % Ash % diff. %__________________________________________________________________________ Oat Bran Hydrocolloid 73 0.4 0.24 6.6 12.1 1.0 3.0 70.0__________________________________________________________________________
EXAMPLE 4
Viscosity of Oat Bran Hydrocolloid and Cooked Oat Bran Samples
Oat bran hydrocolloid was prepared according to the procedure of Example 1, except a single 70 mesh steel sieve was used instead of the stacked steel 50 and 80 mesh sieves. In separate 300 ml beakers, 25 gm samples of the hydrocolloid and cooked oat bran were mixed with 225 ml deionized water, mixed with a spatula, heated to boiling in a 900 watt microwave oven followed by heating at about 90 watts for 5 min (power one). Using ice to cool samples to progressively lower temperatures, the viscosity was measured at three temperature levels.
______________________________________ Viscosity, Poise (P) @10% Solids Temperature (° C.)Sample 3 50 80______________________________________Cooked Oat Bran, control >1000 840 430 Oat Bran Hydrocolloid 95 15 5______________________________________
The rheological properties of the same materials were measured using a CarriMed® CSL 2 500 controlled-stress rheometer with a cone-and plate fixture. The oat bran hydrocolloid of the invention demonstrated its shear-thinning behavior from 1-200 s -1 shear rate at 25° C. and 80° C. with a decreasing viscosity of 200P to 16P and 42P to 7P, respectively.
EXAMPLE 5
Oat Bran/Soy Flour [1:1] Hydrocolloid Coprocessed
In a 5-gal (19 l) container, 8 l of boiling water and 950 g oat bran hydrocolloid (prepared as in Example 3) were mixed with a dispersator (PMC® Model 90, high viscosity head) to give a smooth slurry before adding 950 g soy flour (Bunge/Lauhoff®). The slurry was blended until a smooth texture was formed and a small amount of water was added to make it flowable. The slurry was drum dried to give oat bran/soy flour hydrocolloid, 1650 g, with a crude fiber content of 0.42%.
EXAMPLE 6
Oat Bran/Corn Germ (defatted) [1:1] Hydrocolloid Co-Processed
To 4 l deionized boiling water in a 5 gal (19 l) plastic container, 1000 g of defatted corn germ (Bunge®) was added and mixed with a dispersator for 15 min (PMC® Model 90, high viscosity head, 10,000 rpm) at a maximum speed to maintain a temperature of about 95° C. To the slurry, 5 l of boiling water was added and the solids collected on steel 50 and 80 mesh sieves (Sweco® separator). The solids were washed with 3 l of boiling water, removed from the sieves, and oven dried at 100° C. The sieve liquid was divided into two equal parts. Part A was drum dried to give corn germ (defatted) hydrocolloid with a crude fiber content of 0.82%. Part B was blended by mixing 300 g of oat bran hydrocolloid (see Example 1 for preparation) with the corn germ (defatted) hydrocolloid liquid and drum dried to give oat bran/corn germ (defatted) hydrocolloid with a crude fiber content of 0.59%.
EXAMPLE 7
Oat Flour Hydrocolloid
To 2040 ml deionized water in a 2.5-gal (10 l) container, 360 g of groat oat flour (Quaker Oats®) was mixed with a dispersator (PMC® Model 90, high viscosity head, about 10,000 rpm) at maximum shear speed to generate a temperature in the range of 80-95° C. The temperature was held by a continuous shear force rate for 30 min before adding 2 l of boiling water. The slurry was mixed before jet-cooking at 138-141° C. and 40-45 psi. The hot slurry from the cooker was immediately passed into a separator with 70 and 200 steel mesh sieves. The wet fiber solids were washed with boiling water to yield a dried fiber solids fraction (29 g) with a crude fiber content of 13.2%. The liquid wash was combined with the hydrocolloid liquid and drum dried to give oat flour hydrocolloid, 264 g, with a crude fiber content of 0.12%. Product analysis is given below:
__________________________________________________________________________ Yield Water Crude Soluble Protein Crude Starch by Material % % Fiber % β-Glucan % % Fat % Ash % diff. %__________________________________________________________________________Oat Flour Hydrocolloid 73 7.9 0.12 5.5 15.7 1.9 1.5 67.4 Fiber Fraction 27 3.6 13.2 5.0 24.5 3.9 6.6 49.8 Oat Groat Flour 100 11.1 1.2 4.8 15.3 6.6 2.0 59.0__________________________________________________________________________
EXAMPLE 8
Oat Flour Hydrocolloid
In a 4 l tared plastic container in an insulated steam heated bath, a Polytron® homogenizer with a shredder aggregate (PT-DA-6060/2WEC) was used to mix 300 g of oat flour (Quaker Oats®) with 1.2 l of boiling water (20% solids) with steam heat. The rpm was adjusted to give a maximum agitation (about 5000 rpm). The agitation at high speed was continued for 30 minutes. Water was added to the container to adjust the weight to the original level to compensate for evaporative losses. The viscosity was measured using a Cannon® LV2000 viscometer, spindle # 2 at a temperature of 93° C.
______________________________________ RPM 6 12 30 60______________________________________Viscosity, P 20 17 11 6______________________________________
The slurry was divided into 4 equal parts.
Part A: The slurry was heated at near 90° C. and centrifuged at 1000 rpm for 20 min. The liquid supernatant was decanted and freeze-dried.
Part B: The slurry was heated to near 90° C., the viscosity was measured, and then the slurry was centrifuged at 8000 rpm for 20 min. The liquid supernatant was decanted and freeze-dried, discarding the solids.
Part C: The slurry was cooled to near 30° C., the viscosity was measured, and then the slurry was centrifuged at 1000 rpm for 20 min. The liquid supernatant was decanted and freeze-dried, discarding the solids.
Part D: The slurry was cooled to near 30° C., the viscosity measured, and then the slurry was centrifuged at 8000 rpm for 20 min. The liquid supernatant was decanted and freeze-dried, discarding the solids.
The influence of the relative centrifugal force (RCF) and temperature on the crude fiber contents are shown below:
__________________________________________________________________________Shear Viscosity.sup.2, P Solids Crude Rate.sup.1 Temp RPM RCF.sup.3 Content Hydrocolloid FiberSample RPM ° C. 6 12 30 60 Xg % % %__________________________________________________________________________A 5000 91 19 16 11 6 176 20 73 0.92 B 5000 89 25 20 11 6 11,300 20 66 0.38 C 5000 28 57 28 11 6 176 20 80 1.16 D 5000 26 57 28 11 6 11,300 20 71 0.32__________________________________________________________________________ .sup.1 Brinkmann Polytron ® homogenizer, model PT 6000, shredder generator, PTDA 6060/2WEC. .sup.2 Cannon ® LV 2000, spindle #2. .sup.3 Beckman ® centrifuge, model J221, rotor JA10.
EXAMPLE 9
Oat Flour/Corn Germ (full fat) [1:1] Hydrocolloid Co-Blended
To 3 l deionized boiling water in a 20 l container, 1 kg of full fat corn germ (Quaker Oats®) was added and mixed by a dispersator (PMC® Model 90, high viscosity head, 10,000 rpm) at maximum speed for 15 min. The slurry was jet-cooked by recycling through the jet cooker 4 times before separating the solids using a Sweco® separator with 50 and 80 steel mesh sieves. The wet solids were washed with 2 l of boiling water and oven dried to yield a fiber/solids fraction (284 g) having a crude fiber content of 12.81%. The corn germ (full fat) hydrocolloid liquid was drum dried to give 561 g of solids with a crude fiber content of 1.12%. A dry blend of oat flour hydrocolloid (prepared as in Example 7) and corn germ (full fat) hydrocolloid had a crude fiber content of 0.62%.
EXAMPLE 10
Oat Flour/Wheat Germ (full fat) Hydrocolloid Co-Blended [1:1]
To 3 l deionized boiling water in a 20 l container, 1 kg of full fat wheat germ (Viobin®), was added and mixed by a dispersator for 30 min (PMC® Model 90, high viscosity head, 10,000 rpm) at maximum shear speed which maintained a temperature of about 95° C. The slurry was jet-cooked by recycling 4 times through the jet cooker before separating the solids on a Sweco® separator using 50 and 80 steel mesh sieves. The sieve solids were washed with 2 l boiling water and the hot water wash added to the original liquid. The dried fiber solids, 94 g, had a crude fiber content of 7.35%. The liquid was drum dried to give wheat germ hydrocolloid (680 g) with a crude fiber content of 1.72%. A dry blend of equal portions of an oat flour hydrocolloid (prepared as in Example 7) with the above wheat germ hydrocolloid gave a mixture with a crude fiber content of 0.35%.
EXAMPLE 11
Rice Bran Hydrocolloid
To 6.5 l deionized boiling water in a 20 l container, 2 kg of rice bran (Riviana®, Protex 20-S), was mixed with mild stirring before jet-cooking with recycling 4 times through the jet cooker. The slurry solids were separated by a Sweco® separator with 50 and 80 steel mesh sieves. The separated solids were washed with 4 l of boiling water and the water added to the original separated liquid. The liquid was drum dried to give a rice bran hydrocolloid (984 g) with a crude fiber content of 1.21%. The dried fiber solids, 594 g, had a crude fiber content of 12.36%.
EXAMPLE 12
Oat Flour/Rice Bran [1:1] Hydrocolloid Co-Processed
To 7 l deionized boiling water in a 20 l plastic container, 1 kg of rice bran (Riviana® Protex 20-S) and 1 kg of oat flour (Quaker Oats®), were mixed using a dispersator (PMC® Model 90, high viscosity head, 10,000 rpm) to give a smooth slurry in about 10 minutes. The slurry was jet-cooked by recycling two times before separating on a Sweco® separator using an 80 steel mesh sieve. The solids were washed with 2 l boiling water with the hot water wash being added to the prior separated liquid. Drum drying the liquid gave 1405 g co-processed oat flour/rice bran hydrocolloid [1:1] with a crude fiber content of 0.66%.
EXAMPLE 13
Barley Flour Hydrocolloid
To 12 l deionized boiling water in a 20 l container, 1.5 kg of barley flour (Prowashonupana® ConAgra®), was added and mixed by a dispersator for 15 min at maximum speed (PMC® Model 90, high viscosity head, 10,000 rpm) which maintained a temperature of about 95° C. The slurry was jet-cooked by recycling 2 two times through the jet cooker before collecting the solids using a Sweco® separator with a 80 steel mesh sieve. The solids were washed with 0.5 l boiling water and dried to yield fiber solids (104 g) having a crude fiber content of 7.42%. The combined wash liquid and liquid fraction from the separator was drum dried to give barley flour hydrocolloid (1206 g) with a crude fiber content of 0.42%.
EXAMPLE 14
Barley Flour/Rice Bran Hydrocolloid [1:1] Co-Processed
To 10 l deionized boiling water in a 20 l container, 1 kg of barley flour (ConAgra® Prowashonupana®) and 1 kg of rice bran (Riviana® Protex 20-S) were mixed with a dispersator (PMC® Model 90, high viscosity head, 10,000 rpm) to give a smooth slurry (10 min). The slurry was jet-cooked by recycling three times. The solids were collected on an 80 steel mesh sieve in a Sweco® separator and washed with 1 l boiling water to yield dried fiber solids (436 g) having a crude fiber content of 9.00%. The combined wash liquids and liquid fraction from the separator were drum dried to give 1330 g co-processed barley flour/rice bran hydrocolloid [1:1] with a crude fiber content of 1.68%.
EXAMPLE 15
Oat Bran Hydrocolloid as a Substitute for Coconut Cream in Desserts
Oat bran hydrocolloid prepared by the process of Example 3 and dispersed in hot water at 5% was substituted solids content was substituted at various levels for coconut cream in 8 desserts prepared in the proportions shown in Table I.
Sensory evaluation of products including control was made by 25 trained panelists using a 9-hedonic scale for color, appearance, flavor, taste, texture and acceptability. The results are shown in Table II.
TABLE I__________________________________________________________________________Standard formulas of desserts for 100 grams Coconut Other Products cream Sugar Egg Flour Salt Ingredients Water Others*__________________________________________________________________________Coconut jelly 17.12 25.25 10.70 -- 0.09 1.03 45.38 0.43 (agar powder) Taro conserve 25.61 23.05 -- -- 0.13 51.22 -- -- (mashed taro) Crispy pancake 37.40 20.33 4.07 36.58 0.40 1.22 -- -- (sesame seed) Steamed banana 20.67 23.85 -- 11.13 0.60 39.75 -- 4.0 cake (mashed banana) Pumpkin in 44.40** 11.10 -- -- 0.09 44.40 -- -- coconut syrup (pumpkin) coconut pudding 36.10 11.91 -- 3.97 0.36 10.83 28.88 7.95 (sago) Steamed glutinous 33.71 14.61 -- -- 1.12 50.56 -- -- rice with coconut (glutinous rice) cream Coconut-cantaloup 43.23** 12.97 -- -- 0.29 43.23 -- 0.29 ice cream (cantaloup)__________________________________________________________________________ *including vanilla powder, shredded coconut, lotus seed, pandan leaf juic and gelatin powder respectively. **Addition of water to coconut cream in the ratio of 1:1.
TABLE 2__________________________________________________________________________Sensory evaluation of desserts using oat bran hydrocolloid as coconutcream replacer.sup.a,bProducts Color Appearance Odor Taste Texture Acceptability__________________________________________________________________________Coconut jelly control 6.70b 6.72b 7.38a 7.28a 7.22a 7.38a 60% 7.32a 7.32a 6.68b 6.98ab 6.96ab 6.82b 80% 7.34a 7.54a 6.24c 6.74bc 6.64b 6.66b 100% 7.24a 7.36a 6.48bc 6.58c 6.62b 6.54b Taro conserve control 7.62a 7.65a 7.77a 7.77a 7.56a 7.63a 60% 7.62a 7.62a 7.52ab 7.56ab 7.40a 7.38a 80% 7.58a 7.50a 7.33b 7.50b 7.21ab 7.27a 100% 7.48a 7.50a 7.17b 7.31b 6.85b 6.88b (p > 0.01) (P > 0.01) Crispy pancake control 7.98a 7.92a 8.18a 8.04a 8.06a 8.22a 60% 7.54b 7.62b 7.42b 7.50b 7.72b 7.46b 80% 7.12c 7.52b 7.02b 7.36b 7.52b 7.16b 100% 6.76c 6.92c 6.02c 6.68c 7.00c 6.20c Steamed banana cake control 7.00b 7.26a 7.46a 7.66a 7.42a 7.52a 60% 7.56a 7.44a 7.28a 7.50ab 7.20a 7.30a 80% 7.50a 7.44a 7.14a 7.44ab 7.26a 7.24a 100% 7.52a 7.44a 7.20a 7.2.2b 6.94a 7.02a (p > 0.01) (p > 0.01) (p > 0.01) (p > 0.01) Pumpkin in coconut syrup control 7.62a 7.46a 7.48a 7.56a 7.46a 7.60a 40% 7.56a 7.30a 7.20ab 7.30ab 7.12ab 7.30ab 60% 7.34a 7.30a 6.94b 7.10b 6.78b 6.88b 80% 6.78b 6.52b 6.10c 5.94c 5.94c 5.86c Coconut pudding control 7.94a 7.74a 7.76c 7.68a 7.44a 7.60a 40% 7.06b 6.96b 6.94b 7.10b 6.66b 6.88b 60% 6.18c 6.44c 6.62b 6.84b 6.42b 642c 80% 5.80d 5.94d 5.78c 6.02c 5.46c 5.54d Steamed glutenous rice with coconut cream control 7.92a 7.70a 7.60a 7.70a 7.58a 7.72a 40% 7.52b 7.44a 7.06b 7.16b 7.24b 7.28b 60% 7.00c 6.88b 6.46c 6.78c 6.44d 6.52c 80% 7.10c 6.96b 6.60c 6.68c 6.86c 6.70c Coconut - cantaloup ice cream control 7.92a 7.66a 7.26a 7.54a 7.34a 7.40a 40% 7.56b 7.22b 7.30a 7.46a 7.26a 7.34a 60% 7.36bc 7.02bc 7.10a 7.48a 6.94a 7.24a 80% 7.22c 6.86c 7.00a 7.12a 7.00a 6.94a(p > 0.01) (p > 0.01) (p > 0.01) (p > 0.01)__________________________________________________________________________ .sup.a prepared by blending 5% oat bran hydrocolloid in hot water (by weight) and refrigerated overnight before use .sup.b In a column, means followed by same superscript are not significantly different at p > 0.05 and at p > 0.01 shown with parenthesi by ANOVA and DMRT.
Almost 100% substitution of the coconut cream by oat bran hydrocolloid was possible in all the formulations except for the pumpkin in coconut syrup formulation where high viscosity appeared to be unacceptable at high level substitution. Although a complete substitution for the coconut cream could be possible in the other desserts, many panelists favored an 80% substitution in desserts to allow some coconut flavor in the final product. It is expected that full flavor could be achieved at a higher level of oat bran hydrocolloid substitution by adding a small amount of artificial coconut flavorant to the formulation. All the desserts with oat bran hydrocolloid had very smooth textures characteristic of coconut cream products.
EXAMPLE 16
Oat Bran Hydrocolloid as a Substitute for Shortening or Dairy Cream in Desserts Fudge Brownies for Giving 1.28 g β-glucan/100 g Portion
Oat bran hydrocolloid invention product (50 g) prepared by the process of Example 1 was mixed with 236 g sugar and 120 ml water and blended in a Kitchen Aid® mixer. With continued blending, 2 egg whites (Egg Beaters®) and 70 g cocoa were added. The mixture was beaten throughly, gradually adding and beating in 0.2 tsp (1 ml) vanilla, 90 g oat flour, 0.1 tsp (0.6 g) salt and 0.2 tsp (0.7 g) baking powder. To the batter, 40 ml of water was mixed in to make a smooth batter that was poured into a 8"×8"×2" (20 cm×20 cm×5 cm) pan coated with PAM® vegetable oil spray. The batter was baked 25-30 minutes at 350° F. (177° C.) and cut into pieces. The total batch (663 g) contained a total of 8.5 g β-glucan or 0.76 g β-glucan per 2-ounce portion.
EXAMPLE 17
Oatmeal Cake
Oat bran hydrocolloid (44 g) prepared according to Example 1 was mixed with 220 g white sugar, 200 g brown sugar and 180 ml water to a smooth cream. To the creamed mixture were added 4 egg whites (Egg Beaters®), 200 g applesauce, 1 tsp (6 g) cinnamon, 0.3 tsp (2 g) nutmeg, 0.5 tsp (3 g) salt, 2 tsp (6 g) baking soda. The batter was mixed well with gradually adding and beating in 130 g oat flour and 130 g oatmeal. A small amount of water or applesauce was added to make a smooth pourable batter that was poured into a 8"×8"×2" (20 cm×20 cm ×5 cm) tared pan coated with PAM® vegetable oil. The batter was baked 25-30 min at 350° F. (177° C.) and cooled to give 1312 g of cake. A 3 oz. (85 g) piece contained 1.0 g β-glucan.
EXAMPLE 18
Chewy Oatmeal Cookies
Oat bran hydrocolloid prepared according to Example 1 (35 g) was blended well in a Kitchen Aid® mixer with 65 g white sugar, 65 g brown sugar, 6 g Myvatex® texture lite, 165 ml water. To the mixture 2 egg whites (Egg Beaters®), and 260 g applesauce were mixed in thoroughly before gradually beating in 0.5 tsp. (2.5 ml) vanilla, 0.5 tsp (3 g) cinnamon, 0.5 tsp (3 g) nutmeg, 0.5 tsp (3 g) salt, 1 tsp (3 g) baking soda, 50 g oat flour and 150 g oat flakes. To the batter, 90 g raisins were hand mixed into the mixture prior to pouring onto a cookie tray for yielding about 1-ounce (28 g) cookies. The cookies were baked at 350° F. (177° C.) for 10-20 min or longer until golden brown to give a total cookie batch weight of 784 g. A 45 g protion (2 cookies) contained 0.75 g β-glucan.
EXAMPLE 19
Muffin Preparation
For the standard muffin mix, the following ingredients were weighed at 25° C.:
115 g wheat flour
25 g sugar
5.4 g baking powder
50 g whole egg
99 g milk (2% fat)
24 g soybean oil
The egg was beaten separately and then blended with the milk and oil. In the test samples, oat flour and oat bran replaced part of the wheat flour, oat bran hydrocolloid (OBH) was added, and the oil was omitted. The proportions of the varied components are shown in FIGS. 1 & 2. The dry ingredients, including the oat bran hydrocolloid, were sieved five times to thoroughly blend the ingredients, and the liquid component was added. The batter was stirred with a rubber spatula until just slightly lumpy, and 66-67 g portions were weighed into each hole of a non-stick muffin pan. The number of muffins per batch varied from 7 to 12, depending on the formulation. The muffins were baked for 20 minutes at 220° C., and cooled to room temperature before storing in plastic bags.
Muffin Sensory Panel
Cubes (2.5 cm) cut from the interior of the muffins were evaluated by a trained, experienced analytical sensory panel 2 hours after preparation. Collected data were analyzed using software Compusense 5 (Compusense, Inc. v.2.4, Guelph, Ontario, Canada). The flavor and texture evaluations are summarized in FIGS. 1 and 2, respectively. The flavor intensity scale ranged from 0 for none to 10 for strong. The texture scales were as follows:
______________________________________Texture Scaleattributes 0 10______________________________________smoothness smooth grainy cohesiveness crumbly gummy density light compact moistness dry moist chewiness tender tough______________________________________
EXAMPLE 20
Pasting Properties
The pasting properties were compared for (1) an oat bran hydrocolloid prepared by the method of Example 1, (2) a hydrolyzed oat bran as described in U.S. Pat. No. 5,082,673, and (3) an untreated oat bran control.
Samples were dispersed in water at a solids content of 10% (dry weight basis).
Pasting properties of the samples were determined by using a Rapid Visco Analyzer® (RVA) (Model RVA-4 Newport Scientific, Australia) operated with a total weight of 30 g. The RVA procedure begins with rapid stirring at 960 rpm for 10 sec to disperse the sample followed by stirring at 160 rpm. The sample was heated from 30° C. to the maximum temperature of 95° C. in 10 min, held at 95° C. for 5.5 min and then cooled to 50° C. in 7.5 min.
The viscograms for these samples were plotted together in FIG. 3. | Hydrocolloidal compositions recovered from the liquid fraction obtained by subjecting oat or barley substrates to a heat-shearing treatment are rich in soluble fiber, principally β-glucan, and are substantially free of insoluble fiber particles. Dispersions of these compositions are smooth in texture and are useful as texturizers and nutritional substitutes for dairy products in food compositions. | 2 |
BACKGROUND OF THE INVENTION
The present invention relates generally to an apparatus for detachably mounting a component on a vehicle and, in particular, to an apparatus for facilitating the loading and unloading of a component, such as a spare vehicle tire and wheel assembly, detachably mounted on a vehicle.
Many vehicles in the past carried components, such as a spare vehicle tire and wheel assembly, in the vehicle interior as a smaller “space saver” device physically smaller and lighter than the standard wheel and tire assembly. These spare tires allowed the owner to remove a flat tire and replace it with the smaller spare in order to have the standard tire repaired while still not occupying a large amount of interior volume when the spare is stowed on-board the vehicle.
As larger vehicles are produced, however, correspondingly larger tire and wheel assemblies are required: for these larger vehicles. Because of the larger tire and wheel assemblies, many of the larger vehicles carry an exterior rear mounted spare tire to maximize interior cargo room. The larger spare tires, however, are correspondingly heavier and have become increasingly difficult for the average vehicle owner to maneuver the spare tire safely between the ground and the rear mounting location of the vehicle.
It is desirable, therefore, to provide an apparatus for assisting a person attempting to maneuver a component, such as a spare vehicle tire and wheel assembly, between a rear portion of the vehicle and the ground.
SUMMARY OF THE INVENTION
The present invention concerns an apparatus that is adapted to be attached to a rear portion of a vehicle for facilitating the storing and unloading of a component. The apparatus includes a vehicle attachment arm having a first end that is adapted to be attached to a mounting location on a vehicle and a second end. The apparatus also includes a component attachment arm having a first end that is adapted to be attached to a mounting location on a component and a second end. The apparatus also includes a connector member having a first portion and a second portion. The first portion of the connector member is adapted to be connected to the second end of said vehicle attachment arm and the second portion of the connector member is adapted to be connected to the second end of the component attachment arm. The connector member is operable to move the component between a stored position on the vehicle and an unloaded position on the ground.
Preferably, the component is a vehicle spare tire and wheel assembly and the apparatus is used as a spare tire storage device. Alternatively, the component is a bicycle and the apparatus is utilized as a bicycle rack. Preferably, the attachment point on the vehicle is a hitch receiver located on a rear portion of the vehicle. The hitch receiver has become a generally standard item on larger vehicles such as pickup trucks and sport utility vehicles and its size has become standardized as well to allow for a plurality of different hitches to be attached thereto. The apparatus, therefore, can be attached to a number of different vehicles without extensive modification.
The connector member preferably includes a planetary gear assembly having a ring gear is that disposed radially outwardly of a plurality of planetary gears and meshes with each of the planetary gears. The ring gear is coupled to the second portion of the connector member for rotating the component attachment arm. A sun gear that is disposed radially inwardly of the planetary gears also meshes with each of a plurality of planetary gears. The sun gear is preferably adapted to receive a wrench for applying a torque thereto for lowering the component from the vehicle to the ground.
The apparatus in accordance with the present invention advantageously allows the user of the vehicle to maneuver heavy and/or awkward items, such as a spare vehicle tire and wheel assembly that are attached to the vehicle, between the vehicle attachment point and the ground.
BRIEF DESCRIPTION OF THE DRAWINGS
The above, as well as other advantages of the present invention, will become readily apparent to those skilled in the art from the following detailed description of a preferred embodiment when considered in the light of the accompanying drawings in which:
FIG. 1 is a perspective view of an apparatus for facilitating the storing and unloading of a component in accordance with the present invention;
FIG. 2 is a front perspective schematic view of a planetary gear assembly of the apparatus of FIG. 1 ;
FIG. 3 is a side perspective schematic view of the planetary gear assembly of FIG. 2 ; and
FIG. 4 is a perspective view of an alternative embodiment of an apparatus for facilitating the storing and unloading of a component in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1 , an apparatus in accordance with the present invention is indicated generally at 10 . The apparatus 10 is adapted to be attached to a rear portion of a vehicle 60 for facilitating the storing and unloading of a component, such as a vehicle spare tire and wheel assembly (not shown). The apparatus 10 includes a vehicle attachment arm 12 having an inner member 13 with a first end 14 and an outer member 15 with a second end 16 . The first end 14 of the vehicle attachment arm 12 is adapted to be attached to a mounting location 62 on the vehicle 60 . The vehicle attachment arm 12 is preferably constructed of steel or aluminum square tubing with the inner member 13 telescoping into an interior of the outer member 15 . Alternatively, the vehicle attachment arm 12 is constructed of an alternate material having similar material strength properties or is formed in an alternate profile that is adapted to be attached to the mounting location 62 on the vehicle 60 . The second end 16 of the vehicle attachment arm 12 is attached to a first portion of a connector member 18 .
A component attachment arm 20 includes a generally L-shaped inner member 21 with a first end 22 and an outer member 23 with a second end 24 . The first end 22 is adapted to be attached to a mounting location on the component, such as the hub of a spare tire and wheel assembly. The second end 24 is attached to a second portion of the connector member 18 . The component attachment arm 20 is preferably constructed of steel or aluminum square tubing with the inner member 21 telescoping into an interior of the outer member 23 . Alternatively, the component attachment arm 20 is constructed of an alternate material having similar material strength properties or is formed in an alternate profile that is adapted to be attached to the mounting location on the component.
The vehicle attachment arm 12 is operable to be adjusted in an axial generally horizontal direction indicated by an arrow 26 along a longitudinal axis 28 thereof. The component attachment arm 20 , shown in a component storage position, is operable to be adjusted in an axial generally vertical direction indicated by an arrow 30 along a longitudinal axis 32 thereof. Preferably, the vehicle attachment arm 12 and the component attachment arm 20 can be locked in a plurality of axial positions by spring-loaded locking pins 33 on the inner members 13 and 21 that cooperate with a plurality of axially spaced apertures 34 formed in the outer member 15 of the vehicle attachment arm 12 and the outer member 23 of the component attachment arm 20 . Alternatively, the vehicle attachment arm 12 and the component attachment arm 20 may be locked in a plurality of axial positions by any suitable locking means. Preferably, the component attachment arm 20 includes spring-loading locking pins 33 located on opposite sides of the inner member 21 so that the first end 22 of the component attachment arm 20 may face in opposite directions, discussed in more detail below, when the component attachment arm 20 is attached to the connector member 18 . As discussed below, the connector member 18 permits rotation of the component attachment arm 20 about the longitudinal axis 28 in both directions as indicated by a double headed arrow 36 . By virtue of their axial adjustability, the vehicle attachment arm 12 and the component attachment arm 20 are operable to allow the apparatus 10 to be used with any number of vehicles and components.
Referring now to FIG. 2 , the connector member 18 is shown in detail. The connector member 18 includes a planetary gear assembly, indicated generally at 38 . The planetary gear assembly 38 includes a ring gear 40 having a plurality of teeth (not shown) on an interior surface thereof that mesh with corresponding teeth (not shown) on respective exterior peripheral surfaces of a plurality of planetary gears 42 disposed radially interior therein. The ring gear 40 is attached to the second end 24 of the component attachment arm 20 shown in FIG. 1 . The ring gear 40 , therefore, is a part of the second portion of the connector member 18 . The teeth of the planetary gears 42 also mesh with a plurality of teeth (not shown) on an exterior peripheral surface of a sun gear 44 disposed radially interior therein. The sun gear 44 is rotatably mounted in the connector member 18 and includes an aperture 45 formed in an outwardly facing surface thereof for receiving a wrench (not shown) or the like for turning the sun gear when the apparatus 10 is operated, discussed in more detail below. A cover plate 39 , best seen in FIG. 1 , is attached to an outwardly facing surface of the ring gear 40 , encloses the interior of the planetary gear assembly 38 and protects the meshing gear teeth from foreign object damage.
Referring now to FIG. 3 , each of the planetary gears 42 is rotatably mounted on a separate shaft 46 . The shafts 46 extend rearwardly from the planetary gears 42 generally parallel to one another. Another shaft 48 extends rearwardly from a rear surface of the sun gear 44 generally parallel to the shafts 46 . A generally box-shaped receiver 50 mounts each of the planetary gear shafts 46 , which shafts can be fixed in the receiver with the gears 42 rotating on the shafts, or the shafts can be rotatably mounted in the receiver with the gears fixed on the shafts. The receiver 50 is sized such that it is retained in the interior of the outer member 15 at the second end 16 of the vehicle attachment arm 12 . The receiver 50 , therefore, is a part of the first portion of the attachment member 18 .
The sun gear shaft 48 extends through a central portion of the receiver 50 and has a free end extending from a rear surface of the receiver through a central aperture in a clutch 52 . The clutch 52 is attached to the sun gear shaft 48 with an interference fit and frictionally engages the rear surface of the receiver 50 . Thus, a predetermined amount of torque must be applied to the sun gear 44 to overcome the predetermined frictional holding force applied by the clutch 52 and rotate the sun gear. The holding force can be selected to correspond with a desired maximum component load attached to the first end 22 of the inner member 21 with the component attachment arm 20 fully extended. A locking pin 54 (shown in FIG. 1 ) is releasably insertable into an aperture 56 ( FIG. 1 ) formed in the second end 16 of the outer member 15 of the vehicle attachment arm 12 and an aperture 58 ( FIG. 3 ) formed in the free end of the sun gear shaft 48 for preventing unintentional rotation of the component attachment arm 20 . Alternatively, the apparatus 10 includes another suitable means for locking the arm 20 relative to the vehicle attachment arm 12 .
In operation, the first end 14 of the vehicle attachment arm 12 is attached to the mounting location 62 on the rear portion of the vehicle 60 . The vehicle mounting location 62 is preferably a trailer hitch receiver of the vehicle 60 . The respective lengths of the vehicle attachment arm 12 and the component attachment arm 20 are adjusted so that the first end 22 of the component attachment arm 20 is adjacent a mounting location on the component, such as the center hole in the wheel of the spare wheel and tire assembly that is attached to a component mounting location (not shown) on the vehicle. The spare tire is attached to the first end 22 of the component attachment arm 20 and the vehicle attachment arm 12 is adjusted outwardly so that the spare tire will have a clear path to the ground in the loading/unloading direction 36 . A wrench (not shown) is inserted into the aperture 45 in the sun gear 44 and a torque is provided to the wrench to begin rotating the sun gear 44 . As the sun gear 44 rotates, the planetary gears 42 rotate, and the ring gear 40 rotates. Preferably, the gear ratio between the interconnected sun gear 44 , planetary gears 42 , and the ring gear 40 is at or near 20 to 1, to allow for an optimum mechanical advantage when applying a torque to the wrench. As the torque is applied to the sun gear 44 , the holding force applied by the clutch 52 is overcome, the component attachment arm 20 moves in the loading/unloading direction 36 and lowers the spare tire towards the ground. After the spare tire has touched the ground, the spare tire is removed from the first end 22 of the component attachment arm 20 , and the first end 14 of the vehicle attachment arm 12 is removed from the trailer hitch receiver. The apparatus 10 may also be used to assist in storing the component, such as a flat vehicle tire and wheel assembly, at the component mounting location on the vehicle 60 by attaching the first end 14 of the vehicle attachment arm 12 to the vehicle mounting location 62 and attaching the first end 22 of the component attachment arm to the component and reversing the steps outlined above. The wrench is inserted into the aperture 45 and a torque is provided to rotate the component attachment arm 20 in the loading/unloading direction 36 such that the first end 22 of the component attachment arm 20 is moved adjacent the component mounting location on the vehicle 60 .
Referring now to FIG. 4 , an alternative embodiment of an apparatus for facilitating the storing and unloading of a component is indicated generally at 10 ′. The apparatus 10 ′ includes the vehicle attachment arm 12 and the component attachment arm 20 extending outwardly from the connector portion 18 . The first end 22 of the component attachment arm 20 faces an opposite direction as in FIG. 1 . The component attachment arm 20 includes a component attachment bracket 64 attached to the first end 22 thereof for attaching a component (not shown) thereto. The component is preferably a bicycle or the like and the component attachment bracket 64 includes a cross support member 66 and a pair of attachment rods 68 extending therefrom for facilitating the attachment of the bicycles wheels or frame (not shown) thereto. Alternatively, the component attachment bracket 64 is shaped or configured to attach to any number of components including, but not limited to, skis, surfboards, food cooler chests, or any component where it is advantageous to provide a mechanical advantage for moving the component from the vehicle to the ground.
In operation, the apparatus 10 ′ is operated in the same manner as the apparatus 10 so that the bicycle or other component is lowered to the ground and later raised to a mounting location on the vehicle.
In accordance with the provisions of the patent statutes, the present invention has been described in what is considered to represent its preferred embodiment. However, it should be noted that the invention can be practiced otherwise than as specifically illustrated and described without departing from its spirit or scope. | An apparatus for storing and unloading a component such as a spare tire and wheel assembly mounted at a rear storage location on a vehicle includes a vehicle attachment arm having a first end releasably attached at a mounting location on the vehicle and a component attachment having a first end positioned adjacent the component storage location. The arms each have a second end attached to a connector member that permits the component attachment arm to be rotated between the component storage location and an unloaded position on the ground. The vehicle attachment arm is adjustable in length to move toward and away from the storage location. The component attachment arm is adjustable in length to move toward and away from the component storage location. | 1 |
CROSS REFERENCES TO RELATED APPLICATIONS
[0001] The Present Application claims priority to U.S. patent application No. 61/376,187, filed on Aug. 23, 2010, which is hereby incorporated by reference in its entirety.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] The present invention relates to manufacturing components for golf club heads. More specifically, the present invention relates to a method for manufacturing a face component for a golf club head.
[0005] 2. Description of the Related Art
[0006] The prior art discloses multiple material golf club heads.
[0007] There are various problems with the current process for manufacturing multiple material golf club heads.
[0008] One problem is with the standard compression molding process, the hard metal tooling on both sides of the part makes undercuts impossible without significant increases in tool complexity.
[0009] Another problem is the molding compounds are not designed to be used in parts with very thin walls. When wall thicknesses are below approximately 0.080 inch, most standard molding compounds are difficult to compression mold.
[0010] Another problem is that standard molding compounds are not as strong, stiff, or tough as laminated composites made with similar matrix and fiber types.
[0011] Another problem is the raw materials for the current laminates are quite expensive. The cost is compounded by the very high scrap rate.
[0012] Another problem is that using prepreg requires hand placement of each layer of material into a mold which is a time-consuming and labor-intensive process.
[0013] Another problem is that with current latex bladders we are able to avoid undercut constraints, but we lose definition on the inside of our parts. The metal tooling dictates OML of the parts quite well, but the part thickness and IML are determined by the number of plies placed in each area and the amount of pressure exerted on the area by the bladder during the cure. As a result, it is difficult to predict the mass properties of the Fusion body before a part is made. One-piece bladder molded driver bodies do not work well with a body-over-face joint. The lack of precision on the inside of the head makes it difficult to control the geometry of the body where it would meet up with the face. Bladder molded multiple material driver design had been restricted to body-under-face joints so that the body bond surface is a well controlled OML surface. Typical epoxy-based prepregs are designed to cure in 20-30 minutes. In the current multiple material golf club head fabrication process, the latex bladders used to apply pressure during the cure cycle can only be used 2 or 3 times before they need to be discarded. Bladders are a significant cost in the current multiple material driver manufacturing process.
[0014] Manufacturing a titanium face component for a golf club head is expensive. Use of current carbon fiber techniques to manufacture face components is also expensive.
BRIEF SUMMARY OF THE INVENTION
[0015] A carbon face component is produced b simplifying the construction and forming process. Unidirectional carbon epoxy material can be sourced with diagonal slits, across the pre-impregnated carbon fibers. The slitting allows the material to move during the compression molding process. The ability to move and fill the tool simplifies the manufacturing process. In this invention, layers of the slit unidirectional material are placed in the mold in alternating orientations. The layers of the material do not need to be conformal to the tool nor cover the surface of the tool as the material will move and fill the cavity as the compression mold closes. The material cures quickly by formulation and superior heat transfer in the compression mold. The near net face component emerging from the tool can now be joined to a body. The body can be on many constructions, but preferably is constructed of titanium sheets or carbon composite. The selection of the body construction determines the cost, playing performance and sound of the finished club head.
[0016] Having briefly described the present invention, the above and further objects, features and advantages thereof will be recognized by those skilled in the pertinent art from the following detailed description of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0017] A method for forming a face component is disclosed herein.
[0018] The final golf club head is preferably as disclosed in U.S. Pat. No. 6,582,323 for a Multiple Material Golf Club Head, which is hereby incorporated by reference in its entirety.
[0019] Alternatively, the final golf club head is preferably as disclosed in U.S. Pat. No. 7,320,646 for a Multiple Material Golf Club Head, which is hereby incorporated by reference in its entirety.
[0020] Alternatively, the final golf club head is preferably as disclosed in U.S. Pat. No. 7,431,666 for a Golf Club Head With A High Moment Of Inertia, which is hereby incorporated by reference in its entirety.
[0021] Alternatively, the final golf club head is preferably as disclosed in U.S. Pat. No. 7,390,269 for a Golf Club Head, which is hereby incorporated by reference in its entirety.
[0022] Variable face thickness patterns of the striking plate insert are disclosed in U.S. Pat. No. 6,471,603, for a Contoured Golf Club Face, U.S. Pat. No. 6,368,234 for a Golf Club Striking Plate Having Elliptical Regions Of Thickness, U.S. Pat. No. 6,398,666 for a Golf Club Striking Plate With Variable Thickness, U.S. Pat. No. 7,448,960, for a Golf Club Head With Face Thickness which are all owned by Callaway Golf Company and which pertinent parts related to the face pattern are hereby incorporated by reference.
[0023] The mass of the club head of the present invention ranges from 165 grams to 250 grams, preferably ranges from 175 grams to 230 grams, and most preferably from 190 grams to 205 grams. Preferably, the subassembly preferably has a mass ranging from 140 grams to 200 grams, more preferably ranging from 150 grams to 180 grams, yet more preferably from 155 grams to 166 grams, and most preferably 161 grams. The crown component has a mass preferably ranging from 4 grams to 20 grams, more preferably from 5 grams to 15 grams, and most preferably 7 grams.
[0024] The golf club head preferably has that ranges from 290 cubic centimeters to 600 cubic centimeters, and more preferably ranges from 330 cubic centimeters to 510 cubic centimeters, even more preferably 350 cubic centimeters to 495 cubic centimeters, and most preferably 415 cubic centimeters or 470 cubic centimeters.
[0025] The center of gravity and the moment of inertia of a golf club head are preferably measured using a test frame (X T , Y T , Z T ), and then transformed to a head frame (X H , Y H , Z H ). The center of gravity of a golf club head may be obtained using a center of gravity table having two weight scales thereon, as disclosed in U.S. Pat. No. 6,607,452, entitled High Moment Of Inertia Composite Golf Club, and hereby incorporated by reference in its entirety.
[0026] The moment of inertia, Izz, about the Z axis for the golf club head preferably ranges from 2800 g-cm 2 to 5000 g-cm 2 , preferably from 3000g-cm 2 to 4500 g-cm 2 , and most preferably from 3750 g-cm 2 to 4250 g-cm 2 . The moment of inertia, Iyy, about the Y axis for the golf club head preferably ranges from 1500 g-cm 2 to 4000 g-cm 2 , preferably from 2000 g-cm 2 to 3500 g-cm 2 , and most preferably from 2400 g-cm2 to 2900 g-cm 2 . The moment of inertia, Ixx, about the X axis for the golf club head 40 preferably ranges from 1500 g-cm 2 to 4000 g-cm 2 , preferably from 2000 g-cm 2 to 3500 g-cm 2 , and most preferably from 2500 g-cm 2 to 3000 g-cm 2 .
[0027] The golf club head preferably has a coefficient of restitution a (“COR”) ranging from 0.81 to 0.875, and more preferably from 0.82 to 0.84. The golf club head preferably has a characteristic time (“CT”) as measured under USGA conditions of 256 microseconds.
[0028] From the foregoing it is believed that those skilled in the pertinent art will recognize the meritorious advancement of this invention and will readily understand that while the present invention has been described in association with a preferred embodiment thereof, and other embodiments illustrated in the accompanying drawings, numerous changes, modifications and substitutions of equivalents may be made therein without departing from the spirit and scope of this invention which is intended to be unlimited by the foregoing except as may appear in the following appended claims. Therefore, the embodiments of the invention in which an exclusive property or privilege is claimed are defined in the following appended claims. | A method for manufacturing a face component of a golf club head from slit plies of unidirectional pre-preg material is disclosed herein. The slitting is preferably diagonally along the unidirectional pre-preg material. The slit plies are placed in a mold in an alternating manner and the plies are compressed to form the face component. The slitting allows the pre-preg material to move within the mold during the compressing step. | 0 |
FIELD OF THE INVENTION
The present invention relates to a mirror assembly and, more particularly, to an improved mirror assembly for an automotive vehicle.
BACKGROUND OF THE INVENTION
In vehicle design, meeting aerodynamics and wind noise requirements is increasingly important, as well it is further desirable that a vehicle be capable of meeting occupant comfort requirements. In meeting both requirements, the design and placement of external components on an outer surface of a vehicle play a significant role.
Generally speaking, external components disposed on an outer surface of a vehicle, e.g., a side view mirror assembly, tend to adversely affect aerodynamics and increase passenger compartment noise. Accordingly efforts are made to design external components in conformance with the generally streamlined external surface of a vehicle.
The side view mirror assembly presents an aerodynamic design challenge because the mirror assembly not only has to be mounted on an outer surface of the vehicle, but must extend away from the surface to give the occupant a desired view behind the vehicle. In addition, side view mirrors assemblies are typically disposed at an angle to the vehicle body, as well as provide an adjustment mechanism to accommodate the varying viewing angle of different occupants.
The angular relationship of the mirror assembly to the body in combination with the distance the mirror assembly is typically disposed from the vehicle surface tends to create wind noise. Specifically, forward movement of the vehicle creates air flow over the external surface of the vehicle and over the side view mirror assembly. Generally speaking, this air flow creates wind noise due to the fact that the side view mirror assembly interrupts the flow of air over the vehicle surface and causes a turbulent flow of air behind the mirror assembly. Conventional mirror assemblies mitigate the effect of the air flow around the side view mirror assembly by including an external shell to redirect the air flow behind the mirror generally toward the vehicle body but away from the occupant to reduce the noisy condition.
The external shell of a conventional mirror assembly generally includes a hemispherical shape surrounding the mirror itself and serves to cut through the air flow and reduce wind noise. The hemispherical shape typically extends over the length of the leading edge of the mirror up to the opening of a mirror recess. Because the mirror is disposed at an angular relationship to the occupant the air flow is redirected at an angle generally towards the surface of the vehicle and often reacts against a surface of the vehicle generally rearward of the side view mirror. In this manner, the noise caused by the air flowing over the external shell of the side view mirror bypasses the mirror recess and often reduces the wind noise experienced by the occupant.
Current side view mirror assemblies further include a mirror flag for attachment to a vehicle, whereby the mirror flag joins the side view mirror assembly generally at the base of the mirror and connects to the vehicle body. Conventional mirror flags are often attached to the vehicle at the junction of the door glass frame and the door body and include a sweeping surface disposed between the side view mirror assembly and the vehicle and a triangular shaped portion attached to the vehicle. Mirror flags further cooperate with the generally hemispherical surface of the side view mirror assembly to facilitate movement of the air flow over the side view mirror and away from the mirror recess to a location on the vehicle body generally behind the occupant. In this manner, mirror flags typically assist in redirecting the air flow caused by the moving vehicle generally towards the door and away from the mirror recess.
Conventional side view mirror assemblies and mirror flags, while preventing air flow from entering the mirror recess and reducing wind noise, do not completely satisfy the problem of wind noise caused by the flow of air over the side view mirror assembly. Specifically, conventional side view mirror assemblies and mirror flags generally suffer from the fact that the air flow is forced to flow towards the vehicle where it often contacts other external components such as door handles and weather stripping. Air flow contact with these external components creates additional wind noise. This condition is usually worsened, for example, when the front door glass is down and the door B-pillar is exposed. In this situation, the B-pillar acts as a pocket to catch the air flow from the side view mirror, thus creating pulsation of the passenger compartment air cavity. The noise caused by the pulsation is referred to as buffeting.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a mirror assembly for use on an external surface of a vehicle having a mirrored surface disposed in an external shell and a mirror flag operably connected to the external shell for attachment to an external surface of a vehicle. The mirror flag includes at least one spoiler disposed between the external shell and the mirror flag for directing air flow caused by forward movement of the vehicle. In accordance with one aspect of the present invention, a plurality of spoilers can be employed. Specifically, the at least one spoiler serves to direct the air flow both away from the mirror assembly as well as the vehicle surface, resulting in improved window-down buffeting and reduced turbulence.
Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
FIG. 1 is a partial perspective view of an automotive vehicle including a mirror assembly in accordance with the principals of the present invention;
FIG. 2 is a rear elevational view of the mirror assembly of FIG. 1;
FIG. 3 is a perspective view of a spoiler in accordance with the principals of the present invention;
FIG. 4 is a top elevational view of the mirror assembly of FIG. 1; and
FIG. 5 is a perspective view of a mirror assembly in accordance with the principals of the present invention depicting a spoiler disposed on a bottom surface of the mirror assembly.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following description of the preferred embodiments is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
With reference to the figures, a mirror assembly 10 is provided and includes a mirror 12 , an external shell 14 , and a mirror flag 16 . The mirror 12 is generally disposed within the external shell 14 while the mirror flag 16 serves to support the external shell 14 and the mirror 12 . In one embodiment, the mirror 12 is positionable relative to the external shell 14 , while in another embodiment, the external shell 14 is positionable relative to the mirror flag 16 , as will be discussed further herein below.
The external shell 14 serves as a housing for the mirror 12 and includes a generally hemispherical outer surface 18 , a recess 20 , and a bottom surface 21 . The hemispherical surface 18 extends generally over the entire outer surface of the shell 14 and terminates at the edge of the recess 20 as best shown in FIG. 4. A plane 22 is created at the junction of the recess 20 and the hemispherical outer surface 18 along axis Y as shown in FIG. 4 . The plane 22 establishes the angular relationship of the recess 20 to an external surface, whereby the angular relationship is shown as ψ by way of reference in FIG. 4 . In one embodiment, the external surface is a body panel of a motor vehicle 24 , whereby the external shell 14 serves to fixedly hold the mirror 12 in a fixed relationship to the body 24 . In this manner, the plane 22 defines the angular relationship of the external shell 14 to the external surface of the vehicle 24 . Alternatively, the external surface is a door assembly 52 , whereby the external shell 14 serves to fixedly hold the mirror 12 in a fixed relationship to the door assembly 52 . In this manner, the plane 22 defines the angular relationship of the external shell 14 to an outer surface of the door assembly 52 .
The mirror 12 is disposed in the recess 20 of the external shell 14 and includes a reflective surface 28 . The reflective surface 28 can be shaped such that it completely fills the recess 20 of the shell 14 as best shown in FIG. 2 and is disposed generally along the plane 22 . As such, the relationship of the mirror 12 to the external surface of the vehicle 24 is generally governed by the relationship of the plane 22 to the external surface. In one embodiment the mirror 12 is permitted to rotate relative to the external shell 14 and, therefore, may be positioned at a different angular relationship relative to an external surface than the angular relationship of the plane 22 to the same external surface. In this manner, a slight clearance 30 is provided between an interior surface 32 of the shell 14 and an edge 34 of the mirror 12 to accommodate movement of the mirror 12 within the recess 20 , as best shown in FIG. 2 .
The external shell 14 further includes a first spoiler 36 disposed adjacent the bottom surface 21 of the shell 14 , as best shown in FIG. 5 . The first spoiler 36 is an arcuate fin generally extending along the bottom surface 21 of the shell 14 and serves to redirect the air flow around the mirror assembly 10 and away from the vehicle. With particular reference to FIG. 3, the first spoiler 36 includes a generally straight section 45 extending from the mirror flag 16 and includes a junction 47 formed in cooperation with a surface of the mirror flag 16 . In this manner, the junction 47 causes the air flow to be forced against the mirror flag 16 and subsequently along the first spoiler 36 .
With continued reference to FIG. 3, the straight section 45 extends from a surface of the mirror flag 16 and terminates at a curved portion 49 of the first spoiler 36 . The curved portion 49 includes a convex surface 38 extending away from plane 22 and a concave surface 40 extending generally towards plane 22 . In this manner, the first spoiler 36 extends outwardly towards plane 22 and terminates at a tip 42 . In addition, the first spoiler 36 includes a reaction surface 44 disposed along the length of the first spoiler 36 , generally extending from the straight portion 45 along the concave surface 40 and terminating at the tip 42 .
As previously mentioned, the air flow contacting the junction 47 reacts against the mirror flag 16 and is caused to flow generally along the first spoiler 36 . Specifically, as the air flow moves from the junction 47 , it first contacts the straight portion 45 and generally contacts the reaction surface 44 and the bottom surface 21 of the external shell 14 . Once the air flow reaches the curved portion 49 of the first air foil 36 it continues to react against the bottom surface 21 and the reaction surface 44 but now contacts the concave surface 40 as well and begins to move towards the tip 42 . Once the air flow has traveled sufficiently along the concave surface 40 and reaches the tip 42 it effectively flows over the tip 42 and away from the vehicle 24 . As such, the curvature of the concave surface 40 and location of the tip 42 generally define when and in what direction the air flow will depart the first spoiler 36 .
In one embodiment, the mirror assembly 10 may be mounted to an external surface of a vehicle body 24 as previously discussed. As such, the mirror assembly 10 is subjected to an air flow caused by forward movement of the vehicle (not shown). The external shell 14 , and subsequently plane 22 , are positioned at an angle relative to the external surface of the vehicle 24 to provide the occupants with a view of an area behind the vehicle 24 . In this manner, the air flow will first contact the hemispherical outer surface 18 of the shell 14 and be caused to flow over the mirror assembly 10 .
To mitigate the tendency of the air flow to be trapped by the recess 20 , and thus create wind noise, the first spoiler 36 traps the air flow between the bottom surface 21 and the reaction surface 44 . Because the first spoiler 36 is disposed such that the concave portion 40 faces plane 22 and opens at tip the 42 , the air flow is trapped between the bottom surface 21 of the shell 14 and the reaction surface 44 of the first spoiler 36 . Thus, the air flow is forced along a path following the concave surface 40 towards the tip 42 until it finally is moved away from the mirror assembly 10 . The first spoiler 36 redirects the air flow caused by the forward movement of the vehicle down and away from not only the mirror assembly 10 but also from the vehicle 24 , thereby reducing the wind noise associated with the air flow contacting mirror assembly 10 and the vehicle 24 .
The mirror flag 16 serves to support the external shell 14 and, thus, the mirror 12 , and includes a mounting bracket having a generally triangular shape and an arm 48 interconnecting the mirror flag 16 and the shell 14 . In one embodiment the arm 48 and the external shell 14 are integrally formed such that the shell 14 is not permitted to move relative to the arm, while in another embodiment the arm 48 rotatably supports the shell 14 such that the shell 14 is permitted to rotate relative to the mirror flag 16 .
The mounting bracket of the mirror flag 16 includes a flat portion 50 for engagement with an external surface. In one embodiment, the mounting bracket fixedly mounts to the vehicle 24 , while in another embodiment the mounting bracket fixedly mounts to a door assembly 52 of the vehicle 24 . It should be noted that while a mounting bracket having a generally triangular shape and including a flat portion 50 is disclosed, any shape accommodating an outer surface of a vehicle is anticipated and should be considered within the scope of the present invention.
The arm 48 outwardly extends from the attachment bracket and includes a rounded leading edge 54 and a second spoiler 56 integrally formed thereon. The leading edge 54 serves to cut through an air flow and redirect the air flow towards both the bottom of the shell 14 and the top of the arm 48 such that the air flow contacts the first and second spoilers 36 , 56 .
The second spoiler 56 extends generally between the mounting bracket and the arm 48 and serves to redirect an air flow away from the shell 14 and the recess 20 , thereby reducing wind noise. In one embodiment the mirror assembly 10 is fixedly mounted to the external surface of the vehicle 24 and as such the second spoiler 56 serves to redirect the air flow away from the vehicle 24 . The second spoiler 56 has a generally flat leading edge 58 disposed at an angular relationship to the mounting bracket and includes a reaction surface 60 disposed along its length as best shown in FIGS. 1 and 4. It should be noted that FIGS. 1 and 4 include a shaded surface to better show the leading edge 58 and reaction surface 60 and as such should not be construed as additional structure.
In operation, the second spoiler 56 receives an air flow, whereby the air contacts the reaction surface 60 of the leading edge 58 and is caused to move generally away from the recess 20 and over the leading edge 58 . Specifically, the reaction surface 60 causes the air flow to move at an angle to the vehicle body 24 up until the air flow reaches the leading edge 58 . At this point, the air flow departs the second spoiler 56 and is caused to move away from both the mirror assembly 10 and the vehicle 24 and thus reduces wind noise experienced by the occupant.
While first and second spoilers 36 , 56 have been disclosed as integrally formed with the shell 14 and the mirror flag 16 , it should be understood that the spoilers 36 , 56 could be formed separately and fixedly attached to the mirror assembly 10 such as in an aftermarket condition or as a separate vehicle accessory.
The description of the invention is merely exemplary in nature and, thus, variations that do not depart from the gist of the invention are intended to be within the scope of the invention. Such variations are not to be regarded as a departure from the spirit and scope of the invention. | A mirror assembly is provided for use on an external surface of a vehicle having a mirrored surface disposed in an external shell and a mirror flag operably connected to the external shell for attachment to an external surface of a vehicle. The mirror flag includes at least one spoiler disposed between the external shell and the mirror flag for directing air flow caused by forward movement of the vehicle. Specifically, the at least one spoiler serves to direct the air flow away from the mirror assembly as well as away from the vehicle surface to improve the aerodynamics of the vehicle and reduce wind noise produced by the air flow contacting the mirror. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates to systems for the isolation and removal of impurities in hydrocarbon fluid streams, and in particular to a system for removal of Hydrogen Sulfide (H2S) and/or Carbon Dioxide (CO2) from natural gas via absorption and disassociation utilizing at least one sea water contact apparatus.
[0002] In the preferred embodiment of the present invention, a series of counter current multistage scrubbers are provided, each configured to remove via absorption/disassociation a portion of the impurities, each stage having less pressure than the predecessor, each stage redirecting the purified gas to the preceding stage, until the contaminant level in the hydrocarbon fluid stream has been reduced to an acceptable level.
[0003] The hydrogen sulfide/carbon dioxide contaminants are thereby sequestered in the utilized sea water, which sea water may be further processed and/or re-introduced at shallow depths or into the deep of a body of water, where the contaminants will remain isolated for hundreds of years. Accordingly, the present invention provides an efficient and cost effective method for the purification of natural gas on an offshore platform and a convenient, environmentally safe disposition of the contaminants removed.
GENERAL BACKGROUND DISCUSSION OF THE INVENTION
[0004] The two most common impurities in natural gas are hydrogen sulfide and carbon dioxide, called acid gases. In order to make the contaminated gas suitable for use and sales requires removal of the hydrogen sulfide (H2S) and often partial removal of the carbon dioxide (CO2) component
[0005] Some of the known processes for purifying natural gas utilized offshore are amine absorption and regeneration, solid absorbents, liquid scavengers, and catalytic oxidation. The amine and solvent-based systems have large heats of regeneration, large energy requirements, large cooling loads, and fresh water make-up. Solid absorbents are only applicable to H2S removal and create material handling problems, both with the loading, unloading, and disposal of the spent solid activities that are particularly difficult, hazardous and time consuming on an offshore platform.
[0006] The amine sweetening system produces a waste gas stream consisting principally of hydrogen sulfide gas. The gas can be flared but produces sulfurous acid, a corrosive and toxic air pollutant, regulated under the Clean Air Act. Accordingly, it is an object of this invention to provide a method, which enables a more economical and convenient means of treating the natural gas.
[0007] An example of where removal of H2S and CO2 removal from a gas stream is necessary can be found during the production of natural gas on an offshore production platform. The H2S must be removed for a number of reasons. First of all it is lethal, and at low concentrations it has a very disagreeable odor. It promotes the formation of hydrates in the downstream systems and causes sulfide stress cracking of carbon steel. On the other hand, CO2 in natural gas is objectionable because it is an inert and reduces the heating value. H2S and CO2 are commonly referred to as acid gases. In the U.S., the H2S content of natural gas is nearly always limited to 0.25 gr/100 scf (4 ppmv) and specifications can be as low as 1 ppmv in some countries. The CO2 content is often limited to 2.0 vol % in the U.S.
[0008] A variety of processes have been developed for removing acid gases from natural gas. Only a select few have been applied to offshore gas production. In general the most common processes includes selective absorption by solid absorbents, reaction and physical solution by selective solvents, reaction with specific chemical agents and so forth. The selection of the process depends on the volumes of gas to be treated and the acid gas concentrations.
[0009] Although a few processes have proved successful for acid gas removal in offshore applications, they are usually energy intensive, operationally complex, requiring large, expensive equipment, continual operational attention and need an additional process step to convert the H2S to sulfur. This step is usually referred to as a sulfur removal unit (SRU).
[0010] One typical solvent adsorption process is amine sweetening, utilizing ethanolamine solvent such as MEA, MDEA and DEA. The solvent is circulated to the gas contactor, where it removes the H2S, then to the condensate separator, the rich/lean amine exchanger, and is regenerated in the stripper/reboiler section. Heat is required, usually by way of a gas-fired boiler to regenerate the amine, creating a potential fire hazard on an offshore platform that has limited space to separate process equipment. The reboiler feeds the stripper column that also requires an air or water-cooled condenser to condense the amine to minimize losses. The regenerated amine, still hot from the stripping process, must be cooled before being pumped and returned to the contactor. Typical energy requirements are 20-40 MMBtu/hour, plus 500-1000 horsepower to drive the pumps and coolers.
[0011] In addition, there is a requirement of fresh make-up water. These systems cost from $10-20 million and occupy a large area of the platform. The system must be constantly monitored for solution strength, impurities, corrosion inhibitors, and the addition of fresh solvent, as there is a constant solvent loss with the treated gas. The by-product of the process is a concentrated acid gas stream that usually cannot be flared. A second system is required to remove the H2S and convert it to sulfur. This additional step, usually referred to as an SRU, is also a complex system, costing several million dollars and occupying more area on the already limited offshore platform. The SRU also requires continuous and routine operational attention and maintenance.
[0012] The system envision here would overcome these shortcomings. Seawater scrubbing as presented herein does not require any heaters, there is no make-up solvent or fresh water requirement, the equipment is simple and can be remotely or automatically controlled, creates no acidic gas stream that requires additional treatment, has a minimum of pieces, and low energy requirements.
Non-Patent Publications
[0013] A 1964 Article “New K-Data Show Value of Water Wash”, published in April 1964 issue of Hydrocarbon Processing and Petroleum Refining, (VOL 43, No. 4) discusses that water can be used to remove a large percentage of CO2 and H2S in a gas containing high concentration of these components. The paper describes a water washing system at high pressures and with re-circulation of the fresh water solvent. The writers apparently did not envision using a once-through seawater system, the possibility of disposing of the H2S into the ocean or the way to recover and reuse the energy.
[0014] The 4th Edition of Gas Purification (Gulf Publishing Co., Houston, Tex., ISBN 0-87201-314-6, 1985; 85-4148) pages 265-272 discusses the use of water for removing hydrogen sulfide from gas streams. It expands upon the fact that no heat is required for the acid-gas regeneration and the possibility of lower operating costs over the conventional amine sweetening processes. The articles describe a larger commercial water wash installation operated in Lacq, France. This process, which was only operated for a short time, contains many of the features included in the preferred embodiment of our invention, but does not envision the following:
[0015] (1) An installation located offshore where seawater can provide the water source and does not need to be regenerated since after absorbing the acid gases it can be returned to the ocean.
[0016] (2) The use of an abundant source of water, which allows for more complete gas purification, particularly of H2S.
[0017] (3) That the H2S eventually liberated from the water, requires the installation of a sulfur factory (sulfur removal unit).
[0018] (4) Multi-stage scrubbing and recompression of the gases liberated at lower pressures in order to minimize the loss of natural gas.
[0019] (5) Use of greater water flow rates into the washing column produces high purity gas and avoids the requirement of further treatment
Prior Art Patents
[0020] U.S. Pat. No. 6,017,501, is not suitable for processing natural gas, is related specifically to acid gas, and is more complex and expensive than seawater scrubbing
[0021] U.S. Pat. Nos. 4,235,607 and 4,239,510, do not address the recovery of the natural gases dissolved by the seawater. Dissolved hydrocarbon gases are lost to the atmosphere. There are no provisions for recovering the depressurization energy. Since it provides for only one contactor, it does not recover the gas dissolved in the water. It is not a multi-stage contactor process. Mostly the patent does not address how to adjust and control of seawater flow in relation to the gas rate to obtain the desired purification
[0022] U.S. Pat. No. 5,700,311 teaches the removal of CO2 from a multi component gas stream utilizing nucleated water as a “liquid solvent”.
[0023] U.S. Pat. No. 5,397,553 teaches a system for sequestering CO2 via a clathrate reactor having a seawater feed.
[0024] U.S. Pat. No. 5,364,611 to Mitsubishi of Japan teaches a method for fixing CO2 by mixing same with seawater “at a temperature and pressure required for the formation of carbon dioxide hydrate, and dispersing the CO2 hydrate over the deep ocean floor”.
[0025] U.S. Pat. No. 4,804,523 to Bechtel Group teaches the use of seawater in SO2 absorption of flue gas. See also U.S. Pat. No. 4,085,194 to Hitachi Ltd of Japan for a “Waste Flue Gas Desulfurizing Method” utilizing seawater.
[0026] U.S. Pat. No. 5,562,891 to California Inst Tech teaches a method for sequestering CO2 in sea water, where it can be disposed of in the ocean depths.
[0027] U.S. Pat. No. 4,603,035 discusses the Stretford process, which contemplates an ammonia solution to isolate hydrogen sulfide.
[0028] U.S. Pat. No. 3,970,740 to Exxon Research and Engineering Co contemplates a wet gas scrubbing process utilizing an “aqueous scrubbing mixture maintained within a critical pH range in a jet ejector venturi scrubbing system.”
[0029] Patents covering CO2 hydrates with nucleated seawater, the formation of CO2 hydrates and CO2 clathrates are entirely unrelated
[0030] U.S. Pat. No. 6,280,505 B1 discusses a method for removing acid gas with seawater. It addresses the conventional systems for absorption. Although the patent includes the use of seawater as a solvent for the removal of acid gases (CO2, NOX, H2S, SOX, etc.) using absorption, it does not employ a counter-current contactor, which can be shown to greatly improve the removal efficiency (less solvent and lower pumping cost), and the recovery of the natural gas components dissolved by the seawater
GENERAL SUMMARY DISCUSSION OF THE INVENTION
[0031] Unlike the prior art, the present invention teaches a system for the removal of acid gases (CO2, H2S, SOX, NOX, etc.) from a multi-component gas stream such as sour natural gas and solvent sweetening acid gas which is effective in operation, safer, less costly to build and operate, and more environmentally sustainable than prior art systems.
[0032] The invention utilizes abundant seawater to sequester the acid gas under a wide range of operating conditions and untreated gas compositions and provides for the convenient disposal by returning the seawater to the ocean. It can be demonstrated that the acid gases, specifically CO2 and H2S rich seawater can be safely returned to the ocean, etc.
[0033] The present method is particularly applicable to offshore installations in the deep ocean. The solubility of CO2 in deep ocean waters is twice the solubility in surface or near surface seawaters. By disposing of the CO2 with seawater into deep zones, it will remain sequestered for hundreds of years. Cold, deep seawater in higher latitudes sinks to the bottom of the ocean. It circulates to warmer tropical latitudes, where eventually rising, the CO2 escapes into the atmosphere again. The time interval between the water sinking at the high latitudes and rising in the tropics is estimated at 1000 years.
[0034] Although the end result, i.e. the quantity of CO2 added to the air, will be the same, the oceans will hold the CO2 long enough to reduce the rapid build-up of CO2 associated with the current use of fossil fuels. It is hoped that in hundreds of years, man will have developed a better supply of energy, or will be forced to conserve the scarce combustible fuel supplies.
[0035] The need for an efficient and economic purification system is especially important in the natural gas industry where the percentage of gas produced that requires treatment will increase as uncontaminated reserves of gas are depleted.
[0036] In the preferred embodiment of the present invention, a series of counter current scrubber stages is provided, each configured to remove via absorption/disassociation a portion of the impurities, each stage having less pressure than the predecessor, each stage redirecting recovered gas to the preceding stage where it is recirculated into the system until the contaminant level in the hydrocarbon fluid stream has been reduced to an acceptable level, where is flows from the first stage. Energy recovery means in the form of an energy recovery turbine or the like may also be provided to lessen the energy requirement and increase overall efficiency. Further, the system described herein could be substituted for or work in conjunction with a number of other processes.
[0037] Therefore it is the object of this invention to provide a method which enables a more economical and efficient, environmentally sound, and safer method for purifying natural gas.
[0038] It is another object of the present invention to provide a system for removal of contaminants from a hydrocarbon fluid stream wherein the contaminants are sequestered in seawater for hundreds of years.
[0039] It is another object of the present invention to provide a multi-stage contactor system for the salt-water sequestration of contaminants in a hydrocarbon fluid stream, which results in very little loss of the hydrocarbon stream.
[0040] It is another object of the present invention to provide a system for purification of natural gas, which is energy efficient, comparatively cost effective to build, operate and maintain, and safe in operation.
[0041] It is still another object of the present invention to provide a system for removal of hydrogen sulfide and/or carbon dioxide from a natural gas stream which may be implemented offshore at a lesser cost, increased safety, with decreased environmental impact than prior art systems.
[0042] Lastly, it is an object to provide a multi-stage contactor system for salt water sequestration of contaminants in a hydrocarbon gas stream, which provides sweet gas in situ.
DESCRIPTION OF THE FIGURES
[0043] For a further understanding of the nature and objects of the present invention, reference should be had to the following detailed description, taken in conjunction with the accompanying drawings, in which like parts are given like reference numerals, and wherein:
[0044] [0044]FIG. 1 is a schematic of an embodiment of a multi-stage sour gas sweetening system for practicing the subject invention.
DETAILED DESCRIPTION OF THE INVENTION
[0045] The preferred embodiment of the present invention comprises a system for the purification of natural gas, for example, as produced by and pipelined from an offshore platform.
[0046] In gas production operations, sour natural gas from an HP (high pressure gas-liquid) Separator or gas producing well will generally need to be purified because hydrogen sulfide and/or carbon dioxide concentrations typically exceed sales specifications for the gas. For an offshore installation of the gas purification system the concentration of the hydrogen sulfide component of the sour natural gas is preferably at least 0.01 mole % and more preferably about 0.1 and less than 5.0 mole %, and the carbon dioxide component at least 2 mole % and preferably about 3 or 5 mole %. The balance of the feed stream is normally comprised of light paraffin hydrocarbons, primarily methane.
[0047] The sour gas stream typically would flow at a rate of 10 MMscfd (11,800 m3/hr) and up to about 100 MMscfd (118,000 m3/hr) at a temperature of between about 100 degrees F. (38 C) and 140 degrees F. (60 C) although it is understood by those skilled in the art that the present invention is not limited to the above recited conditions.
[0048] The sour natural gas typically would be fed at a pressure of about 1000 psig, but the invention can be applied to sour gas at various pressures, including pressures from about 100 psig to 2000 psig. The preferred, exemplary embodiment of the present invention will describe a process with a sour feed of about 1000 psig.
[0049] Continuing with FIG. 1, sour gas 1 feed flows 2 into (for example, the lower portion 18 of) the 1st Stage Scrubber 3 or contactor where it flows 4 counter current to a stream 5 of seawater 6 pumped 15 from, for example, the ocean into 16 the upper portion 17 of the first scrubber, which is at an exemplary operational pressure of, for example, 1000 psig. The operational configuration 1st Stage Scrubber 3 may consist of a variety of liquid-gas contact apparatus used in the industry including, for example, a multi-stage contact column containing bubble-cap trays, valve trays, sieve trays, or dumped or structured packing, the design and selection of which are familiar to one skilled in the art.
[0050] Upon contacting the sea water in the first scrubber under pressure, the acid gases (H2S and CO2) within the scrubber will be separated or removed from the sour natural gas by a solvent action of the seawater flowing counter-current to, and contacting with, the gas, providing H2S/CO2 sequestered seawater 7 , (which will also contain sequestered natural gas due to the high pressure) which collects in the base or lower portion 18 of the scrubber.
[0051] After having been processed through the first stage scrubber at high pressure and in counter current-contact with the sour gas, the seawater collected the bottom of the 1st Stage Scrubber will approach chemical equilibrium with the sour gas flowing 2 into the system, thereby providing the sequestered seawater 7 . Exemplary operating criteria for the first stage scrubber would be, for example, an operational pressure of about 1000 PSI, although the pressure will vary depending upon the production system operating conditions as well as wellstream arrival and departing pipeline pressures.
[0052] The diameter and height of the 1st Stage Scrubber will depend upon the sour gas flow rate, the seawater flow rate, the operating pressure and temperature and the degree of purification desired.
[0053] For example, for a feed gas rate of 10 MMscfd at 1000 psig, the 1 st stage scrubber would be 42 in. diameter by 30 ft. tall, and would contain 20 feet of structured packing. The other scrubbers would be relatively smaller, 12-18 inches diameter by 20-25 ft. tall. A seawater flow of about 550 gpm would be required to produce the desired degree of purification. Additional seawater of 5-10 gpm would be added at the other smaller scrubbers. It is also noted that an alkaline agent such as NH3 49 or the like may be injected 50 into the scrubber to enhance the sulfide sequestration efficiency of the seawater.
[0054] The sequestered seawater 7 flows 8 from the 1st Stage Scrubber 3 , and passes through a control valve 9 that reduces the pressure to about 450 psig (31.67 kg/cm2) before entering the 2nd Stage Scrubber. An energy recovery turbine 22 (which may be coupled with a balancing motor) may be utilized at this point to recover some of the energy expended due to the significant pressure reduction to aid in pumping seawater at the higher operating pressure of the scrubber, as will be discussed further.
[0055] The sequestered seawater 7 , after passing through the control valve 9 passes 10 into the second stage scrubber 11 . The reduction in the pressure from the first stage (1000 psig) to the second stage scrubber 11 (450 psig) causes the sequestered water 7 to release a large quantity of natural gas with some H2S and CO2, which flashes into the bottom of the 2nd Stage Scrubber.
[0056] The mixture of these gases 14 is washed in the 2nd Stage Scrubber by additional seawater 20 supplied in a counter-current flow 12 scrubbing out acid gases so as to purify the natural gas released at the lower pressure, providing H2S/SO2 sequestered seawater 19 (which may still contain some entrained natural gas therein, although less natural gas than was entrained in the first stage) collecting in the base or lower portion 24 of the second scrubber, until sufficient level is obtained to open the dump valve, where it is diverted to a third scrubber 21 . The gas 14 not absorbed by the seawater may further be passed through a mist eliminator contained in the scrubber to remove entrained water.
[0057] The flow rates of the seawater to the 1st Stage Scrubber, the 2nd Stage Scrubber and 3rd Stage Scrubber are adjusted to obtain the desired purity of the gases leaving the scrubbers. On-line gas analyzers such as lead acetate tape, photometric, and gas chromatograph analyzers can be employed to analyze the gas for H2S and/or CO2 or the impurity to be removed. The on-line analyzer can be used to automatically control the flow of seawater to the scrubbers to control the purity of the treated gas.
[0058] Gas washed in the 2nd Stage Scrubber, passing 13 from the 2nd stage scrubber at about 450 psig, after (ideally) being passed through a mist eliminator to remove entrained seawater, is compressed by 2nd Stage Compressor 23 to about the pressure of the first scrubber, in this exemplary case, 1000 psig. The moisture retrieved from the mist eliminator, if one is used, may be drained to the seawater 20 passing to the second scrubber. The compressor for the gas leaving the scrubber (in the present scenario) will not require construction of expensive alloys and/or NACE certified materials because the concentration of the corrosive H2S will be very low.
[0059] The gas leaving the compressor will be hot, due to the heat of compression and will be cooled by passing 25 it through the upper portion of the 1 st Stage Scrubber. The hot gas can thereby be cooled by heat exchange with relatively cooler seawater 6 by direct contact with seawater in the top portion of scrubber. This gas is of sufficient purity to meet sales specification, and is thus vented 26 from the first scrubber, so as to provide providing sweet gas.
[0060] If the gas leaving 26 from the first scrubber does not meet the sales specification for natural gas, usually 4 ppmv (maximum), it can be polished with a chemical scavenger. This technology is well known by those skilled in the art of treating small quantities of H2S in natural gas.
[0061] The sequestered seawater 19 collected the bottom of the 2nd Stage Scrubber 11 is at a lower pressure than the first stage, and therefore contains less dissolved natural gas components. The sequestered seawater 19 is drained 27 from the second scrubber, and passes through control valve 28 , where it undergoes a second reduction in pressure, in the present example, to a pressure of about 150 psig (10.55 kg/cm2) the energy of which can also be recovered in a energy recovery turbine 29 to drive the seawater pump, as in the first stage discussion, above.
[0062] Once again, the reduction in pressure causes the water and dissolved gases, which flash upon passing 30 into the bottom of the 3rd Stage Scrubber 21 . Once again more natural gas components are released from solution, along with small amounts of H2S and CO2. The released gas 33 is scrubbed in the 3rd Stage Scrubber by additional seawater added at the top of the scrubber and flowing 34 counter current through the scrubber packing or trays.
[0063] The seawater 31 flow, again controlled by an on-line analyzer, acts as a solvent to remove the desired quantity of H2S and CO2, resulting in sweet natural gas. The sweet gas flowing 35 from the 3rd Stage Scrubber is compressed in the first Stage Compressor 36 to about 450 psig (31.67 kg/cm2) and introduced 37 to the top of the 2nd Stage Scrubber 11 where it is cooled by heat exchange with the seawater 20 flow. Again because the gas flowing from the third stage is sweet because the H2S component has been essentially removed, the first stage compressor 36 will not require expensive special materials of construction, as with the second stage compressor.
[0064] The third stage sequestered seawater 38 , having picked up the acid gas impurities from the 1st Stage, 2nd Stage and 3d Stage Scrubbers flows 39 from the third stage scrubber and undergoes a reduction in pressure to about 50 psig (31.67 kg/cm2) in control valve 40 and the reduction in pressure releases more dissolved gases as it flows 41 into the bottom of the 4th Stage Scrubber 42 , where any gases 43 released by the drop in pressure are scrubbed by seawater 44 flowing 45 counter currently through a multi-stage contact tower, which brings the gas and seawater into equilibrium by way of intimate contact.
[0065] The seawater again removes the acid gas impurities from the natural gas stream, leaving the sweet natural gas components at the scrubber overhead 46 . At this point, the flow rate of this sweet gas stream can be recovered in another compressor, used for fuel gas, or if the quantity is too small to recover economically, it can be flared. The seawater 47 collected on the bottom of the 4th Stage Scrubber is drained 48 or pumped from the scrubber sea, preferably over 100 feet and ideally over 1000 feet deep, where the H2S or CO2 will remain sequestered for hundreds of years.
[0066] The seawater scrubbing system is characterized by the recovery of the energy of the released pressure of the liquids containing gases in solution and a working temperature in the region of ambient temperatures.
[0067] The use of a counter current multistage contactor provides the highly efficient means of purification, in that it maximizes the degree of acid gas removal for the minimum flow of the solvent, e.g. seawater. The selection of the column internals depends on gas and seawater flow rates, pressures, turndown ratio desired, the stability of the offshore platform among other considerations.
[0068] The 2nd, 3rd and 4th Stage Scrubber will be of similar design, although the diameter and height can be considerably different than the 1 st Stage Scrubber.
[0069] The role of the energy recovery turbines can be an important component to the present system, not only from an energy recovery viewpoint, but also as a regulator of the temperature of absorption. Without the turbines, the release in pressure is accompanied by a rise in temperature, which is not negligible and could require that the system include seawater coolers. The temperature of the water has a significant effect on the efficiency of the washing process. Higher temperatures reduce the solubility of the acid gases.
[0070] For higher concentration of acid gas in a natural hydrocarbon gas stream, which can occur on an offshore platform, the desulfurization may need to be carried out in two steps. The first step is the seawater scrubbing system described herein, which removes the bulk of the acid gas impurities. In some cases it may not be feasible to remove the acid gas impurities to the degree desired. A second process step for the desulfurization can be selected from a large array of technologies. The second step desulfurization can be chemical scavenging agents, amine sweetening, physical solvent absorption with regeneration, solid bed absorption, molecular sieves, etc.
[0071] Utilizing the published equilibrium K-valves (see below):
K CH4 = 306 , 000 p + 2.19 t + 3910 t P - 145.0 A G - 121.6 R K H2S = 4.53 - 1087 P + 110.0 t P + 4.65 A G K CO2 = 3500 P + 0.12 t + 360.0 t P + 8.30 A G - 5825 R P
[0072] the concentration of the acid gas components, hydrogen sulfide and carbon dioxide in the seawater can be calculated. Once the concentration of these components in the seawater is known, one can calculate the approximate flow of seawater required to remove the acid gas components. The design calculation is best performed with the use of a process simulation computer program.
[0073] The concentration of the acid gas components in the seawater is a function of the mole % of the components in the gas, the pressure in the scrubber and the temperature. For the same gas composition, the higher the pressure, the greater the concentration of acid gas in the seawater.
[0074] Using seawater scrubbing to remove the bulk of the acid gas has the benefit of low energy consumption, no heat requirements, no chemical costs and the sulfide impurities do not need to be recovered to avoid discharging of sulfurous oxides into the atmosphere, thus avoiding the capital and operating cost of a complex sulfur recovery unit.
[0075] It is strongly iterated that the above exemplary system is not intended to be limiting of the scope of the invention with regard to the number of stages, types of contactors, or specifications as to the range of operations. The number of scrubbers required will be dictated by the quality of the gas, types and concentration of impurities, pressure and flow characteristics of the gas, temperature of the gas, quality/temperature of the seawater, environmental regulations, space allocated for the footprint of the system, supplemental processing apparatus, etc. Further, the use of energy recovery turbines is desirable but is not an absolute necessity. Under some circumstances a single scrubber may be all that is required, others may require two, three, four, or perhaps more in the series arrangement discussed above.
[0076] Further, it is noted that the term “sea water” is utilized as a term to describe water from a large body of water, and is not intended to be limited as to water coming specifically from a body of water termed a “sea”.
[0077] It is also reiterated that the operational concepts of the present invention, exemplified above, are not only suitable for separating CO2 and H2S from a gas stream, but is also effective for removal of other components including SOX, NOX, etc. from a multi-component gas stream such as sour natural gas, as well as other gas streams, including flue gas. Accordingly, the above exemplary embodiment of the invention is not to be considered limiting as to the type of component being removed or the gas stream, which is to be processed.
[0078] The invention embodiments herein described are therefore done so in detail for exemplary purposes only, and may be subject to many different variations in design, structure, application and operation methodology. Thus, the detailed disclosures therein should be interpreted in an illustrative, exemplary manner, and not in a limited sense. | A system for removal of Hydrogen Sulfide (H2S) and/or Carbon Dioxide (C02) from natural gas via absorption and disassociation utilizing a seawater contact system. In the preferred embodiment of the present invention, a series of counter current scrubber stages is provided, each configured to remove via absorption/disassociation a portion of the impurities, each stage having less pressure than the predecessor, each stage redirecting the purified gas to the preceding stage, until the contaminant level in the hydrocarbon gas stream has been reduced to an acceptable level. The hydrogen sulfide/carbon dioxide contaminants are thereby sequestered in the sea water utilized in the scrubber, which sea water my be further processed and/or re-introduced into the deep of a body of water, where the contaminants will remain isolated for hundreds of years. The present invention further contemplates and energy recovery system for greatly enhancing the efficiency of the system. Accordingly, the present invention provides an efficient and cost effective method for the purification of natural gas on an offshore platform. | 1 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This patent application claims priority to U.S. patent application Ser. No. 29/376,374 filed Oct. 6, 2010, the entire contents of which is herein incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present general inventive concept relates generally to medical instruments, and more particularly, to a surgical retractor to retain tissue in a retracted position and expose an interior surface during a surgical procedure.
[0004] 2. Description of the Related Art
[0005] A retractor is a surgical instrument that allows a surgeon to separate edges of a surgical incision or wound. Conventional retractors generally encompass a handheld tool having a narrow blade that can be used to separate tissue and hold the tissue in a retracted state so that a surgical site is exposed. The narrow blade is typically affixed to a single arm or a narrow blade on a pair of linked pivoting arms.
[0006] Conventional retractors generally require a surgeon to maintain the tissue in the retracted state substantially throughout an entire surgical procedure. During the course of the surgical procedure, it is likely that the blade of the retractor will lose its grip on the tissue (e.g., due to the slippery nature of tissue), and that the inadvertent movement of the retractor (e.g., due to movement of the patient or the surgeon) will cause the retractor to deviate from the surgical site. Additionally, during the course of the surgical procedure, it is possible that the surgeon may desire a different perspective of the surgical site.
[0007] Such slips and movement, whether inadvertent or advertent, lengthen the time period required of the surgical procedure, which increases trauma to the patient thus extending recover time of the patient from the surgical procedure, elevates the risks associated with the surgical procedure, and increases the costs of the surgical procedure.
[0008] One such conventional retractor-type device is disclosed in U.S. Pat. No. 5,931,777 to Sava, the entire contents of which is herein incorporated by reference in its entirety. Sava provides a complex device that penetrates bone matter of a patient in order to maintain its position in the patient once established by a surgeon which is undesirable for two reasons. First, it is undesirable to make an incision or otherwise damage any part of the patient via penetrating or the like as such necessarily increases trauma and recovery time. In fact, intentional damage to a patient caused by a surgeon is typically only done only out of necessity. Second, very few surgeries include bone matter adjacent to a surgical field that would permit use of the Sava device as disclosed. In fact, the Sava device is only illustrated in use during spinal surgery.
[0009] Thus, there is a need for a retractor that does not suffer from the limitations of conventional retractors, is versatile to permit use in a wide variety of applications, has a simple design that is easy to use, and does not prolong recovery time or expenses of the patient.
SUMMARY OF THE INVENTION
[0010] A principal object of the present general inventive concept is to provide a retractor that remedies the aforementioned deficiencies in conventional retractors and is ideal for retracting tissue during treatment of any tubular bone fracture including but not limited to the radius, ulna, femur, humerus, fibula, and clavicle.
[0011] Another object of the general inventive concept is to provide a retractor having a plurality of blades that are operable to retain tissue at a surgical site of a patient in a retracted position by leveraging on a portion of the patient at or adjacent to the surgical site so that the surgical site is exposed throughout the course of a surgical procedure. The surgical retractor is self-retaining and includes the plurality of blades are removably mountable on arms of the surgical retractor via a ball-and-socket assembly that permits swiveling and hinging of the opposing blades independent from each other and the arms, i.e., movement of each blade relative to the arms along up to three axes, e.g., an X, Y, and/or Z axes, or along up to three different planes.
[0012] Another object of the general inventive concept is to provide a retractor that is operable to slidably lever on a portion of a surgical site (e.g., a bone) during movement of the retractor from a first configuration (e.g., a stored configuration), to a second configuration (e.g., an in-use configuration) so that tissue is retracted from the surgical site and the surgical site is maximally exposed and subsequent adjustment of the retractor is facilitated via the slidable levering of the retractor.
[0013] Another object of the general inventive concept is to provide a retractor having a blade with edge portions and a talon that cooperatively form a cavity at a center of the blade.
[0014] Another object of the general inventive concept is to provide a retractor for use at a surgical site. The retractor has a tissue-contact portion and a surgical-site contact portion. The tissue-contact portion is of a first size and shape to maximize contact of the retractor with the tissue while conforming to an opening at the surgical site. The surgical-site contact portion is of a second size and shape to minimize contact of the retractor with the surgical site.
[0015] Another object of the general inventive concept is to provide a retractor having a universal coupler that is sized and shaped to connect with blades of different shapes and/or sizes to enable the retractor to adapt to various applications of the retractor. For instance, the present invention is operable to permit substitution of a first blade with a second blade of relatively longer length to enable use of the retractor in applications requiring deeper insertion into areas with thicker and/or deeper soft tissue.
[0016] Another object of the general inventive concept is to provide a retractor and method of use that is easy to use, comparatively simple to manufacture, and especially well adapted for the intended usage thereof.
[0017] The aforementioned objects and advantages of the present general inventive concept may be achieved by providing a self-retaining retractor assembly including an elongated body having opposing arms that are hinged together at a connection point that is spaced from either end of the elongated body. The spacer may be coupled to and depend from each of the arms. Each of the spacers may have a plurality of axes and be operable to independently pivot with respect to the elongated body about each of the plurality of axes. The spacer may be operable to partially enwrap a portion of a surgical site.
[0018] The self-retaining retractor assembly may further include a coupling assembly operable to permit independent removal of one or both spacers from the arms. The coupling assembly may be a ball-and-socket coupling assembly having a ball depending from each of the arms that may be operable to be received via a snap-fit into an aperture in each of the spacers. The aperture may be defined by a circumferential wall having a degree of resiliency. The coupling assembly may provide each of the spacer with a first degree of pivot about the X and Z axes, and a second degree of pivot about the Y axis. The first degree of pivot may be defined by an annular ring on each of the arms. Each of the annular rings may limit the first degree of pivot of each of the spacers to about 45 degrees. The second degree of pivot may be perpetual or 360 degrees. The plurality of axes of each the spacers may intersect at the coupling assembly of each of the spacers. Each of the spacers may include a face surface with side edge portions and a bottom edge portion. The bottom edge portion may have at least one tooth or talon depending therefrom, or may have two, three or more talons of equal size and/or shape, or different size and/or shape depending therefrom. The side edge portion and the at least one talon may be concave to form a cavity on each of the face surfaces.
[0019] The spacer may include at least one talon having a curved surface that may be operable to partially enwrap the portion of the surgical site. The spacer may include two talons each having a curved surface that each may be operable to cooperatively pivot and/or align the spacer with respect to the elongated body when the curved surfaces abut the portion of the surgical site. The talons may be slidable along the portion of the surgical site anytime during use of the self-retaining retractor. The self-retaining retractor does not penetrate any part of a patient (e.g., bone matter). The spacer may include two parallel curved talons with a curved wall extending perpendicular from either side of the two talons to collectively form and surround a cavity between the talons and walls.
[0020] The self-retaining retractor assembly may further include a gripping element on one end of the elongated body having a plurality of finger holes. The self-retaining retractor assembly may further include a locking mechanism on the body that is operable to lock the arms in one of a plurality of orientations with respect to each other. The self-retaining retractor assembly may further include a spring on the locking mechanism that is operable to bias the locking mechanism to a locked configuration. The spacers may be radiolucent blades. The connection point may be a hinge that is operable to permit movement of at least one of the arms with respect to the other of the arms.
[0021] The aforementioned objects and advantages of the present general inventive concept may further be achieved by providing a surgical retractor including a plurality of arms that may be hinged together, and a blade coupled to each of the arms via a friction-fit engagement. The present general inventive concept may include a divider between each of the plurality of arms and each of the blades that may be operable to define a limited range of movement the blade and the arm, and/or separate or at least facilitate separation of the blade from the arm if the blade exceeds the limited range of movement in any one of a plurality of directions. The limited range of movement provided to each of the blades may include a plurality of axes. The plurality of axes may include any one or combination of an X axis, a Y axis, and a Z axis. The plurality of axes may have an intersection point on the blade.
[0022] The aforementioned objects and advantages of the present general inventive concept may further be achieved by providing a method of surgery including the steps of providing a retractor having a plurality of opposing blades depending from hinged arms that are operable to selectively define a void between the plurality of blades, setting the hinged arms in a first configuration with respect to each other, the first configuration defining a first plurality of axes of each of the plurality of blades and permitting independent movement of the plurality of blades along the first plurality of axes, inserting the plurality of blades at least partially into a surgical area with the hinged arms in the first configuration, partially enwrapping a portion of the surgical site via the spacer, and retracting an object or tissue adjacent to the surgical area by moving the hinged arms from the first configuration to a second configuration.
[0023] The second configuration may define a second plurality of axes of each of the plurality of blades and permit independent movement of the plurality of blades along the second plurality of axes. The first and second plurality of axes may each include an X axis, a Y axis, and a Z axis. The X, Y and Z axes may share a common intersection point on the blade.
[0024] The blades may be removable from the arms and may be a set of blades selected from a plurality of blades having different shapes and sizes, and the set of blades may be of equal size and/or shape or different size and/or shape.
[0025] The method may further include the step of pivoting the spacer with respect to the elongated body when the portion of the spacer partially abuts and/or enwraps the portion of the surgical site. The portion of the spacer may be one talon or two talons that may have a curved surface to receive the portion of the surgical site. The curved surface may be contoured with respect to the portion of the surgical site. The portion of the surgical site may be a bone.
[0026] The method may further include the step of levering a portion of the blades on a portion of the surgical area as the hinged arms are moved from the first configuration to the second configuration. The method may further include the step of slidable moving the portion of the blades along the portion of the surgical site after the hinged arms are moved to the second configuration.
[0027] The foregoing and other objects are intended to be illustrative of the present general inventive concept and are not meant in a limiting sense. Many possible embodiments of the present general inventive concept may be made and will be readily evident upon a study of the following specification and accompanying drawings comprising a part thereof. Various features and subcombinations of present general inventive concept may be employed without reference to other features and subcombinations. Other objects and advantages of this present general inventive concept will become apparent from the following description taken in connection with the accompanying drawings, wherein is set forth by way of illustration and example, an embodiment of this present general inventive concept and various features thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] A preferred embodiment of the invention, illustrative of the best mode in which the applicant has contemplated applying the principles, is set forth in the following description and is shown in the drawings.
[0029] FIG. 1 is a perspective view of a retractor in accordance with an exemplary embodiment of the present inventive concept, illustrating the retractor having a plurality of blades connected to arms of the retractor;
[0030] FIG. 2 is a top plan view of the retractor illustrated in FIG. 1 ;
[0031] FIG. 3 is an elevated side view of the retractor illustrated in FIG. 1 ;
[0032] FIG. 4 is a magnified perspective view of the blades and the arms of the retractor illustrated in FIG. 1 with one of the blades exploded from one of the arms;
[0033] FIG. 5 is an elevated rear view of one of the blades illustrated in FIG. 1 ;
[0034] FIG. 6 is an elevated side view of one of the blades illustrated in FIG. 1 ;
[0035] FIG. 7 is a top-plan view of one of the blades illustrated in FIG. 1 ;
[0036] FIG. 8 is a perspective view of the retractor illustrated in FIG. 1 , illustrating the retractor in use with the blades levered against a bone in a first configuration; and
[0037] FIG. 9 is a perspective view of the retractor illustrated in FIG. 1 , illustrating the retractor in use with the blades levered against a bone in a second configuration.
[0038] The drawing figures do not limit the present inventive concept to the specific embodiments disclosed and described herein. The drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the illustrated embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0039] The present inventive concept is susceptible of embodiment in many forms. While the drawings illustrate, and the specification describes, certain embodiments of the invention, it is to be understood that such disclosure is by way of example only. The principles of the present inventive concept are not limited to the particular disclosed embodiments.
[0040] With initial reference to FIG. 1 , a surgical retractor 10 in accordance with the exemplary embodiment of the present inventive concept is illustrated. The retractor 10 has an elongated body 12 that is formed from stainless steel or like material. The elongated body 12 includes opposing arms 14 , 16 at a distal end 18 thereof. The opposing arms 14 , 16 , that are pivotably secured at a connection point or hinge 20 on the elongated body 12 . The hinge 18 is spaced from either end of the elongated body 12 and is operable to permit movement of one or both of the opposing arms 14 , 16 relative to one another. In this manner, the opposing arms 14 , 16 may be selectively distanced from each other in various configurations so that a void 22 between the opposing arms 14 , 16 is thereby defined. A size of the void 22 is variably and selectively determined by the configuration of the opposing arms 14 , 16 .
[0041] On a side of the hinge 20 opposite to the opposing arms 14 , 16 , i.e., at a proximal end 24 of the elongated body 12 , is a grip assembly 26 . The grip assembly 26 includes opposing extensions 28 , 30 that are respectively connected to opposing arms 14 , 16 . Each of the opposing extensions 28 , 30 include an aperture 32 defined by a generally circumferential edge 34 of each of the opposing extensions 28 , 30 . Each aperture 32 is sized and shaped to receive finger(s) and/or thumb(s) of a user or surgeon therethrough to facilitate use and manipulation of the retractor 10 by the surgeon. For purposes herein, the distal end 18 of the retractor 10 or any part thereof is the end closest to a surgical site and distant from the surgeon, while the proximal end 24 the retractor 10 is the end most proximate the surgeon and distant the surgical site.
[0042] Similar to the operation of the opposing arms 14 , 16 , the hinge 18 is operable to permit movement of one or both of the opposing extensions 28 , 30 relative to one another. In this manner, the opposing extensions 28 , 30 may be selectively distanced from each other in various configurations so that a void 36 between the opposing extensions 28 , 30 is thereby defined. Similar to void 22 of the opposing arms 14 , 16 , the size of the void 36 is variable and selectively determined by the configuration of the opposing extensions 28 , 30 .
[0043] A locking assembly 38 that is operable to lock the body 12 in a desired configuration is mounted to the grip assembly 26 . The locking assembly 38 includes a lever 40 , a tab 42 , and a spring 44 . The lever 40 is secured to the extension 30 and is biased into a locked configuration via the spring 44 . The tab 42 is secured to the extension 28 and slidably extends through aperture 46 in the extension 30 . The tab 42 has a plurality of notches 48 along an edge 46 of the tab 38 that are each sized and shaped to partially receive a point 50 that projects from the lever 40 .
[0044] The spring 44 provides a degree of resiliency to the lever 40 so that the point 50 may be selectively pivoted from the locked configuration if the surgeon exerts a force on the lever 40 and automatically returns to the locked configuration if the surgeon releases the lever 40 . When in the unlocked configuration, the tab 42 is slidable within the aperture 46 and the opposing extensions 28 , 30 and opposing arms 14 , 16 may be moved relative to each other. Conversely, when in the locked configuration, the tab 42 is not slidable within the aperture 46 and the opposing extensions 28 , 30 and opposing arms 14 , 16 may not be moved relative to each other
[0045] Turning now to FIGS. 4-7 , a set of opposing blades 52 , 54 are illustrated. The opposing blades 52 , 54 are removably attached to each of the opposing arms 14 , 16 , respectively, at the distal end 18 of the retractor 10 . In the exemplary embodiment, the blades 52 , 54 are of a uniform thickness and each has parallel front and rear surfaces 58 , 60 with a planar face 56 portion in a center thereof. About a perimeter of the front and rear surfaces 58 , 60 are parallel side edges 62 , 64 that are connected by parallel top and bottom edges 66 , 68 . Extending from either end of each face 56 of the blades 52 , 54 is an edge portion 70 with a degree of curvature relative to the face 56 in a range of 30-60 degrees and preferably 45 degrees from the face 56 .
[0046] In the exemplary embodiment, the blades 52 , 54 are of equal size and shape. It is foreseen, however, that the blades 52 , 54 may be of different sizes and/or shapes to enable the retractor 10 to adapt to various applications without deviating from the scope of the present inventive concept. For instance, the degree of curvature of the edge portions 70 may be smaller (e.g., 0 degrees from the face 56 ), larger (e.g., 90 degrees from the face 56 ), and/or differ from each other.
[0047] Depending from the bottom edge 68 of each of the opposing blades 52 , 54 are a plurality of talons 72 . Each of the plurality of talons 72 has a curved body 74 having a degree of curvature that is substantially similar to the degree of curvature of the edge portions 70 extending from the face 56 . At a distal end of the curved body 74 is a point 76 , which is caused to be oriented substantially parallel to the side edges 62 , 64 and the front surface 58 via the curved body 74 . In the exemplary embodiment, the point 76 is sufficiently dull so as to not damage any part of the patient during use of the present invention.
[0048] The curvatures of the edge portions 70 extending from the face 56 and the plurality of talons 72 cooperatively cause the face 56 to be relatively depressed therebetween so that the face 56 is a cavity operable to securely receive a part of the patient therein. Additionally, the curvatures of the edge portions 70 extending from the face 56 are configured to maximize a contact area between the blades 52 , 54 and the incision so that slippage of tissue in contact with the rear surface 60 of each of blades 52 , 54 is less likely to occur relative to conventional retractors. In this manner, trauma to the tissue is minimized and exposure of the surgical site is maximized.
[0049] Each of the blades 52 , 54 is removably secured to one of the opposing arms 14 , 16 by a coupling assembly 78 . In the exemplary embodiment, the coupling assembly 78 is a ball-and-socket assembly 78 that permits various degrees of movement between each of the opposing arms 14 , 16 and its respective blade 52 , 54 . It is foreseen, however, that the coupling assembly 78 could be any like assembly that permits a degree of movement between each of the opposing arms 14 , 16 and its respective blade 52 , 54 .
[0050] The ball-and-socket assembly 78 includes a circumferential ring 80 , a ball 82 , and a socket 84 . The ball 82 depends from the circumferential ring 80 , which is connected to an elbow extension portion 86 of each of the opposing arms 14 , 16 . The ring 80 has a circumferential abutment surface 88 about a perimeter of the ring 80 between the ring 80 and the ball 82 . The ball 82 is sized and shaped to be removably received within and at least partially housed by the socket 84 . The socket 84 is secured to the top edge 66 of each of the opposing blades 52 , 54 has a circumferential wall 90 with an abutment ridge 92 and a cavity 94 therein. The circumferential wall 90 of the socket 84 has a degree of resiliency to permit the ball 82 to snap-fit into the socket 84 and to permit the ball 82 to rotate about the socket 84 without becoming disengaged therefrom.
[0051] Regarding the snap-fit of the ball 82 and the socket 84 , the surgeon may selectively engage or disengage the ball 82 from the socket 84 by applying a degree of force (e.g., by pushing the ball 82 and socket 84 toward each other so that the circumferential abutment surface 88 abuts the abutment ridge 92 at a predetermined angle that causes the ball 82 to separate from the socket 84 , or by pulling the ball 82 and socket 84 away from each other). The degree of force necessary to separate the ball 82 from the socket 84 via abutting the circumferential abutment surface 88 and the abutment ridge 92 is less than the degree of force necessary to separate the ball 82 from the socket 84 via pulling them apart. Additionally, the degree of force necessary to engage or disengage the ball 82 from the socket 84 is greater than the force exerted on the ball-and-socket assembly 78 during usage of the retractor 10 .
[0052] Regarding the rotation of the ball 82 within the socket 84 , each of the opposing arms 14 , 16 provide its respective blade 52 , 54 with a degree of movement independent from its arm 14 , 16 along an X axis, a Y axis, and a Z axis, which are defined by its arm 14 , 16 via the ball 82 . As illustrated in FIG. 4 , the X axis runs parallel to the opposing arms 14 , 16 and elongated body 12 or horizontally (i.e., side to side), the Y axis runs vertically to the X axis (i.e., up and down), and the Z axis runs horizontally at 90 degrees to the X axis. In this manner, when one of both of the blade 52 , 54 are secured to the opposing arms 14 , 16 , that is, when each ball 82 is engaged to each socket 84 , each of the blades 52 , 54 are operable to move in one or more of the X, Y, and Z axes independent from the opposing arms 14 , 16 and each other.
[0053] The range of movement between the ball 82 and the socket 84 along the X and Z axes is limited by the ring 80 . In the exemplary embodiment, the circumferential abutment surface 88 about the perimeter of the ring 80 is operable to abut the ridge 92 of the socket 84 when the ball 82 and socket 84 pivots and reaches its limit along the X and/or Z axes. In the exemplary embodiment, the degree of pivot between the ball 82 and the socket 84 along the X and Z axes is in the range of 30 to 60 degrees and preferably 45 degrees. The degree of pivot between the ball 82 and the socket 84 along the Y axis is unlimited, (i.e., the blade 52 , 54 may continuously rotate with respect to the arm 14 , 16 ). It is foreseen that the ring 80 may be equipped with an extension or backstop (not illustrated) that depends from the ring 80 and is operable to abut the rear surface 60 of the blade 52 , 54 and define a degree of pivot between the ball 82 and the socket 84 along the Y axis of, for example, 270 degrees.
[0054] In use, the surgeon makes a surgical incision 96 adjacent to a surgical site 98 (e.g., a broken bone). The surgeon then grips the retractor 10 so that the void 36 between the opposing extensions 28 , 30 is maximized, which causes the void 22 between the opposing arms 14 , 16 and the blades 52 , 54 to be minimized (i.e., the retractor 10 is in the first or stored configuration). If the retractor 10 is not in the compressed configuration, the surgeon may alter the configuration of the retractor 10 by moving the lever 40 of the locking assembly 38 so that the point 50 disengages from the tab 42 and expanding the opposing extensions 28 , 30 so that the opposing arms 14 , 16 are compressed and are more easily inserted into the incision 96 .
[0055] The blades 52 , 54 are then inserted into the incision 96 so that the rear surface 60 of each of the blades 52 , 54 abuts tissue 100 on either side of the incision 96 and the talons 72 abut an internal part 102 (e.g., portions of the bone adjacent to the broken bone) of the surgical site 98 and/or is received within the cavity of the face 56 . It is foreseen that the talons 72 may be omitted so that the bottom edge 68 , face 56 , and/or the side edges 62 , 64 abut the internal part 102 without deviating from the scope of the present inventive concept.
[0056] Once the retractor 10 has been properly positioned with the talons 72 abutting the internal part 102 or the bottom edge 68 , face 56 , and/or the side edges 62 , 64 abutting the internal part 102 , the blades 52 , 54 are unable to pivot along the Y axis and secure the tissue 100 away from the surgical site 98 . The curved design of the blades advantageously minimizes pressure on the tissue 100 and/or surrounding nerves, vessels, and soft tissues (not illustrated).
[0057] Depending on the application, the surgeon may be required to alter the configuration of the retractor 10 during insertion of the blades 52 , 54 and positioning of the talons 72 to permit the internal part 102 of the surgical site 98 to be accommodated in the void of the planar face 56 between the opposing arms 14 , 16 . Additionally, the blades 52 , 54 may be required to pivot along one or more of the X, Y, and Z axes during insertion of the blades 52 , 54 to accommodate the size and shape of the internal part 102 so that the curved body 74 of the blades 52 , 54 receives, abuts, and partially enwraps the internal part 102 , and the points 76 of the talons 72 extend past the internal part 102 and underneath the internal part 102 , as illustrated in FIG. 8 so that the internal part 102 is received in or adjacent to the cavity of the face 56 . In this manner, a pivot point between the present invention and the internal part 102 is created at or adjacent to the cavity of the face 56 and the blades 52 , 54 are slidably and pivotably secured to the surgical site 98 and particularly to the internal part 102 without piercing the internal part 102 or otherwise damaging any other area of the patient.
[0058] After the talons 72 are abuttingly secured against and/or slightly beneath the internal part 102 of the surgical site 98 , the surgeon unlocks the locking assembly 38 and alters the configuration of the retractor 10 at the pivot point (point of contact between the present invention and the internal part 102 ) so that the void 36 between the opposing extensions 28 , 30 is minimized, which causes the void 22 between the opposing arms 14 , 16 and the blades 52 , 54 to be maximized (i.e., the retractor 10 is moved to the second or in-use configuration), as illustrated in FIG. 9 . At the point, the primary positioning of the retractor 10 is complete. The retractor 10 is also subject to automatic and/or selective secondary positioning as follows.
[0059] As the retractor 10 is altered from the stored configuration to the in-use configuration, each of the blades 52 , 54 pivots independently with respect to the opposing arms 14 , 16 along the X, Y and Z axes. The blades 52 , 54 are not anchored to the internal part 102 and are operable to automatically and slidable move relative to the internal part 102 , if necessary, to minimizes stress on the tissue 100 of the incision 96 . Additionally, as the retractor 10 moves from the stored configuration to the in-use configuration, the surgeon may selectively move the blades 52 , 54 of the retractor 10 further underneath the internal part 102 to further secure the retractor 10 to the internal part 102 and/or obtain a better perspective of the surgical site 98 . This automatic and/or selective secondary movement of the blades 52 , 54 advantageously provides better leverage and a wider opening than what would have been provided without the secondary positioning of the retractor. When the retractor 10 is in the in-use configuration, the contact area between the rear surface 60 and edge portions 70 of each of the blades 52 , 54 , and the tissue 100 on either side of the incision 96 is maximized so that the likelihood of any slippage of the tissue 100 is decreased relative to conventional retractors. The retractor 10 is then locked in the in-use configuration via the locking assembly 38 . It should also be noted that the retractor 10 , enables the surgeon to make slight adjustments, as desired, during the course of a surgical procedure via the secondary movement.
[0060] Accordingly, the retractor 10 is operable to open the surgical site 98 to a maximum while maximizing contact area between the tissue 100 and the blades 52 , 54 and leveraging on the internal part 102 of the surgical site 98 so that slippage of the retained tissue 100 with respect to the blades 52 , 54 and inadvertent movement of the retractor 10 with respect to the surgical site 98 is prevented, and repositioning of the retractor 10 is less likely to be required by the surgeon. Thus, the present inventive concept ensures that the time required to perform a surgical procedure with the retractor 10 is kept to a minimum relative to convention retractors, which causes trauma, recovery time, risk, and costs of the surgical procedure to be minimized relative to convention retractors.
[0061] Having now described the features, discoveries and principles of the general inventive concept, the manner in which the general inventive concept is constructed and used, the characteristics of the construction, and advantageous, new and useful results obtained; the new and useful structures, devices, elements, arrangements, parts and combinations, are set forth in the appended claims.
[0062] It is also to be understood that the following claims are intended to cover all of the generic and specific features of the general inventive concept herein described, and all statements of the scope of the general inventive concept which, as a matter of language, might be said to fall therebetween. | A surgical retractor is provided to retain tissue in a retracted position and expose an interior surface during a surgical procedure. The surgical retractor is self-retaining and includes opposing blades that are removably mountable on arms of the surgical retractor via a ball-and-socket assembly that permits swiveling and hinging of the opposing blades independent from each other and the arms. Each of the opposing blades have a plurality of talons with a curved surface to slidably receive and partially enwrap bone matter so that the plurality of talons securely engage the bone matter while permitting slidable adjustment therebetween. | 0 |
FIELD OF THE INVENTION
The present invention relates, in general, to a device, filtration media, used to purify water and a method of using the same. More particularly, the present invention relates to a filtration media which removes pollutants from water and treats stormwater runoff or other grey water. This filtration media and method can be used in conjunction with many existing filtration systems and devices.
BACKGROUND OF THE INVENTION
Water treatment systems have been in existence for many years. These systems treat stormwater surface run-off or other polluted water. Stormwater surface runoff is of concern for two main reasons: one because of the effects of its volume and flow rate, and two, because of the pollution and contamination it can carry. The volume and flow rate of stormwater is important because high volumes and high flow rates can cause erosion and flooding. Pollution and contamination are important because stormwater is carried into our rivers and streams, from there into our lakes and wetlands, and furthermore because it can eventually reach our oceans. Pollution and contamination that is carried by stormwater can have adverse affects on the health and ecological balance of the environment.
Devices, systems and methods that remove or reduce the pollutants and contaminates and/or control peak flows and volumes are often referred to as best management practices or BMPs. BMPs utilize natural means, artificial or man-made means, and even combinations of either and/or both. Some examples of these BMPs include trash filters, sedimentation basins, retention and detention ponds, wetlands, infiltration trenches, grass swales, various types of media filters, and various types of natural filter systems including sand filters, and aggregate filters including natural and artificial wetlands. These BMPs typically use one or more mechanisms to remove the pollutants and contaminates. These mechanisms include sedimentation, filtration, absorption, adsorption, flocculation, stripping, leaching, bioremediation, and chemical process including oxidation reduction, ion exchange, and precipitation.
Furthermore, stormwater treatment systems can also be classified in relationship to the treatment level in which they are being used. In this respect the term treatment is generally used to describe the unit processes that that are used to reduce the quantities of pollutants and containments in stormwater runoff. For example, basic or pre-treatment typically refers to the removal of gross solids, sediments and larger debris through the processes of settling and screening, while enhanced or advanced treatment typically refers to processes for reducing targeted pollutants; filtration being the main form of enhanced treatment for stormwater. Filtration utilizes a combination of physical, chemical, and biological processes. Types of filtration greatly vary dependent on the media use. Medias can be both inert and/or sorbent and are also strongly linked to natural biological processes that thrive in and/or around the media environment.
There is, thus, a need for a device which is a filtration media which can clean water on its own or be incorporated into existing filtration systems. A device which can treat both wastewater and stormwater. A filtration media which can treat high levels of specific pollutants and contaminants.
SUMMARY OF THE INVENTION
This invention has overcome the downfalls of prior art. It is related to unique and novel method and device for treating polluted water flows, specifically point and non-point source stormwater and wastewater flows. Such flows contain various pollutants in various concentrations that have detrimental effects on the environment and human health. These pollutants/substances include, but are not limited to: sediments, gross debris, construction material, Total Suspended Solids, trash and litter, chemicals, grease and oil, hydrocarbons including polycyclic aromatic hydrocarbons and total petroleum hydrocarbons, particulate and dissolved heavy metals, Total Dissolved Solids, turbidity, conductivity, inappropriate pH, color, total phosphorous, ortho-phosphate, total nitrogen, total kjeldahl nitrogen, nitrate, bacteria/pathogens, herbicides, and pesticides.
These pollutants have various physical, chemical, and biological characteristics such as size, specific gravity, charge, form. Because of these varying characteristics, different filtering and capture processes and techniques have traditionally been implemented, in series, to remove specific pollutants. These existing processes and techniques have proven effective in wastewater treatment where flows are generally low and consistent, however not effective in stormwater conditions because flows are inconsistent and highly variable in flow and volume. The device disclosed in this application, the filtration media, and method have proven to be successful and feasible strategies for both wastewater treatment (sewage) and stormwater treatment, where flows are low and consistent, or, in the alternative, inconsistent and highly variable.
This device is a passive filter method and filtration media that has a specific and engineered combination of physical, chemical, and biological characteristics that will allow it to effectively address most or all of the above pollutants of concern in the quickest time possible. Depending on flow or volume based design, the time range for contact time with a filter media is from 1 seconds to a few hours and therefore requires an innovative and unique method and device that will effectively treat the various pollutants of concern in a very short time.
This invention uses a combination of fibers consisting of high-alumina low silica (HT) wool as filter material. This synthetic vitreous fiber is made of inorganic material and contains alumina and/or calcium silicates. This filtration media consists of inert vitreous silicate mineral wool bonded with a thermosetting phenolic resin which has been urea extended. Only high-alumina low-silica fiber is well suited for stormwater applications because it is one of only a few fibers that are proven not to have adverse affects on the environment or health of humans, animals, and plants. These fibers have a mean diameter of 4 microns and a mean length of 3 mm. The fibers are bonded together and can be shaped in to sheets, granules or blocks of filtration media. This filtration media, sometimes referred to as wool, is beneficial due to its specific chemical composition. This device has a high content of aluminum oxide, giving the material an inherent ability to carry a slightly positive charge. This positive charge can be enhanced with the addition of an aluminum-oxide coating on the surface of the fibers. This positive change assists in the binding, and thus removal of organic, inorganic and microbiological contaminants. Electrostatic attraction generated by the positively charged filter media surface increases removal of the negatively charged pollutants such as phosphates, viruses and bacteria.
This filtration media allows for both perpendicular and parallel flow. This characteristic gives it great advantages over prior materials in that it can be used in the perimeter or a round or rectangular structure such as, but not limited, to catch basins. In this configuration the material of the effluent end of the media can be mounted, placed, or set between the wall of the structure, thus, allowing the water to flow through the media coming from one direction and allowing it to make a 90 degree turn and flow in a different direction. In one embodiment, the media undergoes a pre-treatment process which can further assist in its filtration functions. This filtration media and method can be used as a complete stormwater and waste water treatment system, or combined with existing treatment systems to provide added treatment.
BRIEF DESCRIPTION OF THE 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 objects, advantages, and principles of the invention. In the drawings:
FIG. 1 is a perspective view of an embodiment of a device for purifying water;
FIG. 2 is a perspective view of an embodiment of a device for purifying water which has been modified to increase its surface area by the addition of channels;
FIG. 3 is a perspective view of an embodiment of a device for purifying water which has been modified to increase its surface area by the addition of holes that do not penetrate the media;
FIG. 4 is a perspective view of an embodiment of a device and method for purifying water wherein it has been placed between a porous flow-through matrix and an influent shield;
FIG. 5 is a perspective view of an embodiment of a device and method for purifying water wherein multiple devices shaped as blocks of filtration media have been bonded together and placed between a influent shield and a porous flow through matrix;
FIG. 6 is a end cross sectional view of a catch basin with a device to increase the filtration capabilities.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
After reading this description it will become apparent to one skilled in the art how to implement the invention in various alternative embodiments and alternative applications. However, all the various embodiments of the present invention will not be described herein. It is understood that the embodiments presented here are presented by way of an example only, and not limitation. As such, this detailed description of various alternative embodiments should not be construed to limit the scope or breadth of the present invention as set forth below.
With reference to FIG. 1 , a device for filtering water (“device”) 100 is shown and displayed. This device 100 is made up of filtration media composed of numerous intertwined fibers 102 which have been bonded together. The fibers 102 are bonded together with a thermosetting phenolic resin which has been urea extended. The fibers 102 have a diameter of 1 to 40 microns and a length of 1 to 20 mm each. These fibers 102 are derived from a melt of 30 to 60% of silicon dioxide, 10 to 40% of aluminum oxide, 10 to 20% of calcium oxide, 5 to 20% of magnesium oxide, and 1 to 20% of one or more other types of oxides. The filtration media can be formed in blocks, sheets, or granulets of various thicknesses and lengths depending on the use. The fiber density ranges between 5 to 35% of the volume of each device 100 while the open space between the fibers 102 which allows for water or air to pass through ranges from 65 to 95% of the total volume. One benefit to this device 100 is that it allows for water flow from both perpendicular and parallel directions, thus enabling it to be used in multiple applications. It can be used as a complete stormwater treatment or wastewater treatment system, or in combination with existing treatment systems, as shown below in FIG. 4 through 6 , to provide added treatment.
Stormwater or other water is passed through the device 100 . The influent water enters the filtration media of the device 100 and flows through the fibers 102 where the pollutants, including but not limited to bacteria, phosphorus, and viruses, and other materials are removed. This device 100 functions to remove pollutants, bacteria, viruses and phosphorus from the water which is passed through it. The surface of the filtration media of the device 100 creates electrostatic attraction generated by the positively charged surface and fibers 102 within the device 100 ; this positive charge assists the removal efficiencies as it attracts and binds the negatively charged pollutants.
A process of coating the surface of the filtration media with aluminum oxide can be used to further increases the pollutant removal capabilities of the fibers 102 by increasing the electrostatic attraction. To accomplish this, aluminum-based substances can be added, mixed or bonded to the fibers 102 . While there are many substances which can be used, the preferred substance is an aluminum nitrate solution. The preferred method is saturating the filtration media of the device 100 . Once the material is saturated, the device 100 is allowed to dry. The treated material can be cured by exposure to high temperatures or can be used without the curing process.
With reference to FIGS. 2 and 3 , a surface area increasing mechanism will be described. These mechanisms allow for the device 100 to be further modified to increase its surface area, thereby increasing its loading capacity for pollutants and prolonging the individual density materials clogging rate. An increase in the surface area by this mechanism will allow for more pollutants to be removed from the water passing through the device 100 . These modifications are made to the surface of the device 100 on the influent side where the water enters the device 100 . FIG. 2 is a perspective view of an embodiment of a device 100 which has been modified by adding channels 204 to the surface. There can be one or more channels 204 drilled either horizontally, vertically or both horizontally and vertically into the surface of the media. The depth of these channels 204 can vary depending on the thickness of the media; however, they never extend all the way through the filtration media of the device 100 . FIG. 2 shows a device 100 where there have been numerous channels machined into its surface.
FIG. 3 is a perspective view of an embodiment of a device 100 which has been modified by the machining of holes 206 into its surface. These holes 206 can be machined at various sizes, depths, and diameters. The only restriction on the depth of the holes 206 is that they must be less than the thickness of the media. There can be one or more holes 206 drilled into the surface of the device 100 . In general, the more holes, the greater the surface area of the device 100 . The surface of the device 100 can also be agitated by various hand tools and mechanical devices to create an inconsistent rough texture to the media, which will increase the surface area of the device 100 . The above listed alterations of the device 100 are only a few of the alterations which can be made to increase the surface area and the efficiency of the device 100 .
With reference to FIG. 4 , an embodiment of the device 100 is shown being placed between an influent shield 400 and a porous flow-through matrix 300 . This combination results in a method to further clean the polluted water. The influent shield 400 protects high velocity water currents from making direct contact with the surface of the device 100 and harming the surface. The influent shield 400 also conveys the water to the surface in a controlled manner, in order to provide uniform flow to the filtration media surface. The influent shield 400 will also provide support of the vertical, angled, or horizontal media column. To provide structural support of the media both between and during stormwater and wastewater flow, the effluent side of the device is supported by a flow-through matrix 300 . The flow-through matrix 300 is a ridged structure equipped with multiple holes so the effluent water flowing out of the device 100 , which has been treated by the device 100 , can flow through the flow-through matrix 300 . In an alternate embodiment, the flow-through matrix 300 does not have holes but is just a porous, ridged material. The flow through matrix 300 directs the water flowing out of the device to allow discharge of the treated water as can be seen at arrows 310 and 320 . Here the matrix 300 allows for both perpendicular and parallel discharge of the water. In this configuration the device 100 can be used as a perimeter filter for round or rectangular structures, such as, but not limited, to catch basins. In FIG. 4 , a cross section of the outer wall of the catch basin is shown as 200 .
With reference to FIG. 5 , multiple devices ( 100 ( a ), 100 ( b ) and 100 ( c )) shaped as blocks of filtration media have been bonded together and placed between an influent shield 400 and a porous flow-through matrix 300 . The use of multiple combined devices 100 ( a ), 100 ( b ) and 100 ( c ) creates a long lasting and highly effective system. The multiple devices 100 ( a ), 100 ( b ) and 100 ( c ) can be of varying densities. In FIG. 5 , the first device 100 ( a ) on the influent side is the least dense, the device 100 ( b ) in the middle is more dense, and the device 100 ( c ) on the effluent end is the most dense. This multi-density media device creates multiple levels of treatment. Each device 100 of a different density protects the next device from coarser particles, therefore, extending the life of the system. The devices 100 will encounter a wider range of particles ranging from 0.1 to 5000 microns. The devices 100 ( a ), 100 ( b ), 100 ( c ) layered together can be of varying thicknesses. This system of multiple devices 100 ( a ), 100 ( b ), 100 ( c ) has a higher capacity for pollutant removal and has prolonged clogging rates.
In the configuration shown at FIG. 5 , the effluent end of the device 100 can be mounted, placed, or set against the wall 200 of an existing structure, thus, allowing water to flow through the media in one direction and then making a 90 degree turn and flow in another direction to the end of the catch basin structure. The material used on the effluent end of the device 100 can be attached to the wall with mounts.
With reference to FIG. 6 an existing stormwater catch basin 600 is shown where a device 100 have been added to increase the filtration capabilities. FIG. 6 shows an end cross sectional view of a catch basin where the device 100 is shown on either side of the chamber 600 . The device 100 in this embodiment is formed into a sheet and has been wrapped around the interior surface of the catch basin 600 . Wastewater or stormwater flows into the grate 610 which sits at ground level, commonly on the street or curb. The contaminated water then flows through the first filter 650 of the catch basin 600 and into the interior chamber 660 . The contaminated water then flows through the device 100 where it is further filtered and out the pipes located at the catch basin's wall 640 . The device 100 can be inserted into many existing filtration devices such as this catch basin 600 to further enhance the removal of pollutants.
This invention discloses a method for treating wastewater or stormwater whereby fibers 102 from a melt of oxides are bonded together with a thermosetting phenolic resin which has been urea extended. The bonded fibers are shaped into rolls, granulates, sheets or blocks. Contaminated or polluted water is passed through the bonded fibers 102 where the pollutants are captured. The surface of the bonded fibers 102 can be modified to increase the surface area as disclosed above. The fibers 102 can be made in various densities as disclosed above. Multiple blocks of the fibers 102 can be attached together to increase the pollutant capturing ability of the fibers 102 . In order to further increase the treatment of the water, aluminum oxide can be added to the fibers 102 .
The above description of disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to the embodiments will be readily apparent to those skilled in the art, the generic principals defined herein can be applied to other embodiments without departing from spirit or scope of the invention. Thus, the invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principals and novel features disclosed herein. | A device and method for purifying waste water and stormwater flows by passage through a filter, which can be manufactured in various configurations. The filter has a broad range of thickness ranging from 1 mm to 20 meters. The filter is comprised of fibers from a melt of composition of 50% silicon dioxide, 15% aluminum oxide, 15% calcium oxide, 10% magnesium oxide, and other various oxides at lower percentages. At least the majority of fibers having a mean diameter of 4 microns and a mean length of 3 mm. The fiber solids of content of the material are at most 35% of the volume at a flow rate greater than 1 inch per hour to remove various pollutants from the water flow. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention pertains generally to a system for temporarily halting the flow of one or more incoming mail pieces into an envelope inserter apparatus. More particularly, the subject invention relates to a document buffer system having a controlling program that is utilized in connection with a document interface feeding device, an envelope inserter, and documents being transferred through the interface feeding device into the inserter, wherein one or more of the incoming documents may be temporarily halted, within the interface feeding device, before entry into the envelope inserter and buffered or cued in known order until the controlling program directs any cued documents to once again enter the envelope inserter.
2. Description of Related Art
Traditionally, when a series of document packets (often one or more pages in a billing statement for goods and/or services provided) are delivered by a transport device to an envelope inserter and an error is detected in the process there were three solutions: 1) the transporter is stopped, with the accompanied stoppage in production until the problem is resolved; 2) the transporter continues running, the envelopes filled, and the error is resolved later; and 3) the transporter continues to run with the problem document packets diverted out of the production process. However, there are two significant problems with the traditional solutions: 1) reduced productivity and 2) reduced quality. For whatever reason the inserter stops (there are many and they often occur about every minute, during the average process), the negative results are the same. All document packets that are in transition (frequently, from one to four) stack up either in the inserter track of in a diverter tray. After an operator rectifies the inserter error, the operator must remove the document packet(s), manually separate then from each other, insure that each document packet is complete and correct, and hand place them back into the track one at a time while cycling the inserter between them. Clearly, this corrective action is time consuming and can significantly increase the time to complete a job (often as much as a 30% increase). Also, human intervention of document packet production always increases the chance of making significant quality errors. The operator can inadvertently make several different errors; not separating two document packets that may have nested when stacked will result in two document packets mailed in the same envelope, mixing sheets from one document packet with another when separating them will result in incomplete or incorrect mailed document packets placing document packets in the track in the wrong sequential order will result in improper insert matching, or placing document packets in the track in the wrong orientation will result in undeliverable mail. Plainly, many difficulties existed in the prior error-resolution processes.
Several mechanisms already exist to divert of buffer the flow of documents during document transfers in numerous specific settings, but these mechanisms do not make obvious, teach, suggest, or imply in any manner the subject invention.
U.S. Pat. No. 3,948,564 discloses a fluid bearing apparatus and method that utilizes a selective turntable diverter structure to temporarily store identical items in a buffer station. The buffer station merely maintains a ready pool of identical items to supply the needs of an associated apparatus. No item sequence information is recorded or needed with this device.
Described in U.S. Pat. No. 4,544,146 is an insertion machine with control signals stored on searchable medium. Envelopes are printed with desired information and utilized (buffered and flipped) with an inserter and associated inserter stations.
A control signal buffer for use in an inserter system is related in U.S. Pat. No. 4,707,790. An information control buffer, no physical item is buffered, is provided in which control information from the supervisory controller to the sheet inserter system is buffered so that synchronicity is achieved between the transfer of batches of documents from a web of incoming documents and what is actually inserted into designated envelopes.
A communication network and protocol for real-time control of mailing machine operations is disclosed in U.S. Pat. No. 5,003,538. Information buffers within microprocessors are utilized to facilitate the transfer of controlling information to operate a traditional mailing machine.
U.S. Pat. No. 5,029,832 presents an in-line rotary inserter for use with an envelope inserting machine. A number of diverter stations are disposed ahead of the envelope inserting station for diversion of envelopes and inserts and ahead of the inserted envelope stacking assembly to divert inserted envelopes during normal operation and detected error situations. Upon detection of an error situation, the subject invention halts incoming statements before any envelopes are encountered.
U.S. Pat. Nos. 5,503,388 and 5,538,140 disclose a buffered stacker that selectively diverts horizontally disposed documents from a main conveying path, then stacks and transports the documents to replaceable receiving containers. This system directly diverts the selected documents away from the conveying path and does not allow any selected documents to reenter the main conveying path.
Described in U.S. Pat. No. 5,613,669 relates a control process for use in the production of printed products and means for performing the process. In the sequential assembly of multi-page document sets a controller, using a camera/detector, is utilized to scan and analyze each incoming page to determine if the correct page has been delivered and, if not, to direct corrective actions.
U.S. Pat. No. 5,816,715 outlines an interfacing mechanical buffer that allows two streams of materials to be united, even if the rates of flow of the materials from each of the two streams differ. To merge two streams of documents, each traveling at different speeds, one stream is slowed by having a mechanical buffer receive the documents and then release them in a first-in-first-out order. The mechanical buffer comprises a matched set of four helical-shaped screws that receive a incoming document, rotate to receive additional documents, and permit discharge of the received documents in order of their entrance to the buffer.
U.S. Pat. Nos. 5,826,869 and 6,131,053 present a high throughput document-processing machine having a dynamic speed control. The device merely directs the flow accumulated sets of documents from a first transport pathway to a second transport pathway if a jam is detected in the first pathway.
A transporter buffer and inserter method are disclosed in U.S. Pat. No. 5,860,504. A plurality of sensors detect positions of items in a transfer system and stop the items at predetermined locations based upon when the items should enter a receiving area.
The foregoing patents reflect the state of the art of which the applicant is aware and are tendered with the view toward discharging applicant's acknowledged duty of candor in disclosing information which may be pertinent in the examination of this application. It is respectfully submitted, however, that none of these patents teaches or renders obvious, singly or when considered in combination, applicant's claimed invention.
BRIEF SUMMARY OF THE INVENTION
An aspect of the invention is to provide an information and physical mailing piece buffer to temporarily store at least one mailing piece or document packet and associated information in the event that an error is detected in relation to an inserter that is to receive the mailing piece or document packet for insertion into a mailing envelope.
Another aspect of the invention is to disclose a buffer system, utilized prior to an envelope inserter apparatus, for temporarily halting and holding, upon detection of a processing error, one or more incoming mailing pieces or document pieces and then releasing the held incoming mailing pieces or document packages upon resolving the difficulty that generated the halting error.
A still further aspect of the invention is to relate a computer program controlled document interface feeding device, utilized immediately prior to an envelope inserter, and with documents being transferred through the interface feeding device into the inserter, wherein if an error is detected in the processing of the incoming documents, one or more of the incoming documents may be temporarily halted and held within the interface feeding device, before entry into the envelope inserter and buffered or cued in known order until the controlling program processes the detected error and the error situation is remedied and then directs any cued documents to once again enter the envelope inserter.
The computer controlled subject transporter comprises a supporting frame having a plurality of lower and upper pulleys and belts along the general configuration of a conveyor. Document packets (often mailing pieces) enter the subject transporter either directly or indirectly from the output of a folder, or the like, and are contained between the upper and lower pulleys and belts and passively gripped. The belts are driven by an encoder controlled motor actively linked to the inserter. Along the document packet travel path, under the belts, are computer controlled gates for stopping individual document packets that can each be activated independently. Activation is often by associated pneumatic cylinders of electric solenoids. When activated, each gate moves into the document packet pathway and blocks the movement of the document packet. Since the belts only grip the document packet passively, the belts slip on the document packet for a short duration until the belts cease movement, as directed by the controlling computer. When the error is corrected each gate may be disengaged to permit normal transport.
The general software logic utilized by the controlling computer system detects that the downstream equipment (usually the inserter) is not able to receive a document packet it will determine to “buffer” or halt and hold delivery of the document packet, then it will determine to buffer additional document packets until the upstream equipment can be stopped. As the incoming document packets enter the subject transporter buffer, the first document packet proceeds to the last buffer gate (the furthest downstream) and is held. The following document packet proceeds to the second to last buffer gate and is held, continuing until all of the buffer gates are filled. Once the last statement is buffered, the subject transport belts stop. After the errors are remedied and the inserter is “armed” to begin processing, the system controller is directed to resume production, the inserter cycles to the ready position. The transport belts start movement and the buffer releases the first document packet which is delivered into the insert track. The inserter cycles once more and the buffer releases the second document packet. This continues for all subsequent document packets. Once the subject buffer is empty of held document packets the system begins normal operation automatically. Document packet detection sensors are located in the document packet travel path to indicate the presence or absence of a statement at each subject gate. Each sensor insures that a document packet has arrived at the appropriate gate, as expected, that document packets have not slipped past a gate while buffered, that document packets have not been removed while buffered, and that document packets have departed, as expected. If any of these difficulties occur, the system controller notifies the operator of the condition.
Advantages of the subject invention include, but are not limited to, increased productivity and enhanced quality. If the downstream equipment (the inserter) is not ready to receive document packets (such as the inserter has stopped for a jam), the document packets that have been sent to the inserter (perhaps from a collator and/or folder) continue to be transported toward the inserter. The subject buffer fills up with the incoming document packets and the system stops. After the operator rectifies the inserter stop reason, the operator can begin document packet production without regard to those document packets in the subject buffer. The system automatically delivers the document packets cued in the buffer one at a time into the inserter track with the assurance that no two document packets are nested together, no sheets are mixed up with another document packet, document packets maintain their original sequence order, and document packets are in the proper orientation (i.e. face down, top way, or whatever proper orientation is required). With the assurance of these actions, there is a guarantee that the quality issues have been eliminated (two document packets mailed in the same envelope, incomplete document packets mailed, improper insert matching, or undeliverable mail). Also, the entire time that this process is taking place automatically, the operator is available to attend to other system needs, such as restocking inserter hoppers and unloading completed mail pieces into the mailing trays. By doing so, the operator will be more efficient and can complete the job assignment is a shorter time.
Further aspects of the invention will be brought out in the following portions of the specification, wherein the detailed description is for the purpose of fully disclosing preferred embodiments of the invention without placing limitations thereon.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
The invention will be more fully understood by reference to the following drawings which are for illustrative purposes only:
FIG. 1 is a perspective view of the subject device.
FIG. 2 is a cut-away side view of the subject device showing all four gates in the lowered or retracted positions.
FIG. 3 is a cut-away side view of the subject device showing one gate in the up or extended position and the other three gates in the lowered or retracted positions.
FIG. 4 is a cut-away side view of the subject device shown from the opposite side as seen in FIGS. 2 and 3 .
FIG. 5 is a state transition diagram for the controlling software utilized in the subject invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring more specifically to the drawings, for illustrative purposes the present invention is embodied in the apparatus and software diagram generally shown in FIG. 1 through FIG. 5 . It will be appreciated that the apparatus may vary as to configuration and as to details of the parts, and that the method may vary as to the specific steps and sequence, without departing from the basic concepts as disclosed herein.
It should be appreciated that a conventional envelope inserter apparatus is utilized in conjunction with the subject buffer invention. The envelope insertion operation is generally carried out by conventional inserter apparatus which provides for the collecting or assembling of several sheets of mail materials together into packets, and the insertion of the assembled packets into envelopes to produce a mailing piece. In standard inserter devices, a stream of opened envelopes is generally conveyed past an inserter arm by a conveyor system. Individual inserts are obtained from insert hoppers and added to billing statements (comprised of one or more pages of listed charges for a service rendered and other relevant information) or other items to form the packets, and the assembled packets are sequentially directed by conveyor means to the inserter arm. The inserter arm then inserts or stuffs each packet of mail materials into an opened envelope by pushing the packet with pusher members or pusher fingers. The filled or stuffed envelopes are then generally directed to an envelope sealing operation. The inserter and pre- and post-processing equipment are controlled by a system computer programmed to coordinate mailing piece assembly and to monitor the entire system for errors in assemble and processing.
The controlling computer programming halts the envelope insertion process when an unsuitable occurrence or error is detected at some specific point in the overall process of the document packet or mailing piece assembly. Usually, a document interface feeding device delivers a document packet of mailing items, like billing statements, from a printer, folder, collator, or other device or combination of devices to the envelope inserter. Document packets are transferred through the interface feeding device into the inserter, if the process is interrupted or if an error is detected in the processing of the incoming documents, one or more of the incoming document packets may be temporarily halted, within the subject buffer, before entry into the envelope inserter and buffered or cued in known order until the controlling program processes the detected error and the error situation is remedied (usually by diverting the incoming document packet(s) to a separate hand-processing area) and then directs any cued document packets to once again enter the envelope inserter.
Specifically, as seen in FIG. 1-4 , the subject buffer device 5 comprises a supporting frame generally having two opposing side walls 10 and 15 . The side walls 10 and 15 are secured to one another by any suitable standard means such as the illustrated cross-support members 11 and 12 .
Extending between and secured to the side walls 10 and 15 are a plurality of rotating cylinders or pulleys that support and drive a series of transport belts. Pulleys 20 , 25 , 30 , and 35 generate a lower transport belt path to support and drive the lower transport belts 36 , 37 , and 38 . Pulleys 40 , 45 , 50 , and 25 generate a first upper transport belt path to support and drive first upper transport belts 51 and 52 . Pulleys 55 , 60 , 65 , and 30 generate a second upper transport belt path to support and drive second upper transport belts 61 and 62 . In combination, these pulleys and belts configure a conveyor system to move documents packets into the inserter. In FIGS. 1-4 each document packet enters the subject device from the right and is moved to the left as the pulleys and belts rotate to transport the document packets. Document packets (often mailing pieces) enter the subject transporter (from the right in the illustrations) either directly or indirectly from the output of a folder, or the like, and are contained between the upper and lower pulleys and belts and passively gripped (gripped with enough force for movement, but not enough force to damage the document packets as the belts slide over them should the packets be temporarily halted upon detection of an error). The pulleys/belts are driven by an encoder controlled motor 70 or motors actively linked to operational timing of the inserter.
Along and below the document packet travel path are computer controlled gates 75 , 80 , 85 , and 90 for stopping, when stop-errors are detected, individual document packets at separate specific locations in the travel path. Although other equivalent methods may be utilized to move a gate into and out of the document packet travel path, preferably each gate 75 , 80 , 85 , and 90 pivots about a rotational axis 76 , 81 , 86 , and 91 into the document packet path to block transfer of a document packet and pivots out of the path to release a document packet. Each gate 75 , 80 , 85 , and 90 comprises an elongated plate with suitably positioned notches to accommodate passage of the belts when the gate is pivoted into the document packet path to block a desired document packet.
Each gate 75 , 80 , 85 , and 90 may be independently activated and pivoted into the path to block passage of a document packet or independently deactivated and pivoted away from the path to release a document packet to travel towards or into the inserter. Activation is often by associated pneumatic cylinders or electric solenoids that are suitably interfaced to the controlling computer system for activation or deactivation. Specifically shown in FIG. 4 , compressed air cylinders 100 , 105 , 110 , 115 are utilized to pivot gates 75 , 80 , 85 , and 90 , respectively, into and out of the path. When activated, each gate 75 , 80 , 85 , and 90 moves into the document packet pathway and blocks the movement of the document packet. Since the belts 36 , 51 , and 61 only grip the document packet passively (“passively” meaning with a minimal force sufficient for path movement purposes), the belts slip on the document packet for a short duration until the belts cease movement, as directed by the controlling computer. Specifically, as seen in FIG. 3 , only one gate 90 was activated to pivot about point 91 and into the document packet path to block the document docket. Clearly, one or more gates 75 , 80 , 85 , and 90 may be activated if the situation arises. When the error that produced activation of a gate is remedied or corrected, each gate 75 , 80 , 85 , and 90 may be disengaged by a command of the controlling computer to pivot down and out of the path to permit normal transport of a document packet, as seen in FIG. 2 .
To detect if document packets are actually stopped and present behind any or all of the various gates 75 , 80 , 85 , and 90 or that the document packet path areas behind the various gates 75 , 80 , 85 , and 90 are open and free of document packets, suitable sensors are utilized and appropriately interfaced with the controlling computer system. Although other equivalent types of sensors are contemplated to be within the realm of this disclosure, a preferred sensor configuration is a paired light emitter and light receiver sensor 200 , 205 , 210 , and 215 . If a document packet is present the light between the emitter and receiver is blocked and the controlling system so notes and if no document packet is present the light passes from the emitter to the receiver and, again, the controlling system so notes.
Specifically, as illustrate the FIG. 5 state transition diagram, the subject buffer device utilizes controlling software that interfaces with the controlling system of the associated inserter. When predetermined errors of various types are detected by the controlling system the subject buffer software is activated to control delivery of document packets to the inserter.
For purposes of clarity and by way of example and not by way of limitation, the control logic of the subject buffer gate device is specified by the behavior of a single buffer gate and in terms of the document packet specifically being a billing statement (usually for service provided or products purchased) generated by a suitable device upstream from the subject buffer device. Multiple instances of the same control program are activated, one for each buffer gate (four such gates 75 , 80 , 85 , and 90 are illustrated in FIGS. 1-4 ).
A state transition diagram (shown in FIG. 5 ) is employed to specify the control logic of the subject buffer gate program. An explanation is provided below for the state transition diagram in general and provides specific examples to assist in fully understanding the state transition diagram for the subject buffer gate program. Before describing the subject state transition diagram, it is deemed appropriate to identify and describe the events the subject control program detects and the actions the control program takes. In addition, it is appropriate to list the states the control program occupies and the conditions (data values) the program can access. To fully specify the behavior of the subject program the state transition diagram utilizes four elements: 1) events, 2) actions, 3) states, and 4) conditions.
1) Events
The subject buffer gate program responds to the following events:
TABLE 1
EVENTS RESPONDED TO BY THE SUBJECT PROGRAM
Event
Means of detection
Initialization
This event is common to all control programs and
represents the start of the program.
Statement Message
The statement message is a software signal sent by a
device upstream from the gate to indicate that a
statement has been sent.
Statement Arrival
The statement arrival event is provided by an
encoder system that signals the program when the
transport has reached the position corresponding
to the arrival of a statement at the gate.
Transport Start
This software signal is provided by the system
management software when the transport starts.
Transport Stop
This software signal is provided by the system
management software when the transport stops.
Downstream Ready
This software signal is sent by a device
downstream from the gate when it is able to receive
a statement. For example, when an inserter is
enabled and has an empty slot in its input section
it sends this signal to the buffer gate closest to the
inserter. In addition, each buffer gate sends this
information to the adjacent upstream buffer gate
when it has released a statement and can now
receive a statement.
Downstream
This software signal is sent by the device
Stopped
downstream from the gate when it is not able to
receive a statement. For example when the
inserter jams and has a statement in its input section
it sends this signal to the buffer gate closest to
the inserter. In addition each buffer gate sends
this information to the adjacent upstream buffer
gate when it is holding a statement.
Sensor Poll Clear
This software signal is sent by a standard polling
thread that monitors the state of the sensor at the
buffer gate when the sensor transitions from
blocked to clear.
Path Error
This software signal is sent by various external
programs for various possible reasons. The signal
indicates that the identity or reliability of material
on the transport is no longer certain.
2) Actions
The subject buffer gate control program takes the following actions.
TABLE 2
ACTIONS TAKEN BY THE SUBJECT PROGRAM
Action
Means of actuation
Open Gate
Switch the gate so that each statement is allowed to pass.
Close Gate
Switch the gate so that a statement is held at the gate.
Send Statement
Send a software signal to a downstream device to
Message
indicate that a statement has been released.
Send Ready
Send a software signal to an upstream device to indicate
Message
that the gate can now receive a statement.
Send Stopped
Send a software signal to an upstream device to indicate
Message
that the gate cannot receive a statement because it is
already holding one.
Display Error
Display an error message and stop the insertion system so
that the operator can correct an error.
3) States
The subject buffer gate program is always in one of the following states:
TABLE 3
STATES IN WHICH THE SUBJECT PROGRAM ALWAYS EXISTS
State
Conceptual description
Inactive
The transport is stopped and the buffer gate sensor is clear.
Ready
The transport is running, the gate is open, and no
statements are expected from an upstream device.
Waiting
The transport is running, the gate is open, and a statement
is expected from an upstream device but has not yet arrived.
Holding
The transport is running and a known statement is being
held at the gate.
Stopped
The transport is stopped and a known statement is being
held at the gate.
Faulted
The transport is stopped and unsuitable/unmailable material
is held at the gate.
4) Conditions
The subject buffer gate program can determine the following conditions at any point in time.
TABLE 4
CONDITIONS DETERMINED BY THE SUBJECT PROGRAM
Condition
Means of accessing/maintaining the data
Sensor
The buffer gate program can directly read the state of the
Blocked/Clear
gate sensor at any time.
Downstream
The buffer gate program records the most recent message
Ready/Stopped
from a downstream device to indicate whether it is
currently ready or stopped.
State Transition Diagram—Background (see FIG. 5 )
The subject control program responds to events by taking actions. The specific action taken in response to an event is determined by the state of the program at the time the event occurs and may also depend on the value of one or more conditions. In addition to taking the indicated action, the program also changes its state. The state transition diagram, shown in FIG. 5 , documents the system's behavior as transition arrowed-lines leading from one state to another. Each transition arrowed-line represents an event and may also contain an action. Further, if a transition arrowed-line behavior depends on any condition the transition arrowed-line shows a required value for the condition. To determine the response of the system to a sequence of events the transition arrowed-line of interest is “followed” to observe what action is taken in response to each event.
The Buffer Gate Program and State Transition Diagram (see FIG. 5 )
To clarify the meaning of the state transition diagram seen in FIG. 5 , behavior examples for the subject buffer gate program are provided.
The following tables (Tables 5-8) show example scenarios handled by the subject program. In each scenario a hypothetical sequence of events occurs. Each table shows the action taken in response to each event. The “State” column shows the state of the system at the time the event occurs. (Note that the state of the system on one row is the result of the transition occurring on the previous row.)
Throughout each example sequence the action can be determined from the state transition diagram, FIG. 5 , as follows. First, find the rectangle on the diagram corresponding the state (remembering that the subject program is always in one of the six listed states in Table 3, above). Then examine the arrows leading out of the rectangle and find the one labeled with the event that has occurred. The bold-underlined text indicates the action taken in response to the event.
Note that the same event will trigger a different action in different states. For example, in Sequence 1 the transport start event triggers a Send Ready Message action when the state was Inactive. However, when the state was Stopped the Transport Start triggered no action.
Finally note that in each state only a subset of the list of events has an outbound transition. This is because in each state some events are ignored by the program or simply can not occur. For example, when the buffer gate is in the Faulted state a Downstream Ready message is ignored. In the Waiting state the system does not poll the sensor so the Sensor Poll Clear event can not occur.
TABLE 5
SEQUENCE 1 - NORMAL
State
Event
Response (Action)
None - program
Initialization
(none)
not activated
Inactive
Transport Start
Send Ready Message
Ready
Transport Stop
(none)
Inactive
Transport Start
Send Ready Message
Ready
Statement Message
(none)
Waiting
Statement Arrival
Send Statement Message
[Downstream Ready,
Sensor Blocked]
Ready
Statement Message
(none)
Waiting
Statement Arrival
Close Gate
[Downstream Stopped,
Sensor Blocked]
Holding
Transport Stop
(none)
Stopped
Transport Start
(none)
Holding
Downstream Ready
Open Gate, Send Statement
Message, Send Ready
Message
Ready
For Sequence 2,
TABLE 6
SEQUENCE 2 - STATEMENT FAILS TO ARRIVE AT GATE
State
Event
Response (Action)
Ready
Statement Message
(none)
Waiting
Statement Arrival
Display Error
[Downstream Ready, Sensor
Clear]
Inactive
For Sequence 3,
TABLE 7
SEQUENCE 3 - STATEMENT REMOVED FROM GATE
State
Event
Response (Action)
Ready
Statement Message
(none)
Waiting
Statement Arrival
Send Statement Message
[Downstream Ready, Sensor
Blocked]
Ready
Statement Message
(none)
Waiting
Statement Arrival
Close Gate
[Downstream Stopped,
Sensor Blocked]
Holding
Sensor Poll Clear
Display Error
Inactive
For Sequence 4,
TABLE 8
SEQUENCE 4 - GATE CONTENTS UNKNOWN
State
Event
Response (Action)
Ready
Statement Message
(none)
Waiting
Statement Arrival
Send Statement Message
[Downstream Ready, Sensor
Blocked]
Ready
Statement Message
(none)
Waiting
Statement Arrival
Close Gate
[Downstream Stopped,
Sensor Blocked]
Holding
Path Error
(none)
Faulted
Sensor Poll Clear
(none)
Inactive
Although the description above contains many details, these should not be construed as limiting the scope of the invention but as merely providing illustrations of some of the presently preferred embodiments of this invention. Therefore, it will be appreciated that the scope of the present invention fully encompasses other embodiments which may become obvious to those skilled in the art, and that the scope of the present invention is accordingly to be limited by nothing other than the appended claims, in which reference to an element in the singular is not intended to mean “one and only one” unless explicitly so stated, but rather “one or more.” All structural, chemical, and functional equivalents to the elements of the above-described preferred embodiment that are known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the present claims. Moreover, it is not necessary for a device or method to address each and every problem sought to be solved by the present invention, for it to be encompassed by the present claims. Furthermore, no element, component, or method step in the present disclosure is intended to be dedicated to the public regardless of whether the element, component, or method step is explicitly recited in the claims. No claim element herein is to be construed under the provisions of 35 U.S.C. 112, sixth paragraph, unless the element is expressly recited using the phrase “means for.” | A document transfer buffer device for holding temporarily a document between an upstream document feeding device and a downstream envelope inserter has a transporting device for moving the document from the upstream document feeding device to the envelope inserter and an envelope holding device for temporarily holding the document in a holding location between the upstream document feeding device and the envelope inserter and a controlling program that selectively activates the transporting device and the temporary holding device and is responsive to the upstream feeding device and the envelope inserter possible error conditions that initiate document holding and releasing situations. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a continuation of pending U.S. patent application Ser. No. 12/145,220 filed on Jun. 24, 2008, which claims benefit from Provisional Application No. 60/945,993, filed on Jun. 25, 2007. The disclosures of these documents, including the specifications, drawings, and claims, are incorporated herein by reference in their entireties.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The disclosure relates to the field of treatment of atherosclerosis. Particularly, the disclosure relates to systems for reduction of vascular plaques.
2. Description of the Related Art
Cardiovascular disease is a leading cause of morbidity and mortality worldwide. It occurs due to the formation of plaques within the coronary arteries over time, leading to decreased blood flow to specific organs including brain and heart muscle. Under certain circumstances, this decreased blood flow can cause symptoms of transient ischemic attack, calf pain or angina. If the blockage of the arteries is more significant, it can lead to damage to the brain, legs or heart muscle itself and can be fatal.
One method of treatment of (cardio) vascular disease and avoidance of further tissue damage is through invasive elimination of the plaque. This is typically done through invasive surgery. An alternative approach is through balloon angioplasty, which involves accessing the vessels using catheterization. Arterial stents may also be placed during this procedure. When the nature of the plaque precludes treatment by angioplasty, the plaques may be bypassed by grafting new vessels around the areas of plaque during vascular or cardiac surgery procedure. In some patients, neither angioplasty nor bypass surgery is possible, such as when the advanced age or poor health of the patient precludes such treatments or when the plaque is not amenable to either therapy. In such cases, the patients must attempt to control the disease through medical management such as through the use of medication. Because the surgical treatment of arterial plaques is invasive, the treatment is associated with the risk of complications, and is not suitable for all patients, a less invasive method for reducing or eliminating plaque formations in the arteries is therefore needed.
Non-invasive methods for treatment of unwanted material in tissues and vessels, typically cardiac vessels have been suggested for instance in U.S. Pat. Nos. 5,657,760, 5,590,657, and 5,524,620. However, these methods are not suitable for the reduction of plaques, let alone in the vascular system.
Hence, there is a need for an accurate, reliable system for obviating and reducing vascular plaques with a planned and controlled treatment therapy.
SUMMARY OF THE INVENTION
This disclosure relates to a method and system for reducing vascular plaque.
For the purposes of this specification, the term ‘cardiac rhythm’ refers to all or any of the events related to the flow of blood that occur from the beginning of one heartbeat to the beginning of the next. Every single ‘beat’ of the heart involves three major stages: atrial systole, ventricular systole and complete cardiac diastole.
According to this disclosure, there is provided a method for reducing vascular plaques non-invasively comprises the following steps:
imaging at least a portion of a mammalian body to produce an image; determining the location of at least one vascular plaque in said image; ascertaining the location of the base of said vascular plaque, said location of base being the target location; precisely determining the relative position of said target location with respect to the cardiac rhythm in the body; delivering a beam of ultrasound energy waves from a source to a focal point in the relative position to elevate temperature of said target location in a pre-determined manner; monitoring the temperature of the target location; and discontinuing delivery of ultrasound energy waves when said target location achieves a pre-determined set temperature.
The method in accordance with this disclosure includes the step of displaying said image and said target location. It also includes the step of preparing a therapeutic plan for treatment of said vascular plaque. The frequency of ultrasound energy waves is adjusted to between 0.8 Hertz and about 4 Hertz. The focal point of the beam of said ultrasound energy waves is, for instance, less than about 15 mm 3 The intensity of focus of said ultrasound energy waves is typically adjusted to greater than about 500 W/cm 2 . Further, the duration of the delivery of ultrasound energy waves is typically adjusted based on temperature change. Typically, the time duration for delivery of ultrasound is adjusted to between about 80 ms and about 1 second.
According to another aspect of this disclosure, there is provided a system for reducing vascular plaque including:
imaging device adapted to image at least a portion of a mammalian body; interpreting device adapted to interpret said image to locate at least one vascular plaque and the base of said vascular plaque for determining plaque location; monitoring device to monitor the relative position of said target location with respect to the cardiac rhythm; at least one displaceable ultrasound delivery device adapted to deliver ultrasound energy waves of a predetermined intensity to said target location; temperature monitoring device to monitor temperature of said target location; and device to shut-off delivery of ultrasound energy waves when the target location achieves a predetermined set temperature.
The monitoring device is an ECG machine. The ultrasound delivery device is a High Frequency Ultrasound (HFU) device. The imaging device is a Magnetic Resonance Imaging (MRI) device.
The imaging device and the interpreting device is capable of recognizing plaque in the vascular system of the imaged body and identifying the base of the plaque in the MRI images of the vessels. The HFU device is adapted to deliver HFU to the base of the plaque identified by the imaging and interpreting device as the target location. The temperature monitoring device is capable of monitoring the temperature of the tissue at the target location via the thermal images to determine when HFU delivery is complete.
The system in accordance with this disclosure may be used for treatment of plaques within the carotid, iliac, femoral or coronary arteries. In accordance with an additional feature of this disclosure, an ECG monitoring device is adapted to monitor cardiac rhythm during said therapeutic treatment and process signals from said monitored ECG.
The controlling device controls the timing of MRI images and the delivery of HFU according to data received from the ECG monitoring device, so that HFU delivery and MRI images are triggered at a particular point in the cardiac cycle.
The controlling device is adapted to guide the ultrasound delivery device to emit ultrasound energy waves in confirmation with:
specific angle or location of delivery; intensity of ultrasound energy waves to be emitted; and time duration for delivery of the ultrasound energy waves.
The aforementioned parameters depend upon the size and location of the plaque as mapped by the imaging device.
The system includes a therapeutic treatment plan for determining the parameters of the delivered ultrasound energy waves. It may include a controlling device to receive said therapeutic treatment plan from an automated control unit and/or by manual intervention.
The delivery of HFU to the base of the plaque causes the temperature of the tissue at the target location to rise. MRI monitoring of the target tissue detects the temperature increase. When the temperature increase is adequate, HFU treatment is stopped. The HFU treatment may be repeated at the same target but with an alternative angle of delivery. The HFU treatment may also be repeated at multiple target locations within the same plaques or within different plaques.
For each target, the HFU delivery is continued until an adequate amount of treatment has been delivered to lead to scarring and plaque regression.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is further described in the detailed description which follows, in reference to the noted plurality of drawings by way of non-limiting examples of exemplary embodiments of the present disclosure, in which like reference numerals represent similar parts throughout the several views of the drawings, and wherein:
FIG. 1 illustrates the system for non-invasive reduction of vascular plaques; and
FIG. 2 illustrates the method of treatment for non-invasive reduction of vascular plaques.
DETAILED DESCRIPTION OF THE INVENTION
The particulars shown herein are by way of example and for purposes of illustrative discussion of the embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the present invention. In this regard, no attempt is made to show structural details of the present invention in more detail than is necessary for the fundamental understanding of the present invention, the description taken with the drawings making apparent to those skilled in the art how the forms of the present invention may be embodied in practice.
Referring now to the drawings wherein like characters represent like elements, FIG. 1 illustrates the system for non-invasive reduction of vascular plaques. Treatment is delivered to the patient ( 10 ) using an ultrasound delivery device, typically through a High Frequency Ultrasound (HFU) emitting device ( 20 ). During treatment delivery, the patient ( 10 ) is monitored by both an ECG monitoring device ( 30 ) and a Magnetic Resonance Imaging (MRI) device ( 40 ). Output from the ECG monitoring device ( 30 ) and the MRI device ( 40 ) are sent to a interpreting a processing device ( 50 ) which includes image recognition device ( 60 ) and an image display device ( 70 ). The controller provides output to the HFU steering unit ( 80 ), which directs the delivery of energy by steering and controlling the HFU device ( 20 ).
During the procedure, the patient ( 10 ) is placed in a comfortable position on a treatment table where the patient must remain still. Because the procedure is non-invasive, it may be performed without any sedation and without causing the patient discomfort. The treatment table is located within the MRI device ( 40 ), so that the MRI images may be taken during the procedure to locate target lesions and to monitor the progress of the treatment. The MRI device ( 40 ) must be capable of providing images of the arteries which are sharply detailed so that the base of the plaque can be precisely identified, on the back side of the plaque at the vessel wall. An MRI device ( 40 ) which provides images with the capability to visualize tissue at a nanometer level of resolution, such as a 1.5, 3 or 7 Tesla MRI unit, may be used in features of the disclosure to provide these precise images.
The patient ( 10 ) is also monitored by an ECG monitoring device ( 30 ) throughout the duration of the procedure. The ECG monitoring unit ( 30 ) may be a standard 12-lead ECG or may be performed using fewer leads. Like all other components used in or near the MRI device ( 40 ), the ECG monitoring device ( 30 ) must not include any ferrous material. The beating of the patient's heart results in motion of the heart as well as of all arteries as they expand with each cardiac contraction. The ECG is used to allow the system to compensate for this motion. In order to obtain useful MRI images, the taking of the MRI images is timed to correspond to the beating of the patient's heart, such that each image is taken at the same point in the cardiac cycle. For example, the MRI device can be timed to take images during diastole, the relaxation phase of the heart. Likewise the delivery of the HFU therapy is timed to the cardiac cycle using the ECG monitoring device ( 30 ). After the target location is identified using an MRI image, HFU therapy is applied to the target location. In order to ensure correct localization of the target location during treatment, the point during the cardiac cycle at which the MRI image is taken is the same as the point at which the HFU therapy is delivered. In this way, the target location identified using MRI is the same as the location to which the HFU therapy is delivered.
The ECG data is relayed to a processing device ( 50 ) throughout treatment. The processing device ( 50 ) interprets the ECG data and provides instructions to the MRI device ( 40 ) and the HFU controller ( 80 ). The processing device ( 50 ) also receives data from the MRI device ( 40 ) and includes image recognition device ( 60 ) and an image display device ( 70 ). The image recognition device ( 60 ) may be used to identify plaque within the arteries by interpreting the signal in the MRI images. Alternatively, a clinician may visually identify plaque on the image display ( 70 ) of the MRI images. In some embodiments, the image recognition device ( 60 ) identifies the plaque and the clinician verifies the identification using the image display device ( 70 ). The image recognition device ( 60 ) and/or the clinician identify the location at the base of each plaque which is the target of the HFU therapy.
After one or more target locations are identified by the processing device ( 50 ) and/or the clinician, a treatment plan is developed. A single plaque may include one target location or several target locations along the base of the plaque. In addition, an individual may have multiple plaques. In some cases, the treatment plan will include delivery of HFU to all identified plaque bases. In other cases, it may be desirable to selectively treat only some plaque bases or portions of plaque bases and leave others untreated. Therefore the treatment plan includes the decision regarding which plaque bases will be treated, and these locations become the target locations. For each target location, the ideal alignment of the HFU device ( 20 ) with the patient ( 10 ) must also be determined. This will depend upon the location of the target location as well as factors such as individual patient anatomy.
The following parameters depend upon the size and location of the plaque as mapped by the MRI device ( 40 ):
specific angle or location of delivery; intensity of ultrasound energy waves to be emitted; and time duration for delivery of the ultrasound energy waves.
In some cases, treatment may be delivered by a stationary HFU beam at a single angle. Alternatively, it may be preferable to deliver HFU to a target location using a stationary HFU beam at more than one treatment angle. In some cases, HFU may be delivered as the beam rotates through an arc of treatment angles. In still other cases, HFU may be delivered through multiple arcs of treatment angles. This can be by means of a multilocus transducer. The method includes the step of displacing the source of said beam. The displacement could be linear or angular. By delivering treatment using more than one treatment angle, the amount of energy delivered to tissue outside of the target location is minimized and therefore the risk of damage to other tissue may be decreased or eliminated. For each treatment angle and for each target location, a target temperature must be chosen. Therefore the treatment plan includes the details regarding which target locations are to be treated, the angle at which the HFU will be delivered, whether multiple treatment angles will be used to deliver HFU to a target location, and what the final temperature of the target location will be for each HFU delivery. The delivery of the ultrasound energy waves is either intermittent or pulsed, with the source of ultrasound delivery being displace after each pulse or after a series of pulses. The angle of delivery may be constant or changed after each pulse or a series of pulses. These determinations may be made by the processing device ( 50 ) according to guidelines in its programming, by the clinician, or by the clinician in combination with the processing device ( 50 ).
The delivery of HFU over an arc of treatment angles may be either rotational or stationary. When the treatment plan calls for the rotational delivery of HFU over an arc of angles, HFU treatment is delivered while the HFU device is actively moving. However, the rotational delivery of HFU treatment of the arteries may only be provided during a particular time window in each cardiac cycle, due to motion of the arteries. Therefore, the arc of rotational treatment may be formed by a series of miniarcs, with treatment being delivered as the HFU device rotates through a series of miniarcs with each heart beat. For example, during a first heart beat, treatment may begin at a first angle and rotate to a second angle, forming a first miniarc. With the next heart beat, treatment may resume at the second angle and rotate to a third angle, forming a second miniarc which is consecutive with the first miniarc. Treatment would thus continue rotating across the miniarcs until the miniarcs together formed the planned treatment arc. Alternatively, stationary treatment may be delivered over an arc of angles, without rotating during HFU delivery. For example, during a first heart beat, treatment may be delivered by a stationary HFU beam at a first angle. The HFU device may be adjusted slightly, such as 1 millimeter, and during a second heart beat, treatment would be delivered by the stationary HFU device at a second angle, which may be close to the first angle. The HFU device may continue to adjust to consecutive treatment angles until treatment is delivered at series of angles to form an arc of treatment angles.
Alternative is one multilocus transducer adjusted in size and format to the target vessel or an arc with more than one transducer which delivers energy in a consecutive manner.
The processing device sends instructions according to the treatment plan to the HFU controller ( 80 ), which controls the HFU delivery device ( 20 ). When the HFU delivery device ( 20 ) is inside the MRI device ( 40 ), it must not include any ferrous material. During treatment, the treatment face of the HFU delivery device ( 20 ) is in contact with the surface of the patient ( 10 ) directly or through an intermediate substance such as a gel patch, on the patient's neck, groin or chest, for example. When a gel patch is used, is able to compress to correct for the distance between the patient's surface and the target location in the vessel. The use of a gel patch may therefore be appropriate for treatment plans which call for the rotational delivery of HFU therapy over a treatment arc, so that the distance between the HFU device and the target location remains constant while the HFU device rotates around the target location. The ultrasound delivery device ( 20 ) is mobile and can be precisely positioned and angled relative the patient ( 10 ) in order to direct HFU precisely to the target location. The maximum distance between the ultrasound delivery device ( 20 ) and the target location is preferably less than, about 6 cm. This maximum distance may be taken into account when developing the treatment plan.
The HFU emitting ultrasound delivery device ( 20 ) delivers ultrasonic waves to the target location at the base of the plaque, causing the target location to increase in temperature. The size of the HFU focal point is preferably less than about 15 mm 3 This may be achieved using HFU waves at a frequency of between about 0.8 and about 4 Hertz and with an intensity of the focus of between about 500 and about 3000 W/cm 2 . The HFU delivery device ( 20 ) delivers HFU to the target location in repeated brief intervals which are correlated to a specific point in the cardiac cycle as detected by the ECG, according to instructions from the processing device ( 50 ). The duration of each HFU delivery may be from approximately 80 milliseconds to approximately 1 second. The appropriate duration of each HFU delivery depends upon the individual patient's heart rate. The duration of each HFU delivery could be a short duration appropriate for most or all patients, regardless of the patient's heart rate. Alternatively, the duration of each HFU delivery could determined for each individual patient depending upon the measured heart rate. Finally, the duration of each HFU delivery could vary during each individual patient's treatment in response to measured heart rate.
The HFU delivery device ( 20 ) continues delivering HFU to the target location until the tissue reaches the desired temperature according to the treatment plan. In some embodiments, the maximum desired temperature of the target location is approximately 80 degrees Celsius. The temperature of the target location is determined by the processing device ( 50 ) based on images provided by the MRI device ( 40 ). In order to monitor the temperature increase, the system may periodically take MRI images during the treatment process. For example, the system may take an MRI image after each delivery of HFU treatment. Alternatively, MRI images may be taken during delivery of HFU treatment. For example, an MRI image may be taken during initial treatment, then repeated after several HFU pulses. The MRI images may then be repeated during the treatment to monitor the progress. The signal of the MRI image at the target location changes in a manner which corresponds to the temperature of the tissue. The processing device ( 50 ) includes device which can interpret the changes in the MRI image of the target location to determine the temperature of the tissue. When the desired temperature is reached, the processing device ( 50 ) instructs the HFU controller ( 80 ) to discontinue the delivery of HFU.
FIG. 2 presents a method of treatment according to features of the disclosure. The treatment begins at the start, step 100 . At step 102 , MRI images are taken of the coronary vessels. The MRI images are used to identify plaque and target locations at the base of the plaque at step 104 . Based on the MRI images, a treatment plan is developed at step 106 by the processing device and/or the clinician. HFU therapy is then applied to the precise location in the vessel wall at step 108 through either a stationary beam or a rotational beam. MRI imaging of the target location is performed at step 110 . The MRI image is processed to determine whether the desired temperature has been achieved according to the treatment plan at step 112 . If the desired temperature has not been achieved, the steps of HFU therapy 108 , MRI imaging 110 and MRI image processing 112 are repeated until the desired temperature is achieved.
A determination of whether the treatment plan calls for further treatment angles or arcs of treatment angles to the target location is made at step 114 . If a further treatment angle or arc of angles are planned, the starting location and beginning angle of the HFU emitting device are adjusted at step 116 and HFU therapy is applied again at step 108 to the same target location at a new angle. MRI imaging and image processing are repeated at steps 110 and 112 until the desired temperature is achieved using the new HFU device angle.
When no further treatment angles are planned for a target location, a determination is made regarding whether further treatment is planned for another target location at step 118 . If no treatment is planned for other target locations, then the treatment is at an end at step 122 . However, if further treatment locations are planned, then the location of the HFU device is adjusted at step 120 to deliver HFU to a new target location, and the process is repeated for the new treatment location. This is repeated until all planed target locations have been treated.
By applying HFU to the base of the plaque, the targeted tissue in the vessel wall experiences an increase in temperature. This temperature increase leads to inflammation of the tissue and later to scar formation which is sufficient to reduce or destroy the vaso vasorum, which is the vascular supply to the base of the plaque. It is believed that the loss of vascularization to the vessel wall at the base of the plaque will lead to the eventual regression of the plaque. Because the HFU is very precise, it can deliver energy to the base of the plaque without damaging the vessel wall. In this way, HFU therapy can be used to non-invasively reduce or eliminate plaque.
Features of the disclosure non-invasively treat atherosclerotic disease using targeted ultrasound therapy, thus avoiding the risks inherent to invasive interventions. In addition, by avoiding surgery, the treatment process is easier for the patient and the clinician, can be performed more rapidly and involves less patient discomfort and a quicker and easier recovery. Furthermore, it offers a therapy option for patients who did not qualify for surgical intervention. While some features of the disclosure are appropriate for use in the large arteries, the treatment may also be performed to reduce atherosclerosis in other locations in the body including the coronary arteries.
The image guided cardiac ablation method and system can potentially be used in the following vascular applications:
for eliminating atherosclerosis which includes removal of atherosclerotic plaques typically in a. femoralis , in a. carotis , in a. renalis , or in a coronary artery. It can also be used for eliminating thrombolysis which includes intracranial thrombosis, thrombosis in hemodialysis shunts, thrombosis in left atrial appendage (LAA), venous thrombosis, and pulmonary embolism. It can further be used for eliminating occlusion of vessels typically in medical conditions such as hemorrhage, sealing of punctures, varicosis, pseudoaneurysmata, vascular malformations in the brain, and in bloodless resection of organs, bleeding esophageal varices, and also to separate twins sharing a single placenta.
The image guided cardiac ablation method and system can potentially be extended for use in the following non-vascular applications:
in cases relating to malignancy including prostate carcinoma, breast carcinoma, hepatocellular carcinoma, renal cell carcinoma, urinary bladder carcinoma, pancreas cancer, and osteosarcoma. It can also be used in other non-vascular application not relating to malignancy such as benign prostate hypertrophy, uterus fibroids, fibroadenoma (breast, liver).
Still further, the image guided cardiac ablation method and system can be used for treatment of glaucoma, pain treatment, treatment of functional disorders of the brain (epilepsy, Parkinson's disease), lithotrypsy (urinary, bile), vasectomy, synovectomy (in rheumatoid arthritis), cutaneous lesion recovery (valvular dystrophy, lymphatic drainage, skin care) and also in cases relating to atrial fibrillation (MAZE procedure).
It can also be used in Gene targeting and drug delivery applications.
While considerable emphasis has been placed herein on the specific elements of the preferred embodiment, it will be appreciated that many alterations can be made and that many modifications can be made in the preferred embodiment without departing from the principles of the invention. These and other changes in the preferred embodiment as well as other embodiments of the invention will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the invention and not as a limitation. | A method and system for reducing vascular plaque non-invasively including imaging at least a portion of a mammalian body to produce an image; determining the location of at least one vascular plaque in said image; ascertaining the location of the base of said vascular plaque, said location of base being the target location; precisely determining the relative position of said target location with respect to the cardiac rhythm in the body; delivering a beam of ultrasound energy waves from a source to the relative position to elevate temperature of said target location in a pre-determined manner; monitoring the temperature of the target location; and discontinuing delivery of ultrasound energy waves when said target location achieves a predetermined set temperature. | 0 |
This is a continuation of application Ser. No. 08/225,689 filed Apr. 11, 1994, now abandoned.
BACKGROUND OF THE INVENTION
1. Technical Field
The present invention relates generally to automotive vehicle body structure, and more particularly to the construction of automotive vehicle pillars to accommodate energy absorption.
2. Description of the Prior Art
In the design of modern automotive vehicles, it is has been the goal to provide body structures which manage the absorption of energy in response to the imposition of frontal loads. More recent design activity in the vehicle body arts has been directed to the management of energy imposed on the vehicle occupant compartment in response to loads imposed on the sides of the vehicle and to loading imposed within the vehicle occupant compartment. While the cushioning of surfaces facing the vehicle occupant compartment has long been practiced in the automotive industry, the basic, usually metal, structure of the body itself has been accommodated rather than made an integral part of the energy management design, although early designs, such as that exemplified in U.S. Pat. No. 3,560,020 to Barenyi, indicate the general principle of cushioning such structure is known.
SUMMARY OF THE INVENTION
It is an object of the present invention to define an energy absorbing pillar structure which enhances the capability of the pillar to absorb energy in response to loads laterally imposed with respect to the vehicle.
This is accomplished through providing such a structure that includes an exterior panel, an interior panel, and an intermediate panel secured together to define a pair of energy absorbing chambers between the panels, and providing a trim cover joined to the panels in which energy absorbing media are carried between the trim panel and the outer panel of the pillar in a third energy absorbing chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
The efficacy of the invention pillar structure and its advantages over the prior art will become apparent to those skilled in the automotive body arts upon reading the following description with reference to the accompanying drawings, in which:
FIG. 1 is a partial side view of an automotive vehicle;
FIG. 2 is a cross section taken along line 2--2 of FIG. 1;
FIG. 3 is a cross-sectional view taken along line 3--3 of FIG. 1;
FIG. 4 is a cross-sectional view similar to FIG. 3 illustrating an alternative embodiment; and
FIG. 5 is a cross-sectional view similar to FIG. 3 illustrating yet another alternative embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning now to the drawings, in particular to FIG. 1 thereof, an automobile 10 is illustrated as having a body 12 having a lower portion such as indicated at the door 14, a roof portion 16, and pillars 18, 20. As is conventional, the pillars 18, 20 provide support for the roof 16 in closing the vehicle occupant compartment indicated generally at 22.
According to the present invention, the pillars 18, 20 are constructed to enhance energy absorption in response to loads imposed laterally of the pillars. As used herein, it is to be understood that the pillars 18, 20 extend generally vertically between the lower portion 14 of the vehicle 10 and the roof 16, and that loads imposed generally normal to this vertical extent are referred to as lateral or side loads.
The pillars 18, 20 are preferably fabricated as metal stampings. According to the present invention, they are configured to enhance energy absorption both by the shape and arrangement of the metal stampings and by cooperation with interior trim structure to define an overall energy absorbing pillar structure.
Turning now to FIG. 2, one preferred embodiment for the front or A-pillar 20 is illustrated as including an exterior panel 24, an interior panel 26, an intermediate panel 28, a trim cover 30, and energy absorbing media 32 disposed between the internal panel 26 and the trim cover 30.
The exterior panel 24, which is illustrated in FIG. 1, includes first and second panels 34, 36 joined together as by welding to define an outwardly concave external surface 38. First and second peripheral flange portions 40, 42 bound an outwardly concave section 44 to define a truss-like structure.
The interior panel 26 likewise includes first and second peripheral flanges portions 46, 48 positioned in facing relationship with respect to the flange portions 40, 42 of the exterior panel. A concave inward truss portion 56 extends between the flange portions 46, 48.
Sandwiched between the exterior panel 24 and interior panel 26, the intermediate panel 28 likewise includes peripheral flange portions 52, 54 which are clamped between facing peripheral flange portions of the exterior panel 24 and the interior panel 26, and may be secured thereto by welding or like fixing process. A central bridge truss portion 50 extends between the flange portions 52, 54 and in the embodiment of FIG. 2 is illustrated as being generally concave inwardly.
With the panels 24, 26, 28 so arranged, a first energy absorbing chamber 58 is defined between the exterior panel 24 and the intermediate panel 28, and a second energy absorbing chamber 60 is defined between the interior panel 26 and the intermediate panel 28.
The generally concave inward trim cover 30 is preferably formed as a molded plastic part and is secured to the joined ends of the peripheral flange portions of the panels 24, 26, 28 and defines a third energy absorbing chamber 62 between the interior surface 64 of the trim cover 30 and the exterior surface 66 of the interior panel 26. According to this preferred embodiment, the energy absorbing medium 32 is preferably configured as a plastic honeycomb structure, indicated generally at 68, of known configuration. Such honeycomb structures include a plurality of ribs, such as that indicated at 70, which extend end-for-end from the interior surface 64 of the trim cover 30 to the exterior surface 66 of the interior panel 26 and may define polygonal cells as is well known in the automotive vehicle body arts. The honeycomb structure 68 may be a separate molded part; it may also be molded integrally with cover 30 or may be fixed to cover 30 or to the interior panel 26 through mechanical means such as staking or through adhesives.
Turning next to FIG. 3, adaptation of preferred embodiment of FIG. 1 to the rear or B-pillar 18 of the vehicle 10 is illustrated. As the descriptions of the other embodiments perceived, detailed description of substantially identical components will be avoided and the drawings will be noted to refer to like parts with like numbers, preceded by the figure number of the embodiment being described. In the B-pillar embodiment of FIG. 3, it is to be noted that an intermediate panel 72 is configured to be generally concave outward and parallel to the exterior panel 324. The remainder of the construction is substantially identical to the A-pillar construction of FIG. 2. The exterior panel 324 and the interior panel 326 are joined with the intermediate panel 72 at peripheral flange portions, and a first chamber 358 and a second chamber 360 are formed between these stamped panels. A third chamber 362 is formed between the panel 326 and the molded plastic trim cover 330, and molded plastic honeycomb structure 368, appropriately shaped to the construction of pillar 18, is provided as an energy absorbing medium.
Turning next to FIG. 4, the configuration in this embodiment for the pillar 18 is essentially identical to that in FIG. 3 save the provision of an alternative energy absorbing medium 432, preferably defined as a generally C-shaped, outward opening, resilient spring member 74. Its energy absorbing capability may be enhanced through the provision of turned-back coil portions 84, 86 positioned in juxtaposition with the interior panel 426. The spring member further includes turned-in end portions 78, 80 which are secured to peripheral flange portions 446, 448 through the application of adhesive, indicated generally at 82.
Turning lastly to FIG. 5, yet another energy absorbing medium is indicated at 532, differing from the medium 432 illustrated in FIG. 4 in that the spring member 74 may carry foam material 76 in its interior to enhance its energy absorbing capability.
In each of the embodiments shown, the energy absorbing capability of the structural pillars of the automotive vehicle 10 is improved over the prior art through the provision of three stamped metal panels and a molded plastic trim cover which together define three energy absorbing chambers, the inner one of which houses various preferred energy absorbing media.
While only certain embodiments of the pillar structure of the present invention have been shown and described, others may be occur to those skilled in the automotive vehicle body arts which do not depart from the scope of the appended claims. | An improved structure is provided for supporting pillars of automotive vehicles which provides energy absorption through provision of three stamped metallic panels (24,26,28) defining first and second energy absorbing chambers (56,58) therebetween and an interior trim cover (30) joined to all the panels and defining a third chamber (62) between it and the interior of the three panels and selected energy absorbing media carried between the trim cover and the interior of the panels. Generally C-shaped spring structures (74) and plastic honeycomb structures (68) are preferred for the energy absorbing media. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention concerns a method of sensitizing multidrug resistant (MDR) cells to antitumor agents using phenothiazines (PTZs) and thioxanthenes.
2. Background of the Invention
Phenothiazines and structurally related antipsychotic agents inhibit several cellular enzymes and block the function of critical cellular receptors (Roufogalis, B. D. "Specificity of Trifluoperazine and Related Phenothiazines for Calcium Binding Proteins", In: W. Y. Cheung (ed.) Calcium and Cell Function, Vol III, pp. 129-159, New York, Academic Press, 1982; Pang D. C. and Briggs, F. N., "Mechanism of Quinidine and Chlorpromazine Inhibition of Sarcotubular ATPase Activity, Biochem. Pharmacol., 25, 21-25, (1976); Ruben, L. and Rasmussen, H., "Phenothiazines and Related Compounds Disrupt Mitochondrial Energy Production by a Calmodulin-Independent Reaction", Biochim. Biophys.Acta., 637, 415-422 (1981); Creese, I., and Sibley, D. R., "Receptor Adaptations to Centrally Acting Drugs", Ann.Rev. Pharmacol. Toxicol., 21, 357-391, (1980)).
Prominant among the cellular targets is calmodulin (CaM), the multifunctional calcium binding protein (Levin, R. M., and Weiss, B., "Mechanism By Which Psychotropic Drugs Inhibit Adensine Cyclic 3',5'-monophosphate PDE of Brain", Mol. Pharmacol., 12, 581-589 (1976)).
CaM has been implicated in the regulation of numerous cellular events (Manalan, A. S. and C. B. Klee, "Calmodulin", Advances In Cyclic Nucleotide Protein Phosphorylation Res., 18,227-278 (1984) including that of normal (Veigl, M. L. Vanaman, T. C., and Sedwick, W. D., "Calcium and Calmodulin in Cell Growth and Transformation", Biochem. Biophys. Acta., 738, 21-48, (1984)) and abnormal cellular proliferation (Hait, W. N. and Lazo, J. S. "Calmodulin, "A Potential Target for Cancer Chemotherapeutic Agents", J. Clin. Oncol., 4, 994-1012 (1986)); Rasmussen, C. D. and Means, A. R., "Calmodulin - Regulation of Cell Proliferation", EMBO, 6, 3961-3968 (1987); Wei, J. W., R. A. Hickie, and D. J. Klaassen, "Inhibition of Human Breast Cancer Colony Formation by Anticalmodulin Agents: Trifluoperazine, W-7, and W-13", Cancer Chemother. Pharmacol., 11, 86-90 (1983)). Consistent with these observations was the demonstration that PTZs and other CaM antagonists possess antiproliferative and cytotoxic effects (Ito, H., and H. Hidaka, "Antitumor Effect of a Calmodulin Antagonist on the Growth of Solid Sarcoma", 180, Cancer Lett. 19, 215-220 (1983)) that were proportional to their anti-CaM activity (Hait, W. N., Grais, L., Benz, C., Cadman, E., "Inhibition of Growth of Leukemic Cells by Inhibitors of Calmodulin: Phenothiazines and Melittin", Cancer Chemother. Pharmocol., 14, 202-205 (1985)).
The recent demonstration and elucidation of the phenomenon of multidrug resistance (MDR) has led to the search for drugs that could sensitize highly resistant cancer cells to chemotherapeutic agents. MDR is the process whereby malignant cells become resistant to structurally diverse chemotherapeutic agents following exposure to a single drug (Riordan, J. R., and V. Ling, "Genetic and Biochemical Characterization of Multidrug Resistance", Pharmol. Ther., 28., 51-75 (1985)). MDR cell lines classically have been associated with decreased drug accumulation due to enhanced efflux as well as diminished influx of chemotherapeutic drugs (Inaba M., and R. K. Johnson, "Uptake and Retention of Adriamycin and Daunorubicin by Sensitive and Anthracycline-Resistant Sublines of P388 Leukemia", Biochem. Pharmacol., 27, 2123-2130 (1978) and Fojo, A. S. Akiyama, M. M. Gottesman, and I. Pastan, "Reduced Drug Accumulation in Multiple-Drug Resistant Human KB Carcinoma Cell Lines", Cancer Res., 45, 3002-3007 (1985)). This effect appears to be attributable to the overexpression of a 170,000 dalton membrane glycoprotein (P-glycoprotein) which structurally resembles transport proteins in prokaryotic cells (Chen C., J. E. Chin, K. Ueda, C. P. Clark, I. Pastan, M. M. Gottesman, and I. B. Roninson, "Internal Duplication and Homology with Bacterial Transport Proteins in the mdrl (P-glycoprotein) Gene from Multidrug Resistant Human Cells", Cell, 47, 381-389 (1986)) and may function as an energy-dependent, drug efflux pump in mammalian cells (Hamada, H., and T. Tsuruo, "Purification of the 170- to 180-Kilodalton Membrane Glycoprotein Associated with MDR; 170-to 180-Kilodalton Membrane Glycoprotein is an ATPase, J. Biol. Chem, 263, 1454-1458 (1988) and Akiyama, S., M. M. Cornwell, M. Kuwano, I. Pastan, and M. M. Gottesman, "Most Drugs that Reverse Multidrug Resistance Inhibit Also Photoaffinity Labeling of P-glycoprotein by a Vinblastine Analog", Mol. Pharmacol., 33, 144-147 (1988)).
PTZs have been shown to be among the group of drugs known to modify MDR (Ganapathi, R., and D. Grabowski, "Enhancement of Sensitivity to Adriamycin in Resistant P388 Leukemia by the Calmodulin Inhibitor Trifluoperazine", Cancer Res., 43, 3696-3699 (1983) and Akiyama, S. N. Shiraishi, Y. Kuratomi, M. Nakagowa, and M. Kuwano, "Circumvention of Multiple-Drug Resistance in Human Cancer Cells by Thioridazine, Trifluoperazine and Chlorpromazine", J. Natl. Cancer Inst., 76: 839-844 (1986)). Although the mechanism by which PTZs and other drugs modulate MDR is not yet clear, it has been suggested that their pharmacological properties may be mediated by the calcium messenger system, since the active compounds are known to inhibit voltage-dependent calcium channels (Fleckenstein, A., "Specific Pharmacology of Calcium in Myocardium, Cardiac Pacemakers, and Vascular Smooth Muscle", Ann. Rev. Pharmacol. Toxicol., 17, 149-166 (1977), CaM and protein kinase C (Mori, T., Y. Takai, R. Minakuchi, B. Yu, and Y. Nishizuka, "Inhibitory Action of Chlorpromazine, Dibucaine, and other Phospholipid-Interacting Drugs on Calcium-activated, Phospholipid-Dependent Protein Kinase", J. Biol. Chem., 255 8378-8380 (1980).
Prozialeck, W. C. and Weiss, B., "Inhibition of Calmodulin by Phenothiazines and Related Drugs: Structure-Activity Relationships", J. Parmacol. Exp. Ther., 222, 509-516 (1982) studied the specific structural features which influence the interaction of a large number of PTZ derivatives with CaM, and showed that varying either the PTZ nucleus or the amino side chain altered activity. Specifically, ring-substitutions that increased hydrophobicity increased potency, while modifications of the type or length of the amino side chain affected potency in a manner unrelated to hydrophobicity. Similarly, studies with N-(6-aminohexyl)-1-naphthalenesulfonamide (W-5) and N-(6-aminohexyl)-5-chloro-1-naphthalenesulfonamide (W-7) (Hidaka, H., M. Asano, and T. Tanaka, "Activity-structure Relationship of Calmodulin Antagonists", Mol. Pharmacol, 20, 571-578 (1981)) and a series of 15 derivatives of W-7 (MacNeil, S., M. Griffin., A. M. Cooke, N. J. Pettett, R. A. Dawson, R. Owen, and G. M. Blackburn, "Calmodulin Antagonists of Improved Potency and Specificity for Use in the Study of Calmodulin Biochemistry", Biochem. Pharmacol., 37, 1717-1723 (1988)) demonstrated that both halogenation of the naphthalene ring with chlorine, iodine or cyano groups, and increasing the length of the alkyl side chain from 4 to 12 carbons increased their potency against CaM.
Drug binding studies with synthetic peptides and molecular modeling provided a rationale for the importance of both hydrophobicity and molecular structure for the PTZ-CaM interaction. The induction of alpha-helix formation by the binding of Ca 2+ to CaM results in two distinct regions, a hydrophobic pocket containing two aromatic phenylalanine residues (Phe 89 and 92) oriented to form a charge transfer complex with the aromatic, tricyclic nucleus of the PTZs, and a hydrophilic region at a distance of one-half helical turn formed by glutamic acid residues (Glu 83,84 and 87), which interact with the positively-charged nitrogen atom of the PTZ side chain (Reid, R. E., "Drug Interactions with Calmodulin: The Binding Site", J. Thero. Biol., 105, 63-76 (1983)).
In Johnston et al, The Lancet, Apr. 22, 1978 "Mechanism of the Anti-psychotic Effect in the Treatment of Acute Schizophrenia" pp. 842-851 (1978), a clinical trial of the antipsychotic effects of cis-flupenthixol versus trans-flupenthixol versus placebo showed that while cis-flupenthoxil was a potent neuroleptic (especially for "positive" symptoms), trans-flupenthixol had no activity as an anti-psychotic. Since trans-fluopenthixol is a far less potent dopamine antagonist, and the extrapyramidal side effects associated with antipsychotic therapy are attributed to dopamine receptor binding, trans-flupenthixol lacks these side effects. The apparent lack of anti-psychotic activity or extrapyramidal side effects of trans-flupenthixol make it particularly attractive for use as an anti-multidrug resistance agent, since it is these side effects which have proven problematic in reported trials of phenothiazines plus doxorubicin.
Flupenthixol is disclosed in U.K. Patent 925,538 as having utility as a tranquilizer, ataractic, antiemetic, antihistamine, antispasmodic and general central nervous system depressant. No mention is made of any antitumor activity.
Several thioxanthene derivatives are disclosed in U.K. Patent 863,699 as tranquilizers. Again, no mention of anti-tumor activity is made.
Robin L. Miller, et al, Journal of Clinical Oncology, Vol 6, No. 5, May 1988, 880-888 demonstrated the possible effectiveness of trifluperazine (a phenothiazine) in combination with doxorubicin in a Phase I/II trial in clinically resistant cancer in humans. The dose limiting factor in these trials was the extrapyramidal side effects associated with trifluperazine.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method to sensitize multidrug resistant cells to antitumor agents.
The above object and other objects, aims and advantages are satisfied by the present invention.
The present invention concerns a method for sensitizing multidrug resistant cells to antitumor agents comprising contacting multidrug resistant cells with an effective amount of a compound of the formula ##STR3## wherein n is 1, 2, 3 or 4, X is selected from the group consisting of CF 3 ,--O--CF 3 , Br, I, Cl, C═N and S--CH 3 , and R 1 and R 2 , independent of one another are --CH 3 , --CH 2 --CH 3 , CH 2 OH, H, and CH 2 CH 2 OH or N R 1 R 2 form a ##STR4## wherein R 3 is --CH 3 , --CH 2 --CH 3 , --H, CH 3 OH-- and CH 2 CH 2 OH.
X is preferably CF 3 and n is preferably 3.
R 1 and R 2 with the nitrogen atom they are bound to preferably form the following six membered heterocyclic rings: ##STR5##
Preferred compounds for use in the present invention are as follows: ##STR6## wherein A is CH 3 or CH 2 CH 2 OH.
The structural characteristics of such preferred compound include a hydrophobic thioxanthene ring nucleus with a CF 3 substitution at position 2, an exocyclic double bond in the trans configuration and a piperazinyl side chain amine with a para-terminal methyl group joined by a 4 carbon alkyl bridge to the ring nucleus.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph depicting the correlation between absorbance (A 600 ) of stained cellular protein and cell count. Each point represents the mean of quadruplicate determinations. Bars represent the standard error when greater than the symbol.
FIG. 2 are four graphs (A, B, C and D) which depict the relationship between hydrophobicity and activity of phenothiazine derivatives as antiproliferative and anti-MDR agents. FIG. 2A and FIG. 2B represent the correlation between octanol: buffer partition coefficients, as determined by Prozialcek and Weiss, supra, and the IC 50 's for inhibition of cell growth (r=-0.73, p=0.016) and antagonism of MDR (r=0.86, p=0.0015) for a series of phenothiazine derivatives with ring-substitutions (values from Table 1 hereinbelow). FIG. 2C and FIG. 2D represent the lack of correlation between octanol: buffer partition coefficients and IC 50 's for inhibition of cell growth (r=0.54, p=0.27) and antagonism of MDR (r=0.59, p=0.21) for a series of 2-Cl substituted phenothiazine derivatives with side chain alterations (values from Tables 2 and 3 hereinbelow). Numbered points represent: (1) promazine, (2) 1-chloropromazine, (3) chlorpromazine, (4) 3-chlorpromazine, (5) 4-chlorpromazine, (6) 7-hydroxychlorpromazine, (7) 3,8-dihydroxychlorpromazine, (8)7,8-dihydroxychlorpromazine, (9) thiomethylpromazine, (10) trifluopromazine, (11)2-chloro-10 -[2-(dimethylamino)ethyl]phenothiazine,(12)2-chloro-10-4-(dimethylamino)butyl]phenothiazine, (13) didesmethylchlorpromazine, (14) desmethylchlorpromazine, and (15) chlorproethazine.
FIG. 3 are two graphs depicting the relationship between anti-calmodulin activity and antiproliferative or anti-MDR activity for phenothiazine derivatives. FIG. 3A represents the correlation between the IC 50 's for inhibition of calmodulin-induced activation of phosphodiesterase and the IC 50 's for inhibition of cell growth (r=0.58, p=0.0009) for 27 phenothiazine derivatives (values from Tables 1-5 hereinbelow). FIG. 3B represents the lack of correlation between the IC 50 's for inhibition of calmodulin-induced activation of phosphodiesterase and antagonism of MDR (r=-0.02, p=0.91) for the same group of phenothiazine derivatives (values from Tables 1-5 hereinbelow).
FIG. 4 is a graph depicting the effect on the sensitivity of MDR cells to doxorubicin by phenothiazines and structurally related modifiers. MCF-7/DOX cells (MCF-7 is a human breast cancer cell line and MCF-7/DOX is its multidrug resistant subclone) were exposed to 0-100 μM doxorubicin for 48 hours in the absence ( ) or presence of fluphenazine (10 ), cis-flupenthixol(o), or trans-flupenthixol ( ) at concentrations that alone produced 10% inhibition of cell growth. Cell growth was determined by a microtiter assay.
FIG. 5 is a series of bar graphs depicting the effect of thioxanthene isomers on the accumulation of doxorubicin in sensitive MCF-7 and MDR MCF-7/DOX cells. Cells were incubated for 3 hours with 15 μM doxorubicin in the absence (A) or presence of 3 μM cis-flupenthixol(B) or 6 μM trans-flupenthixol(C). Cell associated doxorubicin was determined spectra-fluorometrically. Values are means from duplicate determinations.
FIG. 6 is a graph depicting an isobologram analysis of the synergistic interaction between doxorubicin and trans-flupenthixol. IC 50 isobole for inhibition of MCF-7/DOX cell growth by various combinations of doxorubicin and trans-flupenthixol ( ) was determined by exposing cells to drug combinations for 48 hours. The straight line represents the predicted IC 50 isobole for drugs which have additive antiproliferative effects. 12μM doxorubicin and 25 μM trans-flupenthixol alone caused 50% inhibition of cell growth.
DETAILED DESCRIPTION OF THE INVENTION
Compounds for use in the present invention having the general formula ##STR7## wherein X, R 3 , R 1 , R 2 and n are preferably as defined below (in order of preference):
______________________________________X R.sup.3 R.sup.1 +/or R.sup.2 n______________________________________--CF.sup.3 --CH.sub.3 --CH.sub.2 --CH.sub.3 3--Cl --CH.sub.2 CH.sub.2 OH --CH.sub.2 OH 2--O--CH.sub.3 --CH.sub.2 CH.sub.3 --CH.sub.3 4--Br --H --H--I CH.sub.2 OH CH.sub.2 CH.sub.3 OH--CN--S--CH.sub.3______________________________________
The results presented herein demonstrate that small changes in the molecular design of the PTZs result in a wide range in their subsequent activity as inhibitors of cell growth and antagonists of MDR, and that these effects appear to be mediated by different mechanisms.
The data presented herein identify certain structural features of the PTZ molecule that affect its activity against cellular proliferative and MDR agents.
Specifically, increasing the hydrophobicity of the PTZ nucleus increased potency against cellular proliferation and against MDR, whereas decreasing the hydrophobicity decreased potency (See Table 1 hereinbelow). Thus, the --CF 3 substituted compounds were the most potent drugs, whereas --OH substituted compounds were the least potent drugs. Chlorpromazine sulfoxide, the oxidative metabolite of chlorpromazine, lost most of its antiproliferative effect. However, it retained its effect against MDR, suggesting that first-pass hepatic metabolism of these drugs may not present a major impediment to their clinical use.
The type of amino group also affected potency against MDR but not against cellular proliferation. For example, tertiary amines were more potent than primary or secondary amines, and piperazinyl amines were more potent than non-cyclic groups Moreover, piperazinyl structures that possessed a para-methyl group had consistently greater activity than others (See Table 2 hereinbelow).
The distance between the amino group and the PTZ nucleus was important for both inhibition of cell growth and antagonism of MDR. A four carbon chain was superior to alkyl bridges of shorter lengths (See Table 3 hereinbelow).
It has been postulated that the effects of PTZs on cells may be due solely to non-specific membrane interactions resulting from their high degree of lipophilicty (Roufogalis, B. D., "Comparative Studies on the Membrane Actions of Depressant Drugs: The Role of Lipophilicity in the Inhibition of Brain Sodium and Potassium-Stimulated ATPase", J. Neurochem., 24, 51-61, (1975)). A careful analysis of the relationship between hydrophobicity and inhibition of cell growth or antagonism of MDR shows that though a correlation exists for ring-substituted PTZ derivatives (FIG. 2A and FIG. 2B), there was no correlation between hydrophobicity and the resultant activity of compounds with specific side chain alterations (FIG. 2C and FIG. 2D). Thus, the degree of lipophilicity of each drug, while important, was not the sole determinant of potency for antiproliferative or anti-MDR activity. The relationship between structure and hydrophobicity of the PTZs and their antiproliferative and anti-MDR activities suggests that in these systems, similar to CaM, the PTZs interact in both a hydrophobic and electrostatic manner with a protein target. Like CaM, it is likely that this target possesses a hydrophobic domain in close proximity to a negatively-charged amino acid.
Although the site of action of PTZs and structurally related compounds for inhibition of cell growth and antagonism of MDR is not yet identified, certain conclusions are suggested from the results herein. The antiproliferative activity of these drugs used individually in the malignant breast cancer cell lines MCF-7 and MCF-7/DOX correlated with their potency as CaM antagonists (FIG. 3A), supporting previous observations with a limited number of PTZs in C 6 astrocytoma cells (G. L. Lee and W. N. Hait, "Inhibition of Growth of C 6 Astrocytoma Cells by Inhibitors of Calmodulin", Life Sci., 36, 347-354, (1985)), HCT-8 human leukemia cells, L1210 murine leukemia cells, and HCT human colonic carcinoma cells (W. N. Hait and G. L. Lee, Biochemical Pharmacology, "Characteristics of the Cytotoxic Effect of the Phenothiazine Class of Calmodulin Antagonists", 34, 3973-3978, (1985)). While these data are consistent with the role of COM in cellular proliferation (Rasmussen and Means, supra), however, the complete lack of correlation between anti-CaM activity and antagonism of MDR points toward an alternative mechanism of inhibition for the pharmacologic reversal of MDR. Thus, the effect of PTZs in potentiating anthracycline cytotoxicity in MDR cells appears to be clearly distinct from their effect on CaM. This is in contrast to conclusions reached by Ganapathi, R., Grabowski, D., Turinic, R., and Valenzuela, R., "Correlation Between Potency of Calmodulin Inhibitors and Effects on Cellular Levels of Cytoxocity Activity of Doxorubicin (Adriamycin)in Resistant P388 Mouse Leukemia Cells", Eur. J. Cancer Clin. Oncol., 20, 799-806, (1984), who compared the anti-CaM and anti-MDR activity of trifluoperazine, chlorpromazine and prochlorperazine in murine P388/DOX cells. In the context of the much larger sample size of CaM antagonists studied herein, this correlation does not remain significant.
Furthermore, the results herein demonstrate that specific structural features and stereoisomeric configurations are required for optimum activity against MDR, and that these structure-activity relationships differ from those important for the inhibition of CaM. Specifically, while the type of PTZ side chain amine group was not critical to anti-CaM activity (Prozialeck et al, supra) tertiary amines were clearly more potent anti-MDR agents than secondary or primary amines.
The information gained from the results herein allowed for the identification of drugs with certain important features for anti-MDR activity. For example, cis and trans-flupenthixol have a --CF 3 substitution at position 2 of the hydrophobic thioxanthene ring, possess a piperazinyl amino side chain, and have a 3 carbon alkyl bridge. While the thioxanthene isomers are more hydrophobic than the PTZs (octanol:buffer partition coefficients (log P) for both flupenthixol isomers=4.25 versus 4.04 for chlorpromazine) (Norman, J. A., and A. H. Drummond, "Inhibition of Calcium-Dependent Regulator-Stimulated Phosphodiesterase Activity by Neuroleptic Drugs is Unrelated to their Clinical Efficacy", Mol. Pharmacol., 16, 1089-1094 (1979)), this alone cannot explain their cellular effects. For example, they are less potent antiproliferative agents than chlorpromazine and other less hydrophobic PTZs. In addition, while the isomers are equally hydrophobic, trans-flupenthixol is a 3-fold more potent anti-MDR agent (FIG. 3) and both isomers are more potent than agents with greater hydrophobicity, such as pimozide (log P=4.88). The orientation of the side chain amine in relation to the tricyclic nucleus appeared to be an important determinant for anti-MDR activity, but not of antiproliferative activity. For example, the trans-thioxanthene isomer displayed greater activity than the cis-isomer against MDR (See Table 5 hereinbelow). Also, studies of the anti-CaM effect of the thioxanthene stereoisomers revealed no difference between cis and trans-flupenthixol (Norman J. A., and A. H. Drummond, supra).
A trivial explanation of the differences in activity observed for the thioxanthene stereoisomers would be differences in their cellular accumulation, however, it is also shown herein that MDR cells accumulate cis and trans-flupenthixol in an equivalent, dose-dependent fashion, in agreement with their nearly identical IC 50 's for inhibition of cell growth. This suggests that the difference in anti-MDR activity between these stereoisomeric thioxanthenes is due to selective differences in their ability to interact with a unique cellular target, rather than differences in their intracellular accumulation.
While the antiproliferative effects of the PTZs and related compounds were approximately equipotent in both the MCF-7 and the MCF-7/DOX malignant cell lines, the ability of these drugs to potentiate the effect of doxorubicin (See Table 5 hereinbelow) as well as their ability to increase the cellular accumulation of doxorubicin (FIG. 5 occurred only in the MDR cell line, suggesting that the latter effects were mediated through a target(s) overexpressed in MDR cells. One logical site would be the putative drug efflux pump, P-glycoprotein, the gene product encoded for by the recently cloned mdrl gene (Chen et al, supra, Gros, P., Y. Ben Neriah, J. M. Croop, and D. E. Housman, "Isolation and Expression of a cDNA (mdr) that Confers Multidrug Resistance", Nature, 323, 728-731 (1986); and Ueda K., C. Cardarelli, M. M. Gottesman, and I. Pastan, "Expression of a Full-length cDNA for the Human mdrl Gene Confers Resistance to Colchicine, Doxorubicin, and Vinblastine", Proc. Natl. Acad. Sci. USA, 84, 3004-3008 (1987)). A current hypothesis regarding the mechanism by which MDR cells reduce cellular accumulation of anthracyclines is through increased expression of this plasma membrane glycoprotein in MDR cells (Riordan and Ling, supra) and that compounds which antagonize MDR compete with cytotoxic drugs for specific drug binding sites on the protein (Cornwell, M. M., I. Pastan, and M. M. Gottesman, "Certain Calcium Channel Blockers Bind Specifically to Multidrug Resistant Human KB Carcinoma Membrane Vesicles and Inhibit Drug Binding to P-glycoprotein", J. Biol. Chem., 262, 2166-2170) (1978). Though calcium channel blockers can inhibit binding of a photoaffinity labelled vinblastine analog to P-glycoprotein, phenothiazines were far less effective (Akiyama et al, supra). However, the failure of PTZs to block vinblastine binding to the mdrl gene product does not rule out the interaction with other sites on the protein. For example, Hamada and Tsuruo have recently demonstrated ATPase activity of the molecule (Hamada and Tsuruo, supra). Since the ATP binding site is at a different location than the putative drug binding region, and since PTZs are known to inhibit other ATPases (Pang and Briggs, supra and Raess, B. U., and F. F. Vincenzi, "Calmodulin Activation of Red Blood Cells (Ca 2+ +Mg 2+ )-ATPase and Its Antagonism by Phenothiazines", Mol. Pharmacol., 18, 253-258 (1980)), it is possible that they interfere with this aspect of P-glycoprotein's proposed function. Alternatively, Center (Center, M. C., "Mechanisms Regulating Cell Resistance to Adriamycin", Biochem. Pharmacol., 34, 1471-1476 (1985)) demonstrated that trifluoperazine increased phosphorylation of this protein in MDR Chinese hamster lung cells and enhanced doxorubicin accumulation and cytotoxicity, suggesting the PTZs may indirectly affect P-glycoprotein. Finally, the lack of direct correlation between the increase in doxorubicin accumulation and increase in sensitivity of MCF-7/DOX cells in the examples herein (FIG. 5) suggests that the thioxanthenes may exert their effect through more than one mechanism.
Several groups have suggested that protein kinase C may play an important role in MDR (Ido, M., T. Asao, M. Sakurai, M. Inagaki, M. Saito, and H. Hidaka, "An Inhibitor of Protein Kinase C, 1-(5-isoquinolinylsulfonyl)-2-methylpiperazine (H-7) Inhibits TPA-induced Reduction of Vincristine Uptake from P388 Murine Leukemic Cell", Leukemia Res , 10, 1063-1069 (1986) and Ferguson, P. F., and Y. Cheng, "Transient Protection of Cultured Human Cells Against Antitumor Agents by 12-O-tetradecanoylphorbol-13-acetate", Cancer Res., 47, 433-441 (1987)). Drugs that stimulated PKC, such as the phorbol esters, produce increased levels of anthracycline resistance in MCF-7/DOX cells, and induce a MDR-like phenotype in sensitive MCF-7 cells (Fine, R. L., J. Patel, and B. A. Chabner, "Phorbol Esters Induce Multidrug Resistance in Human Breast Cancer Cells", Proc. Natl. Acad. Sci. USA, 85, 582-586 (1988)). These effects were reversed by trifluoperazine at concentrations similar to those used in the present study. Furthermore, the MCF-7/DOX cell line had up to a 15-fold increased level of PKC activity compared to the parental MCF-7 cells (Fine et al, supra and Palayoor, S. T., J. M. Stein, and W. N. Hait, "Inhibition of Protein Kinase C by Antineoplastic Agents: Implications for Drug Resistance", Biochem. Biophys. Res. Commun., 148, 718-725 (1987)). Results from studies utilizing the isoquinolinesulfonamide derivative, H-7, a relatively specific PKC inhibitor, were ambiguous with regard to the possible anti-MDR effect of inhibiting PKC. While some reported that H-7 failed to sensitize L1210/DOX cells (Ganapathi, R., and D. Grabowski, "Differential Effect of the Calmodulin Inhibitor Trifluoperazine in Modulating Cellular Accumulation, Retention and Cytoxicity of Doxorubicin in Progressively Doxorubicin-Resistant L1210 Mouse Leukemia Cells", Biochem. Pharmacol., 37, 185-193 (1988)), others found that it does sensitize KC/ADR 10 human breast cells (Ahn, C.-H., R. L. Fine, and W. B. Anderson, "Possible Involvement of Protein Kinase C in the Modulation of Multidrug Resistance", Proc. Am. Assoc. Cancer Res., 29, 1182(1988)). When studied in isolated systems, the concentrations of PTZs required to inhibit PKC (Schatzman, R. C., B. C. Wise, and J. F. Kuo, "Phospholipid-sensitive Calcium-Dependent Protein Kinase: Inhibition by Anti-Psychotic Drugs", Biochem. Biophys. Res. Commun., 98, 669-676 (1981)) are many fold higher than those which were found sufficient to antagonize MDR. For example, the IC 50 's for inhibition of PKC by trifluoperazine, chlorpromazine and fluphenazine were 10 to 50-fold greater than those found to antagonize MDR (See Table 4 hereinbelow). The thioxanthenes are particularly poor inhibitors of PKC, having IC 50 's of 335 to more than 1000 μM (Scatzman, R. C., B. C. Wise, and J. F. Kuo, supra.) whereas concentrations of 3.5 to 10 μM trans-flupenthixol caused a 15 to 37-fold antagonism of MDR. Thus, while the activation and inhibition of PKC offers an attractive hypothesis for the modulation of MDR, it appears that the anti-MDR effects of the PTZs and thioxanthenes are not likely to be mediated solely through this enzyme.
Specific structure-activity relationships for PTZs and thioxanthenes as antiproliferative agents in malignant cells, and as antagonists of MDR in a human breast cancer cell line has been demonstrated herein, suggesting ideal structures for more potent and less toxic compounds. Inhibition of CaM has been shown herein to correlate with the antiproliferative effect of PTZs but a lack of correlation between CaM antagonism and anti-MDR activity has been found, suggesting that the ability of these drugs to reverse MDR is not through interactions with CaM, but through another, as yet unidentified cellular target. Furthermore, it has been shown herein the effect of PTZs in sensitizing cells to doxorubicin to occur only in MDR cells, implying that this target is overexpressed in cells of this phenotype. Finally, these structure-activity relationships have been used to identify a thioxanthene stereoisomer, trans-flupenthixol, which possesses greater activity against MDR in vitro than the previously believed most effective PTZ, trifluoperazine.
Trans-flupenthixol may prove to be particularly suited for clinical use against MDR tumors. Clinical trials of the antipsychotic effects of flupenthixol in humans showed that while cis-flupenthixol was far more effective than trans-flupenthixol, the latter was far less toxic (Johnston, E. C., T. J. Crew, C. D. Frith, M. W. D. Carney and J. S. Price, supra). This observation may be explained by biochemical and crystallographic evidence that cis-flupenthixol is a powerful antagonist of dopamine receptors (Huff, R. M. and B. Molinoff, "Assay of Dopamine Receptors With [alpha- 3 H]Flupenthixol", J. Pharmacol. Exp. Ther., 232, 57-61 (1984) and Post, M. L., U. Kennard, A. S. Horn, "Stereoselective Blockade of the Dopamine Receptor and the X-ray Structures of Alpha and Beta-flupenthoxil", Nature, 256, 342-343 (1975)), whereas trans-flupenthixol, which displays the greater potency against MDR, has virtually no activity as a dopamine antagonist. This lack of anti-dopaminergic activity may explain the apparent lack of extrapyramidal side effects seen with this agent (Nielsen, I. M., V. Pedersen, M. Nymark, K. F. Franck, V. Boeck, B. Fjalland, and A. V. Christensen, "Comparative Pharmacology of Flupenthixol and Some Reference Neuroleptics", Acta.Pharmacol. Toxicol. (Copenh)., 33, 353-362 (1973)). Extrapyramidal side effects have proven to be dose limiting in Phase I trials that combined trifluoperazine with bleomycine (Hait, W. N., J. S. Lazo, D.-L. Chen, and V. Gallicchio, "Preclinical and Phase I-II Studies of Bleomycin (BLEO) With Calmodulin-Antagonist (CaM-A)", Proc. Am. Assoc. Cancer Res., 26, 1283 (1985)) or doxorubicin (Miller, R. L., R. M. Bukowski, G. T. Budd, J. Purvis, J. K. Weick K. Shepard, K. K. Midha, and R. Ganapathi, supra).
The invention will now be described with reference to the following non-limiting examples.
EXAMPLES
Example 1
Cell Lines and Culture
MCF-7 human breast cancer cells, and the multidrug resistant subclone MCF-7/DOX selected by stepwise exposure of parental cells to increasing concentrations doxorubicin, were maintained in exponential growth in 75 cm 2 culture flasks RPMI 1640 medium supplemented with 5% fetal bovine serum in a humidified atmosphere of 5% CO 2 and 95% air. MCF-7/DOX cells were approximately 200-fold more resistant to doxorubicin than the parental cell line, and maintained a stable MDR phenotype while grown in drug free medium for a period of at least 3 months. Cell lines were routinely tested and found to be free of contamination by mycoplasma or fungi.
Example 2
Effect on Drugs on Cell Growth and MDR
Cells in exponential growth were trypsinized (0.5% trypsin in phosphate-buffered saline), disaggregated into single cell suspensions, counted electronically (Coulter, Hialeah, Fla.), and dispensed in 100 μl volumes into 96-well microtiter plates with a multichannel pipet (Flow Labs, Titertek) at a concentration of 0.5-1.0×10 4 cells per well. Cells were allowed to attach to the plastic and to resume growth for 24 hours prior to the addition of 100 μl of drug-containing medium. Drugs were dissolved in small amounts of sterile water or 1% DMSO (final culture concentration<0.05% DMSO) before dilution with medium. Controls were exposed to vehicle-containing medium.
Following a 48 hour incubation at 37° C., the supernatants of each well were gently aspirated, and cells were fixed and stained with 100 μl of 0.5% methylene blue (Sigma) in 50% ethanol (w/v) for 30 minutes at room temperature, as described in Finlay, G. J., B. C. Baguley, and W. R. Wilson, "A Semiautomated Microculture Method for Investigating Exponentially Growing Carcinoma Cells", Anal. Biochem, 139, 272-277 (1984).
Unbound stain was removed by decanting and subsequent emersion in three, one-liter washes of distilled, deionized water. The plates were dried for 12 hours and stained protein solubilized with 200 μl of sodium N-lauroyl sacrosine (Fluka, Switzerland) solution (1% v/v in PBS). The optical density of each well was determined by absorbence spectrophotometry at a wavelength of 600 nm, using a microculture plate reader (Titertek Multiscan MCC/340) interfaced to an Apple IIe computer. Inhibition of cell growth was expressed as a percentage of absorbance of drug-free control culture.
To determine the optimal conditions for this assay, plates were innoculated in duplicate with various initial cell concentrations. One half plate was assayed daily for five consecutive days by standard trypsinazation and electronic counting, while the other half of each plate was stained as described above. FIG. 1 demonstrates the linear correlation between A 600 from stained wells and actual cell number for the MCF-7/DOX cell line with final cell concentrations between 0-50,000 cells per well. (MCF-7/DOX cells were grown in 96-well microtiter plates at initial concentrations of 10,000 cells/well and enumerated after 24, 48, 72, 96 and 110 hours incubations by either absorbance spectrophotemetry or with a Coulter Counter). Similar results were obtained for the sensitive cell line. Final assay conditions were chosen to ensure that optical density measurements fell on the linear portion of this curve. This screening system has proven extremely reproducible, with less than 5% variability between IC 50 values from dose-response curves to doxorubicin from different experiments run on different days.
The effect of PTZs or related drug alone on cell growth was examined by exposing cells to 0-100 μM drug as described above with each condition repeated in quadruplicate. IC 50 was the concentration of drug that reduced staining (A 600 ) of 50% of vehicle treated controls. Final IC 50 values represent the average of between 3 and 5 separate experiments which differed by less than 10%.
The effect of PTZs on MDR was studied by exposing cells to 0-100 μM doxorubicin in the absence or presence of a concentration of a PTZ derivative that alone produced 10% inhibition of cell growth. Dose-response curves were corrected for the 10% inhibition of cell growth caused by the PTZs alone. The MDR Ratio was defined as the ratio of the IC 50 doxorubicin alone divided by the IC 50 for doxorubicin in the presence of modifier. This ratio represents the increase in apparent potency of doxorubicin produced cell by each PTZ derivative. MDR Ratio=IC 50 alone÷IC 50 DOX+drug.
Example 3
Isobologram Analysis
After determining the IC 50 concentrations for doxorubicin and individual MDR modifiers in MCF-7/DOX cells, a series of dose-response curves to a single modifier in the presence of fixed concentrations of doxorubicin were determined by the microtiter assay system described above. The concentration of doxorubicin plus modifier that together resulted in 50% inhibition of MCF-7/DOX cell growth were plotted and the IC 50 isobole compared to the predicted line of additivity, using criteria described in Berenbaum, M. C., "Criteria for Analyzing Interactions Between Biologically Active Agents", Adv. Ca. Res., 35, 269-335, (1981).
Example 4
Cellular Accumulation of Derivatives
Duplicate aliquots of 3×10 6 MCF-7/DOX cells in a total volume of 2 ml were incubated at 37° C. for 3 hours in the presence of 0-100 μM of each drug. Cells were washed three times in cold PBS by centrifugation at 100× g for 10 minutes, resuspended in 2 ml of 0.3N HCl in 50% ethanol, and sonicated for 10 pulses at 200 ws with a Tekmar cell sonicator (Tekmar, Cincinnati, Ohio). Following centrifugation at 1000× g for 30 minutes, the supernatant was removed and assayed for drug content with a Perkin-Elmer 512 spectrofluorometer (Norwalk, Conn.). Optimal excitation and emission wavelengths for both thioxanthene isomers were determined to be 320 nm and 400 nm, respectively. Cellular drug content (nM/10 6 cells) was computed from standard curves prepared with known amounts of drug in 0.3N HCl in 50% ethanol.
Example 5
Cellular Accumulation of Doxorubicin
Duplicate aliquots of 3×10 6 MCF-7 or MCF-7/DOX cells in a total volume of 2 ml were incubated at 37° C. for 3 hours with 15 μM, 1/5μM or 0.15 μM doxorubicin in the absence or presence of either 3 μM cis-flupenthixol or 6 μM trans-flupenthixol (concentrations which alone produce 10% inhibition of cell growth). Cells were washed in cold PBS, extracted with 0.3N HCl in 50% ethanol, sonicated and centrifuged as described above. Supernatants were removed and assayed fluorometrically for doxorubicin content using excitation and emission wavelengths of 470 nm and 585 nm, respectively, as described in Ganapathi et al., supra. Cellular content of doxorubicin was computed from standard curves prepared with known amounts of doxorubicin. The presence of thioxanthene isomers was shown not to effect the spectrofluometric activity of doxorubicin.
Example 6
Drugs
Doxorubicin, obtained by Adria Labs was freshly prepared in distilled water for each experiment. Phenothiazine derivatives and related drugs were obtained as follows: chlorpromazine hydrochloride, trifluoperazine dihydrochloride, chlorpromazine sulfoxide hydrochloride, 2-chloro-10-[2-(dimethylamino)ethyl]phenothiazine hydrochloride, 2-chloro-10-[4-(dimethylamino)butyl]phenothiazine hydrochloride, promazine hydrochloride, trifluopromazine hydrochloride, 2-thiomethylpromazine hydrochloride, 1-chloropromazine hydrochloride, 3-chloropromazine hydrochloride, 4-chloropromazine hydrochloride and prochlororperazine ethanesdisulfonate from Smith Kline and French Laboratories (Philadelphia, Pa.); 7-hydroxychlorpromazine, 3,8-dihydroxychlorpromazine, 7,8-dihydroxychlorpromazine, desmethylchlorpromazine hydrochloride and didesmethylchlorpromazine hydrochloride from the National Institute of Mental Health (Bethesda, Md.); promethazine hydrochloride from Wyeth Laboratories (Radnor, Pa.); chlorproethazine hydrochloride from Rhone-Poulenc (Paris, France); imipramine hydrochloride and 2-chloroimipramine hydrochloride from Geigy Pharmaceuticals (Summit, N.J.); haloperidol, pimozide, penfluridol and 4-(4-chloro,α,α,α-trifluoro-m-tolyl-1-[4,4-bis(p-flourophenyl)butyl]-4-piperidinol (R-6033) from Janssen Pharmaceutica (Beerse, Belgium); quinacrine dihydrochloride from Sterling-Winthrop Research Institute (Renssalear, N.Y.); fluphenazine from E. R. Squibb and Sons; cis and trans-flupenthixol from H. Lundbeck (Copenhagen, Denmark); and perphenazine from Sigma (St. Louis, Mo.).
Example 7
Effect of Modifying the Phenothiazine Nucleus on Cell Growth and MDR
Table 1 shows the structures, IC 50 values for cell growth inhibition and MDR Ratios for a series of promazine derivatives having different substitutents on the PTZ nucleus.
TABLE 1__________________________________________________________________________ ##STR8## Cell Growth Inhibition MDRSubstituent Position Name IC.sub.50 (μM) Ratio__________________________________________________________________________ Promazine 26 1.2Cl 1 1-Chlorpromazine 21 1.3Cl 2 Chlorpromazine 8 1.6Cl 3 3-Chlorpromazine 10 1.3Cl 4 4-Chlorpromazine 15 1.4Cl; OH 2; 7 7-Hydroxychlorpromazine 50 1.0Cl; OH; OH 2; 3; 8 3.8-Dihydroxychlorpromazine 400 0.9Cl; OH; OH 2; 7; 8 7,8-Dihydroxychlorpromazine 63 0.8SCH.sub.3 2 Thiomethylpromazine 20 1.5CF.sub.3 2 Trifluopromazine 16 2.0O 5 Chlorpromazine Sulfoxide 500 2.2__________________________________________________________________________
Inhibition of cell growth was determined by exposing MCF-7/DOX cells to 0-100 μM of each PTZ derivative. IC 50 is the concentration that produced 50% inhibition of cell growth as measured by a microtiter assay system described in methods. To determine the MDR Ratio, MCF-7/DOX cells were exposed to 0-100 μM doxorubicin in the presence or absence of phenothiazine at a concentration which alone produced 10% inhibition of cellular growth. MDR Ratio is the IC 50 for doxorubicine alone divided by the IC 50 doxorubicin in the presence of phenothiazine. All values represent the mean of at least two separate experiments having less than 5% variation between them; each experiment was run in quadruplicate (this also holds true for Tables 2, 3 and 5 hereinbelow).
The unsubstituted PTZ, promazine, inhibited cell growth (IC 50 =26 μM), and sensitized MCF-7/DOX cells to doxorubicin by only 20% (MDR Ratio=1.2). However, substitution of a chlorine at positions 1, 2, 3 or 4 increased potency against cell growth by up to 3-fold, with the most potent compound (chlorpromazine) having a chlorine at position 2 (IC 50 =8 μM). Substituting the chlorine moiety at position 2 also had the greatest effect against MDR, with chlorpromazine sensitizing resistant cells to doxorubicin by 60% (MDR Ratio=1.6). Similarly, substitution at position 2 with a CF 3 group also increased potency against cell growth and MDR. Accordingly, trifluopromazine was 1.6-fold more potent than promazine in inhibiting cell growth (IC 50 =16 μM), and was 67% more potent against MDR (MDR Ratio=2.0). Conversely, adding an --OH group decreased the potency of both effects. For example, 7-hydroxychlorpromazine was 6-fold less potent than chlorpromazine in inhibiting cell growth, while the dihydroxylated analogs 7,8 and 3,8 dihydroxychlorpromazine were up to 50-fold less potent as cell growth inhibitors, with IC 50 's of 63 uM and 400 μM, respectively. In addition, the hydroxylated analogs had no activity against MDR, and further increased resistance to doxorubicin (MDR Ratios<1.0). Oxidation of the bridge sulfur to produce chlorpromazine sulfoxide markedly reduced antiproliferative activity (IC 50 =500 μM), but increased activity against MDR (MDR Ratio=2.2).
Example 8
Effect of Modifying the Side Chain Amino Group on Cell Growth and MDR
To determine the structural importance of the side chain amino group, PTZs possessing different types of amino groups and side chains of varying lengths were studied. Table 2 hereinbelow shows that PTZs containing tertiary amines (chlorpromazine and chlorproethazine), secondary amines (desmethylchlorpromazine), and primary amines (didesmethylchlorpromazine) possess similar activity in inhibiting cell growth (IC 50 's=8-12 μM). However, PTZs having tertiary amines were clearly more potent antagonists of MDR than those with secondary or primary amines, producing a 1.6 to 2.2-fold increase in sensitivity to doxorubicin in MDR cells.
TABLE 2__________________________________________________________________________ ##STR9## Cell Growth Inhibition MDRX R Name IC 50 (μM) Ratio__________________________________________________________________________Cl NH Didesmethylchlorpromazine 11 1.1Cl NHCH.sub.3 Desmethylchlorpromazine 8 1.2Cl##STR10## Chlorpromazine 8 1.6Cl##STR11## Chlorproethazine 12 2.2Cl##STR12## Perphenazine 32 2.0Cl N NCH.sub.3 Prochlorperazine 22 2.6CF.sub.3##STR13## Trifluopromazine 14 2.0CF.sub.3##STR14## Fluphenazine 33 2.5CF.sub.3##STR15## Trifluoperzine 19 3.1__________________________________________________________________________
For example, the IC 50 's of chlorpromazine and desmethylchlorpromazine were equal (8 μM), whereas chlorpromazine was more potent than desmethylchlorpromazine against MDR (MDR ratios=1.6 and 1.2, respectively). Other changes in the type of amino group also affected anti-MDR activity. For example, piperazinyl derivatives increased potency against MDR. Accordingly, the MDR ratios for trifluoperazine (3.1) and fluphenazine (2.5), compounds with piperazinyl amino side chains, were greater than that of trifluopromazine (2.0), a compound with an identical hydrophobic ring-substitution, but possessing an aliphatic side chain. Similarly, perphenazine and prochlorperazine (MDR ratios=2.0 and 2.6) were more potent antagonists of MDR than chlorpromazine (MDR ratio=1.6). This series also points out the importance of the --CF 3 substitution at position 2 for anti-MDR activity. For example, the MDR Ratio for trifluoperazine (3.1) was greater than that of prochlorperazine (2.6). These PTZs have identical structures except that the former has a --CF 3 instead of a --Cl at position 2. A similar relationship is seen by comparing fluphenazine (2.5) to perphenazine (2.0), also identical molecules except for the --CF 3 ring substitution. Finally, a para-methyl substitution on the piperazine appeared more potent than an ethanol group for anti-MDR activity of compounds, as seen by comparing the MDR ratios for prochlorperazine (2.6) to perphenazine (2.0), or trifluoperazine (3.1) to fluphenazine (2.5).
Table 3 hereinbelow shows the effect on cell growth and MDR of a series of 10-[alkyl-dimethylamino]phenothiazines in which the length of the amino-containing side chain was varied. As can be seen, moving from a two to a four carbon alkyl bridge increased the antiproliferative and anti-MDR effects of these compounds. For example, 2-chloro-10-[4-(dimethylamino)butyl]phenothiazine, which as a four carbon chain separating the amino group from the PTZ nucelus, was a more potent antiproliferative agent (IC 50 =7 uM) and anti-MDR agent (MDR Ratio=2.0) than any of the other four compounds with two or three carbon alkyl chains. Conversely, promethazine, which has an isopropyl side chain was a less potent inhibitor of cell growth than promazine, which has a three carbon chain.
TABLE 3__________________________________________________________________________ ##STR16## Cell Growth InhibitionX R Name IC.sub.50 (μM) MDR__________________________________________________________________________ RatioCl##STR17## 2-Chloro-10-[2-(dimethylamino)ethyl] phenothiazine 1 27 1.5Cl##STR18## Chlorpromazine 8 1.6Cl##STR19## 2-Chloro-10-[4-(dimethylamino)butyl] phenothiazine 4 7 2.0##STR20## Promethazine 29 1.9H##STR21## Promazine 27 1.2__________________________________________________________________________
Example 9
Influence of Hydrophobicity of Phenothiazines on Cellular Proliferation and MDR
To determine the influence of hydrophobicity on the effect of PTZs on cellular proliferation and MDR, the octanol: buffer partition coefficients for each of the 10 ring-substituted promazine derivatives as determined by Proziolack and Weiss, supra were compared to the IC 50 's for inhibition of cell growth and to the MDR Ratios. FIGS. 1A and B demonstrate the excellent correlation between hydrophobicity and both antiproliferative activity (r=-0.73, p=0.016) and MDR antagonism (r=0.86, p=0.0015).
To determine if the differences in potency of compounds with side chain alterations were also due to changes in overall hydrophobicity, the octanol: buffer partition coefficients for each of the drugs in Tables 2 and 3 that had --Cl substitutions at position 2 of the PTZ ring were compared to their IC 50 's for inhibition of cell growth and to their MDR Rations (FIGS. 1C and D). In contrast to the results for ring-substituted PTZs, no statistically significant correlation was found between hydrophobicity and potency of compounds with side chain alterations for inhibition of cell growth (r=0.54, p=0.27) or antagonism of MDR (r=0.59, p=0.21).
Example 10
Correlation Between Anti-calmodulin Activity and Inhibition of Cellular Proliferation and MDR
To examine the role of CaM as a possible target for the effect of PTZs on cellular proliferation and MDR, the IC 50 's for the inhibition of CaM by each of the PTZs and structurally related compounds (Table 4) were compared to their potency as inhibitors of cell growth and their effect on MDR. FIGS. 2A and B show a good correlation between anti-CaM activity and antiproliferative activity (r=0.58, p=0.0009), whereas no correlation was found between anti-CaM activity and effect on MDR (r=-0.02, p=0.91).
TABLE 4______________________________________ CalmodulinCompound IC.sub.50 (μM)______________________________________Promazine 1101-Chlorpromazine 74Chlorpromazine 403-Chlorpromazine 244-Chlorpromazine 257-Hydroxychlorpormazine 683,8-Dihydroxychlorpromazine 1837,8-Dihydroxychlorpromazine 82Thiomethylpromazine 42Trifluopromazine 28Chlorpromazine sulfoxide 2200Didesmethylchlorpormazine 38Desmethylchlorpromazine 45Chlorproethazine 28Prochlorperazine 22Trifluoperazine 17Trifluopromazine 282-Chloro-10-[2-(dimethyl- 60amino)ethyl] phenothiazine2-Chloro-10-[2-(dimethyl- 40amino)butyl] phenothiazinePromethazine 340Quinacrine 42Imipramine 1252-Chloroimipramine 42Penfluridol 3Pimozide 7R-6033 40Haloperidol 65______________________________________
IC 50 values represent concentration of drug necessary to inhibit by 50% the calmodulin-induced activation of phosphodiesterase.
Example 11
Effect of phenothiazines and structurally related compounds on doxorubicin-sensitive cells
The activity of all 31 compounds against cell growth and as modulators of sensitivity to doxorubicin was examined against the doxorubicin-sensitive MCF-7 cell line. Each of the drugs tested were equally potent antiproliferative agents against the doxorubicin-sensitive cell line as compared to their activity against the resistant MCF-7/DOX cell line (data not shown). No compound sensitized the MCF-7 cells to doxorubicin.
Example 12
Drug Accumulation Studies
Whether the difference in the anti-MDR activity of the thioxanthenes could be attributed to differences in their cellular accumulation was determined. After a 3 hour incubation in 3-100 μM concentrations of each drug, cell associated cis and trans-flupenthixol concentrations (nmoles/10 6 cells) were 830±80 versus 420±80 at 3 μM, 1420±250 versus 1000±250 at 10 μM and 7000±330 versus 6000±330 at 100 μM.
The effect of the thioxanthenes on the accumulation of doxorubicin in both sensitive and MDR cell lines was also studied. FIG. 5 demonstrates that after a 3 hour incubation in 15 μM doxorubicin, MCF-7/DOX cells accumulated approximately 10-fold less doxorubicin than the sensitive cell line. The addition of 3 uM cis or 6 μM trans-flupenthixol had no significant effect on the accumulation of doxorubicin in the sensitive MCF-7/DOX line. However, they increased by 1.9 and 2.2 fold, respectively, the accumulation of doxorubicin in the resistant MCF-7/DOX cells. Similar results were found after a 3 hour incubation with 1.5 μM and 0.15 μM doxorubicin.
TABLE 5__________________________________________________________________________Effect of Compounds Structurally Related to Phenothiazines on Cell Growthand Multidrug ResistanceIC.sub.50 values for cell growth and MDR ratios were determined asdescribed in legend to Table 1. Each value representsthe mean of quadruplicate determinations. Cell Growth MDRibitionCompound Structure IC.sub.50 RatioM)__________________________________________________________________________cis-Flupenthixol ##STR22## 24 4.8trans-Flupenthixol ##STR23## 25 15.2Quinacrine ##STR24## 3 1.3Imipramine ##STR25## 19 2.52-Chloroimipramine ##STR26## 20 2.0Penfluridol ##STR27## 3 2.0Pimozide ##STR28## 50 1.3R-6033 ##STR29## 27 1.1Haloperidol ##STR30## 750 3.3__________________________________________________________________________
Example 13
Isobologram Analysis
To rigorously study the magnitude of potentiation of doxorubicin by trans-flupenthixol, their multiple drug effects were studied by isobologram analysis. FIG. 6 demonstrates the synergistic action of doxorubicin and trans-flupenthixol, evident by comparing the actual concentrations necessary for 50% inhibition of cell growth to those predicted for drugs which are simply additive.
It will be appreciated that the instant specification and claims are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention. | A method for sensitizing multidrug resistant cells to antitumor agents comprosing contacting multidrug resistant cells, with an effective amount of a compound of the formula ##STR1## wherein n is 1, 2 or 3, X is CF 3 , --O--CH 3 , Br, I, Cl, H, W and S--CH 3 and R 1 and R 2 , independently of each other are --CH 3 --CH 2 --CH 3 , CH 2 CH 2 OHCH 2 OH, or NR 1 R 2 form a ring ##STR2## wherein R 3 is --CH 3 , CH 2 --CH 3 , --H, CH 2 OH and CH 2 CH 2 OH. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for the production of particulate, propellant-containing styrene polymers. More particularly, the present invention relates to a process for producing propellant-containing styrene polymers having a reduced residual monomer content as well as a distinctly lower benzene concentration than prior art materials. The invention also relates to the product propellant-containing particulate polymers themselves, foamed particles thereof and moldings comprising these polymers.
2. Discussion of Background
Particulate foams based on styrenic polymers have achieved considerable industrial importance as packaging and heat insulating materials. These foams are produced on an industrial scale by suspension polymerization of styrene in the presence of a propellant. During processing, the particulate expandable styrene polymer (EPS) is first foamed by applying heat to give foamed particles which may then be welded in closed molds to give moldings.
The suspension polymerization of styrene to produce expandable styrene polymers is usually carried out in a discontinuous process which uses two different temperature steps and two different peroxide polymerization initiators having different half-lives. Usually, dibenzoyl peroxide is used during a first polymerization step at 80° to 90° C. and tert-butyl perbenzoate, which decomposes at a higher temperature than dibenzoyl peroxide, is used during a second polymerization step at 105° to 130° C. in order to provide a product having a residual monomer content which is as low as possible.
Unfortunately, the expandable styrene polymers produced by this process contain benzene in concentrations of 0.002 to 0.01 percent by weight, typically 0.003 to 0.005 percent by weight. While the benzene can be liberated by heat treatment of the styrene polymers during treatment processes, the benzene concentration in the finished product is still from 0.0005 to 0.001 percent by weight.
OBJECTS OF THE INVENTION
An object of the present invention is to produce expandable styrene polymers which have a distinctly reduced benzene content in order to prevent the undesired emission of benzene during any subsequent treatment processes or during use.
Another object of the present invention is the production of substantially benzene-free foamed particles and moldings.
Another object of the present invention is to provide expandable styrene polymers, foamed styrene polymers and molded styrene polymers which are substantially benzene-free.
SUMMARY OF THE INVENTION
The above objects have been achieved through the use of particular styrene-soluble peroxides in place of the second initiator used in the suspension polymerization reaction of styrene described above. Aliphatic and cycloaliphatic perketals having 4 to 8 and 6 to 8 carbon atoms in the aliphatic chain and cycloaliphatic ring, respectively in particular C-C-aliphatic and cycloaliphatic perketals like
2 2-bis(tert-butylperoxy)butene and
1,1-bis(tert-butylperoxy)cyclohexane, and also C-C-monoperoxycarbonates having 12 to 16 carbon atoms like 2-ethylhexyl tert-amyl peroxycarbonate and 2-ethylhexyl tert-butyl peroxycarbonate have been found to provide particulate EPS polymers which have an extremely low concentration of benzene and an extremely low residual monomer concentration when these perketals and/or monoperoxycarbonates are used as the second, higher temperature, initiator in the suspension polymerization reaction of styrene.
While the use of monofunctional and difunctional nonaromatic initiators in the suspension polymerization of styrene has been disclosed in Japanese published applications 56-167706 and 60-031536, the reason such initiators were used in these publications is not for lowering the benzene concentration in the polymer but for achieving a specific molecular weight distribution.
According to the present invention, the benzene content of particulate styrene polymers is reduced to values less than 0.0005 percent by weight by using one of the above-mentioned initiators during the polymerization of styrene; the polystyrene foamed particles and moldings produced from the product EPS polymers by foaming and welding, respectively, have benzene concentrations of less than 0.0002 percent by weight.
The particulate styrene polymers according to the present invention also have a substantially lower residual monomer content as compared to conventional products, such as those polymerized in the presence of tert-butyl perbenzoate. For example, 2-ethylhexyl tert-amyl peroxycarbonate and 2,2-bis(tert-butylperoxy)butane provide particulate styrene polymers with residual monomer contents of less than 0.04 percent by weight using the same polymerization process as that used with tert-butyl perbenzoate.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a process for the production of particulate expandable styrene polymers by polymerization of an aqueous suspension of styrene at temperatures of from 80° to 130° C. in the presence of conventional suspension stabilizers and 3 to 15 percent by weight of a C 3 -C 6 -hydrocarbon as propellant, in which process 0.15 to 0.5 percent by weight of dibenzoyl peroxide or of a peroxide with a comparable half-life (examples of which are dilauroyl peroxide and azoisobutyronitrile) are added and used as low temperature free radical-forming polymerization initiators and wherein 0.05 to 0.6% by weight, preferably 0.1 to 0.4% by weight, of one or more of the above-mentioned perketals and/or monoperoxycarbonates are added and used as a peroxide initiator which decomposes at higher temperature. The present invention also relates to the particulate expandable styrene polymer thus produced, foamed particles thereof and molded products thereof.
Styrene polymers according to the present invention are homopolystyrene and copolymers of styrene containing at least 50% by weight of styrene monomers. Suitable comonomers are, for example, a-methylstyrene, styrenes whose aromatic nucleus is mono- or poly-halogenated in the 2-6 positions, acrylonitrile, acrylic acid esters and methacrylic acid esters of alcohols having 1 to 8 carbon atoms and N-vinyl compounds, such as N-vinylcarbazole.
The expandable styrene polymers of the present invention contain 3 to 15 percent by weight, preferably 5 to 8 percent by weight, of known C 3 to C 6 hydrocarbons such as propane, butane, isobutane, n-pentane, 1-pentane, neopentane, hexane and cyclohexane, or mixtures of these compounds, as propellants.
The suspension stabilizers used in preparing the invention EPS polymers include organic protective colloids, such as polyvinyl alcohol, polyvinylpyrrolidone and hydroxyethylcellulose, as well as water-insoluble dispersing agents, such as finely divided tricalcium phosphate, magnesium oxide and barium phosphate; mixtures of organic protective colloids and water-insoluble dispersing agents may also be used.
The styrene polymers of the present invention can also contain effective amounts of other substances which impart specific properties to the expandable product. Examples include flameproofing agents such as tetrabromocyclooctane, hexabromocyclododecane and brominated polybutadiene, and synergists for flameproofing agents, such as dicumyl peroxide, and other free radical-forming substances which have a half-life of at least two hours at 373 K. The expandable styrene polymers can also contain additives, such as dyes and fillers, and stabilizers.
Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.
EXAMPLE
240 kg of water, 400 g of hydroxyethylcellulose, 800 g of tricalcium phosphate and 24 g of EDTA were initially introduced, as a suspending medium, into a 600 liter reactor. A solution of 960 g of dibenzoyl peroxide and 480 g of 2-ethylhexyl tert-butyl peroxycarbonate in 240 kg of styrene was added thereto as the organic phase.
The mixture was heated to 90° C. over the course of 1 hour, with stirring, and maintained at this temperature for 3.5 hours. 120 g of polyvinyl alcohol and 20.4 kg of pentane were then metered in over the course of 1 hour with simultaneous heating to 110° C. After a further 6.5 hours of polymerization time had passed the batch was cooled and discharged through a suction filter and the particulate polymer was washed with water, dried, sieved and characterized. The results are reported below:
______________________________________Yield: 253 kgK value: 53.9Monostyrene: 385 mg/kgBenzene: 4.7 mg/kgPropellant content: 6.18% by weightWater content: 0.09% by weight______________________________________
Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein. | A process for the production of particulate expandable styrene polymers which have a very low benzene concentration is described using perketal and/or monoperoxycarbonate polymerization initiators. The styrene polymers produced according to the invention can be foamed to give foamed particles and molded, if desired. | 2 |
PRIORITY INFORMATION
[0001] This application is a continuation of U.S. patent application Ser. No. 11/930,969, filed on Oct. 31, 2007, which is a divisional of U.S. Utility application Ser. No. 10/115,072, filed Apr. 4, 2002, which claims priority to Swedish Application Nos. 0101232-7, filed on Apr. 5, 2001, and 0103754-8, filed Nov. 9, 2001, and the benefit of U.S. Provisional Application Ser. No. 60/281,410, filed Apr. 5, 2001, the content of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to new peptides, in particular peptides to be used for immunization therapy for treatment of atherosclerosis, and for development of peptide based ELISA for the determination of immune response against oxidized low density lipoprotein and the diagnosis of the presence or absence of atherosclerosis.
[0004] 2. Brief Description of the Art
[0005] In particular the invention includes:
1) The use of any of the peptides listed in table 1, alone or in combination, native or MDA-modified, preferably together with a suitable carrier and adjuvant as an immunotherapy or “anti-atherosclerosis “vaccine” for prevention and treatment of ischemic 2) cardiovascular disease. 3) The use of the same peptides in ELISA for detection of antibodies related to increased or decreased risk of development of ischemic cardiovascular diseases.
[0009] Atherosclerosis is a chronic disease that causes a thickening of the innermost layer (the intima) of large and medium-sized arteries. It decreases blood flow and may cause ischemia and tissue destruction in organs supplied by the affected vessel. Atherosclerosis is the major cause of cardiovascular disease including myocardial infarction, stroke and peripheral artery disease. It is the major cause of death in the western world and is predicted to become the leading cause of death in the entire world within two decades.
[0010] The disease is initiated by accumulation of lipoproteins, primarily low-density lipoprotein (LDL), in the extracellular matrix of the vessel. These LDL particles aggregate and undergo oxidative modification. Oxidized LDL is toxic and cause vascular injury. Atherosclerosis represents in many respects a response to this injury including inflammation and fibrosis.
[0011] In 1989 Palinski and coworkers identified circulating autoantibodies against oxidized LDL in humans. This observation suggested that atherosclerosis may be an autoimmune disease caused by immune reactions against oxidized lipoproteins. At this time several laboratories began searching for associations between antibody titers against oxidized LDL and cardiovascular disease. However, the picture that emerged from these studies was far from clear. Antibodies existed against a large number of different epitopes in oxidized LDL, but the structure of these epitopes was unknown. The term “oxidized LDL antibodies” thus referred to an unknown mixture of different antibodies rather than to one specific antibody. T cell-independent IgM antibodies were more frequent than T-cell dependent IgG antibodies.
[0012] Antibodies against oxidized LDL were present in both patients with cardiovascular disease and in healthy controls. Although some early studies reported associations between oxidized LDL antibody titers and cardiovascular disease, others were unable to find such associations. A major weakness of these studies was that the ELISA tests used to determine antibody titers used oxidized LDL particles as ligand. LDL composition is different in different individuals, the degree of oxidative modification is difficult both to control and assess and levels of antibodies against the different epitopes in the oxidized LDL particles can not be determined. To some extent, due to the technical problems it has been difficult to evaluate the role of antibody responses against oxidized LDL using the techniques available so far, but, however, it is not possible to create well defined and reproducible components of a vaccine if one should use intact oxidized LDL particles.
[0013] Another way to investigate the possibility that autoimmune reactions against oxidized LDL in the vascular wall play a key role in the development of atherosclerosis is to immunize animals against its own oxidized LDL. The idea behind this approach is that if autoimmune reactions against oxidized LDL are reinforced using classical immunization techniques this would result in increased vascular inflammation and progressive of atherosclerosis. To test this hypothesis rabbits were immunized with homologous oxidized LDL and then induced atherosclerosis by feeding the animals a high-cholesterol diet for 3 months.
[0014] However, in contrast to the original hypothesis immunization with oxidized LDL had a protective effect reducing atherosclerosis with about 50%. Similar results were also obtained in a subsequent study in which the high-cholesterol diet was combined with vascular balloon-injury to produce a more aggressive plaque development. In parallel with our studies several other laboratories reported similar observations. Taken together the available data clearly demonstrates that there exist immune reactions that protect against the development of atherosclerosis and that these involves autoimmunity against oxidized LDL.
[0015] These observations also suggest the possibility of developing an immune therapy or “vaccine” for treatment of atherosclerosis-based cardiovascular disease in man. One approach to do this would be to immunize an individual with his own LDL after it has been oxidized by exposure to for example copper. However, this approach is complicated by the fact that it is not known which structure in oxidized LDL that is responsible for inducing the protective immunity and if oxidized LDL also may contain epitopes that may give rise to adverse immune reactions.
[0016] The identification of epitopes in oxidized LDL is important for several aspects:
[0017] First, one or several of these epitopes are likely to be responsible for activating the anti-atherogenic immune response observed in animals immunized with oxidized LDL. Peptides containing these epitopes may therefore represent a possibility for development of an immune therapy or “atherosclerosis vaccine” in man. Further, they can be used for therapeutic treatment of atheroschlerosis developed in man.
[0018] Secondly, peptides containing the identified epitopes can be used to develop ELISAs able to detect antibodies against specific structure in oxidized LDL. Such ELISAs would be more precise and reliable than ones presently available using oxidized LDL particles as antigen. It would also allow the analyses of immune responses against different epitopes in oxidized LDL associated with cardiovascular disease.
[0019] U.S. Pat. No. 5,972,890 relates to a use of peptides for diagnosing atherosclerosis. The technique presented in said US patent is as a principle a form of radiophysical diagnosis. A peptide sequence is radioactively labelled and is injected into the bloodstream. If this peptide sequence should be identical with sequences present in apolipoprotein B it will bind to the tissue where there are receptors present for apolipoprotein B. In vessels this is above all atherosclerotic plaque. The concentration of radioactivity in the wall of the vessel can then be determined e.g., by means of a gamma camera. The technique is thus a radiophysical diagnostic method based on that radioactively labelled peptide sequences will bound to their normal tissue receptors present in atherosclerotic plaque and are detected using an external radioactivity analysis. It is a direct analysis method to identify atherosclerotic plaque. It requires that the patient be given radioactive compounds.
SUMMARY OF THE INVENTION
[0020] The technique of the present invention is based on quite different principles and methods. In accordance with claim 1 the invention relates to fragments of apolipoprotein B for immunisation against cardiovascular disease as well as a method for diagnosing immuno reactions against peptide sequences of apolipoprotein B. Such immuno reactions have in turn showed to be increased in individuals having a developed atherosclerosis. The present technique is based in attaching peptide sequences in the bottom of polymer wells. When a blood sample is added the peptides will bind antibodies, which are specific to these sequences. The amount of antibodies bound is then determined using an immunological method/technique. In contrast to the technique of said US patent this is thus not a direct determination method to identify and localise atherosclerotic plaque but determines an immunological response, which shows a high degree of co-variation with the extension of the atherosclerosis.
[0021] The basic principle of the present invention is thus quite different from that of said patent. The latter depends on binding of peptide sequences to the normal receptors of the lipoproteins present in atherosclerotic tissue, while the former is based on the discovery of immuno reactions against peptide sequences and determination of antibodies to these peptide sequences.
[0022] Published studies (Palinski et al., 1995, and George et al., 1998) have shown that immunisation against oxidised LDL reduces the development of atherosclerosis. This would indicate that immuno reactions against oxidised LDL in general have a protecting effect. The results given herein have, however, surprisingly shown that this is not always the case. E.g., immunisation using a mixture of peptides #10, 45, 154, 199, and 240 gave rise to an increase of the development of atherosclerosis. Immunisation using other peptide sequences, e.g., peptide sequences #1, and 30 to 34 lacks total effect on the development of atherosclerosis. The results are surprising because they provide basis for the fact that immuno reactions against oxidised LDL, can protect against the development, contribute to the development of atherosclerosis, and be without any effect at all depending on which structures in oxidised LDL they are directed to. These findings make it possible to develop immunisation methods, which isolate the activation of protecting immuno reactions. Further, they show that immunisation using intact oxidised LDL could have a detrimental effect if the particles used contain a high level of structures that give rise to atherogenic immuno reactions.
[0023] WO 99/08109 relates to the use of a panel of monoclonal mouse antibodies, which bind to particles of oxidised LDL in order to determine the presence of oxidised LDL in serum and plasma. This is thus totally different from the present invention wherein a method for determining antibodies against oxidised LDL is disclosed.
[0024] U.S. Pat. No. 4,970,144 relates to a method for preparing antibodies by means of immunisation using peptide sequences, which antibodies can be used for the determination of apolipoproteins using ELISA. This is thus something further quite different from the present invention.
[0025] U.S. Pat. No. 5,861,276 describes a recombinant antibody to the normal form of apolipoprotein B. This antibody is used for determining the presence of normal apolipoprotein B in plasma and serum, and for treating atherosclerosis by lowering the amount of particles of normal LDL in the circulation.
[0026] Thus in the present invention the use of antibodies are described for treating atherosclerosis. However, contrary to the U.S. Pat. No. 5,861,276, these antibodies are directed to structures present in particles of oxidised LDL and not to the normal particle of LDL. The advantage is that it is the oxidised LDL, which is supposed to give rise to the development of atherosclerosis. The use of antibodies directed to structures being specific to oxidised LDL is not described in said US patent.
[0027] Oxidation of lipoproteins, mainly LDL, in the arterial wall is believed to be an important factor in the development of atherosclerosis. Products generated during oxidation of LDL are toxic to vascular cells, cause inflammation and initiate plaque formation. Epitopes in oxidized LDL are recognized by the immune system and give rise to antibody formation. Animal experiments have shown that some of these immune responses have a protective effect against atherosclerosis. Antibodies are generally almost exclusively directed against peptide-based structures. Using a polypeptide library covering the complete sequence of the only protein present in LDL, apolipoprotein B, the epitopes have been identified in oxidized LDL that give rise to antibody formation in man. These peptide-epitopes can be used to develop ELISAs to study associations between immune responses against oxidized LDL and cardiovascular disease and to develop an immunotherapy or anti-atherosclerosis “vaccine” for prevention and treatment of ischemic cardiovascular disease.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] FIG. 1-6 show antibody response to the different peptides prepared in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0029] A molecular characterization of the epitopes in oxidized LDL has been performed that give rise to antibody-dependent immune responses in man. The approach used takes advantage of the fact that immune reactions almost exclusively are directed against 5-6 amino acid long peptide sequences. LDL only contains one protein, the 4563 amino acid long apolipoprotein B. During oxidation apolipoprotein B is fragmented and aldehyde adducts coupled to positively charged amino acids, in particularly lysine. This means that peptide sequences not normally exposed because of the three dimensional structure of apolipoprotein B become accessible to immune cells and/or that normally exposed peptide sequences becomes immunogenic because haptenization with aldehydes.
[0030] It has thereby been determined that the following peptides, native or MDA derivatives possess such an efficiency as producing an immuno-response. These peptides are:
[0000] FLDTVYGNCSTHFTVKTRKG, (SEQ ID NO: 1) PQCSTHILQWLKRVHANPLL, (SEQ ID NO: 2) VISIPRLQAEARSEILAHWS, (SEQ ID NO: 3) KLVKEALKESQLPTVMDFRK, (SEQ ID NO: 4) LKFVTQAEGAKQTEATMTFK, (SEQ ID NO: 5) DGSLRHKFLDSNIKFSHVEK, (SEQ ID NO: 6) KGTYGLSCQRDPNTGRLNGE, (SEQ ID NO: 7) RLNGESNLRFNSSYLQGTNQ, (SEQ ID NO: 8) SLTSTSDLQSGIIKNTASLK, (SEQ ID NO: 9) TASLKYENYELTLKSDTNGK. (SEQ ID NO: 10) DMTFSKQNALLRSEYQADYE, (SEQ ID NO: 11) MKVKIIRTIDQMQNSELQWP, (SEQ ID NO: 12) IALDDAKINFNEKLSQLQTY, (SEQ ID NO: 13) KTTKQSFDLSVKAQYKKNKH, (SEQ ID NO: 14) EEEMLENVSLVCPKDATRFK, (SEQ ID NO: 15) GSTSHHLVSRKSISAALEHK, (SEQ ID NO: 16) IENIDFNKSGSSTASWIQNV, (SEQ ID NO: 17) IREVTQRLNGEIQALELPQK, (SEQ ID NO: 18) EVDVLTKYSQPEDSLIPFFE, (SEQ ID NO: 19) HTFLIYITELLKKLQSTTVM, (SEQ ID NO: 20) LLDIANYLMEQIQDDCTGDE, (SEQ ID NO: 21) CTGDEDYTYKIKRVIGNMCQ, (SEQ ID NO: 22) GNMGQTMEQLTPELKSSILK, (SEQ ID NO: 23) SSILKCVQSTKPSLMIQKAA, (SEQ ID NO: 24) IQKAAIQALRKMEPKDKDQE, (SEQ ID NO: 25) RLNGESNLRFNSSYLQGTNO, (SEQ ID NO: 26) SLNSHGLELNADILGTDKIN, (SEQ ID NO: 27) WIQNVDTKYQIRIQIQEKLQ, (SEQ ID NO: 28) TYISDWWTLAAKNLTDFAEQ, (SEQ ID NO: 29) EATLQRIYSLWEHSTKNHLQ, (SEQ ID NO: 30) ALLVPPETEEAKQVIFLDTV, (SEQ ID NO: 31) IEIGLEGKGFEPTLEALFGK, (SEQ ID NO: 32) SGASMKLTTNGRFREHNAKF, (SEQ ID NO: 33) NLIGDFEVAEKINAFRAKVH, (SEQ ID NO: 34) GHSVLTAKGMALFGEGKAEF, (SEQ ID NO: 35) FKSSVITLNTNAELFNQSDI, (SEQ ID NO: 36) FPDLGQEVALNANTKNQKIR, (SEQ ID NO: 37) as well as the non antibody-producing peptide ATRFKHLRKYTYNYQAQSSS, (SEQ ID NO: 38)
or an active site of one or more of these peptides.
Material and Methods
[0031] To determine which parts of apolipoprotein B that become immunogenic as a result of LDL oxidation a polypeptide library consisting of 20 amino acid long peptides covering the complete human apolipoprotein B sequence was produced. The peptides were produced with a 5 amino acid overlap to cover all sequences at break points. Peptides were used in their native state, or after incorporation in phospholipid liposomes, after oxidization by exposure to copper or after malone dealdehyde (MDA)-modification to mimic the different modifications of the amino acids that may occur during oxidation of LDL.
Peptides
[0032] The 302 peptides corresponding to the entire human apolipoprotein B amino acid sequence were synthesized (Euro-Diagnostica AB, Malmö, Sweden and K J Ross Petersen A S, Horsholm, Denmark) and used in ELISA. A fraction of each synthetic peptide was modified by 0.5 M MDA (Sigma-Aldrich Sweden AB, Stockholm, Sweden) for 3 h at 37° C. and in presence of Liposomes by 0.5 M MDA for 3 h at 37° C. or by 5 μM CuCl 2 (Sigma) for 18 h at 37° C. The MDA-modified peptides were dialyzed against PBS containing 1 mM EDTA with several changes for 18 h at 4° C. The modification of the peptides was tested in denatured polyacrylamide gels (Bio-Rad Laboratories, Hercules, Calif.), suitable for separation of peptides. Peptides were numbered 1-302 starting at the N-terminal end of the protein.
[0033] Other aldehydes can be used for preparing derivatives, such hydroxynonenal and others.
Liposomes
[0034] A mixture of egg phosphatidylcholine (EPC) (Sigma) and phosphatidylserine (PS) (Sigma) in a chloroform solution at a molar ratio of 9:1 and a concentration of 3 mM phospholipid (PL) was evaporated in a glass container under gentle argon stream. The container was then placed under vacuum for 3 hours. A solution containing 0.10 mM peptide (5 ml) in sterile filtered 10 mM HEPES buffer pH 7.4, 145 mM NaCl and 0.003% sodium azide was added to the EPC/PS dried film and incubated for 15 min at 50° C. The mixture was gently vortex for about 5 min at room temperature and then placed in ice-cold water bath and sonicated with 7.5 amplitude microns for 3×3 min (Sonyprep 150 MSE Sanyo, Tamro-Medlab, Sweden) with 1 min interruptions. The PL-peptide mixture, native or modified by 0.5 M MDA for 3 h at 37° C. or 5 mM CuCl 2 for 18 h at 37° C., was stored under argon in glass vials at 4° C. wrapped in aluminum foil and used within 1 week. The MDA-modified mixture was dialyzed against PBS containing 1 mM EDTA with several changes for 18 h at 4° C. before storage. The modification of the mixture was tested in denatured polyacrylamide gels (Bio-Rad Laboratories AB, Sundbyberg, Sweden), suitable for separation of peptides.
Plasma Samples
[0035] Plasma samples from 10 patients with cardiovascular disease (AHP) and 50 plasma samples, 25 women and 25 men, from normal blood donors (NHP) were collected and pooled. The two pools were aliquoted and stored in −80° C.
ELISA
[0036] Native or modified synthetic peptides diluted in PBS pH 7.4 (20 μg/ml), in presence or absence of liposomes, were absorbed to microtiter plate wells (Nunc MaxiSorp, Nunc, Roskilde, Denmark) in an overnight incubation at 4° C. As a reference, one of the peptides (P6) was run on each plate. After washing with PBS containing 0.05% Tween-20 (PBS-T) the coated plates were blocked with SuperBlock in TBS (Pierce, Rockford, Ill.) for 5 min at room temperature followed by an incubation of pooled human plasma, AHP or NHP, diluted 1/100 in TBS-0.05% Tween-20 (TBS-T) for 2 h at room temperature and then overnight at 4° C. After rinsing, deposition of auto-antibodies directed to the peptides were detected by using biotinylated rabbit anti-human IgG- or IgM-antibodies (Dako A/S, Glostrup, Denmark) appropriately diluted in TBS-T. After another incubation for 2 h at room temperature the plates were washed and the bound biotinylated antibodies were detected by alkaline phosphatase conjugated streptavidin (Sigma), incubated for 2 h at room temperature. The color reaction was developed by using phosphatase substrate kit (Pierce) and the absorbance at 405 nm was measured after 1 h of incubation at room temperature. The absorbance values of the different peptides were divided with the absorbance value of P6 and compared.
[0037] The sequences in apolipoprotein B that were recognized by antibodies in human plasma are shown as Seq. Id 1-37 in the accompanying drawing. Both AHP and NHP contained antibodies to a large number of different peptides. Antibodies against both native and modified peptides were identified. Generally antibody titers to MDA modified peptides were higher or equal to that of the corresponding native peptide. Comparison between native, MDA-modified, copper-oxidized peptide showed a high degree of correlation and that the highest antibody titers were detected using MDA-modified peptides. The use of peptides incorporated into liposomes did not result in increased antibody levels. Antibodies of the IgM subclass were more common than antibodies of the IgG subtype.
[0038] The peptides against which the highest antibody levels were detected could be divided into six groups with common characteristics (Table 1):
[0000] (A) High levels of IgG antibodies to MDA-modified peptides (n=3).
(B) High levels of IgM antibodies, but no difference between native and MDA-modified peptides (n=9).
(C) High levels of IgG antibodies, but no difference between native and MDA-modified peptides (n=2).
(D) High levels of IgG antibodies to MDA-modified peptides and at least twice as much antibodies in the NHP-pool as compared to the AHP-pool (n=5).
(E) High levels of IgM antibodies to MDA-modified peptides and at least twice as much antibodies in the NHP-pool as compared to the AHP-pool (n=11)
(F) High levels of IgG antibodies, but no difference between intact and MDA-modified peptides but at least twice as much antibodies in the AHP-pool as compared to the NHP-pool (n=7).
(G) No level of IgG or IgM antibodies
[0000]
TABLE 1
A. High IgG, MDA-difference
P 11.
FLDTVYGNCSTHFTVKTRKG,
(SEQ ID NO: 1)
P 25.
PQCSTHILQWLKRVHANPLL,
(SEQ ID NO: 2)
P 74.
VISIPRLQAEARSEILAHWS,
(SEQ ID NO: 3)
B. High IgM, no MDA-difference
P 40.
KLVKEALKESQLPTVMDFRK,
(SEQ ID NO: 4)
P 68.
LKFVTQAEGAKQTEATMTFK,
(SEQ ID NO: 5)
P 94.
DGSLRHKFLDSNIKFSHVEK,
(SEQ ID NO: 6)
P 99.
KGTYGLSCQRDPNTGRLNGE,
(SEQ ID NO: 7)
P 100.
RLNGESNLRFNSSYLQGTNQ,
(SEQ ID NO: 8)
P 102.
SLTSTSDLQSGIIKNTASLK,
(SEQ ID NO: 9)
P 103.
TASLKYENYELTLKSDTNGK,
(SEQ ID NO: 10)
P 105.
DMTFSKQNALLRSEYQADYE,
(SEQ ID NO: 11)
P 177.
MKVKIIRTIDQMQNSELQWP,
(SEQ ID NO: 12)
C. High IgG, no MDA difference
P 143.
IALDDAKINFNEKLSQLQTY,
(SEQ ID NO: 13)
P 210.
KTTKQSFDLSVKAQYKKNKH,
(SEQ ID NO: 14)
D. NHS/AHP, IgG-ak > 2, MDA-difference
P 1.
EEEMLENVSLVCPKDATRFK,
(SEQ ID NO: 15)
P 129.
GSTSHHLVSRKSISAALEHK,
(SEQ ID NO: 16)
P 148.
IENIDFNKSGSSTASWIQNV,
(SEQ ID NO: 17)
P 162.
IREVTQRLNGEIQALELPQK,
(SEQ ID NO: 18)
P 252.
EVDVLTKYSQPEDSLIPFFE,
(SEQ ID NO: 19)
E. NHS/AHP, IgM-ak > 2, MDA-difference
P 301.
HTFLIYITELLKKLQSTTVM,
(SEQ ID NO: 20)
P 30.
LLDIANYLMEQIQDDCTGDE,
(SEQ ID NO: 21)
P 31.
CTGDEDYTYKTKRVIGNMGQ,
(SEQ ID NO: 22)
P 32.
GNMGQTMEQLTPELKSSILK,
(SEQ ID NO: 23)
P 33.
SSILKCVQSTKPSLMIQKAA,
(SEQ ID NO: 24)
P 34.
IQKAAIQALRKMEPKDKDQE,
(SEQ ID NO: 25)
P 100.
RLNGESNLRFNSSYLQGTNQ,
(SEQ ID NO: 26)
P 107.
SLNSHGLELNADILGTDKIN,
(SEQ ID NO: 27)
P 149.
WIQNVDTKYQIRIQIQEKLQ,
(SEQ ID NO: 28)
P 169.
TYISDWWTLAAKNLTDFAEQ,
(SEQ ID NO: 29)
P 236.
EATLQRIYSLWEHSTKNHLQ,
(SEQ ID NO: 30)
F. NHS/AHP, IgG-ak < 0.5, no MDA-difference
P 10.
ALLVPPETEEAKQVLFLDTV,
(SEQ ID NO: 31)
P 45.
IEIGLEGKGFEPTLEALFGK,
(SEQ ID NO: 32)
P 111.
SGASMKLTTNGRFREHNAKF,
(SEQ ID NO: 33)
P 154.
NLIGDFEVAEKINAFRAKVH,
(SEQ ID NO: 34)
P 199.
GHSVLTAKGMALFGEGKAEF,
(SEQ ID NO: 35)
P 222.
FKSSVITLNTNAELFNQSDI,
(SEQ ID NO: 36)
P 240.
FPDLGQEVALNANTKNQKIR,
(SEQ ID NO: 37)
G.
P 2.
ATRFKHLRKYTYNYQAQSSS.
(SEQ ID NO: 38)
[0039] All of these 38 peptide sequences represent targets for immune reactions that may be of importance for the development of atherosclerosis and ischemic cardiovascular diseases. These peptides may therefor be used to develop ELISAs to determine the associations between antibody levels against defined sequences of MDA-modified amino acids in apolipoprotein B and risk for development of cardiovascular disease.
[0040] These peptides also represent possible mediators of the protective immunity observed in experimental animals immunized with oxidized LDL and may be used for testing in further development of an immunization therapy or “vaccine” against atherosclerosis.
[0041] Thus 38 different sequences in the human apolipoprotein B protein have been identified that give rise to significant immune responses in man. These epitopes are likely to represent what has previously been described as antibodies to oxidized LDL. Since most immune responses are directed against peptide sequences and apolipoprotein B is the only protein in LDL the approach used in this project should be able to identify the specific epitopes for essentially all antibodies against oxidized LDL-particles. A family of phospholipid specific antibodies including antibodies against cardiolipin has been described to react with oxidized LDL but the specificity and role of these antibodies remain to be fully characterized.
[0042] In many cases antibody titers were higher to MDA-modified polypeptides than to native sequences. If antibodies were detected against a MDA modified sequence it was almost always associated with presence of antibodies against the native sequence. A likely explanation to this is that the immune response against an MDA-modified amino acid sequence in apolipoprotein B (the MDA-modification occurring as a result of LDL oxidation) leads to a break of tolerance against the native sequence. For other sequences there was no difference in antibody titers against MDA-modified or native sequences. This would suggest that the immune reactions are directed against the native sequences. There should be no immune response against amino acid sequences in protein normally exposed to the immune system. In the native LDL particle large parts of the apolipoprotein B protein is hidden in phospholipid layer of LDL and therefore not accessible for the immune system. During oxidation of LDL the apolipoprotein B amino acid chain is fragmented leading to changes in the three-dimensional structure. This is likely to lead to exposure of peptide sequences normally not accessible for the immune system and to generation of antibodies against these sequences which may explain the presence of antibodies against native apolipoprotein B sequences observed. Alternatively, the true immune response is against MDA-modified sequences but the cross-reactivity with native sequences is so great that no difference in binding can be demonstrated.
[0000]
TABLE 2
Associations between antibodies to different peptides and atherosclerosis
in the carotid artery assessed as intima/media thickness in 78 subjects
(26 subjects who later developed myocardial infarction, 26 healthy
controls and 26 high-risk individuals without disease).
IgG
IgM
Peptide
Native
MDA-modified
Native
MDA-modified
301
+
10
+
+
11
++
+
25
+
+
++
+++
30
++
31
++
32
33
+
34
+
45
++
++
+++
74
++
+
+
++
99
100
+
++
102
103
+
105
129
++
+++
143
+
+
++
+
148
+
154
+++
++
162
+
++
199
210
+
240
++
+, r > 0.2 < 0.3, p = <0.05; ++, r > 0.3 < 0.4, p = 0.01; +++, r > 0.4, p = <0.001, grey, peptide antibody levels significantly increased in the group suffering from myocardial infarction.
[0043] The possibility that the ELISAs based on these peptides (native or MDA-modified) can be used to determine associations between immune reaction against defined epitopes in oxidized LDL and presence and/or risk for development of cardio-vascular disease was investigated in a pilot study. The study was performed on subjects participating in the Malmö Diet Cancer study a population based study in which over 30,000 individuals were recruited between 1989 and 1993. Antibody levels against the 24 out of 38 peptides listed in Table 1 were determined in base line plasma samples of 26 subjects who developed an acute myocardial infarction during the follow-up period and 26 healthy controls matched for age, gender and smoking. An additional group of 26 subjects, matched for age, gender, and smoking, but all with LDL cholesterol levels above 5.0 mmol/L was also included to study antibody levels in a high-risk group that has not developed cardiovascular disease.
[0044] For 19 out of the 24 peptides analyzed, significant correlations were identified between IgM antibody levels against MDA-modified peptides and the severity of atherosclerosis in the carotid artery (intima/media thickness) as assessed by ultrasound investigation of common carotid artery, i.e., the higher antibody levels the more atherosclerosis (Table 2). For many of these peptides significant correlations also existed between antibody levels to native peptides and carotid intima/media thickness. Only 4 peptides showed a significant correlation between IgG antibodies and carotid intima/media thickness. These observations suggest that ELISA using these MDA-modified peptides (alone or in combination) may be used to identify subjects with increased atherosclerosis.
[0045] Four of the peptides tested were not only associated with increased presence of atherosclerosis but were also significant elevated in the group of subjects that later suffered from a myocardial infarction (Table 2). Data for one of these peptides (peptide 240) is shown in FIG. 7 . These observations also demonstrate that peptide-based ELISA also may be used to identify subjects with an increased risk to develop myocardial infarction.
[0046] There were also significant increases in IgG antibody levels for native peptides 103, 162 and 199, as well as MDA modified 102 in the group that later suffered from myocardial infarction. However, the IgG antibodies against these peptides were not significantly associated with the presence of atherosclerosis in the carotid artery.
[0047] A particularly interesting observation was made with antibodies against MDA-modified peptide 210 for which there was significantly higher levels of IgM antibodies in the healthy controls and the high-risk group (LDL cholesterol above 5.0 mmol/L) than in the group that developed a myocardial infarction. Accordingly antibodies against MDA-modified peptide 210 may represent a marker for individuals with a decreased risk to develop cardiovascular disease.
[0048] It has now been demonstrated that immunization with native and MDA-modified apo B-100 peptide sequences results in an inhibition of atherosclerosis in experimental animals (Nordin Fredrikson, Söderberg et al, Chyu et al). The mechanisms through which these athero-protective immune responses operate remain to be fully elucidated. However, one likely possibility is that the athero-protective effect is mediated by antibodies generated against these peptides sequences. These antibodies could, for example facilitate the removal of oxidatively damaged LDL particles by macrophage Fc receptors.
[0049] Macrophage scavenger receptors only recognize LDL with extensive oxidative damage (9). Recent studies have identified the existence of circulating oxidized LDL (10,11). These particles have only minimal oxidative damage and are not recognized by scavenger receptors. Binding of antibodies to these circulating oxidized LDL particles may help to remove them from the circulation before they accumulate in the vascular tissue (12).
[0050] Several studies have supported a role for antibodies in protection against atherosclerosis. B cell reconstitution inhibits development of atherosclerosis in splenectomized apo E null mice (13) as well as neointima formation after carotid injury in RAG-1 mice (unpublished observations from our laboratory). Moreover, it has been shown that repeated injections of immunoglobulins reduce atherosclerosis in apo E null mice (6).
[0051] As discussed above antibodies against MDA-modified peptide sequences in apo B-100 may be generated by active immunization using synthetic peptides. This procedure requires 2-3 weeks before a full effect on antibody production is obtained.
[0052] In some situations a more rapid effect may be needed. One example may be unstable atherosclerotic plaques in which oxidized LDL is likely to contribute to inflammation, cell toxicity and risk for plaque rupture. Under these circumstances a passive immunization by injection of purified, or recombinantly produced antibodies against native and MDA-modified sequences may have a faster effect.
[0053] Another situation in which a passive immunization by injection of purified, or recombinantly produced antibodies may be effective is coronary heart disease in older individuals. Our studies have shown that a decrease in antibodies against apo B peptide sequences occurs with increasing age in man and is associated with an increase in the plasma level of oxidized LDL (Nordin Fredrikson, Hedblad et al). This may suggest a senescence of the immune cells responsible for producing antibodies against antigens in oxidized LDL and result in a defective clearance of oxidatively damaged LDL particles from the circulation. Accordingly, these subjects would benefit more from a passive immunization by injection of purified, or recombinantly produced antibodies than from an active immunization with apo B-100 peptide sequences.
[0054] Synthetic native peptides (Euro-Diagnostica AB, Malmö, Sweden) used in the following were peptide 1, 2 and 301 from the initially screened polypeptide library. Peptide 1 (amino acid sequence: EEEMLENVSLVCPKDATRFK, n=10; (SEQ ID NO: 15)) and peptide 301 (amino acid sequence: HTFLIYITELLKKLQSTTVM, n=10; (SEQ ID NO: 20)) were found to have higher IgG or IgM antibody response to MDA modified form than native peptide, respectively and both titers are higher in healthy subject. These peptides were chosen based on the assumption that antibody response to these peptides might be protective against atherosclerosis.
[0055] Peptide 2 (amino acid sequence: ATRFKHLRKYTYNYQAQSSS, n=10; (SEQ ID NO: 38)) elicited no antibody response in the initial antibody screening, hence it was chosen as control peptide. Mice receiving Alum served as control (n=9).
[0056] Apo E (−/−) mice received subcutaneous primary immunization at 6-7 weeks of age, followed by an intra-peritoneal booster 3 weeks later. Mice were fed high cholesterol diet from the onset of immunization and continued until sacrifice at the age of 25 weeks. At the time of sacrifice, there was no significant difference in body weight among 4 groups of mice. Nor there was statistically significant difference in serum cholesterol as measured using a commercially available kit (Sigma). Their mean serum cholesterol levels were all above 715 mg/dl.
[0057] The area of the descending aorta covered by atherosclerotic plaque was measured in an en face preparation after oil red 0 staining. In comparison to the control group, mice immunized with peptide No. 2 and No. 301 had substantially reduced atherosclerosis ( FIG. 2 ). Immunization with Peptide No 1 did not produce a significant reduction in atherosclerosis in comparison to control. In contrast to the descending aorta, extent of atherosclerosis in the aortic root and aortic arch did not differ among the 4 experimental groups ( FIG. 3 ).
[0058] There were no difference among 4 groups in terms of aortic sinus plaque size or its lipid content (Table A). Mean plaque sizes in the aortic arches from 4 groups of mice were not different. However, en face evaluation of plaque sizes from descending thoracic and abdominal aorta by oil red 0 staining revealed that control group and peptide No. 1 group had similar amount of atherosclerotic plaque in the aorta, whereas peptide No. 2 and No. 9 groups had a significantly reduced atherosclerotic burden in the aorta (Table A). The observation that peptide immunization did not affect aortic sinus or aortic arch plaque size but reduced descending aortic plaque is intriguing and suggests that peptide immunization might reduce new plaque formation but does not affect the progression of plaques.
[0059] It was further tested whether peptide immunization modulates the phenotype of atherosclerotic plaques. Frozen sections form aortic sinus plaques were immunohistochemically stained with monocyte/macrophage antibody (MOMA-2, Serotec). In concordance with the findings from en face observation, peptide No. 2 significantly reduced macrophage infiltration in the plaques ( FIG. 1 ). Trichrome staining revealed a mean collage content of 40.0±7.7% in the aortic sinus plaques from peptide 2 group; whereas mean collagen content in alum control group, peptide 1 group and peptide 9 group were 32.3±5.3%, 35.6±8.5% and 29.4±9.6%, respectively.
[0060] Antibody response against immunized peptide in each group was determined.
[0061] Antibody titer after immunization increased 6.1±3.1 fold in peptide 1 group, 2.4±1.0 fold in peptide 2 group and 1.8±0.6 fold in peptide 9 group; whereas alum group had a 3.9±2.7 fold increase of antibody titer against peptide 1, 2.0±0.5 fold increase against peptide 2 and 2.0±0.9 fold increase against peptide 9. It is surprising the parallel increase of antibody titer against immunized peptides both in immunized and alum treated group. This may mean the following possibilities: (1) mechanism(s) other than humoral immune response (such as cellular immune response) may be involved in modulating atherosclerosis; or (2) this increase of antibody was a by-stander response to hypercholesterolemia with time.
[0062] Although there is no clear speculative mechanism to explain why peptide immunization reduced atherosclerosis and/or modulate plaque phenotype, the novelty of this invention is the concept of using peptides of LDL as immunogen and its feasibility as an immunomodulation strategy. This peptide-based immunization strategy modulates atherosclerotic plaques. Immunization using homologous oxLDL or native LDL as antigen had been shown to reduce plaque size 1-3 , however, the availability, production, infectious contamination and safety of homologous human LDL make this approach unappealing for clinical application. Here it is demonstrated that peptide-based immunotherapy is feasible although our final results differ from our initial hypothesis that immunization using peptides with higher IgM or IgG antibody response in normal subjects may protect experimental animals from developing advanced atherosclerotic plaques.
[0063] It is surprising to find that immunization using peptide No. 2 protected animal from developing new atherosclerotic lesions in descending aorta and reduced macrophage infiltration and a higher collagen content in plaques since this peptide did not render any antibody response from initial human screen. It may be because (a) peptide No. 2 may be a part of human apo-B-100 protein structure that was not exposed to human immune system. Hence, no antibody was generated and detected from healthy human serum pools; (b) the amino acid sequence of peptide No. 2 is foreign to mice therefore mice developed immune response against this peptide, which modulates new atherosclerotic lesion formation and its phenotype.
[0064] The effect of homologous LDL immunization on plaque size varied when plaque sizes were evaluated at different portions of aortic tree. For example, Ameli et al showed in hypercholesterolemic rabbit native LDL immunization resulted in a reduction of plaque formation in aorta 1 , whereas Freigang et al. showed reduction of plaque size in aortic sinus but not in aorta 2 . Taken their findings and the present ones together, it was speculated that peptide immunization modulates not only plaque sizes but also plaque composition. The plaque-reducing effect was only observed in descending aorta. Apo E (−/−) mice are known to develop atherosclerotic lesions at various stages of evolution in a single animal, especially when fed high cholesterol diet. The initial appearance of atherosclerotic lesion in young animal was in the aortic sinus 6,7 and after 15 weeks on high fat-high cholesterol diet lesions at aortic sinus were advanced plaques; whereas earlier stage of atherosclerosis was present in descending aorta. 6 Since the temporal course of plaque maturation and development in the descending aorta is late compared to that of aortic sinus, the finding that immunization reduced lesion sizes in the descending aorta but not in aortic sinus suggested immunization affects early stage of atherosclerosis formation. It is possible that as animal aged and in the presence of supra-physiological level of serum cholesterol the plaque reducing effect of immunization is overcome by the toxic effect of hypercholesterolemia. It is also possible that aortic sinus plaques mature faster and sacrifice at 25 weeks is too late to detect any difference in plaque size. Though lesion size was not modulated in the aortic sinus plaque, peptide immunization did modulate plaque compositions. The present experimental design prevented from studying the composition of the plaques in their earlier stage of development in descending aorta.
[0065] The experimental findings highlight the feasibility of using peptide sequences of LDL associated apo B-100 as immunogens for a novel approach to preventing atherosclerosis and or favorably modulating plaque phenotype despite severe hyperlipdemia. This peptide-based immunization strategy is potentially advantageous over the use of homologous oxLDL or native LDL as antigen because such a strategy could eliminate the need for isolation and preparation of homologous LDL and its attendant risks for contamination. The plaque-reducing effect of immunization with Peptide No 2 and 301 was only observed in descending aorta. These findings are consistent with previous reports where other therapeutic interventions have also been shown to have a greater effect on descending aorta compared to the aortic arch 14-17 , presumably because lesions develop more rapidly in the aortic root and the arch than the descending aorta thus creating a smaller window of opportunity for intervention 14, 15, 16, 18, 19 . Since the temporal course of plaque maturation and development in the descending aorta is late compared to that of aortic sinus and the aortic arch, the finding that immunization reduced lesion sizes in the descending aorta but not in aortic sinus and arch suggest that immunization preferentially prevents early stage of atherosclerosis formation. It is possible that as animal aged and in the presence of supra-physiological level of serum cholesterol the plaque reducing effect of immunization is overcome by the toxic effect of severe hypercholesterolemia. Though the lesion size was not modulated in the aortic sinus or arch, immunization with Peptide No 2 did modulate plaque composition in a favorable direction creating a more stable plaque phenotype with reduced macrophage infiltration and increased collagen content. In summary, it is demonstrated a novel peptide-based immunomodulatory approach for inhibition of atherosclerosis in the murine model.
[0066] In summary, it is demonstrated a novel peptide-based immunomodulatory approach in modulate atherosclerotic plaques. Although the change in atherosclerosis formation in our model was only modest, yet this peptide-based immunization may provide an alternative tool in studying, preventing or treating atherosclerosis.
Methods
[0067] Peptide preparation. Peptides were prepared using Imject® SuperCarrier® EDC kit (Pierce, Rockford, Ill.) according to manufacturer's instruction with minor modification. One mg peptide in 500 μl conjugation buffer was mixed with 2 mg carrier in 200 μl deionized water. This mixture was then incubated with 1 mg conjugation reagent (EDC, 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide HCl) in room temperature for 2 hours. This was then dialyzed against 0.083 M sodium phosphate, 0.9 M sodium chloride pH 7.2 solution overnight at 4° C. The dialyzed conjugate was diluted with Imject dry blend purification buffer to a final volume of 1.5 ml. Alum was used as immunoadjuvant and mixed with peptide conjugate with 1:1 dilution in volume. The amount of peptide in each immunization was 33 μg/100 μl per injection.
[0068] Animal protocol. Apo E (−/−) mice from the Jackson Laboratories (Bar Harbor, Me) received subcutaneous primary immunization at 6-7 weeks of age, followed by an intra-peritoneal booster 3 weeks later. Mice were fed high cholesterol diet from the onset of immunization and continued until sacrifice at the age of 25 weeks. Blood samples were collected 2 weeks after booster and at the time of sacrifice. Mice receiving Alum served as control. Experimental protocol was approved by the Institutional Animal Care and Use Committee of Cedars-Sinai Medical Center. All mice were housed in an animal facility accredited by the American Association of Accreditation of Laboratory Animal Care and kept on a 12-hour day/night cycle and had unrestricted access to water and food. At the time of sacrifice, mice were anesthetized by inhalation Enflurane. Plasma was obtained by retro-orbital bleeding prior to sacrifice.
[0069] Tissue harvesting and sectioning. To evaluate the effect of peptide immunization on atherosclerosis formation, the plaque size at aortic sinus was assessed, aortic arch and descending thoracic and abdominal aorta. After the heart and aortic tree were perfused with normal saline at physiological pressure, the heart and proximal aorta were excised and embedded in OCT compound (Tissue-Tek) and frozen sectioned. Serial 6-μm-thick sections were collected from the appearance of at least 2 aortic valves to the disappearance of the aortic valve leaflets for aortic sinus plaque evaluation. Typically 3 consecutive sections were on one slide and a total of 25-30 slides were collected from one mouse and every fifth slide was grouped for staining. Ascending aorta and aortic arches upto left subclavian artery were also sectioned and processed similarly. Descending thoracic and abdominal aorta were processed separately for en face evaluation of plaque formation after oil red 0 staining. En face preparation of descending thoracic and abdominal aorta
[0070] Chicken egg albumin (Sigma) in a concentration of 0.8 g/ml water was mixed 1:1 with glycerol. Sodium azide was added to make a final concentration of sodium azide 0.2%. After descending thoracic and abdominal aorta was cleaned off surrounding tissue and fat, the segment of aorta from left subclavian artery to the level of renal artery was then carefully removed for overnight fixation in Histochoice (Amresco). Aorta was then carefully opened longitudinally and placed with luminal side up on a slide freshly coated with egg albumin solution. After albumin solution became dry, the aorta was stained with Oil red O to assess the extent of atherosclerosis with computer-assisted histomorphometry.
[0071] Immunohistochemistry and Histomorphometry. The sections from aortic sinus were immunohistochemically stained with MOMA-2 antibody (Serotec) using standard protocol. Trichrome stain to assess collagen content and oil red O stain for plaque size and lipid content were done using standard staining protocol. Computer-assisted morphometric analysis was performed to assess histomorphometry as described previously. 8
[0072] Antibody titer measurement. To measure the antibody response after peptide immunization, an ELISA was developed. Antibody titer against immunized peptide was measured using blood collected at 2 weeks after booster and at sacrifice. Antibody response against 3 peptides was also determined in Alum group at the same time-points. In brief, native synthetic peptides diluted in PBS pH 7.4 (20 μg/ml) were absorbed to microtiter plate wells (Nunc MaxiSorp, Nunc, Roskilde, Denmark) in an overnight incubation at 4° C. After washing with PBS containing 0.05% Tween-20 (PBS-T) the coated plates were blocked with SuperBlock in TBS (Pierce) for 5 min at room temperature followed by an incubation of mouse serum diluted 1/50 in TBS-0.05% Tween-20 (TBS-T) for 2 h at room temperature and then overnight at 4° C. After rinsing, deposition of antibodies directed to the peptides was detected by using biotinylated rabbit anti-mouse Ig antibodies (Dako A/S, Glostrup, Denmark) appropriately diluted in TBS-T. After another incubation for 2 h at room temperature the plates were washed and the bound biotinylated antibodies were detected by alkaline phosphatase conjugated streptavidin (Sigma), incubated for 2 h at room temperature. Using phosphatase substrate kit (Pierce) developed the colour reaction and the absorbance at 405 nm was measured after 1 h of incubation at room temperature. Mean values were calculated after the background was subtracted.
[0073] Other assay models is of course applicable as well, such any immunoassay detecting an antibody, such as radioactive immunoassay, Western blotting, and Southern blotting, as well as detection of antibodies bound to peptides, enzyme electrodes and other methods for analysis,
Statistics
[0074] Data are presented as mean±Std. Statistical method used is listed in either text, table or figure legend. P<0.05 was considered as statistically significant.
[0000]
TABLE A
Aortic sinus plaque size and its lipid content, aortic arch
plaque size and percent of plaque in descending aorta.
Oil red O (+) area
Total plaque size in
(% of aortic sinus
Aortic arch plaque
% of plaque in
aortic sinus (mm 2 )
plaque)
size (mm 2 )
aorta (flat prep.)
Alum
0.49 ± 0.13
21.7 ± 4.4
0.057 ± 0.040
20 ± 4.7
Peptide 1
0.48 ± 0.14
32.0 ± 8.1
0.054 ± 0.027
17 ± 4.3
Peptide 301
0.46 ± 0.16
23.8 ± 4.1
0.050 ± 0.024
8.9 ± 2.2*
*Significant different from Alum group. ANOVA followed by Tukey-Kramer test was used for statistical analysis.
[0075] Further data on the effect of immunization with apolipoprotein B-100 peptide sequences on atherosclerosis in apo E knockout mice is given below in Table B
[0000]
TABLE B
Effect of immunization with apolipoprotein B-100 peptide
sequences on atherosclerosis in apo E knockout mice
Effect on
atherosclerosis
in the aorta
Immunizations using mixtures of several peptide sequences
1. Peptide sequences 143 and 210
−64.6%
2. Peptide sequences 11, 25 and 74
−59.6%
3. Peptide sequences 129, 148 and 167
−56.8%
4. Peptide sequences 99, 100, 102, 103 and 105
−40.1%
5. Peptide sequences 30, 31, 32, 33 and 34
+6.6%
6. Peptide sequences 10, 45, 154, 199 and 240
+17.8%
Immunizations using a single peptide sequence
1. Peptide sequence 2
−67.7%
2. Peptide sequence 210
−57.9%
3. Peptide sequence 301
−55.2%
4. Peptide sequence 45
−47.4%
5. Peptide sequence 74
−31.0%
6. Peptide sequence 1
−15.4%
7. Peptide sequence 240
0%
[0076] Administration of the peptides is normally carried by injection, such as subcutaneous injection, intravenous injection, intramuscular injection or intraperitoneal injection. A first immunizing dosage can be 1 to 100 mg per patient depending on body weight, age, and other physical and medical conditions. In particular situations a local administration of a solution containing one or more of the peptides via catheter to the coronary vessels is possible as well. Oral preparations may be contemplated as well, although particular precautions must be taken to admit absorption into the blood stream. An injection dosage may contain 0.5 to 99.5% by weight of one or more of the fragments or peptides of the present invention.
[0077] The peptides are normally administered as linked to cationized bovine serum albumine, and using aluminium hydroxide as an adjuvant. Other adjuvants known in the art can be used as well.
[0078] Solutions for administration of the peptides shall not contain any EDTA or antioxidants.
[0079] The peptides can also be used as therapeutic agents in patients already suffering from an atheroschlerosis. Thus any suitable administration route can be used for adding one or more of the fragments or peptides of the invention.
[0080] Initial studies focused on determining which type of oxidative modifications of peptides led to recognition by antibodies in human plasma. These studies were done using peptides 1-5 and 297-302. During oxidation of LDL polyunsaturated fatty acids in phospholipids and cholesteryl esters undergo peroxidation leading to formation of highly reactive breakdown products, such as malondealdehyde (MDA). MDA may then form covalent adducts with lysine and histidine residues in apo B-100 making them highly immunogenic. Oxidation of LDL also results in fragmentation of apo B-100 that may lead to exposure of peptide sequences not normally accessible for the immune system. In these experiments peptides were used in their native state, after MDA modification or after incorporation into phospholipid liposomes followed by copper oxidation or MDA-modification. IgM antibodies were identified against native, MDA- and liposome oxidized peptides, with antibody titers MDA-peptide>MDA-modified liposome peptides>liposome oxidized peptide>native peptide. Specificity testing demonstrated that binding of antibodies to MDA-modified peptides was competed by both MDA-LDL and copper oxidized LDL.
[0081] We then performed a screening of the complete peptide library using pooled plasma derived from healthy control subjects and native and MDA-modified peptides as antigens. Antibodies to a large number of sites in apo B-100 were identified. Using twice the absorbance of the background control as positive titer cut off, antibodies were detected against 102 of the 302 peptides constituting the complete apo B-100 sequence. IgM binding was substantially more abundant than that of IgG. Generally, binding was higher to MDA modified peptide sequences than to the corresponding native sequence, but these was a striking correlation between the two. Binding to both native and MDA modified sequences was competed by addition of MDA-modified LDL and copper oxidized LDL, but not by native LDL. These observations suggest that immune responses against MDA-modified peptide sequences in apo B-100 results in a cross reactivity against native sequences. The inability of native LDL to compete antibody binding to native apo B-100 peptide sequences is intriguing, but may indicate that these sequences only become exposed after the proteolytic degradation of apo B-100 that occurs as a result of LDL oxidation. Both hydrophilic and hydrophobic parts of the molecule were recognized by antibodies. A second screening of the apo B-100 peptide library was performed using pooled plasma from subjects with clinical signs of coronary heart disease (CHD, acute myocardial infarction (AMI) and unstable angina; n=10). Antibodies in pooled CHD plasma bound to the same sequences and with the same overall distribution as for antibodies in healthy control plasma. However, antibody titers to several peptides (#1, 30-34, 100, 107, 148, 149, 162, 169, 236, 252 and 301) were at least twice as high as in control plasma compared to plasma from CHD subjects, whereas titers against a few peptides (#10, 45, 111, 154, 199, 222 and 240) were higher in plasma from CHD patients compared to controls. We then performed a prospective clinical study to investigate if antibody levels against MDA-modified peptide sequences in apo B-100 predict risk for development of CHD. Using a nested case control design we selected 78 subjects with coronary events (AMI or death due to CHD) and 149 controls from the Malmo Diet Cancer Study. Neither cases nor control individuals had a history of previous MI or stroke. The median time from inclusion to the acute coronary event was 2.8 years (range 0.1-5.9 years) among cases. Antibody levels were determined in baseline plasma samples supplemented with antioxidants. Using the carotid intima-media thickness (IMT) as assessed by ultrasonography at baseline we also analyzed associations between antibody levels and degree of existing vascular disease. We studied 8 MDA-modified peptide sequences that in the initial screening studies were associated with high plasma antibody levels (# 74, 102 and 210) and/or marked differences between control and CHD plasma pools (# 32, 45, 129, 162 and 240). Controls were found to have higher IgM levels against MDA peptide 74 (0.258, range 0-1.123 absorbance units versus 0.178, range 0-0.732 absorbance units, p<0.05), otherwise there were no differences in antibody levels between cases and controls. Associations between IMT and IgM against MDA-peptides # 102, 129, and 162 (r=0.233, 0.232, and 0.234, respectively, p<0.05) were observed in cases and between IMT and MDA-peptide 45 (r=0.18, p<0.05) in controls. Weak correlations were observed between antibodies to MDA peptide 129 and total and LDL cholesterol (r=0.19 and r=0.19, p<0.01, respectively), otherwise peptide antibody levels showed no associations with total plasma cholesterol, LDL cholesterol, HDL cholesterol or plasma triglycerides. There were strong co-variations between antibody levels to the different peptides (r values ranging from 0.6 to 0.9). The only exception was antibodies against MDA-peptide 74 that were weakly or not at all related to antibodies against the other peptides.
[0082] Antibodies against all sequences except MDA-peptide 74 was inversely associated with age among cases (r values ranging from −0.38 to −0.58, p<0.010.001), but not in controls. Plasma levels of oxidized LDL, in contrast, increased with age. Again this association was stronger in cases than in controls. To investigate if the associations between immune responses against MDA-modified peptide sequences and cardiovascular disease were different in different age groups a subgroup analysis was performed on cases and controls under and above the median age (61 years). In the younger age group cases had increased antibody levels against peptides 32 and 45 and decreased antibody levels against peptide 74 as compared to controls, whereas no differences were seen in the older age group. Antibodies against all MDA peptide sequences, except peptide 74, were significantly associated with IMT in the younger age group, but not in the older (Table).
[0083] These studies identify a number of MDA-modified sequences in apo B-100 that are recognized by human antibodies. MDA-modification of apo B-100 occurs as a result of LDL oxidation indicating that these antibodies belong to the family of previously described oxidized LDL autoantibodies. This notion is also supported by the observation that antibody binding to MDA-modified apo B-100 peptides is competed by addition of oxidized LDL. Together with the oxidized phospholipids identified by Hörkköet al, these MDA-modified peptide sequences are likely to constitute the large majority of antigenic structures in oxidized LDL. In similarity with the oxidized LDL antiphospholipid antibodies, antibodies against MDA-modified apo B-100 sequences were of IgM type. This may suggest that also the latter antibodies belong to the family of T 15 natural antibodies. T 15 antibodies have been attributed an important role in the early, T cell independent defence against bacterial infections as well as in the removal of apoptotic cells. It remains to be determined if the MDA-peptide antibodies described here have similar functions. Antibodies were also identified against a large number of native apo B-100 sequences. However, the striking co-variation between antibodies to native and MDA-modified sequences suggests that also these antibodies are formed in response to LDL oxidation. It is also possible that antibodies against an MDA-modified peptide sequence cross reacts with the corresponding native sequence. If antibodies against native apo B-100 sequences bind also to native LDL particles this is likely to have a major influence on LDL metabolism. However, the finding that native LDL does not compete antibody binding to native apo B-100 sequences, as well as the lack of correlation between antibodies against native apo B-100 sequences and LDL cholesterol levels against the existence of such a phenomena.
[0084] Antibodies against MDA-modified peptide sequences decreased progressively with age in the cases, but not in the controls. With the exception of MDA-peptide 74, IgM antibodies against MDA-peptides were significantly associated with carotid IMT in the younger age group (below 62 years), but not in the older age group. These findings suggest that significant changes in the interactions between the immune system and the atherosclerotic vascular wall takes place between ages 50 and 70 years. One possibility is that in younger individuals the atherosclerotic disease process is at a more active stage with a more prominent involvement of immune cells. Another possibility is that the decreased levels of antibodies against MDA-modified peptide sequences in older subjects reflect a senescence of the immune cells involved in atherosclerosis. An impaired function of immune cells due to immunosenescence have been proposed to contribute to an increased susceptibility to infection and cancer in the older population. Interestingly, immunosenescence is inhibited by antioxidants indicating involvement of oxidative stress. Immune cells that interact with epitopes in oxidized LDL are likely to be particularly exposed to oxidative stress. Since oxidized LDL is present in arteries already at a very early age these immune response are being continuously challenged for several decades, which may further contribute to a development of immunosenescence.
[0085] Increased antibodies against two sites in apo B-100 were found to predict risk for myocardial infarction and coronary death in subjects below 62 years of age. Antibodies against these sites showed a high level of co-variation suggesting that they were produced in response to the same underlying pathophysiological processes. The fact that the median time from blood sampling to coronary event was only 2.8 years makes these antibodies particularly interesting as makers for increased CHD risk. Antibody levels against MDA-modified apo B-100 peptide sequences showed no associations with other CHD risk factors such as hyperlipidemia, hypertension and diabetes suggesting that they are independent markers of CHD risk. The CHD cases in the present study were not extremely high-risk individuals and in this respect representative of the common CHD patient. The finding that IgM against MDA-modified apo B-100 sequences predicts short-term risk for development of acute coronary events in individuals that would not have been identified as high risk by screening of established risk factors suggest that it may become a useful instrument in identifying individuals in need of aggressive preventive treatment. However, considerably larger prospective studies with multivariate analysis are required before the clinical value of determining antibodies against apo B-100 MDA-modified peptide sequences can be fully established. Another limitation of the present clinical study is that we have only analysed antibodies against a small number of the antigenic sites in apo B-100 and that antibody titers against other sites may be even better markers of cardiovascular risk.
[0086] In subjects below age 60 antibodies against a large number of MDA-modified sites in apo B-100 were correlated with the extent of existing vascular disease as assessed by carotid IMT. IgM antibodies were more closely associated with carotid IMT than IgG antibodies. Although carotid IMT has obvious limitations as a measure of general atherosclerotic burden these observations still suggest that determination of IgM against MDA-modified sequences in apo B-100 may be one method to assess the severity of existing atherosclerosis. These observations are also in line with several previous studies that have reported associations between coronary and carotid artery disease and IgM antibodies against oxidized LDL.
[0087] Antibodies against peptide 74 differed against other apo B-100 peptide antibodies in many respect. They were higher in controls than in cases, they did not decrease with age and were not associated with the extent of carotid disease. Accordingly, antibodies against this peptide sequence represent interesting candidates for an athero-protective immune response.
[0088] An important question is why these associations occur. They clearly demonstrate that immune responses against MDA-modified apo B-100 sites somehow are involved in the atherosclerosic disease process. Since high antibody levels are associated with more severe atherosclerosis and increased risk for development of acute coronary events one obvious possibility is that these immune responses promote atherogenesis. Studies demonstrating that immune responses against heat shock proteins, such as HSP 65, are atherogenic provide some support for this notion. However, experimental animal studies have shown an athero-protective effect of oxidized LDL immunization. B cell reconstitution of spleen ectomized apo E null mice results in a decrease in atherosclerosis. Reduced atherosclerosis has also been observed in apo E null mice given repeated injections of immunoglobulin. The present observations do not necessarily argue against an athero-protective role of immune responses against oxidized LDL. These immune responses are activated by pro-atherogenic processes such as LDL oxidation. Accordingly, they are also likely to be in proportion to the severity of the disease process and could serve as makers of disease severity and CHD risk without contributing to disease progression. The finding that immunization of apo E null mice with apo B-100 peptide sequences inhibits development of atherosclerosis reported in two accompanying papers demonstrates that this is likely to be the case. Indeed, the most important outcome of the present study may well be the identification of structures that could be used as components of a vaccine against atherosclerosis. The observation that the decrease in antibodies against MDA-modified peptide sequences in apo 8-100 that occurs with age is accompanied by an increase in plasma levels of oxidized LDL suggest that an increased clearance of minimally oxidized LDL from the circulation may be one mechanism by which these antibodies could protect against atherosclerosis.
Methods
Study Population
[0089] The study subjects, borr between 1926-45, belong to the Malmö “Diet and Cancer (MDC)” study cohort. A random 50% of those who entered the MDC study between November 1991 and February 1994 were invited to take part in a study on the epidemiology of carotid artery disease. Routines for ascertainment of information on morbidity and mortality following the health examination, as well as definition of traditional risk factors, have been reported.
[0090] Eighty-five cases of acute coronary heart events, i.e. fatal or non-fatal MI or deaths due to coronary heart disease (CHD) were identified. Participants who had a history of myocardial infarction or stroke (n=6) were not eligible for the present study. For each case two controls without a history of myocardial infarction or stroke was individually matched for age, sex, smoking habits, presence of hypertension and month of participation in the screening examination and duration of follow-up. Due to logistic reason (blood samples were not available in sufficient quantity for assessment of peptides) only one control was available for seven cases and no controls for one case. This case was excluded from analysis. Thus the study population consists of 227 subjects, 78 cases and 149 controls, aged 49-67 (median 61) years at baseline.
Laboratory Analyses
[0091] After overnight fasting blood samples were drawn for the determination of serum values of total cholesterol, triglycerides, HDL cholesterol, LDL cholesterol and whole blood glucose. LDL cholesterol in mmol/L was calculated according to the Friedewald formula. Oxidized LDL was measured by ELISA (Mercordia).
B-Mode Ultrasound Vasculography
[0092] An Acuson 128 Computed Tomography System (Acuson, Mountain View, Calif.) with a MHz transducer was used for the assessment of carotid plaques in the right carotid artery as described previously.
[0000] Development of ELISAs against apo B-100 Peptide Sequences
[0093] The 302 peptides corresponding to the entire human apolipoprotein B amino acid sequence were synthesized (Euro-Diagnostica AB, Malmö, Sweden and K J Ross Petersen A S, Horsholm, Denmark) and used in ELISA. A fraction of each synthetic peptide was modified by 0.5 M MDA (Sigma-Aldrich Sweden AB, Stockholm, Sweden) for 3 h at 37° C. and in presence of liposomes by 0.5 M MDA for 3 h at 37° C. or by 5 mM CUCl 2 (Sigma) for 18 h at 37° C. The MDA modified peptides were dialysed against PBS containing 1 mM EDTA with several changes for 18 h at 4° C. The modification of the peptides was tested in denatured polyacrylamide gels (BioRad Laboratories, Hercules, Calif.), suitable for separation of peptides.
[0094] A mixture of egg phosphatidylcholine (EPC) (Sigma) and phosphatidylserine (PS) (Sigma) in a chloroform solution at a molar ratio of 9:1 and a concentration of 3 mM phospholipid (PL) was evaporated in a glass container under gentle argon stream. The container was then placed under vacuum for 3 hours. A solution containing 0.10 mM peptide (5 ml) in sterile filtered 10 mM HEPES buffer pH 7.4, 145 mM NaCl and 0.003% sodium azide was added to the EPC/PS dried film and incubated for 15 min at 50° C. The mixture was gently vortex for about 5 min at room temperature and then placed in ice-cold water bath and sonicated with 7.5 amplitude microns for 3×3 min (Sonyprep 150 MSE Sanyo, Tamro-Medlab, Sweden) with 1 min interruptions. The PL-peptide mixture, native or modified by 0.5 M MDA for 311 at 37° C. or 5 mM CUCl 2 for 18 h at 37° C., was stored under argon in glass vials at 4° C. wrapped in aluminum foil and used within 1 week. The MDA-modified mixture was dialyzed against PBS containing 1 mM EDTA with several changes for 18 h at 4° C. before storage. The modification of the mixture was tested in denatured polyacrylamide gels (BioRad Laboratories AB; Sundbyberg, SE), suitable for separation of peptides.
[0095] Native or modified synthetic peptides diluted in PBS pH 7.4 (20 leg/ml), in presence or absence of liposomes, were absorbed to microtiter plate wells (Nunc MaxiSorp, Nunc, Roskilde, Denmark) in an overnight incubation at 4° C. As a reference, one of the peptides (P6) was ran on each plate. After washing with PBS containing 0.05% Tween-20 (PBS-T) the coated plates were blocked with SuperBlock in TBS (Pierce, Rockford, Ill.) for 5 min at room temperature followed by an incubation of pooled human plasma, diluted 1/100 in TBS-0.05% Tween-20 (TBS-T) for 2 h at room temperature and then overnight at 4° C. After rinsing, deposition of auto-antibodies directed to the peptides were detected by using biotinylated rabbit anti-human IgG- or IgM-antibodies (Dako A/S, Glostrup, Denmark) appropriately diluted in TBS-T. After another incubation for 2 h at room temperature the plates were washed and the bound biotinylated antibodies were detected by alkaline phosphatase conjugated streptavidin (Sigma), incubated for 2 h at room temperature. The color reaction was developed by using phosphatase substrate kit (Pierce) and the absorbance at 405 nm was measured after 1 h of incubation at room temperature. The absorbance values of the different peptides were divided with the absorbance value of P6 and compared.
Statistics
[0096] SPSS was used for the statistical analyses. The results are presented as median and range and as proportions when appropriate. Boxplot and scatterplots were used till illustrate the relationship between age and selected peptides among cases and corresponding controls. Corresponding graphs were also used to illustrate the relationship between age and selected peptides, cases and controls, respectively, below and above the median age (61 year) at baseline and separately for cases and controls below the median age. In cases and controls, separately, partial correlation coefficients, adjusted for age and sex, were computed between selected peptides and blood lipid levels and common carotid IMT. Age- and sex adjusted partial correlation coefficients were also computed between common carotid IMT and selected peptides in cases and controls below and over the median age. An independent sample t-test was used to assess normally distributed continuous variables and a Chi-square test for proportions between cases and controls. Non-parametric test (Mann-Whitney) was used to assess non-normally distributed continuous variables between cases and controls. All p-values are two-tailed.
[0000]
TABLE
Age- and sex adjusted correlation coefficient for different
baseline MDA peptides and common carotid artery intima-media
thickness among younger (49-61 years) and older (62-67 years)
cases with myocardial infarction and their corresponding controls
matched for age, sex, smoking and hypertension.
CASES plus CONTROLS
CASES plus CONTROLS
PEPTIDE
Aged 49-61 year, n = 116
Aged 62-67 year, n = 111
IGM
MDA 32
0.235t
−0.101
MDA 45
0.366$
−0.030
MDA 74
0.178
0.063
MDA 102
0.255$
−0.039
MDA 129
0.330$
−0.009
MDA 162
0.2451
0.001
MDA 210
0.254
0.013
MDA 240
0.284$
0.006
IGG
MDA 215
0.119
−0.059
p < 0.05;
$/x0.01 | The present invention relates to antibodies raised against fragments of apolipoprotein B, in particular defined peptides thereof, for immunization or therapeutic treatment of mammals, including humans, against ischemic cardiovascular diseases, using one or more of said antibodies. | 0 |
This application is a 371 of PCT/EP03/00411 filed on Jan. 16, 2003, which in turn claims priority to European application, 02004880.7 filed on Mar. 4, 2002.
BACKGROUND OF THE INVENTION
The present invention relates to a method of stabilizing caseino-glycomacropeptide (cGMP) in aqueous formulations and reducing an off-flavor formation. In particular, the present invention comprises a formulation, having a pH below about 0.6 and/or, comprising a hydrophobic resin and/or an agent blocking functional groups in the caseino-glycomacropeptide.
Caseino-glycomacropeptide (cGMP) is a glycosylated compound formed during the enzymatic cleavage of kappa-casein from the milk of mammals by the action of rennet or pepsin. To obtain this compound as a starting material, e.g. an acidic casein or a caseinate hydrolyzed by rennet, or even a demineralized, lactose-free sweet whey, is treated with trichloroacetic acid to precipitate the proteins, the supernatant is collected and dialyzed, and finally, the dialysate is dried.
So as to obtain cGMP on an industrial scale acidic casein or sodium or calcium caseinate is treated with rennet which results in the coagulation of para-kappa-casein. The supernatant is then acidified to a pH of about 4–5 in order to precipitate the calcium phospho-caseinate. After separation of the precipitate, the solution is neutralized, demineralized by reverse osmosis, and finally concentrated and dried. Other processes include flocculating whey proteins from whey emanating from cheese production, recovering the supernatant and ultrafiltrating the supernatant using membranes having a cutoff threshold of approximately 15,000 Dalton, thus producing a retentate containing the sialo-glycoproteins.
The cGMP thus obtained is utilized in a variety of different applications, such as in a supplement to nutritional formulas as anti-thrombotic, anti-diarrhoeal compound and for special amino acid diets. Due to its microbizidal activity cGMP is also utilized in formulations for treating bacteria in the buccal cavity which are responsible for the formation of dental plaque and caries. It has been found that the capacity of Actinomyces strains and Streptococcus strains, bacteria populating the buccal cavity and considered to be involved in the initiation and formation of dental plaque, to adhere to buccal epithelial cells, to the surface of teeth coated with saliva and to form co-aggregates with one another may be reduced by providing cGMP in dental formulations, thus diminishing the detrimental effects of said bacterial strains. In addition, cGMP is also described to participate in the effect of a remineralization of demineralized portions of tooth structures.
One of the disadvantages of such formulations, however, resides in that an off-flavor develops during storage thereof. To solve this problem the art has proposed to include binding proteins in the formulations, such as antibodies, as a means of controlling the perceptibility of odoriferous materials which may be present, more specifically undesirable flavors or fragrances or constituents thereof.
Yet, proceeding accordingly is still cumbersome and due to the materials involved also expensive.
SUMMARY OF THE INVENTION
An object of the present invention therefore resides in overcoming the shortcomings of the prior art and to provide a cGMP containing formulation, that exhibits an extended shelf life without developing off-flavor.
During the extensive studies leading to the present invention, the inventors achieved to solve this problem by providing a cGMP containing aqueous composition comprising, a hydrophobic resin and an agent, that blocks specific functional groups in cGMP, responsible for off-flavour formation, and/or by adjusting the pH of the composition to a value of less than about 7.
Surprisingly, an extension of the shelf-life of cGMP containing products may already be obtained by simply lowering the pH-value of the product below about 6. However, for many products, in particular for compositions which are intended to be used on the skin or in the orifice a higher pH-value is desirable. In order to be able provide also cGMP-containing products with a pH-value above about 6, having an extended shelf-life, the present invention proposes the addition of a hydrophobic resin and of an agent blocking the functional groups in cGMP.
Additional features and advantages of the present invention are described in, and will be apparent from, the following Detailed Description of the Invention.
DETAILED DESCRIPTION OF THE INVENTION
One of the main advantages of the present invention is that both, the addition of a hydrophobic resin and of an agent blocking the functional groups in cGMP and the lowering of the pH-value are complementing each other. Depending on the chosen final product and/or the desired shelf-life, a person skilled in the art may obtain stable products by tuning both, the pH-value and the amount of hydrophobic resin and blocking agent to be added. Thus, the present invention offers not only the possibility to stabilize the composition, but also to minimize the amount of the respective additives, by decreasing the pH of the product correspondingly. The minimization of food additives is very desirable both economically and in view of the acceptance of the product, as products having an low amount of food additives are highly estimated by the customers.
Additionally, the composition of the present invention not only exhibits an extended shelf-life, but surprisingly also provides an increased stability and an essentially reduced off-flavor formation, when exposed transiently during storage or transportation to temperatures above room-temperature.
In a second aspect the present invention provides a method of producing a composition, which comprises preparing a composition comprising cGMP, adding an agent, that chemically blocks functional groups in cGMP and a hydrophobic resin, and/or adjusting the pH-value to a value in the range of from about 3 to about 6.
In a third aspect the present invention provides use of the composition in the manufacture of a medicament or a composition for treating or preventing caries, plaque formation, dental diseases, diseases of the mouth cavity or gums.
Preferably, said hydrophobic resin may be selected from the group consisting of SERDOLITH® III polystyrene-divinylbenzene-copolymer resin, LEWATIT® EP-63 polystyrene-divinylbenzene-copolymer resin, LEWATIT® OC 1064 LEWATIT® ion exchange resin, LEWATIT® OC 1066 ion exchange resin, LEWATIT® VC-OC ion exchange resin or AMBERLITE® XAD polystyrene copolymer resin and combines thereof. In a preferred way, a food-tolerable substance is used instead of hydrophobic resin, such as chlorophillin, sodium octenyl succinate starch, hydroxypropyl methyl cellulose or casein. Without being bound to any theory it may be supposed that said hydrophobic resin is acting as a sorbens trapping certain off-flavor substances. The amount of the hydrophobic resin may be selected in the range of from 0.01 to about 5 wt.-%, preferably from 0.05 to about 5 wt.-%, more preferably from 0.1 to about 2 wt.-%, each based on the final product.
The blocking or masking agent may be chosen from any acid anhydride, that may be included in an aqueous formulation, or derivatives thereof. Preferred examples may be selected from the group consisting of succinic anhydride, maleic anhydride, propio-lactone, chlorophillin and derivatives thereof, such as there isomeric forms. In the context of this application the term “derivatives thereof” comprises any compound derived from the above mentioned components by e.g. substituting moieties, as long as the activated acid component, i.e. the anhydride element remains. When utilized in a food product the blocking agent is preferably a food-grade chemical compound. Without being bound to any theory, it is supposed that said acid anhydrides react with chemical moieties of cGMP, in particular with amino groups, and thus prevent e.g. Maillard reactions or Strecker degradation reactions. The amount of the blocking agent is in the range of from about 0.005 to 1 wt.-%, preferably 0.01 to 1 wt.-%, more preferably 0.01 to 0.6 wt.-%, more preferably 0.1 to 0.5 wt.-%, each based on the final product.
The pH of the final product or composition is in the range of from about 3 to about 7, preferably in the range of from about 4 to about 6. For an lowering of the pH-value organic or inorganic acids or acidic buffer systems may be used, in particular e.g. aqueous HCl, H 3 PO 4 and acetic acid.
The composition contemplated by the present invention may be any aqueous formulation, preferably any composition having a water activity between 0.2–1, since in these formulations the detrimental effects of a degradation and/or off-flavor development are prominent. The invention is particularly suited for compositions having a water activity of between 0.7–0.9, more preferably of about 0.8. The term “water activity” is to be understood as defined in e.g. Food Chemistry, Belitz H. D., Grosch W., (1999) p. 4–6, Springer. The measurement of water activity was performed on a Hygroskop DT (Rotronic AG, Zurich, Switzerland).
In principle, the composition of the present invention may be any food or pharmaceutical product containing cGMP, in particular a food product having a sweet taste due to the presence of sugars or sugar substitutes, which tend to be involved in Maillard reactions (that result in an off-flavor of the product), dairy products, such as e.g. an infant formula or a pharmaceutical product, in particular a pharmaceutical product for treating or preventing dental problems, such as e.g. caries or plaque formation, or a cosmetic or an oral composition.
According to a preferred embodiment, the composition of the invention may be a product for oral hygiene or a product for any application in the mouth cavity and/or throat, in particular a tooth paste, a gel, a tooth powder, a mouth wash, a chewing gum, a tablet or a lozenge. In particular, the composition may also be a product for oral hygiene which is present in pre-applied form on any dental cleaning means, such as dental floss.
A preferred embodiment of the invention is a composition comprising cGMP, Serdolith 111, and succinic anhydride or maleic anhydride.
The following examples illustrate the invention in a more detailed manner. It has, however, to be understood that the present invention is not limited to the examples but is rather embraced by the scope of the appended claims.
EXAMPLE 1
Preparation of a cGMP Basis Composition
A cGMP basis composition consisting of 39 wt.-% glycerol, 10 wt.-% cGMP, 0.002 wt.-% chlorohexidine (in this model added as preservative against microbial growth) and water was prepared. The resulting basis composition has an water activity value a w of 0.8, which was determined according to manufacturer instructions (Hygroskop DT, Rotronic AG, Zurich, Switzerland).
EXAMPLE 2
pH-Dependent Off-Flavor Formation
Samples of the cGMP basis composition according to Example 1 were taken and the pH value of each of said samples was adjusted by adding either 1 M hydrochloric acid or 2 M sodium hydroxide to a pH-value in the range of between 5.5 and 8.0. All samples were stored at 49° C. for 3 weeks and were subjected subsequently to organoleptic tests.
No off-flavor was organoleptically detectable in samples having a pH-value of less than 6. During said organoleptic tests, test persons evaluated the odor of the samples adjusted to different pH-values.
These results were confirmed by a volatile flavor analysis by GC-MS. The volatile flavor compounds can be extracted according to the method described by De Frutos M, Sanz J, Martinez-Castro I, (1988) Chromatographia, 25, 861–864. The GC-MS separation and identification was performed accordingly: GC—Hewlett Packard 5890 II, MS—Hewlett Packard 5972, capillary column—Supelcowax 10, 60 m×0.25 mm, 0.15 μm film thickness, Flow—1 ml helium/min, Injection volume—1 μl cold on-column, Temperature gradient—35° C., 50° C./min to 60° C., 4° C./min to 150° C., hold for 4 min, 10° C./min to 240° C. and hold for 20 min, the NIST MS spectra library was used for substance identification. No peaks indicative for a known cGMP degradation product or off-flavor substance in substantial amounts could be detected in samples having a pH-value of less than about 6.
Additionally, also a comparison of the HPLC finger print of a freshly prepared cGMP basis composition and of the above-described samples was performed. Essentially, no changes were observed in the HPLC finger print of samples having a pH-value of less than about 6. The analytical conditions for the separation of cGMP by HPLC were the following: HPLC—Agilent 1100, Quaternary pump, diode array detector at 215 nm, injection volume—25 μl, column—TSK Gel Super ODS, 2 μm, 110A, 2×4.6 mm and 100×4.6 mm, column temperature 50° C., mobile phase—A) 0.05% trifluoric acid in water, B) 0.035% trifluoric acid in acetonitrile, flow 2.5 ml/min, solvent gradient—20% B to 40% B in 6 min, 40% B to 50% B in 1.5 min, 50% B to 95% B in 0.5 min, hold for 0.5 min, 95% B to 20% B in 1.5 min and hold for 2 min.
EXAMPLE 3
Effects of the Addition of Blocking Agent or Hydrophobic Resin on the Off-Flavor Formation
0.4 wt.-% of succinic anhydride anhydride (Merck GmbH, Darmstadt, Germany) or 2 wt.% of Serdolith III (Fluka, Buchs, Switzerland) were added to the cGMP basis composition obtained according to Example 1. Samples were taken, the pH of said samples was adjusted as described in Example 2 to a value of 6.8 respective 6.5 and said samples were stored as described in Example 2.
No off-flavor formation could be detected organoleptically (experimental proceeding, see Example 2) or via GC-MS (experimental proceeding, see Example 2) even in samples having a pH-value of of 6.8 respective 6.5, thus having a pH-value of above 6. For control, otherwise identical samples without the above-mentioned blocking agent and hydrophobic resin were prepared which had a detectable off-flavor in case of an pH-value of above 6.
EXAMPLE 4
Effects of the pH-Adjustment or the Addition of Blocking/Masking Agent or Hydrophobic Resin on the Off-Flavor Formation of Dental Care Products Containing cGMP
Samples of commercially identical dental care products were taken, cGMP was added and the pH value of each of said samples was adjusted by adding either 1 M hydrochloric acid or 2 M sodium hydroxide to a pH-value in the range of between 5.0 and 7.5. All samples were stored at 49° C. for 3 weeks and were subjected subsequently to organoleptic tests.
No off-flavor was organoleptically detectable in samples having a pH-value of less than 6. During said organoleptic tests, test persons evaluated the odor of the samples adjusted to different pH-values.
In a similar experiment, 0.25 wt.-% of succinic anhydride (Merck GmbH, Darmstadt, Germany) or 0.25 wt.-% of maleic acid anhydride (Fluka, Buchs, Switzerland) or 0.1 wt.-% propio-lactone (Acros, Chemie Brunschwig, Basel, Switzerland) or 0.01 wt.-% chlorophillin or 1 wt.-% of Levatit OC 1066 (Fluka, Buchs, Switzerland) were added to the cGMP containing dental care product composition. The pH of said samples were adjusted as described in Example 2 to a value of 7.0 and said samples were stored as described in Example 2.
No off-flavor formation could be detected organoleptically (experimental proceeding, see Example 2) even in samples having a pH-value of 7.0, thus having a pH-value of above 6. For control, otherwise identical samples without the above-mentioned blocking agent and hydrophobic resin were prepared which had a detectable off-flavor in case of a pH-value of above 6.
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. | A cGMP containing aqueous composition exhibiting a reduced off-flavor even after extended storage, comprising a hydrophobic resin; and an agent, that chemically blocks functional groups in cGMP. Methods of preparing and using the product are also provided. | 0 |
FIELD OF THE INVENTION
[0001] The present invention relates to a bacillus composition characterized by fast germination and outgrowth in bile salts (simulated gut environment) and by producing a compound of interest. The bacillus composition may be used as supplement in animal feed where it has a probiotic (health and growth promoting) effect and increases the digestion and availability of nutrients from animal feeds.
BACKGROUND ART
[0002] Probiotic bacteria such as Bacillus subtilis and Bacillus licheniformis are used in the animal feed industry as supplement to the diet. Their usage is related to the ability of bacillus to replace or reduce the use of antibiotics, which are used as growth promoters in the animal feed industry.
[0003] Christian Hansen A/S, Denmark commercializes an example of such a probiotic growth-promoting product under the trade name GalliPro® (deposited as DSM 17231). GalliPro® is a Bacillus subtilis spore cell composition.
[0004] Besides the suggested mode of actions (e.g. immune modulation, gut flora modifier) probiotic bacillus are able to produce many beneficial components, such as enzymes, which are excreted in the gastro intestinal tract (GIT) when used as animal feed supplement. Enzymes such as phytase are excreted and improve the digestion and better uptake of animal feed (higher digestibility). The diet (feed) is mostly composed of plant origin such as grains, corn, soybean, soy oil and amino acids. Overall these effects contribute to the production of cost effective animal products.
[0005] Probiotic bacilli are also able to produce other beneficial components such as essential amino acids.
[0006] Bacillus spores can pass the acidic gastric barrier and germinate and outgrow within the gastrointestinal (GIT) of the animals. This has great advantages, since when ingested they can excrete numerous types of beneficial components, e.g. bacteriocins and also excrete useful essential amino acids. Moreover, the bacillus spores are thermostabile during a feed pelletizing process and are thereby an excellent delivery system to get both bacteriocins and e.g. essential amino acids into the GIT.
[0007] In the survival and proliferation process of bacillus in GIT, the role of bile is important. Bile is produced in the liver and stored in the gallbladder. Bile contains water, lecithin, bilirubin and biliverdin and bile salts.
[0008] It is known from the literature that bile has some negative influences on the survival and germination and outgrowth of bacillus spore cells to vegetative cells in the GIT of animals. Therefore research is ongoing to find probiotic bile resistant Bacillus strains.
[0009] The article (Antonie Van Leeuwenhoek. 2006 August; 90(2): 139-46. Epub 2006 Jul. 4) describes isolation of a number of Bacillus samples/cell directly from the intestine of chickens. The isolated bacillus cells were tested for probiotic activity. The six bacilli with highest probiotic activity were testes for bile salt resistance and it was found that a specific highly probiotic bacillus has a relatively high level of bile salt resistance.
[0010] In this article there is no special focus on any time periods for the testing of bile resistance. In the experimental part the bacillus spore cells are simply tested for resistance after 5 days of presence in bile salt (see paragraph “Simulated small intestinal fluid tolerance test” on page 141).
[0011] US2003/0124104A describes that probiotic conventional bacillus endospores are sensitive to low concentration of bile salts, i.e. spore germination and/or rehydration is inhibited by the presence of even low concentrations of bile salts. This is contrary to other bacteria such as enteric pathogens, such as E. coli or S. aureus (see section [0014] to [0015]). In view of this it is suggested to screen/select for bacillus spores that are resistant to the inhibitory activity of bile salts, and as a result, germinate into vegetative cells, which then colonize the colon (see [0019]).
[0012] The working examples are all in presence and no real experimental data of actually screened specific Bacillus cell are provided in the description.
[0013] Further the bile salt screening conditions are relatively generically described. In particular there are no indications of any time periods for the selections of bile resistance. Said in other words, based on the only broad/generic teaching of this document one may select Bacillus cells that only can outgrow (germinate) slowly, i.e. are capable of germinating from spores to vegetative cells after e.g. 20 hours in presence of relevant amount of bile salt.
[0014] In this document there is no description or suggestion to select for bacillus cells that can outgrow (germinate) rapidly, i.e. capable of germinating and outgrowing from spores to vegetative cells reaching a defined growth point within a certain time interval in presence of a relevant amount of bile salt.
[0015] In summary, the prior art references relating to selection/screening of bile resistant bacillus cells are not focusing on rapid outgrowth/germination from spore cells to vegetative bacillus cells.
[0016] International PCT application with application number PCT/EP2008/057296 was filed Nov. 6, 2008. Applicant is Chr. Hansen A/S and it was NOT PUBLISHED at the filing date of this present application.
[0017] PCT/EP2008/057296 describes novel bacillus spores characterized by having an improved/rapid speed of germination and outgrowth from spore to vegetative cell in presence of a bile salt medium.
[0018] The bacillus spores as described herein have the same improved/rapid speed of germination and outgrowth from spore to vegetative cell as described in PCT/EP2008/057296.
[0019] PCT/EP2008/057296 only describes bacillus vegetative cells that are producing phytase in an increased amount as compared to the reference bacillus cell DSM 19467. As can be seen below, in first aspect and claim 1 herein is disclaimed such high producing phytase bacillus cells of PCT/EP2008/057296.
[0020] When there below is referred to prior art this shall be understood as prior art made available to the public (e.g. published articles/patents) at the filing date of this present application.
SUMMARY OF THE INVENTION
[0021] The problem to be solved by the present invention is to provide a bacillus composition which can excrete high amounts of beneficial compounds in the gastro intestinal tract (GIT) of an animal.
[0022] The solution is based on that the present inventors have developed a novel selection method for the identification of new improved bacillus compositions.
[0023] A novel important step of the herein described new selection method is to specifically screen/select for bacillus spore cells with improved/rapid speed of germination and outgrowth from spores to vegetative cells in the presence of bile salts.
[0024] As described above, the prior art has described methods for selecting bacillus cells capable of growing in presence of bile salts, but the prior art screening/selection methods do NOT focus on the speed of germination and outgrowth in the presence of bile salt. Accordingly, the prior art selected bile resistant bacillus cells do not germinate and grow fast enough to comply with the speed of germination and outgrowth criteria as described herein. For instance, bacillus cells isolated directly from the intestine of e.g. chickens (as e.g. described in the Antonie Van Leeuwenhoek article discussed above) in the gut environment are not selected (under natural pressure) to germinate and outgrow rapidly in the intestine.
[0025] As shown in working examples herein this is also true for the commercial available Bacillus composition GalliPro®, which simply germinates and outgrows too slowly and does not reach the defined growth point within the first 20 hours in presence of physiological levels of bile salts to comply with the speed of germination and out-growth criteria as described herein. GalliPro® is a Bacillus subtilis composition that is commercially successful.
[0026] The herein described novel DSM 19467 was selected by using GalliPro® as a starting strain and a selective pressure method and a subsequent isolation for rapid germination and outgrowth from spores to vegetative cells in presence of bile salt as described herein.
[0027] See e.g. table 1 for further details (GalliPro® may herein also be termed DSM 17231).
[0028] In FIG. 1 herein this is illustrated schematically.
[0029] In summary, it is believed that no prior art describes an isolated Bacillus composition, which comprises from 10 5 to 10 12 CFU/g bacillus cells, wherein the cells of the bacillus composition complies with the rapid germination and outgrowth in the presence of bile salt criteria as described herein.
[0030] Without being limited to theory, the present inventors have identified that rapid germination and outgrowth is a very important aspect of the invention as bacillus spores, which are resistant to bile but do not germinate and outgrow fast enough, will be excreted before any positive characteristics, such as essential amino acid production, can be made in significant amounts by the vegetative bacillus cells. Bacillus spores germinating too slowly will simply pass through the gastro intestinal tract (GIT) before the bacteria can produce any significant amount of e.g. essential amino acids.
[0031] After a number of detailed tests and analysis, the inventors therefore chose to work with a time range up to 20 hours and select the fastest germinating and outgrowing spores within this time period in presence of high physiological concentrations of bile salts. Without being limited to theory and based on the herein disclosed detailed experimental work, the present inventors have identified that it is important to have a rapid germination and outgrowth within the first 18 and 19 hours in the presence of 4 and 6 mM bile salt, respectively.
[0032] The present inventors then identified that once bacillus cells, with rapid germination and outgrowth in bile salt medium, have been selected these cells are highly useful as starting cells for mutagenesis to obtain new cells with improved essential amino acid production.
[0033] As illustrated schematically in FIG. 1 and example 4, the rapid outgrowing bile resistant selected strain, DSM 19467, was used as starting strain for classical mutation and the high essential amino acid producing strain were selected. As can be seen in example 4, some of the selected strains produce at least 5 times more of the essential amino acid leucine than DSM 19467 and GalliPro®.
[0034] As discussed above, in our earlier application PCT/EP2008/057296 DSM 19467 was use to make new high phytase producing strains—see for instance example 4 of PCT/EP2008/057296.
[0035] The description of PCT/EP2008/057296 is incorporated herein by reference.
[0036] Accordingly, one may see DSM 19467 as a very useful kind of e.g. “intermediate” to make new bacillus cells with improved properties such as e.g. higher phytase or essential amino acid production or any other relevant compound of interest.
[0037] Further, it is evident to the skilled person that once the inventors herein have disclosed the ESSENTIAL test assay for testing rapid germination and outgrowth of example 1 plus the identified strain DSM 19467 it will be routine work for the skilled person to select other new bacillus cells complying with the criteria of the first aspect herein—i.e. other alternative bacillus cells with similar characteristic to DSM 19467.
[0038] Accordingly, a first aspect of the invention relates to a bacillus composition, which comprises from 10 5 to 10 12 CFU/g bacillus spore cells, wherein the bacillus composition is characterized by:
[0039] (i): the bacillus spores have a rapid germination and outgrowth from spore to vegetative cell in presence of a bile salt medium comprising 4 and 6 mM bile salts, defined by that the bacillus spores reach a vegetative cell growth point of 0.4 OD 630 within less than 18 and 19 hours, respectively, wherein the vegetative cell growth point is the point in the growth curve where the OD value starts to increase (due to growth of the vegetative cells) in a continuous way and reaches an OD 630 of 0.4;
(I): wherein the bile salt medium is the standard known non-selective Veal Infusion Broth (VIB) medium of example 1 herein supplemented with a bile salt mixture comprising the conjugated bile salts taurodeoxycholate and glycodeoxycholate and the deconjugated bile salt deoxycholate in the proportions 60% of the taurodeoxycholate, 30% of the glycodeoxycholate and 10% of deoxycholate; and wherein the OD assay analysis is performed by the following steps: (a): filling a well in a microtiter plate with 0.150 ml bile salt medium having 10 8 bacillus spores per ml medium (i.e. this is time zero); and (b): incubating the plate at 37° C. under atmospheric conditions and measuring the OD 630 values, using a spectrophotometer and with agitation before each reading, to get a representative growth curve over time; and
[0044] (ii) the bacillus vegetative cells are producing a relevant compound of interest;
[0045] and with the proviso that the bacillus vegetative cells are NOT cells as described in claim 1 of PCT/EP2008/057296, wherein the bacillus vegetative cells of item (ii) are producing phytase in an amount of at least 1.25 times more than the reference bacillus cell DSM 19467, wherein the produced phytase amount is measured by the standard phytase assay of example 2 of PCT/EP2008/057296 after 4 hours growth at 37° C. in the standard known non-selective Heart Infusion Broth (HIB) medium of example 2 of PCT/EP2008/057296; and
[0046] wherein the phytase assay analysis is performed by the following steps:
(a): making a overnight culture of bacillus vegetative cells in a enriched culture medium; and (b): transferring a 1% inoculum from the overnight culture to HIB medium (i.e. this is time zero) and incubation at 37° C. until phytase activity measurement.
[0049] The term “a relevant compound of interest” of point (ii) should be understood broadly. As discussed above, bacillus cells with spores that comply with criteria (i) of first aspect can in principle e.g. be used as a starting strain to screen for bacillus vegetative cells that may e.g. have higher/improved production of any compound of interest—such as e.g. an enzyme of interest.
[0050] As discussed above, the reference bacillus cell DSM 19467 is selected for rapid germination and outgrowth in presence of bile salt by using GalliPro® as starting strain. DSM 19467 is not selected for improved production of a compound of interest (e.g. an essential amino acid). Without being limited to theory, it is believed that the herein relevant production of the vast majority of commercial relevant compounds of interest (e.g. phytase or an essential amino acid) of DSM 19467 corresponds to GalliPro® production of the same compound.
[0051] In relation to point (i) the vegetative cell growth point for GalliPro® is at least 20 hours after incubation in 4 and 6 mM bile salt and for the novel DSM 19467 strain, as described herein, it is after 14 and 15 hours in 4 and 6 mM bile salts, respectively (see FIG. 2 and working example 3 herein).
[0052] It is here relevant to note that the present inventors also tested the commercial available product CALSPORIN® (Calpis Co., Ltd., Japan) to determine the vegetative cell growth point under the conditions of point (i) of first aspect. As for GalliPro® the commercial product CALSPORIN® is a Bacillus subtilis composition used as a probiotic feed additive. The vegetative cell growth point under the conditions of point (i) of first aspect for CALSPORIN® was more than 20 hours at 4 and 6 mM bile salts, respectively. This is considerably more than the 18 and 19 hours required under point (i) and this illustrates that commercially available products have hitherto not been selected for rapid germination and outgrowth. As discussed above, “natural” bacillus cells have not been under any selective pressure to get rapid germination and outgrowth. Without being limited to theory, it is therefore believed that “natural” bacillus cells are not complying with the conditions of point (i) of first aspect.
[0053] Both the bile resistance [of point (i)] and essential amino acid assay [of point (ii)] are based on known, commercially available standard elements (such as e.g. standard media, bile salts; standard OD measurements and standard tests).
[0054] The reference bacillus cell is deposited as DSM 19467 and is therefore publicly available.
[0055] The Bacillus subtilis cell GalliPro® is deposited as DSM 17231 (named “GalliPro®”) and is therefore publicly available.
[0056] Accordingly, based on the detailed assay description herein (see e.g. example 1 herein for bile resistance assay and example 2 herein for essential amino acid assay) the skilled person is routinely able to repeat these assays to objectively determine whether a specific bacillus cell of interest complies with the bile resistance [of point (i)] and essential amino acid [of point (ii)] levels of the first aspect of the invention.
[0057] The novel bacillus composition as described herein may be used as a probiotic supplement to animal feed. The dose and administration may be done according to the art as for instance as done for prior art GalliPro® bacillus compositions.
[0058] Accordingly, a second aspect of the invention relates to a method for feeding an animal comprising administering the bacillus composition of first aspect and herein described related embodiments to an animal in conjunction with other animal feed ingredients.
[0059] A third aspect of the invention relates to a method for screening and isolating a novel bacillus cell comprising the following steps:
(a): selecting and isolating from a pool of individual bacillus spore cells of a new bacillus spore cell that is capable of germinating and outgrowing so rapidly that it reaches a vegetative cell growth point within less than 18 and 19 hours under the conditions of point (i) of first aspect; (b): making a vegetative bacillus cell from the isolated spore cell of step (a) and mutating the novel selected and isolated cell to get a pool of new individual bacillus vegetative cells; (c): selecting and isolating from the pool of new individual bacillus vegetative cells of step (b) a new bacillus vegetative cell that is capable of producing a relevant compound of interest; and (d): analyzing the vegetative bacillus cell of step (c) to confirm that it has maintained the rapid germination and outgrowth of step (a) and isolating the selected bacillus cell.
[0064] It is evident to the skilled person that once the inventors herein have disclosed the relevant test assays (in particular the assay for testing rapid germination and outgrowth of example 1) plus the reference strain DSM 19467 it will be routine work for the skilled person to select other new bacillus cells complying with the criteria of the first aspect herein.
[0065] As discussed herein, by using the novel screening/selection method as described herein the inventors have selected and isolated a number of new improved bacillus cells.
[0066] Embodiment of the present invention is described below, by way of examples only.
[0067] Definitions
[0068] All definitions of herein relevant terms are in accordance of what would be understood by the skilled person in relation to the herein relevant technical context.
[0069] The term “ bacillus cell” relates herein to both a bacillus spore cell and a bacillus vegetative cell.
[0070] The term “ bacillus spore” in relation to bacillus spore cell relates herein to a spore that according to the art may be characterized as a dormant, tough, non-reproductive structure produced by bacillus bacteria. The primary function of spores is generally to ensure the survival of a bacterium through periods of environmental stress. They are therefore resistant to ultraviolet and gamma radiation, desiccation, lysozyme, temperature, starvation, and chemical disinfectants. Spores are commonly found in soil and water, where they may survive for long periods of time. The spore coat is impermeable to many toxic molecules and may also contain enzymes that are involved in germination. The core has normal cell structures, such as DNA and ribosomes, but is metabolically inactive. When a bacterium detects that environmental conditions are becoming unfavorable it may start the process of sporulation, which takes about eight hours.
[0071] The term “ bacillus vegetative cell” relates to functional vegetative bacillus cells, which can divide to produce more vegetative cells.
[0072] The term “germination and outgrowth” relates to that bacillus spores germinate and outgrow to bacillus vegetative cells. As know to the skilled person reactivation of the spore occurs when conditions are favorable and involves germination and outgrowth. Germination involves the dormant spore starting metabolic activity and thus breaking hibernation. It is commonly characterized by rupture or absorption of the spore coat, swelling of the spore, an increase in metabolic activity, and loss of resistance to environmental stress. Outgrowth follows germination and involves the core of the spore manufacturing new chemical components and exiting the old spore coat to develop into a functional vegetative bacterial cell, which can divide to produce more cells.
[0073] Growth curves (OD versus time) of bacillus cells show distinct growth phases. As the spores are transferred to a nutrient rich medium the germination is initiated followed by a temporary decrease in OD (phase I), which is due to the release of dipicolinic acid and consequently hydration of the spore coat. In the second phase (phase II=outgrowth phase) there is a period with a relative little change in OD, until the spores are developed into a functional vegetative bacterial cells, which can divide to produce more cells and thereby give a continuous increase in OD value. The point when one starts to get the continuous increase in OD values reaching an OD of 0.4 is herein termed “vegetative cell growth point”.
[0074] The term “optical density” is defined as a measure of optical absorbance using a spectrophotometer. Optical density (OD) is the absorbance of an optical element for a given wavelength A per unit distance. If OD is e.g. measured at wavelength 630 nm it may be referred to as OD 630 .
DRAWINGS
[0075] FIG. 1 : In this figure the steps to get to the herein novel improved strains are illustrated. The working examples herein were started from DSM 17231 (GalliPro®) which was classically mutated and screened/selected for rapid germination and outgrowth in presence of bile salt to get the novel selected strain DSM 19467. DSM 19467 was used as starting strain for classical mutation and high essential amino acid producing strains were selected.
[0076] FIGS. 2 a and 2 b: These figures show clearly the improved rapid germination and outgrowth of DSM 19467 bacillus spores of the present invention as compared to DSM 17231 in presence of 4 and 6 mM bile salt as described herein.
DETAILED DESCRIPTION OF THE INVENTION
[0077] A Relevant Compound of Interest:
[0078] As discussed above, the term “a relevant compound of interest” of point (ii) should be understood broadly. As discussed above, bacillus cells with spores that comply with criteria (i) of first aspect—such as e.g. DSM 19467—can in principle e.g. be used as a starting strain to screen for bacillus vegetative cells that may e.g. have higher/improved production of any compound of interest—such as e.g. an enzyme of interest.
[0079] Suitable examples of a compound of interest may be enzymes such as e.g. mannanase. A compound of interest could also be an essential amino acid such as leucine.
[0080] In a preferred embodiment of point (ii) of the first aspect the bacillus vegetative cells are producing the compound of interest in an amount that is higher than the reference bacillus cell DSM 19467, wherein both the vegetative cell and reference bacillus cell DSM 19467 are grown under identical conditions.
[0081] In example 4 herein on can see an example of this embodiment—in example 4 herein is described vegetative cells with at least 5 times higher production of the essential amino acid leucine as compared to DSM 19467.
[0082] Further, as discussed above—in example 4 of PCT/EP2008/057296 is described similarly for phytase—i.e. vegetative cells with higher production of phytase as compared to DSM 19467.
[0083] Bacillus Composition:
[0084] The term “ bacillus composition” shall be understood according to the art. It is herein understood as a bacillus composition comprising a number of bacillus spore cells with a characteristic of interest.
[0085] The bacillus composition may comprise different types of bacillus cells (e.g. B. subtilis and Bacillus licheniformis ). In essence the composition shall simply comprise the amount of bacillus spore cells given in the first aspect herein, wherein the bacillus cells comply with the criteria given in the first aspect.
[0086] As known to the skilled person, herein commercially relevant bacillus spore cell compositions are generally made by fermentation. The obtained spore cells are generally concentrated, dried, mixed with a carrier and packed into a suitable container.
[0087] The relevant e.g. 10 5 to 10 12 CFU/g bacillus cells of the composition may be present in a commercially relevant form known to the skilled person.
[0088] Accordingly, in an embodiment 10 5 to 10 12 CFU/g bacillus spore cells of the composition are present as dried (e.g. spray dried) cells or as frozen spore cells.
[0089] In a preferred embodiment the bacillus composition comprises from 10 6 to 10 12 CFU/g bacillus spore cells, more preferably from 10 7 to 10 12 CFU/g bacillus spore cells.
[0090] The term “CFU/g” relates to the gram weight of the composition as such, including suitable relevant additives present in the composition. It does not include the weight of a suitable container used to package the bacillus composition.
[0091] An embodiment relates to that the bacillus composition is packaged into a suitable container.
[0092] As known to the skilled person a commercially relevant bacterial composition generally also comprises other relevant additives such as e.g. one carrier/ingredient of the group belonging to whey, whey permeate, calcium carbonate/limestone and anti caking agents such as aluminum silicates and kieselgur (diatomaceous earth).
[0093] Beside the herein relevant bacillus cells the composition may also comprise other relevant microorganisms of interest such as e.g. lactic acid bacteria of interest.
[0094] Bacillus Cell
[0095] The bacillus cell may be any relevant bacillus cell of interest.
[0096] In a preferred embodiment the bacillus cell is at least one bacillus cell selected from a bacillus species selected from the group consisting of:
[0097] Bacillus subtilis, Bacillus uniflagellatus, Bacillus lateropsorus, Bacillus laterosporus BOD, Bacillus megaterium, Bacillus polymyxa, Bacillus licheniformis, Bacillus pumilus, and Bacillus sterothermophilus, Bacillus coagulans, Bacillus thermophilus, Bacillus mycoides, Bacillus cereus, and Bacillus circulars.
[0098] In a more preferred embodiment the bacillus cell is a B. subtilis cell or a Bacillus licheniformis cell.
[0099] The most preferred is wherein the bacillus cell is a B. subtilis cell.
[0100] Assay to Select for Rapid Germination and Outgrowth in the Presence of Bile Salt
[0101] As discussed above the bile resistance assay of point (i) of first aspect is based on known commercially available standard elements (such as e.g. standard media, bile salts; standard OD measurements).
[0102] Accordingly, based on the detailed assay description herein (see e.g. example 1 herein) the skilled person is routinely able to repeat this assay to objectively determine whether a specific bacillus spore cell of interest complies with the rapid germination and outgrowth from spore to vegetative cell criteria as described in point (i).
[0103] In point (i) it is explained that vegetative cell growth point is the point in a growth curve starting with 10 8 spores/ml corresponding to OD of around 0.2-0.3 until the time where the OD value has increased (due to growth of the vegetative cells) in a continuous way and has reached OD 0.4. This is in accordance with how a skilled person would understand such a vegetative cell growth point and based on a growth curve the skilled person may routinely determine this, within a limited variability of around ±30 minutes, as explained herein.
[0104] Working example 1 herein provides a detailed description of a bile resistance assay suitable to select for rapid germination and outgrowth in the presence of bile salt. The detailed conditions of this example 1 is herein a preferred assay to determine if a bacillus spore cell of interest complies with the criteria of point (i) of first aspect.
[0105] The term “bile salt” relates to the salt of bile acids. Bile acids are steroid acids found predominantly in the bile of mammals. They are produced in the liver by the oxidation of cholesterol, and are stored in gallbladder and secreted into the intestine in the form of salts. They act as surfactants, emulsifying lipids and assisting with their absorption and digestion. The bile salts used in example 1 were prepared mimicking the physiological concentrations and compositions of porcine bile salts. As known to the skilled person porcine bile salts compositions may herein be considered as relatively “harsh” conditions as compared to avian bile salt compositions.
[0106] The term “bile salt medium” relates to medium comprising relevant bacillus growth ingredients such as relevant nutrients and bile salt.
[0107] Vegetative Cell Growth Point—in Bile Salt Assay—Point (i) of First Aspect
[0108] As said above, in relation to point (i) of first aspect the bacillus spore cells, as described herein, have a germination and outgrowth from spore to vegetative cell that is so rapid that they reach a vegetative cell growth point of 0.4 OD within less than 18 and 19 hours at 4 and 6 mM bile salts, respectively.
[0109] As said above, the novel DSM 19467 strain reaches the vegetative cell growth point after 14 and 15 hours incubation in 4 and 6 mM bile salt, respectively.
[0110] Accordingly, in a preferred embodiment the bacillus spores reach the vegetative cell growth point after 17 and 18 hours incubation in 4 and 6 mM bile salt under the conditions of point (i) of first aspect, more preferably the bacillus spores reach the vegetative cell growth point after 15 and 16 hours incubation in 4 and 6 mM bile salt under the conditions of point (i) of first aspect.
[0111] As explained above and shown schematically in FIG. 1 the herein described novel DSM 19467 strain was selected by using the commercially available GalliPro® as a starting strain for mutagenesis and selection for rapid outgrowth in presence of bile salt as described herein.
[0112] GalliPro® is a composition comprising Bacillus subtilis cells and the Bacillus subtilis is deposited as DSM 17231. Accordingly, GalliPro® may herein be seen as a reference strain.
[0113] As said above, the vegetative cell growth starting point for GalliPro® is after 20 hours incubation in 4 and 6 mM bile salts under the conditions of point (i) of first aspect. Accordingly, in an embodiment the bacillus spores reach the vegetative cell growth point at least 3 hours earlier than the reference Bacillus subtilis spores cells deposited as DSM 17231 (“GalliPro®”) under the conditions of point (i) of first aspect, more preferably the bacillus spores reach the vegetative cell growth point at least 4 hours earlier than the reference Bacillus subtilis spores cells deposited as DSM 17231 (“GalliPro®”) under the conditions of point (i) of first aspect, and most preferably the bacillus spores reach the vegetative cell growth starting point at least 5 hours earlier than the reference Bacillus subtilis spores cells deposited as DSM 17231 (“GalliPro®”) under the conditions of point (i) of first aspect.
[0114] Essential Amino Acids
[0115] As known to the skilled person an essential amino acid may be an essential amino acid selected from the group consisting of: phenylalanine, valine, threonine, tryptophan, isoleucine, methionine, leucine, lysine, cysteine, tyrosine, histidine and arginine.
[0116] In a preferred embodiment the essential amino acid is at least one essential amino acid selected from the group consisting of: phenylalanine, valine, threonine, tryptophan, isoleucine, methionine, leucine, and lysine.
[0117] In more preferred embodiment the essential amino acid is at least one essential amino acid selected from the group consisting of: valine, isoleucine and leucine.
[0118] A herein very relevant essential amino is leucine.
[0119] As understood by the skilled person, the bacillus vegetative cells may produce higher amount of more than one essential amino acid, such as e.g. higher amount of two or three or more different essential amino acids.
[0120] Amino Acid Assay
[0121] As discussed above the amino acid assay of point (ii) of first aspect is based on standard known commercially available elements (such as e.g. standard media, standard test).
[0122] Accordingly, based on the detailed assay description herein (see e.g. example 2 herein) the skilled person is routinely able to repeat this assay to objectively determine whether a specific bacillus vegetative cell of interest complies with the produced essential amino acid amount as described in point (ii).
[0123] Working example 2 herein provides a detailed description of a essential amino acid assay.
[0124] The detailed conditions of this example 2 are herein a preferred essential amino acid assay to determine if a bacillus vegetative cell of interest complies with the criteria of point (ii) of first aspect.
[0125] Produced Amount of Essential Amino Acid—Point (ii) of First Aspect
[0126] In relation to point (ii) of first aspect, the Bacillus vegetative cells are preferably producing at least one essential amino acid in an amount of at least 2 times more than the reference Bacillus cell DSM 19467 under the conditions of point (ii) of first aspect.
[0127] In a more preferred embodiment in relation to point (ii) of first aspect, the Bacillus vegetative cells are preferably producing at least one essential amino acid in an amount of at least 4 times more than the reference Bacillus cell DSM 19467 under the conditions of point (ii) of first aspect.
[0128] A Method for Feeding/Administering Bacillus Spores to an Animal
[0129] As said above a second aspect of the invention relates to a method for feeding an animal comprising administering the bacillus composition of first aspect and herein described related embodiments to an animal in conjunction with other animal feed ingredients.
[0130] The animal may be any animal of interest. Preferably, the animal is an animal selected from the group consisting of poultry, ruminants, calves, pigs, rabbits, horses, fish and pets.
[0131] When administering GalliPro® according to the art it is normally done in a dose from around 10 4 -10 8 CFU/g feed, commonly 10 5 -10 6 CFU/g feed or in doses equivalent to normal feed intake/kg live weight animal.
[0132] Alternatively the bacillus spores may be administered to the animal in one of the following ways:
[0133] (1): put it into drinking water for animals;
[0134] (2): sprayed onto animals; or
[0135] (3): application via paste, gel or bolus.
[0136] A Method for Screening and Isolating a Novel Bacillus Cell
[0137] As said above, the third aspect relates to a method for screening and isolating a novel bacillus cell.
[0138] In the method of the third aspect is selected for a bacillus cell capable of fulfilling the conditions of point (i) and (ii) of the first aspect.
[0139] As understood by the skilled person, the specific herein detailed described bile resistance and essential amino acid amount assay (see e.g. example 1 herein for bile resistance assay and example 2 herein for essential amino acid assay) parameters may be changed to make a alternative screening method that still obtains the main goals as described herein, i.e. a bacillus cell that is capable of fulfilling the conditions of point (i) and (ii) of the first aspect.
[0140] In a preferred embodiment, bile resistance assay of example 1 is used in step (a) of the screening method of third aspect and the essential amino acid assay of example 2 is used in step (c) of the screening method of third aspect.
[0141] In step (d) of the screening method of third aspect a vegetative bacillus cell is isolated. This vegetative bacillus cell may be used to make bacillus spores from.
[0142] Accordingly, in an embodiment the screening method of third aspect is followed by a extra step (e), wherein the isolated bacillus vegetative cell of step (d) is fermented to make from 10 5 to 10 12 bacillus vegetative cells and these 10 5 to 10 12 bacillus vegetative cells are used to make 10 5 to 10 12 bacillus spore cells, which are isolated to give a Bacillus composition, which comprises from 10 5 to 10 12 CFU/g bacillus spore cells.
[0143] The end result of step (e) is a novel Bacillus composition, which comprises from 10 5 to 10 12 CFU/g bacillus spore cells, and wherein the bacillus cells are capable of fulfilling the conditions of point (i) and (ii) of the first aspect.
[0144] Accordingly, a separate aspect of the invention relates to a Bacillus composition, which comprises from 10 5 to 10 12 CFU/g bacillus spore cells, and wherein the bacillus cells are capable of fulfilling the conditions of point (i) and (ii) of the first aspect obtainable by the screening method of third aspect followed by extra step (f) described above.
[0145] In step (b) of the screening method of third aspect is made mutations of the earlier selected bile resistant bacillus cell to select for high essential amino acid producing cells in step (c). As understood by the skilled person this may e.g. by classical mutation (e.g. by chemical treatments or UV) of specific exchange of genes to make a so-called Genetic Modified Organism (GMO).
[0146] Deposited Strains
[0147] A sample of the novel Bacillus subtilis strain has been deposited at DSMZ (Deutsche Sammlung von Mikroorganismen and Zellkulturen GmbH, Maschroder Weg 1b, D-38124 Braunschweig) under the accession number DSM 19467 with a deposit date of Jun. 27, 2007. The deposit has been made under the conditions of the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure.
EXAMPLES
Example 1
Bile Resistance Assay
[0148] Medium:
[0149] The medium was a standard non-selective commercial available medium Veal Infusion Broth (VIB) (Difco, 234420).
[0150] At the filing date of the present application the product catalogue (“Difco™/BBL™ Manual) from the provider BD Diagnostic Systems (www.bd.com) read in relation to the Veal Infusion Broth:
[0151] “Infusion from lean veal and peptone provide the nitrogen, vitamins, carbon and amino acids in veal infusion media. Sodium chloride maintains the osmotic balance of the formulations”; and
[0152] The medium was prepared according to manufacture instructions by suspending 25 g of the Veal Infusion Broth powder in 1 L of purified water (2.5% solution) and heat with frequent agitation and boil for 1 minute to completely dissolve the powder.
[0153] A 2.5% Veal Infusion Broth solution comprised per liter:
[0154] Lean Veal, Infusion: 10 g
[0155] Proteose Peptone: 10 g
[0156] Sodium Chloride 5 g
[0157] The medium was distributed into sterile bottles and autoclaved for 15 min at 121° C.
[0158] Bile Salt Solutions/Medium:
[0159] Mixtures of bile salts were prepared mimicking the physiological composition and concentration of bile salts in pig bile and the bile salts were dissolved in the Veal Infusion Broth medium as prepared above to give a final bile salt concentration of 8 mM.
[0160] The conjugated bile salts were taurodeoxycholate (Sigma T-0875, U.S.) and glycodeoxycholate (Sigma G-9910, U.S.) and the deconjugated bile salt deoxycholate (Sigma D-5670 U.S.) and the final 8 mM mixed bile salt solution contained 60% of the taurodeoxycholate, 30% of the glycodeoxycholate and 10% of deoxycholate. Before autoclaving for 15 minutes at 121° C., the solutions were adjusted to pH 7.4 using sodium hydroxide. The prepared 8 mM bile salt medium, were diluted to get bile salt concentrations of 0, 1, 2, 4, 6 and 8 mM.
[0161] The bile salts were added to the Veal Infusion Broth medium in a concentrated form.
[0162] Accordingly, the final amount of lean veal infusion, Proteose Peptone and Sodium chloride were essentially as for the 2.5% Veal Infusion Broth medium before the bile salts were added.
[0163] Spore Suspensions
[0164] To distinguish between vegetative cells and spores and to ensure pure spore products for inoculation, the spore counts of the bacillus product were determined using +/−heat treatment at 80° C. for 10 min. After heat treatment and subsequent cooling to room temperature, serial 10-fold dilutions were conducted in saline peptone water. Duplicates of Tryptose Blood Agar plates (Difco 0232-01) were inoculated with 0.1 ml from the appropriate decimal dilutions. The plates were incubated at 37° C. until the next day. Based on preceding spore count determinations of the products, spore suspensions were prepared in sterile distilled water to reach final calculated spore concentration of 10 8 CFU/ml. The counts of vegetative cells and spores in the final inocula were determined using the method described above. The final concentration of 10 8 CFU/ml corresponded to a start OD 630 at 0.2-0.3.
[0165] Growth Measurement: Optical Density Measurements
[0166] Sterile flat bottom 96 well microtiter plates were used (Greiner Bio-one GmbH, Germany). Each well was filled with 0.150 ml VIB inoculated with spores (˜1×10 8 spores per ml equivalent/corresponding to a start OD 630 ˜0.2-0.3) and the plates were incubated for 20 hours at 37° C. with a 1 minute shaking cycle of intensity 4 (high) before each reading.
[0167] To avoid condensation on the inside of the plate cover, the lids were exposed to a dilute solution of Triton X-100.
[0168] The germination and outgrowth kinetics of Bacillus strains were measured using a spectrophotometer at wavelength 630 nm (OD 630 ) (Bio-tek Instruments, Inc. VE). Readings were performed with 10 minute intervals and analyzed using the KC4™ software (Bio-tek Instruments, Inc., USA). After 20 h, data were exported to Excel® spreadsheets for further analysis, imported in SAS version 9.0 and statistically analyzed.
Example 2
Amino Acid Assay
[0169] The method to measure and quantify the amino acids produced by the bacillus cells used in this study is a standard GC-MS method for aqueous samples, using methyl chloroformate as derivatization agent.
[0170] Growth of Bacillus Cells
[0171] The Bacillus cells are inoculated and grown in a minimal salts growth medium at 37° C., 150 rpm and grown for 2 days and amount of amino acid is then measured in the supernatant as described below.
[0172] The bacillus cells are propagated in a Minimal Salts Medium according to Chapman (1972) with the following composition:
[0000]
(NH 4 ) 2 SO 4 (Merck 1.01217.1000)
1 g/l
K 2 HPO 4 (Merck 1.05101.1000)
7 g/l
KH 2 PO 4 (Merck 1.04873.1000)
3 g/l
MgSO 4 •7H 2 O (Merck 1.05886.1000)
0.1 g/l
[0173] Autoclaved for 15 min at 121° C. and added autoclaved glucose to a final concentration of 0.5%.
[0174] Incubation is done in tubes with 10 ml medium for 2 days at 37° C. and 150 rpm.
[0175] Amino Acid Assay
[0176] The amino acid assay is carried out on cell supernatants, since the amino acids are secreted to the media. Samples are sterile filtered and kept at −20° C. until analysis.
[0177] Reagents:
[0178] Reagent 1: Internal standard solution. Norvaline 1 mM: 0.0172 g Norvaline+100 ml MQW
[0179] Reagent 2: Methanol/Pyridine 32/8 (v/v) (Catalysator)
[0180] Reagent 3: Methyl Chloroformate p.a. (MCF) (Derivatization agent)
[0181] Reagent 4: 1% MCF/CHCl 3 (v/v) (Extraction): 1 ml Methyl Chloroformate p.a.+Chloroform ad 1000 ml.
[0182] Sample Preparation:
Pipette 150 μl (25 μl+125μ MQW) sample into 2 ml injection vial. Add 150 μl IS Add 200 μl 1-Methanol/Pyridine 32/8% (v/v). Mix well. Add 25 μl MCF (Methyl Chloroformate). Mix well until gas development occurs. Add 500 μl 1% MCF/CHCl 3 (v/v), cap and mix vigorously. Phase separation occurs within minutes. If phase separation is too slow, centrifuge the vial (500 rpm/10 min).
[0188] If Norvaline is used as antimetabolite, an external standard or another suitable internal standard should be used instead, and the 150 μl IS substituted with either MQW or sample.
[0189] Samples are run on GC-MS with a standard amino acid column and protocol.
Example 3
Selection of Bile Resistant Bacillus subtilis Cell DSM 19467
[0190] The starting bacillus cell was the Bacillus subtilis cell GalliPro®.
[0191] GalliPro® was mutagenized to get a pool of new individual bacillus cells. Spores were made and selected for rapid germination and outgrowth from spore to vegetative cell in presence of a bile salt medium comprising 4 and 6 mM bile salt a described in example 1 above.
[0192] Bacillus subtilis cell DSM 19467 was selected.
[0193] Table 1 below shows germination and outgrowth data.
[0194] Time (hours) from 10 8 CFU/ml corresponding to OD 0.2-0.3 until OD 0.4 is reached (mean of 3 replicates).
[0000]
B. subtilis
4 mM bile
6 mM bile
Existing product GalliPro ®
>20
>20
(DSM 17231)
Bile tolerant
13 h 40 m
15 h
(DSM 19467)
Commercial product: Calsporin
>20
>20
[0195] Some of the data of this example was made by testing phytase overexpressing DSM 19489. But for the technical result of this example this is herein relatively irrelevant since DSM 19467 has germination and outgrowth roughly as DSM 19489. See PCT/EP2008/057296 for further details.
[0196] Conclusion
[0197] DSM 19467 is a bile resistant strain and clearly germinating and outgrowing faster than GalliPro®.
Example 4
Selection of Amino Acid Over-Producing Bacillus Cells from DSM 19467
[0198] The starting bacillus cell was the Bacillus subtilis cell DSM 19467 selected in example 3.
[0199] DSM 19467, either wildtype or mutants produced by, e.g., UV-mutagenesis, was grown on Minimal Salts Medium agar, described in example 2B above and added 1.5% agar, containing amino acid analogues in suitable inhibitory amounts. Depending on the amino acid to be over-expressed various amino acid analogues could be used, e.g., norvaline or 4-aza-DL-leucine for overproducing leucine (Bardos, 1974, Topics in Current Chemistry 52, 63-98). Colonies resistant to the amino acid analogue were picked, grown in Minimal Salts Medium and assayed for amino acid production. The vegetative cells were selected for producing high amount of amino acid by using the GC-MS method described in example 2B above.
[0200] High amino acid producing Bacillus subtilis cell was selected.
[0201] Results of Amino Acid Measurements
[0202] A number of strains were selected which were producing the essential amino acid leucine in an amount that was significant higher than the reference bacillus cell DSM 19467.
[0203] A number of the selected strains produced at least 5 times more leucine than DSM 19467.
[0204] Conclusions:
[0205] This example shows that one can routinely—based on the instructions herein—screen and identify a strain, which produces at least one essential amino acid (here exemplified by leucine) in an amount that was significant higher than the reference bacillus cell DSM 19467.
[0206] DSM 19467 is originating from GalliPro® and is not selected for high essential amino acid production. Accordingly, it is believed that GalliPro® produces roughly the same amount of essential amino acid as DSM 19467.
Example 5
Bile Resistance “Check” of High Essential Amino Acid Producing Bacillus Cells
[0207] Preferred high essential amino acid producing bacillus cells selected in example 4 are re-checked for their ability of rapid germination and outgrowth from spore to vegetative cells as described in example 1.
[0208] The results are that they—as expected—have maintained roughly the same good rapid germination and outgrowth as the starting cell DSM 19467 used to obtain them.
REFERENCES
[0209] 1. Antonie Van Leeuwenhoek. 2006 August; 90(2):139-46. Epub 2006 July 4
[0210] 2. US2003/0124104A
[0211] 3. US6255098
[0212] 4. PCT/EP2008/057296 | A bacillus composition characterized by fast germination and outgrowth in bile salts (simulated gut environment) and by producing a compound of interest. The bacillus composition may be used as supplement in animal feed where it has a probiotic (health promoting) effect and increases the digestion and availability of nutrients from animal feeds. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of a priority under 35 USC 119 to French Patent Application No. 0015129 filed Nov. 23, 2000, the entire contents of which are incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention concerns medical radiology and, in particular, the galactography technique in mammography.
[0003] Mammography is an imaging technique used, notably, for the detection of breast cancers. It involves an examination which is the first among three stages of medical follow-up, namely: detection, for example, of a breast cancer; diagnosis; and intervention.
[0004] Detection covers women typically in the age bracket of 40 or 50 to 70 years old. At the examination, films are taken at two different angles: one so-called craniocaudal front view, that is, in the direction from head to toe, and a mediolateral oblique (MLO) view. In the latter case, the detector is situated under the axillary space. A film is then taken of the entire mammary gland, of the axillary space and of the whole length of the breast.
[0005] The internal structure of the breast comprises fibrous tissues and adipose tissues, which contain fat. The mammary gland has a structure which resembles a natural sponge. The mass of that sponge comprises the fibrous tissues, the fat being located inside the cells of the sponge. When a projection image is made, which is the case in radiology, it is sought to obtain an image giving the most contrast between those two types of tissue. That normal structure of the breast and possibly so-called superdensity areas, generally associated with lesions which can be either cancerous or benign, are visualized. It is therefore sought to mark those areas and to characterize them in order to determine their nature.
[0006] It is also sought to detect small calcium deposits. When they are of very small size, that is, between 100 microns and 1 millimeter, it is a question of microcalcifications. If it is felt that those calcifications might possibly be malignant, the patient passes from the detection stage to the diagnostic stage. Additional views and geometric enlargements are then made to refine the radiological analysis. Some of the characteristics (density, shape) are used in order to have greater certainty as to the malignant or benign character of the site.
[0007] These analyses can be accompanied by a clinical examination (palpation of the breast, etc.).
[0008] Upon the interventional stage, several procedures are open, particularly a needle puncture on the area which seems suspicious. This protocol is often prompted by observation of an opacity or of a microcalcification.
[0009] In some cases, a nipple discharge occurs. It is then important to study the structure behind the nipple. In addition to adipose and fibrous tissues, there is an arborescent network of ducts called galactophores, which bring the milk to the nipples. The endings of those ducts at the nipple, called galactophorous orifices, typically number fifteen to twenty. When there is a nipple discharge, the galactophorous orifice at the source thereof is marked and the duct concerned is visualized by a so-called galactography technique.
[0010] Up to now, galactography has been carried out solely with images on standard X-ray film. The technique consists of dilating the galactophorous orifice with a needle or a plastic cannula. Once the orifice is sufficiently dilated, an X-ray attenuating contrast medium is injected by that needle or cannula.
[0011] The galactophorous orifice is then closed by a wax-base plug. The breast is compressed by means of a compression plate and a radiological image is made of the entire breast. That makes it possible to see the galactophorous network which has been injected.
[0012] The examination can thus be summed up in the following stages: i) beginning with the uncompressed breast, ii) dilation of the galactophorous orifice, iii) injection of contrast medium, iv) closing of the orifice, and v) compression of the breast on the film.
[0013] By analyzing those structures, some lesions can be marked, for example, galactophorous ducts which are intersected, dilated or otherwise approached, and pathologies situated inside the galactophorous ducts can thus be detected.
[0014] With this technique, a problem arises when the breast is very dense, so that the galactophorous ducts are hardly visible, even with injection of a contrast medium.
[0015] Furthermore, when a film is used, a good contrast (that is, good information legibility) requires the density of the X-ray flux reaching the film to come within a lower limit and an upper limit. As a result, the image can be saturated if the breast is dense and, therefore, does not offer good visibility of the galactophorous ducts.
[0016] Similar difficulties are also encountered in other aspects of mammography.
BRIEF DESCRIPTION OF THE INVENTION
[0017] In light of these problems, the invention proposes a mammography approach which takes advantage of techniques of digital processing of the radiological image in order to improve information legibility.
[0018] According to an embodiment the invention concerns a method of obtaining mammo-graphic images intended for galactography comprising the following stages:
[0019] a. acquiring a first radiological image of the breast in a compressed or immobilized state;
[0020] b. introducing a contrast medium in a part of the breast;
[0021] c. acquiring at least a second radiological image of the breast in the compressed or immobilized state and with contrast medium; and
[0022] d. partial or complete subtraction of the first image in relation to the second image, or vice versa.
[0023] It is observed that, depending on the application of the invention and, notably, the radiation energies used, just holding the breast during the procedure can actually be envisaged, without having to compress it, or compressing it only slightly.
[0024] The first and second radiological images are advantageously obtained by means of a digital X-ray detector.
[0025] The contrast medium can be introduced in at least one galactophorous duct by injection in the nipple via at least one galactophorous duct. The contrast medium is preferably introduced when the breast is in the compressed or immobilized state. In a preferred embodiment, the contrast medium is introduced by a catheter or the like, which can be maintained in an adjustable position along at least one of the following axes: a lateral axis x in the patient's right-left direction; a lateral axis y in the costal grid-nipple direction; and an axis z in the direction of the thickness of the breast and preferably on both lateral axes x and y and axis z. The catheter or the like can be further adjustable in polar orientation. It can also be arranged to synchronize the movement of the catheter or the like along axis z, in the direction of the thickness of the breast, with the movement of compression of the breast.
[0026] The subtraction is advantageously of logarithmic type. Furthermore, a weighting factor can be applied to at least one among the first and second images and so as to obtain controlled visibility of the tissues superposed on the opacified parts. At least one of the weighting factors can be modified in real time in order to change the relative contrast of the opacified part of the breast and, notably, the galactophorous ducts and neighboring tissues.
[0027] With the method, at least one image can be acquired during introduction of the contrast medium in order to obtain information concerning the dynamics of progression of the contrast medium in the breast and, notably, in the galactophorous network.
[0028] The method can further include a stage of resetting of the first and second images before the subtraction, for example, by means of an “elastic” resetting algorithm.
[0029] In a customary application of the invention, the radiological images are obtained with X-rays presenting a maximum number of photons with an energy around 20 keV, which favors contrast of the breast tissues. However, in order to obtain better visibility of the contrast medium, iodinated, for example, an X-ray beam can be used advantageously with a spectrum of higher energy, for example, with a maximum number of photons around 35 keV.
[0030] According to an embodiment of the invention concerns an apparatus specifically adapted for obtaining mammographic images, intended for galactography, comprising combined in one unit: means for maintaining a breast compressed or immobilized; and means for holding a catheter or the like for introducing a contrast medium in the breast.
[0031] The means for holding is arranged to permit adjustable positioning of the catheter or the like along at least one among the aforesaid three axes x, y and z and preferably the set of both lateral axes x and y and axis z. The apparatus can include means of adjustment of the catheter or the like on a polar orientation. The means for holding can include means for grasping the catheter or the like by clipping or clamping. In the preferred embodiment, the means for grasping are guided in direction z of compression of the breast in a block mounted moving on two axes x and y in a lateral plane. If need be, the means for grasping can be arranged for positioning to be adjustable by motor drive for at least one of the axes x, y and z. The apparatus can further include means for synchronization of movement of the catheter or the like in the direction of compression of the breast with the movement of compression of the breast. The means for holding a catheter or the like are advantageously configured to make possible the introduction of the latter in a galactophorous orifice of the breast before compression of the breast and to keep the catheter in that orifice during compression of the breast. A housing can be provided for a digital X-ray detector positioned directly under the breast.
[0032] According to a third embodiment of the invention concerns a mammography system intended for galactography, comprising the apparatus, the latter being set up on the axis of emission of an X-ray source, a digital X-ray detector and its means for control, and means for processing the images obtained by the latter.
[0033] The means for image processing advantageously includes means for a subtraction of images taken, on the one hand, before and, on the other, during and/or after introduction of the contrast medium. The means for image processing can further include means for image resetting used in subtraction.
[0034] An embodiment of the invention also concerns the use of the aforesaid system for digital galactography by image subtraction.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] Other advantages and characteristics of the invention will be more clearly apparent on reading the preferred embodiments, given purely by way of nonlimitative example with reference to the attached drawings in which:
[0036] [0036]FIG. 1 is a simplified functional diagram of a mammography unit of an embodiment of the invention;
[0037] [0037]FIG. 2 a is a plan view of a frame for breast compression and catheter positioning of an embodiment of the invention;
[0038] [0038]FIG. 2 b is a front view of the frame of FIG. 2 b;
[0039] [0039]FIG. 3 a is a general view of a device for holding the catheter in the frame of FIGS. 2 a and 2 b;
[0040] [0040]FIG. 3 b is a profile view of a element for clipping on the catheter of the device of FIG. 3 a;
[0041] [0041]FIG. 4 is a side view of a catheter holding device allowing a polar adjustment of orientation of the latter, according to a variant of an embodiment of the invention; and
[0042] [0042]FIG. 5 is a flow chart summarizing the stages of an image subtraction galactography examination of an embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0043] [0043]FIG. 1 shows schematically the basic elements used in a radiological imaging chain 1 for mammography according to an embodiment of the invention. A generator and an X-ray source 2 are provided, connected to a filter 4 . The latter serves, notably, to eliminate low energy rays, which are useless and harmful to the patient, and makes it possible to transmit an appreciably monoenergetic X-ray beam 6 .
[0044] The beam 6 coming from the filter 4 is directed toward a frame 8 intended to keep a breast 10 in a slightly compressed state. For that purpose, the frame 8 contains a lower block 12 on which the lower part of the breast rests, and an upper plate 14 , called compression plate, which is movable in order to bear on the upper part of the breast and to compress it against the lower block. The movement of the plate can be motor-driven under control of an automatic or semiautomatic system. The lower block 12 integrates a digital X-ray detector 16 , the sensitive surface 16 a of which is turned toward the beam 6 , directly under the breast.
[0045] The detector 16 , made, for example, by solid state technology, replaces the standard radiological film used. Its design and method of operation are well known and will not be described here for the sake of conciseness. It is recalled that its sensitive surface 16 a is composed of a two-dimensional matrix of X-ray sensitive elements. Each element supplies a signal according to a radiation dose received during a period of exposure. That signal, which corresponds to a pixel, is read on the set of elements of the matrix in order to reconstitute a radiological image in electronic form.
[0046] The different sequencing and control signals of the detector 16 are supplied by a control unit 18 which makes it possible, notably, to control exposure times and conditions. The output pixels of the detector are subjected to an initial processing (block 20 ) in order to adjust the signal levels, correct possible pixel defects and order them to deliver an electronic image according to a pre-established standard.
[0047] The images thus obtained are then processed in a unit 22 in order to make various conversions aimed at improving information legibility. Among those functions is digital subtraction imaging, which consists of removing or attenuating the common parts of two images in order to bring out the distinctive part, as will be described in detail below.
[0048] To make digital subtraction mammography possible according to the invention, the frame 8 includes a device for contrast medium injection in the breast, in order to obtain images taken before and after introduction of the contrast medium. This device contains a needle or a catheter, or even an injection cannula 24 intended to be inserted in a galactophorous orifice and connected by a flexible conduit 26 to a contrast medium injection source 28 . A hollow needle with a diameter of around 1 mm can be used as catheter, as well as other instruments used in standard galactography for contrast medium injection.
[0049] [0049]FIGS. 2 a and 2 b illustrate the frame 8 in greater detail with plan and front views respectively. The frame 8 contains a bearing structure 30 , at the base of which the lower block 12 is situated. This block presents a platform 12 a on which the breast 10 rests (FIG. 2 b ) and includes the digital detector 16 , so that the sensitive surface 16 a of the latter is situated just below the platform 12 a . The compression plate 14 is mounted sliding on uprights 32 to allow a controlled compression of the breast either by manual displacement or by electromechanical control.
[0050] The contrast medium injection apparatus contains a structure 34 which keeps the catheter 24 mobile on three perpendicular axes, so as to permit the adjustment of its positioning in a lateral plane (parallel to the platform 12 a ) and vertical plane. More precisely, the structure 34 allows a displacement of the catheter 24 : (a) on a lateral axis in the right-left direction of the patient, making possible an adjustment of position when the breast is placed with a slight rotary motion on the platform 12 a , or when it is desired to place the breast a little on the side of the detector 16 , in the case of small breasts. That degree of freedom is materialized by one or more first rods 36 on axis x, on which a device 38 holding the catheter 24 is mounted sliding, the latter being laterally aligned perpendicular to axis x; (b) on a lateral axis y and in the costal grid-nipple direction (that is, on the axis of the catheter), in order to be adapted to the depth of the breast. This degree of freedom is materialized by a pair of second rods 40 perpendicular to the first rods 36 and to each end of the latter. On each second rod 40 a slide 42 is mounted, on which a respective end of the first rod or rods 36 is fastened, so that the latter can slide along the second rods on axis y. The second rods 40 are connected to the rest of the frame by a crossbeam 44 ; and (c) on an axis z at right angles to the detector (vertical) making possible an adaptation to the thickness of the compressed breast, typically from 2 to 10 cm, the patient generally standing or sitting for this type of examination. This degree of freedom is materialized by a slide in the device 38 holding the catheter 24 , aligned with axis z and on which a catheter-fastening clamp or a clip 46 can be moved.
[0051] [0051]FIGS. 3 a and 3 b are more detailed views of the catheter holding device 38 . It comes in the form of a block 38 having one or more holes 46 at the bottom, each crossed by a respective first rod 36 to enable a controlled slide along the axis x. One of the main faces 38 a of the block contains a window 48 giving access to a pair of parallel slides 50 , aligned along the vertical axis z. An element 46 for fastening the catheter 24 hangs from each slide. Each fastening element can thus be moved along its respective slide on axis z. In the example, the fastening element 46 contains a housing of circular section 46 a configured to follow and hug the contour of the section of the catheter intended to be held. The top of the housing has a flared open part 46 b making it possible to introduce and withdraw the catheter by clipping and unclipping, the width of the opening being less than the diameter of the held section of the catheter 24 . This type of fastening by clipping makes possible a rapid disengagement of the catheter in case of accident.
[0052] The material for the fastening element 46 is chosen for its elasticity and tolerance to sterilization treatment by autoclave or by decontamination agents commonly used in clinical practice.
[0053] The tip 24 a of the catheter is sufficiently disengaged from the holding device 38 for the latter not to disturb the patient's movements.
[0054] According to an embodiment illustrated in FIG. 4, the fastening element 46 is attached to the slide 50 of the block 38 via a ball joint 52 . This arrangement makes it possible to impart a polar adjustment motion by rotation of the fastening element and, therefore, of the catheter 24 for better control of positioning with respect to the nipple. The polar degree of freedom thus allowed is advantageous in order to compensate for a position of the breast slightly in rotation. For greater ease of rotary motion, a single holding element 46 can be provided in the slide 50 rather than a pair of such elements.
[0055] It is observed that one of the functions of the holding device 38 is to prevent the catheter 24 from being disengaged from the nipple under the effect of pressure upon injection of the contrast medium or upon an untimely contact between the patient or the operator and the catheter during an examination. The risks of injury or pain are thus minimized.
[0056] If the attachment entails a clamping of the catheter, one must make sure that this does not cause too great a narrowing of the passage, in order not to disturb the flow of product upon injection. The contrast medium injection device is designed to block any undesirable reflux after injection, for example, by means of a manual or automatic control valve. This arrangement makes it possible to keep the catheter 24 in place after injection and, notably, while the film is being taken with the presence of contrast medium. The plug of the galactophorous orifice is thus advantageously replaced by wax or the like.
[0057] It is, of course, possible to arrange for motor drive of all or some of the positioning movements along axes x, y and z according to various semi-manual or automatic control methods.
[0058] Motor drive can be of particular interest in movement along axis z (which corresponds to the direction of compression of the breast), for it makes it possible to synchronize the movement of the compression plate 14 or subject it to the adjustment movement along axis z of the catheter 24 (or vice versa), so that the catheter descends at the same time as the breast is compressed.
[0059] An example will now be described of use of the mammography chain 1 for a galactography examination by an image subtraction technique. In that application, the image subtraction technique is different from that previously used in angiography, in the sense that it is necessary to compress the breast.
[0060] An image subtraction must be carried out in place, that is, it is necessary to make one image before injection and another after injection, with the breast compressed for each of the two images. The use of a solid state digital detector 16 makes it possible in that case to obtain images with contrast media of iodinated type and with an acceleration voltage in the X-ray tube 2 higher than in standard mammography techniques, that is, with a greater energy spectrum. This is of great importance in increasing the contrast of the structures injected and if reducing the dose delivered to the patient. The possibility of delivering less of a dose also enables images to be made at identical doses for the examination of thicker breasts. This makes it possible to compress the breast less. Injecting the contrast medium when the breast is less compressed can therefore be envisaged.
[0061] Initially, the nipple is dilated, a cannula or a catheter 24 is placed in one of the galactophorous duct orifices and the breast is compressed with the plate 14 . The compression is sufficient for the patient not to move during the examination in order to avoid a blurred image, but not too much, so as to let the contrast medium circulate. The holding device 38 serves to maintain the catheter firmly in the position adjusted along axes x, y, z and thus prevent the catheter from falling during the filming time. The nipple can be slightly off center, which requires an adjustment adapted to the volume of the breast and its positioning according to the patient's size and height in order to take variations of breast thickness into account. These adjustments are made thanks to the three axes of freedom x, y and z allowed by the frame 8 , as explained above, ensuring an adaptation of positioning of the cannula or catheter to the anatomy. Once the cannula or catheter 24 is in place in the nipple, the image acquisition can be undertaken, first without contrast medium and then after injection.
[0062] After the two images are obtained, assuming that there has been no movement, a subtraction can be made, which will advantageously be of logarithmic type. This approach is based on the following considerations. The material analyzed is characterized by two parameters: its thickness and its linear attenuation coefficient. If there are N0 X photons reaching an elementary portion of material on input, there are N photons on output, with a number ΔN of photons absorbed in that portion of material. This number ΔN is proportional to the absorption coefficient μ of the material (the more attenuating the material, the more it is going to absorb photons), to the thickness l (the thicker the material the more it absorbs radiation) and to the number of photons.
[0063] The following condition is therefore obtained:
Δ N=−μ.Δl.N (equation 1).
[0064] The “−” sign is explained by the fact that there is a reduction in number of photons.
[0065] By integrating on the entire thickness, the following condition is obtained:
N=N 0. exp− (μ.1) (equation 2)
[0066] If the material is not homogeneous, but contains several compounds which are going to vary with the location following a function μ (x,y,z), the term μΔ.l is replaced by the integral on the thickness L of function μ (x,y,z) dl, which gives
N=N 0. exp −∫μ( x,y,z ). dl (equation 3)
[0067] This is the general equation, taking as hypothesis a monochromatic radiation corresponding to a single energy.
[0068] In order to do the subtraction, two images are used: one so-called “mask” image, which is the one obtained before injection of contrast medium, and an pacified image, after having sent the contrast medium. Typically, everything visible in the mask image must be visible in the opacified image, except for the elements which are superposed due to injection of the contrast medium. Considering a common point of the image (same coordinates x, y), an intensity expressed in number of photons is seen on the mask image:
l=I 0. exp−∫μ.dl (equation 4)
[0069] For the opacified image, the same thing is obtained, except that possibly the μ factor is going to change (becoming μ′) by reason of the presence of the contrast medium, giving an intensity:
I′=I 0. exp−∫μ′.dl (equation 5)
[0070] If placed in a portion devoid of opacification, the coefficients μ and μ′ will be identical in both images. If placed on a point where there is actually an opacification (in the opacified image), the coefficient μ′ will be different. What is of interest here is the integral of μ.dl and, in particular, the integral of the difference in coefficients μ and μ′ of both images. If placed on the galactophorous duct which has been opacified, there is a difference between coefficients μ and μ′.
[0071] To be able to demonstrate that, the subtraction of I and I′ (equation 5−equation 4) is performed. However, there is not direct access to the integral of the coefficient, but only to the exponential of the integral. To be able to access the integral, the logarithm of the expression I0/I is taken, which is equal to ∫μ.dl for the mask image. The logarithm of the expression I0/I′ is likewise taken for the opacified image, equal to ∫μ.dl. If the logarithmic subtraction is made, one obtains:
Δ Ln =∫(μ−μ′) dl (equation 6)
[0072] where Ln signifies the base logarithm e. This corresponds to the base logarithmic subtraction.
[0073] Only the opacified part of the image then remains, namely, the galactophorous network injected. Sometimes the practitioner prefers to increase the visibility of the galactophorous ducts. while preserving the visibility of the neighboring structure so that it can be marked in space. In that case, instead of making a logarithmic subtraction, which corresponds simply to the difference of the two terms, a part of the mask image is added in order to increase the contrast just on the opacified part. For that purpose, weighting factors are added on each of the two image intensities I and I′, which gives the following general expression for image intensity Is at an elementary point after subtraction:
Is=α.Ln ( I′ )−β. Ln ( I ) (equation 7)
[0074] where: α is the weighting factor of the opacified image, and β is the weighting factor of the mask image.
[0075] In general, α=β=l. If α=l is fixed, the visibility of the tissues superposed on the opacified ducts can be progressively varied by increasing β from 0 to 1. The values of α and β can be modified in real time in order to change the relative contrasts of the opacified ducts and surrounding tissues.
[0076] Logarithmic subtraction constitutes the first step.
[0077] A second step takes into account the fact that the area scanned can, in practice, not remain immobile between the two images. It is therefore sometimes necessary to reset one image on the other, in order to take into account the possible movements of the patient between the acquisitions of the mask image and opacified image. For that purpose, so-called “elastic” reset algorithms can be used, that is, aimed at evaluating the conversion of one image to the other, assuming that the parts imaged can move according to a model which is not rigid. However, it is based on the hypothesis that the movements are not too abrupt, which is the case in nature.
[0078] As for the radiological parameters adapted to subtraction techniques in mammography with an electronic detector, according to the invention, the linear attenuation coefficients are analyzed as a function of the energy of the X-rays sent. The maximum contrast is then established with a given X-ray energy. That energy is chosen as a function of the material it is necessary to differentiate in the object studied. In mammography the tissues are soft and of different kinds: fibers and adipose tissues (fat). Fat attenuates the X-rays less than the fibrous tissues. The applicant determined that good results are obtained when the spectrum of the X-rays transmitted presents a maximum of photons with an energy situated at around 20 keV, in the form of a line characteristic of that energy. The ideal monoenergetic beam which would give the maximum contrast is then approached.
[0079] That line can be produced with an X-ray tube, the path of which is made of a given material, combined with a filter. It is recalled that the path is the emitting surface of a rotating anode of the tube, which is bombarded by accelerated electrons from a cathode heated by a tungsten filament.
[0080] The low-energy X photons are absorbed close to the surface and constitute doses harmful to the skin without being used for the image. The filter is used especially for cutting off the low-energy photons.
[0081] In an advantageous embodiment, molybdenum or rhodium-base paths are utilized. These same materials are utilized for the filters.
[0082] For dense or thick breasts, it is preferable to use rhodium paths and filters at the X-ray source, for rhodium presents a higher energy peak than molybdenum and therefore makes it possible to obtain more penetrating X-rays. This results in a lower dose delivered to the gland, with a slight loss of contrast. However, the digital detectors used make it possible to compensate for that loss by digital processing.
[0083] Thus, a smaller dose is delivered, while having a photon flux at the entrance to the detector which is sufficient to obtain an adequate image. It is altogether possible to have an image with a contrast which can be restored electronically, at a smaller dose (compared to a standard film), for a given compression thickness. If the compression thickness is slightly relaxed, with the same spectrum—rhodium path/rhodium filter—it may be necessary to increase the dose to secure a good image. It is thus possible either to spare the dose or to work at constant dose, in which case the stress on the thickness of the breast can be relaxed.
[0084] With the digital technology used according to the preferred embodiment of the invention, the capacity is obtained to make quick acquisitions with the use of suitable electronics. This also permits a kinetic acquisition making it possible to visualize the course of the contrast medium. In that case, image acquisitions are made during the phase of introduction of the contrast medium, those images also being processed by digital subtraction.
[0085] [0085]FIG. 5 is a flow chart which summarizes the stages of a galactography examination according to the invention. Once the patient's breast is positioned, the catheter 14 is introduced in one of the galactophorous orifices by using the possibilities of displacement of the catheter along axes x, y, z and possibly a polar movement. The catheter is then fixed in injection position by a holding device 38 (stage E 2 ). A compression or an immobilization of the breast is then carried out with the catheter in place (stage E 4 ). A first digital image acquisition is made with the breast compressed or immobilized (stage E 6 ), giving rise to an image before injection of contrast medium (image intensity I) (stage E 8 ). While keeping the breast compressed under the same conditions, the contrast medium is introduced in the galactophorous duct via the catheter 24 , which is already in place (stage E 10 ). Once a given quantity of the fluid has been injected, the injection device is closed to prevent a reflux. The holding device 38 ensures good attachment of the catheter to the breast during that operation. A second digital image acquisition is then made with the breast compressed and the presence of contrast medium (stage E 12 ), giving rise to an image after injection of contrast medium (image intensity I′) (stage E 14 ). The compression plate 14 is then lifted to free the breast. The catheter 24 can be withdrawn before or after that release of the breast. The images thus obtained before and after introduction of contrast medium undergo a relative reset, that is, a digital superposition (stage E 16 ). That operation can introduce an image processing with a view to correcting possible movements between the two films. The image subtraction is then made according to the algorithm described above, that is, α.Ln(I′)−β.Ln(I), with an appropriate choice of coefficients α and β, depending on the conditions of the examination (stage E 18 ). That operation give rise to image Is, consisting of a matrix of digital pixels, revealing the part of the galactophorous ducts having received the contrast fluid. That image can then be displayed, possible after an adaptation to the display standard provided (stage E 20 ). Of course, it is also possible to perform other operations on the image Is (enhancement of contrast and contours, reformatting, printing on support, remote transmission, etc.).
[0086] The invention lends itself to numerous variants possible on both the mechanical and functional levels. Various modifications in structure and/or steps and/or function may be made by one skilled in the art without departing from the scope and extent of the invention as recited in the claims. | Method and apparatus for medical radiology and, in particular, galactography in the field of mammography. The method of obtaining radiological images in galactography comprises acquiring of a first radiological image of the breast in a compressed state: introducing a contrast medium in a part of the breast; acquiring at least a second radiological image of the breast in the compressed state and with contrast medium; and partial or complete subtraction of the first image in relation to the second image, or vice versa. An apparatus for use of the method comprises means for maintaining a breast compressed or immobilized and means for holding a catheter or the like for introducing a contrast medium in the breast. | 0 |
FIELD OF THE INVENTION
[0001] The present invention relates to quinazolines class of compounds and its derivatives as novel β-glucuronidase inhibitors in order to treat various health disorders related to over expression of β-glucuronidase enzyme.
BACKGROUND OF THE INVENTION
[0002] Glucuronidation is known as a defensive process of the body to excrete the toxic chemicals from the biological system by detoxification. The process involves the conjugation of D-glucoronate with the toxin to make them water soluble that can be easily excreted out through urine or bile. β-Glucoronidases form a group of acid hydrolase enzymes which catalyze the hydrolysis of glucoronidase to aglycon and glucoronic acid. This process is known as deglucuronidation.
[0003] Ironically deglucuronidation due to the over expression of β-glucuronidase enzyme is associated with various pathological conditions, including tissue carcinoma, hepatic disorders, renal diseases, urinary tract infection, etc. β-Glucuronidase is reported to be released into the synovial fluid in inflammatory joint diseases, such as rheumatoid arthritis and AIDS. β-Glucuronidase is also found to be involved in the etiology of colon cancer while higher intestinal level of the enzyme is also associated with higher incidence of colon carcinoma.
BRIEF SUMMARY OF THE INVENTION
[0004] The productionof toxic and carcinogenic metabolites may cause the tumor formation. The expression and increasedactivity of β-glucuronidase has been reported in several diseases in human, such as cancer, rheumatoid arthritis and AIDS. β-glucuronidase inhibitorsare also reported to have efficacyto decrease the onset of colonic tumors.
[0005] β-Glucuronidase (EC 3.2.1.31) is a lysosomal enzyme that cleaves β-glucuronic acid linkages from the non-reducing termini of glycosaminoglycans, such as chondroitin sulfate, heparan sulfate, and hyaluronic acid.
[0006] Lucuronidation is a defensive mechanism of the body to get rid of the poisonous chemicals by means of making them water soluble. The studies has suggested that the process of deglucuronidation is stimulated due to the hydrolysis, catalyzed by β-glucuronidase and contributes in the onset of various pathological conditions, such as tumor or carcinogenesis as well as the re-absorption of toxic chemicals. Endogenous biliary β-glucuronidasedeconjugates the glucuronides of bilirubin and causes the expansion of cholelithiasis in human bile.
[0007] Therefore, it is important to reduce the increased activity of β-glucuronidase enzyme present in various organs, body fluids, blood cells, liver, muscle, bile, spleen, kidney, gastric juice, lung, urine, and serum [1].
[0008] Plant-based β-glucuronidase inhibitors, such as 8-hydroxytricetin-7-glucuronide and isovitexin, trihydroxypipecolic acid, and scoparic acids A and C are already in clinical use [4].
[0009] The mechanisms of regulation of enzyme activity and protein targeting of β-glucuronidase have implications in the development of a variety of therapeutics [5].
[0010] Quinazolines and quinazolinone derivatives have diverse applications as chemotherapeutic agents. Several quinazolinone derivatives exhibit a multitude of interesting pharmacological activities including anticonvulsant, antidiabetic [6], analgesic [6], sedative [6] and anti-inflammatory properties [7]. Some quinazoline derivatives are also used as medications for patients with acquired cancer chemotherapy and organ transplantation [8].
[0011] During the current study an in vitro assay was employed to evaluate the β-glucuronidase inhibitory potential of a broad range of chemical compounds. Quinazolines class of compounds was also evaluated by using D-saccharic acid 1,4-lactone as standard (IC 50 =45.75±2.16 μM). As a result, a number of quinazoline derivatives (3, 5-11, 13-16, 18-23, 25) were identified as potent inhibitor of the enzyme thus have potential to be used for the treatment of associated diseases.
[0012] To the best of our knowledge quinazoline class of compounds is reported here as novel β-glucuronidase inhibitors.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a graph off β-Glucuronidase Inhibitory Activity of Quinazolines
DETAILED DESCRIPTION OF THE INVENTION
[0014] The present invention identify a novel class offi-glucuronidase inhibitors, that possesquinazoline basic skeleton, represented by formula (1)
[0000]
[0000] Where, R represents different substituents that caused decrease or increased in the activity Table-1).
[0015] Compounds 1-25 (IC 50 ranges from 0.6±0.45-198.2±2.88 μM) were evaluated for their β-glucuronidase inhibition activity and found that compounds 2 (IC 50 =10.0±0.54 μM), 3 (IC 50 =22.2±0.31 μM), 5 (IC 50 =2.1±0.06 μM), 6 (IC 50 =3.2±0.11 μM), 7 (IC 50 =1.8±0.11 μM), 8 (IC 50 =2.8±0.042 μM),9(IC 50 =30.9±2.64 μM), 10 (IC 50 =1.1±0.05 μM), 11 (IC 50 =0.6±0.45 μM), 13 (IC 50 =2.1±0.073 μM), 14 (IC 50 =0.7±0.016 μM), 15 (IC 50 =1.17±0.124 μM), 16 (IC 50 =1.8±0.01 μM),18 (IC 50 =37.7±1.21 μM), 19 (IC 50 =39.8±2.88 μM), 20 (IC 50 =1.5±0.05 μM), 22 (IC 50 =20.1±0.92 μM),23 (IC 50 =5.5±0.10 μM) and 25 (IC 50 =44.0±3.12 μM) were more active than the standard, D-saccharic acid 1,4-lactone (IC 50 =45.75±2.16 μM).
[0016] β-Glucuronidase activity was determined by the spectrophotometric method by measuring the absorbance at 405 nm ofp-nitropheno,l formed from the substrate. The total reaction volume was 250 μL. The test compound (5 μL) was dissolved in DMSO (100%), which becomes 2% in the ultimate assay (250 μL).Similar conditions were used for the standard (D-saccharic acid 1,4-lactone). The reaction mixture contained 185 μL of 0.1 M acetate buffer, 5 μL of test compound solution, 10 μL of (1U) enzyme solution was incubated at 37° C. for 30 min. The plates were read on a multiplate reader (SpectraMax plus 384, Molecular Devices, USA) at 405 nm after the addition of 50 μL of 0.4 mMp-nitrophenyl-β-D-glucuronide. All assays were run in triplicate. IC 50 Values were calculated by using EZ-Fit software (Perrella Scientific Inc., Amherst, Mass., USA). These values are the mean of three independent assays [1].
[0017] Cytotoxic activity of compounds (1-25) was evaluated in 96-well flat-bottomed micro-plates by using the standard MTT (3-[4,5-dimethylthiazole-2-yl]-2,5-diphenyl-tetrazolium bromide) colorimetric assay. For this purpose, PC-3 cells (Prostrate Cancer)/3T3(Mouse fibroblast) were cultured in Dulbecco's Modified Eagle's Medium, supplemented with 5% of foetal bovine serum (FBS), 100 IU/mL of penicillin and 100 μg/mL of streptomycin in 25 cm 3 flask and kept in 5% CO 2 incubator at 37° C. Exponentially growing cells were harvested, counted with haemocytometer and diluted with a particular medium.
[0018] Cell culture with the concentration of 1×10 5 cells/mL was prepared and introduced (100 μL/well) into 96-well plates. After overnight incubation, medium was removed and 200 μL of fresh medium was added with different concentrations of compounds (1-100 μM). After 72 h, 50 μL MTT (2 mg/mL) was added to each well and incubated further for 4 h. Subsequently, 100 μL of DMSO was added to each well. The extent of MTT reduction to formazan within cells was calculated by measuring the absorbance at 570 nm, using a microplate ELISA reader (Spectra Max plus, Molecular Devices, Calif., USA). The cytotoxicity was recorded as concentration causing 50% growth inhibition forPC-3/ 3T3 cells.
[0000] Synthesis of Quinazolinone derivatives (1-25)
[0000]
[0019] In a typical procedure,quinazolinones 1-25 were synthesized by mixing anthranilamide (2 mmol), substituted benzaldehydes (2.1 mmol) and CuCl 2 .2H 2 O (4 mmol) in ethanol (15 mL). The mixture was refluxed for 16 hrs., while progress of the reaction was monitored through thin layer chromatography. After completion of reaction, it was cooled to room temperature and distilled water was added until the formation of precipitates. The precipitates were filtered and washed with hexane. The yields of title compounds were found to be quantitative.
[0020] 2-Phenylquinazolin-4(3H)-one (1): Yield: 0.43 g, 97%; 1 H NMR: (300 MHz, DMSO-d 6 ): δ H 12.54 (s, 1H, NH), 8.18 (m, 3H, H-5,7,8), 7.83 (d, 1H, J 8,7 =7.2 Hz, H-8), 7.75 (d, 1H, J 4′,3′ =J 4′,5′ =7.8 Hz, H-4′), 7.56 (m, 4H, H-2′,6′,3′,5′); EI MS: m/z (rel. abund. %), 222 (M + , 83.3), 119 (100).
[0021] 2-(2-Hydroxyphenyl)quinazolin-4(3H)-one(2): Yield: 0.27 g, 58%; 1 H NMR: (300 MHz, DMSO-d 6 ): δ H 13.70 (s, 1H, NH), 12.61 (s, 1H, 2′-OH), 8.23 (d, 1H, J 5,6 =7.8 Hz, H-5), 8.16 (d, 1H, J 6′,5′ =7.5 Hz, H-6′), 7.87 (t, 1H, J 7(6,8) =7.2 Hz, H-7), 7.77 (d, 1H, J 8,7 =8.1 Hz, H-8), 7.56 (t, 1H, J 6(5,7) =7.2 Hz, H-6), 7.47 (t, 1H, J 4′(3′,5′) =7.8 Hz, H-4′), 7.01 (m, 2H, H-5′,3′);EI MS: m/z (rel. abund. %), 238 (M + , 100), 119 (77.5).
[0022] 2-(4-Hydroxyphenyl)quinazolin-4(3H)-one (3): Yield: 0.47 g, 99%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.29 (s, 1H, NH), 10.14 (s, 1H, 4′-OH), 8.11 (m, 1H, H-5), 8.03 (d, 2H, J 2′,3′ =J 6′,5′ =8.4 Hz, H-2′,6′), 7.80 (t, 1H, J 7(6,8) =7.2 Hz, H-7), 7.67 (d, 1H, J 8,7 =8.0 Hz, H-8), 7.47 (t, 1H, J 6(5,7) =7.2 Hz, H-6), 6.89 (d, 2H, J 3′,2′ =J 5′,6′ =8.8 Hz, H-3′,5 . );EI MS: m/z (rel. abund. %), 238 (M + , 100), 237 (5.4), 221 (4.6), 119 (82.6).
[0023] 2-(3-Hydroxyphenyl)quinazolin-4(3H )-one (4): Yield: 0.42 g, 88%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.42 (s, 1H, NH), 9.74 (s, 1H, 3′-OH), 8.14 (m, 1H, H-5), 7.84 (m, 1H, H-7), 7.72 (d, 1H, J 8,7 =8.0 Hz, H-8), 7.59 (m, 2H, H-6,2′), 7.52 (m, 1H, H-6′), 7.34 (m, 1H, H-5′), 6.97 (m, 1H, H-4′); EI MS: m/z (rel. abund. %), 238 (M + , 81.6), 237 (8.5), 221 (7.3), 119 (100).
[0024] 2-(3,4-Dihydroxyphenyl)quinazolin-4(3H)-one (5): Yield: 0.49 g, 96%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.21 (s, 1H, NH), 9.64 (s, 1H, 4′-OH), 9.29 (s, 1H, 3′-OH), 8.10 (d, 1H, J 5,6 =8.0 Hz, H-5), 7.78 (d, 1H, J 8,7 =7.2 Hz, H-8), 7.66 (m, 2H, H-7,2′), 7.54 (d, 1H, J 6′,5′ =8.0 Hz, H-6′), 7.46 (t, 1H, J 6(5,7) =7.6 Hz, H-6), 6.83 (d, 1H, J 5′,6′ =8.0 Hz, H-5′); EI MS: m/z (rel. abund. %), 254 (M + , 8.0), 146 (100), 119 (25.5).
[0025] 2-(2,5-Dihydroxyphenyl)quinazolin-4(3H)-one (6): Yield: 0.48 g, 95%; 1 1-1 NMR: (300 MHz, DMSO-d 6 ): δ H 12.60 (s, 1H, NH), 12.29 (s, 1H, 2′-OH), 9.08 (s, 1H, 5′-OH), 8.14 (d, 1H, J 5,6 =7.5 Hz, H-5), 7.86 (t, 1H, J 7(6,8) =7.5 Hz, H-7), 7.73 (d, 1H, J 8,7 =8.1 Hz, H-8), 7.60 (s, 1H, H-6′), 7.54 (t, 1H, J 6(5,7) =7.2 Hz, H-6), 6.92 (m, 2H, H-3′,4′); EI MS: m/z (rel. abund. %), 254 (M + , 100), 119 (36.3).
[0026] 2-[2-Hydroxy-5-(methyloxy)phenyl]quinazolin-4(3H)-one (7): Yield: 0.44 g, 82%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 13.42 (s, 1H, NH), 12.55 (s, 1H, 2′-OH), 8.15 (d, 1H, J 5,6 =7.6 Hz, H-5), 7.84 (m, 3H, H-7,8,6), 7.53 (s, 1H, H-6′), 7.05 (s, 1H, H-4′), 6.94 (d, 1H, J 3′,4′ =7.6 Hz, H-3′), 3.78 (s, 3H, 5′-OCH 3 ); EI MS: m/z (rel. abund. %), 268 (M + , 76.9), 253 (100), 119 (3.8).
[0027] 2-[3-Hydroxy-4-(methyloxy)phenyl]quinazolin-4(3H)-one (8): Yield: 0.53 g, Quantitative; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.30 (s, 1H, NH), 9.35 (s, 1H, 3′-OH), 8.09 (s, 1H, H-5), 7.77 (m, 5H, H-7,8,6,6′,5′), 7.04 (s, 1H, H-2′), 3.85 (s, 3H, 4′-OCH 3 ); EI MS: m/z (rel. abund. %), 268 (M + , 100), 253 (25.9), 119 (82.3).
[0028] 2-[2-Hydroxy-3-(methyloxy)phenyl]quinazolin-4(3H)-one (9): Yield: 0.53 g, Quantitative; 1 H NMR: (300 MHz, DMSO-d 6 ): δ H 13.94 (s, 1H, NH), 12.46 (s, 1H, 2′-OH), 8.16 (d, 1H, J 5,6 =7.5 Hz, H-5), 7.86 (m, 3H, H-7,6,4), 7.56 (t, 1H, J 6′(4′,5′) =7.2 Hz, H-6′), 7.17 (d, 1H, J 8,7 =8.1 Hz, H-8), 6.90 (t, 1H, J 5′(4′,6′) =8.1 Hz, H-5′), 3.82 (s, 3H, 3′-OCH 3 ); EI MS: m/z (rel. abund. %), 268 (M + , 100), 239 (50.2), 225 (53.9), 119 (39.1).
[0029] 2-[4-(Methyloxy)phenyl]quinazolin-4(3H)-one (10): Yield: 0.42 g, 84%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.40 (s, 1H, NH), 8.18 (m, 3H, H-5,2′,6′), 7.80 (m, 2H, H-7,8), 7.47 (s, 1H, H-6), 7.10 (d, 2H, J 3′,2′ =J 5′,6′ =7.6 Hz H-3′,5′), 3.85 (s, 3H, 4′-OCH 3 ); EI MS: m/z (rel. abund. %), 252 (M + , 100), 237 (3.2), 235 (2.9), 119 (64.8).
[0030] 2-[3,4-Bis(methyloxy)phenyl]quinazolin-4(3H)-one (11): Yield: 0.56 g, Quantitative; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.43 (s, 1H, NH), 8.13 (d, 1H, J 5,6 =7.6 Hz, H-5), 7.86 (m, 3H, H-7,8,2′), 7.71 (d, 1H, J 8,7 =8.0 Hz, H-8), 7.49 (d, 1H, J 6′,5′ =7.6 Hz, H-6′), 7.11 (d, 1H, J 5′,6′ =8.4 Hz, H-5′), 3.87 (s, 3H, 4′-OCH 3 ), 3.83 (s, 3H, 3′-OCH 3 ); EI MS: m/z (rel. abund. %), 282 (M + , 100), 267 (21.4), 251 (25.7), 119 (20.6). 2-[3,4,5-Tris(methyloxy)phenyl]quinazolin-4(3H)-one(12) Yield: 0.61 g, 99%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.51 (s, 1H, NH), 8.15 (d, 1H, f 5,6 =7.2 Hz, H-5), 7.82 (m, 1H, H-7), 7.75 (d, 1H, J 8,7 =8.0 Hz, H-8), 7.55 (s, 2H, H-5′,6′), 7.52 (m, 1H, H-6), 3.89 (s, 6H, 3′-OCH 3 , 5′-OCH 3 ), 3.73 (s, 3H, 4′-OCH 3 ); EI MS: m/z (rel. abund. %), 312 (M + , 100), 297 (35.5), 281 (6.8), 119 (6.6).
[0031] 2-[4-(Ethyloxy)phenyl]quinazolin-4(3H)-one (13): Yield: 0.522 g, 98%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.39 (s, 1H, NH), 8.18 (d, 1H, J 5,6 =8.7 Hz, H-5), 8.13 (d, 2H, J 2′,3′ =J 6′,5′ =8.1 Hz, H-2′,6′), 7.82 (t, 1H, J 7(6,8) =7.2 Hz, H-7), 7.70 (d, 1H, J 8,7 =8.1 Hz, H-8), 7.49 (t, 1H, J 6(5,7) =7.2 Hz, H-6), 7.07 (d, 2H, J 3′,2′ =8.7 Hz, H-3′,5′), 4.13 (q, 2H, J=14.0 Hz, 6.9 Hz, CH 2 ), 1.37 (t, 3H, J=6.9 Hz, CH 3 ); EI MS: m/z (rel. abund. %), 266 (M + , 100), 238 (23.1), 221 (3.7), 119 (57.2).
[0032] 2-[2-(Ethyloxy)phenyl]quinazolin-4(3H)-one (14): Yield: 0.52 g, 97%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.03 (s, 1H, NH), 8.14 (t, 1H, J 5(6,7) =6.8 Hz, H-5), 7.84 (m, 1H, H-7), 7.76 (dd, 1H, J 6′,5′ =7.2 Hz, J 6′,4′ =1.2 Hz, H-6′), 7.70 (d, 1H, J 8,7 =8.0 Hz, H-8), 7.53 (m, 2H, H-6,3′), 7.18 (d, 1H, J 3′,4′ =8.4 Hz, H-3′), 7.09 (t, 1H, J 4′(3′.5′) =7.2 Hz, H-4′), 4.16 (q, 2H, J=14.0 Hz, 7.2 Hz, CH 2 ), 1.35 (t, 3H, J=6.8 Hz, CH 3 ); EI MS: m/z (rel. abund. %), 266 (M + , 23.9), 251 (51.8), 238 (14.6), 222 (21.2), 119 (100).
[0033] 2-[3-(Ethyloxy)-4-hydroxyphenyl]quinazolin-4(3H)-one (15): Yield: 0.55 g, 98%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.32 (s, 1H, NH), 9.67 (s, 1H, 4′-OH), 8.11 (d, 1H, J 5,6 =7.6 Hz, H-5), 7.77 (m, 3H, H-7,8,2), 7.68 (d, 1H, J 6′,5′ =8.0 Hz, H-6), 7.47 (t, 1H, J 6(5,7) =7.2 Hz, H-6), 6.91 (d, 1H, J 5′,6′ =8.4 Hz, H5′), 4.16 (q, 2H, J=14.0 Hz, 6.8 Hz, CH 2 ), 1.39 (t, 3H, J=7.2 Hz, CH 3 ); EI MS: m/z (rel. abund. %), 282 (M + , 100), 267 (29.3), 254 (80.9), 238 (11.9), 119 (46.8).
[0034] 2-(2-Chlorophenyl)quinazolin-4(3H)-one (16): Yield: 0.50 g, 98%; 1 H NMR: (300 MHz, DMSO-d 6 ): δ H 12.62 (s, 1H, NH), 8.17 (d, 1H, J 5,6 =7.2 Hz, H-5), 7.84 (s, 1H, H-6′), 7.71 (m, 6H, H-7,8,6,3′,4′,5′); EI MS: m/z (rel. abund. %), 256 (M + , 75.5), 239 (6.9), 221 (8.4), 119 (100).
[0035] 2-(2,4-Dichlorophenyl)quinazolin-4(3H)-one (17): Yield: 0.57 g, 99%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.65 (s, 1H, NH), 8.17 (d, 1H, J 5,6 =7.6 Hz, H-5), 7.85 (m, 2H, H-7,3′), 7.71 (m, 2H, H-8,6), 7.59 (m, 2H, H-6′,5′); EI MS: m/z (rel. abund. %), 290 (M t , 66.4), 273 (3.7), 255 (5.9), 220 (3.0), 119 (100).
[0036] 2-(2,6-Dichlorophenyl)quinazolin-4(3H)-one (18): Yield: 0.56 g, 96%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.79 (s, 1H, NH), 8.19 (d, 1H, J 5,6 =7.2 Hz, H-5), 7.89 (m, 1H, H-7), 7.73 (d, 1H, J 8,7 =8.0 Hz, H-8), 7.65 (m, 4H, H-6,4′,3′,5); EI MS: m/z (rel. abund. %), 290 (M + , 100), 273 (6.1), 255 (68.8), 220 (5.7), 119 (8.5).
[0037] 2-(4-Chlorophenyl)quinazolin-4(3H)-one (19): Yield: 0.48 g, 94%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.60 (s, 1H, NH), 8.20 (d, 1H, J 5,6 =8.4 Hz, H-5), 8.15 (d, 2H, J 3′,2′ =J 5′,6′ =8.0 Hz, H-3′,5′), 7.86 (t, 1H, J 7(6,8) =7.2 Hz, H-7), 7.74 (d, 1H, J 8,7 =8.0 Hz, H-8), 7.63 (d, 2H, J 2′,3′ =J 6′,5′ =8.8 Hz, H-2′,6′), 7.54 (t, 1H, J 6(5,7) =7.2 Hz, H-6); EI MS: m/z (rel. abund. %), 256 (M + , 100), 119 (89.9).
[0038] 2-(2-Nitrophenyl)quinazolin-4(3H)-one (20): Yield: 0.49 g, 92%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.82 (s, 1H, NH), 8.21 (m, 2H, H-3′,5), 7.90 (m, 4H, H-5′,6′,4′,7), 7.65 (d, 1H, J 8,7 =8.4 Hz, H-8), 7.59 (t, 1H, J 6(5,7) =7.2 Hz, H-6); EI MS: m/z (rel. abund. %), 267 (M + , 100), 250 (5.5), 221 (20.8), 119 (57.6).
[0039] 2-(3-Nitrophenyl)quinazolin-4(3H)-one (21): Yield: 0.34 g, 64%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.87 (s, 1H, NH), 9.02 (s, 1H, H-2′), 8.61 (d, 1H, J 4′,5′ =8.0 Hz, H-4′), 8.43 (d, 1H, J 6′, 5 ′=7.2 Hz, H-6′), 8.18 (d, 1H, J 5′,6′ =7.6 Hz, H-5′), 7.87 (m, 3H, H-7,8,6), 7.58 (t, 1H, J 5′(4′, 6′) =7.6 Hz, H-5′); EI MS: m/z (rel. abund. %), 267 (M + , 100), 221 (78.5), 119 (29.6).
[0040] 2-(4-Nitrophenyl)quinazolin-4(3H)-one (22) Yield: 0.48 g, 90%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.84 (s, 1H, NH), 8.42 (m, 4H, H-3′,5′,2′,6′), 8.18 (d, 1H, J 5,6 =8.0 Hz, H-5), 7.89 (m, 1H, H-7), 7.80 (d, 1H, J 8,7 =7.6 Hz, H-8), 7.59 (t, 1H, J 6(5,7) =8 Hz, H-6); EI MS: m/z (rel. abund. %), 267 (M + , 100), 221 (83.1), 119 (87.3).
[0041] 2-[4-(Dimethylamino)phenyl]quinazolin-4(3H)-one (23): Yield: 0.52 g, 99%; 1 H NMR: (400 MHz, DMSO-d 6 ): δ H 12.26 (s, 1H, NH), 8.10 (m, 3H, H-5,2′,6′), 7.79 (m, 1H, H-7), 7.67 (d, 1H, J 8,7 =8.4 Hz, H-8), 7.45 (m, 1H, H-6), 6.81 (d, 2H, J 3′,2′ =J 5′,6′ =8.8 Hz, H-3′,5′), 3.02 (s, 6H, 4′-N(CH 3 ) 2 ); EI MS: m/z (rel. abund. %), 265 (M + , 100), 250 (6.1), 221 (5.2), 119 (33.5).
[0042] 2-(4-Methylphenyl)quinazolin-4(3H)-one (24): Yield: 0.42 g, 89%; 1 H NMR: (400 MHz, DMSO-d 6 ): 802.45 (s, 1H, NH), 8.12 (m, 3H, H-5,2′,6′), 7.82 (t, 1H, J 7(6,8) =7.2 Hz, H-7), 7.72 (d, 1H, J 8,7 =8.0 Hz, H-8), 7.51 (t, 1H, J 6(5,7) =7.6 Hz, H-6), 7.36 (d, 2H, J 3′,2′ =J 5′,6′ =8.4 Hz, H-3′,5′), 2.38 (s, 3H, 4LCH 3 ); EI MS: m/z (rel. abund. %), 236 (M + , 100), 219 (4.1), 119 (96.7).
[0043] 2-(2-Bromo-6-hydroxyphenyl)quinazolin-4(3H)-one (25): Yield: 0.48 g, 76%; 1 H NMR: (300 MHz, DMSO-d 6 ): δ H 13.81 (s, 1H, NH), 12.57 (s, 1H, 2′-OH), 8.45 (s, 1H, H-5), 8.16 (d, 1H, J 8,7 =6.7 Hz, H-8), 7.86 (m, 2H, H-7,6), 7.57 (m, 2H, H-4′,5′), 6.98 (d, 1H, J 5′,4′ =6.6 Hz, H-5′); EI MS: m/z (rel. abund. %), 316 (M + , 100), 238 (3.7), 145 (3.8), 119 (47.2).
[0044] Anthranilamide (2 mmol), substituted benzaldehydes (2.1 mmol) and CuCl 2 .2H 2 O (4 mmol) in ethanol (15 mL), were added in a round bottomed flask. The mixture was refluxed for 16 h, while progress of the reaction was monitored through thin layer chromatography. After completion of reaction, it was cooled to room temperature and distilled water was added until the formation of precipitates. The precipitates were filtered and washed with hexane to afford title compounds in high yield.
[0045] We are reporting here in for the first time, some derivatives of quinazoline class of compounds, with potent β-glucuronidase inhibition activity.
[0046] We have screened twenty-five (25) compounds (1-25) against β-glucuronidase enzyme. Out of which, nineteen compounds 2-3, 5-11, 13-16, 18-20, 22, 23 and 25 showed potent activities with IC 50 values 10.0±0.54, 22.2±0.31, 2.1±0.06, 3.2±0.11, 1.8±0.11, 2.8±0.042, 30.9±2.64, 1.1±0.05, 0.6 ±0.45, 2.1±0.073, 0.7±0.016, 1.17±0.124, 1.8±0.01, 37.7±1.21, 39.8±2.88, 1.5±0.05, 20.1±0.92, 5.5±0.10 and 44.0±3.12 μM, respectively (Table-1). Compounds 11 (2-[3,4-bis(methyloxy)phenyl]quinazolin-4-(3H)-one) and 14 2-[2-(ethyloxy)phenyl]quinazoline-4-(3H)-one) showed excellent activities (IC 50 =0.6±0.45 and 0.7±0.016 μM, respectively) and found more active than the standard (D-saccharic acid 1,4-lactone (IC 50 =45.75±2.16 μM). Compounds 1, 4, 12, 17, 21 and 24 showed a weak inhibitory activity against the enzyme with IC 50 values between 50.3 to 172.7 μM.
[0047] Results indicate that activity of compounds may be due to the presence of different substituents on the benzene ring, attached to C-2 of the quinazoline nucleus. The discussion is given below.
[0048] o-Hydroxy substituted phenyl ring containing compound 2 showed a potent activity with IC 50 =10.0±0.54 μM more active than the standard D-saccharicacid 1,4-lactone (IC 50 =45.75±2.16 μM). However, compound 3 having apara-hydroxy benzene ring appeared to be less active (IC 50 =22.2±0.31 μM) as compared to o-hydroxy benzene ring containing compound 2(IC 50 =10.0±0.54 μM).Further decrease in activity was observed in compound 4 having meta-hydroxy benzene ring (IC 50 =198.2±2.88 μM). Therefore, hydroxyl group at ortho and para positions of benzene ring are found to be beneficial for inhibition offi-glucuronidase activity.
[0049] Significant increase in inhibition activities of compounds 5 and6 was observed with IC 50 values 2.1±0.06 and 3.2±0.11 μM respectively,when hydroxyls were present at meta, para and ortho positions adjacent to each other.
[0050] Introduction of methoxy group found to be beneficial as well andthe activities of derivatives 7-11,13, 14 and 15wit IC 50 values1.8±0.11, 2.8±0.042, 30.9±2.64, 1.1±0.05, 0.6±0.45, 2.1±0.073, 0.7±0.016 and 1.17±0.124 μM, respectively. All these compounds found to be more active than standard D-saccharicacidl,4-lactone (IC 50 =45.75±2.16 μM). The comparison of the activities of methoxy substituted compounds 7, 8, 10 and 11 and ethoxy substituted compounds 14 and 15with their hydroxyl substituted analogues (2, IC 50 =10.0±0.54 μM), (3, IC 50 =22.2±0.31 μM), (4, IC 50 =198.2±2.88 μM), (5, IC 50 =2.1±0.06 μM) and (6, IC 50 =3.2±0.11 μM) showed that alkoxy group (—OCH 3 /—OC 2 H 5 ) are responsible for more potent activities. However o,m,p-tri-methoxy substituted phenyl ring containing compound 12 was found to be least active among the series with IC 50 =120.5±2.54
[0051] Introduction of chlorine on the phenyl ring attached at C-2 of quinazoline ring is also found to be responsible for potent activities as observed in compounds 16-19 (IC 50 =1.8±0.017, 39.8±2.88, 37.7±1.21 and 61.03±6.26 μM, respectively). It was also observed that chlorosubstituted phenyl ring containing compound 16 (IC 50 =1.8±0.017 μM) is found to be most active. The activities of di-orthochloro and m-chloro substituted phenyl ring containing compounds have shown almost similar inhibitory potential with IC 50 values39.8±2.88 and 37.7±1.21, respectively.
[0052] Compound 20 with substitution at ortho position of phenyl ring showed highly potent activity with IC 50 =1.5±0.05 pM, while in compound 22 having p-nitro phenyl ring showed less inhibitory potential with IC 50 =20.1±0.92 μM. Further decrease in inhibitory potential was observed in compound 21 having am-nitro phenyl ring (IC 50 =50.4±1.40 μM).
[0000]
TABLE-1
β-Glucuronidase Inhibitory Activity of Quinazolines
%
IC 50
Structures
Inhibition
(μM) ± SEM
92.5
177.0 ± 5.04
2-Phenylquinazoline-4(3H)-one (1)
99.1
10.0 ± 0.54*
2-(2-Hydroxy-phenylquinazoline-4(3H)-
one (2)
99.6
22.2 ± 0.31*
2-(4-Hydroxy phenyl)quinazoline-
4(3H)-one (3)
78.5
198.2 ± 2.88
2-(3-Hydroxyphenyl)quinazoline-4(3H)-
one (4)
98.8
2.1 ± 0.06*
2-(3,4-Dihydroxyphenyl)quinazoline-
4(3H)-one (5)
99.9
3.2 ± 0.11*
2-(2,5-Dihydroxyphenyl)-quinazoline-
4(3H)-one (6)
99.4
1.8 ± 0.11*
2-[2-Hydroxy-5-(methyloxyphenyl]-
quinazoline-4(3H)-one (7)
84.0
2.8 ± 0.042*
2-[3-Hydroxyl-4-
(methyloxy)phenyl]quinazoline-4(3H)-
one (8)
96.5
30.9 ± 2.64*
2-[2-Hydroxy-3-
(methyloxy)phenyl]quinazoline-4(3H)-
one (9)
99.7
1.1 ± 0.05*
2-(4-Methoxy phenyl)quinazoline-4-
(3H)-one (10)
98.8
0.6 ± 0.45*
2-[3,4-Bis(methyloxy)phenyl]quinazolin-
4(3H)-one (11)
97.6
120.5 ± 2.54
2-[3,4,5-Tris
(methyloxy)phenyl]quinazolin-4(3H)-one
(12)
99.9
2.1 ± 0.073*
2-[4-(Ethyloxy)phenyl] quinazolin-4(3H)-
one (13)
98.9
0.7 ± 0.016*
2-[2-(Ethyloxy)phenyl]quinazoline-
4(3H)-one (14)
99.8
1.17 ± 0.124*
2-[3-(Ethyloxy)-4-hydroxy
phenyl]quinazoline-4(3H)-one (15)
99.6
1.8 ± 0.017*
2-(2-Cholrophenyl)quinazoline-4(3H)-
one (16)
98.4
61.03 ± 6.26
2-(2,4-Dicholrophenyl)quinazoline-
4(3H)-one (17)
94.6
37.7 ± 1.21*
2-(2,6-Dicholro phenyl)quinazolin-4(3H)-
one (18)
99.8
39.8 ± 2.88*
2-(4-Cholro phenyl)quinazoline-4(3H)-
one (19)
99.6
1.5 ± 0.05*
2-(2-Nitrophenyl)quinazoline-4(3H)-one
(20)
95.1
50.4 ± 1.40
2-(3-Nitro phenyl)quinazoline-4(3H)-one
(21)
96.4
20.1 ± 0.92*
2-(4-Nitrophenyl)quinazoline-4(3H)-one
(22)
99.6
5.5 ± 0.10*
2-[4-(Dimethyl amine)phenyl]
quinazolin-4(3H)-one (23)
96.3
172.7 ± 4.84
2-(4-Methyl phenyl)quinazoline-4(3H)-
one (24)
99.7
44.0 ± 3.12*
2-(2-Bromo-6-hydroxy
phenyl)quinazoline-4(3H)-one (25)
*Values lower than standard (i.e. D-saccharic acid 1,4-lactone, IC 50 = 45.75 ± 2.16 μM)
[0053] Compounds 1-25 were tested against PC-3 cells for cytotoxicity the results are shown in Table-2. The IC 50 values of compounds showed no cytotoxicity effects towards PC-3 cells.
[0000]
TABLE 2
Cytotoxicity of Compounds 1-25 for Cytotoxicity
Against PC-3 Cells In Vitro
Compounds
IC 50 (μM) ± SEM
1
>30
2
>30
3
>30
4
>30
5
>30
6
>30
7
>30
8
>30
9
>30
10
>30
11
>30
12
>30
13
>30
14
>30
15
>30
16
>30
17
>30
18
>30
19
>30
20
>30
21
>30
22
>30
23
>30
24
>30
25
>30
Standard (Doxorubicin, IC 50 = 0.912 ± 0.12 μM) | Quinazoline derivatives 1-25, (2-[3,4-bis(methyloxy)phenyl]quinazolin-4-(3H)-one) and 2-[2-(ethyloxy)phenyl]quinazoline-4-(3H)-one) are reported as β-glucuronidase inhibitors useful in the treatment of β-glucuronidase hyperactivity disorders. | 2 |
REFERENCE TO RELATED APPLICATIONS
[0001] This application claims an invention, which was disclosed in Provisional Application No. 60/269,614, filed Feb. 16, 2001, entitled “NOVEL PLANNING TOOL”. The benefit under 35 USC §119(e) of the United States provisional application is hereby claimed, and the aforementioned application is hereby incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention pertains to the field of planning tools. More particularly, the invention pertains to a planning tool that allows information to be modified with regard to date and time without rewriting the information.
[0004] 2. Description of Related Art
[0005] Business associates, salespeople and people who require making a lot of appointments, and scheduling deadlines are all dependent on the need to manipulate and organize information. Disorganization of information in any business or trade can lead the most capable people toward disastrous results. In order to successfully compete and prosper in the business and trade world it is vital to have an organizational tool which will allow you to operate in an efficient, timely, and productive manner.
[0006] No planner or organizer currently exists, which enables the user to manipulate information through out time, without rewriting it. Consequently, because a planner or organizer did not exist that eliminated the necessity of rewriting material; numerous leads, prospects, and vital information has been forgotten, misfiled or lost in the shuffle of paperwork and/or cyberspace.
[0007] A number of organizers and planners are available to assist the public in the organization of information in both computer software programs and hardcopy versions. Computer software programs are unable to eliminate the redundancy and disorganization of information, nor can they give or guarantee instant access and the physical convenience of having a hard handwritten copy of future plans. Hardcopy versions of planners/organizers are also unable to eliminate the redundancy, disorganization of information, and having the need to rewrite information.
SUMMARY OF THE INVENTION
[0008] A planner tool comprising multiple pouch pages, lead cards, printed calendar sheets, a set of cards with the months of the year printed on them, and a set of four color-coded cards.
[0009] Each pouch page has holes that are appropriately spaced apart so that each of the pages can be placed in a binder. The pages also contain at least one pouch for holding different types of cards, such as lead cards or cards with the months printed at the top. The pages also contain a cavity in the center of the pouch page, which is sealed by a zip closure. This cavity is used to store lead cards, cards with the months printed on them, and the color-coded cards.
[0010] The planner tool also has a large number of lead cards. Lead cards have two sets of times of the day and a blank center which are used in conjunction with the printed calendar sheets to make appointments to call, appointments to see others, and keep information regarding the nature of such appointments all in one place. The lead cards are placed in the pouches of the various pages.
[0011] The printed calendar sheets of the planner have the days of the week printed on them with specific columns under each day. The columns have the headings c, m, a, and e, which stand for call, mileage, appointment, and expenses respectively. In terms of dates on the calendar pages, the option as to whether the user wants to have the date already printed on the sheets or whether the user wants to take the time and fill them in himself is available. Furthermore, each calendar page has holes that are appropriately spaced apart to allow the pages to be put into a binder with the pouch pages.
BRIEF DESCRIPTION OF THE DRAWING
[0012] [0012]FIG. 1 shows a standard pouch page.
[0013] [0013]FIG. 2 shows a business card holder.
[0014] [0014]FIG. 3 shows a lead card being stored in a small two-sided pouch page.
[0015] [0015]FIG. 4 ( a & b ) show the printed calendar sheets.
[0016] [0016]FIG. 5 shows a set of cards with the printed name of the months of the year being stored in a small two-sided pouch page.
[0017] [0017]FIG. 6 ( a & b ) shows the first pouch page.
[0018] [0018]FIG. 7 ( a & b ) shows the second pouch page.
[0019] [0019]FIG. 8 ( a & b ) shows a representative of one of the four weekly pouch pages.
DETAILED DESCRIPTION OF THE INVENTION
[0020] The functionality of the planner revolves around two-sided vinyl pouch pages, as seen in FIG. 1, which are used in several ways. A typical planner includes several vinyl pouch pages, with a center cavity and a “zip” closure, a business card holder, lead cards, printed calendar sheets, a set of four colored cards, and a set of cards containing the text with the months of the year.
[0021] The vinyl pouch pages, as seen in FIG. 1, are two sided and made of an “eight gauge duna” vinyl, or other suitable material. The vinyl pouch pages each have at least four slots to fit 3 by 5 inch lead cards on each side of the page. In almost all of the vinyl pouch pages in the present invention, a center cavity is present that can be sealed with a “zip” closure.
[0022] Referring to FIG. 2, a business card holder is shown. This holder is preferably made of vinyl, or other suitable material and is specifically designed to store a plurality of business cards.
[0023] [0023]FIG. 3 shows lead cards being store in the front of a small two-sided pouch page. Lead cards contain two duplicate copies of the time of day down the left and right side of the card. The times of the day that are displayed can vary depending upon which shift is worked. The middle section of the lead card is blank.
[0024] The printed calendar sheets are pages that would be typically found in paper planner currently in use today, with some changes made to the column headings. The calendar week has the days of the week printed at the top, along with the dates. Each printed calendar sheet contains either “Monday”, “Tuesday”, “Wednesday”, or “Thursday”, “Friday”, “Saturday”, and “Sunday”. Every day of the week, with the exception of Sunday, has four columns, each with a different heading, as shown in FIG. 4 ( a & b ). The first column shows the times of the day, which is an exact duplicate of the times printed on the lead cards (FIG. 3) and has the heading C (for calls). The second column has the heading A (for appointments). The third column has the heading E (for expenses). The fourth column has the heading M (for mileage). The meanings and uses of the headings corresponding to the columns are explained in greater detail later on in the detailed description.
[0025] [0025]FIG. 5 shows a set of cards containing the months of the year being stored in a small two-sided pouch page, where each month is printed on one card. The card is preferably 3 by 5 inches.
[0026] [0026]FIG. 6 b shows an example of the color-coded cards in a vinyl pouch page. The color-coded cards are preferably 3 by 5 inches.
[0027] The function of the planner tool is to organize contacts or appointments, while being able to easily change elements of the contacts or appointments without having to rewrite information. The planner tool accomplishes this by utilizing a rotating envelope or pouch through time. The planner is an efficient tool for the business person, but it can be used in specific ways to obtain maximum efficiency. An example of the order of the pages present in the planner and the uses of these pages is given specifically for a sales person. However, the planner can be used by anyone in any profession.
[0028] The first page of the planning tool would be a vinyl pouch page, containing four pouches as shown in FIG. 6 a, where the four pouches would be used for leads or prospects that are “in limbo” but not very “hot.” The back of the first pouch page, (FIG. 6 b ), would be used for filing future prospects or present weeks. Four different colored cards are inserted into the four pouches where each color represents a different week further along in the year. The color-coded weeks are associated with the current month in the year.
[0029] As shown in FIG. 7 a, the next pouch page in the planner is used for the four “future” months of the year. For example, if the user was presently in the month of January, the four future months that would be present in the pouch page would be February, March, April, and May. When the month of February starts, the pouch that held the February card would be placed in the stack of rotating months, which are stored in the back of a small two sided pouch (e.g. FIG. 5). The June card is placed in the remaining slot previously occupied on the pouch page. As time goes on an old month is removed and a new month is always added. The cards used for this pouch page are shown in FIG. 3. The back of the second pouch page, as shown in FIG. 7 b has “limbo”, “follow-up”, and “sold” printed on the pouches themselves. These titles are used for this example, and can be changed to fit the profession of the user.
[0030] The next four pouch pages represent four “generic”, “floating”, or “rotating” weeks. As shown in FIG. 8 a, each of the weekly pouches has four individual pouches on the front and four individual pouches on the back. Each individual pouch has a single label. The individual pouches all have different labels. The four front individual pouches are labeled “Monday”, “Tuesday”, “Wednesday”, or “business cards”. The four back individual pouches are labeled “Thursday”, “Friday”, “Saturday”, or “Sunday”, (FIG. 5 b ). The four weekly pouch pages all have different color paper within the center cavity. One has red, one green, one blue and one yellow, which coincide with the color coded weeks in FIG. 6 b.
[0031] The weekly pouch pages run in series. The first weekly pouch page is inserted in the present week. As shown in FIG. 4 a & b, the printed calendar sheets on either side of the pouch page are for each of the days on either side of the pouch page. Monday's pouch for Monday's printed page, Tuesday's for Tuesday's and so on. The next three pouch pages are to represent the corresponding, following three weeks. As time evolves, the pouch page that represents the current week, expires, the user then takes the pouch page for that week, and puts it in the center of the fourth week. This enables the user to always have 28 days worth of pouches in the future by which to place lead cards.
[0032] The printed calendar sheets as described above begin with “Thursday” through “Sunday” on the front side, as shown above and “Monday” through “Wednesday” on the back side, as shown above. On the top of every day you see the letters: C, A, E and M these letters stand for Call, Appointment, Expenses, and Mileage. The call column is for recording when a person asks to be called at a certain time, just circle the time in the C column. The appointment column is for recording a physical meeting. Simply circle the time on the page and write the customers name under the A column. This information is also written one time only on a lead card where the time is circled on the right side of the lead card.
[0033] The E on the top of every page is for recording expenses. To keep track of expenses, the number of the expense is written on the back of the receipt. The number will be whatever expense came last; for example if the user's first expense of the year will be #1. The user writes the number of the receipt in the E column across from the time and customer name with which it corresponds. All of the receipts go in the “zip” closure pouch for that week. Since the planning tool of the present invention works in groups of four weeks, the user can leave all the expenses for this week in the pouch until it comes through the planner again. At this time the user will have a months worth of receipts which are numbered, separated by week, and can be used as a written record of the time and place of expense.
[0034] The M on the top of the page is for recording mileage. There are two columns for each day. The user can record the mileage going to a business meeting in the first column, (longitudinally) and the return mileage in the next column. The user can draw a line under it and total the mileage for each day. There is a total section located at the bottom of Sunday. This is where the user can put the weekly mileage totals. There are also spaces for your calls, appointments, and sales totals.
[0035] The pouch pages are different colors for the following reason; if the user wishes to schedule a call back with a prospect for any particular week, this can be this week, or three future weeks, the user does not have to arbitrarily “pick a day” to perform that task. All four weeks are color-coded and the first pouch page in the very front of the book has four corresponding colored pouches. To make an appointment to call “this week”, the user simply finds the color of the pouch in the front of the book that corresponds to the week that they are in and places the card in this pouch. This allows the user to have an entire week worth of time in which to call, etc. . . without resigning themselves to any particular time during the day or the week. To make an appointment to call someone next week, or the week after that, or even the week after that, all that the user has to do is find the color in the front pouch page that corresponds to the color of that week and place the lead card in that pouch. If the user wants to schedule a call back but does not have a specific time to do so for a future month he/she can simply find the future month, as long as it is within the four months and place the card in that pouch. If the user does not have a time, day or week, to specifically call a prospect and they demand immediate attention, the user can put that prospect's card in the “limbo” file, which receives and requires daily attention and update. Once the user sells the prospect the good or service, the lead card goes in to the “sold” pouch. The “sold” pouch is used daily by the user to ensure that the customer's sale is going through properly. For example, the user would check to see if the payment went through, the product was delivered and/or installed on time, and that the customer is happy with the sale. After the customer has the product and it has been installed, then the card is placed in the “follow up” pouch, where the user can check up on the customer to make sure that they are happy with the product and attempt to obtain referrals for further sales.
[0036] The lead cards, as shown above, for the book, are printed to enable the user to schedule appointments to “see” and “call” people without writing the time down. The lead cards come with times of the day printed down both sides of the card. The time on the left is a “time to call” and the time on the right is a “time to see”. To make an appointment to call on a specific day, the user circles the time on the left hand side of the lead card, places the lead card in the pouch that represents the day to call, and circles the time on the printed calendar page under the day of the call. To schedule a “time to see” or an actual appointment with someone, the user does the same as the above, only using the right side of the lead card and actually writing the persons name in the slot next to the time on the printed calendar sheet, as shown above. The center of the lead cards is blank to allow for notes, or other pertinent information that is vital, such as how many units the customer is interested in, personal information of the customer, etc . . . , that helps make the sale.
[0037] The last page of the planner is the business card holder, as shown above, which holds business cards for all prospective clients that do not currently have appointments or need to be called at on a specific date and time.
[0038] An example of how a sales person would use the present invention to keep track of a client is as follows. A prospective client has left a number to call about the product that the salesperson sells. The prospect is called and asked a series of questions, of which the answers are jotted down in paraphrases in the center of the lead card as shown above. After talking to the prospective client, they tell you they want a call back next Tuesday at 8:00 am. The salesperson, using the present invention, circles 8:00 am on the left side of the lead card, puts the name of the client on the printed calendar sheets by circling the time under the C heading, as shown above, and puts the lead card into next Tuesday's pouch of the weekly vinyl pouch page. When the following Tuesday occurs, the salesperson checks the printed calendar sheets and see a call needs to made at 8:00 am and goes to the Tuesday pouch of the week and pulls out the card that has all of the necessary information to call the client. During the conversation with the client, they mention they are going to be gone for two weeks and want you to call them back then. Using the present invention, the salesperson looks and sees what color vinyl pouch page would be two weeks from now, as shown above. In this instance the pouch was “red”. The salesperson places the lead card in the limbo file located in the very front of the planner, as shown above. Two weeks go by and the week is now “red”. The lead card contains all the information to make the call and jog the memory as to what the client was interested in. The client makes an appointment for later that week on Thursday. The appointment time is circled on the right side of the card and written down under the A column in the printed calendar sheets, with the time circled. The lead card is then placed in the appropriate pouch regarding the day of the week the appointment is. At the appointment, the lead card is brought with the salesperson to review the necessary information that is important to the client and to write down anything else that is needed to complete the sale or if another call or appointment is needed. If a sale is made, the lead card goes into the sold portion pouch located on the back of the second vinyl pouch page as shown above. The salesperson continually follows up on the sale made in order to ensure that payment, delivery, and installation are completed on time. After the installation is complete, the lead card now goes into the follow up pouch located on the second vinyl pouch page as shown above. The salesperson never had to rewrite any information, nor arbitrarily pick a day two weeks in advance. All of the information was kept in one place and moved where necessary in terms of weeks or days.
Alternatives
[0039] Small differences in printing and construction could easily produce a different planner that performs in the same way. The pouch pages can be made of a different material, such as paper, cardboard or plastic. The envelope in the center could be eliminated. Currently, this is used for the expense function of the book.
[0040] If the user only wanted one pouch for each week instead of having the option to place cards in all seven days of the week, four pouch pages with only one pouch, can be placed in the same position as the current weekly pouch pages (e.g. FIG. 8 a ). The user can go even further and use one side of the one pouch pages for a single day of the week. In this case, the user would be rotating through one week at a time.
[0041] If the printed pages and corresponding pouch pages instead of “Monday”, “Tuesday”, “Wednesday”, were “Monday”, “Tuesday”, “Wednesday”, and “Thursday”, leaving only “Friday”, “Saturday”, and “Sunday” on the reverse side. The book would perform exactly the same. If, instead of colors; numbers, letters, pictures or any of a number of different stimuli were used to label the “future weeks” and their corresponding pouches. The book and its lead cards can be sized to the desires of the consumer.
[0042] One thing that could be added to the planner to make it work better is computer software. Once a prospect is made into a customer it is good at that point to put them in a contact database. This is not to schedule appointments with them. Contact management software is easier to use than word processing programs for writing letters and keeping a database. The software could be designed to fit right along with the book and leave out all of the unnecessary functions and to have the software print lead cards.
[0043] Although the planner is geared primarily towards sales people, the organizational tools it provides could be used in many areas of professional and domestic life. For example, a teacher could use the Planning tool of the present invention to for scheduling homework assignments, exams, parent teacher conferences, etc.; a house wife could use it to schedule her children's appointments and activities and her personal appointments; or a chef could use it to document entrees to be served, past menus, and coming catered events. These are just a few examples of productive and efficient ways to use the planning tool of the present invention.
[0044] Accordingly, it is to be understood that the embodiments of the invention herein described are merely illustrative of the application of the principles of the invention. Reference herein to details of the illustrated embodiments is not intended to limit the scope of the claims, which themselves recite those features regarded as essential to the invention. | A planner tool comprising multiple pouch pages, lead cards, and printed calendar sheets. Each pouch page and calendar sheet has holes that are appropriately spaced apart so that each of the pages can be placed in a binder. The lead cards have two sets of times of the day and a blank center which are used in conjunction with the printed calendar sheets to make appointments to call, appointments to see others, and keep information regarding the nature of such appointments all in one place. The lead cards are placed in the pouches of the pages. The printed calendar sheets of the planner have the days of the week printed on them with specific columns under each day. The columns have the headings c, m, a, and e, which stand for call, mileage, appointment, and expenses respectively. | 1 |
RELATION TO PARENT APPLICATION
This application is a Continuation-In-Part of copending U.S. Pat. application Ser. No. 422,474 filed Dec. 6, 1973 under the same title and now abandoned. This application contains the illustrative examples of the parent application and additional illustrative examples wherein the amounts of thermosettable film-forming material deposited on the metal particles prior to their incorporating into a powder paint are above that illustrated in the parent. The recitational disclosures as to the same in the body of the specification are conformed to take into account the additional examples.
BACKGROUND OF THE INVENTION
One basic technique for the manufacture of powder coating materials is the so-called fusion method. This involves the mixing of solvent-free raw materials in their molten state, usually via some form of extruder, cooling, pulverization and size separation-classification. This method has a number of disadvantages unrelated to pigmentation and an additional short-coming when metal flakes are employed as pigments. The high shear employed in the mixing stage results in deformation of the metal flakes. Additionally, during the pulverization step, the metal flakes are further deformed and reduced in particle size. Coatings produced from such powders are characterized by a low level of brilliance and poor polychromatic appearance.
Another basic technique for the manufacture of powder coating materials is the so-called solution-preparation, solvent-separation technique which can be effected by more than one method. This general technique involves the preparation of a coating material in an organic solvent, separation of the solvent from the paint solids, and size-separation classification. Also, pulverization in some form may or may not be required depending upon the solvent separation method involved.
The separation of the solvent can be carried out by conventional spray drying techniques or by heat exchange separation wherein the components of a paint solution are separated by volatilization of the more volatile solvent and separation of the volatilized solvent from the nonvolatilized paint solids by gravitational forces. Since the metal flakes can be added after pulverization, if pulverization is required when using any of the solvent separation methods, damage to the metal flakes during pulverization can be avoided by using the solution preparation-solvent-separation technique. Problems do arise, however, with respect to distribution and orientation of the metal flakes when the powder coating material is applied to the substrate to be coated. This is particularly true when the method of application is that of electrostatic spray, the method most commonly employed to apply the final coating of paint to automobiles and a variety of other metal manufacturers. In such applications, the flakes tend to orient in a random fashion with a low percentage of the flakes parallel to the substrate. The net result is a high degree of metal protusion with little metallic brilliance and a low gloss factor.
Thus, when either of the aforedescribed methods are used to produce metal-pigmented, powder-paint coatings in accordance with the prior art processes, a substantially higher aluminum to non-metal pigment ratio is required, relative to the same ratio in liquid paints, in order to achieve the same degree of brightness and metallic appearance obtained with liquid paints. Further, the problem of metal flake protrusion remains even when brightness and metallic appearance are achieved.
In liquid paints, it is known to partially coat aluminum flakes used as pigments to increase the electrostatic spray efficiency of such paints. In U.S. Pat. No. 3,575,900, a method is disclosed for precipitating the resin of the solution coating upon the aluminum flake in colloidal form. This solution is then used as such or mixed with another solution for use. The patentee specificially points out that, while it may be convenient to call this encapsulation, it is not intended to denote that the aluminum particles are completely enveloped. The resin disclosed for this purpose is a copolymer of vinyl chloride and monoethylenically unsaturated monomers containing about 60 to about 90 percent by weight vinyl chloride. Aluminum flake is also partially coated in U.S. Pat. No. 3,532,662. Here the coating was carried out with a random copolymer of methyl methacrylate and methacrylic acid adsorbed on the pigment. By this method, a dispersion is made of the solid particles in a liquid continuous phase comprising an organic liquid containing in solution a polymer which is adsorbed by the particles and a stabilizer, and modifying the polarity of the continuous phase so that the polymer is insoluble therein, the stabilizer being a compound containing an anchor component which becomes associated with the adsorbed polymer on the particle surface and a pendant, chain-like component which is solvated by the modified continuous phase and provides a stabilizing sheath around the particles. It is alleged that this improves the "wetting" of the treated particles by the film-forming material dispersion-type coating composition.
Powder paints have certain advantages over conventional liquid paints in that they are essentially free of volatile solvents but they also present problems which differ from the problems encountered with liquid paints. These differences include differences with respect to employment of aluminum flakes as a color producing component. For instance, when flakes partially coated by resin precipitate are employed in liquid paints, there remains the organic solvent and other components of the solution to prevent direct exposure of the flake to the atmosphere and other external influences. Further, in powder paints, if aluminum flake is coated, the coating must be a relatively dry solid and the size, weight and continuity of the organic encapsulation are all factors in affecting the distribution of such particles when electrostatically sprayed with the powder that is the principal film-former of the coating composition.
Coated aluminum flakes, i.e., aluminum flakes individually encapsulated in a continuous thermosettable film, admixed with the particulate principal film-former of a powder paint and electrostatically sprayed on a metal substrate will in a substantial portion orient in parallel relationship to the substrate. This substantially reduces or eliminates flake protrusion. Unfortunately, however, there remains a tendency for these coated to assume a substrate - parallel orientation close to the outer surface of the cured coating. This can produce two undesired results. The first of these is an insufficient appearance of metallic depth in the coating wherein the metal flakes are seen through varying depths of a film which is usually colored with a non-metal color producing component. The second is an undesired "silvery" effect which dominates the non-metal color producing component if the concentration of the near-surface, substrate-parallel flakes is too high.
THE INVENTION
A dominance of "silvery" effect in polychromatic finishes resulting from an overabundance of aluminum flakes near and parallel to the outer surface of a cured coating is avoided and depth variation for the metal color producing component in polychromatic or monochromatic finishes is achieved by including a suitable ammonium salt, preferably a tetraalkyl ammonium halide in the thermosettable coating in which the aluminum flakes are encapsulated prior to admixture with the principal film-forming powder. To avoid unnecessary duplication of disclosure, this invention will be described with reference to using the preferred tetraalkyl ammonium halides.
The use of these salts as catalysts and anti-static agents in the principal film-former of a powder coating composition is known from U.S. Pat. Nos. 3,730,930; 3,758,632; 3,758,633; 3,758,634 and 3,758,635. These salts may be used in the principal film-former of the coating compositions of this invention but such use will not achieve the results of this invention. The respective roles of these salts in the encapsulating film and in the principal film-former of the powder composition are quite interesting. It has been discovered that the effective upper limit for the concentration of such salts in the encapsulating film is substantially higher when the principal film former also contains such salts than it is when the principal film-former does not contain such salts. Thus, when the principal film-former of the powder paint composition contains in excess of about 0.05, e.g., 0.05 to about 0.15, weight percent of these salts, the concentration in the encapsulating film may range between about 0.05 to about 20, preferably 0.05 to 10, parts by weight per 100 parts by weight of the thermosettable film-former used to encapsulate the flakes. On the other hand, if the principal film-former is free of such salts, the effective range for employing such salts in the encapsulating film is about 0.05 to about 12 parts by weight per 100 parts by weight of the thermosettable film-former.
The desired depth variation can also be achieved by mixing nickel powder with the encapsulated aluminum flakes in a weight ratio of nickel powder to coated aluminum flakes in a weight ratio of nickel powder to coated aluminum flakes in the range of 1:4 to 5:1. These coating compositions are disclosed in our U.S. Pat. applications Ser. Nos. 506,487 and 506,491 filed of even date with this application. Nickel powder can be used in the coating compositions of this invention when desired. The use of the tetraalkyl ammonium halides in accordance with this invention permits one to reduce the amount of nickel powder used in conjunction with the coated aluminum flakes to achieve a given result. Ordinarily, such reduction will be by a factor of about 1/10.
The preferred tetraalkyl ammonium halides for use in this invention have 1 to 4 carbons in their alkyl groups, e.g., tetramethyl ammonium bromide, chloride and iodide; tetraethylammonium bromide, chloride and iodide; and tetrabutyl ammonium bromide, chloride and iodide. Other suitable ammonium halides which are suitable include the aryl, alkylauryl, aryloxy, and alkoxy substituted tetraalkyl ammonium halides such as dodecyl dimethyl (2-phenoxyethyl) ammonium bromide, chloride and iodide and diethyl (2-hydroxyethyl) methyl ammonium bromide, etc.
In addition one may also use the hydrohalides of mono-, di, and tertiary amines. Another group of additives which can be used are alkyl-poly (ethyleneoxy) phosphates such as, for example, dibutyl-poly (ethyleneoxy) phosphate or alkylauryl poly (ethyleneoxy) phosphates such as, for example, ethyl benzyl poly (ethyleneoxy) phosphate.
Aluminum flakes which are incorporated in powder paints to provide a metallic color producing component are herein encapsulated in a thin, continuous, thermosettable organic coating through which the aluminum particle is visible to the human eye. This coating is preferably transparent but may be translucent. The term "substantially transparent" as used herein means materials which are either transparent or translucent or partially transparent and partially translucent.
As these metal pigments are most frequently used in polychromatic finishes, the powder coating composition will ordinarily contain at least one non-metal color producing component. The "non-metal color producing component" may be a particulate pigment, dye or tint and may be either organic, e.g., carbon black, or inorganic, e.g., a metal salt.
The aluminum color producing component is most often aluminum flakes in the form of aluminum paste. To avoid unnecessary complication of the description of this invention, such aluminum flakes will be used to illustrate the invention. It should be understood, however, that this method is applicable to any particulate aluminum used as a color producing component in a powder coating material. This includes aluminum particles which are solely aluminum, aluminum coated organic particles, and polymer-sandwiched metal particles having exposed metal edges.
In accordance with this invention, the coated metal particles are admixed, i.e., cold blended, with the balance of the coating material after the principal film-former is in particulate form. The non-metal color producing component may be admixed with the film-forming powder before, after or during the addition of the coated metal particles but such component is preferably added before the coated metal particles. This order of mixing avoids degradation of the metal particles in any of the steps of preparing the film-forming powder.
The film-former used to coat the metal particles in accordance with this invention may be the same as or different than the principal film-former of the powder coating material. The film-former used to coat the metal particles is an organic, thermosetting, film-former which may take the form of a self-crosslinkable polymer or a chemically functional polymer and a crosslinking agent reactable therewith. In the preferred embodiment, it is also crosslinkable with the principal film former of the powder coating composition.
The preferred method for coating the aluminum flakes is to disperse the flakes, preferably in the form of aluminum paste, in a small amount of thermosetting organic film-former and a solvent for the film-former that is suitable for spray drying and in which the tetraalkylammonium halide is intimately dispersed. The dispersion is then spray dried by conventional spray drying techniques. Since there is a small amount of film-former relative to the amount of metal flakes, the net result is a metal flake coated with a relatively thin, continuous, coating of the film-former containing the tetraalkylammonium halide as opposed to a metal flake imbedded in a relatively large particle of the film-former.
More specifically, one first disperses the aluminum flakes in about 2 to about 200 weight percent of thermosettable film-former, based on the actual weight of aluminum flakes, i.e., about 2 to about 200 parts by weight of thermosettable film-former per 100 parts by weight aluminum flakes. In one embodiment wherein the coating of such flakes is relatively light, the aluminum flakes are dispersed in about 2 to about 30 weight percent of thermosettable film-former based on the actual weight of the aluminum flakes, i.e., about 2 to about 30 parts by weight of thermosettable film-former per 100 parts by weight aluminum flakes. In most applications, it will be found advantageous to use between 10 and 200, preferably between about 30 and about 70, parts by weight of thermosettable film-former per 100 parts by weight aluminum flakes. When metal particles of different density are used, the weight of aluminum flakes of the same surface area can be used to determine the amount of film-former to use in coating the metal particles. When less than about 2 weight percent of the film-former is used, complete encapsulation of the metal flakes may not result. When more than about 30 weight percent of the film-former is used, care must be taken in controlling the spray drying operation to minimize the formation of an excessive amount of spherical particles containing more than one metal flake. The incidence of full coverage is high in the 30 to 70 range above described. Such spherical particles can be removed from the other coated aluminum flakes by screening. The inclusion of large, multileafed particles in a cured coating provides an irregular appearance. A similar result may be obtained if one mixes the uncoated metal flakes with the principal film-former of a powder paint while the latter is in liquid state and then removes the solvent.
Aluminum paste is aluminum flakes, usually about 60 to about 70 weight percent, in a smaller amount, usually about 30 to about 40 weight percent, of a liquid hydrocarbon solvent which serves as a lubricant, e.g., mineral spirits. A small amount of an additional lubricant, e.g., stearic acid, may be added during the milling operation which produces the aluminum flakes. Everett J. Hall is credited with originating the method of beating aluminum into fine flakes with polished steel balls in a rotating mill while the flakes are wet with a liquid hydrocarbon. See U.S. Pat. No. 1,569,484 (1926). A detailed description of aluminum paste, its manufacture, flake size, testing, uses in paint, etc. is found in Aluminum Paint and Powder, J. D. Edwards and Robert I. Wray, 3rd Ed. (1955), Library of Congress Catalog Card Number: 55-6623, Reinhold Publishing Corporation, 430 Park Avenue, New York, New York, U.S.A. and the same is incorporated herein by reference.
The film-former used to coat the aluminum flakes may be a self-crosslinking polymer or copolymer or a chemically functional polymer or copolymer and a monomeric crosslinking agent. The preferred film-formers for this purpose include thermosettable copolymer systems comprising: (a) an epoxy-functional copolymer of monovinyl monomers and as crosslinking agent therefor a C 4 - C 20 , saturated, straight chain, aliphatic, dicarboxylic acid crosslinking agent-exemplified by U.S. Pat. application Ser. No. 172,236 filed Aug. 16, 1971, now U.S. Pat. No. 3,752,870: (b) an epoxy-functional copolymer of monovinyl monomers and as crosslinking agent therefor a mixture of about 90 to 98 percent by equivalent weight of a C 4 - C 20 , saturated, straight chain, aliphatic dicarboxylic acid and about 10 to about 2 percent by equivalent weight of a C 10 - C 22 , saturated straight chain, aliphatic, monocarboxylic acid-exemplified by U.S. Pat. No. 3,730,930; (c) an epoxy-functional copolymer of monovinyl monomers and as crosslinking agent therefor a diphenol having a molecular weight in the range of about 110 to about 550 - exemplified by U.S. patent application Ser. No. 172,228 filed Aug. 16, 1971, now U.S. Pat. No. 3,758,634; (d) an epoxy-functional copolymer of monovinyl monomers and as crosslinking agent therefor a carboxy terminated polymerexemplified by U.S. Pat. application Ser. No. 172,229 filed Aug. 16, 1971, now U.S. Pat. No. 3,781,380; (e) an epoxy-functional copolymer of monovinyl monomers and as crosslinking agent a phenolic hydroxy terminated polymer - exemplified by U.S. Pat. application Ser. No. 172,225 filed Aug. 16, 1971, now U.S. Pat. No. 3,787,520; (f) an epoxy-functional, carboxy-functional, self-crosslinkable copolymer of ethylenically unsaturated monomers - exemplified by U.S. Pat. application Ser. No. 172,238 filed Aug. 16, 1971, now U.S. Pat. No. 3,770,848; (g) a hydroxy-functional, carboxy-functional copolymer of monoethylenically unsaturated monomers - exemplified by U.S. Pat. application Ser. No. 172,237 filed Aug. 16, 1971, now U.S. Pat. No. 3,787,340; (h) an epoxy-functional copolymer of monovinyl monomers and as crosslinking agent therefor an anhydride of a dicarboxylic acid - exemplified by U.S. Pat. application Ser. No. 172,224 filed Aug. 16, 1971, now U.S. Pat. No. 3,781,379; (i) a hydroxy-functional copolymer of monoethylenically unsaturated monomers and as crosslinking agent therefor a compound selected from dicarboxylic acids, melamines, and anhydrides - exemplified by U.S. Pat. application Ser. No. 172,223 filed Aug. 16, 1971 and abandoned in favor of continuation application Ser. No. 407,128 filed Oct. 17, 1973 in turn abandoned in favor of continuation-in-part application Ser. No. 526,547 filed Nov. 25, 1974; (j) an epoxy-functional copolymer of monovinyl monomers and as crosslinking agent therefor a compound containing tertiary nitrogen atoms - exemplified by U.S. Pat. application Ser. No. 172,222 filed Aug. 16, 1971, now U.S. Pat. No. 3,758,635; (k) a copolymer of an alpha-beta unsaturated carboxylic acid and an ethylenically unsaturated compound and as crosslinking agent therefor an epoxy resin having two or more epoxy groups per molecule - as exemplified in U.S. Pat. application Ser. No. 172,226 filed Aug. 16, 1971, now U.S. Pat. No. 3,758,633; (1) a self-crosslinkable, epoxy-functional, anhydride-functional copolymer of olefinically unsaturated monomers - exemplified by U.S. Pat. application Ser. No. 172,235 filed Aug. 16, 1971, now U.S. Pat. No. 3,758,632; (m) an epoxy-functional copolymer of monovinyl monomers and as crosslinking agent therefor a carboxy terminated polymer, e.g., a carboxy terminated polymer, e.g., a carboxy terminated polyester, - exemplified by application Ser. No. 223,746 filed Feb. 4, 1972 and now abandoned in favor of continuation-in-part application Ser. No. 489,271 filed Aug. 5, 1974; (n) an epoxy-functional copolymer of vinyl monomers and as crosslinking agent therefor a dicarboxylic acid - exemplified by U.S. Pat. application Ser. No. 228,262 filed Feb. 22, 1972, now U.S. Pat. No. 3,787,521; (o) an epoxy-functional and hydroxy-functional copolymer of monovinyl monomers and as crosslinking agent therefor a C 4 - C 20 , saturated, straight chain, aliphatic dicarboxylic acid - exemplified by U.S. Pat. application Ser. No. 394,874 filed Sept. 6, 1973 and now abandoned in favor of application Ser. No. 552,676 filed Feb. 24, 1975; (p) an epoxy-functional copolymer of monovinyl monomers with optional hydroxy and/or amide functionality and as crosslinking agent therefore (1) a C 4 - C 20 , saturated, straight chain, aliphatic dicarboxylic acid and (2) a polyanhydride - exemplified by U.S. Pat. application Ser. No. 344,881 filed Sept. 6, 1973 and now abandoned in favor of continuation-in-part Ser. No. 552,556 and continuation-in-part Ser. No. 552,557, both filed Feb. 24, 1975; (q) an epoxy-functional amide-functional copolymer of monovinyl monomers and as crosslinking agent therefor an anhydride of a dicarboxylic acid - exemplified by U.S. Pat. application Ser. No. 394,880 filed Sept. 6, 1973 and now abandoned in favor of application Ser. No. 552,572 filed Feb. 24, 1975; (r) an epoxy-functional, hydroxy-functional copolymer of monovinyl monomers and as crosslinking agent therefore an anhydride of a dicarboxylic acid - exemplified by U.S. Pat. application Ser. No. 394,879 filed Sept. 6, 1973 and now abandoned in favor of application Ser. No. 552,511 filed Feb. 24, 1975; (s) an epoxy-functional, amide-functional copolymer of monovinyl monomers and as crosslinking agent therefore a carboxy-terminated polymer - exemplified by U.S. Pat. application Ser. No. 394,875 filed Sept. 6, 1973 and now abandoned in favor of application Ser. No. 552,518 filed Feb. 24, 1975; (t) an epoxy-functional copolymer of monovinyl monomers and as crosslinking agent therefore a monomeric or polymeric anhydride and a hydroxy carboxylic acid - exemplified by U.S. Pat. application Ser. No. 394,878 filed Sept. 6, 1973 and now abandoned in favor of application Ser. No. 552,079 filed Feb. 24, 1975; (u) an epoxy-functional, amide-functional copolymer of monovinyl monomers and as crosslinking agent therefore a monomeric or polymeric anhydride and a hydroxy carboxylic acid - exemplified by U.S. Pat. application Ser. No. 394,877 filed Sept. 6, 1973 and now abandoned in favor of continuation-in-part application Ser. No. 552,078 filed Feb. 24, 1975; and (v) an epoxy-functional, hydroxy-functional copolymer of monovinyl monomers and as crosslinking agent therefore a monomeric or polymeric anhydride and a hydroxy carboxylic acid - exemplified in U.S. Pat. application Ser. No. 394,876 filed Sept. 6, 1973 and now abandoned in favor of continuation-in-part application Ser. No. 552,077 filed Feb. 24, 1975.
The disclosures of the aforementioned patents and patent applications are incorporated herein by reference.
The term "vinyl monomer" as used herein means a monomeric compound having in its molecular structure the functional group ##EQU1## wherein X is a hydrogen atom or a methyl group.
Other thermoset film-formers suitable for use in coating the metal particles include, but not by way of limitation thermosettable systems in which the polymeric component is a polyester, a polyepoxide and urethane-modified polyesters, polyepoxides and acrylics. As with the acrylics heretofore more specifically described, these may be self-crosslinking polymers or may be a combination of functional polymer and a coreactable monomeric compound which serves as crosslinking agent.
The preferred thermosettable powder paints known to applicants for automotive topcoats, the use wherein metallic pigments find their greatest use, consist essentially of an epoxy-functional copolymer of olefinically unsaturated monomers and a crosslinking agent therefor. Such paints, exclusive of pigments, may also contain flow control agents, catalysts, etc. in very small quantities.
The copolymer referred to in the preceding paragraph has average molecular weight (M n ) in the range of about 1500 to about 15,000 and glass transition temperature in the range of about 40°C. to about 90°C. The epoxy functionality is provided by employing a glycidyl ester of a monoethylenically unsaturated carboxylic acid, e.g., glycidyl acrylate or glycidyl methacrylate, as a constituent monomer of the copolymer. This monomer should comprise about 5 to about 20 weight percent of the total. Additional functionality, e.g., hydroxy functionality or amide functionality, may also be employed by inclusion of a C 5 - C 7 hydroxy acrylate or methacrylate, e.g., hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxy propyl acrylate, or hydroxypropyl methacrylate, or an alpha-beta olefinically unsaturated amide, e.g., acrylamide or methacrylamide, among the constituent monomers. When such additional functionality is used, the monomers providing it comprise about 2 to about 10 weight percent of the constituent monomers. The balance of the copolymer, i.e., about 70 to about 93 weight percent of the constituent monomers, are made up of monofunctional, olefinically unsaturated monomers, i.e., the sole functionality being ethylenic unsaturation. These monofunctional, olefinically unsaturated monomers are, at least in major proportion, i.e., in excess of 50 weight percent of the constituent monomers, acrylic monomers. The preferred monofunctional acrylic monomers for this purpose are esters of C 1 - C 8 monohydric alcohols and acrylic or methacrylic acid, e.g., methyl methacrylate, ethyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate and 2-ethylhexyl acrylate. In this preferred embodiment, the remainder, if any, aside from the aforementioned epoxy, hydroxy and amide functional monomers which also have olefinic unsaturation functionality used up in the polymerization formation of the copolymer, is preferably made up to C 8 - C 12 monovinyl hydrocarbons, e.g., styrene, vinyl toluene, alpha methyl styrene and tertiary butyl styrene. Other vinyl monomers which are suitable in minor amounts, i.e., between 0 and 30 weight percent of the constituent monomers, include vinyl chloride, acrylonitrile, methacrylonitrile, and vinyl acetate.
The crosslinking agents employed with the aforedescribed copolymer will have functionality that will react with the functionality of the copolymer. Thus, all of the crosslinking agents heretofore mentioned in the recital of powder paint patents and patent applications, e.g., C 4 - C 20 saturated, aliphatic dicarboxylic acids, mixtures of C 4 - C 20 saturated aliphatic dicarboxylic acids and monocarboxylic acids of carbon number in the same range, carboxy terminated copolymers having molecular weight (M n ) in the range of 650 to 3000, monomeric anhydrides preferably anhydrides having a melting point in the range of about 35° to 140°C., e.g., phthalic anhydride, maleic anhydride, cyclohexane-1,2-dicarboxylic anhydride, succinic anhydride, etc., homopolymers of monomeric anhydrides, and mixtures of such anhydrides and hydroxy acids having a melting point in the range 40° to 150°C., are suitable for use as crosslinking agents for these copolymers. The disclosures of all patents and patent applications recited herein are incorporated herein by reference. In general, these crosslinking agents are employed in amounts such as to provide between about 0.3 and about 1.5, preferably between about 0.8 and about 1.2, functional groups which are reactable with functional groups on the copolymer per functional groups on the copolymer.
The best acrylic, thermoplastic, powder coatings known to applicants are copolymers of alpha-beta olefinically unsaturated monomers. These are made up either solely or predominantly of acrylic monomers, i.e., acrylates, methacrylates, mixtures of acrylates and methacrylates and a small fraction of acrylic or methacrylic acid. In the embodiment wherein the copolymer is made up predominantly of acrylic monomers, i.e., in excess of 51 weight percent acrylic monomers, the acrylic monomers may include up to about 5 weight percent acrylic acid, methacrylic acid or a mixture of acrylic acid methacrylic acids while the balance is made up of C 8 - C 12 monovinyl hydrocarbons, e.g., styrene, vinyl toluene, alpha methyl styrene, and tertiary butyl styrene. The acrylates and methacrylates used in either of these embodiments are preferably esters of a C 1 - C 8 monohydric alcohol and acrylic acid or methacrylic acid or a mixture of acrylic and methacrylic acids. Thus, such a copolymer would contain about 46 to about 100 weight percent of esters of a C 1 - C 8 monohydric alcohol and acrylic or methacrylic acid, 0 to about 49 weight percent of C 8 - C 12 monovinyl hydrocarbons, and 0 to about 5 weight percent acrylic or methacrylic acid with the sum of the aforementioned esters and acrylic or methacrylic acid comprising in excess of 51 weight percent of the comonomers as stated earlier in this paragraph. One such copolymer contains about 76 to about 81 mole percent methyl methacrylate 1 to 3 mole percent acrylic acid or methacrylic acid or a mixture of acrylic and methacrylic acids, and 16 to 23 mole percent butyl methacrylate.
"Alpha-beta unsaturation" as used herein includes both the olefinic unsaturation that is between two carbon atoms which are in the alpha and beta positions relative to an activating group such as a carboxyl group, e.g., the olefinic unsaturation of maleic anhydride, and the olefinic unsaturation between the two carbon atoms which are in the alpha and beta positions with respect to the terminus of an aliphatic carbon-to-carbon chain, e.g., the olefinic unsaturation of acrylic acid, methyl methacrylate or styrene.
DETAILED DESCRIPTION OF THE INVENTION
The preparation of the coated metal flakes is carried out in a solvent for the film-former that is sufficiently volatile for efficient spray drying and which will not chemically react with either the film-former or the metal flakes to a degree that will significantly modify their properties or appearance within the contact timer employed to carry out the spray drying process. A preferred solvent for this purpose is methylene chloride. Other solvents which can be used include toluene, xylene, methyl ethyl ketone, acetone and low boiling petroleum naphthas.
A typical formulation for the feed stock for the spray drier in accordance with this invention would include the following:
Parts by Weight______________________________________aluminum paste 30.00film former 2.00MeCl.sub.2 200.00______________________________________
Typical operating parameters for a convention, 3 ft. diameter spray drier equipped with a conventional two-fluid nozzle atomizer, e.g., a glass and a liquid as in a convention air stomixing (liquid) paint spray gun are as follows:
air flow 197 cubic feet/minutefeed flow 380 ml/min.inlet air temperature 180°F.outlet air tempera- ture 80°F.product rate 6 lbs./hr.
The coated aluminum, as received from the spray drier, is then sieved through a screen of desired particulate size, e.g., a 44 micron screen, to remove excessively large particles. Approximately 20 percent of the product in the form of oversize particles is discarded.
The non-metal powder component, hereinafter called the "powder component" comprises the primary film-forming component and where the finish is to be polychromatic, at least one metal color producing component. This non-metal color producing component may be a pigment, dye or tint. For purposes of this invention, white and black shall be considered colors inasmuch as a light reflecting or light absorbing material must be added to the organic film-former to provide the finish with a white or black appearance in the same manner that a material must be added to the organic film-former which reflects light rays that convey to the eye one color while absorbing others.
The film-forming component of the powder component is preferably a thermosetting film-forming material. Those thermosetting film-forming materials heretofore disclosed for use in coating the metal leaves are suitable for use as the principal film-former of the powder component. The thermosets preferred for the coating of the metal leaves are also the preferred thermosets for this purpose.
In addition, the principal film-former of the powder component of this invention may be a thermoplastic powder, e.g., a thermoplastic acrylic polymer having a molecular weight (M n ) in the range of 30,000 to 80,000 and a glass transition temperature in the range of 60°C. to 110°C. - as exemplified by U.S. Pat. application Ser. No. 172,227 filed Aug. 16, 1971. These coated flakes, of course, can be used with any thermoplastic powder suitable for use as the principal film-former of any thermoplastic powder paint.
The formulation of the non-metal powder component, which in the case of a polychromatic finish contains a nonmetal color producing component, is prepared taking into consideration the particular color chosen for employment with the metallic color component and the amount of the metallic color component to be employed. The powder component is quantitatively formulated taking into account the amount of material to be brought in through the addition of the coated metal particles.
A typical composition for the powder component is as follows:
Parts by Weight______________________________________film-former 94.33flow control additive 0.67pigment 5.00______________________________________
The preparation and processing of the non-metal powder component into powder form is carried out by one of the conventional powder preparation techniques, e.g., extrusion, spray drying, or solvent extraction. Once in powdered form, this material is sieved through a suitable screen, e.g., a 74 micron screen.
The final step in the preparation of the powder coating material of this invention is the blending of the two major components, i.e., the thermoset, organic coated particulate metal component and the non-metal powder component. The exact proportions of the two major components will, of course, depend on the specific formulation and the amount of metal needed. In the typical example aforedescribed, if one blends about 98.5 parts by weight of the non-metal powder component with about 1.5 parts by weight of the coated aluminum, a "low metallic" automotive topcoat paint results.
Appearance of the finished coating will, of course, be a primary factor in selecting the total concentration of aluminum flakes in the total powder paint composition. This concentration will vary from a very low weight percent of the total powder paint composition in some polychromatic finishes, i.e., as low as about 0.005 weight percent, to a much higher weight percent of the total powder paint composition in the so-called "Argent" finishes, i.e., as high as about 25 weight percent when aluminum is the only metal used. If for example, the spray dried coating on the flakes comprises about 2 to about 30 weight percent by weight of the flakes then, the total metal component of the powder paint composition will comprise between about 0.005 to about 32.50, advantageously between about 0.25 to about 28.75, and preferably between about 0.54 to about 28.25, weight percent of the total powder paint composition. These figures will be modified by the weight of nickel powder substituted for a portion of the aluminum. The principal film-forming powder and non-metal pigment, if any, will make up the balance of the powder paint composition. The non-metal pigment will constitute between 0 and about 22 weight percent of the total composition.
This invention will be more fully understood from the following illustrative examples.
EXAMPLE 1
a. Preparation of The Coated Aluminum Flakes
A powder paint in accordance with this invention is prepared from the following materials using the procedures hereinafter outlined:
1. Preparation of an epoxy-functional acrylic copolymer of vinyl monomers is prepared as follows:
Ingredients Parts By Weight______________________________________glycidyl methacrylate 15methyl methacrylate 45butyl methacrylate 40______________________________________
The above named ingredients are mixed together. Three parts by weight of 2,2' - azobis - (2-methyl-propionitrile), hereinafter called AIBN, is dissolved in the monomer mixture. The mixture is slowly added to refluxing toluene (100 parts) which is stirred vigorously under a nitrogen atmosphere. A condenser is provided at the top of the toluene container to condense the toluene vapors and return them to the container. The monomer mixture is added through a regulating valve and the rate of addition is controlled to maintain a reflux temperature (109°C. - 112°C.) with only a small fraction of heat supplied from an external heater. After the addition of the monomer mixture is complete, the refluxing is maintained by external heat source for 3 additional hours.
The solution is poured into shallow stainless steel trays. These trays are placed in a vacuum oven and the solvent evaporated therefrom. As the solvent is removed, the copolymer solution becomes more concentrated. The temperature of the vacuum oven is raised to about 110°C. Drying is continued until the solvent content of the copolymer is below 3 percent. The trays are cooled and the copolymer collected and ground to pass through 20 mesh screen. The copolymer has a glass transition temperature of 53°C. and a molecular weight (M n ) of 4000.
One hundred parts by weight of the ground copolymer are mixed with the following materials:
Parts By Weight______________________________________azelaic acid 10.0tetrabutyl ammonium bromide 0.2poly (lauryl acrylate)(M.sub.n =10,000) 0.5______________________________________
The materials are mixed together in a ball mill for 2 hours. The mixture is mill rolled at 85°C. to 90°C. for 5 minutes. The solid obtained is ground in a ball mill and the powder is sieved with a 140 mesh screen.
Two parts by weight of this thermosettable mixture are combined with 30 parts by weight of aluminum paste (35 percent by weight mineral spirits and 65 percent by weight aluminum flakes that will pass through a 325 mesh screen and have typical surface area of 7.5 m 2 /g, maximum particle diameter below 45 microns and most common particle size distribution in the range of about 7 to about 15 microns) and 200 parts by weight of methylene chloride under low shear agitation so as to disperse the aluminum in the thermosettable material without damage to the aluminum flakes.
Once the above dispersion has been prepared, it is spray dried in a manner which will produce individual aluminum flakes coated with a thin, continuous coating of dry copolymer containing the tetrabutyl ammonium bromide. This is accomplished in a 3 foot diameter spray drier equipped with a two-fluid nozzle in counter-current position using the following conditions:
air flow in drying chamber 200 cubic feet/minutefeed rate of mixture 380 ml/minuteinlet air temperature 180°F.two fluid atomization air pressure 80 lbs.
The product obtained from this process has an overall composition of 19.5 parts by weight of aluminum and 2.0 parts by weight of the thermosettable mixture aforedescribed plus a small amount of residual solvent (i.e., 0.05 to 0.2 parts) that has not completely volatilized during the spray dry process. This product is then screened through a 44 micron screen.
b. Preparation of the Non-Metal Powder Component
A thermosettable material is produced by mixing 166 parts by weight of the epoxy-functional copolymer employed in the thermosettable material used to coat the aluminum flakes in (a) above with the following materials:
Parts By Weight______________________________________azelaic acid 22.65poly (lauryl acrylate) 1.34phthalo green pigment 1.75yellow iron oxide pigment 8.26______________________________________
A homogeneous mixture of the above is obtained by ball milling for 2 hours. This mixture is then extruded at 100°C. from a kneading extruder. The solid thus obtained is pulverized in an impact mill, i.e., an air classified impact mill, and sieved through a 200 mesh screen.
c. Preparation of the Powder Coating Material
A powder coating material in accordance with this invention is produced by mixing 1.65 parts by weight of the coated aluminum flakes with 98.35 parts of the non-metal powder component. A homogeneous mixture of the two components is obtained by rapidly tumbling the material in a partially filled container for 20 minutes, under ambient room conditions, i.e., 65° - 75° F.
It will be noted that in this example the thermosettable material used to coat the aluminum flakes and the thermosettable material used to form the non-metal powder component component are crosslinkable with each other.
The powder thus obtained is then sprayed on an electrically grounded steel substrate with a conventional electrostatic powder spray gun operating at about 50 KV charging voltage. After spraying, the coated substrate is heated to about 350°F. for about 25 minutes. The coating thus obtained has good gloss, good aluminum particle orientation, and good aluminum particle depth. It is resistant to weathering and suitable for automotive top coat application. The coating thus obtained demonstrates a more random metal particle orientation with respect to depth and increased polychromatic light reflection of the cured film than is obtained when this process is duplicated except for omitting the tetrabutylammonium bromide in the coating of the aluminum flakes.
EXAMPLE 2
A powder coating material is prepared following the procedure of Example 1 with the following differences: (1) The coated aluminum flakes are prepared from the following materials.
______________________________________ Parts By by Weight______________________________________aluminum paste 30.000 (65% aluminum flakes and 35% mineral spirits)thermosettable mixture 0.218 (same epoxy-functional copolymer used in example 1 in amount as 195 parts by weight and poly (azelaic anhydride) .023 parts by weighttriethylbenzylammonium chloride 0.02poly (lauryl acrylate) (M.sub.n =10,000) 0.001methylene chloride 197.000______________________________________
The product obtained after spray drying has a composition of 19.50 parts by weight aluminum, 0.218 parts by weight thermosettable material, 0.02 parts by weight triethylbenzylammonium chloride, and 0.001 parts by weight poly (lauryl acrylate).
The coated aluminum thus produced in the amount of 1.52 parts by weight is combined with 98.48 parts by weight of the non-metal powder component of Example 1 to yield a powder which, excluding the triethylbenzylammonium chloride, has the following composition:
Parts By Weight______________________________________aluminum (dry) 1.50thermosettable film-former 92.91 (a) epoxy-functional copolymer 81.74 (b) azelaic acid 11.15 (c) poly (azelaic anhydride) 0.02poly (lauryl acrylate) 0.66phthalo green 0.86yellow iron oxide 4.05______________________________________
This powder coating material is electrodeposited upon a metal substrate and heat cured as in Example 1. The resulting coating demonstrates good gloss, metallic orientation, good aluminum flake depth variation and weathering resistance.
EXAMPLE 3
A powder coating material is prepared following the procedure of Example 1 with the following differences:
1. The starting mixture for preparation of the coated aluminum flakes is of the following composition:
Parts By Weight______________________________________aluminum paste 30.00 (65% by weight aluminum and 35% by weight mineral spirits)thermosettable mixture 5.46 (a) epoxy-functional copolymer 4.88Example 1 (b) poly (azelaic 0.58dride)tetramethylammonium bromide 0.02poly (lauryl acrylate) 0.03methylene chloride 250.00______________________________________
This material is mixed and spray dried as in Example 1 and in the resultant material the flakes have coating about 2.5 times thicker than that of the coated flakes of Example 1. The empirical composition of the spray dried product, excluding the tetramethylammonium bromide, is as follows:
Parts By Weight______________________________________aluminum (uncoated basis) 19.5thermosettable material 5.46 (a) epoxy copolymer of 4.88mple 1 (b) poly (azelaic an- hydride) 0.58poly (lauryl acrylate) 0.03______________________________________
2. Since the amount of coating on the aluminum flakes is here large enough to be a significant factor, it is taken into consideration when formulating the non-metal powder component. Here, the non-metal powder component is prepared by combining 166 parts by weight of the ground epoxy-functional copolymer of Example 1 with the following:
Parts By Weight______________________________________azelaic acid 22.64poly (lauryl acrylate) 1.33phthalo green pigment 1.80yellow iron oxide 8.23______________________________________
Subsequent processing of the non-metal powder component is the same as in Example 1.
3. In the blending of the coated metal component and the non-metal powder component, the ratio of coated aluminum to non-metal powder component is altered because of the thickness of coating of the aluminum flakes. The ratio here is 1.93 parts by weight of coated aluminum with 98.08 parts by weight of the non-metal powder component. The resultant powder coating maintains the pigment level essentially the same as in Example 1.
EXAMPLE 4
The procedure of Example 1 is repeated except for the difference that the amount of tetrabutylammonium bromide dispersed in the methylene chloride is such as to provide in the spray dried coatings on the aluminum flakes an average concentration of 0.5 parts by weight of tetrabutylammonium bromide per 100 parts by weight of the thermosettable organic film-former.
EXAMPLE 5
The procedure of Example 1 is repeated except for the difference that the amount of tetrabutylammonium bromide dispersed in the methylene chloride is such as to provide in the spray dried coatings on the aluminum flakes an average concentration of 10 parts by weight of tetrabutylammonium bromide per 100 parts by weight of the thermosettable organic film-former.
EXAMPLE 6
The procedure of Example 1 is repeated except for the differences that the non-metal powder component contains tetrabutylammonium bromide in the amount of 0.14 weight percent and the thermosettable coatings on the aluminum flakes contain tetrabutylammonium bromide in the average amount of 20 parts by weight per 100 parts by weight of thermosettable, organic, film-former.
EXAMPLE 7
The procedure of Example 1 is repeated except for the differences that the non-metal powder component contains tetrabutylammonium bromide in the amount of 0.07 parts by weight and the thermosettable coating on the aluminum flakes contain tetrabutylammonium bromide in the average amount of 10 parts by weight per 100 parts by weight of thermosettable, organic, film-former.
EXAMPLE 8
The procedure of Example 1 is repeated except for the differences that the non-metal powder component contains tetrabutylammonium bromide in the amount of 0.05 weight percent and the thermosettable coating on the aluminum flakes contains tetrabutylammonium bromide in the average amount of 1 part by weight per 100 parts by weight of thermosettable, organic, film-former.
EXAMPLE 9
The procedure of Example 8 is repeated except for the difference that an equivalent amount of tetrabutylammonium chloride is substituted for the tetrabutylammonium bromide.
EXAMPLE 10
The procedure of Example 8 is repeated except for the difference that an equivalent amount of tetrabutylammonium iodide is substituted for the tetrabutylammonium bromide.
EXAMPLE 11
The procedure of Example 8 is repeated except for the difference that an equivalent amount of tetramethylammonium bromide is substituted for the tetrabutylammonium bromide.
EXAMPLE 12
The procedure of Example 8 is repeated except for the differences that the non-metal powder component contains 1 weight percent of dodecyl dimethyl (2-phenoxyethyl) ammonium bromide in lieu of the tetrabutylammonium bromide and the thermosettable coatings on the aluminum flakes contain, in lieu of the tetrabutylammonium bromide, dodecyl dimethyl (2-phenoxyethyl) ammonium bromide in the average amount of 5 parts by weight per 100 parts by weight of the thermosettable film-former.
EXAMPLE 13
The procedure of Example 8 is repeated except for the differences that the non-metal powder component contains 1 weight percent of diethyl (2-hydroxyethyl) methyl ammonium bromide in lieu of the tetrabutylammonium bromide and the thermosettable coatings on the aluminum flakes contain, in lieu of the tetrabutyl ammonium bromide, diethyl (2-hydroxyethyl) methyl ammonium bromide in the average amount of 3 parts by weight per 100 parts by weight of the thermosettable film-former.
EXAMPLE 14
The procedure of Example 8 is repeated except for the differences that the non-metal powder component contains 0.1 weight percent tetrabutylammonium bromide and the coatings on the aluminum flakes contain tetrabutylammonium bromide in the average amount of 12 parts by weight per 100 parts by weight of the thermosettable film-former.
EXAMPLE 15
The procedure of Example 1 is repeated except for the difference that the coated aluminum flakes are replaced with an equal volume of a mixture of nickel powder and coated aluminum flakes prepared in the same manner as those used in Example 1 and containing the same concentration of tetrabutylammonium bromide contained in the coated flakes of Example 1. The weight ratio of nickel powder to coated aluminum flakes in this example is 1.5 to 1.
EXAMPLE 16
The procedure of Example 15 is repeated except for the difference that the weight ratio of nickel powder to coated aluminum flakes is 2.5:1.
EXAMPLE 17
The powder coating material is prepared following the procedure of Example 1 with the following differences: (1) the coated aluminum flakes are prepared from the following materials:
Parts By Weight______________________________________aluminum paste 30.000 (65% aluminum flakes and 35% mineral spirits)thermosettable mixture 0.218 (same epoxy-functional co- polymer used in Example 1 in amount as 0.195 parts by weight and poly (azelaic an- hydride) 0.023 parts by weighttetrabutylammonium bromide 0.021poly (lauryl acrylate) 0.001 (M.sub.n = 10,000)methylene chloride 197.000______________________________________
The coated aluminum product obtained after spray drying in the amount of 1.52 parts by weight are combined with 98.48 parts by weight of the non-metal powder component of Example 1. This powder coating material is electrodeposited upon a metal substrate and heat cured as in Example 1. The resulting coating demonstrates good gloss, good metallic orientation, good metal depth variation and good weathering resistance.
EXAMPLE 18
The procedure of Example 1 is repeated except for the differences: the coating of the aluminum flakes is prepared from 30 parts by weight of the same aluminum paste used in Example 1 (19.5 parts by weight aluminum) and 4.7 parts by weight of the thermosettable material, i.e., epoxy-functional copolymer of Example 1 and azelaic acid in the proportions used in Example 1, 0.4 parts by weight tetrabutyl ammonium bromide, and 0.03 parts by weight poly (lauryl acrylate).
The cured finish obtained has good physical properties and good depth variation in metal pigment positioning.
EXAMPLE 19
The procedure of Example 1 is repeated except for the differences that the coating of the aluminum flakes is prepared from 30 parts by weight of aluminum paste used in Example 1 (19.5 parts by weight aluminum) and from 2.93 parts by weight of the thermosettable material, i.e., epoxy-functional copolymer of Example 1 and azelaic acid in the proportions used in Example 1, 0.29 parts by weight tetrabutyl ammonium bromide, and 0.02 parts by weight poly (lauryl acrylate).
The cured finish obtained has good physical properties and good depth variation in metal pigment positioning.
EXAMPLE 20
The procedure of Example 1 is repeated except for the following differences: the coating of the aluminum flakes is prepared from 30 parts by weight of the aluminum paste used in Example 1 (19.5 parts by weight aluminum) and 1.76 parts by weight of the thermosettable material, i.e., the epoxy-functional copolymer of Example 1 and azelaic acid in the proportions used in Example 1, 0.18 parts by weight tetrabutyl ammonium bromide, and 0.01 parts by weight poly (lauryl acrylate) - M n = 10,000.
The cured finish obtained has good physical properties and good depth variation in metal pigment positioning.
EXAMPLE 21
The procedure of Example 1 is repeated except for the following differences: the coating of the aluminum flakes is prepared from 30 parts by weight of the aluminum paste used in Example 1 (19.5 parts by weight aluminum) and 2.54 parts by weight of the thermosettable material, i.e., the epoxy-functional copolymer of Example 1 and azelaic acid in the proportions used in Example 1, 0.25 parts by weight tetrabutyl ammonium bromide, and 0.01 parts by weight poly (lauryl acrylate) - M n = 10,000.
The cure finish obtained has good physical properties and good depth variation in metal pigment positioning.
EXAMPLE 22
The procedure of Example 1 is repeated except for the following differences: the coating of the aluminum flakes is prepared from 30 parts by weight of the aluminum paste used in Example 1 (19.5 parts by weight aluminum) and 0.39 parts by weight of the thermosettable material, i.e., epoxy-functional copolymer of Example 1 and azelaic acid in the proportions used in Example 1, 0.04 parts by weight tetrabutyl ammonium bromide, and 0.002 parts by weight poly (lauryl acrylate) - M n = 10,000.
The cured finish obtained has good physical properties and good depth variation in metal pigment positioning.
EXAMPLE 23
The procedure of Example 1 is repeated except for the difference that a functionally equivalent amount of an epoxy-functional and hydroxy-functional copolymer of alpha-beta olefinically unsaturated monomers is substituted for the epoxy-functional copolymer of Example 1 and a functionally equivalent amount of poly (azelaic anhydride) is substituted for the azelaic acid. The epoxy-functional and hydroxy-functional copolymer used in this example is prepared from the below listed components in the manner hereinafter described:
Percent By WeightReactants Grams Of Total Reactants______________________________________glycidyl methacrylate 225.0 15hydroxyethyl methacrylate 75.0 5butyl methacrylate 600.0 40styrene 75.0 5methyl methacrylate 525.0 35______________________________________
The above mentioned monomers are admixed in the proportions above set forth and 70.0 grams (4.5 percent based on the continued weights of reactants) of 2,2' - azobis - (2-methyl propionitrile), hereinafter called AIBN, are added to the monomer mixture. The solution is added dropwise over a 3 hour period into 1500 ml. toluene at 100° - 180°C. under nitrogen atmosphere. Then 0.4 grams of AIBN dissolved in 10 ml. of acetone are added over a 1/2 hour period and refluxing is continued for 2 additional hours.
The toluene-polymer solution is diluted in 1500 ml. acetone and coagulated in 16 liters of hexane. The white powder is dried in a vacuum oven at 55°C. for 24 hours. This copolymer has molecular weight - M w - M n = 6750/3400 and the molecular weight per epoxy group is about 1068.
The cured finish obtained from the aluminum pigmented powder of this example has good physical properties and the aluminum flakes demonstrate good orientation and good depth variation.
EXAMPLE 24
The procedure of Example 23 is repeated with the single difference that about 35 percent of the poly (azelaic anhydride) is replaced with a functionally equivalent amount of 12 - hydroxystearic acid.
EXAMPLE 25
The procedure of Example 1 is repeated except for the difference that an epoxy functional, amide-functional copolymer of alpha-beta olefinically unsaturated monomers is substituted for the epoxy functional copolymer of Example 1 and a functionally equivalent amount of a carboxy-terminated polymer is substituted for the azelaic acid. The epoxy-functional amide - functional copolymer used in this example is prepared from the below listed components in the manner hereinafter described:
Percent By WeightReactants Grams Of Total Reactants______________________________________glycidyl methacrylate 45 15acrylamide 15 5butyl methacrylate 111 37methyl methacrylate 129 43______________________________________
The above mentioned monomers are admixed in the proportions above set forth and 110 grams of 2,2' - azobis - (2 - methylpropionitrile), hereinafter called AIBN, are added to the mixture. The mixture is slowly added to 200 ml. of toluene heated to 80° - 90° C. which is being stirred vigorously under a nitrogen atmosphere. A condenser is provided at the top of the toluene container to condense the toluene vapors and return the condensed toluene to the container. The monomer mixture is added through a regulating valve and the rate of addition is controlled to maintain a reaction temperature of 90° - 110°C. with the rest of the heat supplied from an external heater. After the addition of the monomer mixture is completed (3 hours), 0.8 gram of AIBN dissolved in 10 ml. acetone is added over a 1/2 hour period and refluxing is continued for 2 additional hours.
The resultant toluene-polymer solution is diluted with 200 mls. acetone and coagulated in 2 liters of hexane. The white powder is dried in the vacuum oven at 55°C. for 24 hours. Its molecular weight is determined to be M w /M n = 6700/3200 and WPE (molecular weight per epoxide group) is about 1000.
The carboxy terminated polymer to be used as crosslinking agent is prepared from the following materials in the following manner: five hundred grams of a commercially available epoxy resin, Epon 1001, (epoxide equivalent 450 - 525, melting range 64° - 76°C. - molecular weight average 900°C.), is charged into a 500 ml. stainless steel beaker having a heating mantle. The epoxy resin is heated to 110°C. As the epoxy resin is stirred, 194 grams of azelaic acid are added. After a reaction time of 30 minutes, a homogeneous mixture is obtained. The mixture resin only partially reacted, is poured into an aluminum pan and cooled. The solid mixture is pulverized to pass through a 100 mesh screen by use of a blender. This resin is only partially reacted because if fully reacted it could not be powdered. A portion of the carboxy terminated polymer is weighed out for making a powder coating composition in accordance with this invention.
The cured finish obtained from the aluminum pigmented powder of this example has good physical properties, and the aluminum flakes demonstrate good orientation and good depth variation.
EXAMPLE 26
The procedure of Example 1 is repeated except for the difference that a functionally equivalent amount of a hydroxyfunctional copolymer is substituted for the epoxy-functional copolymer of Example 1 and a functionally equivalent amount of hexamethoxy melamine is substituted for the azelaic acid.
The hydroxy-functional copolymer used in this example is prepared from the below listed components in the manner hereinafter described:
Reactants Parts By Weight______________________________________2-hydroxyethyl methacrylate 15ethyl acrylate 25methyl methacrylate 60______________________________________
A one liter, four-necked flask which contains 150 ml. of methyl ethyl ketone is heated until the contents of the flask are at a refluxing temperature of 85°C. A mixture of the above listed monomers and 4 parts by weight of 2,2' - azobis - (2-methyl propionitrile), hereinafter called AIBN, in the total amount of 208 grams is added in a dropwise fashion over a period of one and a half hours to the reaction mixture which is maintained at 85°C. After the monomer addition is complete, 0.5 grams of AIBN (dissolved in 20 grams of toluene) is added dropwise. The refluxing is continued for an additional one-half hour to complete the polymerization.
The solution is poured into shallow stainless steel trays. These trays are placed in a vacuum oven and the solvent evaporated therefrom. As the solvent is removed, the copolymer becomes more concentrated. The temperature of the vacuum oven is raised to 110°C. Drying is continued until the solvent content of the copolymer is below 3 percent. The trays are cooled and the copolymer collected and ground to pass through a 20 mesh screen.
The cured finish obtained from the aluminum pigmented powder of this example has good physical appearance and the aluminum flakes are distributed with good orientation and depth variation.
EXAMPLE 27
The procedure of Example 1 is repeated except for the difference that a functionally equivalent amount of a self-crosslinking copolymer is substituted for the epoxy-functional copolymer and the azelaic acid.
The self-crosslinking copolymer used in this example is prepared from the following listed components in the manner hereinafter described.
______________________________________Reactants Grams______________________________________glycidyl methacrylate 30methacrylic acid 21methyl methacrylate 129butyl methacrylate 120______________________________________
The monomers above listed are mixed with 12 grams of an initiator, i.e., t-butylperoxypivate. Three hundred grams of benzene is charged into a one liter flask which is equipped with a dropping funnel. The flask is heated to 80°C. and a refluxing of the solvent is achieved. While maintaining the reaction temperature at 80°C., the monomer mixture is added in a dropwise fashion over a 2 hour period. After the addition is complete, the reaction is continued for another two hours. The contents of the flask are then cooled to room temperature. One hundred milliliters of the resultant solution are mixed with 0.3 grams of poly (2-ethylhexyl acrylate). The mixture is dispersed and then is dried in a vacuum over at 70°C. The powder coating obtained is ground to pass through a 200 mesh sieve.
The cured finish obtained from the aluminum pigmented powder of this example has good physical appearance and the aluminum flakes are distributed with good orientation and depth variation.
EXAMPLE 28
The procedure of Example 1 is repeated except for the difference that the poly (lauryl acrylate) is replaced with an equivalent amount of poly (butyl acrylate) - M n = 9000.
EXAMPLE 29
The procedure of Example 1 is repeated except for the difference that the poly (lauryl acrylate) is replaced with an equivalent amount of poly (isododecyl methacrylate).
EXAMPLE 30
The procedure of Example 1 is repeated except for the difference that the poly (lauryl acrylate) is replaced with an equivalent amount of polyethylene glycol perfluoro octonoate (M n =3400).
EXAMPLE 31
The procedure of Example 1 is repeated except for the difference that the principal film-forming material into which is mixed the encapsulated aluminum flakes is a thermoplastic powder coating material prepared from the following materials using the procedure hereinafter described.
______________________________________ Parts By Weight______________________________________poly (methyl methacrylate) 100 M.sub.n = 40,000poly (lauryl methacrylate) 2 M.sub.n = 120,000tetrabutylammonium bromide 0.05______________________________________
The above ingredients are mixed in a twin shell tumbling mixer for 10 minutes and then mill rolled at 190°C. for 15 minutes. The blend is cooled and pulverized to pass through a 200 mesh screen.
The above materials in the amount of 188 parts by weight are mixed with the yellow iron oxide pigment (8.26 parts by weight), phthalo green pigment (1.75 parts by weight) and 1.34 parts by weight of poly (lauryl acrylate).
A homogeneous mixture of the above is obtained by ball milling for 2 hours. This mixture is extended at 100°C. from a kneading extruder. The solid thus obtained is pulverized in an impact mill, i.e., an air classified impact mill, and sieved through a 200 mesh screen.
The aluminum pigmented finished coating thus prepared from these materials exhibits good aluminum particle orientation and depth variation.
EXAMPLE 32
The procedure of Example 1 is repeated with the single difference that the coated aluminum flakes are mixed with the principal film-forming powder in an amount such that they comprise 0.1 weight percent of the total powder paint composition.
EXAMPLE 33
The procedure of Example 1 is repeated with the principal film-forming powder in an amount such that they comprise 32.50 weight percent of the total powder paint composition.
EXAMPLE 34
The procedure of Example 1 is repeated with the single difference that the coated aluminum flakes are mixed with the principal film-forming powder in an amount such that they comprise 0.25 weight percent of the total powder paint composition.
EXAMPLE 35
The procedure of Example 1 is repeated with the single difference that the coated aluminum flakes are mixed with the principal film-forming powder in an amount such that they comprise 28.75 weight percent of the total powder paint composition.
EXAMPLE 36
The procedure of Example 1 is repeated with the single difference that the coated aluminum flakes are mixed with the principal film-forming powder in an amount such that they comprise 0.45 weight percent of the total powder paint composition.
EXAMPLE 37
The procedure of Example 1 is repeated with the differences that the coated aluminum flakes are the sole metal-pigment used and they constitute 10 weight percent of the total powder paint composition. In this example, non-metal pigments are not used.
EXAMPLE 38
The procedure of Example 1 is repeated with the differences that the coated aluminum flakes are the sole metal-pigment used and they constitute 1 weight percent of the total powder paint composition. In this example, the non-metal pigments constitute 21.9 weight percent of the total powder paint composition.
EXAMPLE 39
The procedure of Example 1 is repeated with the following compositional differences. The coated aluminum flakes are mixed with the principal film-forming powder in an amount such that they comprise 31.0 weight percent of the total powder paint composition and the principal film-forming powder contains, as the sole nonmetal pigment, phthalo green pigment in an amount such that it comprises 0.25 weight percent of the total powder paint composition.
EXAMPLE 40
The procedure of Example 1 is repeated with the following compositional differences. The coated aluminum flakes are mixed with the principal film-forming powder in an amount such that they comprise 4.0 weight percent of the total powder paint composition and the principal film-forming powder contains a mixture of metal-free pigments in an amount such that it comprises 22 weight percent of the total powder paint composition. The mixture of metal-free pigments consists predominantly of chrome yellow with flaventhron (yellow organic), red iron oxide and carbon black present from trace amounts to above one weight percent.
EXAMPLE 41
The procedure of Example 1 is repeated with the following compositional difference: The coated aluminum flakes are mixed with the principal film-forming powder in an amount such that they comprise 0.5 weight percent of the total powder paint composition.
EXAMPLE 42
A series of powder paints, A-E are prepared from the following materials in the manner hereinafter set forth and later electrostatically sprayed as in Example 1 for test purposes.
STEP I
The materials listed below are thoroughly mixed.
__________________________________________________________________________ A B C D E Parts By Weight__________________________________________________________________________1. aluminum paste (65% metal) 30.00 30.00 30.00 30.00 30.002. thermosettable mixture 9.75 13.65 19.5 29.25 39.00 (a) resin* 8.58 12.01 17.16 25.74 34.32 (b) polyazelaic anhydride 1.17 1.64 2.34 3.51 4.68 % based on weight of aluminum 50.00 70.00 100.00 150.00 200.003. poly(lauryl acrylate) 0.06 0.08 0.12 0.18 0.234. tetrabutylammonium 0.45 0.63 0.9 1.125 1.8 bromide5. methylene chloride 250.00 250.00 250.00 250.00 250.00__________________________________________________________________________ *epoxy--functional copolymer of Example 1.
STEP II
This mixture is then spray dried as in the preceding examples and a product comprising aluminum flakes encapsulated in a thermosettable mixture of resin and crosslinking agent is obtained wherein the relative weights of the components are as follows:
A B C D E Parts by Weight__________________________________________________________________________1. aluminum flakes 19.5 19.5 19.5 19.5 19.52. thermosettable mixture 9.75 13.65 19.50 29.25 39.003. poly (laurylacrylate) 0.06 0.08 0.12 0.18 0.234. tetrabutylammonium bromide 0.45 0.63 0.9 1.125 1.8__________________________________________________________________________
STEP III
These encapsulated aluminum flakes are sieved through a 44 micron screen. All particles left on the screen are rejected.
STEP IV
A non-metallic powder mixture is made up by thoroughly mixing the below listed materials after which the mixture is pulverized and sieved through a 75 micron screen. All particles left on the screen are rejected.
__________________________________________________________________________ A B C D E Parts by Weight__________________________________________________________________________1. resin* 166 166 166 166 1662. azelaic acid 22.64 22.64 22.64 22.64 22.643. poly(laurylacrylate) 1.34 1.34 1.34 1.34 1.344. Pigments (a) thalo green 2.03 2.03 2.04 2.06 2.08 (b) yellow iron oxide 8.04 8.07 8.11 8.18 8.25__________________________________________________________________________ *epoxy--functional copolymer of Example 1
STEP V
An evenly mixed blend is formed from the encapsulated aluminum flakes of Step III and the nonmetallic powder mixture of Step IV in the following relative proportions:
A B C D E Parts by Weight__________________________________________________________________________1. encapsulated aluminum 2.255 2.256 3.009 3.764 4.518 flakes2. nonmetallic powder 97.745 97.444 96.991 96.236 95.482__________________________________________________________________________
The relative concentrations of ingredients in each of these blends are essentially the same.
The powders thus obtained are sprayed on electrically grounded substrates and baked as in Example 1. Aluminum pigment spacing and orientation is best when the resin encapsulation on the aluminum flakes is in the range of 50 to 70 weight percent of the aluminum with the very best achieved with paint A (50 weight percent encapsulation based on the weight of aluminum flakes).
EXAMPLE 43
Aluminum flakes are encapsulated as in Example 1 except for the differences that solvents other than methylene chloride, i.e., toluene, xylene, acetone, hexane and methyl ethyl ketone, are used to disperse the film-forming material and aluminum flakes prior to spray drying. The spray drying operation is adjusted in conformance with the relative volalities of the solvent used in each test. The encapsulated flakes thus prepared are incorporated into the powder paint of Example 1, electrostatically sprayed upon substrates and the substrates are baked as in Example 1.
Hydrocarbons, alcohols, and ketones boiling in the range of 50°C. to 152°C., preferably 50°C. to 90°C., can be used for this purpose. The amount of solvent used is in excess of the combined weights of the aluminum flakes and the film-former used for encapsulation. Advantageously, the amount of solvent used is in the range of about 3 to 100 times the combined weights of film-former and aluminum flakes.
Apparatus and methods for electrostatically spraying powder coating materials are illustrated and described in U.S. Pat. Nos. 3,536,514; 3,593,678; and 3,598,629.
The term "copolymer" is used herein to mean a polymer formed from two or more different monomers.
Many modifications of the foregoing examples will be apparent to those skilled in the art in view of this specification. It is intended that all such modifications which fall within the scope of this invention be included within the appended claims.
The disclosures of U.S. Pat. application Ser. No. 442,291 filed Feb. 12, 1974 by Santokh S. Labana et al and entitled "Powder Coating Compositions Including Glycidyl Ester-Modified Copolymer" are incorporated herein by reference.
Any and all disclosures appearing in the claims and not specifically appearing in the body of this specification are herewith incorporated in the body of this specification. | Improved powder paint compositions providing greater depth variation of metal pigment particles comprise (1) aluminum flakes individually encapsulated in a thin, continuous, thermosettable, organic film-former containing an ammonium salt selected from tetraalkyl ammonium halides and substituted tetraalkylammonium halides wherein at least one alkyl radical is replaced with an aryl, phenoxy or alkoxy radical and (2) a particulate, organic film-former. The encapsulated aluminum flakes are prepared by intimately dispersing the aluminum flakes in a solution of the thermosettable, organic film-former and the ammonium salt in a volatile solvent and spray drying the resultant dispersion. In the preferred embodiment, the particulate, organic film-former is also a thermosettable material and, in the most preferred embodiment, it is also crosslinkable with the thermosettable coating on the aluminum flakes. | 2 |
FIELD OF THE INVENTION
[0001] The present invention relates generally to a harness for attachment to a catheter bag to maintain the catheter bag in a stable and more comfortable position.
BACKGROUND OF THE INVENTION
[0002] When using a catheter, a collection bag for the urine is often placed along the leg of the patient. Numerous different types of devices have been developed to hold the urine or catheter bag. In most cases if the patient is mobile and active (walking) over time the bag has a tendency to slip down the leg putting stress on the catheter hose that is connected to the patient's bladder.
[0003] In addition when sleeping, if the patient is tossing and turning or moving around in their sleep, strain is again placed on the catheter hose. The bag often begins to rotate on the leg and ends up either around to the other side of the leg or works its way down the leg again, putting pressure on the catheter hose.
[0004] Another problem with many known catheter bags is the catheter bag will have a tendency to bunch up and when this happens it creates an area of chafing and discomfort for the wearer. The bag is long and in cases the bag is positioned close to the knee joint and as the bag slips slightly when sitting or moving around the edges of the bag catch the area where the knee bends, giving the wearer another chafing area.
[0005] There is a need for a better system of holding the catheter or urine bag on the leg of the patient so that it does not slip down the leg. There is also a need for improvements I the design of the catheter bags to provide better comfort to the patient.
SUMMARY OF THE INVENTION
[0006] One embodiment of the present invention provides a harness for holding a catheter or urine bag against a patient's leg, the harness comprising a lower leg strap portion, an upper leg strap portion and a shoulder strap portion.
[0007] The lower leg strap portion is sized and shaped to feed through a pair of slots near a bottom edge of a catheter bag and go around a patient's leg.
[0008] The upper leg strap portion is sized and shaped to feed through a pair of slots near a top edge of a catheter bag and go around a patient's leg.
[0009] The shoulder strap portion is sized and shaped to have one end connect to one side of upper leg strap portion go over the patient's shoulder and the other end connect to another side of upper leg strap portion.
[0010] The shoulder strap portion has an means to adjust the length of the shoulder strap portion when in use to adjust the vertical positioning of the catheter bag on the patient's leg.
[0011] In another embodiment the present invention provides an improved catheter bag comprising a bag portion a top tab portion and a bottom tab portion with a one way entry valve extending through said top tab portion to permit fluid to enter the bag portion, a draining valve in the bottom tab portion operable from an open to a closed position. The catheter bag is provided with a first pair of parallel vertical slots sized and shaped to retain an upper leg strap located below a top edge of the catheter bag within the top tab portion with one of said first pair of slots is located on one side of the one way entry valve and the other of said first pair of slots located on the other side of the one way entry valve and spaced apart but close enough to avoid bunching of the top tab portion when in use. A second pair of parallel vertical slots, sized and shaped to retain a lower leg strap, are located above a bottom edge within the bottom tab portion and with one of said second pair of slots located on one side of the draining valve and the other of said second pair of slots located on the other side of the draining valve and spaced apart but close enough to avoid bunching of bottom tab portion when in use.
[0012] The draining valve is preferably a push-pull valve.
[0013] Two “O” rings may be placed on a stem of the one way entry valve to which a catheter hose is connected to reduce the risk of the hose disengaging from the entry valve.
[0014] The corners of the upper and lower tab portions may be rounded.
[0015] Further features of the invention will be described or will become apparent in the course of the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] In drawings which illustrate by way of example only one embodiment of the invention:
[0017] FIG. 1 illustrates one embodiment of an improved design for a catheter bag in accordance with the present invention.
[0018] FIG. 2 illustrates the catheter bag of FIG. 1 in combination with one embodiment of a harness (schematically shown) in accordance with the present invention for maintaining the catheter bag in position.
[0019] FIG. 3 shows a front view of the catheter bag and harness of FIG. 2 as worn by an individual.
[0020] FIG. 4 shows the back view of the individual shown in FIG. 3 wearing the catheter bag and harness of FIG. 2 .
[0021] Similar references are used in different figures to denote similar components.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] Referring now to the figures in detail FIG. 1 illustrates one embodiment of an improved design of a catheter or urine bag, generally indicated at 1 , in accordance with the present invention.
[0023] Known catheter or urine bags have a draining valve at the bottom of the bag. For security reasons the valve may be a twist valve that requires two hands to twist open. This may pose problems for some patients who are disabled or only have one arm or hand or suffer from arthritis. The prior art valves if not fully closed may open up at some of the most inconvenient times. Accordingly in the embodiment illustrated the draining valve 7 B shown in FIG. 1 is a push-pull valve 7 C. Push to close and pull to open. Instead of a turning motion that requires two hands the valve 7 B is a push pull valve. This valve can be used easily by all, as you need only one hand to open the valve and to close the valve and all you have to do is bend the valve away from the leg and push it closed, making it easier to close. The valve cannot be opened by a twisting motion by the patient while he or she is moving.
[0024] Conventional catheter bag designs feature an entry valve at the top of the bag to which a hose from the patient's bladder is attached. As the patient moves around the strain on the hose may cause it to detach from the catheter bag. In the design according to the present invention illustrated in FIG. 1 , where the hose 4 meets the catheter bag 1 , two “O” rings 5 have been placed on the stem 6 of one way entry valve 7 to reduce the risk of the hose 4 from disengaging from the valve 7 on catheter bag 1 .
[0025] The corners of known catheter or urine bags are typically square and thereby can be a little sharp creating chafing and discomfort. In the design of the catheter bag 1 shown in FIG. 1 the upper 2 and lower 3 corners of the bag 1 have been rounded to help avoid problems encountered with known designs. In addition the design of the catheter bag 1 shown in FIG. 1 is shorter than known bags so that the bag doesn't interfere with the knee joint and the risk of chafing is reduced. The bag 1 shown in FIG. 1 is also wider than known bags, to give the bag 1 a similar volume of liquid that can be retained. In the embodiment illustrated intended for use with adult patients bag 1 is about 20 cm long and about 14 cm wide when empty of fluid. The presented invention is not restricted to bags having these dimensions and bags having different sizes can be provided according to the present invention.
[0026] In order to work with the embodiment of the harness shown in FIG. 2 , catheter bag 1 is provided with a pair of parallel vertical slots 8 , 9 sized and shaped to retain an upper leg strap of the harness according to the present invention shown in FIG. 2 . Slots 8 , 9 are located below the top edge 10 of bag 1 . The top edge 10 is preferably part of a top tab portion 11 of bag 1 that is not designed to retain any fluid. In the embodiment illustrated one of said slots 8 is located on one side of one way entry valve 7 and the other of said slots 9 is located on the other side of valve 7 . The slots 8 , 9 are spaced apart but close enough to avoid bunching of tab portion 11 when in use.
[0027] In the embodiment illustrated in FIG. 1 , catheter bag 1 is further provided with a pair of parallel vertical slots 12 , 13 sized and shaped to retain a lower leg strap of the harness according to the present invention shown in FIG. 2 . Slots 12 , 13 are located above the bottom edge 14 of bag 1 . The bottom edge 14 is preferably part of a bottom tab portion 15 of bag 1 that is not designed to retain any fluid. In the embodiment illustrated one of said slots 12 is located on one side of draining valve 7 B and the other of said slots 13 is located on the other side of valve 7 B. The slots 12 , 13 are spaced apart but close enough to avoid bunching of tab portion 15 when in use.
[0028] Referring to FIGS. 2 to 4 , one embodiment of a harness according to the present invention, generally indicated at 16 , is schematically illustrated in combination with catheter bag 1 . Harness 16 comprises a lower leg strap portion 17 , an upper leg strap portion 18 and a shoulder strap portion 19 .
[0029] Lower leg strap portion 17 is sized and shaped to feed through slots 12 , 13 near the bottom edge 14 of catheter bag 1 and go around the patient's leg. Lower leg strap portion 17 can be made from an elastic material to adapt to different leg sizes or can be provided with a connection at each end to permit the length of the strap 17 when in use to be adjusted.
[0030] Upper leg strap portion 18 is sized and shaped to feed through slots 8 , 9 near the bottom edge 10 of catheter bag and go around the patient's leg. Upper leg strap portion 18 can be made from an elastic material to adapt to different leg sizes or can be provided with a connection at each end to permit the length of the strap 18 when in use to be adjusted.
[0031] When the straps 17 , 18 are attached the straps 17 , 18 go under the bag 1 to the slots 12 , 13 or 8 , 9 up into the slots 12 or 8 over the valves 7 or 7 B and down through the other slot 13 or 9 respectively for the lower leg strap portion 17 and upper leg strap portion 18 . This improvement makes the bag 1 sit firmly against the patient's leg. Bunching of the bag 1 is greatly reduced or eliminated. The bag valves 7 and 7 B sit flat on the patient's leg
[0032] Shoulder strap portion 19 is sized and shaped to have one end 20 connect to one side 21 of upper leg strap portion 18 and the other end 22 connect to the other side 23 of upper leg strap portion 18 . The upper leg strap portion 18 encircles the leg front and back. Without the harness, even if the patient over tightens the straps 17 , 18 the bag 1 still has a tendency to move down the leg. The straps 17 , 18 also pinch the leg.
[0033] Shoulder strap portion 19 is intended to go over the shoulder of the patient, left or right (for catheter bag placed against left leg the shoulder strap 19 goes over the right shoulder and vice versa). In the embodiment illustrated the shoulder strap 19 is about 3 cm wide and the thickness is ¼ mm clear pliable plastic which is 1.8 m to 2 m in length.
[0034] The shoulder strap portion 19 has an area 24 at the one end 20 that is made to go over the shoulder and down the back of the patient and then attached to the rear side 21 upper leg strap 18 . The area 24 , about 6″ long in the embodiment illustrated has a sticky surface. The patient peels off the protective cover (not shown) over area 24 and takes the sticky area which goes under the strap 18 and folds it over the strap 18 to the required line on the shoulder strap portion 19 .
[0035] The other end 22 of shoulder strap portion 19 is intended to go over the patient's shoulder, down the chest and then attached to the front side 23 upper leg strap 18 . The other end 22 has an area 25 that is also sticky with a pressure sensitive release backing paper. The patient peels off the protective cover (not shown) over area 25 and takes the sticky area which goes under the strap 18 and folds it over the strap 18 to position the bag 1 at the most comfortable position on the leg. The patient leaves a little slack in shoulder strap 19 for movement while the patient is moving. This makes it comfortable for the wearer.
[0036] This new and improved catheter bag and harness reduces the strain on the catheter hose, reduces the risk of the catheter bag slipping down the leg and reducing the risk of chafing. The patient is able to run, jog, walk, do chores and even ride a bicycle. Life improves immensely with the harness of the present invention by holding the catheter bag in place with no or very little movement of the bag.
[0037] It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended to limit the broader aspects of the present invention.
[0038] Although various preferred embodiments of the present invention have been described herein in detail, it will be appreciated by those skilled in the art, that variations may be made thereto without departing from the spirit of the invention or the scope of the appended claims. | The disclosure includes embodiments of an improved catheter bag comprising a bag portion, a top tab portion and a bottom tab portion with a one way entry valve extending through said top tab portion to permit fluid to enter the bag portion. A draining valve is provided in the bottom tab portion operable from an open to a closed position. The catheter bag is provided with pairs of parallel vertical slots sized and shaped to retain straps for retaining the bag against the body. | 0 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention relates generally to devices that are retained inside a body passage and in one particular application to vascular devices used in repairing arterial dilations, e.g., aneurysms. More particularly, the invention is directed toward devices that can be adjusted during deployment, thereby allowing at least one of a longitudinal or radial re-positioning of the device prior to final placement of the device.
[0003] 2. Discussion of the Related Art
[0004] The invention will be discussed generally with respect to deployment of a bifurcated stent graft into the abdominal aorta but is not so limited and may apply to device deployment into other body lumens. When delivering a stent graft by intraluminal or endovascular methods, it is important to know the precise location of the device in the vasculature. Controlling this precise location is particularly important when the device is intended to be deployed in close proximity to branch vessels or adjacent to weakened portions of the aortic wall. Typical stent grafts used to repair an aortic aneurysm incorporate a proximal (i.e. portion of the stent graft closest to the heart) anchoring system intended to limit longitudinal displacement of the stent graft. Often this anchoring system must be precisely placed to avoid occlusion of a branch vessel or to avoid placement within a compromised and damaged portion of the aortic wall.
[0005] An improved delivery system for such stent grafts would include a means for allowing precise longitudinal and rotational placement of the stent graft and anchoring system. The precise position of the stent graft and anchoring system would be adjusted and visualized prior to full deployment of the device. Ideally the delivery system would allow the device to be repositioned if the prior deployment position was undesirable.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] The accompanying drawings are included to provide a further understanding of the invention and illustrate certain aspects of the invention.
[0007] In the drawings:
[0008] FIG. 1A is a medical apparatus according to an embodiment of the invention.
[0009] FIG. 1B is an enlarged simplified view of the medical apparatus according to an embodiment of the invention.
[0010] FIG. 1C is a medical apparatus according to an embodiment of the invention.
[0011] FIG. 1D is an enlarged simplified view of the medical apparatus according to a second embodiment of the invention.
[0012] FIG. 2A is a medical apparatus according to an embodiment of the invention.
[0013] FIG. 2B is an enlarged simplified view of a medical apparatus according to an embodiment of the invention.
[0014] FIG. 2C is a medical apparatus according to an embodiment of the invention.
[0015] FIG. 2D is an enlarged simplified view of a medical apparatus according to an embodiment of the invention.
[0016] FIG. 3A is a medical apparatus according to an embodiment of the invention.
[0017] FIG. 3B is an enlarged simplified view of a medical apparatus according to an embodiment of the invention.
[0018] FIG. 3C is an enlarged simplified view of a medical apparatus according to an embodiment of the invention.
[0019] FIG. 4A is a medical apparatus according to an embodiment of the invention.
[0020] FIG. 4B is an enlarged simplified view of a medical apparatus according to an embodiment of the invention.
[0021] FIG. 5A is a medical apparatus according to an embodiment of the invention.
[0022] FIG. 5B is an enlarged simplified view of a medical apparatus according to an embodiment of the invention.
[0023] FIG. 6A is a medical apparatus according to an embodiment of the invention.
[0024] FIG. 6B is an enlarged simplified view of a medical apparatus according to an embodiment of the invention.
[0025] FIG. 7A is a medical apparatus according to an embodiment of the invention.
[0026] FIG. 7B is an enlarged simplified view of a medical apparatus according to an embodiment of the invention.
[0027] FIGS. 8A-8C is a medical apparatus according to an embodiment of the invention.
[0028] FIG. 9A is an apparatus according to an embodiment of the invention.
[0029] FIG. 9B is a cross-sectional view of FIG. 9A along line A to A′.
[0030] FIGS. 10A-10H illustrates a deployment procedure of an apparatus according to FIGS. 2A-2B .
DETAILED DESCRIPTION
[0031] The invention relates generally to a novel medical apparatus that includes a device capable of being retained inside a body passage and in one particular application to vascular devices. More particularly, the invention is directed toward devices that can be adjusted during deployment, thereby allowing at least one of a longitudinal or radial re-positioning of the device.
[0032] In an embodiment of the invention, the medical apparatus includes a catheter assembly having a proximal end portion and distal end portion. A hub can optionally be arranged on the distal end portion of the catheter assembly. A stent is arranged on the proximal end portion of the catheter. The stent has an inner surface and an outer surface. The stent can be any suitable configuration. In one embodiment, the stent is configured from multiple turns of an undulating element. A graft member can be arranged about at least a portion of the stent. The stent may be self-expandable, balloon-expandable or a combination of self-expandable and balloon-expandable.
[0033] A tube extends from the proximal end portion to the distal end portion of the catheter. A first movable element, having a first and second end, is arranged around the outer surface of the stent. The first and second end of the first movable element are capable of extending out the distal end portion of the tube and the first movable element is capable of radially compressing at least a portion of the stent.
[0034] Optionally, a second movable element can be in communication with the first movable element, wherein the second movable element is arranged around the outer surface of stent and the first movable element is looped over the second movable element. A sheath material can cover at least a portion of the stent, wherein the sheath material is capable of holding the stent at a first diameter. A filament can surround the stent and a pin can extend from the tube and is capable of holding the filament surrounding the stent at a second diameter which is greater than the first diameter. The pin extending from the tube is capable of releasing the filament surrounding the stent to a third diameter which is greater than the second diameter.
[0035] In some embodiments, the stents can be used to at least fix the medical apparatus inside a portion of patient's anatomy. The stent can be constructed from materials that are flexible and strong. The stent can be formed from, for example, degradable bioabsorable materials, biodigestible materials, polymeric materials, metallic materials and combinations thereof. In addition, these materials may be reinforced and/or coated with other materials, such as polymeric materials and the like. The coating may be chosen to reduce acidic or basic effects of the gastrointestinal tract, e.g., with a thermoplastic coating such as ePTFE and the like.
[0036] The stents can be fabricated using any suitable methods and materials. For example, stents can be fabricated according to the teachings as generally disclosed in U.S. Pat. No. 6,042,605 issued to Martin, et al., U.S. Pat. No. 6,361,637 issued to Martin, et al. and U.S. Pat. No. 6,520,986 issued to Martin, et al. For example, stents can have various configurations as known in the art and can be fabricated, for example, from cut tubes, wound wires (or ribbons), flat patterned sheets rolled into a tubular form, combinations thereof, and the like. Stents can be formed from metallic, polymeric or natural materials and can comprise conventional medical grade materials such as nylon, polyacrylamide, polycarbonate, polyethylene, polyformaldehyde, polymethylmethacrylate, polypropylene, polytetrafluoroethylene, polytrifluorochlorethylene, polyvinylchloride, polyurethane, elastomeric organosilicone polymers; metals such as stainless steels, cobalt-chromium alloys and nitinol and biologically derived materials such as bovine arteries/veins, pericardium and collagen. Stents can also comprise bioresorbable materials such as poly(amino acids), poly(anhydrides), poly(caprolactones), poly(lactic/glycolic acid) polymers, poly(hydroxybutyrates) and poly(orthoesters).
[0037] The stents can be formed into a variety of different geometric configurations having constant and/or varied thickness as known in the art. The geometric configurations may include many conventional stent configurations such as a helically wrapped stent, z-shape stent, tapered stent, coil stent, combinations thereof, and the like. The stents can be formed in a variety of patterns, such as, a helix pattern, ring pattern, combinations thereof, and the like.
[0038] Grafts can have various configurations as known in the art and can be fabricated, for example, from tubes, sheets or films formed into tubular shapes, woven or knitted fibers or ribbons or combinations thereof. Graft materials can include, for example, conventional medical grade materials such as nylon, polyester, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylchloride, polyurethane and elastomeric organosilicone polymers.
[0039] Stents can be used alone or in combination with graft materials. Stents can be configured on the external or internal surface of a graft or may be incorporated into the internal wall structure of a graft. Stent or stent grafts can be delivered endoluminally by various catheter based procedures known in the art. For example self-expanding endoluminal devices can be compressed and maintained in a constrained state by an external sheath. The sheath can be folded to form a tube positioned external to the compressed device. The sheath edges can be sewn together with a deployment cord that forms a “chain stitch”. To release and deploy the constrained device, one end of the deployment cord can be pulled to disrupt the chain stitch, allowing the sheath edges to separate and release the constrained device. Constraining sheaths and deployment cord stitching can be configured to release a self-expanding device in several ways. For example a constraining sheath may release a device starting from the proximal device end, terminating at the distal device end. In other configurations the device may be released starting from the distal end. Self expanding devices may also be released from the device center as the sheath disrupts toward the device distal and proximal ends.
[0040] Details relating to constraining sheath materials, sheath methods of manufacture and stent graft compression techniques can be found in, for example, U.S. Pat. No. 6,352,561 issued to Leopold, et al., and U.S. Pat. No. 6,551,350 issued to Thornton, et al.
[0041] The catheter and hub assemblies can comprise conventional medical grade materials such as nylon, polyacrylamide, polycarbonate, polyethylene, polyformaldehyde, polymethylmethacrylate, polypropylene, polytetrafluoroethylene, polytrifluorochlorethylene, polyether block amide or thermoplastic copolyether, polyvinylchloride, polyurethane, elastomeric organosilicone polymers, and metals such as stainless steels and nitinol.
[0042] Turning to the figures, FIG. 1A is a medical apparatus according to an embodiment of the invention. FIG. 1B is an enlarged simplified view of a portion of the medical apparatus shown in FIG. 1A .
[0043] Referring to FIGS. 1A and 1B , the medical apparatus is generally depicted as reference numeral 100 A. The medical apparatus 100 A includes catheter assembly 102 , stent 104 arranged on the proximal end portion of the catheter assembly 102 . The stent 104 has an inner surface, an outer surface, and in this embodiment is configured from multiple turns of an undulating element 105 . The undulating element 105 can be configured, for example, in a ring or helical pattern.
[0044] The stent 104 has a proximal end portion 106 and distal end portion 108 . The distal end portion 108 is formed into a branch having a first leg 110 and a second leg 112 .
[0045] A graft member 114 is arranged about the stent 104 .
[0046] The stent 104 and graft member 114 are constrained into a compacted delivery state by a first sheath 116 and second sheath 118 . As shown in FIG. 1A , the first sheath 116 has been released, allowing at least a portion of the stent 104 to expand as shown. The second sheath 118 is coupling the second leg 112 to the catheter assembly 102 as shown.
[0047] A tube 120 extends from a proximal end portion to a distal end portion of the catheter assembly 102 . In the figure, the tube 120 is positioned adjacent the outer surface of the stent 104 and graft 114 . The tube 120 is attached to the catheter assembly 102 and not attached to the stent 104 or graft 114 . A movable element 122 (e.g., a fiber cord, string, wire, etc.) having a first end 124 and second end 126 surrounds the stent 104 and graft member 114 . The first end 124 and second end 126 of the movable element 122 extend out a distal end portion of the tube 120 . For example, the movable element 122 is threaded through the tube from a distal end to a proximal end and is looped around the proximal end portion 106 of the stent 104 and graft member 114 . As shown in FIG. 1B , by pulling the first end 124 and the second end 126 in a distal direction the movable element 122 is capable of radially compressing at least a portion of the stent 104 as indicated by arrows 128 .
[0048] FIG. 10 is a medical apparatus according to an embodiment of the invention. FIG. 1D is an enlarged simplified view of a portion of the medical apparatus shown as FIG. 10 .
[0049] Referring to FIGS. 10 and 1D , the medical apparatus is generally depicted as reference numeral 100 B. The medical apparatus of FIGS. 10 and 1D is similar to the medical apparatus as shown in FIGS. 1A and 1B . The medical apparatus includes catheter assembly 102 , stent 104 arranged on the proximal end portion of catheter assembly 102 . Stent 104 has an inner surface, an outer surface, and is configured from multiple turns of an undulating element 105 . The undulating element 105 may be configured, for example, in a ring or helical pattern.
[0050] The stent 104 has a proximal end portion 106 and distal end portion 108 . The distal end portion 108 is formed into a branch having a first leg 110 and a second leg 112 .
[0051] A graft member 114 is arranged about the stent 104 .
[0052] The stent 104 and graft member 114 are constrained into a compacted delivery state by a first sheath 116 and second sheath 118 . As shown in FIG. 10 , the first sheath 116 has been released allowing at least a portion of the stent to expand as shown. The second sheath 118 is coupling the second leg 112 to the catheter assembly 102 as shown.
[0053] A tube 120 extends from a proximal end portion to a distal end portion of the catheter assembly 102 . The tube 120 is positioned adjacent the outer surface of the stent 104 and graft 114 . The tube 120 is attached to the catheter assembly 102 and not attached to the stent 104 or graft 114 . A movable element 122 A having a first end 124 and second end 126 surrounds the stent 104 and graft member 114 . The first end 124 and second end 126 of the movable element 122 A extend out a distal end portion of the tube 120 . For example, the movable element 122 A is threaded through the tube from a distal end to a proximal end and is looped around the proximal end portion 106 of the stent 104 and graft member 114 .
[0054] Moreover, an additional movable element 122 B having first end 132 and second end 134 surrounds the stent 104 and graft member 114 . The first end 132 and second end 134 of the additional movable element 122 B extend out a distal end portion of the tube 120 . The additional movable element 122 B is threaded through the tube from a distal end to an intermediate opening 136 in the tube 120 and is looped around an intermediate portion of the stent 104 and graft member 114 . As shown in FIG. 1D , by pulling the ends of the moveable elements in a distal direction the movable element 122 A and the additional movable element 122 B are capable of radially compressing at least a portion of the stent 104 as indicated by arrows 128 . It should be understood that additional moveable elements can be provided.
[0055] FIG. 2A is a medical apparatus according to an embodiment of the invention, shown in a partially deployed state. FIG. 2B is an enlarged simplified view of a portion of the medical apparatus shown in FIG. 2A .
[0056] Referring to FIGS. 2A and 2B , the medical apparatus is generally depicted by reference numeral 200 A. The medical apparatus 200 A includes a catheter assembly 202 , and stent 204 arranged on the proximal end portion of the catheter assembly 202 . The stent 204 has an inner surface, an outer surface, and is configured from multiple turns of an undulating element 205 . The undulating element 205 can be configured, for example, in a ring or helical pattern.
[0057] The stent 204 has a proximal end portion 206 and distal end portion 208 . The distal end portion 208 is formed into a branch having a first leg 210 and a second leg 212 .
[0058] A graft member 214 is arranged about the stent 204 .
[0059] The stent 204 and graft member 214 are constrained into a compacted delivery state by a first sheath 216 and second sheath 218 . As shown in FIG. 2A , the first sheath 216 has been released allowing at least a portion of the stent to expand. The second sheath 218 is coupling the second leg 212 to the catheter assembly 202 as shown.
[0060] A tube 220 extends from a proximal end portion to a distal end portion of the catheter assembly 202 . In this embodiment, the tube 220 is positioned adjacent the outer surface of the stent 204 and graft 214 . In this embodiment, the tube 220 is attached to the catheter assembly 202 and not attached to the stent 204 or graft 214 .
[0061] A second movable element 236 is in communication with a first movable element 222 . The second movable element 236 surrounds the stent 204 and the first movable element 222 is looped through the second movable element 236 .
[0062] The first end 224 and second end 226 of the first movable element 222 extend out a distal end portion of the tube 220 . For example, the first movable element 222 is threaded through the tube from a distal end to a proximal end and is looped through the second movable element 236 .
[0063] As shown in FIG. 2B , when the two ends 224 and 226 of the first movable element are pulled in a distal direction, the movable element 222 pulls on the second movable element 236 , radially compressing at least a portion of the stent 204 as indicated by arrows 228 .
[0064] FIG. 2C is a medical apparatus according to an embodiment of the invention. FIG. 2D is an enlarged simplified view of a portion of the medical apparatus shown in FIG. 2C .
[0065] Referring to FIGS. 2C and 2D , the medical apparatus is generally depicted by reference numeral 200 B. The medical apparatus of FIGS. 2C and 2D is similar to the medical apparatus as shown in FIGS. 2A and 2B .
[0066] Shown in FIGS. 2C and 2D , a second movable element 236 A is in communication with a first movable element 222 A. The second movable element 236 A surrounds the stent 204 and the first movable element 222 A is looped through the second movable element 236 A.
[0067] An additional first movable element 222 B along with an additional second movable element 236 B are incorporated into the medical apparatus 200 B.
[0068] As shown in FIG. 2D , when tension is applied to the two ends 224 and 226 of the first movable element 222 A, the first movable element 222 A pulls on the second movable element 236 A, radially compressing at least a portion of the stent 204 as indicated by arrows 228 . Similarly, when tension is applied to the two ends 232 and 234 of the additional first movable element 222 B, the additional first movable element 222 B pulls on the additional second movable element 236 B, radially compressing at least a portion of the stent 204 as indicated by arrows 228 .
[0069] FIG. 3A is a medical apparatus according to an aspect of the invention. FIG. 3B is an enlarged simplified view of a portion of the medical apparatus shown in FIG. 3A .
[0070] Referring to FIGS. 3A and 3B , the medical apparatus is generally depicted by reference numeral 300 A. The medical apparatus 300 A includes a catheter assembly 302 , and stent 304 arranged on the proximal end portion of the catheter assembly 302 . The stent 304 has an inner surface, an outer surface, and is configured from multiple turns of an undulating element 305 . The undulating element 305 may be configured in a ring or helical pattern.
[0071] The stent 304 has a proximal end portion 306 and distal end portion 308 . The distal end portion 308 is formed into a branch having a first leg 310 and a second leg 312 .
[0072] A graft 314 is arranged about the stent 104 .
[0073] In one preferred embodiment, the stent 304 and graft 314 are constrained into a compacted delivery state by a first sheath 316 and second sheath 318 . As shown in FIG. 3A , the first sheath 316 has been released allowing at least a portion of the stent 304 to expand as shown. The second sheath 318 is coupling the second leg 312 to the catheter assembly 302 as shown.
[0074] A tube 320 extends from a proximal end portion to a distal end portion of the catheter assembly 302 . The tube 320 is positioned within and surrounded by the stent 304 . The tube 320 is attached to the catheter assembly 302 and not attached to the stent 304 or graft 314 . A movable element 322 having a first end 324 and second end 326 surrounds the stent 304 and graft 314 . The first end 324 and second end 326 of the movable element 322 extend out a distal end portion of the tube 320 . The movable element 322 is threaded through the tube from a distal end to a proximal end and is looped around the proximal end portion 306 of the stent 304 and graft 314 . A further embodiment for “surrounding” the stent with the moveable element includes threading the moveable element 322 through the graft 314 or through the stent 304 as shown in FIG. 3B . As shown in FIG. 3B , the movable element 322 is capable of radially compressing at least a portion of the stent 304 as indicated by arrows 328 when tension is applied to the movable element ends 324 and 326 . Additional movable elements may be added similar to those configurations described in FIGS. 1D and 2D .
[0075] FIG. 3C is an enlarged simplified view of a portion of a medical apparatus according to an embodiment of the invention. As shown in FIG. 3C , second movable element 336 is in communication with first movable element 322 . The second movable element 336 surrounds the stent member 304 and the first movable element 322 is looped through the second movable element 336 . The second movable element 336 may also be threaded through the graft 314 or threaded through the stent 304 as shown in FIG. 3C .
[0076] The first end 324 and second end 326 of the first movable element 322 extend out a distal end portion of the tube 320 . For example, the first movable element 322 is threaded through the tube from a distal end to a proximal end and is looped through the second movable element 336 .
[0077] As shown in FIG. 3C , when tension is applied to the two ends 324 and 326 of the first movable element 322 , the first movable element 322 pulls on the second movable element 336 , radially compressing at least a portion of the stent 304 as indicated by arrows 328 . Additional movable elements may be added similar to those configurations described in FIGS. 1D and 2D .
[0078] FIG. 4A is a medical apparatus according to an embodiment of the invention. FIG. 4B is an enlarged simplified view of a portion of the the medical apparatus shown in FIG. 4A .
[0079] Referring to FIGS. 4A and 4B , the medical apparatus is generally depicted by reference numeral 400 . The medical apparatus 400 includes a catheter assembly 402 , and stent 404 arranged on the proximal end portion of the catheter assembly 402 . The stent 404 has an inner surface, an outer surface, and is configured from multiple turns of an undulating element 405 . The undulating element 405 may be configured in a ring or helical pattern.
[0080] The stent 404 has a proximal end portion 406 and distal end portion 408 . The distal end portion 408 is formed into a branch having a first leg 410 and a second leg 412 .
[0081] A graft 414 is arranged about the stent 404 .
[0082] The stent 404 and graft 414 are constrained into a compacted delivery state by a first sheath 416 and second sheath 418 . As shown in FIG. 4A , the first sheath 416 has been released allowing at least a portion of the stent 404 to expand as shown. The second sheath 418 is coupling the second leg 412 to the catheter assembly 402 as shown.
[0083] A tube 420 extends from a proximal end portion to a distal end portion of the catheter assembly 402 . The tube 420 is positioned adjacent the outer surface of the stent 404 and graft 414 . The tube 420 is attached to the catheter assembly 402 and not attached to the stent 404 or graft 414 . A second movable element 436 is in communication with a first movable element 422 . The second movable element 436 surrounds the stent 404 . The second movable element 436 is looped through the first movable element 422 . A release pin 450 is threaded through the second movable element 436 , thereby releasably attaching the second movable element 436 to the first movable element 422 .
[0084] The first end 424 and second end 426 of the first movable element 422 extend out a distal end portion of the tube 420 along with the distal end of the release pin 450 .
[0085] As shown in FIG. 4B , when tension is applied to the two ends 424 and 426 of the first movable element 422 , the first movable element 422 pulls on the second movable element 436 , radially compressing at least a portion of the stent as previously shown, for example, in FIG. 2B .
[0086] The release pin 450 can be translated in a distal direction as shown by direction arrow 452 , thereby releasing the second movable element 436 from the first movable element 422 .
[0087] FIG. 5A is a medical apparatus according to an embodiment of the invention. FIG. 5B is an enlarged simplified view of a portion of the medical apparatus shown in FIG. 5A .
[0088] Referring to FIGS. 5A and 5B , the medical apparatus is generally depicted as reference numeral 500 . The medical apparatus 500 includes a catheter assembly 502 , and stent 504 arranged on the proximal end portion of the catheter assembly 502 . The stent 504 has an inner surface, an outer surface, and is configured from multiple turns of an undulating element 505 . The undulating element 505 may be configured in a ring or helical pattern.
[0089] The stent 504 has a proximal end portion 506 and distal end portion 508 . The distal end portion 508 is formed into a branch having a first leg 510 and a second leg 512 .
[0090] A graft 514 is arranged about the stent 504 .
[0091] In a preferred embodiment, the stent 504 and graft 514 are constrained into a compacted delivery state by a first sheath 516 and second sheath 518 . As shown in FIG. 5A , the first sheath 516 has been released allowing at least a portion of the stent 504 to expand as shown. The second sheath 518 is coupling the second leg 512 to the catheter assembly 502 as shown.
[0092] A tube 520 extends from a proximal end portion to a distal end portion of the catheter assembly 502 . The tube 520 is positioned adjacent the outer surface of the stent 504 and graft 514 . The tube 520 is attached to the catheter assembly 502 and not attached to the stent 504 or graft 514 .
[0093] A movable element 522 is threaded through the tube 520 and is circumferentially arranged around the stent 504 . The movable element 522 is looped over release pin 550 , thereby releasably attaching the movable element 522 to the release pin 550 .
[0094] As shown in FIG. 5B , when tension is applied to the two ends 524 and 526 of the movable element, the movable element 522 radially compresses at least a portion of the stent as previously shown, for example, in FIG. 2B . When desired, the release pin 550 can be translated in a distal direction as shown by direction arrow 552 , thereby releasing the movable element 522 from the release pin 550 allowing the movable element 522 to be withdrawn.
[0095] FIG. 6A is a medical apparatus according to an embodiment of the invention. FIG. 6B is an enlarged simplified view of a portion of the medical apparatus shown in FIG. 6A .
[0096] Referring to FIGS. 6A and 6B , the medical apparatus is generally depicted as reference numeral 600 . The medical apparatus 600 includes a catheter assembly 602 , and stent 604 arranged on the proximal end portion of the catheter assembly 602 . The stent 604 has an inner surface, an outer surface, and is configured from multiple turns of an undulating element 605 . The undulating element 605 may be configured in a ring or helical pattern.
[0097] The stent 604 has a proximal end portion 606 and distal end portion 608 . The distal end portion 608 is formed into a branch having a first leg 610 and a second leg 612 .
[0098] A graft 614 is arranged about the stent 604 . The stent 604 and graft 614 are constrained into a compacted delivery state (or first diameter) by a first sheath 616 and second sheath 618 . As shown in FIG. 6A , the first sheath 616 has been released allowing at least a portion of the stent 604 to expand as shown. The second sheath 618 is coupling the second leg 612 to the catheter assembly 602 as shown.
[0099] After the release of the first sheath 616 , the stent 604 is allowed to self expand into a second diameter that is greater than the initial compacted first diameter. The second diameter is defined by a secondary constraint 654 . The secondary constraint 654 can be comprised, for example, of a flexible filament that encircles a proximal end portion 606 of the stent and graft. The secondary constraint 654 prevents further self expansion of the stent.
[0100] As shown in FIG. 6B , the secondary constraint 654 is looped around the stent (not shown) and is threaded through a first end of the secondary constraint 654 . The second end of the secondary constraint 654 is looped onto a release pin 650 . Once the apparatus 600 is properly positioned within a vessel target site, the secondary constraint 654 can be released by translating the release pin 650 in a distal direction as shown by direction arrow 652 . By translating the release pin 650 , the stent is released from the secondary constraint and thereby allowed to further expand into a third diameter that is greater than the second and first diameters.
[0101] Optionally, a retrieval cord or filament 656 can be used to join the secondary constraint 654 to the release pin 650 . Therefore when the release pin is translated distally, the secondary constraint 654 is withdrawn along with the release pin 650 .
[0102] FIG. 7A is a medical apparatus according to an embodiment of the invention. FIG. 7B is an enlarged simplified view of a portion of the medical apparatus shown in FIG. 7A .
[0103] Referring to FIGS. 7A and 7B , the medical apparatus is generally depicted as reference numeral 700 . The medical apparatus 700 includes a catheter assembly 702 , and stent 704 arranged on the proximal end portion of the catheter assembly 702 . The stent 704 has an inner surface, an outer surface, and is configured from multiple turns of an undulating element 705 . The undulating element 705 may be configured in a ring or helical pattern.
[0104] The stent 704 has a proximal end portion 706 and distal end portion 708 . The distal end portion 708 is formed into a branch having a first leg 710 and a second leg 712 .
[0105] A graft 714 is arranged about the stent 704 . The stent 704 and graft 714 are constrained into a compacted delivery state (or first diameter) by a first sheath 716 and second sheath 718 . As shown in FIG. 7A , the first sheath 716 has been released allowing at least a portion of the stent 704 to expand as shown. The second sheath 718 is coupling the second leg 712 to the catheter assembly 702 as shown.
[0106] After the release of the first sheath 716 , the stent 704 is allowed to self expand into a second diameter that is greater than the initial compacted first diameter. The second diameter is defined by a secondary constraint 754 . The secondary constraint 754 is comprised of a flexible band that encircles a proximal end portion 706 of the stent graft. The secondary constraint prevents further self expansion of the stent graft.
[0107] As shown in FIG. 7B , the secondary constraint 754 is looped around the stent and is threaded through a latch 758 located near a first end of the secondary constraint 754 . A release pin 750 is threaded through the latch 758 to prevent further expansion of the secondary constraint 754 . Once the apparatus 700 is properly positioned within a vessel target site, the secondary constraint 754 can be released by translating the release pin 750 in a distal direction as shown by direction arrow 752 . By translating the release pin 750 , the stent 704 is released from the secondary constraint 754 and thereby allowed to further expand into a third diameter that is greater than the second and first diameters. Optionally, a retrieval cord or filament 756 can be used to join the secondary constraint 754 to the release pin 750 . Therefore when the release pin is translated distally, the secondary constraint 754 is withdrawn along with the release pin 650 .
[0108] FIGS. 8A through 8C depict a medical apparatus according to an embodiment of the invention.
[0109] Referring to FIGS. 8A through 8C , the medical apparatus is generally depicted as reference numeral 800 . The medical apparatus 800 includes a catheter assembly 802 , and stent arranged on the proximal end portion of the catheter assembly 802 . As shown in FIG. 8A the medical apparatus 800 has a stent constrained into a small delivery diameter 856 . The stent is held in this small delivery diameter by constraining sheaths 850 and 854 . The sheath 850 constrains the trunk of the stent while the sheath 854 constrains the extended leg portion of the stent. A third constraining sheath 852 is contained within the sheath 850 .
[0110] Referring to FIG. 8B , when the medical apparatus 800 is positioned within a target site, the sheath 850 can be released, allowing at least a portion of the stent to expand to a diameter 858 that is larger than the initial small delivery diameter 856 . The sheath 852 therefore constrains the stent 804 to an intermediate diameter. The sheath 854 constrains the extended leg portion of the stent onto the catheter assembly 802 , thereby allowing the medical apparatus to be repositioned, rotated or precisely aligned to the target site. As shown in FIG. 8C , when the medical apparatus is precisely positioned, the sheath 852 can be released, allowing the stent to fully expand to a large deployed diameter 860 . The deployed diameter 860 is larger than the intermediate diameter 858 . The intermediate diameter 858 is larger than the delivery diameter 856 as shown in FIGS. 8A through 8C . Stent anchoring barbs or hooks 862 (when provided) are therefore constrained to the intermediate diameter 858 during final manipulation and positioning of the medical apparatus and allowed to expand and engage a vessel when the constraining sheath 852 is released.
[0111] FIG. 9A is a partial side view of a medical apparatus 900 , having a constrained medical device 960 located near or at the distal end of a catheter assembly 962 . The catheter assembly 962 has a catheter shaft 964 and a distal guidewire port 966 . FIG. 9B is a cross-sectional view of the catheter shaft 964 . Shown contained within the catheter shaft 964 is a guidewire 970 , a release member 972 and an adjustment member 974 . The release member can be a cord, thread, wire, pin, tube or other element used to release a stent (or other medical device) from a constraint, thereby allowing the device to expand from a first compacted delivery profile to a second larger profile. The adjustment member can be a cord, thread, wire, pin, tube or other element used to alter the second profile of at least a portion of the medical device. A catheter used to deliver a medical apparatus can have one, two, three, four or five or more release members combined with one, two, three, four or five or more adjustment members. The release members and adjustment members can be contained in separate or shared lumens within the catheter shaft 964 .
[0112] FIGS. 10A and 10B show generalized views of a medical apparatus according to an embodiment of the invention (previously described in FIGS. 2A and 2B ). Shown in FIG. 10A is a medical apparatus 1000 , comprised of a stent 1002 having anchor barbs or hooks 1004 . Shown is a tube 1006 having a first movable element 1008 located therein. The first movable element 1008 is shown looped through a second movable element 1010 . As shown in FIG. 10B , when tension 1012 is applied to the ends of the first movable element 1008 , the second movable element 1010 is drawn into the tube 1006 . When the second movable element 1010 is drawn into the tube 1006 , the stent graft is compressed in the direction indicated by arrows 1014 . The anchors or barbs 1004 are therefore retracted and pulled inwardly away from a vessel wall. The retraction of the anchors or barbs will allow the medical apparatus 1000 to be longitudinally and/or rotationally adjusted. When in the precise target area the tension 1012 on the movable element can be removed, allowing the stent to self expand and engage the anchors or barbs into a vessel wall.
[0113] FIGS. 10C through 10H show a generalized delivery sequence according to an embodiment of the invention. Shown in FIG. 10C is a medical apparatus 1000 , having a first constraining sheath 1020 , a second constraining sheath 1022 and a catheter assembly 1024 . Constrained and contained within the first and second sheaths 1020 , 1022 is a bifurcated stent having a trunk, a first short leg and a second long leg. As shown in FIG. 10D , when the medical apparatus is positioned at a target site, the first constraining sheath 1020 is released allowing a portion of the stent and first short leg to self expand. A portion of the stent is held in a constrained small diameter state by movable element 1026 . The movable element 1026 is located in tube 1028 . The stent anchors or barbs 1030 are constrained and pulled inwardly by the movable element 1026 , so that the anchors or barbs do not engage a vessel wall. The second constraining sheath 1022 compresses the stent graft second long leg onto the catheter assembly 1024 . Thus the medical apparatus is captured by the catheter assembly, allowing subsequent repositioning of the medical apparatus.
[0114] As shown in FIG. 10E , the medical apparatus 1000 can now be readjusted in the longitudinal direction 1032 and/or in the angular direction 1034 through manipulations of the catheter assembly 1024 .
[0115] As shown in FIG. 10F , when the medical apparatus is precisely positioned, tension on first movable element 1036 is relaxed, allowing second movable element 1038 to expand. As second movable element 1038 expands, the stent is allowed to further expand in the direction 1040 , engaging the anchors or barbs 1030 into a vessel wall.
[0116] As shown in FIG. 10G , the second constraining sheath 1022 can be released, allowing the second long leg to self expand.
[0117] As shown in FIG. 10H , one end of first movable element 1036 can be tensioned, allowing first movable element 1036 to be un-looped from second movable element 1038 . First movable element 1036 can then be withdrawn through the tube 1028 . The expanded stent graft is now unattached from the catheter assembly, allowing withdrawal 1042 of the catheter assembly.
[0118] It will be apparent to those skilled in the art that various modifications and variation can be made in the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. | Controlled deployable medical devices that are retained inside a body passage and in one particular application to vascular devices used in repairing arterial dilations, e.g., aneurysms. Such devices can be adjusted during deployment, thereby allowing at least one of a longitudinal or radial re-positioning, resulting in precise alignment of the device to an implant target site. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to an apparatus for sterilizing objects, particularly mattresses, blankets, wooden furniture, clothing, etc.
2. The Prior Art
There have been many different apparatuses for sterilizing objects, but they all have the disadvantage that complicated technical facilities are required to operate them. Use of such a sterilizer at home is not possible in the vast majority of cases, because of the high costs incurred.
SUMMARY OF THE INVENTION
It is therefore an object of the invention to provide an apparatus for sterilizing objects that is easy and inexpensive to use.
This object is achieved by providing a sterilizing apparatus having a microwave source assigned to the sterilization chamber.
This minimizes the costs incurred. Mites, fleas, bacteria, woodworms or similar organisms can be killed simply by the microwave radiation.
In a preferred embodiment, the microwave source is in the form of a magnetron and is provided with a shield. The microwave radiation is directed towards the sterilization chamber as a result.
In another embodiment, a device is provided that can interrupt the microwaves. This means that the microwave radiation can be applied to the sterilization chamber in a pulsed manner. It is advantageous if at least one metallized propeller is provided for the periodic interruption of the microwave radiation. The microwave radiation is simple to interrupt in this way.
It is advantageous if the walls of the sterilization chamber are designed to that they reflect microwave radiation. This prevents microwaves from leaving the sterilization chamber. An additional effect is that the whole of the sterilization chamber is reached by the microwaves.
It is also advantageous if the walls fo the sterilization chamber consist of an at least partially metallized plastic film and/or a metal foil. This means that the sterilization chamber can be designed to be flexible, as a result of which it can be folded or rolled together when it is not in use.
In another embodiment, the walls of the sterilization chamber consist of a grid screen that reflects microwaves. A grid screen makes sure that there is adequate reflection and shielding, while material can be saved at the same time. The sterilizer can thus be used even more flexibly.
In another embodiment, the walls of the chamber consist of any rigid or flexible material that is metallized or provided with a second layer that reflects microwave radiation. Permanent sterilization chambers, for stationary applications, can be built with this material too.
In another embodiment, a screen is provided between the microwave source and the sterilization chamber to distribute the microwave radiation more effectively.
Depending on its mesh width and geometric shape, such a screen makes sure that the radiation emitted by the microwave source is distributed as consistently as possible in the sterilization chamber by means of interference and superposition.
It is also advantageous if two or more microwave sources are provided, which can be located on one side of the sterilization chamber and/or on different sides of the sterilization chamber. The capacity of the sterilizer can be set almost at will as a result. It is also possible to guarantee good coverage, by arranging microwave sources on opposite sides of the sterilization chamber. It is also advantageous if a device is provided which allows one or more microwave sources to be moved automatically or manually, particularly along the sides of the sterilization chamber. This means that one or more microwave sources can be moved over the object that is to be sterilized, as a result of which very large objects such as mattresses can be sterilized too.
Preferably, a door, flap or something similar is provided to open and close the sterilization chamber. Objects can be brought into and removed again from the sterilization chamber simply as a result.
In another advantageous embodiment, a safety device is provided which prevents accidental emission of microwave radiation, particularly when the sterilization chamber is not closed. Unintentional injury to people is effectively prevented as a result.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects and features of the present invention will become apparent from the following detailed description considered in connection with the accompanying drawings. It is to be understood, however, that the drawings are designed as an illustration only and not as a definition of the limits of the invention.
In the drawings, wherein similar reference characters denote similar elements throughout the several views:
FIG. 1 shows a diagram of a sterilizer in accordance with the invention; and
FIG. 2 shows a diagram of another sterilizer in accordance with the invention; and
FIG. 3 shows a diagram of an additional sterilizer in accordance with the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now in detail to the drawings, FIG. 1 shows a sterilizer for killing mites, fleas, lice, bacteria, woodworms, or similar organisms with a microwave source 2 and a sterilization chamber 3 . Microwave source 2 is surrounded by a shield 4 , which makes sure that the microwaves can only escape in the direction of sterilization chamber 3 . Sterilization chamber 3 is located right next to the shield 4 of the microwave source 2 and is open towards it.
Sterilization chamber 3 is surrounded in all other directions by a metallized plastic film 5 , which reflects the microwave radiation and thus stops it, leaving the sterilization chamber 3 . Sterilization chamber 3 can be opened with a zip 6 and can then be loaded.
Sterilizer 1 is suitable for sterilizing mattresses, blankets, wooden furniture or similar objects. After sterilization chamber 3 has been loaded with the objects that are to be sterilized 7 , zip 6 is closed again.
Microwave source 2 is activated for a short time for sterilization purposes. The microwave radiation makes sure that the pests are killed by heating them.
After the microwave source 2 has been switched off, the objects that have been sterilized 7 can be taken out of sterilization chamber 3 . A standard magnetron similar to the type used in microwave ovens can be used as microwave source 2 .
A screen 8 , which guarantees consistent distribution of microwave radiation throughout the sterilization chamber 3 by means of refraction, interference and superposition, is located between microwave source 2 and sterilization chamber 3 . The mesh width and geometry of screen 8 are adapted to the wavelength of the microwaves and the design of sterilization chamber 3 . Screen 8 can be produced from a metal or metallized material like plastic.
The walls of sterilization chamber 3 can be also be produced from a metal foil, a conductive screen of such rigid materials as metal, plastic or wooden boards. Materials that let microwaves through need to be provided with a shield made of metal foil, a metallized material, a screen or something similar.
A door or something similar to it can also be provided to open the sterilization chamber 3 instead of zip 6 . It is also conceivable that zip 6 of a door or something similar to it has a safety device 9 which switches off microwave source 2 if and when the sterilization chamber 3 is opened while sterilizer 1 is in operation. If sterilizer 3 is designed to be flexible, it can be rolled up when not in use, so it takes up only a minimum of space.
Several microwave sources 2 can be provided along the sterilization chamber too, which guarantee particularly good coverage of sterilization chamber 3 when they are located opposite each other. Microwave source 2 can be moved across the sterilization chamber and/or over objects that are to be sterilized 7 , possibly with its shield 4 , and thus passes over the whole of the objects that are to be sterilized 7 during the time it is switched on.
FIG. 3 shows a diagram of another embodiment of the sterilizer according to the invention. Here, metallized propellers 10 are installed to periodically interrupt the microwaves, so that the radiation can be applied in a pulsed manner. The microwave sources are movable along the sides of chamber 3 , along the arrows shown.
Accordingly, while only a few embodiments of the present invention have been shown and described, it is obvious that many changes and modifications may be made thereunto without departing from the spirit and scope of the invention. | An apparatus for sterilizing objects has a sterilization chamber and a microwave source for applying microwave radiation to objects inside the sterilization chamber. | 0 |
TECHNICAL FIELD
The present invention generally relates to a spray gun capable of electrostatically spraying a to-be-painted object with a highly conductive paint such as a water-based paint, metallic paint or the like with an optimum efficiency and an excellent safety and operability. More particularly, the present invention relates to an electrostatic-painting spray gun of an external charging type in which a high voltage is applied to an external electrode disposed in a position off an area sprayed with the paint from the spray gun to cause a discharge at the ground-potential side of the to-be-painted object, thereby forming an electric field in which fine particles of the paint passing through the discharging area are electrostatically charged.
BACKGROUND ART
The electrostatic painting or coating is a widely adopted painting technique in which an electrostatic-painting spray gun is used to coat an object with a paint with a high efficiency by charging fine particles of a paint sprayed are charged with a high-voltage static while forming an electric field on the object. The paints used in such electrostatic painting are generally classified, from the viewpoints of action and effect, into a solvent type high in electrical resistance, and a highly conductive type low in electrical resistance, such as a water-based paint or metallic paint. An appropriate one the painting methods and painting apparatuses should be selected for a selected one of such paints.
Because of the recent movement for being friendly to the earth, it has been demanded to limit the use of the solvent type paints containing a volatile organic compound, and use the water-based paints instead. In the case of the conventional electrostatic-painting spray gun, however, when sprayed fine particles of a paint are directly charged with a high-voltage static to improve the efficiency of electrostatic paint adhesion, the applied voltage goes to a grounded paint supply source via the paint particles, resulting in that no electrostatic effect can be assured and the high voltage arriving at the paint supply source will possibly cause a danger. On this account, there is used an approach to make an electrostatic spraying with the paint supply source being insulated from the ground potential while maintaining the high voltage. However, a vast amount of charge on the paint supply source will inevitably lead to an increased danger. To make a continuous work of painting in order to attain a higher industrial efficiency of painting, it will be necessary to use a paint feeder as disclosed in the Japanese Patent Application Laid Open No. 198228 of 1994. It is required to introduce a larger-scale painting apparatus not readily usable and of which the maintenance is not easy. These problems cause the electrostatic spraying of water-based and metallic paints not to have been more prevailing and the environmental pollution not to be limited or stopped early and effectively.
In the field of electrostatic painting. there are well known the direct charging technique in which fine particles of a paint are directly charged and also the external charging technique in which paint particles are not directly charged but they are charged when passing through an air space ionized by discharging from an external electrode disposed outside a sprayed area, carried on electric lines of force (electric field) formed toward a to-be-painted object, and adhere or stick to the latter. For example, electrostatic-painting painting apparatuses formed each integrally with a spray gun and cooperating with the latter are known from the disclosure in the Japanese Patent No. 2770079 and Japanese Patent Application Laid Open No. 213958 of 1995. The electrostatic-painting painting apparatus of the external charging type is such that a high voltage is applied to an external electrode disposed in a position off an area sprayed with fine particles of a paint from the spray gun to cause discharging at the ground potential side of a to-be-painted object, to thereby form an electric field and charge the paint particles passing through the discharging area and carry them on an electric field formed toward the object, thereby promoting the paint particles to well adhere to the object. In comparison with the aforementioned direct charging technique, however, the paint particles passing through the discharging area cannot be charged so effectively as to assure a sufficient electrostatic effect.
Generally, the direct charging used mainly with a solvent-type paint is adopted in an electrostatic-painting spray gun usable effectively on the commercial base. In this case, the voltage applied to the electrode is on the order of −30 to −70 kV. The larger the potential difference, the greater the electrostatic effect is. However, because of a greater danger due to a spark discharge or shock discharge with application of a high voltage and the dielectric-strength design of the apparatus or the like, the applied voltage is required to be as low as possible. Therefore, the voltage applied to the electrode is about −50 kV in many cases. On the other hand, normally in the external charging, the electrode is applied with a voltage having a larger potential difference. In comparison with the direct charging technique in which the charging electrode is disposed in the center of paint spray for efficient charging, the external charging technique needs a higher voltage for a greater practical effect and the charging electrode is disposed ahead of the atomizer to prevent any dangerous discharging to the paint spray nozzle as a substantial ground potential side of the apparatus, and drop of the voltage caused by the discharging at the charging electrode.
Generally, the commercial-use spray gun is designed so that the charging electrode is positioned 80 to 150 mm ahead of the paint spray nozzle. Namely, the charging electrode is projected largely ahead of the paint spray nozzle. Therefore, many of the commercial-use spray guns are used as a hand-held automatic spray gun connected to, and driven by, an automatic painting apparatus in many cases. More specifically, in this hand-held spray gun, the charging electrode is projected largely ahead and positioned aside off the center axis of spraying to prevent the function from being lessened due to adhesion of the sprayed paint, with the result that the spray gun is a large and not easy to handle and operate. Thus, the worker engaged in painting with this spray gun will be correspondingly more burdened.
Also, a hand-held type electrostatic-painting spray gun is disclosed in the Japanese Patent Application Laid Open No. 30646 of 1978. In this spray gun, the electrode projected to the forward end of the gun leads to a poor operability and is likely to be broken due to collision during operation. These problems caused this spray gun not to be more popular. Also, in comparison with the direct charging technique in which the paint particles are directly charged, the extent of charging by discharging from the electrode disposed outside is rather smaller. Thus, the external charging technique is required to use a higher voltage for a higher degree of charging while assuring a higher safety and improve the efficiency of paint adhesion by the effective charging.
Since the aforementioned external charging cannot assure any sufficient charging, consideration should be given to the use of a higher voltage, measures against a danger and dielectric breakdown possibly caused by the application of the high voltage. Namely, the apparatus of this external charging type has many problems to solve, such as a compact design and practical applicability thereof as a hand-held spray gun.
Also, the painting spray guns including the electrostatic-painting spray gun and other types of spray guns are used each as an automatic spray gun in painting a series of many objects in a lot in an automated line of production in a factory. In a post along the production line where there is effected a painting upon which the quality of the paint film depends, the worker uses a hand-held spray gun in many cases. However, many of the spray guns of this hand-held type are problematic in safety and operability. Namely, improved ease of handling and operation of the spray gun leads directly to an improved economical efficiency such as higher efficiency of paint adhesion as well as to improved work efficiency, quality and stability of painting, which will be extremely important factors from the overall and long-term viewpoints.
The conventional electrostatic-painting spray guns are designed each for use as an automatic spray gun mounted on an automatic painting apparatus. Therefore, the hand-held type electrostatic-painting spray gun should be designed easier to handle and operate, strictly safer against possibly direct danger to the worker, and more compact.
Any external electrode to be provided in a conventional hand-held spray gun should be disposed largely ahead of the paint spray nozzle. Therefore, it is essential that the electrode should be lightweight. However, major consideration being given to a combination of necessary members in the spray gun, the problems for easier handling and operability of the spray gun, which are most important for the worker using the spray gun, have not yet been solved.
Also, in the case of the conventional hand-held type electrostatic-paining spray gun, a high-voltage cable from an external high-voltage generator is connected to the spray gun for receiving a high voltage. However, there have not yet been solved the problems such as incorporation, integrally in the spray gun, of the high-voltage generator to apply a voltage to the electrode in order to free the worker from the weight of the high-voltage cable and prevention of a danger of the high voltage applied to the electrode disposed ahead of the paint spray nozzle. The spray gun should be a comprehensively high-practicality one in which such solutions are implemented.
Also, if a paint is continuously sprayed with the paint being adhering to the external electrode and electrode holder or receptacle, the sprayed paint particles will be heaped up and drip off, which will spoil the quality of a finish coat. Of course, the spray gun with such a result is not reliably usable. In case a paint easily solidified and not soluble with the solvent, such as a water-based paint, is used, the solid content of the paint will act as an insulator and adhesion thereof to the electrode will greatly degrade the action and effect of the electrode. Therefore, the electrostatic-painting spray gun should be durable for a long term of use and able to readily be restored to its normal condition even if it should have the function thereof lessened or disabled.
SUMMARY OF THE INVENTION
Accordingly, the present invention has an object to overcome the above-mentioned drawbacks of the related art by providing an electrostatic-painting spray gun which is easy to handle and operate as a hand-held one, safe to the user thereof and can assure an improved efficiency of paint adhesion so that it will be able to contribute to the more popular use of water-based paints which are very friendly to the environment.
The above object can be attained by providing an electrostatic-painting spray gun including a high-voltage generator, atomizer, and an external electrode disposed outside, and projected ahead of the atomizer while being separated, with an electric insulation being kept, from a passage through which a paint is supplied to the atomizer, wherein the apparatus is a hand-held spray gun having an electroconductive grip provided at the back of the atomizer; and the external electrode can be connected to, and disconnected from, an electrode receptacle provided outside the apparatus. Because the external electrode is thus removable from the electrode receptacle, even if it is contaminated with the adhering paint and has the function thereof lessened or if it is broken due to collision during operation, it can readily be replaced and the spray gun can be restored to its normal condition.
For designing the external electrode so small as not to impair the operability of the spray gun, the electrode receptacle is disposed between the atomizer and the grip provided at the back of the atomizer. For the safety, a first high-resistance resistor is provided at the high voltage output of an electrical receptacle while a second high-resistance resistor is provided at the forward end of the external electrode, whereby it is possible to reduce the electrostatic capacity of the forward-end electrode charged with a high voltage.
Also, the external electrode has a plug-in portion so formed that the distance from a electric connection with the high voltage output of the high-voltage generator to the exposed end of the outer surface of the plug-in portion is sufficient for prevention of creepage discharging. Thus, even if an object acting as a ground potential is placed near the outer surface of the plug-in portion or under the influence of a contamination of the outer surface with the paint, it is possible to prevent creepage discharging of a high voltage to the forward end of the spray gun or to the ground potential side of the grip.
As a means for effectively preventing the creepage discharging in case the electrode receptacle and barrel of the spray gun are designed short, there is provided a corrugated or zigzagged boundary surface between the electric connection with the high-voltage output and the exposed end of the plug-in portion outer surface to be fitted in the electrode receptacle. To define the corrugated boundary surface, concentric deep grooves are formed in the electrode receptacle while corresponding ridges are formed in the plug-in portion of the external electrode. When the plug-in portion is fitted or plugged in the electrode receptacle with the ridges being inserted into the corresponding grooves, the corrugated boundary surface is defined to provide a long creepage distance which can prevent creepage discharging to the outer surface. Thus, the insulation between the electrode receptacle at a high voltage and the outer surface of the plug-in portion of the external electrode can be maintained, and the length of the electrode receptacle at the spray gun body and that of the external electrode which can freely be attached to, and removed from, the electrode receptacle can be reduced. Thereby, the hand-held spray gun can be handled more easily.
The present invention is further characterized in that the insulative material forming the external electrode is a flexible, resilient material to prevent the electrode body from being broken or deformed due to any unexpected collision or the like. The material will absorb the shock against a temporary deformation and prevent the electrode body from being broken. Thus, the electrode body is improved in durability. Also, according to the present invention, a portion of the electrode body is formed to be weaker than the other part. With this weak portion, it is intended that if the electrode body is broken under a large shock applied, the electrode body itself will just be disengaged from the electrode receptacle or partially broken without any critical damage to the electrode receptacle, namely, the application of a large shock will result in only a minimum damage, and the spray gun can quickly recover its normal condition only with replacement of the broken electrode body.
Also, the external electrode includes a charging electrode formed at the forward end thereof. With the forward end being positioned 30 to 80 mm ahead of the atomizer to prevent paint spray flow from being applied to the charging electrode. Also, with the forward end of the electrode being positioned as near to the paint spray flow as possible, it is possible to assure a highest efficiency of paint adhesion and safety.
The position where the charging electrode will not be applied with the paint spray flow is laterally separate from the center axis of spraying, and the distance from the center axis is not more than a half of the distance between the charging electrode and the front of the atomizer. Thereby, it is possible to prevent the sprayed paint particles from adhering to the charging electrode, so that the charging electrode can maintain the effect of charging the paint particles to assure a high electrostatic effect.
Also, the forward-end electrode, namely, the charging electrode, is positioned at such a distance as will not cause any streamer discharge having an electrically concentrated flow toward the paint spray flow or the paint spray nozzle at the ground potential side, and opened from the axis of spraying not to be applied with the paint spray flow.
To assure an efficiency of paint adhesion considered as effective with a practical electrostatic-painting spray gun, the charging voltage should be maintained at −70 to −90 kV, discharge current from the electrode be 60 to 150 μA, and a resistor of more than 150 MΩ is provided between the electrode and high voltage output for prevention of any dangerous shock discharging.
The external electrode is replaceable, and can be installed to the electrode receptacle at an angle for gradual separation from the center axis of spraying as it goes toward the forward end thereof so that it will not be applied with the paint spray flow. Also, the external electrode can easily be positioned appropriately for the length of the electrode body removably attached to the spray gun.
These objects and other objects, features and advantages of the present invention will become more apparent from the following detailed description of the best mode for carrying out the present invention when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be described in detail concerning the embodiment thereof with reference to the accompanying drawings, in which:
FIG. 1 is an axial-sectional view of an embodiment of the spray gun according to the present invention.
FIG. 2 schematically illustrates the construction of the high-voltage generator.
FIG. 3 is a partial axial-sectional view of the receptacle or holder for the external electrode.
FIG. 4 explains the location where the external electrode is installed.
FIG. 5 is an axial-sectional view of the external electrode.
FIG. 6 is a cross-sectional view taken along the line A-A in FIG. 5 .
FIG. 7 is an axial-sectional view of the external electrode.
FIG. 8 is a side elevation, viewed from the forward end, of the spray in FIG. 1 .
FIG. 9 graphically illustrates the tendency of the electrostatic effect on the current from the electrode.
FIG. 10 graphically illustrates the test results showing the variation of current depending upon the position of the external electrode.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIG. 1 , there is schematically illustrated in the form of an axial-sectional view the hand-held type electrostatic-painting spray gun adopting the external charging technique, as an embodiment of the present invention. The spray gun is generally indicated with a reference numeral 1 . As shown, the spray gun 1 includes a grip 2 , trigger 3 , barrel 4 , atomizer 5 provided at the forward end of the barrel 4 , high-voltage generator 6 disposed at the top of the barrel 4 , and an external electrode 7 provided outside the spray gun 1 . The spray gun is to be operated while being held at the grip 2 . The barrel 4 controls the paint to be sprayed from the atomizer 5 while controlling the high voltage for application to a forward-end electrode 71 of the external electrode 7 by controlling the input and output of a low-voltage power source for application to the high-voltage generator 6 .
In this embodiment of the spray gun, the atomizer 5 atomizes a paint with a compressed air. For this purpose, an air cap or nozzle head 51 is provided around a paint spray nozzle 52 to form a desired pattern of spray for coating a to-be-painted object with the paint. The above construction is similar to that of the conventional spray gun. For the purpose of electrostatic painting, however, the barrel 4 , paint spray nozzle 52 and air cap 51 are made of an electrically insulative material. In the spray gun used with a water-based or highly conductive paint and provided outside thereof with the charging electrode, since the paint passage is connected to the ground potential, a needle valve 53 in the paint spray nozzle 52 is made of a metal and thus electrically connected to the grip 2 located at the rear portion of the barrel 4 . The grip 2 is electroconductive as in the conventional electrostatic-painting spray gun. In this embodiment, the grip 2 is made of such a semi-conductive resin as to have the ground potential when held in hand by the worker using the spray gun.
As shown in FIG. 2 , the high-voltage generator 6 includes a cartridge 64 formed by molding an insulative resin to house a low-frequency transformer 61 , Cockcroft-Walton accelerator 62 and a protecting high-resistance resistor 63 together therein.
The cartridge 64 electrically maintains an insulating strength except at an input terminal 65 at the low-voltage input side and an output terminal 66 at the high voltage output.
The cartridge 64 is inserted in a housing 11 formed atop the barrel 4 of the spray gun 1 made of an insulative material, and the output terminal 66 of the high-voltage generator 6 is connected to one end of a conductor 12 laid extending through the barrel 4 . An electrode receptacle 13 for receiving the external electrode 7 is also provided at the outer back of the atomizer 5 on the barrel 4 of the spray gun 1 , and the other end of the conductor 12 is exposed as a connecting terminal 14 inside the electrode receptacle 13 made of an insulative material.
The forward-end electrode 71 is exposed at the forward end of the external electrode 7 which is to be fitted into the electrode receptacle 13 , and a plug-in portion 72 is formed at the rear end of the external electrode 7 . The external electrode 7 as a whole is made of an insulative material. A connecting terminal 73 is exposed at one end of the plug-in portion 72 . A conductor 74 is connected between the connecting terminal 73 and forward-end electrode 71 . When the external electrode 7 is inserted at the plug-in portion 72 thereof into the electrode receptacle 13 of the barrel 4 , the connecting terminal 73 is put into contact with the connecting terminal 14 at the barrel 4 to have an electrical connection with the connecting terminal 14 . In this embodiment, the connecting terminal 73 at the external electrode 7 is shaped in the form of a helical spring for positive connection, and the connecting terminal 14 at the barrel 4 may also be formed so.
By inserting the plug-in portion 72 of the external electrode 7 into the electrode receptacle 13 and turning it a little until an engagement piece 75 is engaged in a retention recess 15 , the external electrode 7 can be fixed to have the forward-end electrode 71 thereof locked in place as partially shown in FIG. 4 . The forward-end electrode 71 may be locked otherwise. That is, it may be locked so with a conventional engaging technique, namely, by a selected one of a technique in which the engagement piece 75 is simply inserted into the retention recess 15 for close fitting due to their dimensional precision to assure a necessary force of fixation based on a force of friction, and a technique in which both the engagement piece 75 and retention recess 15 are formed so that they can be put into mesh with each other and disengaged from each other by releasing the engagement piece 75 .
The external electrode 7 is easily replaceable because it is simply configured and can be easily attached to, and removed from, the electrode receptacle 13 . Even if the forward-end electrode 71 is contaminated with the paint or broken during paint spraying, the external electrode 7 can readily be replaced to assure a continuous work of painting without any long interruption. Because the electrode receptacle 13 is disposed at the back of the atomizer 5 , only the forward end of the external electrode 7 , which is shaped thin, can be placed in an area sprayed with paint particles and in a position so near the object as to charge the sprayed paint particles effectively within a range of no influence on the spraying.
The plug-in portion 72 of the external electrode 7 has concentric deep grooves 76 formed therein about the conductor 74 and connecting terminal 73 and the electrode receptacle 13 of the barrel 4 has formed therein concentric grooves 16 , as shown in FIG. 5 . Thus, each of the plug-in portion 72 of the external electrode 7 and the electrode receptacle 13 has the grooves and ridges (i.e., projections), and the plug-in portion 72 is fittable into the electrode receptacle 13 with the ridges being received in the respective grooves. With the external electrode 7 being inserted at the plug-in portion 72 into the electrode receptacle 13 of the barrel 4 , the creepage surface (creepage length) along the corrugated boundary surfaces, defined by the grooves 16 and ridges, of the electrode receptacle 13 extends to an exposed end 77 at the outer surface of the electrode receptacle 13 . Therefore, since a sufficient creepage-discharge prevention distance to the exposed end 77 at the outer surface of the electrode receptacle 13 is ensured for a high voltage applied to the connecting terminal 73 , even if a to-be-painted object at the ground potential touches the exposed end 77 at the outer surface, it is possible to prevent any unexpected discharge or dielectric breakdown from taking place.
Normally, the creepage-discharge prevention distance should be about 15 mm per 10 kV. According to the present invention, the creepage length of the electrode receptacle 13 can be sufficient because of the corrugated or zigzagged boundary surfaces, defined by the grooves 16 and ridges of the electrode receptacle 13 and grooves 76 and ridges of the plug-in portion 72 of the external electrode 7 . The plug-in portion 72 of the external electrode 7 can be formed shorter accordingly, and thus the spray gun itself can also be formed correspondingly shorter for easier handling.
Since a high voltage is applied via the protecting high-resistance resistor 63 to the high voltage output terminal 66 of the high-voltage generator 6 provided at the spray gun 1 , the external electrode 7 is not electrically shocked accidentally.
However, the static charge in the conductor 74 extended through the external electrode 7 will inevitably be discharged suddenly. On this account, a second high-resistance resistor 78 is provided as a current-limiting resistor in the vicinity of the forward-end electrode 71 of the external electrode 7 as shown in FIG. 7 to assure a higher safety. The second high-resistance resistor 78 has a size selected for the external electrode 7 not to impair the ease of operation and handling of the spray gun.
Thus, such use of the second high-resistance resistor 78 allows the protecting high-resistance resistor 63 provided at the high-voltage generator 6 to be smaller in size, which will contribute to a reduced size of the high-voltage generator 6 and thus to a more compact and lightweight design of the spray gun itself.
Further, according to the present invention, the external electrode 7 is made of a flexible, resilient material. More specifically, an electrode body 70 is formed from a resin such as polyethylene to protect the electrode body 70 from being broken due to an accidental drop, collision with any object or the like during operation and handling of the spray gun.
Also, according to the present invention, a part 79 of the external electrode 7 is made of a material low in bending strength to make the electrode receptacle 13 at the spray gun body side relatively stronger. This feature will assure that even if the external electrode 7 is given a heavy mechanical shock, the electrode body 70 will only be broken at that weak portion 79 and the spray gun 1 can quickly recover its normal condition only with replacement of the electrode body 70 .
According to the present invention, the external electrode 7 is positioned under the following conditions.
As shown in FIG. 4 , the forward-end electrode 71 of the external electrode 7 connected to the electrode receptacle 13 is positioned 70 mm (X in the drawing) ahead of the forward end of the paint spray nozzle 52 of the atomizer 5 , and 30 mm (Y in the drawing) laterally away from the longitudinal axis (C in the drawing) of spraying.
The electrode receptacle 13 at the barrel 4 is formed at an angle B of about 10 deg. outwardly divergent from the longitudinal axis C of spraying. Thus, the external electrode 7 is more distant from the longitudinal axis C of spraying as it is nearer to the forward end thereof. Therefore, with a spraying rate and spreading of the paint spray falling within the range of requirements for the normal painting, the paint will not adhere to the forward-end electrode 71 positioned as in this embodiment and thus the paint spraying can continuously be done without interruption. When the voltage application and other painting conditions are changed, however, the positioning of the external electrode 7 should be changed in some cases. Also, with a longer external electrode 7 , the forward-end electrode 71 can be positioned more distant from the paint spray nozzle 52 and also from the axis of spraying to prevent the paint from adhering to the forward-end electrode 71 .
The results of various tests made by the Inventors of the present invention revealed that the efficiency of paint adhesion in the electrostatic painting with the external charging should be about 10% higher than in the painting with no voltage application, namely, in the ordinary painting. On this account, the voltage for application to the external electrode 7 should be −70 to −90 kV, which is higher than that used in the electrostatic painting with the direct charging. Thus, some safety measures should be taken. The protecting high-resistance resistor 62 is provided at the output of the high-voltage generator 6 to limit the discharge current to 200 μA for assuring the safety when the forward-end electrode 71 is near the ground potential. The protecting high-resistance resistor 62 should have a resistance of at least 150 Ma
When a paint is actually sprayed, the current is reduced to about 150 μA, and this current value is taken as the maximum current value for the electrostatic painting. The Inventors of the present invention conducted many tests under the practical, average painting conditions including a spraying pressure of 300 kPa, spraying distance of 300 mm, paint spraying rate of 300 ml/min, current-limiting resistance of 150 to 300 MΩ, distance of 30 to 80 mm between the forward-end electrode 71 and the paint spray nozzle and a charging voltage of 30 to 90 kV. The test results are shown in FIG. 10 . As graphically shown in FIG. 9 , the electrostatic effect was found improved for a current of about 120 μA. With charging with a higher voltage, however, no remarkable change was found but the danger will be rather higher. Therefore, the maximum current should be 120 μA.
The current of 150 μA, which is considered to have no danger to the apparatus and human body, did not result in any difference in substantial effect. Contrarily, with a current of about 60 to 70 μA, the electrostatic effect was abruptly lower. Namely, such values of the current are practically useless.
With the use of a higher-resistance resistor, the safety will be correspondingly higher but the current will be smaller. No sufficient discharge will take place, resulting in poorer charging of the paint particles and lower electrostatic effect. Therefore, the high resistance of 300 MΩ is taken as the practically highest one.
The electrostatic effect referred to herein is of such an extent that the paint spray ill flow around and adhere to sides and back of a to-be-painted object, other than a to-be-painted surface the spray flow will apply directly. The higher the electrostatic effect, the better the paint will adhere to a to-be-painted object, so that of the electrostatic painting, the process can be reduced and efficiency be improved effectively. Also, it has also been proved that the electrostatic effect is in correlation with the efficiency of paint adhesion.
Further, the forward-end electrode 71 of the external electrode 7 is positioned as follows. It is well known that when discharging is made from the electrode at a high voltage to the paint spray nozzle 52 at the ground potential side or to paint particles being sprayed, the longer the distance between the electrode and nozzle or paint particles, the larger the current is. However, the electrostatic painting needs discharging with a high efficiency of ionization, and if the distance is so short that a discharge current is focused on the paint spray nozzle 52 , no electrostatic effect will be obtainable. The results of many tests made by the Inventors of the present invention showed that when the spray gun is used under the practically applicable painting conditions, the forward-end electrode 71 should be positioned 30 mm or more off a position where the paint spraying is started, that is, a position where the paint atomization is started.
More particularly, in case the practically required charging voltage is −70 kV and a resistor having a high voltage of 200 MΩ is used in the spray gun, the position of the forward-end electrode 71 where a current of 120 to 150 μA can be sustained is about 30 mm ahead of the atomization starting position. If this distance is shorter, a streamer discharge will take place, and the discharge current rises abruptly to lower the safety. Therefore, in case a current-limiting resistance of 300 MΩ is selected as above to maintain the efficiency of paint adhesion, the shortest distance to the forward-end electrode 71 should desirably be about 30 mm.
Also, in case the forward-end electrode is positioned over the predetermined distance or a longer distance, the discharge current almost depends upon the aforementioned resistance of the current-limiting resistor. It is stable and no marked change is found in the electrostatic effect, as shown in FIG. 10 . Therefore, with consideration given to the safety, the forward-end electrode is positioned in a remote position where the electrostatic effect will little be affected, namely, in the intermediate position in relation to an object to be painted.
With the ease of handling the spray gun being taken in consideration, however, it is apparent that the electrode laid ahead of the atomizer should desirably be small and positioned nearer to the atomizer. The positioning as in this embodiment will permit to implement safe and highly efficient electrostatic painting.
On the other hand, since the paint spray flows in a predetermined spread toward a to-be-painted object in the practical painting, it is also an important factor for the spray gun that for prevention of the paint spray from applying the forward-end electrode, the latter should be positioned so distant from the atomizer as to positively prevent the paint particles from adhering to the electrode. The paint adhering to the electrode will insulate the electrode and thus block discharging from the electrode. In this case, the electrostatic effect will abruptly be lower.
According to the present invention, the forward-end electrode 71 is positioned as near the axis of spraying as possible to prevent the paint spray from applying the electrode 71 . In the spray gun, the forward-end electrode 71 is positioned at a shorter radius of an elliptical spray pattern. At this shorter radius of the spray pattern, the spread of spray is stably small. At the start point of spraying, the spray will abruptly spread. Thereafter, the spraying is made in a stable spread of about 10 deg. in angle as in the spread of the spraying air flow.
Note that the external charging type electrostatic-painting spray gun is to be used for spray-painting of a conductive paint such as a water-based paint. Fine particles of the paint sprayed from the atomizer are charged when passing through an area of ionization formed due to discharge from the forward-end electrode provided ahead of the atomizer, and electrostatically adhere to a to-be-painted objected placed opposite to the electrode. It should be noted that the atomizer is not limited to the one used in the air spray gun according to the embodiment of the present invention.
As having been described in the foregoing, since the external electrode can simply be attached to, or removed from, the hand-held electrostatic-painting spray gun incorporating the high-voltage generator, the spray gun can be used being held in hand under different painting conditions. Namely, the present invention can provide a high-practicality electrostatic-painting spray gun of the external charging type, excellent in ease of operation and handling.
Also, since the forward-end electrode of the external electrode is located in a position where it will work most effectively, the electrostatic effect is highest and efficiency of paint adhesion is improved.
Further, because of the corrugated boundary surface of the external electrode, a necessary creepage-discharge prevention distance can be assured. So, the external electrode itself can be designed smaller and thus the spray gun itself can be designed compact. Thus, the present invention can solve the problems for easy installation, and improved ease of handling and operability of the spray gun.
Furthermore, since the external electrode is designed simplest and easily replaceable, breakage thereof will not lead to any damage of the spray gun body. Only with replacement of the external electrode which is inexpensive as above, the spray gun once put out of operation can quickly recover the normal condition. Thus, the damage can be minimized and the down time is shortest.
INDUSTRIAL APPLICABILITY
In the field of electrostatic paint, there have been used mainly the solvent-type paints whose electric resistance is high. Because of the recent movement for being friendly to the earth, it has been demanded to limit the use of the solvent type paints containing a volatile organic compound, and use the water-based paints instead. To solve the problems such as the possible danger caused by the use of a water-based paint or metallic paint whose electric resistance is low and large size of the painting apparatus, which causes the use of such water-based paint and metallic paint not to have been more prevailing, the present invention provides an electrostatic-painting spray gun including an external electrode which can freely be attached to, and removed from, the spray gun and a high-voltage generator, and which is highly safe, excellent in ease of handling and operation, and capable of an optimum efficiency of painting. The spray gun according to the present invention will be able to contribute much to the use of more water-based paint which is friendly to the environment. | A spray gun for electrostatic painting in which an external electrode sustaining a high voltage can be fixed/removed while sustaining insulation from a spray unit on the ground potential side by limiting current supply to paint appropriately when electrostatic painting is performed using conductive paint, e.g. water based paint, and safety and handling performance are enhanced while ensuring the painting efficiency as the spray gun for electrostatic painting. On the outside of the spray gun ( 1 ) having the spray unit ( 5 ) at the forward end thereof, the external electrode ( 7 ) having an electrode projecting from the forward end part thereof is provided removably at the part ( 13 ) of the gun body being connected with the electrode while being separated from the paint passage such that it can be replaced readily. The part being connected with a high voltage output end part through a high resistor for limiting current can be shortened while sustaining safety by providing a turn-up part so that a sufficient creeping discharge preventing distance is ensured up to the exposed part on the outer surface. Furthermore, the electrode body itself is simplified so that it can be replaced with one touch, and it is composed of a flexible resilient material in order to prevent damage. | 1 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a division of application Ser. No. 832,868 filed Sept. 13, 1977.
BACKGROUND OF THE INVENTION
1 Field of the Invention
This invention relates to certain 2-(acyclic substituted) phenols and derivatives thereof having at the 5-position a --Z--W group wherein Z is alkylene having from one to thirteen carbon atoms or (alk 1 ) m --O--(alk 2 ) n --wherein each of m and n is 0 or 1 and each of (alk 1 ) and (alk 2 ) is alkylene having from one to thirteen carbon atoms with the proviso that the summation of carbon atoms in (alk 1 ) plus (alk 2 ) is not greater than thirteen; and W is hydrogen, phenyl, fluorophenyl, chlorophenyl or pyridyl; derivatives thereof, intermediates therefor and process for their preparation. The products are useful as CNS agents, especially as analgesics, tranquilizers, sedatives and antianxiety agents in mammals, including man, and/or as anticonvulsants, diuretics and antidiarrheal agents in mammals, including man.
2. Description of the Prior Art
Despite the current availability of a number of analgesic agents, the search for new and improved agents continues, thus pointing to the lack of an agent useful for the control of broad levels of pain and accompanied by a minimum of side-effects. The most commonly used agent, aspirin, is of no practical value for the control of severe pain and is known to exhibit various undesirable side effects. Other potent analgesic agents such as d-propoxyphene, codeine, and morphine, possess addictive liability. The need for improved and potent analgesic agents is, therefore, evident.
More recently, great interest in cannabinol-type compounds as analgesic agents has been exhibited. (R, Mechoulam Ed., "Marijuana. Chemistry, Pharmacology, Metabolism and Clinical Effects", Academic Press, New York, N.Y., 1973; Mechoulam, et al., Chemical Reviews, 76, 75-112 [1976]).
SUMMARY OF THE INVENTION
It has now been found that certain 5-substituted phenols having at the 2-position an acyclic ketone or alcohol group are effective as CNS agents, especially as analgesics, tranquilizers, sedatives and antianxiety agents in mammals, including man, and/or as anticonvulsants, diuretics and antidiarrheal agents in mammals, including man (formulae I and II below). Also included in this invention are various derivatives of said compounds which are useful as dosage forms of the compounds, intermediates therefor and methods for their preparation. The compounds and derivatives thereof have the formulae ##STR2## (in which stereochemistry is not represented) wherein: R is selected from the group consisting of hydrogen and alkanoyl having from one to five carbon atoms;
R 1 selected from the group consisting of hydrogen, benzyl, alkanoyl, having from one to five carbon atoms --P(O)(OH) 2 and the mono- and disodium and potassium salts thereof, --CO(CH 2 ) 2 --COOH and the sodium and potassium salts thereof, and --CO--(CH 2 ) p --NR 5 R 6 wherein p is 0 or an integer from 1 to 4; each of R 5 and R 6 when taken individually is selected from the group consisting of hydrogen and alkyl having from one to four carbon atoms; R 5 and R 6 when taken together with the nitrogen to which they are attached form a 5- or 6-membered heterocyclic ring selected from the group consisting of piperidino, pyrrolo, pyrrolidino, morpholino and N-alkylpiperazino having from one to four carbon atoms in the alkyl group;
each of R 2 and R 4 is selected from the group consisting of hydrogen, alkyl having from one to six carbon atoms, phenyl, pyridyl and phenylalkyl having from one to four carbon atoms in the alkyl moiety;
R 3 is selected from the group consisting of hydrogen and methyl;
Z is selected from the group consisting of (a) alkylene having from one to thirteen carbon atoms; (b) --(alk 1 ) m --O--(alk 2 ) n --wherein each of (alk 1 ) and (alk 2 ) is alkylene having from one to thirteen carbon atoms, with the proviso that the summation of carbon atoms in (alk 1 ) plus (alk 2 ) is not greater than thirteen; each of m and n is 0 or 1; and
W is selected from the group consisting of hydrogen, fluoro and chloro. ##STR3## wherein w 1 is selected from the group consisting of hydrogen flouro and chloro.
Also included in this invention are the pharmaceutically acceptable acid addition salts of those compounds of formulae I and II which contain a basic group. In compounds having two or more basic groups present, such as those wherein the W variable is pyridyl and/or OR 1 represents a basic ester moiety, polyacid addition salts are, of course possible. Representative of such pharmaceutically acceptable acid addition salts are the mineral acid salts such as the hydrochloride, hydrobromide, sulfate, phosphate, nitrate; organic acid salts such as the citrate, acetate, sulfosalicylate, tartrate, glycolate, malate, malonate, maleate, pamoate, salicylate, stearate, phthalate, succinate, gluconate,2-hydroxy-3-naphthoate, lactate, mandelate and methane sulfonate.
Compounds of formula II can exist in diastereomeric forms by virtue of the asymmetric center at which the OR group is attached. Additionally, compounds of fomulae I and II may contain asymmetric centers in the 4-position substituent (Z-W) of the phenyl ring.
For convenience, the above formulae depict the racemic compounds. However, the above formulae are considered to be generic to and embracive of the racemic modifications of the compounds of this invention, the diastereomeric mixtures, the pure enantiomers and diastereomers thereof. The utility of the racemic mixture, the diastereomeric mixture as well as of the pure enantiomers and diastereomers is determined by the biological evaluation procedures described below.
Compounds of formula I wherein R 1 is H exist, in solution, in equilibrium with their hemiketal forms. Spectral evidence indicates the hemiketal to be the predominant form. In the solid state, spectral evidance indicates the compounds exist substantially completely in the hemiketal form. The keto and hemiketal forms of compounds of formula I are included in this invention.
Favored because of their greater biological activity relative to that of other compounds described herein, are compounds of formulae I-II wherein R is hydrogen; R 2 is hydrogen or alkyl; R 1 is hydrogen or alkanoyl; R 3 is hydrogen or methyl; and Z and W have the values shown below:
______________________________________Z m n W______________________________________alkylene having from 5 to 10 -- -- Hcarbon atomsalkylene having from 2 to 6 carbon atoms -- -- ##STR4##(alk.sub.1).sub.mO(alk.sub.2).sub.n 0 1 ##STR5##(alk.sub.1).sub.mO(alk.sub.2).sub.n 1 0 ##STR6##______________________________________
Preferred compounds of formulae I-II, and especially of formula II, are those preferred compounds wherein Z and W have the values shown:
______________________________________Z W______________________________________C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.5 HOCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5______________________________________
and each of R, R 1 and R 3 is hydrogen; and each of R 2 and R 4 is alkyl.
DETAILED DESCRIPTION OF THE INVENTION
Compounds of formula I are prepared by conjugate addition of an appropriate 2-bromo-5-(Z-W substituted) phenol to an α,β-unsaturated ketone via the Grignard reaction. The process comprises, as first step, protection of the phenolic hydroxy group.
Suitable protecting groups are those which do not interfere with subsequent reactions and which can be removed under conditions which do not cause undesired reactions at other sites of said compounds or of products produced therefrom. Representative of such protective groups are methyl, ethyl, benzyl, or substituted benzyl wherein the substituent is, for example, alkyl having from one to four carbon atoms, halo (Cl, Br, F, I) and alkoxy having from one to four carbon atoms.
The exact chemical structure of the processing group is not critical to this invention since its importance resides in its ability to perform in the manner described above. The selection and identification of appropriate protecting groups can easily and readily be made by one skilled in the art. The suitability and effectiveness of a group as a hydroxy protecting group are determined by employing such a group in the herein-illustrated reaction sequences. It should, therefore, be a group which is easily removed to regenerate the hydroxy group. Methyl is a favored protecting group since it is easily removed by treatment with pyridine hydrochloride. The benzyl group, also a favored protecting group, is removed by catalytic hydrogenolysis or acid hydrolysis.
The protected 2-bromo-5-(Z-W substituted)phenol is then converted to the corresponding Grignard reagent in known manner as, for example, by refluxing a mixture of one molar proportion of the bromo reactant and two molar proportions of magnesium in a reaction-inert solvent, e.g. cyclic and acylic ethers such as tetrahydrofuran, dioxane and dimethyl ether of ethylene glycol. The resulting mixture is then cooled to about 0° C. to -20° C. and a cuprous salt (CuBr, CuCl or CuI) added followed by the appropriate α,β-unsaturated ketone. A cuprous salt is generally added to increase conjugate addition of the Grignard reagent to the α,β-unsaturated ketone. The amount of cuprous salt used is not critical but can vary widely. Molar proportions ranging from about 0.2 to about 0.02 moles per mole of bromo reactant afford satisfactory yields of conjugate addition product.
Appropriate α,β-unsaturated ketones are those of formula III below: ##STR7## wherein R 2 , R 3 and R 4 are as defined above.
Many of the α,β-unsaturated ketones of formula III are known compounds. Those that are not known are conveniently prepared via the reaction of appropriate phosphate carbanions with appropriate aldehydes or ketones according to the Wadsworth-Emmons modifications of the Wittig reaction (J. Am. Chem. Soc., 83, 1733-8, 1961). The reaction, in general, comprises treating a dialkylacylphosphonate with an aldehyde or ketone in an aprotic solvent, e.g. 1,2-dimethoxyethane, diglyme, at a temperature of from about room temperature to about 110° C. Additionally, Grieco et al., J. Am. Chem. Soc., 95, 3071-2 (1973) describe a procedure for preparing dimethyl-(2-oxoalkyl)phosphonates which serve as valuable starting materials in the above-mentioned Wadsworth-Emmons modification of the Wittig reaction. The dialkyl acylphosphonates required for these procedures are prepared by the Michaelis-Arbuzov reaction (Kosolapoff, "Organophosphorous Compounds", 1st Ed., J. Wiley and Sons, Inc., New York, N.Y., 1950, Chapter 7) which comprises reacting a trialkyl phosphite with an appropriate alkyl or aralkyl halide.
A convenient method for preparing compounds of this invention wherein --Z--W is --O--(alk 2 ) n --W comprises the use of 4-bromo resorcinol as starting material. The process comprises protecting the two hydroxy groups of the resorcinol by benzylation according to standard procedures. The benzyl group is favored as protecting group in this method since it can easily be removed by catalytic hydrogenation without cleaving the ether group --O--(alk 2 ) n --W. Other protecting groups groups such as alkyl (e.g., methyl or ethyl) can, of course, also be used. However, the benzyl protecting group is favored since it gives rise to fewer side reactions. The protected 4-bromo resorcinol is then subjected to the Grignard reaction and reacted with the appropriate α,β-unsaturated ketone in a reaction-inert solvent in the manner described above. The (2,4-dibenzyloxyphenyl)alkanone thus produced is then subjected to catalytic hydrogenation over palladium-on-carbon to produce the corresponding (2,4-dihydroxyphenyl)alkanone which exists principally in the form of its hemiketal. The hemiketal is then converted to the corresponding C 1-4 alkyl, e.g., methyl, ketal by reaction with, for example a trialkyl orthoformte, such as trimethylorthoformate in a suitable solvent such as a C 1-4 alcohol, e.g., methanol, in the presence of concentrated sulfuric acid. The thus-produced alkyl ketal is then alkylated with the appropriate alkyl or aralkyl methane sulfonate or tosylate in the presence of anhydrous sodium or potassium carbonate in a suitable reaction-inert solvent such as N,N-dimethylformamide at a temperature of from about 75°-100° C. This method has the advantage of permitting the use of simpler compounds throughout the entire sequence of reactions. The O-alkylated oraralkylated/ketal is then deketalized by reaction with, for example, hydrochloric acid, to produce the corresponding (2-hydroxy-4-[O-(alk 2 ) n ]phenyl) alkanone which exists principally in the form of its hemiketal.
The 2-bromo-5-(Z-W substituted) phenol reactants are prepared by bromination of the appropriate 3-(Z-W substituted) phenol according to standard procedures as, for example, by treatment with bromine in carbon tetrachloride at a temperature of from about 20°-30° C. The necessary 3-(Z-W substituted) phenols, if not known compounds, are prepared by procedures illustrated herein. A convenient method for preparing such reactants wherein the Z moiety is alkylene or (alk 1 --O--(alk 2 ) n --comprises the Wittig reaction on an appropriate aldehyde such as 2-(3-hydroxyphenol)-2- methyl propionaldehyde, the hydroxy group of which is protected by benzyl ether formation. The said aldehyde is then treated with the appropriate alkyltriphenylphosphonium bromide, the alkyl group of which extends the propionaldehyde group to the desired length. In a typical procedure, the aldehyde reactant is added to a slurry of dimsyl sodium and alkyl triphenylphosphonium bromide in dimethyl sulfoxide at a temperature below 30° C., e.g. from about 10° to 30° C. When reaction is complete, the alkene substituted protected phenol is recovered by known methods. Hydrogenation of the alkene over palladium-on-carbon then affords the desired 3-(Z-W substituted)phenol. Judicious choice of the starting (3-hydroxyphenyl)-substituted aldehyde and alkyl triphenylphosphonium bromide reactants affords the required 3-(Z-W-substituted)phenol reactants.
A further procedure for making 3-(Z-W substituted) phenols wherein Z is alkylene or (alk 1 )--O--(alk 2 ) n --comprises the Wittig reaction on an appropriate phenolic aldehyde or ketone, e.g, 3-hydroxybenzaldehyde or a 3-(hydroxyphenyl)alkyl ketone, in which the phenolic hydoxy group is protected as by conversion to the benzyl, methyl or ethyl ether. By choice of appropriate reactants, compounds having straight or branched alkylene groups (Z) can be produced. When a ketone, e.g., 3-hydroxyacetaphenone is used as reactant, compounds wherein Z has a methyl group on the carbon atom adjacent to the phenyl group obtained.
Substitution of a methyl or ethyl group at other sites, e.g., the β-carbon atom of the alkylene group, is achieved by choice of the appropriate carboalkoxy alkylidene triphenylphosphorane, e.g., (C 6 H 5 ) 3 P+C(R')--COOC 2 H 5 . The unsaturated ester thus produced is reduced to the corresponding alcohol by reacton with lithium aluminum hydride, generally in the presence of a small amount of aluminum chloride. Alternatively, when the phenolic protecting group is other than benzyl (e.g. methyl), the alcohol is produced by catalytic reduction of the unsaturated ester using palladium-carbon, followed by treatment of the saturated ester thus produced with lithium aluminum hydride. Conversion of the alcohol thus produced to the corresponding tosylate or mesylate followed by alkylation of the tosylate or mesylate with an alkali metal salt of the appropriate HO--(alk 2 )--W reactant, and finally removal of the protecting group affords the desired resorcinol 3-(Z--W substituted) phenol.
A variation of the above sequence comprises bromination of the alcohol rather than converting it to a tosylate or mesylate. Phosphorous tribromide is a convenient brominating agent. The bromo derivative is then reacted with the appropriate HO--(alk 2 )--W in the presence of a suitable base (Williamson reaction).
The bromo compounds also serve as valuable intermediates for increasing the chain length of the alkylene moiety in the above sequence to give compounds wherein Z is --alkylene--W. The process comprises treating the bromo derivative with triphenyl phosphine to produce the corresponding triphenylphosphonium bromide. Reaction of the triphenylphosphonium bromide with the appropriate aldehyde or ketone in the presence of a base such as sodium hydride or n-butyl lithium affords an unsaturated derivative which is then catalytically hydrogenated to the corresponding saturated compound
An alternative method for introducing an alkyl or aralkyl group into the aromatic nucleus, and specifically such a group wherein the carbon atom adjacent the aromatic nucleus is a tertiary carbon atom, comprises acid catalyzed electrophilic substitution of guaiacol with a tertiary alcohol in the presence of an acid. e.g. methane sulfonic acid. The general procedure consists in reacting a mixture of methanesulfonic acid and equimolar amounts of guaiacol and tertiary alcohol at temperatures of from about 30° C. to about 80° C. until reaction is substantially complete. The product is isolated by pouring the reaction mixture onto ice followed by extraction with a suitable solvent such as methylene chloride. The 2-methoxy-4-alkyl phenol is then converted to the desired 3-alkyl phenol by removal of the phenolic hydroxy group. The process comprises converting the hydroxy group to a dialkyl phosphate group by reaction with a dialkyl chlorophosphonate, e.g. diethyl chlorophosphonate, or with diethyl phosphonate and triethylamine. Treatment of the dialkyl phosphate with lithium/ammonia followed by demethylation of the resulting alkylated methyl ether with boron tribromide or pyridine hydrochloride or other known demethylating agents affords the desired 3-alkylphenol.
Esters of compounds of formulae I and II wherein R 1 is alkanoyl or --CO--(CH 2 ) p NR 4 R 5 are readily prepared by reacting formulae I and II compounds wherein R 1 is hydrogen with the appropriate alkanoic acid or acid of formula HOOC--(CH 2 ) p --NR 4 R 5 in the presence of a condensing agent such as dicyclohexylcarbodiimide. Alternatively, they are prepared by reaction of a formula I or II compound with the appropriate alkanoic acid chloride or anhydride, e.g., acetyl chloride or acetic anhydride, in the presence of a base such as pyridine.
Phosphate esters are prepared by treating the appropriate compound of formula I or II with potassium hydride followed by dibenzylphosphorochloridate. Catalytic hydrogenation of the dibenzylphosphate ester affords the desired phosphate ester. Cautious neutralization with sodium or potassium hydroxide provides the corresponding sodium or potassium salts.
The analgesic properties of the compounds of this invention are determined by tests using nociceptive stimuli.
Tests Using Thermal Nociceptive Stimuli
(a) Mouse Hot Plate Analgesic Testing
The method used is modified after Woolfe and MacDonald, J. Pharmacol. Exp. Ther., 80, 300-307 (1944). A controlled heat stimulus is applied to the feet of mice on a 1/8-inch thick aluminum plate. A 250 watt reflector infrared heat lamp is placed under the bottom of the aluminum plate. A thermal regulator, connected to thermistors on the plate surface, programs the heat lamp to maintain a constant temperature of 57° C. Each mouse is dropped into a glass cylinder (61/2-inch diameter) resting on the hot plate, and timing is begun when the animal's feet touch the plate. The mouse is observed at 0.5 and 2 hours after treatment with the test compound for the first "flicking" movements of one or both hind feet, or until 10 seconds elapse without such movements. Morphine has an MPE 50 =4-5.6 mg./kg. (s.c.).
(b) Mouse Tail Flick Analgesic Testing
Tail flick testing in mice is modified after D'Amour and Smith, J. Pharmacol. Exp. Ther., 72, 74-79 (1941) using controlled high intensity heat applied to the tail. Each mouse is placed in a snug-fitting metal cylinder, with the tail protruding through one end. This cylinder is arranged so that the tail lies flat over a concealed heat lamp. At the onset of testing an aluminum flag over the lamp is drawn back, allowing the light beam to pass through the slit and focus onto the end of the tail. A timer is simultaneously activated. The latency of a sudden flick of the tail is ascertained. Untreated mice usually react within 3-4 seconds after exposure to the lamp. The end point for protection is 10 seconds. Each mouse is tested at 0.5 and 2 hours after treatment with morphine and the test compound. Morphine has an MPE 50 of 3.2-5.6 mg./kg. (s.c.).
(c) Tail Immersion Procedure
The method is a modification of the receptable procedure developed by Benbasset, et al., Arch. int. Pharmacodyn., 122, 434 (1959). Male albino mice (19-21 g.) of the Charles River CD-1 strain are weighed and marked for identification. Five animals are normally used in each drug treatment group with each animal serving as its own control. For general screening purposes, new test agents are first administered at a dose of 56 mg./kg. intraperitoneally or subcutaneously, delivered in a volume of 10 ml./kg. Preceding drug treatment and at 0.5 and 2 hours post drug, each animal is placed in the cylinder. Each cylinder is provided with holes to allow for adequate ventilation and is closed by a round nylon plug through which the animal's tail protrudes. The cylinder is held in an upright position and the tail is completely immersed in the constant temperature waterbath (56° C.). The endpoint for each trial is an energetic jerk or twitch of the tail coupled with a motor response. In some cases, the endpoint may be less vigorous post drug. To prevent undue tissue damage, the trial is terminated and the tail removed from the waterbath within 10 seconds. The response latency is recorded in seconds to the nearest 0.5 second. A vehicle control and a standard of known potency are tested concurrently with screening candidates. If the activity of a test agent has not returned to baseline values at the 2-hour testing point, response latencies are determined at 4 and 6 hours. A final measurement is made at 24 hours if activity is still observed at the end of the test day.
Test Using Chemical Nociceptive Stimuli
Suppression of Phenylbenzoquinone Irritant-Induced Writhing
Groups of 5 Carworth Farms CF-1 mice are pretreated subcutaneously or orally with saline, morphine, codeine or the test compound. Twenty minutes (if treated subcutaneously) or fifty minutes (if treated orally) later, each group is treated with intraperitoneal injection of phenylbenzoquinone, an irritant known to produce abdominal contractions. The mice are observed for 5 minutes for the presence or absence of writhing starting 5 minutes after the injection of the irritant. MPE 50 's of the drug pretreatments in blocking writhing are ascertained.
Tests Using Pressure Nociceptive Stimuli
Effect on the Haffner Tail Pinch Procedure
A modification of the procedure of Haffner, Experimentelle Prufung Schmerzstillender. Mittel Deutch Med. Wschr., 55, 731-732 (1929) is used to ascertain the effects of the test compound on aggressive attacking responses elicited by a stimulus pinching the tail. Male albine rats (50-60 g.) of the Charles River (Sprague-Dawley) CD strain are used. Prior to drug treatment, and again at 0.5, 1, 2 and 3 hours after treatment, a Johns Hopkins 2.5-inch "bulldog" clamp is clamped onto the root of the rat's tail. The endpoint at each trial is clear attacking and biting behavior directed toward the offending stimulus, with the latency for attack recorded in seconds. The clamp is removed in 30 seconds if attacking has not yet occurred, and the latency of response is recorded as 30 seconds. Morphine is active at 17.8 mg./kg. (i.p.)
Tests Using Electrical Nociceptive Stimuli
The "Flinch-Jump" Test
A modification of the flinch-jump procedure of Tenen, Psychopharmacologia, 12, 278-285 (1968) is used for determining pain thresholds. Male albino rats (175-200 g.) of the Charles River (Sprague-Dawley) CD strain are used. Prior to receiving the drug, the feet of each rat are dipped into a 20% glycerol/saline solution. The animals are then placed in a chamber and presented with a series of 1-second shocks to the feet which are delivered in increasing intensity at 30-second intervals. These intensities are 0.26, 0.39, 0.52, 0.78, 1.05, 1.31, 1.58, 1.86, 2.13, 2.42, 2.72 and 3.04 mA. Each animal's behavior is rated for the presence of (a) flinch, (b) squeak and (c) jump or rapid forward movement at shock onset. Single upward series of shock intensities are presented to each rat just prior to, and at 0.5, 2, 4 and 24 hours subsequent to drug treatment.
Results of the above tests are recorded as percent maximum possible effect (%MPE). The %MPE of each group is statistically compared to the %MPE of the standard and the predrug control values. The %MPE is calculated as follows: ##EQU1##
The compounds of the present invention are active analgesics via oral and parenteral administration and are conveniently administered in composition form. Such compositions include a pharmaceutical carrier selected on the basis of the chosen route of administrtion and standard pharmaceutical practice. For example, they can be administered in the form of tablets, pills, powders or granules containing such excipients as starch, milk sugar, certain types of clay, etc. They can be administered in capsules, in admixtures with the same or equivalent excipients. They can also be administered in the form of oral suspensions, solutions, emulsions, syrups and elixirs which may contain flavoring and coloring agents. For oral administration of the therapeutic agents of this invention, tablets or capsules containing from about 0.20 to about 250 mg. are suitable for most applications.
The physician will determine the dosage which will be most suitable for an individual patient and it will vary with the age, weight and response of the particular patient and the route of administrtion. Generally, however, the initial analgesic dosage in adults may range from about 1.0 to about 1500 mg. per day in single or divided doses. In many instances, it is not necessary to exceed 250 mg. daily. The favored oral dosage range is from about 1.0 to about 300 mg./day; the preferred range is from about 1.0 to about 100 mg./day. The favored parenteral dose is from about 1.0 to about 100 mg./day; the preferred range from about 1.0 to about 50 mg./day.
This invention also provides pharmaceutical compositions, including unit dosage forms, valuable for the use of the herein described compounds as analgesics and other utilities disclosed herein. The dosage form can be given in single or multiple doses, as previously noted, to achieve the daily dosage effective for a particular utility.
The compounds (drugs) described herein can be formulated for administration in solid or liquid form for oral or parenteral administration. Capsules containing drugs of this invention are prepared by mixing one part by weight of drug with nine parts of excipient such as starch or milk sugar and then loading the mixture into telescoping gelatin capsules such that each capsule contains 100 parts of the mixture. Tablets containing said compounds are prepared by compounding suitable mixtures of drug and standard ingredients used in preparing tablets, such as starch, binders and lubricants, such that each tablet contains from 0.20 to 250 mg. of drug per tablet.
Suspensions and solutions of these drugs are frequently prepared just prior to use in order to avoid problems of stability of the drug (e.g. oxidation) or of suspensions or solution (e.g. precipitation) of the drug upon storage. Compositions suitable for such are generally dry solid compositions which are reconstituted for injectable administration.
Their activity as diuretic agents is determined by the procedure of Lipschitz et al., J. Pharmacol., 197, 97 (1943) which utilizes rats as the test animals. The dosage range for this use is the same as that noted above with respect to the use of the herein described compounds as analgesic agents.
Antidiarrheal utility is determined by a modification of the procedure of Neimegeers et al., Modern Pharmacology-Toxicology, Willem van Bever and Harbans Lal, Eds., 7, 68-73 (1976). Charles River CD-1 rats (170-200 gms) are housed in group cages 18 hours before testing. The animals are fasted overnight with water available ad libitum prior to administration of castor oil. The test drug is administered subcutaneously or orally at a constant volume of 5 ml./kg. of body weight in a 5% ethanol, 5% Emulphor EL-620 (a polyoxyethylated vegetable oil emulsifying agent available from Antara Chemicals, New York, N.Y.), and 90% saline vehicle followed one hour later with a challenge of castor oil (one ml., orally). The animals are placed in small individual cages (20.5×16×21 cm.) having suspended wire floors. A disposable cardboard sheet is placed beneath the wire floors and examined one hour after castor oil challenge for the presence or absence of diarrhea. A vehicle/castor oil treatment group serves as control for each day's testing. Results are recorded as the number of animals protected at one hour post challenge. In general, the dosage levels for use of these compounds as antidiarrheal agents parallels those with respect to their use as analgesic agents.
The tranquilizer activity of the compounds of this invention is determined by orally administering them to rats at doses of from about 0.01 to about 50 mg./kg. of body weight and observing the subsequent decreases in spontaneous motor activity. The daily dosage range in mammals is from about 0.01 to about 100 mg.
Anticonvulsant activity is determined by subcutaneously administering the test compound to male Swiss mice (Charles River) weighing 14-23 g. in a vehicle of the type used for antidiarrheal utility. The mice are used in groups of five. The day before use, the mice are fasted overnight but watered ad lib. Treatments are given at volumes of 10 ml. per kg. via a 25 gauge hypodermic needle. Subjects are treated with the test compound and, one hour after challenge, electroconvulsive shock, 50 mA. at 60 Hz. administered transcorneally. Controls are simultaneously run in which the mice are given only the vehicle as control treatment. The electroconvulsive shock treatment produces tonic extensor convulsions in all control mice with a latency of 1.5-3 seconds. Protection is recorded when a mouse exhibits no tonic extensor convulsions for 10 seconds after administration of electroconvulsive shock.
Antianxiety activity is determined in a manner similar to that for evaulating anticonvulsant activity except that the challenge convulsant is pentylenetetrazole, 120 mg./kg. administered intraperitoneally. This treatment produces clonic convulsions in less than one minute in over 95% of control mice treated. Protection is recorded when the latency to convulse is delayed at least 2-fold by a drug pretreatment.
Sedative/depressant activity is determined by treating groups of six mice subcutaneously with various doses of test agents. At 30 and 60 minutes post treatment, the mice are placed on a rotorod for one minute and evaluated for their performance on the rotorod. Inability of the mice to ride the rotorod is taken as evidence of sedative/depressant activity.
EXAMPLE 1
4-[2-Benzyloxy-4-(1,1-dimethylheptyl)phenyl]-2-butanone
A solution of 3.89 g. (0.010 mol.) of 1-bromo-2-benzyloxy-4-(1,1-dimethylheptyl)benzene in 15 ml. of tetrahydrofuran is slowly added to 0.36 g. (0.015 mol.) of 70-80 mesh magnesium metal. The resultant mixture is refluxed for 20 minutes and is then cooled to -10° C. Cuprous iodide (0.115 g., 0.006 mol.) is added and stirring continued for 10 minutes. To the resultant mixture is slowly added a solution of 0.701 g. (0.010 mol.) of methyl vinyl ketone in 5 ml. of tetrahydrofuran at such a rate that the reaction temperature could be maintained below 0° C. The reaction mixture is stirred for 30 minutes longer (t<0° C.) and is then added to 100 ml. of 1N hydrochloric acid and 100 g. of ice. The quenched reaction is extracted three times with 150 ml. portions of ether. The combined ether extract is washed twice with 100 ml. portions of water, twice with 100 ml. portions of saturated sodium chloride, dried over magnesium sulfate and evaporated to an oil. The oil was purified via column chromatography on 180 g. of silica gel eluted with 20% ether-cyclohexane to yield 1.07 g. (28%) of the title compound as an oil.
PMR δ CDCl .sbsb.3 TMS 0.80 (m, terminal sidechain methyl), 1.22 (s, gem dimethyl), 2.03 (s, CH 3 CO), 2.72 (m, two methylenes), 5.00 (s, benzyl ether methylene), 6.6-6.8 (m, ArH), 6.90 (d, J=8 Hz, ArH) and 7.22 (bs, PhH).
The above procedure is repeated but using the appropriate alkenone as reactant in place of methyl vinyl ketone and the appropriate 1-bromo-2-benzyloxy-4-(Z-W)benzene to prepare:
4-[2-benzyloxy-4-(1,1-dimethylheptyl)phenyl]-2-pentanone as an oil (3.99 g., 66%) from 1.26 g. (0.0154 mol.) of 3-penten-2-one and 6.0 g. (0.0154 mol.) of 1-bromo-2-benzyloxy-4-(1,1-dimethylheptyl)benzene.
PMR: δ CDCl .sbsb.3 TMS 0.81 (m, terminal sidechain methyl), 1.24 (s, gem dimethyl), 2.00 (s, CH 3 CO), 2.65 (m, OCCH 2 ), 3.2-4.0 (m, benzylic methine), 5.07 (s, benzyl ether methylene), 6.85 (m, ArH), 7.07 (d, J=8 Hz, ArH) and 7.34 (bs, PhH).
IR: (CHCl 3 ) 1715, 1613 and 1575 cm -1 .
MS: m/e 394 (M + ), 337, 323 and 309.
EXAMPLE 2
4-[4-(1,1-Dimethylheptyl)-2-hydroxyphenyl]-2-butanone
A mixture of 0.5 g. (1.31 mmols.) of 4-[2-benzyloxy-4-(1,1-dimethylheptyl)phenyl]-2-butanone, 360 mg. of solid sodium bicarbonate, 100 mg. of 10% palladium-on-carbon and 10 ml. of ethanol is stirred under one atmosphere of hydrogen pressure for one hour. The reaction mixture is filtered through diamtomaceous earth with ethyl acetate and the filtrate evaporated to an oil. The oil is purified via column chromatography on 100 g. of silica gel eluted with 50% ether-cyclohexane to yield 247 mg. (93%) of the title compound as an oil.
PMR: δ CDCl .sbsb.3 TMS 0.82 (m, terminal sidechain methyl), 1.22 (s, gem dimethyl), 1.60 and 2.15 (s, ratio 1:3, hemiketal and ketone forms), 2.80 (bs, two methylenes) and 6.7-7.3 (m, ArH).
IR: (CHCl 3 ) 3636, 3571, 3289, 1706, 1623, 1603 and 1572 cm -1 .
MS: m/e 290 (M + ), 275, 272, 257, 205 and 187.
By means of the above procedure, the following compound is prepared from the appropriate compound of Example 1.
4-[4-(1,1-dimethylheptyl)-2-hydroxyphenyl]-2-pentanone (0.49 g., 35%) from 1.8 g. (4.60 mmols.) of 4-[2-benzyloxy-4-1,1-dimethylheptyl)phenyl]-2-pentanone; M.P. 79.5°-80.5° C. (from pentane).
PMR: δ CDCl .sbsb.3 TMS 0.84 (m, terminal sidechain methyl), 1.27 (s, gem dimethyl), 1.64 and 2.07 (s, hemiketal and methyl ketone methyls), 6.75-7.25 (m, ArH).
IR: (CHCl 3 ) 3571, 3333, 1706 (w), 1623 and 1572 cm -1 .
MS: m/e 304 (M + ), 289, 271, 247 and 219 cm -1 .
Analysis: Anal. Calc'd. for C 20 H 32 O 2 : C, 78.89; H, 10.59%. Found: C, 79.06; H, 10.56%.
EXAMPLE 3
4-[2-Benzyloxy-4-(1,1-dimethylheptyl)phenyl]-2-butanol
To a -15° C. solution of 0.5 g. (1.31 mmols.) of 4-[2-benzyloxy-4-(1,1-dimethylheptyl)phenyl]-2-butanone (the produce of Example 1) in 5 ml. of methanol is added 50 mg. (1.31 mmols.) of sodium borohydride. The reaction mixture is stirred for 30 minutes and is then added to 100 ml. of saturated sodium chloride-150 ml. ether. The ether extract is washed once with 100 ml. of saturated sodium chloride, dried over magnesium sulfate and evaporated to an oil. The oil is purified via column chromatography on 100 g. of silica gel eluted with 1:1 ether:cyclohexane to yield 419 mg. (84%) of the title compound as an oil.
PMR: δ CDCl .sbsb.3 TMS 0.8 (m, terminal sidechain methyl), 1.10 (d, J=7 Hz, carbinol methyl), 1.23 (s, gem dimethyl), 2.6-2.9 (m, two methylenes), 3.63 (sextet, carbinol methine), 5.00 (s, benzyl ether methylene), 6.8-7.3 (m, ArH) and 7.30 (bs, PhH).
In like manner, the 2-pentanone compound of Example 1 is reduced to give:
4-[2-benzyloxy-4-(1,1-dimethylheptyl)phenyl]-2-pentanol (273 mg., 15%) of diastereomer A and 825 mg. (45%) of diastereomer B, both as oils, from 1.8 g. (4.60 (mmols.) of 4-[2-benzyloxy-4-(1,1-dimethylheptyl)phenyl]-2-pentanone.
Diastereomer A:
PMR: δ CDCl .sbsb.3 TMS 0.85 (m, terminal sidechain methyl), 1.08 (d, J=6 Hz, methyl), 1.29 (s, gem dimethyl), 3.5 (m, carbinol and benzylic methines), 5.09 (s, benzyl ether methylene), 7.0 (m, ArH) and 7.40 (bs, PhH).
IR: (CHCl 3 ) 3497, 1613 and 1572 cm -1 .
MS: m/e 396 (M + ), 381, 311 and 91.
Diastereomer B:
PMR: δ CDCl .sbsb.3 TMS 0.85 (m, terminal sidechain methyl), 1.28 (s, gem dimethy), 3.40 (m, methine), 3.80 (m, methine), 5.10 (s, benzyl ether methylene), 6.90 (m, ArH), 7.17 (d, J=8 Hz, ArH) and 7.42 (bs, PhH).
IR: (CHCl 3 ) 3546, 1616 and 1575 cm -1 .
MS: m/e 396 (M + ), 381,311 and 91.
EXAMPLE 4
4-[4-(1,1-Dimethylheptyl)-2-hydroxyphenyl]-2-butanol
A mixture of 390 mg. (1.02 mmols.) of 4-[2-benzyloxy-4-(1,1-dimethylheptyl)phenyl]-2-butanol, 360 mg. of solid sodium bicarbonate, 100 mg. of 10% palladium-on-carbon and 10 ml. of ethanol is stirred under one atmosphere of hydrogen for 20 minutes. The reaction mixture is filtered through diatomaceous earth with ethyl acetate and evaporated to an oil. The oil is purified via rapid column chromatography on silica gel eluted with ether to give a quantitative yield of the title compound as an oil.
PMR: δ CDCl .sbsb.3 TMS 0.85 (m, terminal sidechain methyl), 1.25 (s, gem dimethyl), 1.62 (m, C-3 methylene), 2.6 (m, C-4 methylene), 3.9 (m, C-2 methine and two OH), 6.90 (dd, J=8 and 2 Hz, ArH), 6.86 (d, J=2 Hz, ArH) and 7.02 (d, J=8 Hz, ArH).
IR: (CHCl 3 ) 3597, 3300, 1629 and 1575 cm -1 .
MS: m/e 292 (M + ), 274, 233, 207 and 189.
Similarly, the following compounds are prepared from corresponding benzyl ethers:
4-[4-(1,1-dimethylheptyl)-2-hydroxyphenyl]-2pentanol diastereomer A, (179 mg., 98%) from diastereomer A of 4-[2-benzyloxy-4-(1,1-dimethylheptyl)phenyl]-2-pentanol (236 mg., 0.595 mmol.) as an oil.
PMR: δ CDCl .sbsb.3 TMS 0.85 (m, terminal sidechain methyl), 1.28 (s, gem dimethyl), 3.50 (m, carbinol and benzylic methine), 6.82 (d, J=2 Hz, ArH), 6.84 (dd, J=8 and 2 Hz, ArH) and 7.16 (d, J=8 Hz, ArH).
IR: (CHCl 3 ) 3610, 3333, 1634 and 1577 cm -1 ,
MS: m/e 306 (M + ), 291, 288, 273, 221 and 203.
Anal. Calc'd. for C 20 H 34 O 2 : C, 78.38; H, 11.18%. Found: C, 78.26; H, 11.07%. 4-[4-(1,1-dimethylheptyl)-2-hydroxyphenyl]-2-pentanol diastereomer B (quantitative yield) from 804 mg. (2.03 mmols.) of 4-[2-benzyloxy-4-(1,1-dimethylheptyl)phenyl]-2-pentanol diastereomer B, as an oil.
PMR: δ CDCl .sbsb.3 TMS 0.85 (m, terminal sidechain methyl), 3.19 (sextet, J=6 Hz, benzylic methine), 3.99 (sextet, J=6 Hz, carbinol methine), 6.82 (d, J=2 Hz, ArH), 6.88 (dd, J=8 and 2 Hz, ArH) and 7.13 (d, J=8 Hz, ArH).
IR: (CHCl 3 ) 3610, 3378, 1629 and 1575 cm -1 .
MS: m/e 306 (M + ), 291, 288, 221 and 203.
EXAMPLE 5
The compounds tabulated below are prepared from appropriate 2-bromo-5-(Z-W substituted)phenol benzyl ethers and α,β-unsaturated reactants R 4 --CO--CH═CR 2 R 3 according to the procedures of Examples 1-2. They exist principally in the hemiketal form.
__________________________________________________________________________ ##STR8##R.sub.4 R.sub.2 R.sub.3 Z W__________________________________________________________________________n-C.sub.3 H.sub.7 H H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 Hi-C.sub.3 H.sub.7 H H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 Ht-C.sub.4 H.sub.9 H H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 Hn-C.sub.6 H.sub.13 H H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HC.sub.6 H.sub.5 H H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H(CH.sub.2)C.sub.6 H.sub.5 H H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H(CH.sub.2).sub.4 C.sub.6 H.sub.5 H H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HC.sub.2 H.sub.5 CH.sub.3 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 Hn-C.sub.4 H.sub.9 CH.sub.3 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HC.sub.6 H.sub.5 CH.sub.3 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 C.sub.2 H.sub.5 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 n-C.sub.3 H.sub.7 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 n-C.sub.6 H.sub.13 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 C.sub.6 H.sub.5 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 C.sub.6 H.sub.5 CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HC.sub.2 H.sub.5 n-C.sub.3 H.sub.7 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 i-C.sub.3 H.sub.7 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HC.sub.2 H.sub.5 i-C.sub.3 H.sub.7 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.2 C.sub.6 H.sub.5 n-C.sub.4 H.sub.9 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.2 C.sub.6 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 C(CH.sub. 3).sub.2 (CH.sub.2).sub.6 HCH.sub.2 C.sub.6 H.sub.5 CH.sub.2 C.sub.6 H.sub.5 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.2 C.sub.6 H.sub.5 C.sub.6 H.sub.5 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H(CH.sub.2).sub.4 C.sub.6 H.sub.5 CH.sub.3 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H(CH.sub.2).sub.4 C.sub.6 H.sub.5 n-C.sub.6 H.sub.13 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H(CH.sub.2).sub.3 C.sub.6 H.sub.5 n-C.sub.4 H.sub.9 CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 H CH.sub.3 CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.5 HCH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.5 Hn-C.sub.3 H.sub.7 H CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.8 HCH.sub.3 H CH.sub.3 (CH.sub.2).sub.13 Hn-C.sub.6 H.sub.13 H CH.sub.3 (CH.sub.2).sub.13 Hi-C.sub.3 H.sub.7 H CH.sub.3 (CH.sub.2).sub.9 HC.sub.6 H.sub.5 CH.sub.3 CH.sub.3 (CH.sub.2 ).sub.11 H(CH.sub.2).sub.3 C.sub.6 H.sub.5 H CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.10 HCH.sub.3 H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 4-FC.sub.6 H.sub.4sec-C.sub.4 H.sub.9 C.sub.2 H.sub.5 H CH(CH.sub.3)(CH.sub.2).sub.4 4-ClC.sub.6 H.sub.4C.sub.2 H.sub.5 n-C.sub.5 H.sub.11 H (CH.sub.2).sub.9 C.sub.6 H.sub.5C.sub.6 H.sub.5 CH.sub.3 H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4CH.sub.3 (CH.sub.2).sub.3 C.sub.6 H.sub.5 H C(CH.sub.3).sub.2 (CH.sub.2).sub.10 C.sub.6 H.sub.5CH.sub.3 H CH.sub.3 O(CH.sub.2).sub.4 C.sub.6 H.sub.5i-C.sub.6 H.sub.13 H CH.sub.3 OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5C.sub.6 H.sub.5 CH.sub.3 CH.sub.3 OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5(CH.sub.2).sub.2 C.sub.6 H.sub.5 C.sub.2 H.sub.5 H O(CH.sub.2).sub.3 4-ClC.sub.6 H.sub. 4CH.sub.3 C.sub.6 H.sub.5 H O(CH.sub.2).sub.4 C.sub.6 H.sub.5n-C.sub.6 H.sub.13 (CH.sub.2).sub.4 C.sub.6 H.sub.5 H O(CH.sub.2).sub.4 C.sub.6 H.sub.5C.sub.6 H.sub.5 C.sub.6 H.sub.5 H O(CH.sub.2).sub.10 4-ClC.sub.6 H.sub.4CH.sub.2 C.sub.6 H.sub.5 C.sub.6 H.sub.5 CH.sub.3 OCH(CH.sub.3)(CH.sub.2).sub.8 C.sub.6 H.sub.5CH.sub.3 (CH.sub.2).sub.4 C.sub.6 H.sub.5 H OCH(CH.sub.3)(CH.sub.2).sub.10 4-FC.sub.6 H.sub.4C.sub.6 H.sub.5 C.sub.6 H.sub.5 H O(CH.sub.2).sub.13 C.sub.6 H.sub.5(CH.sub.2).sub.2 C.sub.6 H.sub.5 i-C.sub.6 H.sub.13 H O(CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 H (CH.sub.2).sub.3 O(CH.sub.2).sub.3 Hn-C.sub.6 H.sub.13 CH.sub.3 H (CH.sub.2).sub.4 OCH.sub.2 HCH.sub.3 CH.sub.3 H (CH.sub.2).sub.13 O Hn-C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 H C(CH.sub.3).sub.2 (CH.sub.2).sub.2 O(CH.sub.2).sub.4 HC.sub.6 H.sub.5 H CH.sub. 3 (CH.sub.2).sub.4 O C.sub.6 H.sub.5CH.sub.3 C.sub.6 H.sub.5 H (CH.sub.2).sub.6 O(CH.sub.2).sub.7 HCH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.4 C.sub.6 H.sub.5 H CH(CH.sub.3)(CH.sub.2).sub.2 O C.sub.6 H.sub.5n-C.sub.6 H.sub.13 H H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HC.sub.6 H.sub.5 H H C(CH.sub.3).sub.2 (CH.sub.2).sub.7 HCH.sub.2 C.sub.6 H.sub.5 H H CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.5 H(CH.sub.2).sub.3 C.sub.6 H.sub.5 H H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5t-C.sub.4 H.sub.9 H H O(CH.sub.2).sub.4 C.sub.6 H.sub.5C.sub.6 H.sub.5 H H (CH.sub.2).sub.6 O 4-FC.sub.6 H.sub.4CH.sub.2 C.sub.6 H.sub.5 H H (CH.sub.2).sub.13 O 4-FC.sub.6 H.sub.4(CH.sub.2).sub.4 C.sub.6 H.sub.5 H H (CH.sub.2).sub.6 O(CH.sub.2).sub.7 C.sub.6 H.sub.5i-C.sub.4 H.sub.9 H H CH O(CH.sub.2).sub.2 CH(CH.sub.3).sub.2 C.sub.6 H.sub.52-pyridyl H H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H3-pyridyl H H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H4-pyridyl H H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H4-pyridyl H CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H2-pyridyl CH.sub.3 CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H4-pyridyl n-C.sub.3 H.sub.7 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H2-pyridyl i-C.sub.6 H.sub.13 CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H4-pyridyl C.sub.6 H.sub.5 CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H3-pyridyl C.sub.6 H.sub.5 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H2-pyridyl CH.sub.2 C.sub.6 H.sub.5 CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H4-pyridyl (CH.sub.2).sub.3 C.sub.6 H.sub.5 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H4-pyridyl 4-pyridyl H O(CH.sub.2).sub.4 C.sub.6 H.sub.52-pyridyl 2-pyridyl H OCH(CH.sub.3)(CH.sub.2).sub. 3 C.sub.6 H.sub.5__________________________________________________________________________
EXAMPLE 6
The compounds of Example 5 are reduced and debenzylated according to the procedures of Examples 3 and 4 to produce diastereomeric compounds having the formula wherein R 2 , R 3 , R 4 , Z and W are as defined in Example 5: ##STR9##
EXAMPLE 7
4 -[2-Acetoxy-4-(1,1-dimethylheptyl)phenyl]-2-butanone
A solution of 2.0 g. of 4-[2-hydroxy-4-(1,1-dimethylheptyl)phenyl]-2-butanone in 15 ml. of pyridine is treated at 10° C. with 10 ml. acetic anhydride and the mixture stirred for 18 hours under nitrogen. It is then poured onto ice/water and acidified with dilute hydrochloric acid. The acidified mixture is extracted with ethyl acetate (2×100 ml.), the extracts combined, washed with brine and dried (MgSO 4 ). Evaporation under reduced pressure affords the title product as an oil.
Similarly, the remaining compounds of this invention of formulae I-II are converted to their monoacetoxy esters (of the phenolic hydroxy group) and by substitution of anhydrides of propionic, butyric and valeric acid for acetic anhydride, to the corresponding ester derivatives.
EXAMPLE 8
2-Acetoxy-4-[2-acetoxy-4-(1,1-dimethylheptyl)phenyl]pentane Diastereomer A
To a solution of 2.0 g. of 4-[2-hydroxy-4-(1,1-dimethylheptyl)phenyl]-2-pentanol diastereomer A in 20 ml. of pyridine at 10° C. is added 20 ml. of acetic anhydride and the mixture stirred under nitrogen for 18 hours. It is then poured onto ice/water and acidified with dilute hydrochloric acid. The product is isolated by extraction with ethyl acetate (2×100 ml.). The combined extracts are washed with brine, dried (MgSO 4 ) and evaporated to give the diacetyl derivatives as an oil.
In like manner, the compounds of formula I wherein R is hydrogen and R 1 is hydrogen are converted to their diacyl derivatives. Replacement of acetic anhydride by propionic, butyric or valeric acid anhydrides affords the corresponding diacyl derivatives.
EXAMPLE 9
4-[2-(4-morpholinobutyryloxy)-4-(1,1-dimethylheptyl)phenyl]-2-pentanone
Dicyclohexylcarbodiimide (0.227 g., 1.1 mmole) and 4-N-piperidylbutyric acid hydrochloride (0.222 g., 1.0 mmole) are added to a solution of 4-[4-(1,1-dimethylheptyl)-2-hydroxyphenyl]-2-pentanone (0.303 g., 1.0 mmole) in methylene chloride (25 ml.) at room temperature. The mixture is stirred for 18 hours and is then cooled to 0° C. and filtered. Evaporation of the filtrate affords the title product as its hydrochloride salt.
Similarly, the reactant of this example and the remaining phenolic compounds of this invention are converted to the basic esters of the phenolic hydroxy group by reaction with the appropriate basic reagent. Esters wherein the R 1 moiety has the following values are thus prepared:
--COCH 2 NH 2
--CO(CH 2 ) 2 N(C 4 H 9 ) 2
--CO(CH 2 ) 2 --N--(methyl)piperazino
--COC(CH 3 ) 2 (CH 2 ) 2 --piperidino
--CO(CH 2 ) 3 N(C 2 H 5 ) 2
--COCH(CH 3 )(CH 2 ) 2 --morpholino
--CO(CH 2 ) 3 --pyrrolo
--CO(CH 2 ) 3 --pyrrolidino
--COCH 2 --pyrrolo
--CO(CH 2 ) 3 --piperidino
--CO(CH 2 ) 4 NH 2
--CO(CH 2 ) 3 NH(C 3 H 7 )
--CO(CH 2 ) 2 --N--butylpiperazino
Careful neutralization of the hydrochloride salts affords the free basic esters which are converted to other acid addition salts according to the procedure of Example 10. In this manner, the hydrobromide, sulfate, acetate, malonate, citrate, glycolate, gluconate, succinate, sulfosalicylate and tartrate salts are prepared.
EXAMPLE 10
General Hydrochloride Salt Formation
Excess hydrogen chloride is passed into a solution of the appropriate compound of formulae I-II having a pyridyl group and the resulting precipitate separated and recrystallized from an appropriate solvent, e.g. methanol-ether (1:10).
The remaining compounds of formulae I-II which have a pyridyl group are converted to their hydrochlorides in like manner.
Similarly, the hydrobromide, sulfate, nitrate, phosphate, acetate, butyrate, citrate, malonate, maleate, fumarate, malate, glycolate, gluconate, lactate, salicylate, sulfosalicylate, succinate, pamoate, tartrate and embonate salts are prepared.
EXAMPLE 11
4[4-(1,1-Dimethylheptyl)-2-hydroxyphenyl]-2-butanol 2'-O-Hemisuccinate Ester Sodium Salt
To a 0° C. solution of 1.00 g. (3.14 mmoles) of 4-[4-(1,1-dimethylheptyl)-2-hydroxyphenyl]-2-butanol in 3 ml. of dichloromethane is added 0.383 g. (3.14 mmoles) of 4-N,N-dimethylaminopyridine. To the resultant solution is slowly added 0.314 g. (3.14 mmoles) of succinic anhydride in one ml. of dichlormethane. The reaction mixture is stirred for 4 hours at 0° C. and then 3.14 ml. of 1N hydrochloric acid is slowly added. The reaction mixture is stirred 5 minutes longer and then added to 100 ml. water-100 ml. dichloromethane. The dichloromethane extract is dried over magnesium sulfate and evaporated. The residue is dissolved in 5 ml. of ethanol and 3.14 ml. of 1 N sodium hydroxide in ethanol added. Addition of ether causes crystallization. Recrystallization from ethanol-ether yields the title compound.
Replacement of sodium hydroxide by potassium hydroxide in the above procedure affords the potassium salt.
By means of this procedure, the remaining compounds described herein are converted to their hemisuccinate esters.
EXAMPLE 12
4-[4-(1,1-Dimethylheptyl)-2-hydroxyphenyl]-2-butanol 2'-O-Phosphate Ester Monosodium Salt
To a 0° C. slurry of 0.126 g. (3.14 mmoles) of potassium hydride in 3 ml. of dimethylformamide is added a solution of 1.00 g. (3.14 mmoles) of 4-[4-(1,1-dimethylheptyl)-2-hydroxyphenyl]-2-butanol in 3 ml. of dimethylformamide. After gas evolution ceases (˜10 min.) 0.932 g. (3.14 mmoles) of dibenzylphosphorochloridate is slowly added. The reaction mixture is stirred for one hour and then added to 200 ml. ether-100 ml. water. The ether extract is washed with two 100 ml. portions of water, dried over magnesium sulfate and evaporated to a residue. The residue is mixed with 1.0 g. of 5% platinum on carbon and 25 ml. of ethanol and stirred under one atmoshere of hydrogen for 3 hours. The reaction mixture is filtered through diatomaceous earth and 3.14 ml. of 1 N sodium hydroxide in ethanol slowly added to the filtrate. Addition of ether causes crystallization of the product. Recrystallization from ethanol then yields the title compound.
Similarly, the remaining compounds described herein are converted to their phosphate ester monosodium salts and, by replacement of sodium hydroxide with potassium hydroxide, to their corresponding potassium salts.
EXAMPLE 13
One hundred mg. of 4-[4-(1,1-dimethylheptyl)-2-hydroxyphenyl]-2-butanol are intimately mixed and ground with 900 mg. of starch. The mixture is then loaded into telescoping gelatin capsules such that each capsule contains 10 mg. of drug and 90 mg. of starch.
EXAMPLE 14
A tablet base is prepared by blending the ingredients listed below:
Sucrose: 80.3 parts
Tapioca starch: 13.2 parts
Magnesium Stearate: 6.5 parts
Sufficient trans-4-[4-(1,1-dimethylheptyl)-2-hydroxyphenyl]-2-butanone is blended into this base to provide tablets containing 0.5, 1, 5, 10 and 25 mg. of drug.
EXAMPLE 15
Suspensions of 4-[4-(1,1-dimethylheptyl)-2-hydroxyphenyl]-2-pentanone are prepared by adding sufficient amounts of drug to 0.5% methylcellulose to provide suspensions having 0.1, 0.5, 1, 5 and 10 mg. of drug per ml.
PREPARATION A
2-(3-Benzyloxyphenyl)-2-methylpropionitrile
To a solution of 1500 ml. of dimethylsulfoxide saturated with methyl bromide is simultaneously added a solution of 294 g. (1.32 mole) of 2-(3-benzyloxyphenyl)acetonitrile in 200 ml. dimethyl sulfoxide and a solution of 420 ml. of 50% aqueous sodium hydroxide. Methyl bromide is continuously bubbled through the reaction mixture during the above addition (30 minutes) and then for 1.5 hours longer while the reaction temperature is maintained at ≦50° C. with ice cooling. The reaction mixture is added to 2 liters of water-2 kg. ice and the resultant mixture extracted four times with 1 liter of ether. The combined ether extracts are washed twice with one liter of water, once with one liter of saturated sodium choride, dried over magnesium sulfate and evaporated to yield 325 g. (98%) of product as an oil.
PMR: δ CDCl .sbsb.3 TMS 1.70 (s, methyl), 5.12 (s, methylene), 6.8-7.5 (m, ArH) and 7.45 (s, PhH).
IR: (CHCl 3 ) 2247, 1616 and 1603 cm -1 .
MS: m/e 251 (M 30 ), 236, 160 and 91.
PREPARATION B
2-(3-Benzyloxyphenyl)-2-methylpropionaldehyde
To a 15° C. solution of 325 g. (1.25 mole) of 2-(3-benzyloxyphenyl)-2-methylpropionitrile in 1.85 liters of tetrahydrofuran is added 1.6 moles of diisobutylaluminum hydride as a 1.3 M solution in hexane (reaction temperature is maintained at 15°-18° C.). The reaction mixture is allowed to warm to room temperaure and is stirred 2 hours longer. It is then quenched by addition to a solution of 170 ml. of concentrated sulfuric acid in 670 ml. of water (temperature ≦30° C.). The resultant mixture is allowed to warm to room temperature and is then stirred an additional 2 hours. The organic layer is separated and the aqueous phase extracted once with one liter of ether. The combined organic phase is washed with 500 ml. of water and 500 ml. of saturated sodium chloride, dried over magnesium sulfate and evaporated to yield 315 g. (99%) of the title product.
PMR: δ CDCl .sbsb.3 TMS 1.43 (s, methyls), 5.08 (s, methylenes), 6.8-7.5 (m, ArH), 7.4 (s, PhH) and 9.55 (s, aldehyde).
PREPARATION C
2-(3-Benzyloxyphenyl)-2-methyl-cis-oct-3-ene
To a 15° C. solution of 1.8 moles of dimsyl sodium (from sodium hydride and dimethyl sulfoxide) in 2 liters of dimethyl sulfoxide is added, portionwise, 768 g. (1.8 moles) of pentyltriphenylphosphonium bromide. The resultant slurry is stirred 15 minutes at 15°-20° C. and then 315 g. (1.24 moles) of 2-(3-benzyloxyphenyl)-2-methylpropionaldehyde is slowly added (reaction temperature ≦30° C.). The resultant mixture is stirred for 4 hours at room temperature and is then added to 6 liters of ice water. The quenched reaction is extracted four times with one liter portions of 50% ether-pentane. The combined extract is washed twice with one liter of water and once with one liter of saturated sodium chloride and is then dried over magnesium sulfate and evaporated to yield an oil. Crystallization of this oil in 50% etherpentane (to remove triphenylphosphine oxide), filtration and evaporation of the filtrate gives 559 g. of oil. The crude oil is purified via column chromatography on 2 kg. of silica gel eluted with 20% hexane-dichloromethane to yield 217 g. (57%) of 2-(3-benzyloxyphenyl)-2-methyl-cis-oct-3-ene.
PMR: δ CDCl .sbsb.3 TMS 0.75 (bt, J=6Hz, terminal methyl), 1.1 (m, two side-chain methylenes), 1.43 (s, gem dimethyl), 1.60 (m, allylic methylene), 5.09 (s, benzylic methylene), 5.28 (dt, J=12 and 6 Hz, vinyl H), 5.70 (dd, J=12 and 1 Hz, vinyl H), 6.7-7.5 (m, ArH) and 7.42 (s, PhH).
IR: (CHCl 3 ) 1610 and 1587 cm -1 .
MS: m/e 308 (M + ), 293, 274, 265, 251, 239, 225, 217 and 91.
similarly, 1-benzyloxy-3-(1,1-dimethyloct-2-enyl)benzene (13.5 g., 70%) is prepared from 15.75 g. (0.062 mol.) of 2-(3-benzyloxyphenyl)-2-methylpropionaldehyde and 37.5 g. (0.0899 mol.) of hexyltriphenylphosphonium bromide. The product is an oil.
PMR: δ CDCl .sbsb.3 TMS 0.78 (m, terminal sidechain methyl), 1.40 (s, gem dimethyl), 4.97 (s, benzyl ether methylene), 5.23 (m, vinyl H), 5.57 (d, J=11 Hz, vinyl H) and 6.6-7.4 (m, ArH and PhH).
IR: (CHCl 3 ) 1608 and 1583 cm -1 .
MS: m/e 322 (M + ), 307, 279, 274, 265 and 231.
PREPARATION D
2-(3-Hydroxyphenyl)-2-methyloctane
A mixture of 65 g. (0.211 mole) of 2-(3-benzyloxyphenyl)-2-methyl-cis-oct-3-ene and 7.5 g. of 10% palladium-on-carbon in 100 ml. of ethanol is hydrogenated for one hour on a Parr apparatus at 50 p.s.i. hydrogen pressure. Additional 7.5 g. portions of 10% palladium-on-carbon are added after one and two hours of reaction and the reaction continued for 12 more hours. The reaction mixture is filtered through distomaceous earth with ethanol and the filtrate evaporated to an oil. The oil is purified via column chromatography on one kg. of silica gel eluted with 50% hexane-dichloromethane to yield 105 g. (78%) of 2-(3-hydroxyphenyl)-2-methyloctane.
PMR: δ CDCl .sbsb.3 TMS 0.85 (bt, terminal methyl), 1-1.9 (m, methylenes), 1.29 (s, gem dimethyl), 4.98 (s, phenol H) and 6.6-7.4 (m, ArH).
IR: (CHCl 3 ) 3571, 3311 and 1592 cm -1 .
MS: m/e 220 (M + ), 205 and 135.
In like manner, 2-(3-hydroxyphenyl)-2-methylnonane is prepared in 82% (7.8 g.) yield from 13.0 g. (0.0406 mol.) of 1-benzyloxy-3-(1,1-dimethyl-oct-2-enyl)benzene. It is obtained as an oil having the characteristics:
PMR: δ CDCl .sbsb.3 TMS 0.85 (m, terminal methyl), 1.27 (s, gem dimethyl), 5.25 (bs, OH) and 6.6-7.4 (m, ArH).
IR: (CHCl 3 ) 3571, 3279, 1563 and 1527 cm -1 .
MS: m/e 234 (M + ), 219, 191, 178, 164, 149, 135 and 121.
PREPARATION E
2-(4-Bromo-3-hydroxyphenyl)-2-methyloctane
To a 0° C. solution of 110 g. (0.50 mole) of 2-(3-hydroxyphenyl)-2-methyloctane in 200 ml. of carbon tetrachloride is added dropwise a solution of 80 g. (0.50 mole) of bromine in 90 ml. of carbon tetrachloride (reaction temperature ≦30° C. with cooling). The reaction mixture is stirred an additional 15 minutes and is then evaporated to yield 150 g. (100%) of 2-(4-bromo-3-hydroxyphenyl)-2-methyloctane.
PMR: δ CDCl .sbsb.3 TMS 0.85 (bt, terminal methyl), 0.8-1.9 (m, methylenes), 1.28 (s, gem dimethyl), 5.4 (bs, phenolic H), 6.78 (dd, J=8 and 2Hz, C-6 ArH), 7.02 (d, J=2Hz, C-2 ArH) and 7.37 (d, J=8Hz, C-5 ArH).
In like manner, 2-(4-bromo-3-hydroxyphenyl)-2-methylnonane is prepared in 82% (8.5 g.) yield as an oil from 7.8 g. (0.033 mol.) of 2-(3-hydroxyphenyl)-2-methylnonane:
PMR: δ CDCl .sbsb.3 TMS 0.86 (m, terminal methyl), 1.27 (s, gem dimethyl), 5.50 (bs, OH), 6.83 (dd, J=8 and 2Hz, ArH), 7.08 (d, J=2Hz, ArH) and 7.43 (d, J=8 Hz, ArH).
IR: (CHCl 3 ) 3279, 1613, and 1587 cm -1 .
MS: m/e 314, 312 (M + ), 212, 210, 185 and 187.
PREPARATION F
2-(3Benzyloxy-4-bromophenyl)-2-methyloctane
To a -18° C. slurry of 23.0 g. (0.575 mole) of potassium hydride in 400 ml. of N,N-dimethylformamide is added over a 45 minute period a solution of 150 g. (0.5 mole) of 2-(4-bromo-3-hydroxyphenyl)-2-methyloctane in 400 ml. of N,N-dimethylformamide (reaction temperature ≦-15° C.). The reaction mixture is stirred 15 minutes longer after which a solution of 98.3 g. (0.575 mole) of benzyl bromide in 200 ml. of N,N-dimethylformamide is added. The mixture is then warmed to room temperature and stirred 30 minutes longer. It is quenched by addition to 6 liters of ice water. The quenched mixture is extracted six times with 500 ml. of ether. The combined extract is washed twice with one liter portions of water and once with one liter of saturated sodium chloride, dried over magnesium sulfate and evaporated to a quantitative yield of the title product.
PMR: δ CDCl .sbsb.3 TMS 0.85 (bt, terminal methyl), 0.8-2.0 (m, methylenes), 1.22 (s, gem dimethyl), 5.17 (s, benzylic methylene) and 6.7-7.6 (two multiplets, ArH and PhH).
IR: (CHCl 3 ) 1592 and 1575 cm -1 .
MS: m/e 390, 388, (M + ), 375, 373, 354, 352, 305, 303and 91.
And, 2-(3-benzyloxy-4-bromophenyl-2-methylnonane is prepared in 95% (10.4 g.) yield from 2-(3-hydroxy-4-bromophenyl)-2-methylnonane (8.5 g., 0.027 mol.), sodium hydride (0.744 g., 0.031 mol.) and benzyl bromide (5.3 g., 0.031 mol.) as an oil.
PMR: δ CDCl .sbsb.3 TMS 0.87 (terminal methyl), 1.23 (s, gem dimethyl), 5.18 (s, benzyl ether methylene), 6.8 (dd, J=8 and 2Hz, ArH), 6.97 (d, J=2Hz, ArH) and 7.43 (m, ArH and PhH).
IR: (CHCl 3 ) 1600 and 1575 cm -1 .
MS: m/e 404, 402 (M + ), 305, 303, 91.
The compounds tabulated below are prepared according to the procedures of Preparations C-F from appropriate reactants:
______________________________________ ##STR10##Z W______________________________________C(CH.sub.3).sub.2 (CH.sub.2).sub.2 HC(CH.sub.3).sub.2 (CH.sub.2).sub.10 HC(CH.sub.3).sub.2 (CH.sub.2).sub.4 C.sub.6 H.sub.5C(CH.sub.3).sub.2 (CH.sub.2).sub.4 4-pyridylC(CH.sub.3).sub.2 (CH.sub.2).sub.3 2-pyridylC(CH.sub.3).sub.2 (CH.sub.2).sub.10 C.sub.6 H.sub.5CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.6 H.sub.5CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4CH(C.sub.2 H.sub.5)(CH.sub.2).sub.4 4-FC.sub.6 H.sub.4(CH.sub.2).sub.5 H(CH.sub.2).sub.11 H(CH.sub.2).sub.13 H(CH.sub.2).sub.4 C.sub.6 H.sub.5(CH.sub.2).sub.8 H______________________________________
PREPARATION G
3-Benzyloxy-4-bromophenol
To a 0° C. slurry of 1.7 g. (42.5 mmoles) of potassium hydride in 35 ml of N,N-dimethylformamide is slowly added a solution of 7.22 g. (38.2 mmoles) of 4-bromoresorcinol. The resultant mixture is stirred for 30 minutes and then 4.54 ml. (38.2 mmoles) of benzyl bromide is slowly added. The reaction mixture is stirred 3 hours longer at 0° C. and then added to 200 ml. of cold water and 200 ml. of ether. The ether extract is washed twice with 200 ml. portions of water, dried over magnesium sulfate and evaporated to an oil. The crude oil is purified via column chromatography an 400 g. of silica gel eluted with 25% ether-pentane to yield (in order of elution) 2.2 g. (16%) of 2,4-dibenzyloxybromobenzene, 0.21 g. (2%) of 5-benzyloxy-2-bromophenol and 3.52 g. (33%) of 3-benzyloxy-4-bromophenol.
5-Benzyloxy- 2-bromophenol
PMR: δ CDCl .sbsb.3 TMS 4.98 (s, benzyl ether), 5.46 (bs, OH), 6.40 (dd, J=8 and 2Hz, ArH), 6.60 (d, J=2Hz, ArH), 7.17 (d, J=8Hz, ArH) and 7.33 (s, PhH).
IR: (CDCl 3 ) 3521, 3221, 1610 and 1600 cm -1 .
MS: m/e 280, 278 (M + ), 189, 187 and 91.
3-Benzyloxy-4-bromophenol
PMR: δ CDCl .sbsb.3 TMS 5.00 (s, benzyl ether methylene), 5.33 (bs, OH), 6.21 (dd, J=8 and 2Hz, ArH), 6.38 (d, J=2Hz, ArH) and 7.30 (m, ArH and PhH).
IR: (CHCl 3 ) 3546, 3257, 1603 and 1585 cm -1 .
MS: m/e 280, 278 (M + ) and 91.
PREPARATION H
2-Benzyloxy-4-[2-(5-phenylpentyloxy)]bromobenzene
A mixture of 3.50 g. (12.5 mmoles) of 3-benzyloxy-4-bromophenol, 3.48 g. (14.4 mmoles) of 2-(5-phenylpentyl)methanesulfonate and 5.17 g. (37.5 mmoles) of anhydrous potassium carbonate in 20 ml. of N,N-dimethylformamide is heated at 85° C. for 6 hours. It is then closed and added to 200 ml. of water and 200 ml. of ether. The organic extract is washed twice with 150 ml. portions of water, dried over magnesium sulfate and evaporated to an oil. The oil is purified via column chromatography on 400 g. of silica gel eluted with 2:1 pentane:methylene chloride to yield 4.39 g. (82%) of the desired product as an oil.
PMR: δ CDCl .sbsb.3 TMS 1.21 (d, J=6Hz, sidechain methyl), 1.7 (m, sidechain methylenes), 2.60 (m, sidechain benzyl methylene), 4.25 (m, sidechain methine), 5.00 (s, benzyl ether methylene), 6.22 (dd, J=8 and 2Hz, C-5 ArH), 6.39 (d, J=2Hz, C-3 ArH) and 7.30 (m, PhH and C-6 ArH).
IR: (CHCl 3 ) 1587 cm -1 . MS: 426, 424 (M + ), 280, 278 and 91.
The following compounds are similarly prepared from the appropriate mesylate CH 3 SO 3 --Z--W.
______________________________________ ##STR11##(alk.sub.2) W______________________________________(CH.sub.2).sub.4 4-FC.sub.6 H.sub.4(CH.sub.2).sub.8 C.sub.6 H.sub.5(CH.sub.2).sub.10 4-ClC.sub.6 H.sub.4CH(CH.sub.3)(CH.sub.2).sub.8 C.sub.6 H.sub.5CH(CH.sub.3)CH.sub.2 4-FC.sub.6 H.sub.4C(CH.sub.3).sub.2 (CH.sub.2).sub.3 C.sub.6 H.sub.5CH.sub.2 CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5CH(CH.sub.3)(CH.sub.2).sub.10 HC(CH.sub.3).sub.2 (CH.sub.2).sub.5 HC(CH.sub.3).sub.2 (CH.sub.2).sub.7 H(CH.sub.2).sub.13 H(CH.sub.2).sub.13 C.sub.6 H.sub.5CH(CH.sub.3)(CH.sub.2).sub.6 4-FC.sub.6 H.sub.4C(CH.sub.3).sub.2 (CH.sub.2).sub.10 4-FC.sub.6 H.sub.4(CH.sub.2).sub.12 C.sub.6 H.sub.5CH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 4-ClC.sub.6 H.sub.4C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H(CH.sub.2).sub.2 C(CH.sub.3).sub.2 (CH.sub.2).sub.2 H(CH.sub.2).sub.6 C.sub. 6 H.sub.5(CH.sub.2).sub.12 HCH(CH.sub.3)(CH.sub.2).sub.3 4-pyridyl(CH.sub.2).sub.2 4-pyridylCH(CH.sub.3)(CH.sub.2).sub.3 2-pyridyl(CH.sub.2).sub.5 3-pyridyl(CH.sub.2).sub.10 2-pyridylCH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-pyridyl______________________________________
PREPARATION I
1Bromo-2,4-dibenzyloxybenzene
A mixture of 75.0 g. (0.397 mol.) of 4-bromoresorcinol, 95.1 ml. (0.80 mol) of benzylbromide and 331 g. (2.4mol.) of anhydrous potassium carbonate in 400 ml. of N,N-dimethylformamide is stirred for 12 hours at 25° C. and for 4 hours at 85° C. The reaction mixture is cooled and added to one liter of ice-200 ml. pentane-100 ml. ether. The organic phase is washed with three 500 ml. portions of water, dried over magnesium sulfate and evaporated to an oil. The oil is rapidly chromatographed on 400 g. of silica gel eluted with 20% ether-pentane to yield 80 g of oil. The chromatographed oil is crystallized from pentane at 0° C. to yield 45.0 g. (30%) of the title compound, M.P. 37°-38° C.
PMR: δ CDCl .sbsb.3 TMS 5.0 (s, C-4 benzylether methylene), 5.08 (s, C-2 benzylether methylene), 6.45 (dd, J=8 and 2Hz, C-5H), 6.63 (d, J=2Hz, C-3H), 7.2-7.6 (m, PhH and ArH).
IR: (CHCl 3 ) 1605 and 1590 cm -1 .
MS: m/e 370 (M + ), 368 and 91.
Analysis: Anal. Calc'd for C 20 H 17 BrO 2 : C, 65.03; H, 4.64; Br, 21.65. Found: C, 64.95; H, 4.55; Br, 21.48.
PREPARATION J
2-(3-Methoxyphenyl)-5-phenylpentane
A solution of 1-bromopropylbenzene (51.7 g.) in ether (234 ml.) is added dropwise over a 2-hour period to a refluxing mixture of magnesium (7.32 g.) in ether (78 ml.). The reaction mixture is refluxed for 30 minutes longer and then a solution of 3-methoxy-acetophenone (41.6 g.) in ether (78 ml.) is added dropwise and the mixture heated to reflux for 1.5 hours. The reaction is quenched by addition of saturated ammonium chloride (234 ml.), the ether layer is separated and the aqueous phase extracted with ether (3×200 ml.). The combined ether extracts are dried over magnesium sulfate and concentrated under vacuum to yield an oil. The oil is hydrogenated in a mixture containing ethanol (300 ml.), concentrated hydrochloric acid (2 ml.) and 5% palladium-on-carbon (5 g.). The catalyst is filtered off and the ethanol removed under vacuum. The residue is distilled under vacuum to give the title product.
PREPARATION K
2-(3-Hydroxyphenyl)-5-phenylpentane
A mixture of 2-(3-methoxyphenyl)-5-phenylpentane (18.4 g.) and pyridine hydrochloride (94 g.) under nitrogen is heated to 190° C. for 2 hours with vigorous stirring. The reaction mixture is cooled, dissolved in 6N hydrochloric acid (200 ml.) and diluted with water to 600 ml. The aqueous solution is extracted with ethyl acetate (4×100 ml.), the ethyl acetate extracts dried over sodium sulfate and concentrated under vacuum to yield the crude product. The product is purified by silica gel chromatography.
The following compounds are prepared from appropriate reactants by the method of Preparation J and that of the above preparation:
______________________________________ ##STR12##Z W______________________________________CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.6 H.sub.5CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4CH(C.sub.2 H.sub.5)(CH.sub.2).sub.4 4-FC.sub.6 H.sub.4(CH.sub.2).sub.5 H(CH.sub.2).sub.11 H(CH.sub.2).sub.13 H(CH.sub.2).sub.4 C.sub.6 H.sub.5(CH.sub.2).sub.8 H______________________________________
Bromination of the above compounds according to the procedure of Preparation E affords the corresponding 4-bromo derivatives, e.g. 2-(4-bromo-3-hydroxyphenyl)-5-phenylpentane.
PREPARATION L
Ethyl 3-(3-Benzyloxyphenyl)crotonate (Wittig Reaction)
A mixture of 3-benzyloxyacetophenone (29.4 g., 0.13 mole) and carbethoxymethylenetriphenylphosphorane (90.5 g., 0.26 mole) is heated under a nitrogen atmosphere at 170° C. for 4 hours. The clear melt is cooled to room temperature, triturated with ether and the precipitate of triphenyl phosphine oxide removed by filtration. The filtrate is concentrated under vacuum to an oily residue which is chromatographed over silica gel (1500 g. ) and eluted with benzene:hexane solutions of increasing benzene concentration beginning with 40:60 and ending with 100% benzene. Concentration of appropriate fractions gives the product as an oily residue.
PREPARATION M
3-(3-Benzyloxyphenyl)butyl Tosylate
A solution of ethyl 3-(3-benzyloxyphenyl)crotonate (17.8 g., 60 mmole) in ether (250 ml.) is added to a mixture of lithium aluminum hydride (3.42 g., 90 mmole) and ether (250 ml.). Aluminum chloride (0.18 g., 1.35 mmole) is added and the mixture refluxed for 12 hours and then cooled. Water (3.4 ml.), sodium hydroxide (3.4 ml. of 6N) and water (10 ml.) are then added successively to the reaction mixture. The inorganic salts which precipitate are filtered off and the filtrate is then concentrated in vacuo to give the 3-(3-benzyloxyphenyl)butanol as an oil.
Tosyl chloride (11.1 g., 58.1 mmole) is added to a solution of 3-(3-benzyloxyphenyl)-1-butanol (14.5 g., 57 mmole) in pyridine (90 ml.) at -45° C. The reaction mixture is held at -35° C. for 18 hours and is then diluted with cold 2N hydrochloric acid (1500 ml.) and extracted with ether (5×200 ml.). The combined extracts are washed with saturated sodium chloride solution (4×250 ml.) and then dried (Na 2 SO 4 ). Concentration of the dried extract affords the product as an oil.
PREPARATION N
3-(3-Benzyloxyphenyl)-1-phenoxybutane
A solution of phenol (4.56 g., 48.6 mmole) in dimethylformamide (40 ml.) is added under a nitrogen atmosphere to a suspension of sodium hydride (2.32 g., 48.6 mmole) of 50% previously washed with pentane) in dimethylformamide (70 ml. at 60° C. The reaction mixture is stirred for one hour at 60°-70° C., after which a solution of 3-(3-benzyloxyphenyl)butyl tosylate (18.9 g., 46 mmole) in dimethylformamide (80 ml.) is added. The reaction mixture is stirred at 80° C. for a half hour and is then cooled to room temperature, diluted with cold water (2500 ml.) and extracted with ether (4×400 ml.). The combined extracts are washed successively with cold 2 N hydrochloric acid (2×300 ml.) and saturated sodium chloride solution (3×300 ml.) and then dried (Na 2 SO 4 ). Removal of the solvent under reduced pressure affords the product as an oil. The oil residue is dissolved in benzene and filtered through silica gel (100 g.). Concentration of the filtrate under reduced pressure gives the product as an oil.
Repetition of Preparations L through N but using the 3-benzyloxy derivatives of benzaldehyde, acetophenone or propiophenone, the appropriate carbethoxy (or carbomethoxy) alkylidenetriphenylphosphorane, and the appropriate alcohol or phenol affords the following compounds.
______________________________________ ##STR13##(alk.sub.1) n (alk.sub.2) W______________________________________(CH.sub.2).sub.3 1 (CH.sub.2).sub.3 H(CH.sub.2).sub.3 1 (CH.sub.2).sub.5 H(CH.sub.2).sub.5 1 (CH.sub.2).sub.8 H(CH.sub.2).sub.6 1 (CH.sub.2).sub.7 H(CH.sub.2).sub.3 1 (CH.sub.2).sub.7 H(CH.sub.2).sub.3 1 (CH.sub.2).sub.10 H(CH.sub.2).sub.10 1 (CH.sub.2).sub.2 HC(CH.sub.3).sub.2 (CH.sub.2).sub.2 1 (CH.sub.2).sub.4 H(CH.sub.2).sub.4 1 CH.sub.2 C.sub.6 H.sub.5(CH.sub.2).sub.6 0 -- C.sub.6 H.sub.5(CH.sub.2).sub.13 0 -- H(CH.sub.2).sub.6 0 -- H(CH.sub.2).sub.6 1 CH.sub.2 4-ClC.sub.6 H.sub.4(CH.sub.2).sub.6 0 -- 4-FC.sub.6 H.sub.4CH(CH.sub.3)(CH.sub.2).sub.2 0 -- C.sub.6 H.sub.5CH(CH.sub.3)(CH.sub.2).sub.3 0 -- C.sub.6 H.sub.5CH(CH.sub.3)(CH.sub.2).sub.6 0 -- H(CH.sub.2).sub.3 0 -- 4-pyridyl(CH.sub.2).sub.3 0 -- 3-pyridyl(CH.sub.2).sub.3 1 CH(CH.sub.3) 2-pyridylCH(CH.sub.3)(CH.sub.2).sub.2 1 (CH.sub.2).sub.4 4-pyridylCH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 1 CH(CH.sub.3) 2-pyridyl(CH.sub.2).sub.4 1 (CH.sub.2).sub.5 4-pyridyl(CH.sub.2).sub.8 1 (CH.sub.2).sub.5 4-pyridyl______________________________________
Bromination of the products according to the procedure of Preparation E affords the corresponding 2-bromo-5-[(alk 1 )-O-(alk 2 ) n -W]-phenolbenzyl ethers.
PREPARATION O
4-(3-Hydroxyphenyl)-1-(4-pyridyl)pentane
A mixture of 3-(3-methoxyphenyl)butyl triphenylphosphonium bromide (17.5 g., 35.4 mmoles) in dimethylsulfoxide (50 ml.) is added to 4-pyridinecarboxaldehyde (3.79 g., 35.4 mmoles) in tetrahydrofuran (40 ml.). The resulting mixture is then added dropwise to a slurry of 50% sodium hydride (1.87 g., 39 mmoles) in tetrahydrofuran (20 ml.) under a nitrogen atmosphere at 0°-5° C. Following completion of addition, the mixture is stirred for one hour at 0°-5° C. and then concentrated under reduced pressure. The concentrate is diluted with water (200 ml.) and then acidified with 6 N HCl. The aqueous acid solution is extracted with benzene (4×50 ml.) It is then made basic and extracted with ethyl acetate (3×50 ml.). Evaporation of the combined extracts after drying (MgSO 4 ) affords 4-(3-methoxyphenyl)-1-(4-pyridyl)-1-pentene as an oil.
Catalytic hydrogenation of the thus-produced pentene derivative in ethanol at 45 p.s.i. in the presence of Pd/C (1 g. of 10%) and concentrated HCl (1 ml.) affords the title product.
The pentane derivative thus obtained is demethylated by heating a mixture of the compound (25 mmoles) and pyridine hydrochloride (35 g.) under a nitrogen atmosphere at 210° C. for 8 hours. The hot mixture is poured into water (40 ml.) and the resulting solution made basic with 6 N sodium hydroxide. Water and pyridine are removed by distillation in vacuo. Ethanol (50 ml.) is added to the residue and the inorganic salts which precpitate are filtered off. The filtrate is concentrated in vacuo and the residue chromatographed on silica gel using as eluting agents 5% ethanol/benzene (4 liters), 10% ethanol/benzene (1 liter), 13% ethanol/benzene (1 liter), and 16% ethanol/benzene (5 liters). The product is isolated by concentration of appropriate fractions of the eluate.
The 3-(3-methoxyphenyl)butyltriphenylphosphonium bromide is prepared by refluxing a mixture of 1-bromo-3-(3-methoxyphenyl)butane (78.5 mmoles) and triphenyl phosphine (78.5 mmoles) in xylene (60 ml.) for 18 hours. The reaction mixture is then cooled to room temperature and filtered. The filter cake is washed with ether and the product dried in a vacuum desiccator.
Repetition of this procedure but using the appropriate bromo-(3-methoxyphenyl)alkane and the appropriate aldehyde or ketone affords the following compounds.
______________________________________ ##STR14##Z W______________________________________(CH.sub.2).sub.3 2-pyridyl(CH.sub.2).sub.4 4-pyridylCH(CH.sub.3)CH(CH.sub.3)CH.sub.2 3-pyridylCH(CH.sub.3)CH(CH.sub.3)CH.sub.2 4-pyridylCH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-pyridyl(CH.sub.2).sub.10 4-pyridyl______________________________________
Bromination of the above compounds according to the method of Preparation E gives the corresponding 2-bromo-5-(Z-W)-phenols.
PREPARATION P
3-Methoxy-α-methylstyrene Oxide
To a solution of dimethylsulfoxonium methylide (69.4 mmoles) in dimethyl sulfoxide (65 ml.) at room temperature is added solid 3-l -dimethoxyacetophenone (8.33 g., 55.5 mmoles). The reaction mixture is stirred for one hour at 25° C., for one-half hour at 50° C. and is then cooled. The mixture is diluted with water (50 ml.) and added to a mixture of ice water (200 ml.)--ether (250 ml.)--low boiling petroleum ether (25 ml.). The organic extract is washed twice with water (250 ml.), dried (MgSO 4 ) and evaporated to an oil which is fractionally distilled.
PREPARATION Q
2-(3-Methoxyphenyl)-2-hydroxypropyl-2-phenylethyl Ether
A mixture of dry 2-phenylethanol (30 ml., 251 mmoles) and sodium metal (690 mg., 30 mmoles) is heated at 110° C. for 30 minutes. The resulting 1 M solution of sodium 2-phenylethoxide is cooled to 60° C., 3-methoxy-α-methylstyrene oxide (1.69 g., 10.3 mmoles) added and the reaction heated 15 hours at 60° C. The reaction mixture is cooled and added to a mixture of ether and water. The ether extract is dried over magnesium sulfate and evaporated. Excess 2-phenylethanol is removed by vacuum distillation (b.p.˜65° C., 0.1 mm.). The residue is purified via column chromatography on silica gel 60 (300 g.) and eluted in 15 ml. fractions with 60% ether-pentane.
PREPARATION R
2-(3-Methoxyphenyl)propyl 2-Phenylethyl Ether
To a 0° C. solution of 2-(3-methoxyphenyl)-2-hydroxypropyl 2-phenylethyl ether (498 mg., 1.74 mmole) in pyridine (2 ml.) is added dropwise phosphorous oxychloride (477 μl., 5.22 mmole). The reaction is allowed to warm to 20° C. over a 1.5 hour period. It is then stirred for 1.5 hours at 20° C. and then added to ether (150 ml.) and 15% sodium carbonate (100 ml.). The organic phase is separated and washed with 15% sodium carbonate (3×50 ml.), dried over magnesium sulfate and evaporated to an oil. The oil is dissolved in absolute ethanol (15 ml.), 10% palladium-on-carbon (100 mg.) added and the mixture stirred under one atmosphere of hydrogen gas. When hydrogen uptake ceases the reaction is filtered through diatomaceous earth and the filtrate evaporated to an oil. The oil is purified via preparative layer chromatography on silica gel plates, eluted twice with 6:1 pentane:ether to yield the title compound.
PREPARATION S
2-(3-Hydroxyphenyl)propyl 2-Phenylethyl Ether
A mixture of 2-(3-methoxyphenyl)propyl 2-phenylethyl ether (176 mg., 0.65 mmole), pyridine (0.4 ml., 4.96 mmole) and dry pyridine hydrochloride (4 g., 34.6 mmole) is heated at 190° C. for 6 hours. The reaction mixture is cooled and added to a mixture of water (100 ml.) and ether (150 ml.). The ether extract is washed once with water (50 ml.) and, along with a second ether extract (50 ml.) of the aqueous phase, is dried over magnesium sulfate and evaporated to an oil. The oil is purified via preparative layer chromatography on silica gel plates, eluted six times with 30% ether-pentane to yield the title product.
The following compounds are prepared from appropriate alkanols by the methods of Procedures Q and R:
______________________________________ ##STR15##(alk.sub.2) W______________________________________(CH.sub.2).sub.7 H(CH.sub.2).sub.6 C.sub.6 H.sub.5(CH.sub.2).sub.5 HCH(CH.sub.3)CH.sub.2 HCH(CH.sub.3)(CH.sub.2).sub.5 H(CH.sub.2) 4-FC.sub.6 H.sub.4(CH.sub.2).sub.2 4-pyridyl(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4(CH.sub.2).sub.2 CH(CH.sub.3)(CH.sub.2).sub.3 HCH(CH.sub.3)CH.sub.2 HC(CH.sub.3).sub.2 CH.sub.2 H(CH.sub.2).sub.10 HCH.sub.2 C.sub.6 H.sub.5______________________________________
PREPARATION T
3-Methoxy-β-methylstyrene Oxide
To a -78° C. solution of diphenylsulfonium ethylide (1.0 mole) in tetrahydrofuran (one liter) is slowly added 3-methoxybenzaldehyde (1.0 mole). The reaction mixture is stirred at -78° C. for 3 hours and then allowed to warm to room temperature. It is then added to ether-water and the ether phase separated. The ether phase is washed with water, dried (MgSO 4 ) and evaporated. Fractional distillation of the residue gives the title product.
PREPARATION U
3-(3-Hydroxyphenyl)-2-propylbutyl Ether
To a solution of sodium butoxide in butanol (0.5 liters of 1M) is added 3-methoxy-β-methylstyrene oxide (6.33 mole). The mixture is heated for 18 hours at 70° C. and is then cooled and added to a mixture of ether-water. The ether solution is separated, dried (MgSO 4 ) and evaporated to give the crude product 2-(3-methoxyphenyl)-3-hydroxy-2-propylbutyl ether. It is purified by column chromatography on silica gel with ether-pentane elution.
By means of the procedure of Preparation R the title product is produced.
Similarly, the following are prepared from appropriate alcohols:
______________________________________ ##STR16##(alk.sub.2) W______________________________________(CH.sub.2).sub.2 H(CH.sub.2).sub.7 H(CH.sub.2).sub.3 C.sub.6 H.sub.5(CH.sub.2).sub.2 4-FC.sub.6 H.sub.4(CH.sub.2).sub.2 4-pyridylCH(CH.sub.3)(CH.sub.2).sub.2 HCH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 HCH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5CH.sub.2 H(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4______________________________________
PREPARATION V
1-Bromo-3-(3-methoxyphenyl)butane
A solution of phosphorous tribromide (5.7 ml., 0.06 mole) in ether (30 ml.) is added to a solution of 3-(3-methoxyphenyl)-1-butanol (30.0 g., 0.143 mole) in ether (20 ml.) at -5° C. to -10° C. and the reaction mixture stirred at -5° C. to -10° C. for 2.5 hours. It is then warmed to room temperature and stirred for an additional 30 minutes. The mixture is poured over ice (200 g.) and the resulting mixture extracted with ether (3×50 ml.). The combined extracts are washed with 5% sodium hydroxide solution (3×50 ml.), saturated sodium chloride solution (1×50 ml.) and dried (Na 2 SO 4 ). Removal of the ether and vacuum distillation of the residue affords the title product.
The following compounds are prepared from 3-methoxybenzaldehyde, 3-methoxyacetophenone and 3-methoxypropiophenone and the appropriate carbethoxyalkylidene triphenylphosphorane by the procedures of Preparations L, M and the above procedure.
______________________________________ ##STR17## Z______________________________________ (CH.sub.2).sub.3 (CH.sub.2).sub.4 CH(C.sub.2 H.sub.5)CH.sub.2 CH(CH.sub.3)CH.sub.2 CH(CH.sub.3)(CH.sub.2).sub.3______________________________________
PREPARATION W
β-(2-Pyridyl)vinyl phenyl ketone
A slurry of sodium hydride (50%, 2.4 g., 0.05 mole) in 100 ml. of dry 1,2-dimethoxyethane is cooled to 20° C. and diethyl phenacylphosphonate (11.4 g., 0.05 mole) added dropwisse with stirring. The mixture is stirred at room temperature until gas evolution ceases. Then, 2-pyridinecarboxaldehyde (5.36 g., 0.05 mole) is added dropwise at 20° C. The mixture is stirred for one hour at 20°-25° C. and then refluxed for one hour. It is then cooled, a large excess of water added and the product extracted with ether. The extract is dried (MgSO 4 ) and evaporated to give the product.
By means of this procedure, the following α,β-unsaturated ketones and are prepared from appropriate dialkyl (dimethyl or diethyl) acyl phosphonates [(CH 3 O) 2 P(O)--CH 2 COR 4 ] and appropriate aldehydes or ketones (R 2 R 3 CO).
______________________________________R.sub.4COCHCR.sub.2 R.sub.3R.sub.2 R.sub.3 R.sub.4______________________________________H H 2-pyridylH H 3-pyridylH H 4-pyridylH H CH.sub.2 C.sub.6 H.sub.5H H (CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 H 4-pyridyln-C.sub.4 H.sub.9 H 4-pyridyln-C.sub.3 H.sub.7 H 4-pyridyln-C.sub.6 H.sub.13 H 4-pyridylCH.sub.3 H 2-pyrdiyli-C.sub.6 H.sub.13 H 2-pyridylCH.sub.3 H 3-pyrdiyln-C.sub.5 H.sub.11 H 3-pyridylC.sub.6 H.sub.5 H 2-pyridylC.sub.6 H.sub.5 H 3-pyridylC.sub.6 H.sub.5 H 4-pyridylCH.sub.2 C.sub.6 H.sub.5 H 4-pyridyl(CH.sub.2).sub.3 C.sub.6 H.sub.5 H 4-pyridylCH.sub.2 C.sub.6 H.sub.5 H 3-pyridylCH.sub.2 C.sub.6 H.sub.5 H 2-pyridyl(CH.sub.2).sub.4 C.sub.6 H.sub.5 H 2-pyridyl4-pyridyl H 4-pyridyl4-pyridyl H 2-pyridly2-pyridyl H 2-pyridyl4-pyridyl H 3-pyridyl4-pyridyl H H2-pyridyl H H3-pyridyl H HC.sub.6 H.sub.5 H CH.sub.2 C.sub.6 H.sub.54-pyridyl H C.sub.6 H.sub.53-pyridyl H C.sub.6 H.sub.52-pyridyl H C.sub.6 H.sub.54-pyridyl H CH.sub.34-pyridyl H n-C.sub.3 H.sub.74-pyridyl H i-C.sub.6 H.sub.132-pyridyl H CH.sub.32-pyridyl H n-C.sub.4 H.sub.93-pyridyl H n-C.sub.3 H.sub.73-pyridyl H CH.sub.2 C.sub.6 H.sub.54-pyridyl H CH.sub.2 C.sub.6 H.sub.54-pyridyl H (CH.sub.2).sub.4 C.sub.6 H.sub.52-pyridyl H (CH.sub.2).sub.3 C.sub.6 H.sub.5H H C.sub.6 H.sub.5CH.sub.2 C.sub.6 H.sub.5 H CH.sub.2 C.sub.6 H.sub.5CH.sub.2 C.sub.6 H.sub.5 H (CH.sub.2).sub.3 C.sub.6 H.sub.5(CH.sub.2).sub.4 C.sub.6 H.sub.5 H CH.sub.2 C.sub.6 H.sub.5CH.sub.2 C.sub.6 H.sub.5 H C.sub.6 H.sub.5(CH.sub.2).sub.3 C.sub.6 H.sub.5 H C.sub.6 H.sub.5CH.sub.2 C.sub.6 H.sub.5 H CH.sub.3(CH.sub.2).sub.4 C.sub.6 H.sub.5 H CH.sub.3CH.sub.2 C.sub.6 H.sub.5 H n-C.sub.6 H.sub.13CH.sub.3 H CH.sub.2 C.sub.6 H.sub.5n-C.sub.4 H.sub.9 H CH.sub.2 C.sub.6 H.sub.5CH.sub.3 H (CH.sub.2).sub.4 C.sub.6 H.sub.5n-C.sub.6 H.sub. 13 H (CH.sub.2).sub.4 C.sub.6 H.sub.5n-C.sub.5 H.sub.11 H n-C.sub.6 H.sub.13i-C.sub.6 H.sub.13 H CH.sub.3n-C.sub.6 H.sub.13 H n-C.sub.6 H.sub.13CH.sub.3 CH.sub.3 CH.sub.3n-C.sub.4 H.sub.9 CH.sub.3 CH.sub.3CH.sub.3 CH.sub.3 n-C.sub.4 H.sub.9CH.sub.3 CH.sub.3 n-C.sub.6 H.sub.13C.sub.6 H.sub.5 CH.sub.3 CH.sub.3t-C.sub.4 H.sub.9 CH.sub.3 CH.sub.3CH.sub.3 CH.sub.3 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5C.sub.2 H.sub.5 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 C.sub.6 H.sub.5n-C.sub.6 H.sub.13 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 4-pyridyln-C.sub.4 H.sub.9 CH.sub.3 4-pyridyli-C.sub.6 H.sub.13 CH.sub.3 2-pyridylCH.sub.3 CH.sub.3 2-pyridylC.sub.6 H.sub.5 CH.sub.3 4-pyridyl4-pyridyl CH.sub.3 C.sub.6 H.sub.54-pyridyl CH.sub.3 4-pyridylCH.sub.2 C.sub.6 H.sub.5 CH.sub.3 2-pyridylC.sub.6 H.sub.5 CH.sub.3 n-C.sub.5 H.sub.11CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 C.sub.6 H.sub.5C.sub.6 H.sub.5 CH.sub.3 CH.sub.2 C.sub. 6 H.sub.5i-C.sub.3 H.sub.7 H CH.sub.3i-C.sub.3 H.sub.7 H C.sub.2 H.sub.5______________________________________ | Compounds useful for pharmacological and medicinal purposes having the formulae ##STR1## wherein R is H, C 1 -C 5 alkanoyl; R 1 is H, benzyl, C 1 14 C 5 alkanoyl, P(O)(OH) 2 , --CO(CH 2 ) 2 COOH or a basic acyl group; each of R 2 and R 4 is H, C 1 -C 6 alkyl, phenyl, pyridyl or (CH 2 ) y C 6 H 5 ; y is 1-4; R 3 is H or CH 3 ; Z is C 1 -C 13 alkylene or --(alk 1 ) m --O--(alk 2 ) n --; each of (alk 1 ) and (alk 2 ) is C 1 -C 13 alkylene with the proviso that the summation of carbon atoms in (alk 1 ) plus (alk 2 ) is not greater than 13; each of m and n is 0 or 1; and W is H, pyridyl, phenyl, fluorophenyl or chlorophenyl; intermediates therefor and methods for their preparation and use. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application No. 60/373,342 filed in the United States Patent Office on Apr. 5, 2002.
ORIGIN OF THE INVENTION
[0002] This invention was jointly made by employees of the United States Government and a contract employee during the performance of work under a NASA contract which is subject to the provisions of Public Law 95-517 (35 USC 202) in which the contractor has elected not to retain title and may be manufactured and used by or for the government for governmental purposes without the payment of royalties thereon or therefor.
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] The present invention relates generally to polyimides. It relates particularly to novel polyimides prepared from 2,3,3′,4′-biphenyltetracarboxylic dianhydride and aromatic diamines.
[0005] 2. Description of the Related Art
[0006] Since 1960, more attention has focused on polyimides than any other high performance/high temperature polymers. This is due primarily to the availability of polyimide monomers (particularly aromatic dianhydrides and diamines), the ease of polymer synthesis, and their unique combination of physical and mechanical properties. A significant amount of technology has been developed such that polyimides have found wide spread commercial use as adhesives, coatings, composite matrices, fibers, films, foams, membranes and moldings. Although there are many different synthetic routes to polyimides, the most popular is the reaction of an aromatic dianhydride with an aromatic diamine to form a soluble precursor polyamide acid (amic acid) that is subsequently chemically or thermally converted to the polyimide.
[0007] Over the years a tremendous amount of work has been performed on structure/property relationships in polyimides to obtain fundamental information that could be used to develop polyimides with unique combination of properties for demanding applications. More recently, nanoparticles (e.g. clays, carbon nanotubes, inorganic nanoparticles, etc.) have been incorporated within polyimides to enhance certain mechanical and physical properties.
[0008] The National Aeronautics and Space Administration has several space applications that currently use or are evaluating polyimides. These include thin films as membranes on antennas, concentrators, coatings on second-surface mirrors, solar sails, sunshades, thermal/optical coatings and multi-layer thermal insulation (MLI) blanket materials. Depending upon the application, the film will require a unique combination of properties. These may include atomic oxygen resistance, UV and VUV resistance, low color/low solar absorption, electron and proton resistance, tear/wrinkle resistance for packaging and deployment, and high mechanical properties (strength, modulus and toughness). Atomic oxygen resistance coupled with low color and UV stability has been introduced into polyimides by using phenylphosphine oxide containing monomers.
[0009] A significant amount of work has concentrated on the polyimide from the reaction of pyromellitic dianhydride and 4,4′-oxydianiline. Several products are based upon this polymer [poly(4,4′-oxydiphenylenepyromellitimide)] such as Pyre ML® wire enamel [I. S. T. (MA) Corporation], commercial films (Kapton® produced by Du Pont and Apical® produced by Kaneka) and a Du Pont molded product, Vespel®. Another well-known film made via a polyamide acid from the reaction of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) and 1,4-phenylenediamine is Upilex® S produced by Ube Industries, Ltd.
[0010] Despite all of the known polyimides with good properties, there exists a need for a novel polyimide having low color, good solubility, high thermal emissivity, low solar absorptivity and high tensile properties.
[0011] It is therefore a primary object of the present invention to provide novel polyimides with excellent properties.
[0012] It is another object of the present invention to provide novel polyimides made from 2,3,3′,4′-biphenyltetracarboxylic dianhydride and aromatic diamines.
[0013] It is yet another object of the present invention to provide novel polyimides having low color, good solubility, high thermal emissivity, low solar absorptivity and high tensile properties.
[0014] It is a further object of the present invention to provide novel polyimides suitable for thin films as membranes on antennas, concentrators, coatings on second-surface mirrors, solar sails, sunshades, thermal/optical coatings and MLI blanket materials.
SUMMARY OF THE INVENTION
[0015] According to the present invention, the forgoing and additional objects are obtained by synthesizing novel polyimides with 2,3,3′,4′-biphenyltetracarboxylic dianhydride (a-BPDA).
[0016] Specifically, the novel polyimides were obtained by reacting a-BPDA and a diamine selected from the group consisting of:
[0017] wherein X is selected from the group consisting of: SO 2 , C(CH 3 ) 2 , C(CF 3 ) 2 , C(CH 3 )phenyl, C(CF 3 )phenyl, 3,4′-O, 3,3′-O,
[0018] wherein Y is selected from the group consisting of CH 3 , phenyl, chloro and bromo;
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] For a more complete understanding of the present invention, including its objects and attending benefits, reference should be made to the Detailed Description of the Invention, which is set forth in detail below. This Detailed Description should be read together with the accompanying drawings, wherein:
[0020] [0020]FIG. 1 is a table providing monomer information.
[0021] [0021]FIG. 2 is a table providing further monomer information.
[0022] [0022]FIGS. 3, 4, 5 and 6 are tables presenting various polyimide structures and their properties.
[0023] [0023]FIG. 7 is a table presenting properties of a-BPDA polymers and films cured at different temperatures.
[0024] [0024]FIG. 8 is a table presenting properties of s-BPDA polymers and films cured at different temperatures.
[0025] [0025]FIG. 9 is a table presenting thermogravimetric analysis of films in nitrogen.
[0026] [0026]FIG. 10 is a table presenting solar absorptivity and thermal emissivity of polyimide films.
[0027] [0027]FIG. 11 is a graph representing light transmission of a-BPDA/1,3,3-APB film.
DETAILED DESCRIPTION OF THE INVENTION
[0028] Novel polyimides were made from a-BPDA and various aromatic diamines. The properties of a sample of a-BPDA polyimides were compared with those of polyimides prepared from the reaction of s-BPDA with the same aromatic diamines. Films of the a-BPDA polyimides had higher glass transition temperatures (Tgs) and less color than the corresponding s-BPDA polyimide films. Light transmission at 500 nm, solar absorptivity and thermal emissivity were also determined on certain films. Films of similar polyimides based upon a-BPDA and s-BPDA containing meta linkages and others containing para linkages were each cured at 250, 300, and 350° C. The films were characterized primarily by Tg, color and tensile properties. The a-BPDA meta linked polyimide films had tensile strengths and moduli higher than films of the s-BPDA para linked polyimide. The same phenomenon was not observed for the s-BPDA meta and para linked polyimides.
[0029] Monomers and other chemicals. The monomers in FIG. 1 and FIG. 2 were obtained from commercial sources, custom synthesis houses or synthesized in-house. The synthesis of monomer 10 is described below. Anhydrous (99.8%) N,N-dimethylacetamide (DMAC) was obtained from Aldrich and used as-received. Meta-Cresol was obtained from Fluka and redistilled under a nitrogen atmosphere. All other chemicals were obtained from commercial sources and used as-received.
[0030] Preparation of [2,5-bis(4-aminophenoxy)phenyl]diphenylphosphine oxide (monomer 10). Into a flame dried 2 L three neck round bottomed flask equipped with a mechanical stirrer, nitrogen gas inlet, pressure equalizing addition funnel, and drying tube were charged p-benzoquinone (30.16 g, 0.2790 mol) and toluene (750 mL). Diphenylphosphine oxide (56.42 g, 0.2790 mol) in toluene (250 mL) was added dropwise over 0.5 hour to the stirred solution at room temperature under nitrogen. The solution color changed from a dark brown to yellow with the formation of a gum. Upon further stirring, a grey solid formed. The solid was isolated, washed with toluene and then diethyl ether, and dried at 110° C. in flowing air to afford 74.0 g (85% crude yield) of an off-white solid. Recrystallization from ethanol afforded 2,5-dihydroxyphenyldiphenylphosphine oxide as a white solid (62.86 g, 73% recovery), m.p. 216-218° C.
[0031] 2,5-Dihydroxyphenyldiphenylphosphine oxide (27.62 g, 0.0890 mol), 1-chloro-4-nitrobenzene (28.05 g, 0.1780 mol), potassium carbonate (28.00 g, 0.2026 mol), DMAC (150 mL) and toluene (130 mL) were charged into a 1 L three neck round bottom flask equipped with a mechanical stirrer, nitrogen inlet, and a Dean-Stark trap. The mixture was heated to a gentle reflux while removing water via azeotropic distillation. After ˜4 hours, the toluene was removed from the reaction and the resultant solution heated at ˜165° C. for ˜16 hours. The reaction mixture was cooled to room temperature and then poured into water with vigorous stirring to afford a light brown solid. The crude solid was collected via filtration, washed twice with hot water, and air dried in an oven at 110° C. to afford 47.6 g (97% crude yield). Recrystallization from 2-ethoxyethanol afforded [2,5-bis(4-nitrophenoxy)phenyl]diphenylphosphine oxide as a yellow solid (39.21 g, 80% recovery), m.p. 239-242° C. 1 H NMR (DMSO-d6) δ: 6.8 (1H, d), 7.3 (1.5H, m), 7.5 (4H, m), 7.7 (2H, m), 8.05 (1H, d), 8.3 (1H, d). 13 C (DMSO-d6) ppm: 117.705, 118.186, 125.652, 126.325, 126.516, 126.820, 128.646, 128.808, 130.993, 131.296, 131.432, 132.107, 132.144, 132.410, 142.638, 142.903, 151.402, 151.577, 152.194, 152.226, 161.091, 162.177. Anal. Calcd for C 30 H 21 N 2 O 7 P: C, 65.22%; H, 3.83%; N, 5.07%; P, 5.61%. Found: C, 65.27%; H, 3.93%; N, 5.08%; P, 5.07%.
[0032] Into a 250 mL Parr hydrogenation flask were charged [2,5-bis(4-nitrophenoxy) phenyl]diphenylphosphine oxide (5.4 g, 0.0098 mol) and 1,4-dioxane (100 mL). The solution was warmed to effect dissolution with subsequent cooling to room temperature upon which 10% Pd/C (0.59 g) was added. The mixture was degassed prior to the introduction of hydrogen gas. The mixture was agitated under a hydrogen atmosphere for ˜24 hours at room temperature. After degassing the solution, the Pd/C was removed by filtration and the solution added to stirred water to afford an off-white solid. The crude solid was collected via filtration, washed with water, and dried at room temperature to afford 4.1 g (76% crude yield). Recrystallization from aqueous ethanol afforded [2,5-bis(4-aminophenoxy)phenyl]diphenylphosphine oxide as a tan solid (3.2 g, 80% recovery), m.p. 205-208° C. Anal. Calcd. for C 30 H 25 N 2 O 3 P: C, 73.16%; H, 5.12%; N, 5.69%; P, 6.29%. Found: C, 72.87%; H, 5.08%; N, 5.78%; P, 5.64%.
[0033] Polyamide Acid Preparation. The polyamide acids were prepared by placing the diamine in DMAC in a nitrogen atmosphere and stirring at room temperature to form a solution or slurry and subsequently adding a stoichiometric quantity of the dianhydride as a solid or in some cases as a slurry in DMAC. The solids content was adjusted to 20.0% (weight to weight, w/w) by the addition of DMAC. The reaction was stirred at ambient temperature for about 24 hours to form a viscous solution of the polyamide acid. The inherent viscosities of the polyamide acids are presented in FIGS. 3 - 6 .
[0034] A 30,000 g/mole endcapped polyimide was also prepared as follows. The polyamide acid was prepared as described above by upsetting the stoichiometry in favor of the diamine. After stirring the polyamide acid solution in a nitrogen atmosphere for about 24 hours at ambient temperature, a stoichiometric quantity of phthalic anhydride was added as the endcapping agent and the reaction was stirred for 6 hours to yield a polyamide acid with an inherent viscosity of 0.55 dL/g. The polyamide acid was thermally converted to polyimide as described in the “films” section below.
[0035] Polyimide Preparation in Meta-Cresol. Polyimides were prepared directly in m-cresol because the DMAC solutions of the polyamide acids would not form flexible films after curing at 250 or 300° C. The polyimides indicated in FIGS. 5 and 6 were prepared by adding the diamine to m-cresol containing a catalytic amount of isoquinoline and stirring under a nitrogen atmosphere for about 0.5 hour at room temperature. A stoichiometric quantity of dianhydride was added, the solids content was adjusted to 20.0% (w/w), the reaction was heated to 200° C. and stirred at 200° C. under a nitrogen atmosphere for 4-6 hours to form a viscous solution. The cooled polyimide solution was diluted with m-cresol and poured into methanol in a blender to precipitate a fibrous solid that was isolated, subsequently washed in boiling methanol twice and dried in air at 150° C. for 4 hours. The polyimides were dissolved in DMAC for inherent viscosity measurements and film casting. Polymer characterization is presented in FIGS. 5 and 6.
[0036] Films. Thin films (0.025 to 0.076 mm) were cast from polyamide acid and polyimide solutions in DMAC generally at 20% solids (w/w) content. In some cases the solutions of highly viscous polyamide acid solutions were diluted to 10-15% solid contents to allow bubbles to escape from the solution prior to film casting. The solutions were generally centrifuged and the decantate doctored onto clean, dry plate-glass and dried to a tack-free form in a low humidity air chamber overnight at room temperature. At 20% solids content, a wet film of 0.64 mm was doctored onto the glass plate. The films were stage-cured in forced air ovens by heating for 1 hour each at 100, 150, 200, and 250° C. and in some cases for an additional hour at 300° C. and another hour at 350° C. No attempt was made to control the heatup and cooldown rates of the ovens. In most cases, the, thin films were removed from the glass by immersion in water. Specimens (15.2 cm long, 0.51 cm wide, 0.038 to 0.056 mm thick) were cut with a JDC Precision Sample Cutter, Thwing-Albert Instrument Company. The tensile properties were determined following the general procedure in ASTM D882 using four to five specimens per test condition. The test specimen gauge length was 5.1 cm and the crosshead speed for film testing was 0.51 cm/minute using a Sintech 2 instrument with an Eaton Model 3397-139 11.4 kg load cell.
[0037] Other Characterization. Melting points were determined on a Thomas-Hoover capillary melting point apparatus and are uncorrected. Differential scanning calorimetry (DSC) was conducted on a Shimadzu DSC-50 thermal analyzer with the sample sealed in an aluminum pan. Glass transition temperatures (Tgs) were determined with DSC at a heating rate of 20° C./min with the Tg taken at the inflection point of the ΔT versus temperature curve. The crystalline melting points (Tms) were taken at the endothermic peak. Inherent viscosities (η inh ) were obtained on 0.5% (w/v) polyamide acid and polyimide solutions in DMAC at 25° C. Dynamic thermogravimetric analyses (TGA) were determined on films using a Seiko Instrument SSC 5200 at a heating rate of 2.5° C./min in a nitrogen atmosphere. Elemental Analyses were performed by Desert Analytics, Tucson, Ariz. The % light transmission through thin films was measured using a Perkin-Elmer Lambda 900 ultraviolet/visible/near infrared spectrometer. Solar absorptivities (a) of thin films were measured on an Aztek Model LPSR-300 spectroreflectometer with measurements taken between 250 to 2800 nm with a vapor deposited aluminum on Kapton® film (1 st surface mirror) as a reflective reference per ASTM E903-82. An Aztek Temp 2000A infrared reflectometer was used to measure the thermal emissivity (ε) of thin films.
[0038] Synthesis. Polyimides in FIGS. 3 - 6 were made via the polyamide acids from the reaction of an aromatic diamine with an aromatic dianhydride in DMAC at 20.0% solids content (w/w) or in m-cresol. Polymers 6-1/A and 6-1/S in FIG. 6 were made in m-cresol containing a catalytic amount of isoquinoline because polyamide acids with inherent viscosities >0.40 dL/g could not be obtained. Polymer 5-1/A in FIG. 5 was made via the polyamide acid but also in m-cresol in an attempt to obtain a higher molecular weight version. The synthesis in m-cresol provided an improvement in the molecular weight (inherent viscosities in DMAC increased from 0.72 dL/g for the polyamide acid to 0.83 dL/g for the polyimide). The polymer reported herein (5-1/S) was made via the polyamide acid and had an inherent viscosity in DMAC of 1.46 dL/g and a Tg of 280° C.
[0039] In preparing the various polymers, it was apparent that the reactivity of a-BPDA was significantly less than that of s-BPDA. Using the same diamine, the DMAC solution viscosity of the polyamide acid from s-BPDA increased substantially within 1 hour of reaction time whereas the viscosity of the polyamide acid from a-BPDA increased slowly over several hours and only in a few cases attained a solution viscosity comparable to that of the corresponding s-BPDA polyamide acid. The a-BPDA polyamide acid had a higher inherent viscosity than the analogous s-BPDA polyamide acid in only one set of polymers (polymers 4-2/A and 4-2/S in FIG. 4).
[0040] Glass Transition Temperatures. All of the polyamide acids in FIG. 3 from the reaction of diamine monomers 1-3 with a-BPDA and s-BPDA were made in high molecular weights as indicated by inherent viscosities of 0.95 to 2.13 dL/g. In FIG. 3, the a-BPDA polyimides had Tgs higher than the corresponding s-BPDA derived polyimides.
[0041] All of the polyamide acids in FIG. 4 were prepared in relatively high molecular weights with inherent viscosities of 0.73 to 2.20 dL/g. The same Tg trend was observed where all of the a-BPDA polyimides had Tgs higher than the s-BPDA polyimides. The diamines were meta catenated [monomer 4, 1,3-bis(3-aminophenoxy)benzene, 1,3,3-APB], meta para connected [monomer 5, 1,3-bis(4-aminophenoxy)benzene, 1,3,4-APB] and all para catenated [monomer 6, 1,4-bis(4-aminophenoxy)benzene, 1,4,4-APB].
[0042] [0042]FIG. 5 contains information on four polyimides containing trifluoromethyl groups from diamine monomers 7 and 8. Again the a-BPDA polyimides had Tgs higher than the s-BPDA polyimides. The rigid biphenylene polymers (5-1/A and 5-1/S) had Tgs significantly higher than the hexafluoroisopropylidene containing polymers.
[0043] Four polyimides containing the phenylphosphine oxide group from monomers 9 and 10 are reported in FIG. 6. The polyimides from 1,3,3-APB containing phenylphosphine oxide had Tgs about 30° C. less than polyimides from the more rigid 1,4,4-APB containing phenylphosphine oxide. The s-BPDA/1,4,4-APB phenylphosphine oxide polyimide failed to show any crystallinity apparently because the bulky diphenylphosphine oxide group disrupts the symmetry or regularity leading to ordered regions.
[0044] Films. In forming films, all of the polyamide acid and polyimide solutions in FIGS. 3 - 6 were doctored onto clean plate glass and stage-dried in a forced air oven for 1 hour each at 100, 150, 200 and 250° C. No intentional orientation was performed although some could have occurred while curing on the glass plates. The films were generally removed from the glass plates by immersion in water. In most cases, the film pulled glass from the surface of the plates, resulting in wrinkles. Although the Tg of several of the cured films exceeded 250° C., all of the initial films were cured at 250° because film color was of particular interest. Generally polymers are cured beyond the Tg because the molecular motion above the Tg allows tenaciously held molecules (e.g. solvent) to depart more easily and induces molecular packing. However, most films described herein cured at temperatures >250° C. in air tended to darken slightly in color. Near colorless films turned pale yellow while yellow films often became more intense yellow to orange. Some films were also cured at temperatures >250° C. Higher cure temperatures generally improved the tensile properties at the sacrifice of color. Curing in a nitrogen atmosphere would have been desired and probably would have helped reduce the color of some films but the ovens could not be properly rigged to provide a good nitrogen atmosphere. Since the presence of residual solvent and complete conversion of the polyamide acid to polyimide was a concern, a study was performed primarily to evaluate color, Tg, and tensile properties as a function of cure temperature.
[0045] All of the thin film tensile properties are reported as averages of 4 to 5 specimens. The coefficient of variation (COV) within 4 to 5 specimens for the tensile strengths was 2 to 10% while the COV for the moduli was about 0.2 to 8%. The COV for the elongation was high with values ranging from 7 to 50%. Film elongation is more sensitive to flaws within the test specimens caused by foreign particles (e.g. gel particles and dust), minor specimen misalignment during the test, wrinkles, etc. The 23° C. tensile properties, particularly strength and modulus, of the s-BPDA based polyimide films were higher, and in some cases significantly higher, than those of the a-BPDA based polyimide films with few exceptions. The highest overall 23° C. tensile properties are those for the film from polymer 6-2/S in FIG. 6 with strength of 151.0 MPa, modulus of 4.34 GPa and elongation of 31%. Polymer 4-2/S had the highest elongation (90%) while polymer 5-1/S gave the highest film modulus (5.18 GPa).
[0046] Films of a 30,000 g/mole phthalic anhydride endcapped polyimide of polymer 4-1/A in FIG. 4 were cured for 1 hour at 250° C. and 1 hour at 300° C. in air. The films showed slightly lower Tgs as mentioned previously but no visual difference in color when compared with the corresponding films in FIGS. 4 and 7. The thin film 23° C. tensile properties for the 250 and 300° C. cured films were virtually the same with strength of 100.0 MPa, modulus of 3.02 GPa and elongation of 4.0%. These values compare favorably with the tensile properties of the corresponding films in FIGS. 4 and 7.
[0047] Films Cured at Different Temperatures. Films of the four polyimides (4-1/A, 4-1/S, 4-3/A and 4-3/S) were cured on clean plate glass in a forced air oven for 1 hour each at temperatures of 250, 300 and 350° C. FIG. 7 contains information on the a-BPDA polyimides while FIG. 8 presents the data on the s-BPDA polyimides. In FIG. 7, the properties of two batches of the polyamide acids from a-BPDA/1,3,3-APB and a-BPDA/1,4,4-APB and their films cured at different temperatures are presented. Two batches of each of the two polymers were made to assess the reproducibility of the polyamide acid formation and polyimide properties. The inherent viscosity of the polyamide acids and the Tg, color and tensile properties of the films overall showed excellent reproducibility. The only large variation was the 43.7% elongation of one 350° C. cured film. As observed for the same polyimides in FIG. 4 (4-1/A and 4-3/A) and previously discussed, the tensile strength and especially the modulus of the a-BPDA/1,3,3-APB films were higher than those of the a-BPDA/1,4,4-APB films. The advantageous effects of curing at high temperatures are evident in the increase in Tgs for both polymers and the increase in film elongation for the 1,4,4-APB polymer.
[0048] In FIG. 8, the properties of the s-BPDA/1,3,3-APB and 1,4,4-APB polyamide acids and polyimide films are presented. Unlike that of the a-BPDA polymers, the s-BPDA polyimides showed the expected trend with the polyimide from the more rigid diamine (1,4,4-APB) having the higher tensile strength and modulus. Overall the properties of the 250° C. cured films in FIG. 8 compared favorably with the properties of the corresponding polymers (4-1/S and 4-3/S) in FIG. 4. The Tg and the elongation of the 1,4,4-APB polymer film increased with an increase in the cure temperature.
[0049] Thermogravimetric Analysis of Films. Samples of the films in FIG. 7 were characterized by TGA in nitrogen at a heating rate of 2.5° C./minute. Prior to TGA, the films were dried for 0.5 hour at 100° C. in nitrogen to remove absorbed moisture. The weight losses at different temperatures are reported in FIG. 9. This analysis was performed on films of 2 polymers cured at 250, 300, and 350° C. to determine the weight loss as a function of curing temperature. As presented in FIG. 10, very low weight losses (0.09 and 0.12%) were detected at 300° C. for the 250° C. cured films. The Tg of the a-BPDA/1,3,3-APB polyimide was 204° C. while the Tg for the a-BPDA/1,4,4-APB polyimide was 276° C. Hence curing the later film at 250° C., significantly less than the Tg, had virtually no effect upon retention of residual DMAC from film casting. The low weight losses at 300 and even 350° C. are presumably due to residual DMAC and/or water from further cyclodehydration of the amide acid to the imide. Other films were not characterized by TGA because it was assumed that the results would be similar. The excellent thermal stability of the polymers is obvious from the low weight losses at 500° C. at a heating rate of only 2.5° C./minute.
[0050] Color, Solar Absorptivity and Thermal Emissivity. In virtually all cases, the a-BPDA films had less color than the corresponding s-BPDA films. A few of the a-BPDA films cured at 250° C. were virtually colorless. The color designation in FIGS. 3 - 8 follows the trend from lightest to most intense or darkest: near colorless<pale yellow<light yellow<yellow<intense yellow<light orange<orange. The optical transparency or % light transmission through the film at a wavelength of 500 nm (the solar maximum) was determined for several films with the values reported in FIGS. 7 and 8. Film thickness varied from 0.38 to 0.046 mm. The thickest film was the a-BPDA/1,3,3-APB polyimide and it had the highest optical transparency. The a-BPDA films in FIG. 7 have a higher % light transmission than the corresponding s-BPDA films in FIG. 8. The films derived from the polyimides made with the flexible 1,3,3-APB diamine had greater light transmission than those made from the more rigid 1,4,4-APB diamine. Light transmission decreased as the cure temperature of the film increased and this is clearly shown in FIG. 11 for the a-BPDA/1,3,3-APB film in FIG. 7. The % light transmission at 500 nm for 4 other lightly colored films is 87 for 5-1/A (0.83 dL/g polymer), 85 for 5-1/S, 85 for 6-1/A and 75 for 6-1/S. Again the a-BPDA films had better optical transparency than the s-BPDA films.
[0051] Two of several properties of importance for space applications are absorptivity (α) and thermal emissivity (ε). Solar absorptivity pertains to the fraction of incoming solar energy that is absorbed by the film or more precisely a measure of light reflected by a second surface mirror between 250 and 2500 nm. The (ε) is a measure of the film to radiate energy from the surface or more specifically a measure of the infrared transmission of the film. Both of these properties were measured for films in FIGS. 4 - 6 and are reported in FIG. 10. Film thickness must be considered in comparing values. Depending upon the space application, the ratio of (α) to (ε) is more important than the individual values because it helps to determine the temperature a film will reach in a particular orbit. The ability of a material to undergo minimal changes in these properties upon exposure to radiation in space is of significant importance. In general, the a-BPDA polymeric films exhibited lower αs than films from s-BPDA polyimides. | The present invention relates generally to polyimides. It relates particularly to novel polyimides prepared from 2,3,3′,4′-biphenyltetracarboxylic dianhydride and aromatic diamines. These novel polyimides have low color, good solubility, high thermal emissivity, low solar absorptivity and high tensile strength. | 2 |
[0001] This application is a continuation in part of and claims priority from co-pending U.S. patent application Ser. No. 08/717,959, filed Sep. 23, 1996, which is a continuation in part of U.S. patent application Ser. No. 08/646,039, filed May 7, 1996, now U.S. Pat. No. 5,616,841.
FIELD OF THE INVENTION
[0002] The present invention relates generally to landfill metering devices, and more particularly to devices for measuring the flow of gases from landfills through gas extraction wells.
BACKGROUND
[0003] Waste products decompose in landfills, and after the free oxygen in the landfill is depleted, the waste product decomposition generates methane gas. It is desirable to recover this methane gas for environmental and safety reasons, and because subsequent to recovery the gas can be used as a source of energy.
[0004] Accordingly, systems have been developed to extract the methane. One such system is disclosed in U.S. Pat. No. 5,458,006, which discloses that its system and other such systems typically include a plurality of vertical pipes, referred to as “well casings”, that are vertically advanced at various locations into the landfill. The well casings are perforated along their lower-most segment, so that gas from the landfill can enter the casings. A network of horizontal pipes on or near the surface of the landfill interconnects the well casings, with a source of vacuum being in fluid communication with the network of horizontal pipes to evacuate the network and, hence, to evacuate methane gas from the well casings.
[0005] It happens that as methane gas is evacuated from a landfill, oxygenated air seeps back in. To avoid adversely affecting the generation of methane, however, the rate of oxygen inflow to the landfill must be controlled. Stated differently, to ensure continued methane gas production, the rate of gas extraction from the landfill and, thus, the rate of oxygen inflow to the landfill must be established to remain below a predetermined flow rate.
[0006] Not surprisingly, the methane gas extraction systems mentioned above typically provide for measuring gas flow rate through the well casings. In response to the measured rate, valves in the systems can be manipulated as appropriate to establish a desired flow rate through the well casings.
[0007] Several methods exist for measuring gas flow through the well casings. These methods typically involve measuring gas flow through a metering pipe that is in fluid communication with the well casing. One method simply involves measuring pressure at two points of the metering pipe that are longitudinally separated from each other. As is well understood, pressure head is inevitably lost in a pipe between an upstream location and a downstream location, with the magnitude of the pressure head loss being related to the gas flow rate through the pipe. Consequently, the pressure differential between any two longitudinally-spaced points in a pipe can be measured and then correlated to a gas flow rate.
[0008] Other methods for measuring gas flow rates through metering pipes include disposing an obstruction such as an orifice or a pitot tube in the pipe and then measuring the pressure differential across the orifice or at the taps of the pitot tube. The pressure differentials are then correlated to gas flow rates in accordance with widely understood principles. The use of orifices advantageously permits the use of relatively short metering pipes, vis-a-vis metering pipes which simply measure head loss.
[0009] With particular regard to orifices, the '006 patent mentioned above teaches a metering pipe having an upstream segment and a downstream segment, with the segments being joined by a pipe coupler and with only the uppermost end of the downstream segment protruding through a bushing above the well casing. The remainder of the metering pipe, including an orifice used to generate pressure signals for calculating flow rate, is located in the well casing. As contemplated by the '006 patent, the metering pipe segments are made of polyvinylchloride (PVC), and the coupler is a PVC coupler formed with an internal ridge against which the pipe segments are advanced. The orifice is formed in a separate disc-shaped orifice plate made of plastic or steel which is sandwiched between the ridge of the coupling and one of the pipe segments. Thus, flow through the pipe does not encounter only a flat disc-shaped planar surface of an orifice plate, but the orifice plate circumscribed by the ridge of the coupling which rises from the plane of the plate. The combined effect of the ridge and plate can cause flow turbulence and thus decreased measurement accuracy.
[0010] Not surprisingly, therefore, the '006 patent teaches that the pressure taps which are formed in the metering pipe segments upstream and downstream of the orifice must be longitudinally distanced from the orifice plate by distances that are multiples of the diameter of the metering pipe, to ensure accurate flow rate measurement. For this reason, pressure lines must extend through the bushing, requiring modification of the bushing and rather elaborate pressure line-bushing fittings to ensure that gas does not leak between the pressure lines and bushing. As a further undesirable result, it will readily be appreciated that such a structure inhibits easily raising or lowering the metering pipe as might be required, e.g., to compensate for well casing settling. Like the '006 patent, U.S. Pat. No. 4,562,744 to Hall et al. teaches that pressure sensors in an orifice meter must be distanced from the orifice plate such that “minimum swirl or turbulence exists”. As recognized by the present invention, however, a metering pipe orifice plate in combination with an internally ridged PVC coupling need not create turbulence. Further, the present invention recognizes that upstream and downstream pressure taps in a metering pipe containing an orifice need not be distanced from the orifice, but may be formed adjacent the orifice, thereby simplifying construction and design of the flow metering device while still ensuring accurate flow measurement.
[0011] Still further, the present invention understands that an easy and desirable way to engage flow sensor connectors to the ports of an orifice system is by threaded engagement. However, we have discovered that for some pipe sizes, the wall thickness is not sufficient to securely maintain and/or support the threaded engagement. The present invention addresses this problem.
SUMMARY OF THE INVENTION
[0012] A pipe coupling includes a single unitary hollow, preferably PVC body defining a fluid entrance segment and a fluid exit segment. An orifice plate is disposed in the body between the segments. The orifice plate defines an orifice and is made integrally with the body. Thus, the orifice plate and body preferably are one single unitary structure. An upstream port is closely juxtaposed with the orifice plate between the plate and the fluid entrance segment, and a downstream port is closely juxtaposed with the orifice plate between the plate and the fluid exit segment. As intended herein, the ports are configured for engaging respective flow rate metering connectors.
[0013] In the preferred embodiment, the coupling defines a longitudinal axis and the orifice defines a center that is distanced from the axis. Preferably, the ports are formed in the PVC body opposite the orifice relative to the axis.
[0014] In accordance with the present invention, the ports are internally threaded, to engage threaded flow sensor connectors. To support threaded engagement in the case of smaller couplings, the fluid entrance and exit segments of the coupling can define a first wall thickness, with the body including a port section between the entrance and exit segments and defining a second wall thickness greater than the first wall thickness. The ports are formed in the relatively thick port section. For butt-weld couplings, the port section has the same inner diameter as the fluid entrance and exit segments and a greater outer diameter, whereas for couplings designed to receive pipe segments in a surrounding relationship, the port section has the same outer diameter as the fluid entrance and exit segments, but a smaller inner diameter.
[0015] In another aspect, a fluid flow rate metering device includes an orifice plate defining an orifice and a plastic pipe body made integrally with the orifice plate. Threaded upstream and downstream sensor ports are formed in the body upstream and downstream, respectively, of the orifice plate for engaging connectors of a fluid flow rate sensor.
[0016] The details of the present invention, both as to its structure and operation, can best be understood in reference to the accompanying drawings, in which like reference numerals refer to like parts, and in which:
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] [0017]FIG. 1 is perspective view of the present coupling, shown in an exploded relationship with upstream and downstream landfill pipe segments;
[0018] [0018]FIG. 2 is a cross-sectional view as seen along the line 2 - 2 in FIG. 1;
[0019] [0019]FIG. 3 is perspective view of an alternate coupling for effecting a butt-weld connection between two relatively small pipes;
[0020] [0020]FIG. 4 is a cross-sectional view as seen along the line 4 - 4 in FIG. 3;
[0021] [0021]FIG. 5 is perspective view of an alternate coupling for effecting a telescoping connection between two relatively small pipes; and
[0022] [0022]FIG. 6 is a cross-sectional view as seen along the line 6 - 6 in FIG. 5.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0023] Referring initially to FIG. 1, a coupling is shown, generally designated 10 , for joining upstream and downstream pipes 12 , 14 of a landfill 16 while providing a means to sense fluid flow rate through the coupling 10 . The coupling 10 includes a unitarily-molded single piece cylindrical body 18 , preferably made of polyvinylchloride (PVC), although high density polyethylene (HDPE), fiberglass, or steel may be used.
[0024] As shown in FIG. 1, the body 18 defines a fluid entrance segment 20 and a fluid exit segment 22 , with the segments 20 , 22 being coaxial with each other. In cross-reference to FIGS. 1 and 2, the particular coupling 10 shown is intended to be butt-welded to pipes 12 , 14 that are about 4.5″ in diameter and that have cylindrical walls that are about a half inch thick. Accordingly, the segments 20 , 22 are butt attachment segments, each having an outer diameter D 1 of about 4.5″ and a wall thickness t 1 of about a half inch.
[0025] It can be appreciated in reference to FIGS. 1 and 2 that a disc-shaped orifice plate 24 is disposed in the body 18 between the segments 20 , 22 . The orifice plate 24 defines a preferably circular orifice 26 . In accordance with the present invention, the orifice plate 24 is made integrally with the body 18 , and the center of the orifice 26 is distanced from the longitudinal axis “A” of the coupling 10 as shown. Thus, the orifice 26 may not be concentric with the orifice plate 24 , but can be formed off center (eccentric) relative to the plate 24 , although concentric orifices can be used. In any case, it may now be understood that with the combination of structure shown in FIGS. 1 and 2, a flat planar surface is presented completely across the passageway of the coupling 10 both upstream and downstream of the orifice plate 24 . The present invention is thus in contrast to, e.g., the above-mentioned '006 patent, in which the ridge of the coupling overlaps the orifice plate to present an interrupted surface to fluid flow and consequently to cause turbulence and concomitant reduced flow rate measurement accuracy. Still further, the present orifice plate 24 facilitates the close juxtaposition of the ports as described below.
[0026] To facilitate sensing pressure on the upstream and downstream sides of the orifice plate 24 (and, hence, to determine fluid flow rate through the coupling 10 ), upstream and downstream ports 28 , 30 are respectively formed in the coupling 10 on opposite sides of the orifice plate 24 from each other. Both ports 28 , 30 are formed opposite the orifice 26 relative to the longitudinal axis “A” of the coupling 10 . Preferably, each port 28 , 30 has a diameter of about one sixteenth of an inch to one quarter of an inch ({fraction (1/16)}″-¼″). Importantly, the ports 28 , 30 are closely juxtaposed with the orifice plate 24 , i.e., the ports 28 , 30 are located within a few millimeters of the orifice plate 24 , in any case as close as possible to the plate 24 . Furthermore, the ports 28 , 30 are internally threaded from the outer surface 31 a of the coupling inwardly toward, but not completely to, the inner surface 31 b of the coupling, for purposes to be shortly disclosed.
[0027] Taking the upstream port 28 shown in FIGS. 1 and 2 as an example, the port 28 can define an oblique angle with respect to the radial axis “R” of the coupling 10 . Upstream and downstream hollow pressure sensor connectors 32 , 34 are threadably engaged with the ports 28 , 30 and thus are in fluid communication with the fluid passageway of the coupling 10 upstream and downstream, respectively, of the orifice plate 24 . Each sensor connector 32 , 34 is respectively engaged with a pressure sensor 36 , 38 , with the sensors 36 , 38 being associated with a flow meter 40 for providing a signal or other indication of fluid flow rate through the orifice 26 by means well-established in the art.
[0028] It may now be appreciated that owing to the above-described combination of structure, the ports of the present invention need not be distanced from the orifice plate 24 . Instead, the ports 28 , 30 are closely juxtaposed with the orifice plate 24 and are integrated into the coupling 10 , resulting in a compact structure that establishes the present flow metering function, without deleterious measurement effects due to flow turbulence arising. In other words, the present cooperation of structure avoids the need to distance the ports from the orifice to ensure accurate flow measurement, thereby integrating the flow metering function in a single, easily accessible coupling that does not require pressure line feed-throughs in a well casing bushing or extensively long upstream and downstream piping to reduce flow turbulence.
[0029] Furthermore, the pressure sensors 32 , 34 are easily accessed for maintenance. Also, owing to oblique ports 28 , 30 , forming the ports 28 , 30 immediately next to the orifice plate 24 is facilitated. And, as mentioned above the ports 28 , 30 are not threaded completely to the inner surface 31 b of the coupling, but instead are smooth near the inner surface 31 b , such that the pressure sensors 32 , 34 do not extend to the inner surface 31 b , much less do they protrude into the fluid passageway formed by the coupling. Consequently, the likelihood that matter inside the metering pipe 32 will foul the sensor connectors 32 , 34 is reduced.
[0030] We have discovered that when the pipes 12 , 14 to be joined by the present coupling have the dimensions described above, the uniformly thick wall of the coupling 10 shown in FIGS. 1 and 2 is sufficiently thick to support threaded engagement between the ports 28 , 30 and the connectors 32 , 34 . However, to join, in a butt weld, smaller pipes, e.g., pipes having an outer diameter of about 3.5″ and a wall thickness of about a quarter inch or less, while supporting threaded engagement between the ports and the connectors, the coupling 50 shown in FIGS. 3 and 4 advantageously can be used.
[0031] As shown in FIGS. 3 and 4, the coupling 50 is in all essential respects identical to the coupling 10 shown in FIGS. 1 and 2, with the following exceptions. Fluid entrance and exit segments 52 , 54 have outer diameters D 3 of about 2.5″ and wall thicknesses t 3 of about 0.2″, to facilitate butt welding the segments 52 , 54 onto pipes having the same outer diameters and thicknesses. However, in contrast to the coupling 10 shown in FIG. 1, the coupling 50 shown in FIGS. 3 and 4 has a relatively thick port section 56 intermediate the segments 52 , 54 , with the port section 56 having the same inner diameter as the segments 52 , 54 but having a greater outer diameter D 2 of about 3.5″. Consequently, the wall thickness t 2 of the port section 56 is about a half inch, which we have discovered is sufficient to support threadable engagement of ports 58 , 60 with threaded connectors. As was the case with the ports 28 , 30 shown in FIGS. 1 and 2, taking the port 58 as an example, the port 58 has a radially outer internally threaded bore segment 58 a and a smooth radially inner bore segment 58 b . An orifice plate 62 having an orifice 64 formed therein is formed within the port section 56 unitarily therewith.
[0032] [0032]FIGS. 5 and 6 show an alternate coupling, generally designated 70 , that is in all essential respects identical to the above-disclosed couplings, with the following exceptions. The coupling 70 is intended to telescopically receive 2.5″ pipes instead of effecting a butt engagement. Accordingly, the coupling 70 includes fluid entrance and exit segments 72 , 74 having outer diameters D 4 of about three inches and inner diameters D 5 of about 2.5″ for receiving 2.5″ pipes therein, leaving the segments 72 , 74 with wall thicknesses t 5 of about one quarter of an inch. If desired, the inner walls of the entrance and exit segments 72 , 74 can be smooth to slidably receive pipes therein, or they can be threaded to threadably engage pipes.
[0033] To adequately provide for threaded upstream and downstream sensor ports 76 , 78 that straddle an orifice plate 80 , a port section 82 is provided intermediate the upstream and downstream segments 72 , 74 . As shown, the port section 82 has the same outer diameter D 4 as the segments 72 , 74 , but a smaller inner diameter and, hence, a greater wall thickness. Preferably, the wall thickness t 4 of the port section 82 shown in FIGS. 4 and 5 is about 0.5″.
[0034] While the particular FLOW METERING DEVICE FOR LANDFILL GAS EXTRACTION WELL as herein shown and described in detail is fully capable of attaining the above-described objects of the invention, it is to be understood that it is the presently preferred embodiment of the present invention and is thus representative of the subject matter which is broadly contemplated by the present invention, that the scope of the present invention fully encompasses other embodiments which may become obvious to those skilled in the art, and that the scope of the present invention is accordingly to be limited by nothing other than the appended claims. | A coupling having an integral orifice plate engages upstream and downstream segments of a landfill piping system. Upstream and downstream ports are respectively formed through the walls of the coupling adjacent the orifice plate. The difference in pressure at the ports is correlated to a flow rate through the pipe. Sensor fittings are threadably engaged with the ports, and to support the threadable engagement, the wall of the coupling through which the ports are formed has a thickness of at least around one-half inch. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates to a process for the preparation of pantoprazole, as well as to the novel intermediate compounds used therein and to the process for the preparation of said intermediate compounds.
PRIOR ART
[0002] Pantoprazole is the international non-proprietary name of the chemical product 5-(difluoromethoxy)-2-[[(3,4-dimethoxy-2-pyridinyl)methyl]sulfinyl]-1H-benzimidazole of formula
[0003] This product is an active ingredient used in the treatment of gastric ulcers, usually in the form of its sodium salt.
[0004] The product was described for the first time in European patent application EP-A-0166287 that also describes several processes for the preparation of products assignable to a general formula among which pantoprazole is to be found. The reaction sequences of these processes, applied precisely to the preparation of pantoprazole, are given in Scheme 1.
[0005] In Scheme 1, the variables Y, Z, Z′ and Z″ are leaving groups, for example atoms of halogen, and the variables M and M′ are atoms of alkali metals.
[0006] Austrian patent AT-B-394368 discloses another process based on a different route of synthetis, the reaction sequence of which is given in Scheme 2.
[0007] Nevertheless, this process has obvious drawbacks, since the methylation can take place not only in OH in the 4-position of the pyridine ring, but also in the nitrogen linked to a hydrogen of the benzimidazole ring, which can give place to mixtures of the desired product with the two possible methylated isomers of the benzimidazole compounds obtained, 3-methyl or 1-methyl, which means that additional chromatographic purification steps are needed and the yields obtained are low.
[0008] PCT application W097129103 discloses another process for the preparation of pantoprazole, the reaction sequence of which is given in Scheme 3.
[0009] As may be seen, different synthesis strategies have been proposed for the preparation of pantoprazole, some of them recently, which is an indication that the preparation of the product is still not considered to be sufficiently well developed, whereby there is still a need for developing alternative processes that allow pantoprazole to be prepared by means of simpler techniques and more accessible intermediate compounds and with good chemical yields.
SUMMARY OF THE INVENTION
[0010] The object of the present invention is a novel process for the preparation of pantoprazole that needs only easily obtainable intermediate compounds.
[0011] Also part of the object of the invention are the novel intermediate compounds used in the aforesaid process, as well as the processes for the preparation of such intermediates.
BRIEF DESCRIPTION OF THE DRAWING
[0012] FIG. 1 shows the IR spectrum of the compound of formula (IV),
[0013] on KBr.
DESCRIPTION OF THE INVENTION
[0014] The process of the invention is characterized by starting from a compound of general formula (I)
[0015] where X is an atom of halogen and n=0 or 1, and which
[0016] a) when n=1, is reacted with a methoxylating agent, or
[0017] b) when n=0, is first oxidised to n=1 and thereafter is reacted with the methoxylating agent,
[0018] to obtain pantoprazole, of formula (II)
[0019] X is preferably an atom of chlorine.
[0020] The methoxylation can be conducted with an alkali metal methoxide, preferably sodium or potassium, or using mixtures of methanol and an alkaline hydroxide, in a polar, preferably aprotic, solvent, such as for example dimethylform, amide, dimethylacetamide and dimethylsulfoxide among others. If desired, the reaction may be completed with the aid of tetrakistriphenylphosphine palladium, holding the reaction temperature within a range comprised between room temperature and 80° C.
[0021] It will be evident to one skilled in the art that, if the substituent X corresponds to another leaving group equivalent to an atom of halogen, equivalent results may be obtained.
[0022] The oxidation can be conducted in the presence of peracids, as for example the perbenzoic acid, although it is preferable to use ammonium permolybdate or pertungstate, with hydrogen peroxide. An aqueous alcoholic mixture, for example of methanol and water, is appropriate as solvent, and the reaction may be conducted at a temperature ranging from 0° C. to 30° C.
[0023] It should be pointed out that the process of the invention overcomes the drawback characteristic of the process of the above mentioned Austrian patent, AT-B-394368, since the methoxylation is selective towards the 4-position of the pyridine ring and does not affect the nitrogen of the benzimidazole ring. This allows better yields and easier-to-purify crude reaction products to be obtained.
[0024] The compounds corresponding to the general formula (I)
[0025] where X and n have the meaning given above, are novel whereby, as such compounds, they are also part of the object of the invention and, in particular, the compounds corresponding to formulas (III) and (IV) are claimed as novel:
[0026] Compound (IV) is prepared by oxidation of compound (III), using a method similar to the one already explained, until the corresponding sulfoxide is obtained.
[0027] On the other hand, compound (III) can be prepared through the reaction detailed in Scheme 5.
[0028] that is to say, reacting the chioromethylpyridinle compound (VI) with the mercaptan derivative of benzimidazole (VII), in the presence of a base, such as tetramethylguanidine (TMGH).
[0029] In turn, the chioromethylpyridine compound (VI) can be prepared by a process following the reaction sequence of Scheme 6
[0030] In this way, the starting product 2-methyl-3-methoxy-4-chloropyridine N-oxide (X) is reacted with the acetate salt of formula
[0031] previously formed by reacting acetic anhydride with 4-dimethylaminopyridine, to obtain the acetoxylated compound (IX). Said acetoxylated compound is then hydrolysed in an aqueous alkaline medium to obtain the carbinol (VIII) that is finally reacted with the reactant of formula
[0032] formed by reacting thionyl chloride (SOCl 2 ) with N,N-dimethylformamide (DMF), to obtain the chloromethylpyridine compound (VI).
[0033] The different steps for preparing compound (VI) are preferably continuous (“one pot”), without isolating the intermediate compounds obtained.
[0034] Following the method described, it is possible to simply and effectively obtain pantoprazole with good yield.
[0035] The invention is illustrated but in no way limited by the following Examples:
EXAMPLES Example 1
[0036] Preparation of Compound (IX)
[0037] 47.5 ml (0.502 mol) of acetic anhydride were mixed with 1.65 g (0.0135 mol) of 4-dimethylaminopyridine, giving a transparent yellow solution which was heated to 65°-70° C. This temperature was held by cooling since the reaction is exothermic. 25 g (0.1441 mol) of 2-methyl-3-methoxy-4-chloropyridine N-oxide (X) were added over a period of about 70 minutes. Once the addition was completed, the reaction was held at 65°-70° C. for a further 2 h 20 minutes and after this time it was allowed to cool down to below 65° C. and 90 ml of methanol were added gradually, while holding the temperature below 65° C. The resulting reaction mass was distilled at reduced pressure in a rotavap to remove the volatile components and the residue containing compound (IX) was used as such for the following reaction. Thin layer chromatography on silica gel 60 F 254 , eluting with CHCl 3 /MeOH (15:1), showed a single spot at Rf=0.82, indicating that the reaction has been completed.
Example 2
[0038] Preparation of Compound (VIII)
[0039] 11.5 ml methanol and 11.5 ml of water were added over the crude residue from Example 1 containing compound (IX), and thereafter, while holding the temperature to between 25° and 30° C. with a water bath, the residual acetic acid contained in the crude residue was neutralized by the addition of 33% aqueous NaOH. Once the residual acid had been neutralized, 19 ml (0.2136 mol) of the 33% aqueous NaOH were added over 20 minutes, while holding the temperature to between 25° and 30° C., and, on completion of the addition, the hydrolysis reaction at pH 11.7-11.8 was held for 2 h 30 minutes, to between 25° and 30° C. On completion of the reaction, the pH was adjusted to 7.0-7.5 by the addition of HCl 35%, while holding the temperature to 25° C. Thereafter, 50 ml of methylene chloride were added and, after stirring and allowing to rest, the phases were decanted. A further five extractions were carried out with 30 ml methylene chloride each and the pooled organic phases were dried with anhydrous sodium sulfate, were filtered and washed, and were evaporated at reduced pressure in a rotavap, providing a solid residue having a melting point around 73° C. and containing compound (VIII). Thin layer chromatography on silica gel 60 F 254 , eluting with CHCl 3 /MeOH (15:1), gave a main spot at Rf=0.55, showing that the reaction was complete. The thus obtained crude residue was used as such in the following reaction.
[0040] Example 3
[0041] Preparation of Compound (VI)
[0042] 24.5 g of the residue obtained in Example 2, containing approximately 0.142 mol of the compound 2-hydroxymethyl-3-methoxy-4-chloropyridine (VIII), were mixed with 0.5 ml of DMF and 300 ml of anhydrous methylene chloride, to give a brown solution which was cooled to 0°-5° C. in an ice water bath. Thereafter, a solution of 11.5 ml (0.1585 mol) of thionyl chloride in 50 ml of anhydrous methylene chloride was added over 20 minutes, while holding the above-mentioned temperature,. Once the addition was complete, the reaction was held at 0°-5° C. for a further 90 minutes and then 120 ml of water and NaOH 33% were added to pH 5-6, requiring approximately 29 ml of NaOH. The phases were then decanted and separated. The organic phase was extracted with a further 120 ml of water and the pooled aqueous phases were extracted with a further 4×25 ml of methylene chloride, in order to recover the greatest possible amount of product. The pooled organic phases were dried over anhydrous sodium sulfate, filtered and washed, and evaporated at reduced pressure in a rotavap, to give a residue containing the compound 2-chloromethyl-3-methoxy-4-chloropyridine (VI). Thin layer chromatography on silica gel 60 F 254 , eluting with CHCl 3 /MeOH (15:1), showed a main spot at Rf=0.83, indicating that the reaction was complete. The thus obtained crude residue was used as such in the following reaction.
Example 4
[0043] Preparation of Compound (III)
[0044] 26.11 g of the residue obtained in the Example 3 containing approximately 0.136 mol of the compound 2-chloromethyl-3-methoxy-4-chloropyridine (VI) were mixed with 370 ml of methylene chloride, to give a brown solution over which were added, at 20°-25° C., 29.3 g (0.136 mol) of 5-difluoromethoxy-2-mercaptobenzimidazole (VII) and 17.10 ml (0.136 mol) of tetramethylguanidine (TMGH). The mixture was stirred at this temperature for 2 hours, after which 450 ml of water were added, with the pH being held to between 9.5 and 10. Thereafter the phases were decanted and the organic phase was washed 5×50 ml of a 1N NaOH aqueous solution and, thereafter, with 2×50 ml of water. The organic phase was treated with 50 ml of water and an amount of HCl 30% sufficient to adjust the pH to between 5 and 6. Thereafter, the phases were decanted, and the organic phase was dried over anhydrous sodium sulfate, was filtered and washed, and evaporated at reduced pressure in a rotavap, to give a solid residue of melting point 64°-73° C. that contains the compound (III). Thin layer chromatography on silica gel 60 F 254 , eluting with CHCl 3 /MeOH (15:1), presented a main spot at Rf=0.52. Yield 82%. The thus obtained compound 5-(difluoromethoxy)-2-[[(3-methoxy-4-chlorine-2 pyridinyl)methyl]mercapto]-1H-benzimidazole (III) was used as such in the following reaction
Example 5
[0045] Preparation of Compound (IV)
[0046] 25.8 g (0.0694 mol) of the compound (III) obtained in the Example 4 were mixed with 88 ml of methanol, to give a brown solution to which 3.7 ml of water, 0.99 g of ammonium molybdate and 0.78 g of sodium carbonate were added. The system was cooled to 0° C.-5° C., 3.4 ml (0.0756 mol) of 60% hydrogen peroxide were added, and the reaction mixture was held at 0° C.-5° C. for 1-2 days, the end point of the reaction being checked by thin layer chromatography on silica gel 60 F 254 , eluting with CHCl 3 /MeOH (15:1).
[0047] During the reaction the presence of hydrogen peroxide in the reaction medium was controlled by testing with potassium iodide, water and starch. When effected on a sample containing hydrogen peroxide, it provides a brown-black colour. If the assay is negative before the chromatographic control indicates completion of the reaction, more hydrogen peroxide is added.
[0048] On completion of the reaction, 260 ml of water were added, the system was cooled to 0° C.-5° C. again and the mixture was stirred for 2 hours at this temperature. The solid precipitate was filtered, washed with abundant water, and dried at a temperature below 60° C., to give 5-(difluoromethoxy)-2-[[(3-methoxy-4-chlorine-2-pyridinyl)methyl]sulfinyl]-1H-benzimidazole (IV), melting point 130°-136° C., with an 83.5% yield. Thin layer chromatography on silica gel 60 F 254 , eluting with CHCl 3 /MeOH (15:1), gave a main spot at Rf=0.5.
[0049] Compound (IV) can be purified, if desired, by the following crystallization method:
[0050] 5 g of crude product was suspended in 16 ml of acetone and was heated to boiling until a dark brown solution was obtained. Thereafter the thus obtained solution was allowed to cool down to room temperature and then was then chilled again to −20° C., at which temperature the mixture was held for 23 hours without stirring. Thereafter the solid was filtered and washed with 6×4 ml of acetone chilled to −20° C. Once dry, the resulting white solid weighed 2.73 g, had a point of melting of 142° C. and gave a single spot in thin layer chromatography. The IR spectrum of the compound on KBr is given in FIG. 1.
[0051] The acetonic solution comprising the mother liquors of filtration and the washes was concentrated to a volume of 20 ml and a further 5 g of crude compound were added. The above described crystallization process was repeated to obtain a further 4.11 g of purified product of characteristics similar to the previous one.
[0052] The acetonic solution from the previous crystallization was concentrated to a volume of 17 ml and a further 4 g of crude compound were added. The above described crystallization process was repeated to obtain a further 2.91 g of purified product of similar characteristics to the previous ones.
[0053] The acetonic solution from the previous crystallization was concentrated to a volume of 15 ml and a further 4 g of crude compound were added. The above described crystallization process was repeated to obtain a further 3.3 g of purified product of similar characteristics to the previous ones.
[0054] The acetonic solution from the previous crystallization was concentrated to a volume of 16 ml and a further 4.36 g of crude compound were added. The above described crystallization process was repeated to obtain a further 3.62 g of purified product of similar characteristics to the previous ones.
[0055] Finally, the acetonic solution from the previous crystallization was concentrated to a volume of 10-12 ml and held at −20° C. for two-days without stirring. Thereafter, the solid was filtered and washed with 5×3 ml of acetone chilled to −20° C. Once dry, the solid weighed 1.26 g and had similar characteristics to the previous ones.
[0056] The total yield of all the crystallizations was 80%.
[0057] Example 6
[0058] Preparation of Pantoprazole
[0059] 12.95 g (0.0334 mol) of compound (IV) purified by crystallization of Example 5 were mixed with 38 ml of N,N-dimethylacetamide and thereafter 7.03 g (0.1003 mol) of potassium methoxide were added, while holding the temperature to between 20° C. and 30° C., whereby a dark brown mixture was obtained. The system was held at approximately 25° C. for about 23 hours, after which, once the reaction was complete, the pH was adjusted to 7 with the addition of 3.82 ml of acetic acid. The N,N-dimethylacetamide was removed at reduced pressure at an internal temperature of not more than 75° C. 65 ml of water and 50 ml of methylene chloride were added over the thus obtained residue, followed by decantation of the phases. Once the phases were decanted, the aqueous phase was extracted a with further 3×25 ml of methylene chloride, the organic phases were pooled and the resulting solution dried over anhydrous sodium sulfate, was filtered and washed, and evaporated at reduced pressure in a rotavap, to give a crude residue over which 55 ml of water were added, to give a suspension (if the product does not solidify at this point the water is decanted and a further 55 ml of water are added to remove remains of N,N-dimethylacetamide that hinder the solidification of the product). The solid was filtered and, after drying, 11.61 g of crude pantoprazole of reddish brown colour were obtained (Yield 90%).
[0060] The thus obtained crude product was decoloured by dissolving the crude product in 150 ml of methanol, whereby a dark brown solution was obtained. 7.5 g of active carbon were added, while maintaining stirring for 45 minutes at 25° C.-30° C., after which the carbon was filtered out and the filter was washed. The methanol was then removed in the rotavap at reduced pressure, a temperature below 40° C. 10.33 g of a solid residue were obtained and were mixed with 14.9 ml of methylethylketone, and the suspension was heated to 45° C. for about 10 minutes, after which it was cooled, first to room temperature and then to −20° C. This temperature was held over night and thereafter the solid was filtered, washed with 6×5 ml of methylethylketone chilled to −20° C. Once dry, 7.75 g of a white solid, melting point 140° C.-141° C., were obtained. Thin layer chromatography on silica gel F 254 , eluting with CHCl 3 /MeOH (15:1), gave a single spot at Rf=0.41 and a IR spectrum corresponding identically with that of pantoprazole.
[0061] The ketonic solution comprising the mother liquors of filtration and the washes, was concentrated to 9.7 ml, was heated to 40° C., was held at this temperature for about five minutes and was then cooled, first to room temperature and then to −20° C., this temperature being held for 4 hours. At the end of this time, the solid was filtered and was washed with 4×2 ml of methylethylketone chilled to −20° C. Once dry, 0.42 g of a white solid of similar characteristics to the previous one was obtained.
[0062] The ketone solution from the previous treatment was concentrated to 3.1 ml, was heated to 40° C., was held to this temperature for about five minutes and then was cooled, first to room temperature and then to −20° C., this temperature being held for 4 hours. At the end of this time, the solid was filtered and was washed with 5×3 ml of methylethylketone chilled to −20° C. Once dry, 0.41 g of a white-beige solid of similar characteristics to the previous one was obtained.
[0063] The total yield, including purifications, was 67%.
[0064] If a whiter solid is desired, one or several washes can be carried with isopropyl acetate as follows: 6.6 g of pantoprazole from the methylethylketone treatment were suspended in 50 ml of isopropyl acetate. The system (white suspension) was stirred for about 30 minutes at 25° C., was then cooled to 0° C.-5° C., was stirred for about 15 minutes at this temperature and the solid was then filtered, was washed with 3×15 ml of isopropyl acetate. Once dry, 6.26 g of a pure white solid were obtained. | A novel process is described for the preparation of the active principle pantoprazole based on the use of novel intermediate compounds of general formula (I) where X is an atom of halogen and n=0 or 1, so that when n=1, the intermediate compounds are methoxylated, and when n=0 said intermediate compounds are first oxidized to n=1 and thereafter are methoxylated. Also described are the novel intermediates, as well as the process for the preparation thereof. | 2 |
BACKGROUND OF THE INVENTION
[0001] This application is a Divisional of co-pending application Ser. No. 10/443,880 filed on May 23, 2003, the entire contents of which are hereby incorporated by reference and for which priority is claimed under 35 U.S.C. § 120 and which application also claims priority under 35 U.S.C. § 119(a) on Patent Application No. 1020682 filed in The Netherlands on May 27, 2002, which is herein incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to an ink composition which is solid at room temperature and liquid at elevated temperature, said ink composition containing a resin and being suitable for use in an inkjet printer.
RELATED ART
[0003] It is known to use resins in relatively large quantities in meltable ink compositions (hot melt inks) for inkjet printers. Inks of this kind are solid at room temperature and melt at elevated temperature. Typical melting points are in the range of 60 to 120° C. The melted inks are jetted at a temperature at which they are thinly viscous, typically 100 to 160° C., by means of an inkjet printer as adequately known from the prior art. Resins enable the ink to be sufficiently tough after cooling so that the ink is more resistant to mechanical loads on the printed receiving material, such as gumming, scratching and folding. Although crystalline materials are generally harder, they are also much more brittle, so that printed matter made using a mainly crystalline ink composition is fairly sensitive to damage. The use of resins in ink compositions also has the advantage that dyes can be dissolved relatively well therein and pigments can be dispersed relatively easily therein. In addition, resins have the advantage that after solidification they are often transparent so that it is possible to make color prints using subtractive color mixing. The disadvantage of resins is that generally they are relatively viscous, even after they have been softened at high temperature, and cannot therefore be used in large quantities in hot melt inks.
[0004] Amorphously solidifying monomeric resins are known from U.S. Pat. No. 6,071,986. Resins of this kind, which solidify completely amorphously, have the advantage that they are not very viscous, because of their relatively low molecular weight. The disadvantage of these resins, however, is that their amorphous state is not sufficiently stable. As a result, these resins will also crystallise after a shorter or longer period. Even if these known resins are used in an ink composition, there will be some post-crystallization of the resins. This in turn has the result that the quality of a printed image, i.e. after the corresponding ink has solidified on the receiving material, will deteriorate in the course of time.
[0005] Esters of 2,2′-biphenol and aromatic acids are known from EP 0 978 548. These are also examples of monomeric amorphously solidifying resins. However, these resins still appear to have some tendency to post-crystallization so that the properties of the solidified ink change in the course of time, particularly when printed receiving materials are stored under extreme conditions, for example at relatively high temperatures.
SUMMARY OF THE INVENTION
[0006] The object of the present invention is to provide an ink composition suitable for use in an inkjet printer, which ink composition contains a resin having a low viscosity at the inkjet printer operating temperature, which resin solidifies amorphously and exhibits little post-crystallization if any. To this end, in a first embodiment of the ink composition according to the present invention the resins present therein contain a compound which is the reaction product of a di-alkanolamine and a monofunctional aromatic acid. It has surprisingly been found that a resin of this kind which has a low melt viscosity (technically it is more correct to refer to “softening viscosity” but this is unusual in the technical area concerned) solidifies amorphously despite its low molecular weight and exhibits practically no tendency to post-crystallization.
[0007] According to a second embodiment of the present invention, the ink composition contains resins which contain a compound which is the reaction product of a di-alkanolamine and a monofunctional aromatic acid and a difunctional acid. These resins also have a very low melt viscosity and yet it solidifies amorphously and has practically no tendency to post-crystallization. The resin according to this second embodiment of the present invention often contains a mixture of monomeric and oligomeric reaction products, the precise composition of which depends, inter alia, on the ratio of the reactants and the reaction conditions. Despite the fact that the average molecular weight of this resin is higher than that of the pure monomeric product according to the first embodiment of the invention, it has been found that the melt viscosity is scarcely higher, if at all. The amorphous state of this resin has been found to be more stable than that of the first embodiment of the present invention. This is probably a result of the fact that this resin is often a mixture of related compounds.
[0008] From WO 96/10051 a polyamide resin is known which is suitable for use in hot melt inks, said resin being the product of the reaction between an amino alcohol, a monofunctional acid and a di-acid. These resins have the disadvantage that they are waxy and often not sufficiently transparent in the solidified state because they are partially crystalline.
[0009] From U.S. Pat. No. 4,066,585 a synthetic polyamide resin is known for intaglio and flexographic printing, which resin is the condensation product of (1) an acid component comprising a dimerised fatty acid and a monofunctional carboxylic acid and (2) an amine component comprising a diamine and a diol and/or an alkanol amine. These resins are also fairly waxy and often not sufficiently transparent in the solidified state. These resins therefore are hardly suitable for use in inkjet printers subject to high requirements such as, for example, quality, speed, reliability, variety of media for printing, and so on (“high demand” printers).
[0010] U.S. Pat. No. 5,698,017 describes resins as a vehicle material for an ink composition. These resins, e.g., oxazolines, are the reaction product of an organic acid and an amino alcohol. Resins of this kind have the disadvantage that they solidify in crystalline form and therefore result in brittle ink layers on media. Such layers have poor resistance to mechanical impacts such as gumming, scratching and folding.
[0011] Progress in Organic Coatings , Volume 40 (2000), pages 203-214, describe hyperbranched polyester amides derived from cyclic anhydrides and di-alkanolamines. These resins are described as a constituent in liquid film-forming compositions for coating applications. The use in solid meltable compositions which do not form films is not described. Also, use in hot melt ink compositions is not possible because the resins described are much too viscous to be considered for such an application.
[0012] In another embodiment of the first-mentioned embodiment of the present invention, the compound is the reaction product of di-isopropanolamine and benzoic acid, the latter being optionally substituted by an alkyl and/or alkoxy group. It has been found that the compound of this ink composition is thermally very stable in respect of visco-elastic properties. This is an advantage in the printing of hot melt ink because the ink in the actual print head generally has to experience a number of heating-up/cooling cycles (printer on/off) before the ink is actually jetted. Also, this compound has the advantage that it can be made without the addition of a catalyst. This is also an advantage in use in a hot melt ink since any contamination in the ink, no matter how small, may have a negative influence on the functioning of the inkjet printer (unstable jet behavior, nozzle clogging, wetting problems, and so on).
[0013] In a further embodiment, the benzoic acid is substituted by a C1-C4 alkyl and/or a C1-C4 alkoxy group. The physical properties of the compound and hence of the resin can be adjusted more accurately by the use of a substituted benzoic acid.
[0014] In a further embodiment of the present invention in which the compound, for the same reasons as indicated hereinbefore, is the reaction product of di-isopropanolamine and benzoic acid optionally substituted by an alkyl and/or alkoxy group, the difunctional acid is restricted to an organic acid containing an aliphatic, aromatic or alicyclic main group (i.e. the longest non-functional chain in the acid) with 12 carbon atoms at maximum. It has been found that this leads to very stable compounds. In a further embodiment, the difunctional acid contains an aliphatic or alicyclic main group. It has been found that the compound has a relatively low glass transition temperature (Tg) and a low melt viscosity. In yet another embodiment, the difunctional acid is selected from the group consisting of succinic acid, adipic acid and cyclohexane dicarboxylic acid (cis and/or trans form). The use of such acids results in ink compositions which are relatively tough after cooling and thus very resistant to mechanical loads on the image printed therewith.
[0015] Preferably, the ink compositions according to the present invention contain a meltable crystalline material and optionally an amorphously solidifying monomer as known from U.S. Pat. No. 6,071,986. In this way the properties of the ink composition can be accurately adjusted and adapted, for example to the typical properties of the printer, the selected receiving material, the type of image, and so on.
[0016] Preferably, the ink composition contains a viscosity control agent, for example a gelling agent as known from EP 1,067,175. In this way, for example, the solidification behavior of the ink composition can be accurately adjusted. In addition to such viscosity control agents, the ink may contain additives such as UV protectors, anti-oxidants and other preservative substances, surfactants, and other additives as known from the prior art. As is known for hot melt inks generally, inks of this kind can be used in different types of inkjet printers and in combination with different receiving materials. The receiving material used may, for example, be a cheap plain paper because hot melt inks are generally relatively insensitive to feathering. Alternatively, hot melt inks can be transferred to receiving materials particularly suited for inket uses, such as Bond paper, Laminate bond paper, EconoBond, DuraBanner, Removable Tyvek, EconoVinyl and WaterFast Removable Vinyl made by Colorspan; 600 016-1474-00 Smooth white bond, 016-1476-00 Photograde paper, 016-1478-00 Premium tracing/Backlit paper, 016-1479-00 Backlit display film and 016-1496-00 Transparency film made by Tektronix; NC Photodry made by Zanders; Photoglossy paper GP201 and High gloss photofilm made by Canon; Photo quality glossy film SO41073 and SO 41071 made by Epson; Premium water resistant H75000 and H75007 made by Felix Schoeller, Ilfojet dry satin made by Ilford; 3290 IJP200 made by Sihl; backlit IJM562 made by Océ. If required, the printing of hot melt ink on such receiving materials may be combined with heating the receiving material, particularly just before or after printing. In this way it is often possible to obtain a specific degree of gloss, for example matt, silk gloss or high gloss.
[0017] The invention will now be explained further by reference to the following examples. Where these examples refer to a “part” of a specific reactant, then unless otherwise indicated this means a “molar part”.
DETAILED DESCRIPTION OF THE INVENTION
[0018] Table 1 shows the reaction products of di-isopropanolamine and aromatic acids;
[0019] Table 2 shows the reaction product of di-isopropanolamine, an aromatic acid and a difunctional aliphatic acid, before and after thermal loading; and
[0020] Table 3 shows ink compositions comprising the reaction products of Tables 1 and. 2.
[0021] Example 1 shows a process for making reaction products as indicated in Table 1.
[0022] Example 2 shows a process for making reaction products as indicated in Table 2.
Table 1
[0023] Table 1 shows a number of reaction products of di-isopropanolamine and various aromatic acids. The first product is formed by the reaction of one part of di-isopropanolamine and three parts of benzoic acid. The second product is formed by the reaction of one part of di-isopropanolamine and three parts of 2-methylbenzoic acid. The third product is formed by the reaction of two parts of di-isopropanolamine, three parts of 2-methylbenzoic acid and three parts 4-t-butylbenzoic acid. The fourth product is formed by the reaction of one part of di-isopropanolamine and three parts 4-methoxybenzoic acid. The fifth and last product in this Table is formed by the reaction of one part of di-isopropanolamine and three parts 4-methylbenzoic acid.
[0024] The second column of Table 1 shows the glass transition temperatures of the respective compounds. These are measured using a Differential Scanning Calorimeter (DSC), namely the DSC-7 made by Perkin Elmer, Norwalk, Conn. The glass transition temperature of a resin in this test is equated with the onset of the bending point of the enthalpy increase corresponding to the glass transition as measured in the heating of a resin at 20° C./min. To know the thermal history of a resin, each resin is heated once, prior to measurement, to above its glass transition temperature (20° C./min) and then rapidly cooled to room temperature (“quenching”).
[0025] Finally, Table 1 gives, for each of the compounds, the viscosity at three measurement temperatures. This viscosity is measured using a steady shear viscosimeter, namely the DSR-200 made by Rheometric Scientific, Piscataway, N.Y., using the known plate-cone geometry. The viscosity follows from the ratio between the stress required to shear the resin and the shearing speed in equilibrium.
[0026] The reaction products given in this Table are monomeric distinct compounds. They can be used as resins in a hot melt ink, alone or in mixture with one or more other resins. These amorphous compounds have a relatively low viscosity at typical jet temperatures of 130-160° C. and are thermally stable. Both properties are favorable for use in a high-demand ink jet printer. The compounds solidify amorphously and their amorphous state is very stable. Even after a long time and under extreme conditions (for example storage above the glass transition temperature) there practically is no perceptible post-crystallization. As a result, images printed with an ink composition in which these amorphous compounds have been used as resin retain their initial quality for a long period of time.
TABLE 1 Reaction products of di-isopropanolamine and aromatic acids. Tg Viscosity [mPa · s] No Reaction product of: [° C.] (measuring temperature in ° C.) 1 di-isopropanolamine (1 part) and 7 37 (110) 16 (130) 8 (150) benzoic acid (3 parts) 2 di-isopropanolamine (1 part) and 3 37 (110) 16 (130) 9 (150) 2-methylbenzoic acid (3 parts) 3 di-isopropanolamine (2 parts) and 14 127 (110) 39 (130) 17 (150) 2-methylbenzoic acid (3 parts) 4-t-butylbenzoic acid (3 parts) 4 di-isopropanolamine (1 part) and 23 91 (120) 34 (140) 16 (160) 4-methoxybenzoic acid (3 parts) 5 di-isopropanolamine (1 part) and 19 40 (120) 17 (140) 9 (160) 4-methylbenzoic acid (3 parts)
Table 2
[0027] Table 2 is an example of a compound according to the second embodiment of the present invention. It relates to the reaction product as indicated under Example 2. This product is not a distinct compound but a mixture of monomeric and oligomeric compounds in accordance with formula 1 (n=0, n=1, n=2, and so on), this being the notation for the most probable molecule structure of the resulting compounds. Despite its fairly high molecular weight, this mixture nevertheless has a relatively low viscosity at the typical jet temperatures.
[0028] The second row of Table 2 gives the same reaction product, but in this case the product was thermally loaded for two weeks at 130° C. in an oven. In the practice of inkjet printing, such a loading would be expected only under extreme conditions (printer continuously on but with hardly any printing if at all). It has been found that the physical properties of the reaction product after this heavy loading have scarcely altered. The viscosity has dropped slightly and there is minimal brown coloration. Changes could scarcely be perceived with NMR after loading. There was found to be a small increase in the free benzoic acid (and this may possibly explain the fall-off in viscosity).
TABLE 2 Reaction product of di-isopropanolamine, an aromatic acid and difunctional aliphatic acid, before and after thermal loading. Tg Viscosity [mPa · s] No Product [° C.] (measuring temperature) 6 Resin in accordance 17 80 (120) 30 (140) 15 (160) with Example 2 6′ Ditto, two weeks thermal 15 70 (120) 26 (140) 14 (160) loading at 130° C.
Table 3
[0029] Table 3 gives a number of ink compositions according to the present invention. A hot melt ink can be made up, for example, by combining one or more resins, for example as shown in Tables 1 and 2 of U.S. Pat. No. 6,071,986, Table 3a and 3b of EP 1 067 157 and Table 1 of EP 0 978 548, with one or more crystalline materials, for example as shown in Table 3 of U.S. Pat. No. 6,071,986, Table 2 of EP 1 067 157 and Table 3 of the Netherlands Patent Application 1017049, which is not a prior publication, and providing the same with additives as dyes and/or pigments, anti-oxidants, wetting agents, viscosity control agents (for example a gelling agent as known from Table 1 of EP 1 067 157), UV-protectors, and so on.
[0030] Table 3 gives the basic composition or the vehicle composition of three inks according to the present invention. Each of the inks has a basic composition made up of 70% by weight of a crystalline component and 30% of a resin according to the invention. In each case in this example, the crystalline component is a bis-ester of a low alkane diol (respectively 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol) and an aromatic acid (respectively 4-methoxybenzoic acid, 4-methylbenzoic acid and 4-methoxybenzoic acid). The resins are selected from the products given in Tables 1 and 2. Each of these inks is provided with viscosity control agents (not shown in the Table) namely 1% (one part by weight per 100 parts by weight of ink), pentaerythritol tetrabehenate and 1% bis-ester amide of 1,10-dodecanedi-acid and 3-methoxypropylamine. In addition, each of these inks contains a dye, in this case 1.5% Waxoline Blue AP made by ICI. As further additives the inks contain 0.1% Byk 309 (surfactant) and 0.5% Vanox 1005 (antioxidant).
TABLE 3 Basic composition of inks according to the invention Ink Crystalline component (70% by weight) Resin (30% by weight) a) Bis-ester of propanediol and 4- product no 6 (table 2) methoxybenzoic acid b) Bis-ester of butanediol and 4- product no 4 (table 1) methylbenzoic acid c) Bis-ester of hexanediol and 4- product no 1 (table 1) methoxybenzoic acid
EXAMPLE 1
[0031] This Example describes a process for making product No. 1 from Table 1, the process also being suitable for making comparable reaction products, particularly products 2 to 5 as shown in Table 1.
[0032] Synthesis of product 1 was carried out as follows. A 250 ml 3-neck round-bottom flask was provided with a mechanical agitator, a thermometer and a DeanStark arrangement. 64.97 g (0.488 mol) of di-isopropanolamine (Aldrich) and 178.70 g (1.463 mol) benzoic acid (Aldrich) were placed in the flask. A small quantity of o-xylene was also added, about 20 ml, as entraining agent to remove the liberated water. The reaction mixture was heated to 180° C. and kept under a nitrogen atmosphere. After half an hour, the temperature was again raised to 190° C. After three hours, the flask was evacuated to remove the o-xylene. When the o-xylene had been removed, after about three-quarters of an hour, the reaction mixture was drawn off. This mixture contained mainly product 1 (Table 1), this product being identical to the formula 1 compound with n=0.
EXAMPLE 2
[0033] This Example describes a process used for making reaction product 6 as indicated in Table 2, namely a reaction product of di-isopropanolamine, benzoic acid and succinic acid anhydride. A 1 litre reaction flask was provided with a mechanical agitator, a thermometer and a DeanStark arrangement. 261.06 g (1.960 mol) of di-isopropanolamine (type S, BASF) 540.88 g (4.429 mol) benzoic acid (Aldrich) and 69.69 g (0.696 mol) of succinic acid anhydride (Aldrich) were placed in the flask. A small quantity of o-xylene, about 60 ml, was added as entraining agent to remove the liberated water. The reaction mixture was kept under a nitrogen atmosphere and heated for 1 hour at 165° C., whereafter the reaction temperature was raised to 180° C. After 6 hours the temperature was reduced to 160° C. and the flask was evacuated to remove the o-xylene. It was possible to draw off the reaction mixture after about 1 hour. Analysis showed that the number-averaged molecular weight (M n ) was 583 and the weight-averaged molecular weight (M w ) was 733. The ratio between M w and M n (1.26) showed that there was a mixture of compounds formed. The diagram below (formula 1) indicates what compounds may form during the reaction between di-isopropanolamine, benzoic acid and succinic acid (it should be noted that formula 1 is the most probable structure of the resulting compounds). The reaction shows the formation of a mono-disperse compound. The ratio in respect of reactants as indicated in the formula belongs to a chosen value for n. This ratio need not necessarily be identical to the ratio for the overall reaction, where in fact a mixture of compounds with different values for n is formed. In the reaction according to this example, a ratio has been chosen which is equal to 2.82:6.36:1 (di-isopropanolamine:benzoic acid: succinic acid anhydride). This means that there are 3×2.82=8.46 mol equivalents of reactive NH/OH groups in the amine, as against 6.36+2×1.00=8.36 mol equivalents of acid groups in the benzoic acid and anhydride. There is therefore only a very small excess (about 1%) of di-isopropanolamine.
[0034] A GPC analysis showed that the mixture contained approximately 45% by weight of the compound with n=0, about 40% by weight of the compound with n=1 and about 15% by weight of compounds with n=2 or higher. This is approximately equivalent to 60 mol. % of the compound with n=0; 30 mol. % of the compound with n=1 and 10 mol. % of compound with n=2 or higher.
[0035] Other compounds for ink compositions according to the invention can be made in a similar manner to that given in Examples 1 and 2. Changes in the ratio of the reactants or the type of reactants (for example an anhydride instead of the acid and/or vice-versa) may influence the synthesis. In this way, the skilled man can obtain an ink composition tailored to his purpose.
[0036] The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims. | A meltable ink composition, which is solid at room temperature and liquid at elevated temperature, which ink composition is suitable for use in an inkjet printer, the ink composition being provided with a resin which contains a compound which is the reaction product of a di-alkanolamine and a monofunctional aromatic acid and optionally a difunctional acid. | 2 |
The invention herein described may be manufactured and used by or for the Government for governmental purposes without the payment to us of any royalty therefor.
This application is a continuation of application Ser. No. 358,396, filed Mar. 15, 1982, for PRODUCTION OF GRANULAR AMMONIUM-POLYPHOSPHATE WITH AN INLINE REACTOR AND DRUM GRANULATOR now Defensive Publication No. T102,601, published Jan. 4, 1983.
INTRODUCTION
The present invention relates to methods for production of granular fertilizer; more particularly, the present invention relates to methods for the manufacture of granular phosphate fertilizers from ammonium phosphate melt produced in an inline reactor from ammonia and wet-process phosphoric acids, which melt serves to bond small fertilizer particles into granules; even more particularly, the present invention relates to methods for production of ammonium phosphate fertilizers which contain part of the phosphate present therein in the polyphosphate form; and still more particularly, the present invention relates to methods of production of ammonium phosphate fertilizers and fertilizer intermediates which contain critically sufficient minimum polyphosphate, said minimum polyphosphate effected by adjustments of the degree of reactor heat input and said minimum polyphosphate sufficient to improve storage and physical characteristics and also to enable the subsequent production of fluid suspension fertilizers produced therefrom with unusually excellent physical characteristics while utilizing a process that is more energy efficient than those disclosed in the prior art and thus can be operated more economically.
BACKGROUND OF THE INVENTION
1. Field of the Invention
Ammonium phosphates produced by the reaction of ammonia with phosphoric acid became the leading phosphatic fertilizers produced in the United States in the late 1960s and since that time their manufacture and use have continued to increase. Both diammonium and monoammonium phosphates are commonly produced. Initially both of these fertilizers were produced using a slurry type process such as that taught in U.S. Pat. No. 3,153,574, Achorn et al, assigned to the assignee of the present invention, which was designed principally for production of diammonium phosphates. Other processes were developed that offered distinct advantages when producing monoammonium phosphates. These processes involved a new technique of granulation called melt granulation in which an inline type reactor, such as a pipe reactor or pipe-cross reactor, was used to produce an essentially anhydrous ammonium phosphate melt. This allows much better conservation of heats of reaction and thus reduces or totally eliminates any drying requirement or step during subsequent treatment of fertilizer material exiting the granulator. Cost savings are realized because fuel requirement for heating is decreased and capital investment requirements are also decreased because complicated slurry production and handling equipment, such as a preneutralizer, and drying equipment are no longer required. Thus, in summary, operating costs are decreased because not only fixed but also variable expenses are decreased.
2. Description of the Prior Art
Several processes have been developed using the melt granulation technique including those taught in U.S. Pat. No. 3,825,414, Lee et al, assigned to the assignee of the present invention, where a pug mill granulator is used; in U.S. Pat. No. 3,985,538, Hicks et al, also assigned to the assignee of the present invention, where a drum granulator is used, but a preneutralizer is also used in the reaction system. There are certain inherent disadvantages to these two processes, however. The former process used not only a complicated reaction system that included a spray reactor and vapor disengager in addition to the pipe reactor, but also used a pug mill granulator which is typically more expensive to operate and maintain than a drum granulator and is much less commonly used in the fertilizer industry. The latter process used a drum granulator but also had a much more complicated reaction system whereby a preneutralizer tank is also included with the pipe reactor.
Later processes were developed that were more suited to production of ammonium phosphate fertilizers in drum granulators. In U.S. Pat. No. 3,954,942, Achorn et al, assigned to the assignee of the present invention, taught the use of a pipe-cross reactor as the reaction system. With this type of inline reactor, sulfuric acid can also be fed and co-neutralized along with the phosphoric acid inside the reactor so that a fertilizer can be produced that contains additional sulfate, if needed. This process was improved, as taught in U.S. Pat. No. 4,134,750, Norton et al, assigned to the assignee of the present invention. Norton et al modified the earlier process of Achorn, supra, so that higher temperatures could be maintained in the pipecross reactor and ammonium phosphate fertilizers containing polyphosphate were produced. Although both the Achorn and Norton processes, to wit, '942 and '750, supra, obtain a granular product without external heat; both utilize sulfuric acid fed to the pipe-cross reactor to furnish the required and necessary additional chemical heat to the process.
The Lee process, to wit, U.S. Pat. No. 3,825,414, supra, produced a product in which a 20-percent polyphosphate content was the minimum acceptable for granular material which is intended to be subsequently used as an intermediate for production of suitable suspension fertilizers. In this process, a pug mill granulator was used. This type of granulator has not been well accepted by the granular fertilizer industry. The pug mill is a complicated piece of granulation equipment and because of this it has a higher investment cost than other more common granulators, such as a drum granulator, and is more difficult to maintain in good operating condition, thus increasing maintenance costs. Since more energy, especially electrical energy, is required to operate the pug mill, operating costs are further increased. Because a pug mill cannot be easily or readily hooded, it is more difficult to scrub the fumes from a pug mill and pollution control is more expensive. Investment costs and operating costs are higher because of the use of the pug mill granulator and because of the more complicated reaction system comprising a spray reactor, vapor disengager, and pipe reactor. For a better understanding of the theory, construction, and operation of the spray reactor and vapor disengager, see FIGS. 5 and 6 of U.S. Pat. No. 3,733,191, Meline et al, assigned to the assignee of the present invention, in which the spray reactor is referred to as the first-stage reactor and the vapor disengager as a horizontal tube and rotor-type disengager. The spray reactor must be operated at high temperatures and low pH so that the material of construction is a material such as Hastelloy G that is not normally used in the industry, especially for large pieces of equipment, because of its high costs. The vapor disengager is a rather complicated piece of equipment to operate and is considered by some to be above the normal state of the art practiced by the industry. Parts of this vapor disengager would be expected to require an expensive material of construction. In addition, maintenance costs are high because of the rotary nature of the disengager and close tolerances maintained so that highly skilled maintenance personnel are required.
SUMMARY OF THE INVENTION
The novelty of the present invention resides in the fact that granular ammonium polyphosphate fertilizers are produced without external heat with an inline reactor and drum granulator and that predetermined product polyphosphate contents can be obtained. External heat is used herein in the sense to mean heat supplied to the system in addition to the latent and potential chemical heat contained therein as, for example, that supplied by burning fossil fuel or by adding additional chemical such as in the case of a side stream of sulfuric acid to the reactor, as in Achorn or Norton, supra, or even by adding additional preheat to bolster the amount of latent heat in the system. Practices of the instant invention are accomplished by control of the net heat input of the phosphoric acid and ammonium feed materials to the reactor by predetermining the insulation required for selected equipment to control heat losses therefrom. Since a miximum theoretical heat input is available, the net heat input to the reactor can be adjusted by increasing or decreasing process reaction system heat losses. The present invention not only identifies the parameters for producing products of various polyphosphate contents, but has identified that the minimum polyphosphate content required in granular products for producing suspensions is only 12 percent. Specifically, the process of this invention uses a reaction system and scrubbing system in which the scrubber and reactor and their auxiliary feed and drain lines are heavily insulated. Air ducts to the scrubber are also insulated, which allows the polyphosphate content of the granular product to be predetermined by control of the heat losses from the process by the quantity of insulation used so that varying amounts of the theoretical maximum process heat input can be utilized.
ADVANTAGES OF THE INVENTION
Developments in fertilizer use and application have shown that there are definite advantages for a granular ammonium polyphosphate fertilizer as compared with a granular monoammonium phosphate fertilizer. Ammonium polyphosphate fertilizers exhibit improved physical characteristics. Because chemical water is removed as polyphosphates are formed, ammonium polyphosphate fertilizers exhibit better storage and physical properties because the polyphosphate can absorb some water and hydrolyze back to the orthophosphate form and this buffering action lessens the tendency for the material to become wet or sticky because of ambient environmental conditions. The materials containing polyphosphate are also harder, smoother, and less dusty; hence, the storage properties thereof are improved. The material can also be used as an intermediate in granulation plants. The material has a high phosphate and total plant nutrient content and can be shipped to granulation plants at cheaper rates than fluid forms of phosphate such as phosphoric acid. The material is readily used to make bulk blends of solid material fertilizers and again is an excellent phosphate source because of its high concentration of plant nutrients. And lastly, but perhaps most importantly, such ammonium polyphosphate granular fertilizer material is an excellent intermediate material for producing fluid suspension fertilizers. The polyphosphate present in the ammonium polyphosphate is very important when producing a suspension fertilizer from an intermediate granular material. The presence of polyphosphate prevents gelation of iron and aluminum compounds generic with the wet-process phosphoric feed acid and allows production of higher grades, which in turn gives the advantages of lower shipping costs and lower storage costs. Fluid suspensions having lower viscosities can be produced and these suspensions have lower solidification temperatures which allow use and storage in colder climates. Polyphosphate containing material will also dissolve more quickly than monoammonium phosphate material resulting in higher production rates and subsequently lower manufacturing costs.
In the past it has been well established that it is most desirable to have at least about 20 percent phosphate of the solid intermediate in the polyphosphate form. One of the discoveries underlying the inventive concept of the present invention is that lower quantities of polyphosphate are sufficient to make acceptable storing suspensions. We have found that suspensions containing as little as 10 percent of the phosphate in polyphosphate form perform well. This requires a 12-percent polyphosphate granular intermediate material since about 2 percent polyphosphate is hydrolyzed during manufacture of a suspension fertilizer therefrom. Under these conditions, a nominal 11-33-0 grade material can be made that will store acceptably for at least 60 days at 80° F. and have a solidification temerature of at least -5° F., or below. This is in direct comparison to a suspension made from monoammonium phosphate which will have a maximum grade of only 9-27-0 or sometimes even 8-24-0 when the solid granular intermediate orthophosphate material has a grade less than 11-55-0. Suspensions produced from said orthophosphate intermediates have acceptable storage properties for 60 days at 80° F., but have a solidification temperature greater than 0° F. Studies show a solidification temperature of -5° F., or less, is required for suitable storage, transport, and application in areas of the northern United States (see "New Developments in Fertilizer Technology," 13th Demonstration, Oct. 7-8, 1980--TVA Bulletin Y-158).
OBJECTS OF THE INVENTION
It is therefore an object of the present invention to provide an improved method of producing a granular ammonium polyphosphate fertilizer whereby the specific critical minimum content of polyphosphate as desired or required can be obtained.
Another object of the present invention is to provide the critical ammonium polyphosphate content of suspension intermediate material while employing the old standby, to wit, the inclined rotating drum granulator and the inline single-stage reactor with resulting lower energy and production costs because of energy conservation methods utilized therein.
A further object of the present invention is to provide a granular ammonium polyphosphate fertilizer material that exhibits superior physical properties (i.e., harder, smoother, and less dusty) and that is ideally suited for use as a solid granulation intermediate product for subsequent production of fluid suspension fertilizers, thus reducing costs since solid intermediates can be shipped cheaper on a per unit of plant food basis than the fluid intermediates that would otherwise normally be used. The critical minimum polyphosphate content for the process of our invention is about 12 percent polyphosphate in the granular material used as an intermediate to produce a suspension containing the required minimum 10 percent polyphosphate.
Still further and more general objects and advantages of the present invention will appear from the more detailed description set forth below, it being understood, however, that this more detailed description is given by way of illustration and explanation only and not necessarily by way of limitation since various changes therein may be made by those skilled in the art without departing from the true spirit and scope of the present invention.
Thus the novelty of the present invention resides in a new method of producing granular ammonium polyphosphate fertilizer materials having a predetermined critical minimum content of polyphosphate required for the particularly desired end use, said method effected in a common drum type granulator utilized in conjunction with a single-stage inline reactor, said method characterized by the fact that substantially no external heat energy need be applied thereto.
DESCRIPTION OF THE DRAWINGS
The present invention, together with further objects and advantages thereof, will be better understood from a consideration of the following description taken in connection with the accompanying drawings in which:
FIG. 1 is a flow diagram illustrating the principal novel process which results in a granular ammonium polyphosphate being produced in which the minimum polyphosphate content required can be effected.
FIG. 2 is a sketch of a pipe reactor which uses a 11/2-inch horizontal reaction tube made of Type 316 stainless steel.
FIG. 3 is a sketch of a pipe reactor which uses a vertical 8-inch reaction tube.
FIG. 4 represents a graphical plot of the relationship between granular product polyphosphate content to the temperature of the feed phosphoric acid fed to the inline reactor.
FIG. 5 represents a graphical plot of the relationship between the granular product polyphosphate content to the heat content of the input feeds to the inline reactors, including both sensible heats and heats of reaction.
FIG. 6 represents a graphical plot of the relationship between the polyphosphate content and the solidification temperature for suspensions of a nominal 11-33-0 grade made from granular ammonium polyphosphate materials.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now more particularly to FIG. 1, a stream of wet-process phosphoric acid 1 from a source not shown is introduced into insulated granulator exhaust scrubber 2 wherein a portion thereof is recirculated via insulated line 3. Water vapor is discharged to the atmosphere via line 4. A side stream of phosphoric acid via insulated line 5 is fed into the pipe reactor shown and comprising standard pipe tee 6 followed by a length of insulated standard pipe 7 wherein said phosphoric acid reacts very rapidly with a stream of gaseous anhydrous ammonia fed from a source not shown via line 8 into pipe reactor 6 and 7. The melt reaction product from pipe reactor 6 and 7 discharges from insulated reaction tube 7 into insulated drum granulator 9, and coats particles of recycled finely divided product fed from recycle feeder 10 via line 11 and binds them together to form fertilizer granules. Drum granulator 9 is particularly suited to containment of the discharged vapors. The vapors discharging from pipe reactor 6 and 7 are contained by insulated hood 12 and exhausted by insulated duct 13 to insulated granulator exhaust gas scrubber 2. Granulator discharge stream 14 is fed to rotary cooler 15 wherein the fertilizer granules are contacted with airstream 16 for removal of sensible heat. The cooled material is subsequently introduced into size classifier screens 17. Onsize product is taken off via line 18. Oversize via line 19 is crushed in chainmill or similar crusher 20 and the resulting crushed material recycled to screens 17 via line 21. The undersize material from screens 17 is returned to granulator 9 via line 22. A more detailed description of the quantity and quality of insulation required on equipment pieces 2, 3, 5, 6, 7, and 12, supra, is defined in Example I below.
Referring now more specifically to FIGS. 2 and 3, the reaction tube, a length of suitably corrosion-resistant pipe, is preceded by a standard pipe tee. Type 316 stainless steel is recommended. A horizontal pipe reaction tube configuration is shown in FIG. 2; a vertical configuration is shown in FIG. 3. The significance of the configurations and sizes can be better understood by examining Example I, infra.
Referring now more specifically to FIGS. 4-6, the graphical relationships shown therein are better understood and appreciated when taken in conjunction with descriptions of various examples discussed infra. Accordingly, more detailed and specific discussion of FIGS. 4 and 5 are found in the discussion of Example I, infra, and detailed and specific discussion of FIG. 6 is found in the discussion of Example II, infra.
EXAMPLES
In order that those skilled in the art may better understand how the present invention can be practiced, the following examples are given by way of illustration and not necessarily by way of limitation.
EXAMPLE I
Several series of tests have been conducted on pilot-scale equipment. The granulation pilot plant had a nominal production capacity of 0.5 tons per hour of granular ammonium polyphosphate fertilizer material. The material was produced with a process that utilized a pipe reactor as the sole reaction system and a drum granulator. An ammonium polyphosphate melt was produced from reaction of anhydrous ammonia and wet-process phosphoric acid in the pipe reactor, and the resulting melt was subsequently distributed onto a bed of recycle solids in a drum granulator and the formation of granular material resulted with the granulator discharge product being cooled and sized and the undersized material returned as recycled solids to the granulator. An anomaly of this process is that a loss of polyphosphate occurs within said drum granulator which is not noticed when using another type of granulator--the pug mill. These tests were made in an effort to predict the polyphosphate contents of the product that could be obtained, this being otherwise difficult because of the polyphosphate losses that occur in process. A merchant-grade wet-process phosphoric acid was used in these tests. The average analysis (weight percent) of the feed acid was as follows:
Total P 2 O 5 --53.3,
Al 2 O 3 --1.6,
Fe 2 O 3 --1.5,
MgO--0.67,
F--1.0,
SO 3 --2.9,
CaO--0.14,
Water-insoluble solids--2.1,
Total H 2 O--17.9.
This information from the tests can be best assimilated if it is presented in summary graphical form, as shown in FIG. 4, which shows the polyphosphate contents obtained in granular ammonium polyphosphate product for various phosphoric acid feed temperatures to the reactor. External preheat was used for the higher temperatures solely and only for the purpose of defining invention parameters. We do not contemplate the use of external heat in the process to obtain the minimum critical polyphosphate. All heat is obtained from chemical heats of reaction. FIG. 5 shows that the information from FIG. 4 can be brought to a common basis and plotted as product polyphosphate content versus the total heat input to the reactor where the sensible heats of the feed phosphoric acid and ammonia and the heat of reaction of the ammonia and phosphoric acid is included. This shows that for a given acid concentration, the polyphosphate content desired can be obtained by the addition of a given heat input to the reactor as dictated by the relationship given in FIG. 5. This heat is adjusted by the quantity of insulation which, by controlling the rate of heat losses, can maintain a given reactor heat input, since a maximum theoretical heat input is available to the process from chemical heats of reaction. In this series of tests, for example, a nominal 11-55-0 grade granular fertilizer is produced by neutralization reaction of gaseous ammonia and phosphoric acid where an NH 3 :H 3 PO 4 mole ratio of 1.0 was maintained. The total heat available from the chemical reaction is 795 Btu/pound P 2 O 5 for a heat of reaction value of 3284 Btu/pound of ammonia reacted. The reactants are at ambient temperatures and the sensible heat is considered negligible because a zero heat enthalpy datum base of 70° F. is used, so the total heat available to the process is equivalent to the total chemical heat of reaction. As shown specifically in FIG. 5, to obtain the minimum critical polyphosphate content of 12 percent, insulation of a predetermined R-value is used which is sufficient to reduce the heat losses so that of the total theoretical heat of 795 Btu/pound P 2 O 5 only 50 Btu/pound P 2 O.sub. 5 of heat is lost from the reaction and scrubbing systems resulting in a net heat input to the reactor of at least 745 Btu/pound P 2 O 5 . As the NH 3 :H 3 PO 4 mole ratio is increased from 1.0 upwards to 1.25, which represents the total range through which effective and desirable granulation of the polyphosphate material can be achieved, the total theoretical heat available in the process ranges from 795 Btu/lb P 2 O 5 upwards to 902 Btu/lb P 2 O 5 . Thus, with a required net heat input to the reactor of at least 745 Btu/lb P 2 O 5 , the present invention, when operating at a NH 3 :H 3 PO 4 mole ratio of 1.25, would allow a heat loss of upwards of 157 Btu/lb P 2 O 5 . Another way of looking at this is pointed out infra in the example wherein in an installation having the proper amount of heat conservation measures, to wit, insulation on the reactor, granulator, scrubber, and feed and drain lines, to yield a 12-percent polyphosphate product when operated at a NH 3 :H 3 PO 4 mole ratio of 1.0, will yield a product having higher amounts of polyphosphate as the mole ratio of ammonia to acid is increased upwards to about 1.25. Since the heat of reaction value for ammonia throughout this range is constant, both the increase in polyphosphate points or the increase in amount of heat loss allowable is approximately linear.
Although the pipe reactor itself will operate very well at NH 3 :H 3 PO 4 mole ratios up to 1.5, when the pipe reactor is included in a granulation process, it is not desirable to operate the pipe reactor at NH 3 :H 3 PO 4 mole ratios above about 1.25 because ammonia evolution from the pipe reactor and the granulator increases very rapidly as the mole ratio is increased and this ammonia must be removed in a scrubber, which subsequently must be larger and more expensive. Additionally, as the mole ratio increases, the solubility of the resultant product also increases rapidly so that granulation is effected detrimentally and a larger rate of recycled solids must be supplied to maintain granulation. Larger, more expensive transfer equipment is consequently required.
In this particular series of tests, a drum granulator 3 feet in diameter and 6 feet long, insulated with 1 inch of rigid calcium silicate, was used. A pipe reactor with an insulated 11/2-inch-diameter pipe reaction tube, as shown in FIG. 2, was used. One inch of rigid calcium silicate insulation was used. The fumes and dust from the drum granulator and the reactor discharge inside the drum granulator were pulled by a fan-induced draft through an 8-inch diameter duct (heat transfer surface area of 29 ft 2 ) insulated with a 11/2-inch thickness of calcium silicate, and into the scrubber. The ammonia present in the exhaust stream, usually less than 10 percent of the total ammonia fed to the process, was removed as it reacted with the recirculating stream of phosphoric acid in the scrubber. The scrubber used was a vertically oriented packed bed scrubber which was 2 feet in diameter and 10 feet high (total heat transfer surface area of 69 ft 2 ) and insulated with a 11/2-inch thickness of calcium silicate insulation. A 15-inch diameter and 18-inch high seal tank (7 ft 2 of heat transfer surface) was installed underneath the scrubber so that no air in leakage would occur as the recirculating phosphoric acid scrubbing media exited the bottom of the scrubber. This seal tank was also insulated with a 11/2-inch thick layer of calcium silicate, as were the 1-inch diameter pipes used to feed acid to the scrubber and the 11/4-inch diameter drain line in which the phosphoric acid exiting the bottom of the scrubber drained back to a holding tank from which acid was pumped back to the scrubber and a side stream of acid fed to the reactor. These lines had a total heat transfer surface area of 54 ft 2 . The acid feed lines to the reactor were 1/2-inch diameter and comprised a total length of about 106 feet. Of the total 23 ft 2 of heat transfer surface area of these acid feeds, 17 ft 2 was insulated with a 1-inch thickness of calcium silicate. The pipe reactor to which the phosphoric acid was fed had a total heat transfer surface area of 3 ft 2 and was also insulated with a 1-inch thickness of calcium silicate. These thicknesses of insulation were not necessarily the ideal thicknesses required since the tests were structured so as to define the parameters of the process. In some instances, as mentioned previously, external heat was added to the process to define upper limits of the parameters. It was discovered from the test data that the insulation required could be defined from the following relationship.
Heat loss from system=(Heat loss from scrubber system and acid feed and drain piping)+(Heat loss from reactor)+(Heat loss from granulator shell)
This can be shown as the following equation:
(Q.sub.L)P·w.sub.P.sbsb.2.sub.O.sbsb.5 =k/x[A.sub.1 (T.sub.1 -T.sub.A)+A.sub.2 (T.sub.2 -T.sub.A)+A.sub.3 (T.sub.3 -T.sub.A)]
where
Q L =allowable heat loss as shown in FIG. 5, Btu/lb P 2 O 5
P=production rate of product, lb/h
w P .sbsb.2 O .sbsb.5 =weight fraction of P 2 O 5 in product
k=thermal conductivity of insulation, Btu/(hr-ft 2 -°F./inch thickness)
x=thickness of insulation, in.
A 1 =heat transfer area of scrubber and acid feed and drain piping, ft 2
A 2 =heat transfer area of reactor, ft 2
A 3 =heat transfer area of granulator, ft 2
T 1 =mean temperature of acid in scrubber and flow lines, °F.
T 2 =mean temperature of reactor melt, °F.
T 3 =mean temperature of granulator, °F.
T A =ambient temperature
For example for a 12 percent product polyphosphate a reactor heat input of 745 Btu/lb P 2 O 5 is required. For this series of tests, a 1.0 NH 3 :H 3 PO 4 mole ratio was maintained and a theoretical maximum heat input was 795 Btu/lb P 2 O 5 . Since a heat loss of only 50 Btu/lb P 2 O 5 could occur, the previous equation simplifies to
50(700)(0.55)=k/x[232.5(175-80)+3(400-80)+56.5(200-80)]
where the ambient temperature was 80° F. and all values and units are appropriate as defined for the equation. Rearranging and solving this equation we find that the k/x term equals 0.645. Therefore, if calcium silicate, which, under conditions of this series of tests, has a thermal conductivity of 0.39 Btu/(hr-ft 2 -°F.-inch thickness) is used, a thickness, x, of 0.6 inch is required. Although calcium silicate is used as an example, other types of insulating material could be used as long as the value of k/x for that insulation is 0.645. This equation can be used equally well for other production rates and for scaleup to larger size units since both production rate and total area for heat transfer are included. The ammoniation rate has a two-fold effect on polyphosphate content. The added heat of reaction obtained with a higher ammoniation rate increases the water removal in the pipe reactor, increases the melt temperature, and thus increases the polyphosphate content. Bench-scale pipe reactor tests showed that increasing the ammoniation rate from a reactant feed NH 3 :H 3 PO 4 mole ratio from 1.0 to 1.5 increased the polyphosphate content of the melt by 4 percentage points. Secondly, a higher ammoniation rate increases the pH of the granulator product and higher pH reduces polyphosphate losses by hydrolysis, thus increasing product polyphosphate contents. Pipe reactor feed NH 3 :H 3 PO 4 mole ratios in the range only up to 1.25 have been succcessfully tested in the pilot-scale granulation studies. Higher ratios exagerate scrubbing considerations, supra.
EXAMPLE II
Several granular product ammonium polyphosphate materials were produced that had various levels of polyphosphate contents. These materials were used as intermediates to produce fluid suspensions to test the effects of polyphosphate contents. In U.S. Pat. No. 4,066,432, Jones et al teach that the best suspensions are produced if the nitrogen to phosphate ratios are maintained in a range where the desired type of crystals are formed and which is at or near the point of maximum solubility. This corresponds to an N:P 2 O 5 weight ratio of about 0.32-0.34, so all tests for comparison in the series were made at this ratio and the products had a nominal grade of 11-33-0.
The test data is summarized in FIG. 6 where solidification temperatures are given versus polyphosphate contents for various fluid ammonium polyphosphate suspensions. Viscosities of all suspensions were suitable. No suspension had a viscosity higher than 450 centipoises at 80° F. and 900 centipoises at 0° F. Solidification temperatures of -5° F. are needed in ammonium phosphate suspensions if they are to be used successfully in the northern United States; therefore, FIG. 6 is significant in that it shows that only about 10 percent polyphosphate as percent of the total P 2 O 5 is required to obtain a solidification temperature of -5° F. Although higher polyphosphate contents are desired for lower solidification temperatures (for example, a 20 percent polyphosphate content suspension will have a -10° F. solidification temperature), the data indicate the minimum desired suspension polyphosphate content, as percent of total P 2 O 5 , is 10 percent. When suspension is made from intermediate granular ammonium polyphosphate, it is desirable to use the minimum acceptable polyphosphate content of granular material since any lowering of polyphosphate content results in reducing the heat input required for the manufacturing process, including eliminating the need for external heating. The tests indicate that 2 percentage points of polyphosphate content is lost during production of suspension from granular ammonium polyphosphate so that a granular ammonium polyphosphate product containing 12 percent polyphosphate as percent of the total P 2 O 5 is recommended. FIG. 6 shows also that suspensions made from monoammonium phosphate without polyphosphate solidifies at much higher temperatures (+5° F.) as compared with suspensions containing the critical minimum polyphosphate directed by the present invention.
INVENTION PARAMETERS
After sifting and winnowing through the data supra, as well as other results of tests and operation of our new, novel, and improved method for production of granular ammonium polyphosphate fertilizer, we now present the acceptable and preferred parameters and variables.
Results of test data show that a granular ammonium polyphosphate product should contain a minimum of 12 percent polyphosphate as percent of the total P 2 O 5 if it is to be used suitably as an intermediate in producing suspension fertilizers in the United States. Results also show that a process using an inline reactor and a drum granulator is suitable for producing the granular ammonium polyphosphate and that polyphosphate losses inherent in this process can be predicted and conditions maintained so that specific critical minimum polyphosphate contents desired can be maintained and produced. This can be accomplished by control of the heat input of the feed reactants to the reactor, as indicated by the resultant temperature of the reactor product to be granulated, by control of process heat losses by the heat conservation methods of insulation of scrubber, reactor, and related piping and ductwork of the reaction system.
The quantity and quality of insulation required can be determined by the equation given in Example I, supra. For a given type of insulation, the thermal conductivity is set and the given thickness, x, of that insulation can be calculated using the equation from Example I, supra, as rearranged and shown below: ##EQU1## Once an installation of the process of this invention is defined, the heat transfer surface areas A 1 , A 2 , and A 3 can be determined. For a specific product grade formulation to be produced the production rate, P, and the phosphate fraction as P 2 O 5 , w P .sbsb.2 O .sbsb.5, are obtained. For the desired or required polyphosphate selected, the heat input to the reactor can be found in FIG. 6; the theoretical heat input is determined for the product grade formulation selected; and the difference between the two values is the allowable heat loss, Q L . Now with the ambient temperature selected for design purposes or actual operating conditions and with the thermal conductivity, k, as set by the type insulation selected for study or use, all values are available for the right side of the equation and the insulation thickness, x, can be calculated. This is the required insulation thickness required on the various insulated pieces of equipment discussed in DESCRIPTION OF THE EMBODIMENTS, supra.
While we have shown and described particular embodiments of the present invention, modifications and variations thereof will occur to those skilled in the art. We wish it to be understood, therefore, that the appended claims are intended to cover such modifications and variations which are within the true scope and spirit of the present invention. | Method for production of granular ammonium polyphosphate fertilizer in which ammonium polyphosphate melt is prepared in a simple inline reactor and distributed onto a bed of solids in a drum granulator to bind smaller fertilizer particles into granules. The desired polyphosphate content can be obtained in the granular product by adjusting the total heat input of the feed reactants to the reactor by means of energy conservation modifications to the system. Energy losses are controlled by use of a predetermined quantity of insulation so that varying amounts of the maximum theoretical heat input can be utilized to produce products of polyphosphate contents as desired. The quantities of insulation and the resulting heat inputs to the reactor have been identified which will produce the given critical polyphosphate content material, determined to be 12 percent of total phosphate as polyphosphate in a granular material, which will give 10 percent polyphosphate in a suspension fertilizer made from the granular material. No external heat is required and energy and production savings can be readily realized. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority of U.S. Provisional Patent Application No. 61/449,358 filed Mar. 4, 2011, which is incorporated herein by reference in its entirety.
FIELD
[0002] The present disclosure relates generally to sleep disorder diagnostics. More particularly, the present disclosure relates to cannulae and airflow sensors used in sleep disorder diagnostics.
BACKGROUND
[0003] Sleep apnea is characterized by a cessation or reduction of breathing that lasts at least 10 seconds and that is repeated at least 5 times an hour while the patient is sleeping. Obstructive sleep apnea (OSA) refers to apnea syndromes due primarily to collapse of the upper airway during sleep. It is estimated that 2 to 4% of middle aged people have OSA. OSA has two specific classifications of events: apnea and hypopnea. An apnea event is defined as an absence of airflow and a hypopnea event as a reduction in airflow associated with a blood oxygen reduction (desaturation) of 3 to 4%.
[0004] The American Academy of Sleep Medicine's Manual for the Scoring of Sleep and Associated Events©2007 (AASM) requires the use of an oral/nasal thermal sensor for the detection of apnea and a nasal air pressure transducer hypopnea. Both of these devices require the use of different technologies to measure the same physical phenomena, which is the movement of air in and out of the patient.
[0005] In the case of apnea, to measure nasal air pressure, it is standard to use a nasal cannula coupled to a pressure transducer. In the case of hypopnea, to measure air temperature, it is standard to mechanically attach the thermal sensor to the cannula. The coupling of the pressure transducer and the thermal sensor to the cannula can interfere with the patient's flow of air (i.e., can interfere with the patient's breathing), cause the thermal sensor to be deflected away from the flow of air (i.e., cause the thermal sensor to be misaligned with the flow of air), and have the thermal sensors actually come in contact with the patient's skin. All of these effects will cause errors in the thermal sensor signal, which can lead to incorrect diagnostics.
[0006] Example of known air flow sensors can be found in U.S. Pat. Nos. 5,558,099; 5,832,592; and 5,161,541 to Bowman et al. However, the air flow sensor assemblies in these references are adhered directly adhered to the patient's upper lip and do not allow the use of a nasal cannula, as required by the AASM for scoring hypopneas, without mutual interference between the cannula and the air flow sensor assemblies. The same issue exists in the disclosures of U.S. Pat. Nos. 5,311,875, 6,491,642 and 7,608,047 to Stasz and in the disclosure of U.S. Pat. Nos. 6,254,545 and 6,485,432 to Stasz et al. None of these prior references allow the use of the required cannula without either affecting the flow of air in or the patient's comfort.
[0007] With respect to diagnosing hypopnea, state of the art measurement requires the separate attachment of the thermal sensor to the cannula and of the cannula to the patient. This is a tedious and laborious task as the individual patient setup must secure the thermal sensor to the cannula, place both the cannula and the thermal sensor on the patient and then, secure the cannula and the thermal sensor on the patient (for example, by using adhesive tape). Securing the thermal sensor to the cannula must be made precisely and in relation to the patient: that is, the thermal sensor should be in the path of the airflow, the thermal sensor should not be touching any objects that can influence the sensors ability to sense the temperature of the airflow, the cannula should be centered on the nares of the patient, and the cannula should not be occluded by the thermal sensor. All this must be done just before the cannula and the thermal sensors are secured (taped down) to the patient.
[0008] Further, the sleep industry also uses combination nasal/oral cannulae as described in U.S. Pat. No. 7,337,780 to Curti et al, an in U.S. Design Pat. No. D559,383 to Nalagatla et al. These combination nasal/oral cannulae allow the measuring of both nasal and oral airflows. Such nasal/oral cannulae have nasal prongs to measure the nasal air pressure as well as some form of ducting that protrudes into or over the oral cavity. The combined use of oral thermal sensor and these nasal/oral cannulae would cause the oral thermal sensors to be ineffective in that they would occlude the ducting opening or would require the oral ducting on the cannula to be shifted in order for the oral thermal sensor to be properly positioned, which would cause the oral ducting to properly capture the oral airflow component.
[0009] Furthermore, sleep laboratories are looking towards medical devices that are single patient use for the diagnosis of OSA on patient's with highly infectious conditions. However, there are presently no acceptable single use thermal sensors for measuring apnea that can function properly in combination with a nasal or nasal/oral cannula. U.S. design Pat. Nos. D590,058 and D607,993 to Cowen show airflow sensors shaped to work with cannulae using existing concepts for reusable sensors. These designs will not allow the manufacturing of a cost effective device for single patient use.
[0010] Bowman, referenced above, and others disclose using an adhesive to hold the thermal sensor in place while on the patient. However, this requires the use of non aggressive medical adhesive. These thermal sensors cannot be placed on the cannula as this type of adhesive will not last the duration of a sleep study.
[0011] Several of the prior art references disclose the addition of an adhesive being applied that will attach the thermal sensor directly to the patient. However, the shape and the properties of the flexible substrate that is usually comprised in the thermal sensor do not allow for the thermal sensor to be easily attached to the patient.
[0012] Some prior art approaches allow for the placement of the thermal sensing element on top of a substrate. Such approaches require the thermal wave to pass through the substrate before reaching the sensor. This can lead to incorrect reading of the air temperature.
[0013] Therefore, improvements in thermal sensors for cannulae are desirable.
SUMMARY
[0014] In a first aspect, the present disclosure provides a thermal sensor assembly to measure a temperature of air expelled by an individual, the thermal sensor assembly to be secured to a cannula having nasal prongs, the thermal sensor assembly secured to the cannula and the cannula secured to the individual defining an installed position. The thermal sensor assembly comprises: a substrate having a sensor portion, the substrate further having a sensor side and a backside, the backside being opposite the sensor side, the sensor portion defining an alignment aperture, the alignment aperture to receive at least one of the nasal prongs to align the thermal sensor assembly to the cannula; at least one nasal thermal sensor formed on the sensor side of the substrate and at the sensor portion of the substrate, the at least one nasal thermal sensor being adjacent to the alignment aperture, the at least one thermal sensor to sense, in the installed position, a temperature of air expelled through a nasal opening of the individual; and an adhesive layer formed on the backside of the substrate and at the sensor portion of the substrate, the adhesive layer to adhere the sensor portion of the substrate to the cannula.
[0015] In another aspect, the present disclosure provides a thermal sensor assembly to measure a temperature of air expelled by an individual, the thermal sensor assembly to be secured to a cannula having nasal prongs, the thermal sensor assembly secured to the cannula and the cannula secured to the individual defining an installed position. The thermal sensor assembly comprises: a substrate having a sensor portion, the substrate further having a sensor side and a backside, the backside being opposite the sensor side, the sensor portion defining an alignment feature, the alignment feature to receive at least one of the nasal prongs to align the thermal sensor assembly to the cannula; at least one nasal thermal sensor formed on the sensor side of the substrate and at the sensor portion of the substrate, the at least one nasal thermal sensor being adjacent to the alignment feature, the at least one thermal sensor to sense, in the installed position, a temperature of air expelled through a nasal opening of the individual; and an adhesive layer formed on the backside of the substrate and at the sensor portion of the substrate, the adhesive layer to adhere the sensor portion of the substrate to the cannula.
[0016] Other aspects and features of the present disclosure will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments in conjunction with the accompanying figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Embodiments of the present disclosure will now be described, by way of example only, with reference to the attached Figures.
[0018] FIG. 1 shows an embodiment of a thermal sensor assembly of the present disclosure secured to a cannula.
[0019] FIG. 2 shows a top view of the thermal sensor assembly of FIG. 1 .
[0020] FIG. 3 shows a bottom view of the thermal sensor assembly of FIG. 1 .
[0021] FIG. 4 shows a side view of the thermal sensor assembly of FIG. 1 .
[0022] FIG. 5 shows a front view of the thermal sensor assembly of FIG. 1 being secured to a nasal portion of a cannula.
[0023] FIG. 6 shows a rear view of the thermal sensor assembly of FIG. 1 being secured to the nasal portion of a cannula.
[0024] FIG. 7 shows a front view of the thermal sensor assembly of FIG. 1 secured by a tab to a cannula.
[0025] FIG. 8 shows a rear view of the thermal sensor assembly of FIG. 1 secured to by a tab to a cannula.
[0026] FIG. 9 shows another front view of the thermal sensor assembly of FIG. 1 secured by a tab to a cannula.
[0027] FIG. 10 shows another rear view of the thermal sensor assembly of FIG. 1 secured to by a tab to a cannula.
[0028] FIG. 11 shows a front view of the thermal sensor assembly of FIG. 1 being secured to a nasal portion of an oronasal cannula.
[0029] FIG. 12 shows a rear view of the thermal sensor assembly of FIG. 1 being secured to a nasal portion of an oronasal cannula.
[0030] FIG. 13 shows a front view of the thermal sensor assembly of FIG. 1 secured by a tab to an oronasal cannula.
[0031] FIG. 14 shows a rear view of the thermal sensor assembly of FIG. 1 secured by a tab to an oronasal cannula.
[0032] FIG. 15 shows a front view of the thermal sensor assembly of FIG. 1 being secured by tabs to an oral section of an oronasal cannula.
[0033] FIG. 16 shows a rear view of the thermal sensor assembly of FIG. 1 being secured by tabs to an oral section of an oronasal cannula.
[0034] FIG. 17 shows a bottom view of another embodiment of a thermal sensor assembly in accordance with the present disclosure.
[0035] FIG. 18 shows a bottom view of another embodiment of a thermal sensor assembly in accordance with the present disclosure.
[0036] FIG. 19 shows a bottom view of another embodiment of a thermal sensor assembly in accordance with the present disclosure.
DETAILED DESCRIPTION
[0037] Generally, the present disclosure provides a thermal sensor assembly that can be securely fixed to a cannula, in the correct position on the cannula, before the cannula is secured to the patient. The technician handling the cannula and the thermal sensor assembly only needs to be concerned about placing the cannula properly on the patient. The present disclosure allows for an easier and more accurate placement of the thermal sensor assembly and the cannula with respect to each other and with respect to the patient. Once the thermal sensor assembly is secured to the cannula, the technician simply has to tape the cannula in place, on the patient, and does need to be concerned about separately placing thermal sensors on the patient. The present disclosure allows for the placement of the thermal sensor directly in the path of the airflow. That is, there are no obstacles or materials between the thermal sensor and the flow of air. The present disclosure further allows the accurate placement of thermal sensors (thermal sensor assembly) on most nasal and oral/nasal cannulae presently on the market.
[0038] FIG. 1 shows an embodiment of a thermal sensor assembly 300 of the present disclosure. The thermal sensor assembly 300 is secured to a nasal cannula 10 , which is secured to a patient 302 . The thermal sensor assembly 300 has a sensor portion 308 that can be adhesively secured to the cannula 10 at the nasal portion 304 . Similarly an oronasal cannula with an oral section 110 as shown at FIGS. 11 and 12 could have the oral section 20 of the sensor attached. The sensor portion 308 has nasal thermal sensors 16 and 18 positioned to receive air flowing out the nasal openings 306 of the patient 302 . The cannula 10 has nasal prongs 307 inserted into the nasal openings 306 (nares). The nasal prongs 307 propagate air flowing out of the nasal openings 306 towards, for example, an air pressure monitor. The shape and size of nasal prongs 307 are such that only a portion of the air flowing out of the nasal openings 306 enters the nasal prongs 307 . Another portion of the air flowing out of the nasal openings 306 impinges on the nasal thermal sensors 16 and 18 . Additionally, the thermal sensor assembly 300 has a tail portion 8 and an intermediate portion 6 that physically connects the sensor portion 308 to the tail portion 8 . As will be described in greater detailed below, the thermal sensor assembly 300 of FIG. 1 also has a tab 14 that can be used to further secure the thermal sensor assembly to the cannula 10 .
[0039] The thermal sensor assembly 300 can comprise a thin, flexible non-electrically-conductive substrate (an electrically insulating substrate) such as, for example, mylar, polyester, and any other suitable type material that can be made thin and flexible.
[0040] FIG. 2 shows a top view of the thermal sensor assembly 300 with such a substrate 310 . The substrate 310 has electrically conductive traces 312 defined thereon. The electrically conductive traces 312 terminate at electrodes 28 , which are defined at the tail portion 8 and which can be connected to any suitable measurement apparatus through any suitable connector arrangement. The electrical conductive traces 312 also electrically interconnect the nasal thermal sensors 16 and 18 , as well as an oral thermal sensor 22 , which can be secured to the oral section 120 of the cannula 10 . The nasal and oral thermal sensors of the embodiment of FIG. 12 are electrically connected in series; however, any other type of electrical connection between the nasal and oral thermal sensors is also within the scope of the present disclosure. The electrically conductive traces 312 can include, for example, a conductive ink or any other suitable type of electrical conductor.
[0041] In another embodiment, instead of having two nasal thermal sensors 16 and 18 , there can be only one nasal thermal sensor 17 that extends such as to receive air flowing out of either of the nasal openings 306 .
[0042] The tail portion 8 can have defined therein a hole 26 that can be used to receive a cooperating part of a connector adapted to connect the electrodes 28 to the aforementioned measurement apparatus. The hole 26 receiving the cooperating part of the connector can help secure the electrodes 28 , and the tail portion 8 to the connector.
[0043] The substrate 310 also defines the tab 14 , which, as shown at FIG. 1 , can be used to secure the thermal sensor assembly 300 to the cannula 10 . The tab 14 is shown as extending perpendicularly from the intermediate portion 6 ; however, this need not be the case. For example, in another embodiment, the tab 14 can extend obliquely from the intermediate portion 6 and away from the sensor portion 308 . Such an embodiment would also allow the oblique tab to secure the thermal sensor assembly as in the previous embodiment; however, in applications where it may be desired to remove the thermal assembly sensor 300 from the cannula 10 , the oblique tab can facilitate the removal of the thermal sensor assembly 300 from the cannula 10 in that it can be easier for a technician to grab the end of the oblique tab for removal of the tab from the cannula 10 . In yet another embodiment there can be no tab 14 .
[0044] Further, the nasal sensor portion 308 of the thermal sensor assembly 300 has defined therein holes 32 and 34 , which can receive the nasal prongs 307 of the cannula 10 . The holes 32 and 34 define an alignment feature of the substrate 310 and of the thermal sensor assembly 300 . The nasal prongs 307 define an alignment feature of the cannula 10 . The alignment feature of the cannula (the prongs 307 ) cooperate with the holes 32 and 34 to align the thermal sensor assembly 300 to the cannula. As such, the thermal sensor assembly 300 is self aligning with respect to the cannula 10 . That is, a technician placing the thermal sensor assembly 300 onto the cannula 10 only needs to place the nasal prongs 307 into the holes 32 and 34 and to join the thermal sensor assembly 300 to the cannula 10 . By doing so, the nasal thermal sensors 16 and 18 are aligned to receive air from the nasal openings 306 .
[0045] The substrate 310 also defines a substrate oral portion 314 which has the oral thermal sensor 22 formed thereon. The substrate oral portion 314 can have tabs 24 which can be used to secure the substrate oral section 314 to the cannula oral section 110 .
[0046] The nasal thermal sensors 16 and 18 , and the oral thermal sensor 22 can be thermocouple sensors, thermistor sensors, bead sensors, or any other suitable type of sensor that allows for the measurement of temperature. Additionally, the nasal thermal sensors 16 and 18 , and the oral thermal sensor 22 can be made of thin deposits of electrically conductive ink. An electrically insulating, thermally conductive protective layer (e.g., a bio-compatible electrically insulating epoxy) can be formed over the nasal thermal sensors 16 and 18 , the oral thermal sensor 22 , and the electrically conductive traces 312 to allow proper temperature measurement of the air coming out of the patient and to avoid any extraneous electrical signal being picked up by the sensors and the conductive traces. An bio-compatible electrically insulating epoxy such as Loctite HYSOL M-31CL could be used.
[0047] The side of the substrate shown in the thermal sensor assembly 300 of FIG. 2 is the sensor side of the substrate. That is, the side of the substrate 310 that has the thermal sensors formed thereon.
[0048] The side of the substrate opposite to the sensor side (the backside) can have an adhesive layer portion secured thereto. The adhesive layer portion allows the thermal sensor assembly 300 to be secured to the cannula 10 . The side of the substrate opposite to the sensor side can also have a stiffener secured thereto, to facilitate the electrical connection of the electrodes 28 to a measurement apparatus through an electrical connector and to protect the electrodes against excessive bending. FIG. 3 shows such a stiffener 38 formed at the tail portion 8 and an adhesive layer portion 36 formed at the sensor portion 308 . As will be understood by the skilled worker, the adhesive layer portion 36 need not be applied over the entire backside of the sensor portion of the thermal sensor assembly 300 . The stiffener 38 can be made of any suitable rigid or semi-rigid material such as, for example plastic. As another example, a double layer of substrate material, or a thicker layer of substrate material could be used as a stiffener. The stiffener 38 can be secured to the substrate 310 with any suitable adhesive or through any other suitable means.
[0049] FIG. 4 shows a side view thermal sensor assembly 300 , which is shown with the stiffener 38 secured to the substrate 310 , the adhesive layer portion 36 formed on the substrate 310 , and a peel-way backing 44 that protects the adhesive layer 36 until the thermal sensor assembly 300 is ready to be secured to the cannula 10 . Also shown in FIG. 4 are the nasal thermal sensors 16 and 18 , and the oral thermal sensor 22 . Additionally, a layer of electrically insulating, thermally conductive material is shown, at reference numeral 46 , formed over the nasal thermal sensors 16 and 18 , and the oral thermal sensor 22 . An example of material that can be used at 46 is Loctite® HYSOL™ M-31CL. Any other suitable material can be used.
[0050] The thermal sensor assembly 300 is such that, when secured to the cannula 10 and with the cannula being secured to a patient (individual), the nasal thermal sensors 16 and 18 , and the oral thermal sensor 22 line-up with the nasal openings 306 and with the mouth of the patient 302 . Further, the tab 14 , which has the adhesive portion 36 formed thereon, facilitates the connection of the thermal sensor assembly 300 to the cannula 10 and can provide relief of strain applied at the tail portion 8 . The thermal sensor assembly being secured to the cannula and the cannula being secured to the individual can be referred to as the thermal sensor assembly installed position or simply as the installed position.
[0051] To secure the thermal sensor assembly 300 to the cannula 10 , the user (technician, clinician, etc.) first removes the peal-away backing 44 to expose the adhesive layer portion 36 . The user then slides the nasal prongs 307 of the cannula into the holes 32 and 34 to begin securing the sensor portion 308 to the nasal portion 304 of the cannula 10 by adhering the sensor portion 308 to the cannula 10 . This is shown in a front view at FIG. 5 , and in a rear view at FIG. 6 .
[0052] Subsequently, the user can wrap the tab 14 to the cannula 10 and back onto itself, as show in front and rear views at FIGS. 7 and 8 respectively.
[0053] If the thermal sensor assembly 300 is used with a nasal-only cannula, the tabs 24 may be cut off as shown in front and rear views at FIGS. 9 and 10 respectively. As such, the oral thermal sensor 22 dangles from the cannula 10 and faces the mouth of the patient 302 . The electrically insulating, thermally conductive material 46 mitigates interference from any contact of the oral thermal sensor 22 with the patient.
[0054] FIGS. 11 and 12 show respectively a front view and a rear view of the thermal sensor assembly 300 being secured to an oronasal cannula 10 prior to the tab 14 being secured to the cannula 10 . FIG. 11 also shows an oral section 110 of the cannula 10 and FIG. 12 an opening 120 for the oral pressure wave. The thermal sensor assembly 300 can be dimensioned such that, when the thermal sensor assembly is secured to the oronasal cannula 10 , the oral thermal sensor 22 does not occlude the opening 120 . For example, in the view shown at FIG. 12 , the oral thermal sensor 22 lies above the opening 120 and does not occlude the opening 120 .
[0055] FIGS. 13 and 14 show respectively a front view and a rear view of the thermal sensor assembly 300 secured to an oronasal cannula 10 with the tab 14 wrapped around the cannula 10 .
[0056] FIGS. 15 and 16 show respectively a front view and a rear view of the thermal sensor assembly 300 secured to an oronasal cannula 10 with the tabs 24 wrapped adhered to the cannula 10 . Although the tabs 24 are shown extending parallel to the intermediate portion 6 shown at FIG. 2 , this need not be the case. The tabs 24 can be at any suitable angle to the intermediate portion 6 without departing from the scope of the present disclosure.
[0057] FIG. 17 shows another embodiment of a thermal sensor assembly of the present disclosure. The thermal sensor assembly 500 of FIG. 17 has one elongated opening 502 , which can also be referred to as an alignment aperture or feature, that can fit over nasal prongs of a cannula to align and secure the thermal sensor assembly 500 the cannula in question.
[0058] FIG. 18 shows another embodiment of a thermal sensor assembly of the present disclosure. The thermal sensor assembly 504 of FIG. 18 has one opening 506 , and a slot 508 , both of which can also be referred to as alignment apertures or alignment features, that can fit over nasal prongs of a cannula to align and secure the thermal sensor assembly 504 the cannula in question.
[0059] FIG. 19 shows another embodiment of a thermal sensor assembly of the present disclosure. The thermal sensor assembly 510 of FIG. 19 has recesses 512 , both of which can also be referred to as alignment apertures or alignment features, that can fit over nasal prongs of a cannula to align and secure the thermal sensor assembly 510 the cannula in question.
[0060] The views of the thermal sensor assemblies of FIGS. 17 to 19 are bottom views. That is, the thermal sensors of the thermal sensor assemblies are on the opposite side of the side shown in FIGS. 17 to 19 .
[0061] In the preceding description, for purposes of explanation, numerous details are set forth in order to provide a thorough understanding of the embodiments. However, it will be apparent to one skilled in the art that these specific details are not required.
[0062] The above-described embodiments are intended to be examples only. Alterations, modifications and variations can be effected to the particular embodiments by those of skill in the art without departing from the scope, which is defined solely by the claims appended hereto. | An airflow sensor (thermal sensor assembly) that is designed to adhesively attach to different styles of a cannula and that can detect the movement of respiratory air through the nasal and/or oral cavities. When secured to the cannula, the airflow sensor has its nasal and oral sensing elements in positions that will maximize signal accuracy, minimize airflow signal artifacts, and minimize occurrences of signal loss due to direct patient skin contact. The airflow sensor does not disturb the flow of air from the patient or add any discomfort to the patient. The airflow sensor can be attached to most nasal or nasal/oral cannulae used in sleep disorder diagnostics. | 0 |
BACKGROUND OF THE INVENTION
The present invention relates to tungsten carbide hardfacing compositions and products produced therefrom. It especially relates to those hardfacing compositions which contain monocrystalline monotungsten carbide particles, hereinafter referred to as macrocrystalline WC.
Many tungsten carbide hardfacing compositions and methods for applying these compositions are known in the art. Examples of these compositions and methods are described in U.S. Pat. Nos. 3,768,984; 4,243,727; 3,800,891; 3,334,975; and 3,329,487. Hardfacing compositions have been applied to components used in earth drilling equipment to prolong the lifetime of these components by increasing their wear resistance. For example, the teeth of multiple cone roller bits have been rebuilt using hardfacing retipping rod.
One type of retipping rod utilized contained a blend of -40 +100 mesh eutectic W 2 C-WC, AISI 4600 steel powder, iron powder, carbon binder in the form of sugar, 0.9 to 1.32 weight percent -325 mesh niobium metal powder, and 2.07 to 4.14 weight percent -100 mesh molybdenum metal powder. This blend of hardfacing powder was contained within a hollow mild steel rod which was consumably melted onto the multiple cone teeth to be rebuilt.
Also, in the field of earth drilling, it has been observed that bulk hardfaced drill pipe couplings with a larger diameter than the drill pipe have a tendency to abrade and damage the drill casing, especially during deep well drilling. The abrasion of the casing has been related to the fact that the tungsten carbide particles in the hardfacing protrude above the steel matrix of the weld pool. One attempt to provide improved submergence of the tungsten carbide particles in the weld pool (see U.S. Pat. No. 4,243,727) involved dropping cemented tungsten carbide granules directly into the weld puddle at the arc, rather than at a point following the arc, as had been the practice. The higher temperatures found in the weld puddle at the arc, however, result in greater dissolution of the tungsten carbide into the steel matrix and can lead to a reduction in the toughness of the steel matrix.
Drill couplings have also been bulk hardfaced by dropping macrocrystalline WC into the weld pool. While drill couplings hardfaced in this manner are usable, they have significant amounts of macrocrystalline WC protruding above the weld pool and exhibit a significant number of cracks at the weld deposit surface.
It is, therefore, an object of the present invention to provide hardfacing powder mixtures which can be applied to wear surfaces using conventional hardfacing techniques and result in submergence of substantially all of the tungsten carbide particles in the weld pool.
It is also an object of the present invention to provide a hardfacing powder mixture utilizing macrocrystalline WC.
It is a further object of this invention to provide hardfaced wear products containing macrocrystalline WC and which are substantially free from surface cracks.
These and other objectives of the present invention will become more clearly apparent upon review of the following specification in conjunction with the attached drawings.
BRIEF SUMMARY OF THE INVENTION
In accordance with the above objectives, a hardfacing composition is provided containing tungsten carbide particles, and niobium metal powder in a small, but effective, amount to substantially submerge the tungsten carbide in the steel matrix of the weld pool while, also, producing a weld pool substantially free of cracking. Preferably, the powder mixture contains 0.05 to 0.5 weight percent niobium metal powder, 0.05 to 1.0 weight percent molybdenum metal powder, with the remainder being tungsten carbide particles.
The tungsten carbide particles utilized in the powder mixture according to this invention may be selected from the group comprising macrocrystalline WC, cast tungsten carbide (an eutectic of monotungsten carbide and ditungsten carbide), cemented tungsten carbide, and mixtures of the foregoing types of tungsten carbide particles. Macrocrystalline WC is preferred because of its greater resistance to melting and dissolution during hardfacing and its superior resistance in high abrasion environments compared to the other aforementioned tungsten carbide materials.
Most preferably, the macrocrystalline WC used should be a product of the thermit process for preparing WC disclosed in U.S. Pat. No. 3,379,503, assigned to applicant corporation.
Also provided, in accordance with the present invention, are wear components having a hardfacing layer containing macrocrystalline WC particles wherein substantially all of said particles are submerged beneath the surface of the steel matrix comprising the hardfacing weld pool. Preferably, the hardfacing steel matrix also contains niobium in a small, but effective, amount to substantially eliminate cracking and provide good submergence of the tungsten carbide in the weld pool. Molybdenum in small, but effective, amounts to enhance the effect of the niobium, also may be present in the hardfacing steel matrix.
BRIEF DESCRIPTION OF THE DRAWINGS
The exact nature of the present invention will become more clearly apparent upon reference to the following detailed specification, taken in connection with the accompanying drawings, in which:
FIG. 1 is a side view of a portion of a drill pipe coupling having a hardfacing composition according to the present invention.
FIG. 2 is an end-on view of a coupling being hardfaced according to the present invention.
FIG. 3 is a longitudinal cross section of the drill pipe coupling taken along view III--III in FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
It has been found, in accordance with the present invention, that bulk hardfacing of drill pipe couplings can be greatly facilitated by the addition of at least a small, but effective, amount of niobium metal powder and molybdenum metal powder, to the tungsten carbide granules that are being applied in the hardfacing operation.
It has been found that 0.05 to 0.5 weight percent niobium metal powder and 0.05 to 1.0 weight percent molybdenum metal powder, when blended with macrocrystalline WC, will result in a drill pipe coupling hardfacing in which the tungsten carbide has been substantially submerged below the surface of the steel matrix comprising the weld pool.
FIG. 1 shows a side view of a portion of a drill coupling 1 having annular bonds of hardfacing 3 that have been applied in accordance with the present invention. The hardfacing is applied in a single application by rotating the drill pipe and providing an arc between a consumable steel wire and the coupling to create a weld puddle while, also, reciprocating the wire parallel to the coupling axis. A hardfacing band is created as the macrocrystalline WC, niobium and molybdenum are being fed into the weld puddle directly behind the arc as is the usual technique practiced in the industry.
It has been found, surprisingly, that the addition of niobium and molybdenum in these small, but effective, amounts is sufficient to produce a smooth hardfacing surface in drill couplings using existing bulk hardfacing equipment without modifications as required according to U.S. Pat. No. 4,243,727. This mixture of hardfacing powders also produces a smooth surface hardfacing band which is essentially free of cracking which is a distinct advantage not typically experienced in hardbanding.
FIG. 2 is an end-on view of a coupling being hardfaced according to the present invention. A MIG automatic argon unit 5 is shown striking an arc between the consumable steel wire 9 and the coupling surface 1, while the coupling is being rotated in the direction of arrow A. Argon gas is used as a shield around the weld pool and the mixture of powders according to the present invention is dropped from a feeding device 7 which follows the mild steel electrode 9 and falls into the weld pool behind the arc area.
A section through the resulting hardfacing or hardband 11 is shown in FIG. 3. It can be seen that substantially all of the carbide particles 13 are submerged beneath the surface of the hardband deposit.
The deposits produced contain approximately 40 to 60 weight percent tungsten carbide granules and 60 to 40 weight percent steel matrix. Upon cooling of the hard surfaced weld, typical surface cracking has not been observed and the weld is essentially free from such cracks. The hardfacing deposit itself is harder near the bottom than at the surface, and this is due to the higher concentration of tungsten carbide at the bottom of the weldment. Typical hardnesses range between 50 to 60 Rockwell "C".
While macrocrystalline WC is the preferred form of tungsten carbide to be used in this application, other forms of tungsten carbide, such as cast tungsten carbide, cemented tungsten carbide, and their mixtures with each other and macrocrystalline WC may also be used. The good submergence of the carbide and the freedom from cracking is believed to be primarily due to the addition of the niobium metal powder which is added to the mixture as a -100 mesh powder. The addition of molybdenum enhances the effect of the niobium in promoting submergence and freedom from cracking. However, molybdenum cannot be added alone to the mixture, whereas niobium can be, while still obtaining some of the benefits of the present invention. Molybdenum is also added as a -100 mesh powder.
The tungsten carbide particles themselves may have a size between 10 and 200 mesh; however, specific ranges within the broad range are preferred. For certain applications, a coarse mesh size within the range of -10 to +40 mesh are preferred, whereas in other applications, a fine mesh size within the range of -40 to +150 mesh is preferred.
The following are specific examples of hardbanded pipe couplings according to the present invention. In the following examples, a pipe coupling, as shown in the figures, was hardfaced using a MIG automatic argon unit. The pipe coupling was rotated at a speed of one revolution every 84 seconds. An arc was struck at a potential of 32 volts between a consumable mild steel weld wire and the coupling surface. The mixture of tungsten carbide, molybdenum and niobium was then fed behind the arc into the weld pool at a feed rate of 120 grams per minute to produce a deposit containing approximately 50 weight percent tungsten carbide.
EXAMPLE NO. 1
A fluid weld with good submergence of tungsten carbide and one minor crack produced on cooling was produced by the utilization of a blend of material containing 1000 grams of -60 +80 mesh macrocrystalline WC blended with 0.5 grams of -100 mesh niobium metal powder and 0.8 grams of -100 mesh molybdenum metal powder.
EXAMPLE NO. 2
This example is the sme as Example No. 1, except that the amount of additives was increased. Five grams of niobium and 8 grams of molybdenum were contained in the blend used in this example. No cracking was observed on cooling of the weld pool and a 35 volt potential was used in this example.
EXAMPLE NO. 3
In this example, the same conditions were also used, as in Example No. 1, except that niobium was added in the amount of one gram and molybdenum was added in the amount of 1.6 grams. A smooth weld surfce and excellent wetting of the carbide was produced with substantial submergence of all carbide beneath the surfaces of the weld.
Modifications may be made within the scope of the appended claims. | This invention relates to mixtures of tungsten carbide, niobium metal, and molybdenum metal powders for use in the hardfacing of drill pipe couplings used in earth boring operations. It has been found that the addition of small amounts of niobium metal alone, or in combination with molybdenum, are effective to substantially submerge the tungsten carbide particles in the weld pool produced during hardfacing while, also, minimizing the occurrence of cracks which may be produced as the weld pool freezes. | 1 |
TECHNICAL FIELD
This invention relates generally to refuse compactors, and particularly to a display for indicating a full condition of a household compactor.
BACKGROUND OF THE INVENTION
A conventional type of household compactor has a ram that is positioned within a cabinet above a receptacle containing refuse to be compacted. During a cycle of operation, an electric motor drives the ram downward into the receptacle to compact refuse therein and then returns the ram to its rest position above the receptacle. The motor is controlled by a number of electrically interlocking switches and relays to move the ram during a refuse compaction cycle and protect the user from injury by the ram. For example, the motor is de-energized automatically if the receptacle is opened or tilted, or if the ram reaches its rest position at the completion of a compaction cycle. The direction of rotation of the motor reverses automatically to reverse the direction of movement of the ram following compaction of the refuse or upon a jam, detected by a centrifugal switch mechanically coupled to the motor, to return the ram to the rest position.
The refuse is generally contained in a disposable bag within the receptacle to be discarded when the bag becomes filled to its capacity. Because the interior of the receptacle of the compactor is not readily viewed, however, it is not convenient for the user to determine when the refuse bag should be removed and replaced. Even as the interior of the receptacle is viewed by the user as he or she slides the receptacle open prior to a compaction cycle, it cannot be determined by visual inspection whether the bag should be replaced prior to the next compaction cycle because the refuse added has not yet been compressed. It accordingly is desirable to provide a display to indicate whether the refuse bag of a compactor is full without requiring visual inspection of the bag by the user.
Apparatus in the prior art for providing a "full bag" indicator require the addition of multiple electrical components and therefore add excessively to the cost of the compactor. For example, in U.S. Pat. No. 3,831,513 to Tashman, a limit switch extending downward on a pipe from an upper surface of an industrial compactor contacts an abutment member on the ram when the ram is extended downward to a position corresponding to a full condition of the receptacle. The reactive pressure of refuse in the receptacle against the ram is detected by a centrifugal switch coupled to the motor that closes when the speed of the motor is reduced below about 1375 rpm as the ram compresses the refuse. If the limit switch is closed when the direction of the ram reverses in response to reactive pressure of the refuse in the receptacle, the receptacle is determined to be full. A relay having its actuator coil in series with the limit switch and centrifugal switch closes to energize a "full compactor" indicator lamp when both switches are closed simultaneously.
An additional pair of contacts of the indicator lamp relay, when the contacts are closed, electrically bypasses the limit switch and centrifugal switch to latch the indicator lamp on until the compactor is emptied and the relay reset.
This system, although effective to turn on the "full compactor" lamp when the receptacle of the compactor is full of refuse, requires in addition to standard compactor control circuitry as well as a downwardly extending limit switch and its suspension hardware, a further pair of relay contacts together with associated wiring for latching the indicator lamp on, and accordingly, is too costly for incorporation as a "full bag" indicator in a household compactor.
It is therefore an object of this invention to provide a "full bag" indicator for a compactor that is less expensive than indicators of the prior art.
Another object of the invention is to provide a "full bag" indicator for a compactor that uses a minimum number of additional parts and is easily installed during manufacture of the compactor.
Another object is to provide a "full bag" indicator for a compactor that uses existing electrical components for controlling the compactor to detect a full bag.
A further object of the invention is to provide a "full bag" indicator for a compactor that uses a mininum number of electrical components to maximize the reliability of the indicator.
SUMMARY OF THE INVENTION
The above and other objects of the invention are satisfied by a full bag indicator for a compactor that comprises an indicator lamp energized by a relay connected electrically in series with a limit switch and a centrifugal switch coupled to a reversible motor within the compactor. The limit switch is located in a position on a wall of the cabinet to be closed by a ram when the ram is extended by the motor into a receptacle to a level corresponding to a full refuse bag. The centrifugal switch closes when the speed of the motor slows under the reactive force of the refuse as the refuse is compacted by the ram, to reverse the motor and return the ram to its rest position above the receptacle. The indicator lamp thus is energized when the direction of movement of the ram is reversed at the time that the ram is in a "full bag" position within the receptacle.
Latching circuitry latches the indicator lamp on when the lamp is energized by simultaneous closure of the limit switch and centrifugal switch to indicate a full bag condition of the receptacle. In one embodiment of the invention, the latching circuitry includes an additional pair of switch contacts of the lamp relay that, when closed, electrically bypasses the limit switch and centrifugal switch to maintain the lamp on. In another embodiment, the lamp relay contacts are connected electrically in series, and the lamp is connected electrically in parallel, with the actuator coil of the lamp relay for latching.
Still other objects and advantages of the present invention will become readily apparent to those skilled in this art from the following detailed description, wherein only the preferred embodiment of the invention are shown and described, simply by way of illustration of the best mode contemplated of carrying out the invention. As will be realized, the invention is capable of other and different embodiments, and its several details are capable of modifications in various obvious respects, all without departing from the invention. Accordingly, the drawing and description are to be regarded as illustrative in nature, and not as restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a refuse compactor having a "full bag" indicator incorporating the principles of the invention.
FIG. 2 is a side view of the refuse compactor with a portion broken away to expose the ram, refuse receptacle and limit switch arranged in accordance with an aspect of the invention.
FIG. 3 shows contact between the ram and limit switch other during downward movement of the ram into the receptacle.
FIGS. 4A-4C show the operation of the ram and limit switch when the refuse receptacle is not full.
FIGS. 5A-5C show the operation of the ram and limit switch when the refuse receptacle is full.
FIG. 6 is a circuit diagram of the compactor control and full bag display, in accordance with one embodiment of the invention.
FIG. 7 is a circuit diagram of the compactor control and full bag display, in accordance with another embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to FIGS. 1 and 2, a refuse compactor 10 incorporating the invention comprises a cabinet 12 having a top surface 14 and opposite sidewalls 16, 18 defining an access opening 20 for receiving a movable receptacle 22, and a rear wall 34. The receptacle 22 may be provided with a disposable bag (not shown) to hold refuse to be compacted. A ram 24, within the cabinet 12 of the compactor is mounted on drive screws 26 on opposite sides of the receptacle (only one drive screw 26 is shown in FIG. 2), and is normally maintained in a "rest" position above the receptacle 22 when the compactor is not carrying out a refuse compaction cycle of operation.
To compact refuse within the receptacle 22, following manual operation of "start" button 28 in FIG. 1, the screws 26 are rotated by an electrical drive motor (not shown) in a direction to move the ram 24 downward into the receptacle 22. As the ram begins to compact refuse within the receptacle 22, the back pressure of the refuse on the ram 24 slows the motor until a centrifugal switch (not shown) mechanically coupled to the motor closes to reverse the direction of the motor and thereby return the ram to its rest position above the receptacle. A number of electrically interlocking switches deenergize the motor at the end of the compaction cycle as well as upon an occurrence of an open or tilted receptacle, or of a jam during movement of the ram 24, in a known manner.
A "full bag" indicator lamp 30 on the cabinet 12 of the refuse compactor is energized and latched on when the receptacle is determined to be full. The full condition of the receptacle 22 is detected by a limit switch 32 mounted on a rear wall 34 of the cabinet. The limit switch 32 has an operator or throw 36 (see FIG. 3) that is contacted by a contact member 38 extending from the rear portion of the ram 24 when the ram is located within the receptacle at a position corresponding to a "full bag". Accordingly, if the limit switch 32 is closed at the time the drive motor reverses, indicating that the ram has compacted refuse within a full bag, the receptacle 22 is determined to be full, and the "full bag" indicator 30 is energized.
Determination of a full receptacle by a simultaneous closure of the limit switch 32 and motor centrifugal switch is made more clear with reference to FIGS. 4A-4C and 5A-5C.
In FIGS. 4A-4C, a sequence of movements of the ram 24 is carried out with the bag or receptacle not full of refuse. The ram 24 is driven downward by the drive motor in FIG. 4A, past the limit switch 32. The limit switch 32 is momentarily closed, but the motor centrifugal switch does not become closed to reverse the ram until the ram is below the limit switch 32 in the position shown in FIG. 4B. The ram 22 now returns to its rest position above the limit switch 32, again momentarily closing the limit switch. At no time during the cycle shown in FIG. 4A-4C are the limit switch and centrifugal switch closed simultaneously.
In FIGS. 5A-5C, however, the ram 22 driven downward in FIG. 5A is reversed at the position shown in FIG. 5B, corresponding to a full bag or receptacle, to return the ram to its rest position shown in FIG. 5C. With the limit switch 32 and motor centrifugal switch closed simultaneously when the ram 22 is in the position shown in FIG. 5B, the indicator lamp 30 on the cabinet 12 of the refuse compactor is energized.
The contact member 38 extending from the ram 24 is configured with an arcuate contact surface 40, as shown in FIG. 3, to slide along the arcuate switch operator 36, and close the switch 32 as the ram reciprocates during each compaction cycle. The member 38 preferably is secured to the ram 24 by bolts 42, and the rear wall 34 is spaced from the ram 24 by a distance sufficient to provide contact between the switch operator 36 and contact member 38. The location of switch 32 on the rear wall 34 as provided herein is more economically installed and substantially less prone to failure than one suspended from upper surface 14 of the compactor as in U.S. Pat. No. 3,831,513, supra.
A first embodiment 44 of a circuit for controlling the ram 24 as well as the full bag indicator 30, during a compaction cycle of operation, comprises a "hot" line 46 and a neutral line 48 connectable to a power supply at L 1 , L 2 for applying current to motor 52 coupled to ram drive screws 26 (FIG. 2). Motor 52, which is a conventional reversible A.C. motor, includes a run winding 50 and a pair of start windings 52a, 52b energized, selectively, by a double pole, double throw top limit-directional switch 60 and a centrifugal switch 64 mechanically coupled to the motor. The centrifugal switch 64 conventionally is a double pole-double switch which closes when the rate of rotation of motor is greater than a predetermined rate; only one half-section of the switch is used in the embodiment of FIG. 6.
A receptacle safety switch 54, a run switch 56 and start switch 58 are connected in series with wire 46 and run winding 50 of motor 52. A receptacle tilt switch 62 is connected in series with one throw 60a of the top limit-directional switch 60.
The operation of switches 54, 58, 60 and 62, within a compactor control circuit of a type known in the prior art, is described in Miller et al U.S. Pat. No. 4,062,282, assigned to the assignee of this invention. During a compaction cycle, throws 60a, 60b of the switch 60 are in the positions shown by solid lines in FIG. 6, and throw 64a of centrifugal switch 64 is closed when the ram 24 is in its "rest" position above the receptacle 22. As the start switch 58 is manually closed by the user, cw (clockwise) start winding 50 of motor 52 is energized by supply L1, L2 through wires 66, 67, 69, 71 and 73, and simultaneously run winding 50 is energized through wire 66 to drive ram 24 downward into receptacle 22, to compress refuse therein. As the ram descends downward, centrifugal switch 64 opens to deenergize the start winding 52a, and the throws 60a, 60b of top limit switch 60 switch into the positions shown in dotted lines in FIG. 6.
As the decent of the ram 24 and the speed of rotation of the motor 52 slow upon compaction of refuse in the receptacle 22, centrifugal switch 64 again closes, applying a current to counterclockwise start winding 52b through wires 66, 67, 75, 71 and 73 while run winding 50 remains energized through wire 66 to reverse the direction of the motor and return the ram 24 to its rest position above the receptacle.
Switch 32, closed by ram contact member 38 (FIG. 3) when the ram is in a position within the receptacle corresponding to a "full bag" is in series with an actuator coil 68a of a relay 68 having normally open throws 68b, 68c. The first throw 68b, when closed while centrifugal switch 64 is also closed, energizes "full bag" indicator lamp 30 by passing current through a series circuit consisting of switches 54, 56, lamp 30 and switch 68b and 64. The second throw 68c of relay 68 latches the lamp 30 on by electrically bypassing switches 64 and 32, so that the lamp 30 remains energized independent of the position of the ram 24 or of movement of motor 52, until the relay 68 is manually reset by the user momentarily opening a reset switch 70 in series with actuator coil 68a.
In the embodiment of FIG. 7, circuit 72 eliminates the second set of relay contacts 68c by connecting "full bag" limit switch 32 in series with both existing throws 64a, 64b of centrifugal switch 64, and connecting indicator lamp 30 in parallel with actuator relay 68a. When limit switch 32 is closed while centrifugal switch throws 64a, 64b, are also closed, indicating that the refuse bag 24 is full, lamp 30 and relay actuator coil 68a are both energized. The actuator coil 68a closes relay contacts 68b which bypasses the switches 32, 64 to latch the lamp 30 on.
The lamp 30 thus is controlled by the "full bag" limit switch 32 and motor centrifugal switch 64 of circuits 44 and 72 to become energized and latched on when the direction of movement of motor 52 is reversed by centrifugal switch 64 simultaneously with closure of limit switch 32 by contact 38 member of the ram 24. Switch 32 is advantageously located on an inner wall 34 of the cabinet 12, to be operated by contact member 38 of ram 24 as the ram is driven downward on screws 26 to compact refuse. In the circuit of FIG. 6, the full bag indicator relay is latched on by a second pair of contacts 68c that, when closed, bypasses the full bag limit switch 32 and centrifugal switch 64. In FIG. 7, the second pair of contacts 68c of lamp relay 68 is eliminated by connecting throw 68b electrically in series with the actuator coil 68a; the additional throw 64b of the centrifugal switch 64 required in this embodiment is already extant within the conventional switch.
In this disclosure, there is shown and described only the preferred embodiment of the invention, but, as aforementioned, it is to be understood that the invention is capable of use in various other combinations and environments and is capable of changes or modifications within the scope of the inventive concept as expressed herein. | In a refuse compactor wherein refuse in a disposable bag within a receptacle is compacted by a ram driven by a reversible electric motor, a "full bag" indicator lamp is energized when the refuse compacted in the receptacle is at a predetermined level. The motor drives the ram downward into the receptacle to compact the refuse, and when the ram slows in response to the reactive load of the refuse, a centrifugal switch reverses the direction of the motor to return the ram to a rest position above the receptacle. The bag is diagnosed full to energize the indicator lamp if the ram is at a predetermined level in the receptacle when the motor reverses. The indicator lamp is controlled by a latching relay that requires only one pair of contacts to energize and latch on the lamp. | 1 |
CROSS-REFERENCES TO RELATED APPLICATIONS
This application is a divisional application of U.S. patent application Ser. No. 11/381,411, filed May 3, 2006, now U.S. Pat. No. 7,240,612.
BACKGROUND OF THE INVENTION
The present invention is directed to an improved strapping machine. More particularly, the present invention is directed to a strapping machine having an improvements in conveyance and handling of loads in the machine and access to internal systems for maintenance.
Strapping machines are in widespread use for securing straps around loads. One type of known strapper includes a strapping head and drive mechanism mounted within a frame. A chute is mounted to the frame, through which the strapping material is fed.
In a typical stationary strapper, the chute is mounted at about a work surface, and the strapping head is mounted to a horizontal portion of the chute, below the work surface. The drive mechanism is also mounted below the work surface, near to the strapping head. The drive mechanism “pulls” or feeds strap material from a source, such as dispenser into the machine. The drive mechanism urges or feeds the strap through the strapping head, into and around the chute, until the strap material returns to the strapping head. The drive mechanism also retracts the strap material to tension the strap around the load.
It has also been found that it is often necessary to access the strapping head (and more specifically the weld head) by removing portions of the work surface. This may be necessary to dislodge misfed strap, to clear the strapping head or weld head, or for general maintenance or repair of the machine. Quite often, it is necessary to access the strap path (by moving the strap chute) at the weld head.
Often strapping machines are positioned or located in a product line such that the working surface of the strapper is at a higher elevation than a conventional work surface. In such instances, it can be difficult to open the various panels and the like to permit access to the internal portions of the machine. This is particularly the case with moving or removing the working surfaces of the strapper to access the strapping head and the feed/retraction mechanism.
Many such machines are employed in processes that maximize the use of fully automated operation. To this end, machines are configured for automated in-feed and out-feed, such that a load (to be strapped) is automatically fed into the machine by an in-feed conveyor, the strapping process is carried out, and the strapped load is automatically fed out of the machine by an out-feed conveyor. However, there may be times that loads are physically too small to be moved into the strapping area by known conveyors, or other times that loads come into the strapping area that are askew and require squaring or straightening, or may need to be compressed before being strapped.
Accordingly there is a need for an improved strapping machine that facilitates package or load handling and strapping. Desirably, such a machine facilitates the handling and strapping of loads that may otherwise be difficult to handle. More desirably, such a machine eases movement or removal of the work surfaces to access the internal portions of the machine.
BRIEF SUMMARY OF THE INVENTION
A strapping machine is configured to feed a strapping material around a load, position, tension and seal the strapping material around the load. The machine includes a work surface for supporting the load. At least a portion of the work surface is upwardly pivotal.
A conveyor is mounted within the work surface that has a friction belt drive. The conveyor includes a pair of end rollers that define a plane and the conveyor rollers are engaged by the belt along the plane. Intermediate rollers are disposed between the end rollers. A tension roller maintains tension in the belt. The conveyor is configured so that a load present on the conveyor increases a force between the conveyor rollers and the drive belt to drive the conveyor.
A strap chute carries the strapping material around the load and releases strap from the strap chute. A load compression assembly is mounted to the frame and disposed above the work surface. The compression assembly includes a reciprocating gate that moves toward the work surface to contact and compress the load prior to conveying the strap around the load. The gate is actuated by a rod-type cylinder operably connected to the machine frame and to an uppermost point on the gate. The cylinder and rod are below the uppermost point of the gate when the gate is in the feed or the compressed state. Preferably, the cylinder is enclosed within the arch enclosure of the chute. The gate can be formed from a transparent or translucent material to permit viewing the load through the gate.
The conveyor roller closest to the strap chute has end portions and a middle portion that has a smaller diameter than the end portions. The end and middle portions are fitted together to rotate as a unitary element. The roller includes a pair of spindles, one in each end portion extending toward the middle portion. The spindles are rotatable independent of their respective end portions and independent of one another.
The machine includes a side squaring assembly that aligns the load in the direction transverse to the load direction. The side squaring assembly includes a pair of side plates that substantially simultaneously move toward one another to square the load on the conveyor. The side squaring assembly includes a drive having a pair of substantially mirror image cylinders
The side plates can each include a forward squaring plate mounted to the side plate transverse to the side plate. The forward squaring plate squares the load in the machine direction. The machine can also include a longitudinal squaring drive having a pair of rotating engaging elements for squaring the load in a longitudinal direction. Load contact elements are loosely mounted to the rotating engaging elements such that the load is driven forward by the contact elements when there is low resistance to movement and when the load resists movement the contact elements stop and the rotating engaging elements rotate freely of the stopped contact elements.
A strap guide extends between the pre-feed assembly and the feed assembly and includes a fixed portion and a movable portion. The movable portion moves toward and away from the fixed portion to form a guide path that is opened to access the guide path.
An enclosure is mounted to the machine frame below the work surface. The sealing head and the feed assembly are located within the enclosure and are accessed by an interlocked, openable access panel and an interlocked access door on the panel.
These and other features and advantages of the present invention will be apparent from the following detailed description, in conjunction with the appended claims.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The benefits and advantages of the present invention will become more readily apparent to those of ordinary skill in the relevant art after reviewing the following detailed description and accompanying drawings, wherein:
FIG. 1 is a perspective view of a strapping machine illustrating in phantom a work surface lift system of the present invention;
FIG. 2 is a partial perspective view of the underside of the work surface illustrating the lift lever and arm;
FIG. 3 is view of the lever and arm showing the arm engaging the work surface;
FIG. 4 is a perspective view of the strapping machine illustrating in phantom a load weight engaging conveyor system of the present invention;
FIG. 5 is an enlarged, partial perspective view of the weight engaging conveyor system with a single roller in place;
FIG. 6 is a top perspective view of the conveyor system with the rollers removed for ease of illustration;
FIG. 7 is an exploded view of the conveyor system again, with the rollers removed for ease of illustration;
FIG. 8 is a bottom view of the drive assembly for the conveyor system;
FIG. 9 is an exploded view of the conveyor system, rollers and support elements;
FIG. 10 is a perspective view of the strapping machine illustrating a load compression system of the present invention;
FIG. 11 is a partial perspective view of the load compression system frame and support assembly illustrating the cylinder mounting arrangement;
FIG. 12 is a partial view of a corner of the compression screen showing the cylinder mount;
FIG. 13 is a illustrates an outside wall of the compression mount frame;
FIG. 14 is an enlarged view of the cylinder mount;
FIG. 15 is a view of the compression mount cylinder in the retracted state;
FIG. 16 is an enlarged view of a section of the compression assembly;
FIG. 17 is a perspective view of the strapping machine illustrating a load side squaring system of the present invention;
FIG. 18 is a perspective view of the squaring system illustrating the squaring plates and machine rollers;
FIG. 19 is a bottom perspective view of the squaring system illustrating the drive system;
FIG. 20 is a top perspective view of the system with the rollers removed for ease of illustration;
FIG. 21 is a perspective view of the strapping machine illustrating a load stack friction drive system of the present invention;
FIG. 22 is a perspective view of the system as it is on the machine rollers;
FIG. 23 is a front view of the load stack friction drive system;
FIG. 24 is a perspective view of the strapping machine illustrating a conveyor nose roller of the present invention;
FIG. 25 is a perspective view of the nose roller positioned in the conveyor, adjacent to the area at the strapping head;
FIG. 26 is an enlarged partial view of the nose roller;
FIG. 27 is a perspective view of the nose roller removed from the conveyor system;
FIG. 28 is an exploded view of the nose roller;
FIG. 29 is a perspective view of the strapping machine illustrating in phantom a strap guide and opening system of the present invention;
FIG. 30 is a partial view of the strap guide and opening system with the guide in the open state;
FIG. 31 is a view similar to that of FIG. 30 with the guide in the closed state;
FIG. 32 is a perspective view of the strapping machine illustrating in phantom a drop down front enclosure panel;
FIG. 33 is a partial view of the drop down panel;
FIG. 34 is a partial view of the frame sides showing the hinges and interlocks;
FIG. 35 is another partial view illustrating the panel interlock;
FIG. 36 is a view of the panel side;
FIG. 37 shows, in phantom, the slide action of the access door within the drop down panel;
FIG. 38 illustrates the access to and action of the lift arm;
FIG. 39 illustrates the interlock on the access door;
FIG. 40 illustrates the door residing in the drop down panel in phantom; and
FIG. 41 illustrates the rear of the access door as it resides within the panel.
DETAILED DESCRIPTION OF THE INVENTION
While the present invention is susceptible of embodiment in various forms, there is shown in the drawings and will hereinafter be described a presently preferred embodiment with the understanding that the present disclosure is to be considered an exemplification of the invention and is not intended to limit the invention to the specific embodiment illustrated.
It should be further understood that the title of this section of this specification, namely, “Detailed Description Of The Invention”, relates to a requirement of the United States Patent Office, and does not imply, nor should be inferred to limit the subject matter disclosed herein.
Referring to the figures and in particular FIG. 1 , there is shown generally a strapping machine 10 embodying the principles of the present invention. The strapping machine 10 includes, generally, a frame 12 , a strap chute 14 , a feed assembly 16 and a weld head 18 (both shown briefly in FIG. 25 ). A controller 20 provides automatic operation and control of the strapper 10 . A table top or work surface 22 is disposed on the strapper 10 at the bottom of the chute 14 . The work surface 22 is configured as a conveyor 24 and will be discussed in more detail herein. A strap supply or dispenser 26 supplies strapping material S to the feed assembly 16 and weld head 18 .
The work surface 22 , again as will be discussed below, is configured having in-feed and out-feed conveyors 28 , 30 that are formed as part of the work surface 22 and pivot upwardly and outwardly (relative to the strap chute 14 ) to provide access to the internal components, e.g., the feed assembly 16 and the weld head 18 . This is often necessary to conduct maintenance or inspection of these areas. It will also be appreciated that the work surface 22 is often at a height that is greater than a conventional work surface height. That is, the work surface 22 is positioned at a height that is complementary to the other aspects of whatever operation the strapper 10 is part of. As such, the work surface 22 could be at a height that makes it difficult to lift the conveyors 28 , 30 to access the internal components.
The present strapping machine 10 includes a novel work surface lift system 32 to facilitate lifting the conveyors 28 , 30 to raise and hold them in an open condition. As seen in FIGS. 2 and 3 , the lift system 32 includes an arm 34 that is pivotally mounted to the frame at an arm pivot 36 . The arm 34 includes a lever portion 38 that extends from an end 40 of the arm 34 , about transverse thereto. The lever portion 38 has a roller 42 mounted at a free end 44 that engages a lip edge 46 of the conveyor 28 , 30 . The pivot 36 is defined at the juncture 50 of the lever portion 38 (at about the elbow), at which the arm 34 is mounted to the frame 12 . A hand grip portion 52 is mounted to an opposite end 54 of the arm 34 (opposite of the lever portion 38 ) and is used to manually operate the arm 34 . The grip 52 (arm) is accessed from a front access door 56 in the access panel 58 of the machine enclosure 60 for ease of use.
The hand grip 52 is pulled toward the front of the machine 10 (toward the operator). The mechanical advantage afforded by the longer travel of the arm 34 facilitates lifting of the work surface 22 (conveyor 28 or 30 ) by the shorter lever portion 38 . A cylinder 62 serves to maintain the arm 34 in the engaged (lifted) position and a spring 64 aids in providing the force to return the surface 22 to the closed condition. When in the open state, the lever roller 42 engages a notch 66 formed in the lip edge 46 of the conveyor 28 , 30 to prevent the lever roller 42 from slipping along the lip 46 (to inadvertently close).
A load weight engaging conveyor drive system 68 is illustrated in FIGS. 4-9 . The system 68 is configured so that the conveyor rollers 70 are driven as the weight on the rollers 70 (the conveyor section) increases. The drive system 68 includes a motor 72 , preferably a direct current (DC) driven motor that drives a drive belt 74 . The belt 74 is maintained in a generally planar state (relative to the conveyor 28 , 30 and rollers 70 ) by a pair of end rollers 76 that define a plane P 76 at about their peripheries and intermediate rollers 78 that are also, at their peripheries, about at the end roller plane P 76 .
The belt 74 encircles the rollers 76 , 78 and a drive roller 80 on the motor 72 . A tension roller 82 is mounted to a pivoting arm 84 that is biased (by a spring 86 ) to maintain tension in the belt 74 . The motor 72 and the rollers (the end 76 and intermediate 78 rollers) are mounted to a carriage or frame 88 that is mounted to the pivoting work surface 22 (conveyor sections 28 , 30 ) to facilitate maintenance on or removal of the drive system 68 .
The frame 88 includes slots 90 in which the conveyor roller ends (spindles 92 ) reside during operation. The roller spindles 92 “float” in the slots 90 so that the rollers 70 “float” on the drive belt 74 . In this manner, the normal force between the rollers 70 and the belt 74 is created by the weight of the rollers 70 combined with the load L on the belt 74 . It will be appreciated that the conveyor rollers 70 sit along a top or outer surface 94 of the belt 74 while the end and intermediate rollers 76 , 78 (those that are part of the drive 68 ), sit along a bottom or inner surface 96 of the belt 74 . In addition, the location at which the conveyor rollers 70 sit on the belt 74 is between adjacent end/intermediate rollers 76 , 78 and, likewise, the end/intermediate rollers 76 , 78 support the belt 74 between adjacent conveyor rollers 70 . In this manner, the conveyor rollers 70 are in effect cradled by the belt 74 between drive rollers 76 , 78 .
FIGS. 10-16 illustrates a load compression assembly 98 . Load compression is provided by a compression gate 100 that is actuated by a cylinder 102 , located on a side of the gate 100 . The compression assembly 98 is configured to compress the load L prior to strap S being positioned and tensioned around the load. This reduces the amount of strap that has to be fed out and in turn retracted to strap the load. It also provides a pre-load on the load which in turn reduces the amount of work that has to be done by the feed and strapping (weld) heads 16 , 18 .
As set forth above, compression gate drive is provided by a rod-type cylinder 102 , located on a side of the gate 100 . The cylinder 102 is mounted within the chute arch enclosure 104 , which is the frame structure that houses the strap chute 14 . In this manner, one end 106 of the cylinder 102 is mounted to the frame 12 at about the work surface elevation 22 and the other end 108 (the rod) is mounted to the gate 100 . Accordingly, no additional space is required, nor addition structure required to house the gate 100 and cylinder 102 above the topmost extension of the gate 100 . Advantageously, this reduces the overall head space required for the compression assembly 98 , and when the gate 100 is in the lowered position (e.g., the compression position), the cylinders 102 are fully retracted and thus the overall machine 10 height is less than known machines (that have overhead mounted cylinders).
FIGS. 17-20 illustrate a side squaring system 110 that is configured to square the lateral sides of a load L and to restrain the forward movement of the load (which in effect squares the longitudinal (front) edges of the load. The squaring system 110 includes a pair of opposed laterally moving side squaring plates 112 . In the illustrated embodiment, both side plates 112 have forward edge squaring plates 114 , however, it will be recognized that the forward squaring plate 114 can be present on only one of the side plates 112 and will function effectively.
The side plates 112 are mounted to a drive system 116 that is mounted to the machine 10 below the rollers 70 . In this manner, the drive mechanism 116 does not interfere with the operation of the strapper 10 . It will also be appreciated that the side squaring system 110 is mounted upstream (forward) of the strap chute 14 , again so that it does not interfere with the operation of the strapper 10 .
The drive system 116 is configured to move laterally (sideways) to square the sides of the load L. For example, when strapping magazines, the load can be moved up to the side squaring system 110 and the side plates 112 moved inward so that the leading ends (edges) of the magazines square up to the forward squaring plates 114 . The side plates 112 can then move further inward to square up the side edges of the magazines. Once the forward and side edges are squared, the side plates 112 can be retracted and the load can be conveyed forward into the strap chute 14 .
The drive system 116 is configured to move the side plates 112 simultaneously toward and away from each other so that squaring is carried out relatively symmetrically. Accordingly, the drive 116 includes a pair of rod-type cylinders 118 mounted in mirror image relation to one another with the rod ends 120 mounted to the plates 112 (to laterally move the plates 112 ) and the cylinder ends fixed within the assembly carriage. The rod ends 120 are mounted to bearing plates 126 that traverse along rod bearings 128 to provide smooth movement of the plates 112 . As seen in FIGS. 18 and 20 , the side plates 112 are mounted to the bearing plates 126 by supports 129 that are positioned and extend up from between rollers 70 so as to prevent any interference.
FIGS. 21-23 illustrate a longitudinal squaring drive 130 that functions with the forward edge squaring plates 114 . The forward squaring drive 130 includes a pair of opposing, rotating central elements 132 and a plurality of loosely mounted rotating rings 134 . The drive element 132 and rings 134 are formed from a resilient, low friction material, such as neoprene or the like. The rings 134 are loosely mounted or fitted to their respective drive elements 132 so that the rings 134 will rotate when they are in contact with the central drive element 132 . However, when the friction or contact force between the rings 134 and the load L or material being driven is too great, the rings 134 will not rotate. Rather the friction between the rings 134 and the load L is too great to permit the rings 134 to move. Accordingly, when, for example, a load of material (such as the exemplary magazines) is introduced to the forward squaring drive 130 , the magazines that may be out of longitudinal (forward to rearward) alignment contact the rotating rings 134 and are driven into the forward squaring plates 114 . When, however, the magazines contact the forward squaring plates 114 , the friction that results at the rings 134 /magazine interface is too great for the rings/drive element 134 / 132 to overcome, and the rings 134 stop rotating relative to the drive elements 132 .
FIGS. 24-28 illustrate a necked-down roller 136 . It will be appreciated that the roller or those rollers closest to the strap chute often cannot be full length rollers due to interferences or, as illustrated, plates P that may overlie a portion of the chute at about the strapping head. Because these rollers are not full length (that is, they do not fully extend across the conveyor), they are not driven rollers. Instead, these rollers are idler or passive rollers that only provide a bearing surface across which the package can move. This can be problematic, especially with smaller items or packages that are not sufficiently long to extend from one driven roller (on the infeed side), across the chute area, and on to the next driven roller (on the outfeed side).
The present necked-down roller 136 overcomes these drawbacks by providing a roller having a smaller diameter portion at about the middle of the roller 138 and larger outer sections 140 (that are the same diameter as the other rollers 70 ) that is driven together with the remaining rollers 70 on the conveyor 28 , 30 . In this manner, accommodation is made for the interference (plate 142 ) while still maintaining the roller outer sections 140 at the same diameter so as to properly convey smaller loads into the strapper chute 14 area.
The roller 136 outer roller sections 140 are the same diameter as the other rollers 70 of the conveyor 28 . 30 . The middle, necked-down transition section 138 bridges the two outer sections 140 . A spindle 144 extends through each of the outer roller sections 140 from the end 146 of the outer section 140 to a bearing 148 at the necked-down transition 138 . The spindles 144 are held within the roller sections 138 , 140 by a plurality of bearings 148 , 150 , which as illustrated, can include inner and outer bearings on each of the outer sections 140 . Accordingly, the outer sections 140 can rotate while the spindles 144 remain fixed with the ends 152 residing within the conveyor drive frame slots 90 (see FIG. 5 ). The smaller diameter transition section 138 is press-fit to the outer sections 140 so that the entirety of the roller 136 functions as a single element with the stationary spindles 144 .
FIGS. 29-31 illustrate a strap guide and opening system 154 that is configured for a machine 10 such as the elevated work surface 22 machine discussed above. The opening strap guide 154 provides a pathway (indicated generally at 156 ) through the machine 10 from the supply 26 to the strapping head (or the feed system 16 ) so that the strap S can traverse in a controlled and unobstructed manner. Such a guide 154 is important to prevent the strap from twisting, kinking or otherwise jamming as it is fed from the strap supply 26 .
It is also important to be able to access the guide 154 so that strap S can be removed as needed (e.g., sections of jammed strap material). Accordingly, the present strapper guide 154 has a drop down access section 158 that extends from a pre-feed assembly 160 (which is a driven element that is located at the inlet to the machine 10 ) to the feed head 16 . The guide 154 is formed from an upper guide portion 162 that remains stationary and the lower movable guide portion 158 . The lower guide portion 158 is actuated (moved) by movement of a handle 164 and moves along a pair of pins 166 that are fixed to the machine 10 . The lower guide 158 has arcuate slots 168 along which the guide 158 moves between the open position ( FIG. 30 ) and the closed position ( FIG. 31 ). The arcuate slot 168 shape (as opposed to linear, e.g., vertical shape) provides for lateral movement of the lower guide 158 away from the pre-feed assembly 160 (as the guide 154 is opened) to provide better access in and around the pre-feed 160 area. And in that the strap S is fed about a roller 170 at the feed head 16 (exiting the guide 154 ), the movement of the lower guide 158 away from the roller 170 at the feed head 16 entrance does not adversely effect strap moving along the strap path 156 .
FIGS. 32-41 are a series of illustrations showing the front enclosure 60 , the enclosure access panel 58 and the access panel door 56 and the interlocks 172 , 174 , respectively, for the panel 58 and door 56 . As seen in FIG. 32 , the enclosure panel 58 (which includes the door 56 ) is mounted to the machine frame 12 by hinges 176 to allow the panel to pivot downwardly from the frame 12 to provide complete frontal access to the machine enclosure 60 . The panel 58 includes pins 178 that extend outwardly from the lower sides of the panel 58 that are received in hinge sleeves 180 in the frame 12 . The panel 58 includes interlocks 172 on the frame 12 ( FIG. 34 ) and the panel 58 ( FIG. 36 ) that isolate power to the machine 10 when the interlock elements 172 are disengaged from one another.
Likewise, the access door 56 , which is a two-piece sliding door that slides within a track 173 in the panel 58 , also includes interlocks 174 on the door 56 ( FIG. 39 ) and in the door frame 182 , which is within the enclosure panel 58 ( FIG. 35 ) that isolate power to the machine 10 when the interlock elements 174 are disengaged from one another. It will be appreciated that both the lift arm 34 and the guide opening handle 164 are accessible from either the open access door 56 or the lowered enclosure panel 58 .
All patents referred to herein, are hereby incorporated herein by reference, whether or not specifically done so within the text of this disclosure.
In the present disclosure, the words “a” or “an” are to be taken to include both the singular and the plural. Conversely, any reference to plural items shall, where appropriate, include the singular.
From the foregoing it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitation with respect to the specific embodiments illustrated is intended or should be inferred. The disclosure is intended to cover all such modifications as fall within the scope of the claims. | A strapping machine feeds strapping material around a load, positions, tensions and seals the material around the load. The machine includes a work surface, a portion of which is upwardly pivotal. A conveyor mounted within the work surface has a friction belt drive. The conveyor roller closest to the strap chute has a middle portion that has a smaller diameter than the end portions. The middle portions are fitted together to rotate as a unitary element. A load compression assembly is mounted at the strap chute. A side squaring assembly aligns the load in the direction transverse to the load direction. A strap guide extends between a pre-feed assembly and the feed assembly and includes a fixed portion and a movable portion forming a guide path that is opened to access the guide path. An interlocked enclosure is mounted to the machine frame below the work surface to access the sealing head and the feed assembly. | 1 |
This application is a continuation of PCT/GB91/00684 filed on Apr. 30, 1991.
BACKGROUND OF THE INVENTION
The present invention relates to a detection technique and apparatus based on a substrate regenerating biosensor for use specifically but not exclusively for the sensing of cyanide. Various techniques have been devised for the detection of cyanide and determination of its concentration and these include sensitive colorimetric methods, electrochemical analysis and techniques requiring sophisticated instrumentation such as atomic absorption spectroscopy and computer assisted pattern recognition. However, there are certain inherent difficulties in the detection and determination of cyanide with many of the procedures requiring purification or volatilization of cyanide. Furthermore, most methods suffer from a lack of specificity and problems of interference. The application of physical techniques to a method of continuous monitoring is still being sought.
Biosensors for cyanide have been investigated based on cyanide's toxicity towards the biochemical activity of cytochrome oxidase. By binding to cytochrome oxidase, which is the terminal component in the electron transport chain of mitochondria, cyanide blocks an electron transfer and consequently stops electron flow in the respiratory chain.
By monitoring the electrochemical activity of cytochrome oxidase it is possible to detect the presence of toxic compounds such as cyanide, sulphide and azide from the inhibition of current. Inhibition sensors, such as those based on cytochrome oxidase operate under conditions of an enzyme limited signal rather than a transport limited one and these sensors are therefore sensitive to changes in enzyme activity.
Unfortunately inhibition sensors are susceptible to non-specific denaturation of the enzyme as well as the specific inhibitors resulting in the signal derived from the enzyme gradually decreasing even in the absence of inhibitor and limiting the operational lifetime. Furthermore substrate utilization eventually results in operational failure or the biosensor when the substrate is exhausted.
Consequently there is a need for a method for the detection and determination of concentration or toxins such as cyanide which overcomes or at least mitigates the disadvantages of the described techniques.
SUMMARY OF THE INVENTION
Accordingly there is provided a method for the detection and determination of concentration of a toxin which inhibits the electron transfer activity of an enzyme which comprises the steps of:
(a) providing in an environment an enzyme selected from peroxidase, catalase and oxygenase whose electron transfer activity is inhibited when bound to the toxin:
(b) providing hydrogen peroxide in the environment to oxidize the enzyme;
(c) reducing the oxidized enzyme with an electron transfer agent, the agent being oxidized in the process;
(d) detecting the presence and concentration of the inhibiting toxin by the change and extent to which the electron transfer agent is regenerated from its oxidized state.
As the ability of the electron transfer agent to be regenerated is dependent upon the enzyme's ability to oxidize the agent there is a proportional relationship between the two. In an enzyme limited system where the enzyme's electron transfer activity is depleted through inhibition by electro-active or electro-passive interferents the effect will be manifested in there being less oxidized electron transfer agent to regenerate back to its reduced state. Consequently this provides the basis for a detector for compounds which exhibit toxicity towards the electron transfer activity of the enzyme. Detection is achieved by noting a decrease in the level of regeneration of electron transfer agent while the degree to which regeneration is affected by enzyme inhibition provides an indication of the concentration of inhibitor present.
Preferably the enzyme is a peroxidase.
Preferably the environment is an aqueous environment so that the hydrogen peroxide is produced from oxygen dissolved in the aqueous environment, the hydrogen peroxide subsequently being reduced to water in raising the oxidation level of the enzyme. Alternatively the environment could be organic, etc., but it is in any case preferable that the environment is capable of providing enough protons and dissolved oxygen to produce the hydrogen peroxide rather than the hydrogen peroxide needing to be added from an external source. Preferably the reduction of oxygen to hydrogen peroxide takes place at a primary electrode and regeneration of the electron transfer agent takes place at a secondary electrode. The rate of generation of hydrogen peroxide at the primary electrode is controlled by the applied potential. The current at the secondary electrode which results from electron transfer agent regeneration is diagnostic of the catalytic state of the enzyme and hence the level of toxin inhibition.
Preferably the aqueous solution is able to absorb oxygen from either the atmosphere or some alternative source so that there is continuous generation of the substrate hydrogen peroxide by the primary electrode with the secondary electrode ensuring the regeneration of the electron transfer agent. Preferably the aqueous solution is well buffered if the oxygen source is atmospheric. This type of sensor may therefore be self-supporting and does not require constant maintenance and replenishment.
Because the catalytic activity of an enzyme is very specific to its substrate it can also be very sensitive to the presence of specific compounds which inhibit the enzyme's catalytic activity. Consequently the technique of the present invention can be made very specific in the detection of compounds and the enzyme used is chose with regard to the inhibitory effect a compound requiring detection will have upon the enzyme's activity. Furthermore compounds which exhibit high toxicity towards the enzyme will be more easily detected than those showing lower toxicity as the former will have a more profound effect upon enzyme activity and hence have a greater effect on regeneration of electron transfer agent.
It is intended that the biosensor will be used mainly for toxins in the gaseous phase. However the toxins could alternatively be in the liquid or solid phase provided that they can ultimately inhibit enzyme activity.
Conveniently the enzyme used is immobilized to provide better control over its catalytic activity and to increase the lifetime of the biosensor. Immobilization of the enzyme at the primary electrode can prevent protein fouling of the secondary electrode and allows improved control of the catalytic activity through the enzyme's restriction to a specific site. Immobilization at the secondary electrode has the advantage of limiting the reduction of ferricinium which tends to occur in the case of primary electrode immobilization. In certain cases it may be preferable to immobilize the enzyme at some other point than the primary or secondary electrodes.
The immobilization of the enzyme can also increase the efficiency of the electrode thus enabling biosensor detection equipment to be reduced in size.
Preferably enzyme immobilization is achieved using a bovine serum albumin (BSA) linker which avoids direct amino acid attachment to the electrode. This may have the benefit of decreasing enzyme denaturation.
Preferably the enzyme is coupled to BSA through carbohydrate moieties which have previously been oxidised with NaIO 4 . Carbohydrate attachment has the advantages of immobilizing the enzyme in a manner so as to decrease the risk of restricting substrate diffusion to the active site of the enzyme. Furthermore the large carbohydrate composition of enzymes allows for multiple sites of immobilization which help securing and stabilizing of the enzyme on the electrode. The BSA link has the yet further advantages of creating a protein cushion which protects the enzyme from reductive potentials, providing a buffering microenvironment for the electrode surface electrochemistry (such as pH changes) and preventing the electron transfer agent being reduced directly at the electrode.
Additionally, the electron transfer agent can also be bound to the enzyme, which may be peroxidase, so that there is no need to add separately electron transfer agent to a detection system. This enables a more integrated detection system to be developed by having electrode, enzyme and electron transfer agent bound together. Electron transfer agent immobilization of an amino ferrocene can be achieved by oxidation of a carbohydrate group on the enzyme with sodium periodate and reaction with the amino ferrocene to form a Schiff base. This unstable imine is then reduced with sodium borohydride.
The inventors have found that where detection of cyanide is required the enzyme is preferably horseradish peroxidase (HRP). HRP has the advantage of being a very stable enzyme once immobilized and being commercially available as a very pure preparation.
The overall enzyme reaction of the HRP biosensor can be represented as: ##STR1##
Compound 1 is the oxidized form of HRP which is 2 oxidation states above the resting state. The enzyme is reduced to compound 2 and subsequently to the resting state by the electron transfer agent (D(red)).
The electron transfer agent is preferably a metallocene compound. Ideally the electron transfer agent is a ferrocene or ferrocene analogue. Ferrocenes have the advantages of being easily reduced at the secondary electrode and being stable in the reduced form. Furthermore they are not sensitive to light or pH.
A particularly useful feature of ferrocenes is that their structure enables the synthesis of many analogues and ferrocenes therefore can be designed to be electroactive donors towards particular enzymes. Preferred ferrocene derivatives for use with HRP are hydroxymethyl ferrocene, monocarboxylate ferrocene, dimethylaminomethyl ferrocene and 1,1' dicarboxylate ferrocene.
By utilizing a reducing current at the primary electrode for the production of hydrogen peroxide the only source of regenerated ferrocene is through enzymic oxidation which manifests itself in the cathodic secondary electrode current.
Detection and determination can be accomplished by analyzing the inhibition of secondary electrode current by steady state kinetics or by a binding equation.
The pH of the system should be chosen to be within the limits for enzyme activity suitable for the detection method and in the case of HRP is preferably between pH 5 and 8. Ideally the pH is 7 as the enzyme is most stable at this pH.
The operable temperature of the system slay be between 5° and 40° C. but the temperature of the system is preferably towards the middle and upper end of the range as chemical equilibrium is achieved more quickly.
With an aqueous system based on HRP as described herein it is possible to detect under optimum conditions submicromolar (ppb) concentrations of cyanide by the inhibition of ferrocene regeneration current at the secondary electrode.
The typical response time for detection of introduced cyanide is less than 1 second. The rate limiting factor in the detection of cyanide is the diffusion from the gaseous phase into the aqueous phase. Because the binding of cyanide to HRP is a reversible reaction the sensor of the present invention can be repetitively used for the detection of cyanide and because of the inherent stability of sensors made according to the invention it is possible for sensors to be made stable and operable for over six months.
According to a further aspect of the present invention there is provided a biosensor for the detection and determination of concentration of toxins which inhibit enzymic electron transfer activity which comprises:
(i) means for the production of hydrogen peroxide
(ii) an enzyme selected from peroxidase, catalase and oxygenase capable of being oxidized by (i);
(iii) an electron transfer agent capable of reducing an oxidized enzyme (ii);
(iv) means for regenerating the electron transfer agent, and
(v) means for detecting the change and extent to which the electron transfer agent is regenerated from an oxidized state.
As the biosensor operates in a manner in accordance with the method for detection and determination which utilises substrate regeneration the various embodiments described for that method are applicable in relation to the biosensor itself and consequently do not need to be reiterated in full.
Preferably the enzyme is a peroxidase. Preferably the enzyme is horseradish peroxidase.
Preferably the hydrogen peroxide is produced from solution which contains the enzyme and electron transfer agent. Preferably the solution is aqueous.
The electron transfer agent is preferably a metallocene compound and is ideally a ferrocene or ferrocene analogue.
Preferably the means for production of hydrogen peroxide and the means for regenerating the electron transfer agent are electrodes. The electrode system used maybe a rotating ring-disc electrode (RRDE). Alternatively the electrodes may be of the interdigitated or microband type. An advantage in using interdigitated electrodes is that they have high collection efficiencies. In the case of a RRDE the disc forms the primary electrode and preferably at least the surface is of oxidized carbon. The use of an oxidized carbon electrode enables BSA to be fixed to the electrode by carbodiimide activation. The transport of solution to the electrode is controlled by the rotation rate of the disc with the solution being subsequently transferred from the disc to the secondary ring electrode by the action of disc rotation.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described by way of example only and with reference to the accompanying Drawings of which:
FIG. 1 shows a representation of monitored HRP activity using two working electrodes;
FIG. 2 shows the reactions of FIG. 1 occurring at the surface of a rotating ring disc electrode;
FIG. 3 shows a graph of the currents resulting at the primary and secondary electrodes of the ring disc electrode with the ring held at 0V, a scan speed of 0.1V/s, electrode (disc) rotation rate of 4 cps and in the presence of hydroxymethyl ferrocene 0.3 mM, HRP 1.25 uM, KCl 0.1M, and buffer KHPO 4 0.05M at pH 7;
FIG. 4 shows the effect of primary (disc) electrode rotation rate on the secondary (ring) electrode current in the presence of hydroxymethyl ferrocene 1 mM, HRP 2.5 uM and at a disc potential of -1.2V during a disc potential sweep of 0.1V/s;
FIG. 5 shows the measurement of enzymatic oxidation of ferrocene by amperometric means and by spectrophotometric means. For amperometric analysis there was HRP 1.25 uM, hydroxymethyl ferrocene 0.3 mM, the spectrophotometric assay was undertaken with HRP 1.25 uM, hydroxymethyl ferrocene 0.5 mM, H 2 O 2 10 mM. Buffers used: pH 3-5.5 acetate, pH 5-7.5 potassium phosphate, pH 7-9 Tris, all at 50 mM;
FIG. 6 shows the fractional ring current remaining following the introduction of potassium cyanide. Hydroxymethyl ferrocene 0.3 mM, HRP 2.5 uM at a disc potential of -1.2V disc sweep of 0.1 V/s and ring at 0V. The current was measured after 1 minute equilibration following the addition of cyanide;
FIG. 7 shows a Scatchcard analysis of the data shown in FIG. 4 using the equation: % I/[CN]=-% I/K 1 +I max /K 1 . Points represent the means of 5 determinations+the standard deviation. The K 1 represents the free concentration of cyanide required for 50% inhibition;
FIG. 8 shows the inhibition constant for cyanide determined at different rates of H 2 O 2 production as determined by the disc potential HRP 1.25 uM, hydroxymethl ferrocene 0.3 mM; and
FIG. 9 shows a closed loop cyanide sensor.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to FIGS. 1 and 2, a dual working electrode system (1)comprises a rotating ring disc electrode (RRDE) of which a rotating disc forms the primary electrode (2) and a ring the secondary electrode (3). The primary electrode (2) is formed as a glassy carbon disc and is sealed in araldite or Kel-F the disc having a diameter of 0.7 cm. The secondary electrode (3) is made as a platinum ring and is also sealed in araldite or Kel-F, having an inner diameter of 0.75 cm and outer diameter of 0.8 cm and being separated from the disc by a 0.05 cm spacer. Both electrodes are polished with a 0.3μ aluminium oxide slurry and subsequently sonicated in a water bath. The remainder of the equipment is described without reference to the figures.
A four electrode analogue potentiostat (not shown) which is optionally computer controlled is used to control the potentials at the working electrodes (2) and (3). The disc electrode (2) is connected to a triangular wave generator (not shown) for potential sweeps and the ring electrode (3) is connected to a constant DC voltage source. The electrode rotation is controlled by a Ursar Scientific rotator. All potentials are quoted with respect to a saturated calomel electrode (SCE) with a 1 cm 2 platinum gauze serving as the counter electrode.
The electrodes (2), (3) fit within a electrochemical cell of volume 5-10 mls, the cell being equipped with water jackets for temperature regulation and with the water being supplied from a water bath. The electrodes are positioned so as to minimize solution resistance. In use the collection efficiency was determined experimentally using ferrocene monocarboxylate to be 0.16 which agreed with the predicted value. The purity of horseradish peroxidase (HRP) obtained as highly pure preparations (RZ>3.0) from Biozyme was determined by sodium dodecyl sulfate (SDS) gel electrophoresis. The concentration of enzyme was measured from the absorbance at 403 nm using an extinction coefficient of 90,000M-1 cm-1.
Hydroxymethyl ferrocene obtained from Kodak was made up to the desired concentration on a weight basis. The dissolved oxygen was determined by the Winker method to be 240 μM which agreed with values obtained from a nomegram.
All experiments were carried out at 22° C.
The glassy carbon disc was activated by a combined chemical and electrochemical technique as described by Bourdillon, J. Am. Chem. Soc. 1984, 106, 4701-4706. The disc was held at +2.2V for 30 seconds and during this time the platinum ring was held at -0.2V. The electrode was transferred to a solution of 0.5M NaKPO 4 , pH 7.0 and the platinum ring was cleaned by cycling between -0.3V and +1.0V for several hours until a stable voltammogram resulted. The disc was then activated with a carbodiimide (0.1M for 1 hr in 0.1M sodium acetate buffer pH 5.0). Following washing with deionized water the electrode was immersed in a solution of bovine serum albumin (BSA, 20 mg/ml in 0.1M sodium acetate, pH 5.0 for 2 hours) obtained from Sigma. Glycoside moieties of HRP were oxidized with NaIO4 (8 mM.pH 8.3, 0.1M NaHCO 3 ), 2 hours and the unreacted NaIO 4 was removed by adding an excess of ethanediol and passing the protein through a Sephadex G-25 column. The BSA modified electrode was immersed in an oxidized peroxidase solution and slowly rotated for 2 hours in a sodium bicarbonate buffer (0.1M at pH 9.0). The resulting imine bond linking BSA to HRP was reduced with NaBH 4 (100 ml of 5 mg/ml for 1 hour and repeated once). The electrode was rotated in 0.1M NaKPO 4 and the ring cycled between -0.3V and +1.0V for 2 hours to help remove any loosely absorbed protein.
The enzyme modified electrode was analyzed for peroxidase activity by a colorimetric method. The electrode was immersed in an assay mixture and rotated at a speed which overcame any diffusion limitations (>20 rpm). Absorbance changes were monitored by means of a spectrophotometer at a single wavelength. The actual enzyme activity was then determined from a standard curve. In this way, the electrodes were checked for activity rather than for the amount of protein that was immobilized. The amount of enzyme immobilized based on its activity was approximately 2×10 -13 mol cm 2 , which is similar to concentrations achieved through other immobilization procedures.
The electrocatalytic activity of HRP as shown in FIGS. 1 and 2 was typically assessed by immersing the rotating ring disc electrode in a buffered solution containing peroxidase and hydroxymethyl ferrocene mediator. The electrode was rotated at a constant speed to control the transport of material to the disc electrode and subsequently out to the ring. A cathodic potential sweep was applied to the glassy carbon disc at 0.1V/S. The platinum ring was held at constant potential of 0V and the current at the ring as a function of the disc potential was measured. Before determination of the peroxidase generated ring current, following electrode immersion, the ring current (background current) was allowed to stabilize (about 5 min). A cathodic ring current resulting from the reduction of enzymically oxidized mediator was then measured at disc potentials which resulted in the partial reduction of molecular oxygen. The catalytic current was defined as the net reductive current occurring at a disc potential of 0 volts.
The actual profile of the reduction current seen at the ring electrode is a function of the concentrations of the enzyme and substrates, as well as the rotation rate of the electrode, the sweep rate at the disc and the potential of the ring. The magnitude of this current also depends on the fraction of enzymatically generated ferricinium (oxidized ferrocene) which actually reaches the ring.
A trace depicting ring current as a function of disc potential is shown in FIG. 3. The continuous line is indicative of ferrocene reduction at the ring while the dotted line indicates oxygen reduction at the disc (x10 -2 ). Distinct regions of faradic activity result at the ring as the disc becomes more cathodic. Initially the horizontal nature of the trace (a) indicates that there is no ferrocene mediated electroactivity at the ring. At potentials more negative than -0.3V (b) there is an increase in cathodic ring current as the disc becomes more reducing. This increase is directly proportional to the production of hydrogen peroxide at the disc. As the rate of peroxide generation increases the magnitude of the ring current becomes controlled by the reaction rate of the enzyme. Thus in region (c) the enzyme kinetics dominate the current profile with the current produced by regeneration of ferrocene from ferricinium being dominated by HRP enzyme kinetics.
Several ferrocenes shown in Table 1 were tested for their ability to act as mediators for HRP reduction. The ring current as a function of ferrocene structure and redox potential is demonstrated with HRP 2.5 μM and currents taken at a disc potential of -1.2V. In Table 1 Ep 1/2 is the redox potential and demonstrates that there is no relationship between the current produced and the redox potential and therefore that ferrocene reducing agents should not be chosen as mediators just because they are easily oxidized.
TABLE 1______________________________________Ferrocene Derivative Ep.sub.1/2 Current Relative(0.5 mM) (mv) (mA) Current______________________________________Hydroxymethyl 210 3.8 100%FerroceneMonocarboxylate 295 0.64 17%FerroceneDimethylaminomethyl 490 0.22 6%Ferrocene1,1' Dicarboxylate 420 0.10 3%Ferrocene______________________________________
Spectrophotometric assays measuring the rate of ferrocene oxidation were carried out with HRP, hydroxymethyl ferrocene, hydrogen peroxide and buffer, the rate of change in absorbance was monitored at 330 nm using a Philips PU 8720 spectrophotometer.
Determination of the effect of rotation rate on ring current revealed that ring current decreased with increasing rotation rate. Under the conditions described in FIG. 4 the maximum current was achieved at a rotation rate of 2 cps. Ring currents at rotation rates of less than 2 cps were complicated by a decrease in collection efficiency.
Currents also decreased because of the increasing dominance of oxygen reduction limited kinetics. As a result most experiments were performed at a rotation rate of 4 cps which gave a good flux of ferricinium to the ring and a sufficient transit time for enzyme reaction in solution.
FIG. 5 shows the effect of pH on ring current with maximal response being achieved at pH 4.0. However a pH of 7.0 was chosen as being convenient because the ring current showed little fluctuation and the enzyme stability was improved.
The inhibitory effect of cyanide on HRP generated ring current was measured under steady state conditions. Cyanide was added from stock solution to the electrochemical system and binding was allowed to reach equilibrium (about 30 sec). The ring current generated under conditions of substrate oxidation limited kinetics was determined by cycling the disc between 0 and -1.2V. The net ring current resulting from the catalytic activity of HRP in the region of H 2 O 2 production was determined by subtracting the ring current occurring at 0V. Thus, the ring current is a direct measure of the ability of HRP to oxidize ferrocene.
FIG. 6 shows the effect that cyanide had on the catalytic ring current. The inhibition of ring current can be standardized by expressing it as a percent inhibition of total current. These results can be analyzed in the first instance using a binding equation. If it is assumed that cyanide binds with HRP on a one to one basis and that the complex formation is directly proportional to the inhibition of current then: ##EQU1## where [CN]is the free inhibitor concentration (=[CN] T -[HRP-CN], [CN] T is the total cyanide added), and [HRP-CN]=[HRP] T ×(% inhibition).
FIG. 7 shows a Scatchcard analysis of a typical set of data. K 1 is the apparent inhibition constant for cyanide. From inhibition curves the K 1 was calculated by both linear and non-linear regression methods to be about 2 uM. This concentration corresponds to 52×10 -6 mg/ml or 52 ppb.
FIG. 8 displays the apparent K 1 values for cyanide as a function of disc potential. As the disc potential becomes more negative, the K 1 for cyanide decreases. Under condition of low hydrogen peroxide production the ring current is proportional to the disc current and an excess of enzyme exists. Thus the ring current is determined by the peroxide produced and current inhibition is not proportional to enzyme inhibition. Below a disc potential of -0.8V the inhibition of HRP by cyanide reaches a maximal efficiency.
The modified electrode was found to remain stable for more than 6 months when stored in 1M phosphate buffer at pH7.
FIG. 9 shows a version of a closed loop cyanide sensor. The oxygen necessary for production of hydrogen peroxide and cyanide enter the sensor through a gas permeable membrane (4) of large surface area. These gases dissolve in solution and a pump (5) is used to transfer them between the primary (2) and secondary (3) electrodes on a continuous basis as shown by the arrows. The primary electrode which has HRP bound to it (not shown) generates hydrogen peroxide . The secondary electrode detects ferricinium which has been oxidized from ferrocene by oxidized HRP, the HRP having been oxidized by the hydrogen peroxide. A meter (6) gives the extent of conversion of ferrocene to ferricinium through the current passed in reduction back to ferrocene. A further electrode (7) scavenges for unreacted peroxide or unreduced ferricinium etc. The electrode is positioned downstream of the primary and secondary electrodes but before the gas permeable membrane. This self contained system which is open to environmental gases can detect by inhibition of HRP enzymic activity the presence and concentration of cyanide or similar inhibitory gases.
Detection apparatus produced in accordance with the invention has the capability for continuous monitoring. | A biosensor for the detection and determination of the concentration of toxins by use of enzyme inhibition. Inhibition biosensors are affected by non-specific denaturation and substrate utilization which both result in a limited operational lifetime. These problems are mitigated by providing in an environment an enzyme which is oxidized by hydrogen peroxide the oxidized enzyme being reduced by an electron transfer agent, such as ferrocene, which is itself oxidized in the process. The electron transfer agent is capable of regeneration back to the reduced state and the extend of electron transfer regeneration gives a measure of enzyme inhibition by toxin. Electro-chemical technique allows for the generation of hydrogen peroxide from oxygen in aqueous media and the reduction of oxidized electron transfer agent. Immobilization of the enzyme to an electrode increases efficiency while potentially reducing denaturation. The biosensor can be used for the environmental determination of toxins like cyanide. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This patent application claims priority to provisional atent pplications Application No. 61/325,339, filed Apr. 18, 2010, entitled “ULTRASOUND NEUROMODULATION OF THE BRAIN, NERVE ROOTS, AND PERIPHERAL NERVES.” The disclosures of this patent application are herein incorporated by reference in their entirety.
INCORPORATION BY REFERENCE
[0002] All publications, including patents and patent applications, mentioned in this specification are herein incorporated by reference in their entirety to the same extent as if each individual publication was specifically and individually indicated to be incorporated by reference.
FIELD OF THE INVENTION
[0003] Described herein are systems and methods for Ultrasound Neuromodulation of the occipital nerve and related neural structures.
BACKGROUND OF THE INVENTION
[0004] It has been demonstrated that focused ultrasound directed at neural structures can stimulate those structures. If neural activity is increased or excited, the neural structure is said to be up-regulated; if neural activated is decreased or inhibited, the neural structure is said to be down-regulated. One or a plurality of neural elements can be neuromodulated.
[0005] Potential application of ultrasonic therapy of deep-brain structures has been covered previously (Gavrilov L R, Tsirulnikov E M, and I A Davies, “Application of focused ultrasound for the stimulation of neural structures,” Ultrasound Med Biol. 1996; 22(2):179-92. and S. J. Norton, “Can ultrasound be used to stimulate nerve tissue?,” BioMedical Engineering OnLine 2003, 2:6). It was noted that monophasic ultrasound pulses are more effective than biphasic ones.
[0006] The effect of ultrasound is at least two fold. First, increasing temperature will increase neural activity. An increase up to 42 degrees C. (say in the range of 39 to 42 degrees C.) locally for short time periods will increase neural activity in a way that one can do so repeatedly and be safe. One needs to make sure that the temperature does not rise about 50 degrees C. or tissue will be destroyed (e.g., 56 degrees C. for one second). This is the objective of another use of therapeutic application of ultrasound, ablation, to permanently destroy tissue (e.g., for the treatment of cancer). An example is the ExAblate device from InSightec in Haifa, Israel. The second mechanism is mechanical perturbation. An explanation for this has been provided by Tyler et al. from Arizona State University (Tyler, W. J., Y. Tufail, M. Finsterwald, M. L. Tauchmann, E. J. Olsen, C. Majestic, “Remote excitation of neuronal circuits using low-intensity, low-frequency ultrasound,” PLoS One 3(10): e3511, doi:10.137/1/journal.pone.0003511, 2008)) where voltage gating of sodium channels in neural membranes was demonstrated. Pulsed ultrasound was found to cause mechanical opening of the sodium channels, which resulted in the generation of action potentials. Their stimulation is described as Low Intensity Low Frequency Ultrasound (LILFU). They used bursts of ultrasound at frequencies between 0.44 and 0.67 MHz, lower than the frequencies used in imaging. Their device delivered 23 milliwatts per square centimeter of brain—a fraction of the roughly 180 mW/cm 2 upper limit established by the U.S. Food and Drug Administration (FDA) for womb-scanning sonograms; thus such devices should be safe to use on patients. Ultrasound impact to open calcium channels has also been suggested.
[0007] Alternative mechanisms for the effects of ultrasound may be discovered as well. In fact, multiple mechanisms may come into play, but, in any case, this would not effect this invention.
[0008] Patent applications have been filed addressing neuromodulation of deep-brain targets (Bystritsky, “Methods for modifying electrical currents in neuronal circuits,” U.S. Pat. No. 7,283,861, Oct. 16, 2007 and Deisseroth, K. and M. B. Schneider, “Device and method for non-invasive neuromodulation,” U.S. patent application Ser. No. 12/263,026 published as US 2009/0112133 A1, Apr. 30, 2009).
[0009] Transcranial Magnetic Stimulation (TMS) has been used for characterization of the motor system. TMS stimulation of the motor cortex is employed to see the motor response in the periphery. The response can be in alternative ways such as Motor Evoked Potentials (MEPs) or measurement of mechanical output. One application is the measurement of conduction time from central to peripheral loci, which can have diagnostic significance. Another is the demonstration of the degree of functional connectivity between the loci. Stimulation more distally such as in the spinal cord nerve roots or the spinal cord itself to measure connectivity from the spinal cord to the periphery. Irrespective of the point of stimulation with the central nervous system, an application is the monitoring of the level of anesthesia present.
[0010] While motor-system functions performed using TMS are valuable, they use expensive units, typically costing on the order of $50,000 in 2010 that are large, take a relatively high power, require cooling of the electromagnet stimulation coils, and may be noisy. It would be highly beneficial to be able to perform the same functions using lower-cost stimulation mechanism.
SUMMARY OF THE INVENTION
[0011] It is the purpose of this invention to provide methods and systems and methods for ultrasound stimulation of the cortex, nerve roots, and peripheral nerves, and noting or recording muscle responses to clinically assess motor function. In addition, just like Transcranial Magnetic Stimulation, ultrasound neuromodulation can be used to treat depression by stimulating cortex and indirectly impacting deeper centers such as the cingulate gyms through the connections from the superficial cortex to the appropriate deeper centers. Ultrasound can also be used to hit those deeper targets directly. Positron Emission Tomography (PET) or fMRI imaging can be used to detect which areas of the brain are impacted. Compared to Transcranial Magnetic Stimulation, Ultrasound Stimulation systems cost significantly less and do not require significant cooling.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 shows ultrasound transducers and EMG sensors at various portions of the nervous system.
[0013] FIG. 2 shows a diagram of the ultrasound sensor, ultrasound conduction medium, ultrasound field, and the target.
[0014] FIG. 3 shows a block diagram of the control circuit.
DETAILED DESCRIPTION OF THE INVENTION
[0015] It is the purpose of this invention to provide methods and systems and methods for ultrasound stimulation of the cortex, nerve roots, and peripheral nerves, and noting or recording muscle responses to clinically assess motor function. In addition, just like Transcranial Magnetic Stimulation, ultrasound neuromodulation can be used to treat depression by stimulating cortex and indirectly impacting deeper centers such as the cingulate gyms through the connections from the superficial cortex to the appropriate deeper centers. Ultrasound can also be used to hit those deeper targets directly. Positron Emission Tomography (PET) or fMRI imaging can be used to detect which areas of the brain are impacted. In addition to any acute positive effect, there will be a long-term “training effect” with Long-Term Depression (LTP) and Long-Term Potentiation (LTD) depending on the central intracranial targets to which the neuromodulated cortex is connected.
[0016] Ultrasound stimulation can be applied to the motor cortex, spinal nerve roots, and peripheral nerves and generate Motor Evoked Potentials (MEPs). MEPs elicited by central stimulation will show greater variability than those elicited stimulating spinal nerve roots or peripheral nerves. Stimulation results can be recorded using evoked potential or electromyographic (EMG) instrumentation. Muscle Action Potentials (MAPs) can be evaluated without averaging while Nerve Action Potentials (NAPs) may need to be averaged because of the lower amplitude. Such measurements can be used to measure Peripheral Nerve Conduction Velocity (PNCV). Pre-activation of the target muscle by having the patient contract the target muscle can reduce the threshold of stimulation, increase response amplitude, and reduce response latency. Another test is Central Motor Conduction Time (CMCT), which measures the conduction time from the motor cortex to the target muscle. Different muscles are mapped to different nerve routes (e.g., Abductor Digiti Minimi (ADM) represents C8 and Tibialis Anterior (TA) represents L4/5). Still another test is Cortico-Motor Threshold. Cortico-motor excitability can be measured using twin-pulse techniques. Sensory nerves can be stimulated as well and Sensory Evoked Potentials (SEPs) recorded such as stimulation at the wrist (say the median nerve) and recording more peripherally (say over the index finger). Examples of applications include coma evaluation (diagnostic and predictive), epilepsy (measure effects of anti-epileptic drugs), drug effects on cortico-motor excitability for drug monitoring, facial-nerve functionality (including Bell's Palsy), evaluation of dystonia, evaluation of Tourette's Syndrome, exploration of Huntington's Disease abnormalities, monitoring and evaluating motor-neuron diseases such as amyotrophic lateral sclerosis, study of myoclonus, study of postural tremors, monitoring and evaluation of multiple sclerosis, evaluation of movement disorders with abnormalities unrelated to pyramidal-tract lesions, and evaluation of Parkinson's Disease. As evident by the conditions that can be studied with the various functions, neurophysiologic research in a number of areas is supported. Other applications include monitoring in the operating room (say before, during, and after spinal cord surgery). Cortical stimulation can provide relief for conditions such as depression, bipolar disorder, pain, schizophrenia, post-traumatic stress disorder (PTSD), and Tourette syndrome. Another application is stimulation of the phrenic nerve for the evaluation of respiratory muscle function. Clinical neurophysiologic research such as the study of plasticity.
[0017] When TMS is applied to the left dorsal lateral prefrontal cortex and depression is treated ‘indirectly” (e.g., at 10 Hz, although other rates such as 1, 5, 15, and 20 Hz have been used successfully as well) due to connections to one or more deeper structures such as the cingulate and the insula as demonstrated by imaging. The same is true for ultrasound stimulation.
[0018] A benefit of ultrasound stimulation over Transcranial Magnetic Stimulation is safety in that the sound produced is less with a lower chance of auditory damage. Ironically, TMS produces a clicking sound in the auditory range because of deformation of the electromagnet coils during pulsing, while ultrasound stimulation is significantly above the auditory range.
[0019] The acoustic frequency (e.g., typically in that range of 0.3 MHz to 0.8 MHz or above whether cranial bone is to be penetrated or not) is gated at the lower rate to impact the neuronal structures as desired. A rate of 300 Hz (or lower) causes inhibition (down-regulation) (depending on condition and patient). A rate in the range of 500 Hz to 5 MHz causes excitation (up-regulation)). Power is generally applied at a level less than 60 mW/cm2. Ultrasound pulses may be monophasic or biphasic, the choice made based on the specific patient and condition. Ultrasound stimulators are well known and widely available.
[0020] FIG. 1 illustrates placement of ultrasound stimulators EMG and sensors related to head 100 , spinal cord 110 , nerve root 120 , and peripheral nerve 130 . Ultrasound transducer 150 is directed at superficial cortex (say motor cortex). For any ultrasound transducer position, ultrasound transmission medium (e.g., silicone oil in a containment pouch) and/or an ultrasonic gel layer. When the ultrasound transducer is pulsed [typically tone burst durations of (but not limited to) 25 to 500 μsec, the conduction time to the sensor at nerve root 170 and/or associated muscles further in the periphery 190 . Alternatively ultrasound transducer 160 may be positioned at a nerve root 120 and the conduction time to the electromyography sensor 190 measured. Further, an ultrasound transducer 180 may be positioned over peripheral nerve 130 and the conduction tine to electromyography sensor 190 measured.
[0021] Cortical excitability can be measured using single pulses to determine the motor threshold (defined as the lowest intensity that evokes MEPs for one-half of the stimulations. In addition, such single pulses delivered at a level above threshold can be used to study the suppression of voluntarily contracted muscle EMG activity following an induced MEP.
[0022] Ultrasound transducer 200 with ultrasound-conduction-medium insert 210 are shown in front view in FIG. 2A and the side view in FIG. 2B . FIG. 2C again shows a side view of ultrasound transducer 200 and ultrasound-conduction-medium insert 210 with ultrasound field 220 focused on the target nerve bundle target 230 . Depending on the focal length of the ultrasound field, the length of the ultrasound transducer assembly can be increased with a corresponding increase in the length of ultrasound-conduction-medium insert. For example, FIG. 2D shows a longer ultrasound transducer body 250 and longer ultrasound-conduction-medium insert 260 . The focus of ultrasound transducer 200 can be purely through the physical configuration of its transducer array (e.g., the radius of the array) or by focus or change of focus by control of phase and intensity relationships among the array elements. In an alternative embodiment, the ultrasonic array is flat or other fixed but not focusable form and the focus is provided by a lens that is bonded to or not-permanently affixed to the transducer. In a further alternative embodiment, a flat ultrasound transducer is used and the focus is supplied by control of phase and intensity relationships among the transducer array elements.
[0023] Keramos-Etalon can supply a 1-inch diameter ultrasound transducer and a focal length of 2 inches, which with 0.4 Mhz excitation will deliver a focused spot with a diameter (6 dB) of 0.29 inches. Typically, the spot size will be in the range of 0.1 inch to 0.6 inch depending on the specific indication and patient. A larger spot can be obtained with a 1-inch diameter ultrasound transducer with a focal length of 3.5″ which at 0.4 MHz excitation will deliver a focused spot with a diameter (6 dB) of 0.51.″ Even though the target is relatively superficial, the transducer can be moved back in the holder to allow a longer focal length. Other embodiments are applicable as well, including different transducer diameters, different frequencies, and different focal lengths. In an alternative embodiment, focus can be deemphasized or eliminated with a smaller ultrasound transducer diameter with a shorter longitudinal dimension, if desired, as well. Other embodiments have mechanisms for focus of the ultrasound including fixed ultrasound array, flat ultrasound array with lens, non-flat ultrasound array with lens, flat ultrasound array with controlled phase and intensity relationships, and ultrasound non-flat array with controlled phase and intensity relationship. Ultrasound conduction medium will be required to fill the space. Examples of sound-conduction media are Dermasol from California Medical Innovations or silicone oil in a containment pouch. If patient sees impact, he or she can move transducer (or ask the operator to do so) in the X-Y direction (Z direction is along the length of transducer holder and could be adjusted as well).
[0024] Transducer arrays of the type 200 may be supplied to custom specifications by Imasonic in France (e.g., large 2D High Intensity Focused Ultrasound (HIFU) hemispheric array transducer)(Fleury G., Berriet, R., Le Baron, O., and B. Huguenin, “New piezocomposite transducers for therapeutic ultrasound,” 2nd International Symposium on Therapeutic Ultrasound—Seattle— 31 / 07 -Feb. 8, 2002), typically with numbers of ultrasound transducers of 300 or more. Keramos-Etalon in the U.S. is another custom-transducer supplier. The design of the individual array elements and power applied will determine whether the ultrasound is high intensity or low intensity (or medium intensity) and because the ultrasound transducers are custom, any mechanical or electrical changes can be made, if and as required. Blatek in the U.S. also supplies such configurations.
[0025] FIG. 3 illustrates the control circuit. Control System 310 receives its input from Intensity setting 320 , Frequency setting 330 , Pulse-Duration setting 340 , and Firing-Pattern setting 350 . Control System 310 then provides output to drive Ultrasound Transducer 370 and thus deliver the neuromodulation.
[0026] The various embodiments described above are provided by way of illustration only and should not be construed to limit the invention. Based on the above discussion and illustrations, those skilled in the art will readily recognize that various modifications and changes may be made to the present invention without strictly following the exemplary embodiments and applications illustrated and described herein. Such modifications and changes do not depart from the true spirit and scope of the present invention. | Disclosed are methods and systems for non-invasive ultrasound neuromodulation of superficial cortex of the brain or stimulation of nerve roots or peripheral nerves. Such stimulation is used for such purposes as determination of motor threshold, demonstrating whether connectivity to peripheral nerves or motor neurons exists and performing nerve conduction-speed studies. Neuromodulation of the brain allows treatment of conditions such as depression via stimulating superficial neural structures that have connections to deeper involved centers. Imaging is optional. | 0 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of U.S. patent application Ser. No. 07/453,819, filed on Dec. 19, 1989 and assigned to the same assignee as the assignee of the present invention, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to fastener driving tools, and more particularly, to a new and improved fastener driving tool that utilizes an energy storing flywheel that is selectively engaged by a fastener driving member in order to drive the member into engagement with a fastener, such as a nail or a staple, for the purpose of driving the fastener into a workpiece.
2. Description of the Prior Art
Fastener driving tools have utilized an energy storing flywheel for the purpose of storing energy to drive a fastener into a workpiece. Examples of representative fastener driving tools of this type are disclosed in U.S. Pat. Nos. 4,121,745; 4,129,240; 4,189,080; 4,298,072; 4,323,127; 4,519,535; 4,544,090; 4,558,747 and 4,721,170. In addition, U.S. Pat. No. 4,928,868, the inventor and assignee of which are the same as in the case of the present invention, discloses a fastener driving tool wherein an energy storing flywheel cooperates with an idler wheel to selectively engage a ram for driving a fastener into a workpiece. These patents disclose an elastic cord and pulley arrangement to return the ram to its starting position. Such elastic cords, besides requiring a fairly complex supporting structure, require periodic replacement.
U.S. Pat. Nos. 4,042,036; 4,129,240; 4,161,272; 4,204,622 and 4,290,493 disclose other fastener driving tools having a return mechanism that includes a helical tension spring to return the ram to its starting position. In general, such an arrangement requires undesirable headroom for the contracted spring. In addition, tension springs, in accordance with Hooke's Law, exert linearly increasing resistance to the ram as it is driven during a driving stroke such that the force by which a fastener is driven into the workpiece may be negatively affected.
The rams or blades utilized by the tools disclosed in a number of prior art patents are relatively complex in that they require friction pads that are engaged by the flywheel to transmit energy to the ram (see for example, U.S. Pat. Nos. 4,042,036, 4,555,747 and 4,323,127 which show blades having friction pads that require assembly). Alternatively, some rams are formed with narrowed or thinned portions. When the narrowed portion is disposed adjacent the flywheel, the flywheel is not able to drive the ram thereby providing a way of disengaging the blade from the flywheel at the end of a drive stroke.
SUMMARY OF THE INVENTION
It is an object of the present invention to solve many of the problems associated with the prior art fastener driving tools.
It is another object of the present invention to provide a new and improved fastener driving tool having a simple and inexpensive return mechanism associated with a driver blade or ram.
It is also an object of the present invention to provide a new and improved flywheel type fastener driving tool which is both easily manufactured and inexpensive.
It is another object of the present invention to provide a new and improved flywheel type fastener driving tool that may have a self-contained power supply such as a battery.
It is a further object of the present invention to provide a new and improved fastener driving tool having a relatively inexpensive and easily manufactured fastener driving member.
It is another object of the present invention to provide a new and improved flywheel type fastener driving tool having a nip between the flywheel and an idler wheel which is easily and accurately adjustable in size.
It is still another object of the present invention to provide a new and improved fastener driving tool with a lever mechanism to force an idler wheel into engagement with a fastener driving member upon the actuation of a solenoid so that the fastener driving member is driven by a rotating flywheel and the idler wheel is maintained in that position after the solenoid has been deenergized until the fastener driving member has exited from a nip formed between the idler wheel and the flywheel.
In accordance with these and many other objects of the present invention, a fastener driving tool embodying the present invention includes a ram that is to be driven from a first or non-actuated position to a second or driving position. In order for the ram to be so driven, the fastener driving tool has a continuously rotating flywheel and an idler wheel positioned adjacent to the flywheel so as to define a nip between the flywheel and the idler wheel. The ram normally is disposed in the nip between the flywheel and idler wheel. The position of the idler wheel is movable relative to the flywheel to adjust the size of the nip from an open position when the ram is not forced against the flywheel to a closed ram engaging position when the ram is forced against the flywheel such that the ram is driven toward a fastener during a fastener driving stroke.
In order to initiate the fastener driving stroke, a trigger may be depressed such that a solenoid is actuated for a short period of time (this period of time should be at least less than the time it takes for the ram to travel from its non-actuated position to a position when it has exited the nip). The actuation of the solenoid retracts the armature of the solenoid that is coupled to a lever mechanism that moves the idler wheel towards the flywheel to thereby close the nip. As a result, the ram is forced against the flywheel and is propelled through the nip until the top of the ram exits the nip. Even after the solenoid has been deenergized and while a portion of the ram is still within the nip between the flywheel and the idler wheel, the lever mechanism maintains the solenoid armature retracted and the idler wheel forced against the ram notwithstanding the force applied to the retracted armature by a return spring associated with the solenoid.
Once the ram exits the nip, the force applied by the return spring against the solenoid armature overcomes the force applied against the armature by the lever mechanism because the idler wheel can move into the nip to thereby release the lever mechanism. With the return spring moving the armature to its normal position, the idler wheel is returned to its non-actuated position by the lever mechanism. The returning of the idler wheel to this non-actuated position opens the nip and the ram is allowed to be retracted to its non-actuated position by means of a double torsion spring.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view of one embodiment of the fastener driving tool according to the present invention;
FIG. 2 is a front elevational view taken along line 2--2 of FIG. 1 showing the blade of the fastener driving tool in its retracted position;
FIG. 3 is a partially cut-away cross-sectional view taken along line 3--3 of FIG. 2;
FIG. 4 is a partially cut-away plan sectional view taken along line 4--4 of FIG. 3;
FIG. 5 is a partially cut-away plan sectional view taken along line 5--5 of FIG. 3;
FIG. 6 is a partially cut-away plan sectional view taken along line 6--6 of FIG. 3;
FIG. 7 is a partially cut-away cross-sectional view taken along line 7--7 of FIG. 3;
FIG. 8 is a partially cut-away cross-sectional view similar to FIG. 3 with the blade of the fastener driving tool shown in its driven position;
FIG. 9 is a partially cut-away cross-sectional view taken along line 9--9 of FIG. 8;
FIG. 10 is a side elevational view of a second embodiment of the fastener driving tool according to the present invention;
FIG. 11 is a front elevational view, partially broken away, of FIG. 10 taken along line 11--11 of FIG. 10 with the blade of the fastener driving tool shown in its retracted position;
FIG. 12 is a partially cut-away cross-sectional view taken along line 12--12 of FIG. 11;
FIG. 13 is a partially cut-away plan sectional view taken along line 13--13 of FIG. 12;
FIG. 14 is a partially cut-away plan sectional view taken along line 14--14 of FIG. 12;
FIG. 15 is a partially cut-away plan sectional view taken along line 15--15 of FIG. 12;
FIG. 16 is a cross-sectional view similar to FIG. 12 with the blade of the fastener driving tool shown in its driven position; and
FIG. 17 is an example of a timing circuit that may be used in the fastener driving tool of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings and with particular attention to FIG. 1, there is shown a fastener driving tool according to the present invention and generally designated by the reference numeral 10. The fastener driving tool 10 illustrated in FIG. 1 includes a housing 12 having a vertical portion 14 and a handle portion 16. A magazine 18 is affixed to the housing 12 and contains the fasteners to be driven. Typically, the magazine 18 will automatically advance and position a fastener 19 in a driving position at the completion of each drive stroke. In the illustrated embodiment, the magazine 18 is designed to hold U-shaped staples, but other suitable magazines including those designed to hold nails or other fasteners may be used with appropriate modifications to the tool.
The fastener driving tool 10 includes a nose-piece 20, an electric motor 22, which may be powered either from an AC main source or a battery powered source, a flywheel 24 and an idler wheel 26. A shaft 28 (FIG. 5) serves as both the drive shaft of the motor 22 and the shaft of the flywheel 24. The shaft 28 serves to rotate the flywheel 24 by means of a pin 30 whenever the motor 22 is energized. The motor shaft 28 is supported within the housing 12 by bearings 32, which may be ball bearings, needle bearings or other suitable bearings.
A fastener driving member 36, which also may be referred to as a blade or ram, is formed of metal, for example, a relatively inexpensive metal such as S2 tool steel. The blade 36 is stamped and hardened and does not require any complex machining or assembly step in its manufacture. The blade 36 is supported within the vertical portion 14 of the housing 12 by a double torsion spring 38. The spring 38 is mounted in the housing 12 by means of a pin 40 on a drum 42 in the handle 16 of the tool 10. The center of the double torsion spring 38 is engaged by the pin 40, and the turns of the spring 38 are wrapped around the drum 42 in a counter-clockwise direction as shown in FIG. 3. The double torsion spring 38 has a pair of ends 44 each of which engages one of a pair of apertures 46 located on a T-shaped end 48 of the blade 36 (FIG. 2). The torsion spring 38 is tensioned to hold the T-shaped end 48 of the blade 36 in a first non-actuated or retracted position in contact with a cylindrical upper limiting bumper 50 (FIGS. 2 and 3). The amount of tension on the spring 38 is dependent on the diameter of the spring 38, the material of the spring 38, and the bend of the spring 38, all of which are preselected to exert a minimum upward force against the upper limiting bumper 50 when the blade 36 is in the first non-actuated position. This upward force will increase as the torsion spring 38 is pulled downwardly with the blade 36 during a driving stroke. The upper limiting bumper 50 is formed of a resilient material, such as, for example, rubber or neoprene or other similar material, and is located within a housing cavity 51 to act as a stop whenever the torsion spring 38 returns the blade 36 to the first or non-actuated position, as will be described hereinafter.
The idler wheel 26 is supported by a shaft 56 which is positioned within two slots 52 and 54 (FIG. 5) of the housing 12. A bearing 58, which may be a needle bearing or a bearing fabricated from any suitable material, permits the idler wheel 26 to rotate freely about the shaft 56. The idler wheel shaft 56 is movable laterally within the slots 52 and 54 by a toggle mechanism 60 that includes a pair of sidearms 62 and 64 that are located on the exterior of the housing 12 and support the shaft 56. The sidearms 62 and 64 are mounted on a pair of eccentric pivot axles 66 which are formed intergally with a shaft 68 mounted on the housing 12. The upper ends of the sidearms 62 and 64 are joined by a shaft 70 through slots 72 and 74 (FIG. 4) in the housing 12. The toggle mechanism 60 also includes a pair of actuator arms 76 and 78 pivotably mounted at a first end on the shaft 70 within the housing 12. The actuating arms 76 and 78 are pivotably mounted at their second end on a shaft 80 passing through an armature 82 of a solenoid 84 which is in turn pivotably mounted on the housing 12 by means of a shaft 86. When the solenoid 84 is not energized, a compression spring 88 maintains the armature 82 in contact with a resilient protective bumper 90 mounted in a cavity 91 of the housing 12.
The toggle mechanism 60 further includes a pair of pivot arms 92 and 94 (FIG. 4). One end of each of the pivot arms 92 and 94 is pivotably mounted on the shaft 80 and the other end is pivotably mounted on a shaft 96 passing through an extension 98 of the housing 12. A manually actuated trigger or push button 100 is mounted on a shaft 102 in the handle 16. The trigger 100 actuates a trigger switch 104 which in turn actuates the solenoid 84 through a timing circuit (for example, the timing circuit shown in FIG. 17).
The blade 36 passes between the flywheel 24 and the idler wheel 26 and thereafter through an aperture 106 in a removable, rectangular retainer 108 positioned at the upper end of a cavity 110 by a lower limiting bumper 112. The removable retainer 108 prevents the T-shaped end 48 of the blade 36 from directly engaging the lower bumper 112. The lower bumper 112 is held in place by the retainer 108 and lugs 111, and is formed of a resilient material such as rubber or neoprene. In the first non-actuated or retracted position, the blade 36 will continue through the cavity 110 into an aperture 113 in the housing 12. In this first position shown in FIG. 3, the lower end of the blade 36 terminates at the upper end of a drive path 114 formed between the nosepiece 20 and a forward portion 116 of the magazine 18. The alignment of blade 36 is controlled by the drive path 114. An upper portion 118 of the magazine 18 inserted within a chamber 120 of the housing 12 removably connects magazine 18 to the housing 12 by a fastener 122.
To insure optimum driving conditions for the engagement of the idler wheel 26 and the flywheel 24, a grooved portion 124 of the lower limiting bumper 112 is frictionally engaged with the shaft 68 to allow the pivot points of the eccentric pivot axles 66 of the toggle mechanism 60 to be adjusted by means of a knob 126. The knob 126 is mounted on an extension 128 of the pivot axles 66 by means of a pin 130 and allows the spacing between the idler wheel 26 and the flywheel 24 to be adjusted by revolving the pivot axles 66 about the shaft 68. This effectively moves the idler wheel 26 closer to or farther from the flywheel 24 and adjusts the size of a nip 140 formed between the idler wheel 26 and the flywheel 24.
Operation of the fastener driving tool 10 is controlled by an on/off switch 132 mounted on a portion 134 of the handle 16 which is also affixed in a conventional manner to the magazine 18. The switch 132 allows power to be supplied to the tool 10 from a power cord 136 or a battery 138, which may be located within the handle 16 or which may be external to the tool 10, for example, worn on a side of an operator. With the switch 132 in the "on" position, power is supplied to the electric motor 22 which then runs continuously. The blade 36 is in its first position shown in FIG. 3, but the rotation of flywheel 24 has no effect because the nip 140 formed between the flywheel 24 and the idler wheel 26 is held in its open position by the toggle mechanism 60 until the trigger 100 is actuated.
The actuation of the trigger 100 serves to apply power for a short period of time to the solenoid 84 and retract the armature 82. As the armature 82 is retracted, the movement of the pivot arms 92 and 94 forces the solenoid 84 to pivot about the shaft 86 from a substantially vertical alignment shown in FIG. 3 to an alignment angled from the vertical in a clockwise direction as shown in FIG. 8. As the pivot arms 92 and 94 force the shaft 80 away from the blade 36 in the direction indicated by an arrow A, the actuating arms 76 and 78 also are pulled in the same direction and the movement of the actuating arms 76 and 78 pulls the sidearms 62 and 64 with them. This movement of the sidearms 62 and 64 forces the idler wheel 26 into contact with the ram 36, thus closing the nip 140 formed between idler wheel 26 and the flywheel 24. The idler wheel 26 is held against the blade 36 with sufficient force that the rotation of flywheel 24 now forces the blade 36 through the nip 140 with a substantial mechanical advantage, down drive path 114 and into contact with a fastener 19, the force of the blade 36 then driving the fastener 19 into the workpiece. In order to insure that the idler wheel 26 applies a sufficient amount of force against the blade 36, the shaft 56 is made of a deflectable material.
Once the nip 140 is closed, a conventional timing circuit may be used to deenergize the solenoid 84 at least prior to the time when the ram 36 has cleared the nip 140 (for example, as shown in FIG. 8 of the drawings). Such a timing circuit could include a microchip which causes the solenoid 84 to remain in its energized state while the microchip counts clock interrupts until the requisite time period has elapsed. Once this requisite time period has elapsed, the solenoid is deenergized. An alternative timing circuit is shown in FIG. 17 wherein an appropriately selected capacitor 141 maintains power to the solenoid 84 for the requisite time for the armature 82 to be retracted and the idler wheel 26 to be moved into engagement with the ram 36. Alternatively, a monostable multivibrator may be used for a portion of the timing circuit.
When the timing circuit deenergizes the solenoid 84, the armature 82 of the solenoid 84 will be maintained in its actuated position as shown in FIG. 8 notwithstanding the fact that the compression spring 88 is applying a force on the solenoid armature 82 attempting to return it to the position shown in FIG. 3. However, the force applied to the armature 82 at the shaft 80 by the toggle mechanism 60 including the pivot arms 92 and 94, the actuating arms 72 and 74 and the side arms 62 and 64 due to the engagement of the idler wheel 26 against the ram 36 is sufficient to maintain the pivot arms 92 and 94, the actuating 72 and 74 and the side arms 62 and 64 locked in the position indicated in FIG. 8.
Once the blade 36 clears the nip 140 (as, for example, shown in FIG. 8), the force being exerted on the lever arms 62 and 64 as a result of the deflection of the shaft 56 due to the engagement of the idler wheel 26 against the blade 36 is released because the idler wheel 26 can move towards the flywheel 24 into the now vacated nip 140. With the release of the forces against the lever arms 62 and 64, the force exerted by the compression spring 88 is sufficient to move the armature 82 back to its static or normal position shown in FIG. 3 such that the solenoid 84 returns to its vertically aligned position shown in FIG. 3. As this occurs, the pivot arms 92 and 94, the actuating arms 76 and 78, and the side arms 62 and 64 also are returned to their static position shown in FIG. 3. As a result, the idler wheel 26 is moved away from the flywheel 24 to open the nip 140. With the nip 140 open and after the downward movement of the blade 36 has been stopped by the lower bumper 112, the double torsion spring 38 can return the blade 36 to its non-actuated position in contact with the upper limiting bumper 50 as shown in FIG. 3 because the clearance of the nip 140 between the idler wheel 26 and the flywheel 24 becomes greater than the thickness of the blade 36.
FIGS. 10 through 16 of the present application show an alternative embodiment of the present invention wherein a larger flywheel 142 replaces the flywheel 24 and other modifications necessary to accommodate the larger flywheel 142 have been made. As the design and operation of the embodiments shown in FIGS. 1-9 and FIGS. 10-16 are substantially similar, only the differences will be described. Similar reference numerals are used for each embodiment where the elements are substantially the same.
In the alternative embodiment of FIGS. 10-16, the solenoid 84 has been repositioned to make room for the larger flywheel 142. As shown in FIG. 12, the solenoid 84 is in a horizontal position instead of a vertical position shown in FIGS. 1-9. Nevertheless, the solenoid 84 operates essentially in the same manner. However, due to the fact that the solenoid armature 82 is now operating in a horizontal direction, a pair of triangular pivot plates 144 and 146 joined by three shafts 148, 150 and 152 replaces the pivot arms 92 and 94. The shaft 148 passes through a housing extension 154 and provides a fixed pivot point for the pivot plates 144 and 146. The shaft 150 passes through the armature 82 of the solenoid 84 and allows the solenoid 84 to move the toggle mechanism between the positions shown in FIG. 12 and FIG. 16. The shaft 152 provides a linkage between the actuating arms 76 and 78 and the pivot plates 144 and 146.
A driving blade 158 having a cross-shaped upper end 160 can be used with the fastener driving tool 10 shown in FIGS. 10-16. Each arm of the cross-shaped upper end 160 of the blade 158 has an aperture 162 through which a hooked end 164 of a double torsion spring 166 is engaged. A smaller upper limiting bumper 156 is provided so that there is sufficient clearance for the operation of the solenoid armature 82 and for the longer blade 158. The double torsion spring 166 is affixed to a drum 168 by means of pin 170, the drum 168 being attached to the housing 12 in a conventional manner. An expanded area 172 of the housing 12 is provided to give the flywheel 142 additional room.
As was the case with the embodiment disclosed in FIGS. 1-9, the shaft 68 is frictionally engaged within a groove 174 in a lower limiting bumper 176 to allow the knob 126 to adjust the toggle mechanism's pivot point and consequently, the size of the nip 140. The bumper 176 is held in place by a rectangular retaining plate 178 and lugs 180.
The operation of the embodiment disclosed in FIGS. 10-16 is similar to that of the embodiment disclosed in FIGS. 1-9. When the on/off switch 132 is in the "on" position, the flywheel 142 commences to rotate in a counterclockwise direction when viewed in the orientation shown in FIG. 12. However, the rotation of the flywheel 142 does not affect the position of the blade 158 until the nip 140 is closed.
When the trigger 100 is actuated, the solenoid 84 is energized for a short period of time and the solenoid armature 82 is retracted such that the shaft 150 is pulled with it. This causes the pivot plates 144, 146 to pivot about the shaft 148 and pull the sidearms 62 and 64 towards the solenoid 84 by means of the actuating arms 76 and 78. The idler wheel 26 is carried by the sidearms 62 and 64 and is therefore moved toward the flywheel 142 to thereby close the nip 140. When the nip 140 is closed, the idler wheel 26 forces the blade 158 against the flywheel 142 with sufficient force that the rotating flywheel 142 propels the blade 158 down the drive path 114 against the fastener 19 and the fastener 19 is driven into the workpiece.
As previously discussed in connection with the embodiment shown in FIGS. 1-9, a conventional timing circuit may be used to deenergize the solenoid 84 after the nip 140 is closed. The solenoid 84 is deenergized at least prior to the time when the ram 158 has cleared the nip 140 (for example, as shown in FIG. 16 of the drawings). When the timing circuit deenergizes the solenoid 84, the armature 82 of the solenoid 84 will be maintained in its actuated position as shown in FIG. 16 notwithstanding the fact that the compression spring 88 is applying a force on the solenoid armature 82 attempting to return it to the position shown in FIG. 12. However, the force applied to the armature 82 at the shaft 150 by the toggle mechanism including the pivot plates 144 and 146, the actuating arms 72 and 74 and the side arms 62 and 64 due to the engagement of the idler wheel 26 against the ram 158 is sufficient to maintain the pivot plates 144 and 146, the actuating 72 and 74 and the side arms 62 and 64 locked in the position indicated in FIG. 16.
Once the blade 158 clears the nip 140 (as, for example, shown in FIG. 16), the force being exerted on the lever arms 62 and 64 as a result of the deflection of the shaft 56 due to the engagement of the idler wheel 26 against the blade 158 is released because the idler wheel 26 can move towards the flywheel 24 into the now vacated nip 140. With the release of the forces against the lever arms 62 and 64, the force exerted by the compression spring 88 is sufficient to move the armature 82 back to its static or normal position shown in FIG. 12 such that the solenoid 84 returns to its horizontally aligned position shown in FIG. 12. As this occurs, the pivot plates 144 and 146, the actuating arms 76 and 78, and the side arms 62 and 64 also are returned to their static position shown in FIG. 12. As a result, the idler wheel 26 is moved away from the flywheel 142 to open the nip 140. With the nip 140 open and after the downward movement of the blade 36 has been stopped by the lower bumper 112, the double torsion spring 166 can return the blade 158 to its non-actuated position in contact with the upper limiting bumper 156 as shown in FIG. 12 because the clearance of the nip 140 between the idler wheel 26 and the flywheel 142 becomes greater than the thickness of the blade 158.
While there have been described what are at present considered to be the preferred embodiments of the present invention, it will be understood that various modifications may be made therein which are within the true spirit and scope of the invention. | A lightweight fastener driving tool capable of being battery powered utilizes a low cost fastener driving ram or blade that is normally located in a nip defined between a motor driven flywheel and an idler wheel. Upon the actuation of a trigger operated timing circuit, a solenoid is energized. The solenoid controls a toggle mechanism to adjust the position of the idler wheel with respect to the flywheel so as to force the blade against the flywheel and thereby to close the nip for a sufficient amount of time to initiate the driving of the blade downwardly through the nip. The timing circuit deenergizes the solenoid prior to the time that the blade exits the nip but the toggle mechanism maintains the idler wheel against the blade such that the blade continues to be driven by the flywheel. When the top of the blade exits the nip, the idler wheel can move towards the flywheel and the toggle mechanism releases the idler wheel so that the nip is open. With the nip open and the downward movement of the blade halted by a lower bumper, the blade is permitted to be raised to its non-actuated position by a double torsion spring. | 1 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of co-pending prior application Ser. No. 528,437 filed on Nov. 29, 1974 for "Decoding Clutching System for Minicomputers" of the same inventive entity and co-ownership herewith, now abandoned.
BACKGROUND OF THE INVENTION
There are many types of electronic data processing minicomputers, such as the Burroughs Series-L machine which is described in Burroughs Technical Manual Form 1033388 entitled "Series-L Electronic Billing Computer" which was copyrighted in 1969 by Burroughs Corporation, which employ a decoder to convert electrical signals which are coded in digital values into equivalent mechanical movements. Such decoders are often driven continuously from a main motor. The continuous operation of the decoder results in a greater amount of noise, wear and tear to the decoder unit itself, and to a shortened machine life and excessive power consumption.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a decoder clutching system for reducing the noise inherent in a continuously-operated decoder.
It is a further object of the present invention to reduce mechanical wear on the decoder while also reducing power consumption.
It is a further object of the present invention to provide a decoder clutching system wherein an electro-magnetic clutch is secured to the motor which drives the decoder unit and wherein the decoder clutching system includes a control system for selectively energizing or de-energizing the electromagnetic clutch in response to command signals.
It is still a further object of the present invention to provide a decoder clutching system wherein a master clutch is secured to the motor which drives the decoder unit, wherein a clutch control system operates to selectively energize or de-energize the master clutch in response to generated command signals, and wherein a drive trip latch assembly associated with the keyboard of the minicomputer employing the decoder is used to sense the depression of any key for generating such command signals.
These and other objects and advantages of the present invention are accomplished in a decoder clutching system wherein an electromagnetic master clutch is secured to a drive motor which drives a decoder unit. A control system is used to selectively energize or de-energize the electromagnetic clutch so as to terminate the drive to the decoder unit during those intervals in which its use is not required, thereby reducing noise and increasing the life of the unit. A drive trip latch mechanism from the keyboard assembly is modified so that the depression of any key on the keyboard will cause the logic to energize and hold the clutch energized for a sufficient time delay pre-set in the clutch control logic to maintain drive power to the decoder for a predetermined time interval of anticipated binary to decimal conversion requirement by the minicomputer. The clutch control logic also responds to other command signals from the remainder of the minicomputer for similarly energizing the electromagnetic master clutch in response to the demands of the system.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of an electronic data processing system such as a minicomputer employing the decoder clutching system of the present invention;
FIG. 2 is a perspective illustration of a portion of a keyboard apparatus used in the minicomputer system of FIG. 1 showing the key lever operation and drive trip latch assembly used in prior art keyboard apparatus;
FIG. 3 is an exploded view of a modified drive trip latch assembly utilized in the present invention;
FIG. 3a is a perspective view of a latching trip 50 and collar 47 of the assembly of FIG. 3;
FIG. 4 is a schematic diagram of the electrical portion of the clutch control system of the present invention; and
FIG. 5 is a perspective view of the decoder clutching system of the present invention illustrating a belt and gear system through which the main motor and master clutch may drive the decoder.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a block diagram of an electronic data processing system such as a minicomputer employing the decoder clutching system of the present invention. The block 11 which is formed by dotted lines represents an electronic data processing computer or minicomputer such as the Burroughs Series-L or TC-Series line of business machines. The minicomputer system 11 is shown as containing a decoder unit 13 and a main motor 15 which are used to drive the decoder unit. An electromagnetic master clutch 17 is secured to the motor via securing means such as a shaft 19, and the electromagnetic master clutch 17 contains a clutch coil 143 (FIG. 4) which can be energized, as known in the art, to enable the master clutch 17 to supply drive energy to the decoder 13 via coupling means 21, such as a shaft, described in more detail with reference to FIG. 5.
The electronic clutch control system of the present invention is represented by block 23 and responds to an alert or other command signals present at clutch control inputs 25 and 27 to control the generation of an energization signal onto lead 29. When an energization signal is supplied from the clutch control system 23 to the electromagnetic master clutch 17 via lead 29, the clutch coil 143 (FIG. 4) is energized and the electromagnetic master clutch 17 operates to enable the motor 15 to drive the decoder 13, as explained hereinafter. When the clutch coil 143 (FIG. 4) of clutch 17 is de-energized, the motor drive is decoupled from the decoder 13 for reducing noise and energy consumption while also saving wear and tear on the decoder unit. The minicomputer 11 is also shown as having a keyboard assembly 31 and the present invention teaches a modification of the keyboard assembly as illustrated in FIGS. 3 and 3a, such that an alert command signal will be generated in response to the depression of any of the keys of the keyboard 31 and passed via lead 25 to the clutch control system 23 for energizing or de-energizing the master clutch 17. Block 33 represents the remainder of the minicomputer and it is capable of supplying a command signal via lead 27 to clutch control system 23 under either of two conditions. Under the first condition, block 33 will pass a control signal on lead 27 when the decoder is restored to its home position a predetermined time after the decoder is initially turned on. Under the second condition, a command signal will be passed via lead 27 to the clutch control system 23 whenever the minicomputer is executing any kind of a program or set of internal instructions which could require the operation of the decoder unit 13.
The decoder unit of block 13 converts electrical signals coded in digital values into equivalent mechanical movement as known in the art. Electrical signals which were coded in binary form are converted into mechanical movements of equivalent decimal values. In the decoder unit described in the Burroughs manual previously cited and which is incorporated by reference herein, various alphanumeric characters are arranged in columns and rows around the outside periphery of a sphere. The column and row of the alpha-numeric character determines its digital address. Selection of a particular character to be printed causes a decoding matrix to provide electrical pulses to the solenoids in the decoder which permit mechanical movement for high speed serial printing. Character selection may be indexed by the depression of a key, tape fed into the memory loader, or characters read from storage in memory. Each of the solenoids in the decoder operates an individually associated half revolution clutch which enables the movement of an eccentrically mounted ring member to one of two positions. Each position of the eccentric ring member represents a binary quantity. The movement of the rings through a linkage produces a mechanical movement which is equal to the decimal equivalent of the binary output from the decoding matrix. Such decoder units are well-known in the art. For a more thorough understanding of such a decoder, reference should be made to U.S. Pat. No. 3,250,464 issued to G. K. Caspari on May 10, 1966 for "Binary to Decimal Converter", which is of co-ownership herewith and hereby expressly incorporated by reference.
The specific type of drive motor 15, the specific type of electromagnetic master clutch 17, and the specific details of the overall arrangement of the minicomputer itself are not necessary for a complete understanding of the present invention. FIG. 2 shows a portion of a prior art keyboard assembly with particular detail shown for the key lever operation and the drive trip latch mechanism. When any of the keys of the keyboard apparatus are depressed, the key lever 35 is depressed. When key lever 35 is depressed, its pass-by pawl 37 contacts interposer 39 so as to lower the interposer against the upward bias of a latch spring 41. As interposer 39 moves downward, it contacts trip bail 43 causing it to rotate in a counterclockwise fashion as shown by the arrow in FIG. 2. Trip bail 43 has rigidly secured thereto a shaft 45 which in turn rotates counterclockwise, as viewed in FIGS. 2 and 3a, with the rotation of trip bail 43. At the far end of shaft 45 is a collar element 47 which is rigidly secured to and rotates with the shaft 45. A drive trip latch mechanism 49 has a latching tip 50 which normally rests against an outward projection 46 (FIG. 3a) of the collar 47. However, when the collar 47 is rotated counterclockwise by the shaft 45 in response to the rotation of the bail 45, the latching tip 50 of the drive trip latch 49 is released from the collar 47 and raised via the upward bias of a spring 51. When the drive trip latch 49 is raised by the spring 51, it enables filter shaft 53 to be rotated 180° by allowing the 180° cam mechanism 55, which is rigidly secured to the filter shaft 53 to rotate 180° in a clockwise direction as seen in FIGS. 2 and 3. As the filter shaft 53 rotates clockwise, it drives the interposer 39 forward or toward the right as viewed in FIG. 2, and urges the lower projection 57 of interposer 39 to engage the bail mechanism 59, thereby moving it also forward. The forward movement of the bail mechanism 59 enables the bail foot 61 to release the keyboard flag latches as shown in the art. This enables the spring 62 to move flag 65 forward while spring 63 urges flag 67 rearward to contact slide 69. When the cam member 71, which is rigidly secured to the filter shaft 53, is rotated, spring 73 pulls the slide 69 rearward, or to the left as viewed in FIG. 2, permitting all of the released keyboard flags to position in front of their respective cores (not shown). As previously stated, this type of keyboard apparatus is old in the art and a more detailed description may be obtained by reference to the previously cited Burroughs manual or to U.S. Pat. No. 3,562,493 issued to B. J. Malkowski et al on Feb. 9, 1971, of co-ownership herewith and hereby expressly incorporated by reference.
FIG. 3 shows the modified drive trip latch mechanism of the present invention. The basic drive trip latch 49 remains the same as was shown in FIG. 2 and its effect upon the 180° cam mechanism 55 likewise remains the same. The drive trip latch mechanism is shown in solid lines for its normal position and in dotted lines to represent its released position. A latch extension member 74 is attached to the foward end or right side as viewed in FIG. 3 of the latch mechanism 49 and extends vertically upward therefrom. An inside face of the upper end of the extension member 74 is polished or otherwise reflective.
A photoelectric assembly 75 is positioned immediately above the upper end of extension member 74 when the drive trip latch mechanism 49 is in its normal position. The photoelectric assembly 75 includes a light emitting diode (LED) 83 which directs a beam of light toward the reflective inner face of the extension member 74 disposed opposite the photoelectric assembly 75 when the extension member is released by the collar into its raised position. A phototransitor 79 receives the light reflected from the reflective inner face of the extension member 74 when it is in the raised position. The phototransistor 79 then responds to the presence of the reflected light for generating an electrical alert or command signal.
With reference to FIGS. 2, 3 and 3a, the operation of the drive trip latch mechanism of the present invention is as follows: When any key of the keyboard assembly of block 31 (FIG. 1) is depressed, a corresponding key lever 35 (FIG. 2) will be depressed and the bail 43 will rotate in a counterclockwise manner as shown in FIG. 2. This counterclockwise rotation of bail 43 will cause the shaft 45 to turn the collar 47 in a counterclockwise direction. As can be seen from FIG. 3 and FIG. 3a, the normal position of the collar 47 before it is rotated in a counterclockwise manner, holds the forward end 50 of the drive trip latch mechanism 49 so as to retain the drive trip latch mechanism in the "normal" position with the reflective surface of the upper end of the extension member 74 disposed below the level of the photoelectric assembly 75. When a key depression causes the counterclockwise rotation of sleeve 47, the forward end 50 of the drive trip latch mechanism 49 is released and the drive trip latch mechanism 49 will be raised under the influence of spring 51 to its upward or "released" position as shown by the dotted lines of FIG. 3. In the "released" position, the reflective face of the extension member 74 is in front of the photoelectric assembly 75 and the beam of light which is emitted from the light emitting diode 83 is reflected from the reflecting surface of extension member 74 onto the phototransistor 79. The phototransistor 79 is activated as described in the description of the electrical circuit of the present invention found in FIG. 4. When the latch trip mechanism is in the released position, the 180° cam member 55 is rotated clockwise as seen in FIGS. 2 and 3 through 180° causing it to reset the drive trip latch mechanism 49 to its "normal" position. When the 180° cam 55 is rotated, filter shaft 53 rotates clockwise as viewed in FIG. 2 and drives the interposer 39 (FIG. 2) forward allowing spring 41 (FIG. 2) to raise the interposer 39. This is possible since the key lever 35 is restored to its normal position under the bias applied by spring 34 when pressure is removed from the key. This also enables trip bail 43 to be moved clockwise as seen in FIG. 2. This clockwise rotation of trip bail 43 causes the collar 47 to be positioned to its original position, thereby latching the latching tip 50 of the lowered drive trip latch mechanism 49 in its "normal" position until another key is depressed.
FIG. 4 illustrates a schematic diagram of the clutch control system of the present invention. The phototransistor 79 of FIG. 3 is shown as having its emitter coupled to ground via lead 81 and to a -12 volt source of potential via a series path comprising a light emitting diode (LED) 83 and a resistor 85. The anode of the LED diode 83 is coupled to the emitter of phototransistor 79 and the cathode of the LED diode 83 is connected to one end of resistor 85 whose other end is connected to the -12 volt source of potential. The collector of the phototransistor 79 is coupled via lead 87 to the base input of a transistor 89. The base input of transistor 89 is connected through a resistor 91 to a +5 volt source of potential. The emitter of transistor 89 is connected to ground via lead 93 and the collector is coupled via lead 95 to the input of a NAND gate driver 97. The collector of transistor 89 is also connected via lead 95 and a resistor 99 to a +5 volt source of potential. The output of NAND gate driver 97 is connected to a common input node 101. The node 101 is also connected to the output of a NAND gate driver 103 which has an input 105 and to the output of NAND gate 107 which has an input 109. This provides for a logical "OR" function at the node 101 which serves as an input to a multivibrator-pulse absence detector 111 which may be a standard, off-the-shelf item such as a TTuL 9601 or the like. The delay multivibrator 111 is shown as having a capacitor 113 coupled between one input 115 and a second input. The input 115 is also coupled through a variable resistor 117 to a +5 volt source of potential. The output of the multivibrator 111 is connected via lead 119 to the input of a NAND gate driver 121 whose output is connected to the anode of a diode 123. The output of NAND gate 121 is also connected through a resistor 125 to a +5 volt source of potential. The cathode of diode 123 is connected to the base of an output transistor 127 and the base is also connected to ground through a resistor 129. The emitter of output transistor 127 is coupled directly to ground via lead 131 and the collector is coupled to an output node 133 via lead 135. Output node 133 is coupled to the anode of a diode 137 whose cathode is connected to a +5 volt source of potential and is coupled through a resistor 139 and lead 141 to a clutch coil 143 whose other end is connected to a +5 volt source of potential. The clutch coil 143 is the portion of the electromagnetic clutch of block 17 which is energized or de-energized to control the operation of the clutch.
In operation, the presence of a command signal at any of the inputs of NAND gates 97, 103 or 107, will cause a low pulse to appear at input node 101. This low will trigger the multivibrator-pulse absence detector 111 and cause it to continue to output a low signal on lead 119 so long as the multivibrator 111 continues to be reset by the presence of a low pulse at input node 101 within the time delay which is pre-set into the multivibrator 111. As long as one of the NAND gates 97, 103 and 107 continues to provide a low pulse to input node 101 before the delay pre-set into multivibrator 111 has elapsed, the low which is outputted on lead 119 will cause NAND gate 121 to supply a high to the base of transistor 127. This will cause transistor 127 to conduct and thereby provide an electrical control signal to the clutch coil 143. This energization of the clutch coil 143 will cause the clutch 17 to engage and enable the motor 15 to drive the decoder unit 13 as described hereinafter with reference to FIG. 5. When normal operation ceases, the required low pulses will no longer be supplied to input 101 before the pre-set delay has elapsed and a high will appear at the output of multivibrator 111. This high is inverted in NAND gate 121 and used to switch the transistor 127 to a non-conductive state, thereby de-energizing clutch coil 143 and causing the clutch 17 to disengage the motor drive from the decoder 13.
As indicated above, the low pulse which is required at input node 101 for clutch coil energization can be supplied via NAND gate 103 and 107 in addition to the photoelectric input from NAND gate 97. Inputs 105 and 109 are taken from block 33 of FIG. 1 which represents the remainder of the minicomputer itself. A command signal will be produced at input 105 when a restoration signal is generated a predetermined time after the machine is turned on to restore the decoder unit to its home position. Similarly, a command signal will be presented to input 109 whenever the minicomputer indicates that the machine is executing a program or other stored instructions which may require the use of the decoder unit. Those skilled in the art could generate these signals by any number of means and no invention or experimentation would be required.
Referring now to FIG. 5, the manner in which the main motor 15 drives the decoder, generally referred to as 13, is described in more detail. The master clutch 17 is coupled to the main motor 15 by a shaft or coupling means 19 for receiving continual rotational input therefrom. The intermittent rotary output of the master clutch 17 is controlled via energization of the master clutch coil under control signals received via line 29 from the control circuit 23, as previously described. When the master clutch 17 is energized, its rotational output may be imparted to the decoder 13 by coupling means or a drive belt 21. The drive belt 21 may be a continuous loop grooved drive belt transmitting rotational output from the main motor 15 through the master clutch 17 to a fly wheel 24 which in turn operates to provide rotational input to the decoder unit 13 via fly wheel shaft 26. The fly wheel shaft 26 in turn imparts rotary motion to the gear system 28 which in turn provides rotary power via gear shaft 18 which supports one of a plurality of eccentrically mounted decoder rings, as described in U.S. Pat. No. 3,250,446 which has already been incorporated by reference herein. It will be obvious to those of ordinary skill in the mechanical decoder art that various other drive systems may be used to provide power from the main motor 15 through the energized master clutch 17 to the decoder unit 13.
Although specific apparatus has been shown for the purpose of describing applicants' invention, it will be apparent to those skilled in the art that other variations and modifications in the specific structure illustrated may be made without departing from the spirit and scope of the present invention which is limited only by the appended claims. | A decoder clutching system for use in a minicomputer such as the Burroughs Series-L or TC-Series minicomputer is employed to reduce noise and extend the life of the decoder while minimizing power consumption. An electromagnetic master clutch is secured to a main motor which enables a decoder to be intermittently driven in response to decoder alert or command signals representing anticipated binary to decimal conversion by the decoder. The motor operates continuously so as to drive the decoder only when the electromagnetic master clutch is energized and to release the drive to the decoder when the master clutch is de-energized. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a continuation of U.S. application Ser. No. 13/184,926, filed Jul. 18, 2011, now issued as U.S. Pat. No. 8,404,702; which is a continuation of U.S. application Ser. No. 12/487,263, filed Jun. 18, 2009, issued as U.S. Pat. No. 7,981,905; which is a division of U.S. application Ser. No. 11/732,663, filed on Apr. 4, 2007, now issued as U.S. Pat. No. 7,563,801; which claims priority from U.S. Provisional Application 60/789,514, filed on Apr. 5, 2006.
FIELD OF THE INVENTION
This application generally relates to pharmaceutically useful formulations comprising salts of 8-[{1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}methyl]-8-phenyl-1,7-diaza-spiro[4.5]decan-2-one and treatment methods employing the same.
BACKGROUND OF THE INVENTION
The preparation of diazaspirodecan-2-ones named (in accordance with Bielstein nomenclature) 8-[{1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one, for example, (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one (the compound of Formula I) is disclosed in published U.S. Pat. No. 7,049,320 issued May 23, 2006 (the '320 patent), which is incorporated herein by reference in its entirety.
The compounds disclosed in the '320 patent are classified as Tachykinin compounds, and are antagonists of neuropeptide neurokinin-1 receptors (the “NK-1” receptor antagonists). “NK-1” receptor antagonists have been shown to be useful therapeutic agents. For example, U.S. Pat. No. 5,760,018 (1998) describes some “NK-1” receptor antagonists as useful in the treatment of pain, inflammation, migraine and emesis (vomiting), and each of U.S. Pat. No. 5,620,989 (1997), WO 95/19344 (1995), WO 94/13639 (1994), and WO 94/10165 (1994) have described additional “NK-1” receptor antagonists which are useful in the treatment of treatment of pain, nociception and inflammation. Additional NK 1 receptor antagonists are described in Wu et al, Tetrahedron 56, 3043-3051 (2000); Rombouts et al, Tetrahedron Letters 42, 7397-7399 (2001); and Rogiers et al, Tetrahedron, 57, 8971-8981 (2001). Among many compounds disclosed in the abovementioned '320 patent are several novel diazaspirodecan-2-ones, including the compound of Formula I, which is believed to be useful in the treatment of nausea and emesis associated with chemotherapy treatments (Chemotherapy-induced nausea and emesis, CINE). Emesis has been a problem in chemotherapy. Chemotherapeutic agents, for example, cisplatin carboplatin and temozolomide have been associated with both acute and delayed onset nausea and vomiting. It is known to administer chemotherapeutic agents with an anti-emetic, for example, as described in U.S. Pat. No. 5,939,098, which describes coadministration of temozolomide and with ondansetron, however such therapy is not effective in preventing delayed onset nausea and vomiting.
Compounds which have been identified as having therapeutic activity must be provided in a formulation suitable for administration to a patient in need of the therapeutic properties of the compound. In general, dosage forms suitable for oral administration are preferred due to the ease of administration, negligible invasiveness of the administrative procedure, and the convenience of providing the medicament in a variety of discrete dosage sizes. In general it is preferred to provide a solid oral dosage form which administers the therapeutic agent to a recipient through the gastrointestinal tract.
OBJECTIVES AND SUMMARY OF THE INVENTION
In view of the foregoing, what is desired is a solid orally administerable dosage form containing a salt of the compound of Formula I. What is desired also is a dosage form that provides therapeutically effective serum levels of the therapeutic agent and is robust toward degradation under the environmental conditions in which it is handled and stored.
These and other objectives are provided by the present invention, which in one aspect provides a granular pharmaceutical formulation comprising a crystalline hydrochloride salt of the compound of Formula I in admixture with one or more excipients, and optionally, one or more 5HT-3 receptor antagonists, and optionally, a corticosteroid. When employed, preferably the 5HT-3 receptor antagonist is selected from Zofran (ondensetron), Kytril (granisetron), Aloxi (palonosetron), Anzemet (dolasetron), Navoban (tropisetron), and when employed, preferably the corticosteroid is selected to be dexamethasone. In some preferred embodiments the granular composition comprises crystalline hydrochloride monohydrate salt of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one, lactose monohydrate, microcrystalline cellulose, croscarmellose sodium, pregelatinized starch, and magnesium stearate. In some embodiments the granular composition is contained in a gelatin capsule.
In some embodiments the pharmaceutical composition comprises a salt of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one selected from a hydrochloride salt and a tosylate salt. In some preferred embodiments the salt is a crystalline monohydrate hydrochloride salt having characteristic X-ray Powder Diffraction peaks present at a diffraction angle equal to those shown in Table I expressed in terms of 2θ (all values reflect an accuracy of ±0.2), with the associated lattice “d” spacing (in angstroms) and relative peak intensities (“RI”):
TABLE I
Diffraction angle
Lattice Spacing
(2θ, ± 0.2
RI
(Å ± 0.04)
16.1
Medium
5.49
18.4
Medium
4.83
21.6
Strong
4.11
23.5
Weak
3.78
Another aspect of the present invention is the provision of a solid oral dosage in capsule form comprising 2.5 mg/dose of a crystalline hydrochloride monohydrate salt form of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one (the hydrochloride monohydrate compound of Formula II),
having characteristic X-ray Powder Diffraction peaks present at a diffraction angle equal to those shown in Table II, expressed in terms of 2θ (all values reflect an accuracy of ±0.2), with the associated lattice “d” spacing (in angstroms) and relative peak intensities (“RI”):
TABLE II Diffraction angle Lattice Spacing (2θ, ± 0.2 RI (Å ± 0.04) 16.1 Medium 5.49 18.4 Medium 4.83 21.6 Strong 4.11 23.5 Weak 3.78;
and having characteristic 12 sample average dissolution profile in 900 mL of dissolution medium comprising 0.25% sodium lauryl sulfate solution buffered with 0.05 M sodium acetate at pH 4.5 determined using a USP 2 Apparatus Paddle Stirrer with sinkers operated at 75 RPM of that shown in Table III.
TABLE III
Time
Average (% of active initially
Range of % active released
(min.)
present released)
over n samples
5
69%
64%-74%
15
88%
83%-94%
30
94%
90%-100%
45
97%
93%-102%
60
98%
94%-103%
Another aspect of the present invention is the provision of a solid oral dosage in capsule form comprising 10.0 mg/dose of a crystalline hydrochloride monohydrate salt form of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one (the hydrochloride monohydrate compound of Formula II)
having characteristic X-ray Powder Diffraction peaks present at a diffraction angle equal to those shown in Table IV, expressed in terms of 2θ (all values reflect an accuracy of ±0.2), with the associated lattice “d” spacing (in angstroms) and relative peak intensities (“RI”):
TABLE IV Diffraction angle (2θ, ± 0.2 RI Lattice Spacing (Å ± 0.04) 16.1 Medium 5.49 18.4 Medium 4.83 21.6 Strong 4.11 23.5 Weak 3.78
and having a characteristic 12 sample average dissolution profile in 900 mL of dissolution medium comprising 0.25% sodium lauryl sulfate solution buffered with 0.05 M sodium acetate at pH 4.5 determined using a USP 2 Apparatus Paddle Stirrer with sinkers operated at 75 RPM of that shown in Table V.
TABLE V
Time
Average (% of active initially
Range of % active released
(min.)
present released)
over n samples
5
87%
82%-91%
15
95%
91%-98%
30
98%
94%-100%
45
98%
95%-101%
60
99%
96%-100%
Another aspect of the present invention is the provision of a solid oral dosage in capsule form comprising 50.0 mg/dose of a crystalline hydrochloride monohydrate salt form of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one (the hydrochloride monohydrate compound of Formula II)
having characteristic X-ray Powder Diffraction peaks present at a diffraction angle equal to those shown in Table VI, expressed in terms of 2θ (all values reflect an accuracy of ±0.2), with the associated lattice “d” spacing (in angstroms) and relative peak intensities (“RI”):
TABLE VI Diffraction angle (2θ, ± 0.2 RI Lattice Spacing (Å ± 0.04) 16.1 Medium 5.49 18.4 Medium 4.83 21.6 Strong 4.11 23.5 Weak 3.78
having a characteristic 12 sample average dissolution profile in 900 mL of dissolution medium comprising 0.25% sodium lauryl sulfate solution buffered with 0.05 M sodium acetate at pH 4.5 determined using a USP 2 Apparatus Paddle Stirrer with sinkers operated at 75 RPM of that shown in Table VII.
TABLE VII
Time
Average (% of active initially
Range of % active released
(min.)
present released)
over n samples
5
88%
74%-96%
15
97%
91%-101%
30
99%
94%-102%
45
100%
95%-102%
60
100%
96%-103%
Another aspect of the present invention is the provision of a pharmaceutical formulation comprising a hydrochloride monohydrate salt of Formula II in a capsule oral dosage form which has a Pharmacokinetic (PK) profile obtained under single dose rising rate study conditions in accordance with Table VIII (average of eight study subjects).
TABLE VIII
Dose
Cmax*
Half Life
(mg)
(ng/mL)
Tmax**
AUC***
T½ (hours)
5
27.3
2
931
not calc.
10
52.7
2.5
1820
not caic
25
119
2.5
17200
183
50
276
3
33600
171
100
475
2
74400
181
200
944
4
148000
169
*Mean maximum plasma concentration following single administration.
**Median time (hours) of maximum plasma concentration from administration.
***Area under the plasma concentration time curve in ng hr/mL for 0 to 72 hours post administration.
The invention further provides a method of treating nausea and/or emesis. It is believed that medicament of the invention comprising salts of the compound of Formula I may be useful in the provision of anti-nausea and anti-emesis treatment for nausea and emesis arising from any cause, for example, arising from chemotherapy, from radiation therapy, arising during a post-operative recovery period, arising from motion sickness, arising from morning sickness, and arising from inner ear disturbances and infections. However, it is believed that the compound of Formula I will be most effective in the provision of anti-nausea and/or anti-emesis treatment for delayed onset nausea and/or emesis associated with chemotherapy treatments, radiation treatments, and arising during a post-operative period. In some embodiments it is preferred to coadminister an NK-1 dosage form of the invention with other therapeutic agents, for example, a chemotherapeutic agent, for example, temozolomide and cisplatin, preferably temozolomide. In some embodiments the administration of additional therapeutic agents is selected from contemporaneous administration of additional therapeutic agents contained in a separate dosage form and simultaneous administration of a dosage form containing the granulate of the present invention along with one or more therapeutic agents.
An example of contemporaneous administration is administering before, during, or after administration of a medicament comprising the granulate of the present invention, one or more additional therapeutic agents contained in one or more additional dosage forms. An example of simultaneous administration is a dosage form containing a medicament comprising multiple therapeutic agents. An example of the latter administration scheme is a capsule dosage form containing the NK-1 therapeutic agent together with one or more additional therapeutic agents, for example, a chemotherapeutic agent, for example, temozolomide. In some dosage forms containing more than one therapeutic agent it is preferred to prepare the formulation contained in the dosage form by introducing an admixture of all therapeutic agents into the formulation in place of the single drug substance, for example, the NK-1 salt of the present formulation.
In one form the therapy comprises administering a particulate form of a medicament comprising crystalline hydrochloride monohydrate salt of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one (the monohydrate salt of Formula II), lactose monohydrate, microcrystalline cellulose, croscarmellose sodium, pregelatinized starch, and magnesium stearate in an amount providing a therapeutically effective serum level of the hydrochloride monohydrate salt of Formula II for the treatment and/or prevention of nausea and emesis. In the administration of such particulate medicament, preferably the particulate is contained in a capsule.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 presents a characteristic x-ray powder diffraction pattern of the crystalline hydrochloride monohydrate salt form of the compound of Formula I [Vertical Axis: Intensity CPS, counts (square root)); Horizontal Axis: Two Theta (degrees)].
FIG. 2 presents a plasma concentration vs time profile following a single dose administration of a medicament containing a hydrochloride salt of the compound of Formula I administration to healthy human volunteers.
FIGS. 3A and 3B present a pharmacokinetic profile showing the plasma concentration vs time following a single day (Day 1; FIG. 3A ) and multiple day (Day 10; FIG. 3B ) administration of a medicament containing a hydrochloride salt of the compound of Formula I to healthy human volunteers, horizontal axis is post administration time (hours), vertical axis is plasma concentration (ng/mL).
FIG. 4 presents the median and individual AUC values (area under the curve from 0 to 72 hours post single dose administration), vertical axis—AUC in ng hr/mL plasma, horizontal axis—single dose administered in mg of hydrochloride monohydrate salt of the compound of Formula I.
DETAILED DESCRIPTION OF THE INVENTION
The preparation of tachykinin compounds useful as NK-1 receptor antagonists has been described in U.S. Pat. No. 7,049,320, filed Dec. 17, 2002 (herein, the '320 patent, which is incorporated herein by reference in its entirety), including (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one (the compound of Formula I).
The preparation of salts of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one (the compound of Formula I), including the monohydrate hydrochloride salt of Formula II (shown above) and various tosylate salts, having physical and chemical properties useful in the provision of medicaments are disclosed in U.S. application Nos. 60/789,280 and 60/789,513, each of which is incorporated herein in its entirety by reference.
Two of the most debilitating side effects of cytotoxic chemotherapy are nausea and vomiting (emesis). There is both acute-phase chemotherapy induced nausea and emesis (CINE) and delayed-phase CINE. Acute-phase CINE occurs in the first 24 hours after chemotherapy administration while delayed-phase CINE manifests from between 2 days and 5 days post chemotherapy administration. Acute-phase CINE has been managed by administering 5HT3 receptor antagonists, often in combination with a corticosteroid, for example, dexamethasone, this treatment has not been effective in managing delayed-phase CINE. It is believed that acute-phase CINE and delayed-phase CINE arise from different physiological phenomena. It is believed that administration of an NK-1 receptor antagonist, for example, salts of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one, either alone or in combination with one or more of a corticosteroid, for example, dexamethasone and/or a 5HT3 receptor antagonist, for example, ondensetron, granisetron, palonosetron, dolasetron, or tropisetron will provide a therapy effective in treatment of CINE in humans.
In general, oral dosage forms which administer a therapeutic agent to a subject through the gastrointestinal tract are desirable because such dosage forms offer ease of administration with minimal invasion of the subject receiving the therapy. Oral medicaments which are in a solid form, for example, tablets and capsules containing a particulate medicament, offer a discrete dosage form of the medicament, and provide the medicament in a form which is generally more robust in the environment in which the medicament is handled and stored in comparison to liquid dosage forms. Accordingly, it is desirable to provide medicaments containing these NK-1 receptor antagonists in a solid dosage form amenable to oral administration.
The inventors have discovered that a particulate containing a salt of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one (active salt) can be prepared which has useful pharmacokinetic (PK) and dissolution properties in the provision of therapy to address CINE and other conditions amenable to treatment by the administration of an NK-1 inhibitor, for example, nausea and/or emesis due to other causative factors, for example, motion sickness and morning sickness. Surprisingly, this particulate can be prepared by combining an amount of the active salt with lactose monohydrate, croscarmellose sodium, and pregelatinized starch and granulating the mixture with purified water, drying the granulate, blending the granulate with magnesium stearate and an additional amount of microcrystalline cellulose and croscarmellose sodium, and filling the resulting granulate blend into a gelatin capsule at a fill weight that provides the dosage form with the desired amount of active salt. Surprisingly, the medicament of this formulation suitably provides a serum therapeutic level of the active salt when administered orally. It is believed that this formulation, when administered in an effective dosage amount, and optionally, administered along with a separate medicament containing either a 5HT3 receptor antagonists, for example, ondensetron, granisetron, palonosetron, dolasetron, or tropisetron and/or one or more corticosteroid, for example, dexamethasone, will be useful in the management of CINE. Optionally, the formulation of the invention can additionally include one or more 5HT3 receptor antagonist, for example ondensetron, granisetron, palonosetron, dolasetron, or tropisetron, and/or one or more corticosteroid, for example, dexamethasone, in the provision of therapy in the treatment of both acute-phase and delayed-phase CINE. Whether administered as a separate medicament, or included in the formulation of the present invention, when utilized is it preferred for the 5HT3 receptor antagonist to be selected from ondensetron, granisetron, palonosetron, dolasetron, and tropisetron, and when utilized, whether as a separate medicament or included in the formulation of the present invention, it is preferred for the corticosteroid to be selected from dexamethasone.
The present formulation can also contain additional therapeutic agents, for example, chemotherapeutic agents, for example, temozolomide, providing a single medicament for administering chemotherapeutic treatment and relief and/or prevention of nausea and/or vomiting associated with such chemotherapeutic agent administration. Examples of dosage levels of temozolomide are described in U.S. Pat. No. 5,939,098 (the '098 patent), issued Aug. 17, 1999, European Patent 0858341 B1 (the '341 patent), Grant date Oct. 24, 2001, and published U.S. patent application no. 2006/0100188, published May 11, 2006 (the '188 publication). Each of the '098 patent and '341 patent describes coadministration of temozolomide with a 5HT3 inhibitor to provide therapy for immediate onset nausea and vomiting associated with chemotherapy. The '188 publication, in Tables 1 and 2 (pages 2 to 3 therein) describes detailed dosing regimens for dosing temozolomide. In some embodiments it is preferred to provide a combination of a salt of the compound of Formula I prepared in accordance with the present invention, or a pharmaceutical composition containing the salt, and other therapeutic agents, for example, a chemotherapeutic agent, for example, temozolomide and cisplatin, preferably temozolomide.
As used herein a combination includes: physically combined therapeutic agents in a pharmaceutical composition for administering in a single dosage form; a medicament or kit containing multiple therapeutic agents in one or more containers; and providing therapy that includes providing a therapeutically effective level of the compound of Formula I and other therapeutic agents, for example, by contemporaneous or simultaneous administration, as described herein, of more than one therapeutic agent. When a kit combination is provided, generally multiple medicaments are supplied in a form that will provide, upon administration to a patient in need of such therapy, a therapeutically effective amount of the active pharmaceutical ingredient(s) contained therein.
It is believed also that this medicament may be useful in the treatment of other conditions amenable to treatment by administration of an NK-1 inhibitor, including, but not limited to, cough, morning sickness, and nausea and/or vomiting arising from motion sickness.
Preferably the active salt used in the formulations of the present invention is the crystalline hydrochloride monohydrate salt of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one, and a crystalline tosylate salt of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one, which salt has the X-ray powder diffraction pattern shown in FIG. 1 . This salt has four most characteristic X-ray Powder Diffraction peaks present at a diffraction angle equal to those shown in Table IX, expressed in terms of 2θ (all values reflect an accuracy of ±0.2), with the associated lattice “d” spacing (in angstroms) and relative peak intensities (“RI”):
TABLE IX
Diffraction angle (2θ, ± 0.2
RI
Lattice Spacing (Å ± 0.04)
16.1
Medium
5.49
18.4
Medium
4.83
21.6
Strong
4.11
23.5
Weak
3.78
In general, salts suitable for use in the formulation of the present application may be prepared in accordance with the procedures described in U.S. provisional application No. 60/789,280 entitled “HYDROCHLORIDE SALTS OF 8-[1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxymethyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one”, filed on Apr. 5, 2006, and in U.S. patent application No. 11/732,548 (now U.S. Patent No 8,178,550), filed on Apr. 4, 2007, each of which is incorporated herein by reference. Other suitable salts may be prepared in accordance with the procedures described in U.S. Provisional application No. 60/789,513 entitled “SALTS OF 8-[1-(3,5-Bis-(trifluoromethyl)phenylyethoxymethyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one AND PREPARATION PROCESS THEREFOR”, filed on Apr. 5, 2006, which is incorporated herein by reference. Particularly preferred is the monohydrate hydrochloride salt of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one, identified therein as the monohydrate hydrochloride form 1 salt of the compound of Formula I, and depicted graphically above as the salt of Formula II.
EXAMPLES
Standard pharmaceutical manufacturing processes are utilized in the preparation of formulations of the present invention, including sieving, granulation, milling, fluid bed drying and powder mixing. For preparation of a granulate formula of the present invention these operations are carried out in accordance with the following general procedures. Blending operations are carried out in a high shear granulator manufactured by Dionsa. Granulation is carried out in the Dionsa granulator after the dry materials are blended to a homogeneous mixture. Wet milling is carried out in a Quadro Comil 197 equipped with a #5 mesh screen. Drying operations are carried out in a Strea Aeromatic T2 Fluid Bed dryer. Dry milling operations are carried out in a Quadro Comil 197 equipped with a 16 mesh screen. Blending operations are carried out in a Pharmatech Double Cone blender.
Unless noted to the contrary, all materials utilized in the formulations were articles of commerce meeting the current requirements of the United States Pharmacopeia/National Formulary (USP/NF), and active salts were obtained using the procedures in the above described in the above described in U.S. Provisional Application Nos. 60/789,280 and 60/789,513 filed concurrently on Apr. 5, 2006 which are incorporated herein by reference in their entirety, and U.S. Provisional Application No. 60/919,666, filed on Mar. 22, 2007.
X-ray powder diffraction spectroscopic analysis of hydrochloride monohydride salts was performed using a Rigaku Miniflex spectrometer, employing the following procedure. Specimens for analysis were lightly packed onto a low-background plate. The specimens were exposed to the room environment with ambient temperature and humidity. The Rigaku spectrometer was equipped with a six-plate carousel that rotated the specimen at 54 rpm, minimizing preferred orientations of the crystals in the sample studied. The Rigaku spectrometer was equipped also with a copper Ka radiation source utilized without a Kα2 filter. The spectrometer was equipped also with a variable divergence slit and 0.3 mm receiving slit. Scan range was carried out from 2.0 to 40° 2θ. Instrument calibration was verified using the Cu Kα1 peak for the 111 plane. During scanning, the step size was 0.02 degrees over step durations of 0.6 seconds. Data analysis was accomplished using Jade Plus (release 5.0.26) analysis software. The data were smoothed with a Savitzky-Golay parabolic filter at 11 points. Typically reported “d” spacing values are accurate to within ±0.4 A.
Samples preparation analysis in accordance with the above-described procedure were subjected to minimal preparation to prevent any form changes. Sample particles were lightly packed into the sample holder to insure that they formed a smooth surface and did not clump together. No solvents, drying or other preparation steps were used for other than the solvate samples prepared in accordance with the procedure described above.
Example I
Granulate Formulation
The drug substance used in the following procedure was the hydrochloride monohydrate salt of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one (herein, the hydrochloride monohydrate salt) has an X-ray powder pattern shown in Figure I. The powder pattern of Figure I has four most characteristic peaks observed at 2θ=16.1 (m), 18.4 (m), 21.6 (s), and 23.5 (w)), produced in accordance with the above-referenced procedures. A granular formulation for filling into gelatin capsules containing the hydrochloride monohydrate salt for the provision of dosage forms containing the salt in an amount of 2.5 mg/dose or 10 mg/dose and 50 mg/dose was prepared in accordance with the following procedure. The weight of each of the granulate constituents used is reported below in Table XIII, which varies slightly in the amount of filler employed for each dosage strength of capsule produced from the granulate. The granulate was produced such that 300 mg of the powder provided the indicated amount of drug substance. The granulate for all dosage strengths was prepared in accordance with the following procedure.
Drug substance was hand sieved through a 600 micron screen, and the remaining excipients were screened through a 1000 micron screen prior to use. The amount of drug substance indicated in Table XIII and the amount of lactose monohydrate (impalpable grade) indicated in Table XIII as “premix” were placed into the granulator and blended for 2 minutes at an impeller speed of 133 RPM to create a uniform blend. The amount of lactose monohydrate (impalpable grade) indicated in Table XIII as “main mix”, the amount of croscarmellose sodium (NF Phr. Europe) indicated in Table XIII as intergranular, and the amount of starch indicated in Table XIII were added to the granulater and blended for 2 minutes at a 133 RPM impeller speed. With the granulator operating, purified water was pumped into the dry-blended materials (up to 3600 ml at an addition rate of 75 g/min) to agglomerate the blended materials until a granulate having 32 wt. % water content was thereby formed. The wet granulate was wet-milled and sized using a conical screen mill equipped with a #5 mesh screen to provide classified wet granulate. The classified wet granulate was transferred into the fluid bed dryer and dried to a target weight of less than 3 wt. % free water (determined by loss on drying). The dried granulate was milled in the conical mill through a 16 mesh screen. The dry-milled granulate is transferred to the blender along with the weight of croscarmellose sodium indicated in Table XIII as “extragranular”, and the weight of microcrystalline cellulose (Avicel PH102) indicated in Table XIII. The constituents were blended for 20 minutes at 15 RPM. The weight of magnesium stearate (Non-bovine, NF) indicated in Table XIII was screened through a 425 micron screen and added to the blender. The constituents were blended for 10 minutes at 15 RPM, and the blended formulation was discharged for encapsulation.
As mentioned above, Table XIII, which follows, shows the weights of each of the constituents used for preparing granulate which was used to fill capsules in the indicated dosage range.
TABLE XIII
Constituent
2.5 mg dosage
10 mg dosage
50 mg dosage
Active Salt
100.0
g
400.0
g
1000.0
g
Lactose Monohydrate
1600.0
g
1600.0
g
1600.0
g
(premix)
Lactose Monohydrate
5560.0
g
5260.0
g
1030.0
g
(main mix)
Microcrystalline Cellulose
2400.0
g
2400.0
g
1200.0
g
Pregelatinized Starch
1800.0
g
1800.0
g
900.0
g
Croscarmellose Sodium
240.0
g
240.0
g
120.0
g
(intergranular)
Croscarmellose Sodium
240.0
g
240.0
g
120.0
g
(extragranular)
Magnesium Stearate
60.0
g
60.0
g
30.0
g
Samples of capsules filled with a granulate mixture that provides 2.5 mg, 10 mg, and 50 mg of the active salt were subjected to dissolution tests. The dissolution testing apparatus was a USP2 apparatus Paddle Stirrer filled with 900 mL of dissolution medium consisting of 0.25% sodium lauryl sulfate solution buffered with 0.05 M sodium acetate at pH 4.5. Tests were conducted at ambient temperature. The test was carried out by stabilizing the dissolution medium at the test temperature with the paddles set at 75 RPM. Test capsules are dropped into the dissolution medium with the paddles actuated. Periodically aliquot samples of the dissolution media are withdrawn and analyzed by HPLC for active content. The total amount of active present in the dissolution media is calculated based on the HPLC determination, and reported as a percentage of the total amount of active contained in the capsule introduced into the dissolution media. The results for each sample are shown below in Table X. It will be found that capsules prepared in accordance with the above-described procedure when tested under S-1 conditions as a 6 tablet average with have a Q-45 of not less than 75% with no single tablet exceeding 80%.
TABLE X
Time
Average (% of active initially
Range of % active released
(min.)
present released)
over n samples
5
88%
74%-96%
15
97%
91%-101%
30
99%
94%-102%
45
100%
95%-102%
60
100%
96%-103%
Single doses of the encapsulated formulation ranging from 5 mg of the active salt (2×2.5 mg capsules) to 200 mg of active salt (4×50 mg capsules) were administered to 6 cohorts each consisting of 10 healthy human volunteers, eight of whom were randomly selected to receive the active drug and two of whom were randomly selected to receive placebo. Blood samples were collected from each volunteer at predose (hour 0) and 0.25, 0.5, 0.75, 1, 1.5, 2, 3, 4, 6, 8, 12, 16, 24, 36, 48, and 72 hours. The serum drug levels of the volunteers receiving active drug are present graphically in FIG. 2 . The pharmacokinetic (PK) data from this study is summarized in Table XI below.
TABLE XI
Dose
Cmax*
Half Life
(mg)
(ng/mL)
Tmax**
AUG***
T½ (hours)
5
27.3
2
931
not calc.
10
52.7
2.5
1820
not calc
25
119
2.5
17200
183
50
276
3
33600
171
100
475
2
74400
181
200
944
4
148000
169
*Mean maximum plasma concentration following single administration.
**Median time (hours) of maximum plasma concentration from administration.
***Area under the plasma concentration time curve in nghr/mL for 0 to 72 hours post administration.
FIG. 4 presents the AUC data graphically, both with respect to individual data points (black circles) and statistical mean of the test group (line). These data indicate that the formulation provides the active salt in a form that is rapidly absorbed and provides increasing exposure of the active in a dose-related manner.
In a second study, three cohorts of 8 healthy volunteers each were administered 10, 25, or 50 mg per day for each of 10 days. Administration in every case followed a 10 hour fast. Blood samples were collected from each volunteer at predose (hour 0) and 0.25, 0.5, 0.75, 1, 1.5, 2, 3, 4, 6, 8, 12, 16, 24, 36, 48, and 72 hours on each of days 1 and 10. The results of this study are present graphically in FIGS. 3A (day 1) and 3 B (day 10), and summarized in Table XII below.
TABLE XII
Cmax*
Half Life
Dose
(ng/mL)
Tmax**
AUC***
T½ (hours)
Day 1 Data
10 mg
48.6
3
673
not caic.
25 mg
139
2
1950
not caic
50 mg
254
3
3400
not caic
Day 10 Data
10 mg
180
3
3590
238
25 mg
491
2
9720
not calc.
50 mg
895
2.5
17700
172
*Mean maximum plasma concentration following single administration.
**Median time (hours) of maximum plasma concentration from administration.
***Area under the plasma concentration time curve in ng · hr/mL for 0 to 72 hours post administration.
These data show that the active is rapidly absorbed and that exposure increases with increasing dose. The half-life is independent of dose and consistent with that observed from the single dose studies. Accumulation is consistent with the long half life of the active and is approximately 5-fold of the single dose. | Pharmaceutical formulations containing salts of (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl]-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one, represented by Formula I, are disclosed. Disclosed also are methods of treatment utilizing such dosage forms. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims benefit of U.S. application Ser. No. 60/592,099 filed Jul. 29, 2004, entitled “Device for Percutaneous Treatment of Spinal Stenosis,” which is incorporated herein by reference in its entirety.
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a minimally invasive method, device and system for treating spinal disorders using imaging guidance. This invention also relates to devices used to reduce stenosis and increase the cross-sectional area of the spinal canal and to devices used to treat excess fat within the spinal canal or epidural lipomatosis. This invention also relates to methods, devices, therapies and medications used to treat disorders that involve the epidural space.
BACKGROUND OF THE INVENTION
The spine comprises a stack of vertebrae with an intervertebral disc between adjacent vertebrae. As shown in FIG. 1 , each vertebra 10 includes a vertebral body 12 that supports a bony ring 14 . The bony ring 14 consists of laminae 16 , spinous process 18 , transverse processes 20 , superior articular processes 22 , and pedicles 24 . Together with vertebral body 12 , these vertebral components define the spinal canal. The laminae 16 are joined in the midline by the spinous process 18 . In the cervical and thoracic region the dural sac 32 contains the spinal cord, which comprises nerves 34 surrounded by cerebrospinal fluid. The fluid-filled sac is therefore compressible. The ligamentum flavum 26 is an elastic yellow ligament connecting the laminae of adjacent vertebrae.
In degenerative conditions of the spine, narrowing of the spinal canal (stenosis) can occur. Lumbar spinal stenosis is often defined as a dural sac cross-sectional area less than 100 mm 2 or an anteroposterior (AP) dimension of the canal of less than 10-12 mm for an average male.
The source of most cases of lumbar spinal stenosis is thickening of the ligamentum flavum. Spinal stenosis may also be caused by subluxation, facet joint hypertrophy, osteophyte formation, underdevelopment of spinal canal, spondylosis deformans, degenerative intervertebral discs, degenerative spondylolisthesis, degenerative arthritis, ossification of the vertebral accessory ligaments and the like. A less common cause of spinal stenosis, which usually affects patients with morbid obesity or patients on oral corticosteroids, is excess fat in the epidural space. The excessive epidural fat compresses the dural sac, nerve roots and blood vessels contained therein and resulting in back and leg pain and weakness and numbness of the legs. Spinal stenosis may also affect the cervical and, less commonly, the thoracic spine.
Patients suffering from spinal stenosis are typically first treated with exercise therapy, analgesics and anti-inflammatory medications. These conservative treatment options frequently fail. If symptoms are severe, surgery is required to decompress the canal and nerve roots.
To correct stenosis in the lumbar region, an incision is made in the back and the muscles and supporting structures are stripped away from the spine, exposing the posterior aspect of the vertebral column. The thickened ligamentum flavum is then exposed by removal of the bony arch (lamina) covering the back of the spinal canal (laminectomy). The thickened ligament can then be excised with sharp dissection with a scalpel or punching instruments such as a Kerison punch that is used to remove small chips of tissue. The procedure is performed under general anesthesia. Patients are usually admitted to the hospital for approximately five to seven days depending on the age and overall condition of the patient. Patients usually require between six weeks and three months to recover from the procedure. Many patients need extended therapy at a rehabilitation facility to regain enough mobility to live independently.
Much of the pain and disability after an open laminectomy is due to the tearing and cutting of the back muscles, blood vessels and supporting ligaments and nerves that occurs during the exposure of the spinal column. Also, because these spine stabilizing back muscles and ligaments are stripped and cut off, the spine these patients frequently develop spinal instability post-operatively.
Minimally invasive techniques result in less post-operative pain and faster recovery compared to traditional open surgery. Percutaneous interventional spinal procedures can be performed with local anesthesia, thereby sparing the patient the risks and recovery time required with general anesthesia. Another advantage is that there is less damage to the paraspinal muscles and ligaments with minimally invasive techniques reducing pain and preserving these important stabilizing structures.
Various techniques for minimally invasive treatment of the spine are known. Microdiscectomy is performed by making a small incision in the skin and deep tissues to create a portal to the spine. A microscope is then used to aid in the dissection of the adjacent structures prior to discectomy. The recovery for this procedure is much shorter than traditional open discectomies. Percutaneous discectomy devices with fluoroscopic guidance have been used successfully to treat disorders of the disc but not to treat spinal stenosis or the ligamentum flavum directly. Arthroscopy or direct visualization of the spinal structures using a catheter or optical system have also been proposed to treat disorders of the spine including spinal stenosis however these devices still use miniaturized standard surgical instruments and direct visualization of the spine similar to open surgical procedures. These devices and techniques are limited by the small size of the canal and these operations are difficult to perform and master. Also these procedures are painful and often require general anesthesia. The arthroscopy procedures are time consuming and the fiber optic systems are expensive to purchase and maintain.
In addition, because the nerves of the spine pass through the core of the spine directly in front of the ligamentum flavum, any surgery, regardless of whether is open or percutaneous includes a risk of damage to those nerves.
Hence, it remains desirable to provide a simple method and device for treating spinal stenosis and other spinal disorders without requiring open surgery. It is further desired to provide a system whereby the risk of damage to the thecal sac containing the spinal nerves can be reduced.
SUMMARY OF THE INVENTION
The present invention provides a method, device and system for treating spinal stenosis or other spinal disorders using image guidance in combination with percutaneous techniques. The present system is referred to as a minimally invasive ligament decompression (MILD) device. In some embodiments, the present invention provides a means for compressing the thecal sac within the epidural space so as to provide a safety zone in which further surgical procedures may be performed without risk of damaging nearby tissues or the thecal sac itself.
In further embodiments, the present method comprises the steps of a) percutaneously accessing the epidural space in a region of interest with image guidance; b) at least partially compressing the thecal sac in the region of interest by injecting a fluid into the epidural space to form a safety zone; c) percutaneously accessing a working zone in at least one of the ligamentum flavum and overlying dorsal tissues with image guidance, where the safety zone lies between the working zone and thecal sac; d) inserting a tissue removal tool into the working zone; e) using the tool remove tissue so as to reduce the stenosis; and f) utilizing at least one imaging system to identify tissues for removal. By way of example, radiologic imaging may be used to safely guide the tool(s) to target tissues and visualize the position of the tool during at least part of the process.
In preferred embodiments, the device provides an anchored pathway to the working zone so that excised tissue can be shuttled out of the area for successive extractions without time consuming repositioning of the tool(s). In other embodiments, the tool can be repositioned as often as is necessary to achieve the desired modifications. In still other embodiments, the present invention includes percutaneous methods for placing a retractable anchor in the ligamentum flavum and attaching it to the fascia or bone so as to retract the ligamentum flavum, thus expanding the spinal canal. In still other embodiments, the invention includes a percutaneous mechanical suture system and method for placing a stitch in the ligament and then anchoring the stitch so as to retract the ligamentum flavum. The laminotomy site can serve as a site for a bone anchor and/or flange for a suture to anchor the ligament.
Particular embodiments of the invention include a method for treating stenosis in a spine, the spine including a thecal sac and a canal and an epidural space therebetween, wherein the stenosis determines a region of interest in the spine. The method may comprise the steps of a) percutaneously accessing the epidural space in the region of interest, b) compressing the thecal sac in the region of interest by injecting a fluid to form a safety zone and establish a working zone, with the safety zone lying between the working zone and the thecal sac, c) inserting a tissue removal tool into tissue in the working zone, d) using the tool to percutaneously reduce the stenosis. It is preferred to use at least one imaging system to visualize the position of the tool during at least a part of step d).
Step d) may include 1) engaging adjacent tissue in the working zone, 2) excising the engaged tissue, 3) removing the resulting tissue section from the working zone, and 4) repeating steps 1) through 3) until a desired amount of tissue has been removed. The removed tissue may comprise a portion of the ligamentum flavum, fat, and/or bone. Alternatively, the step d) may include i) providing an anchor having first and second tissue-engaging ends, ii) engaging the ligamentum flavum with the first tissue-engaging end, iii) using the engaged first end to pull at least a portion of the ligamentum flavum into a desired position, and iv) using the second tissue-engaging end to anchor the anchor such that the ligamentum flavum is retained in a desired position. The anchor may be anchored to paraspinous tissue or to other bone.
The invention also relates to an injectable fluid, which may include a contrast agent and may have a temperature-dependent viscosity such that it is more viscous at 37° C. than at 30° C.
The tool of steps c) and d) may include an outer cannulated scalpel or needle, a tissue-engaging means, and a cutting or resecting element and may further include means for removing tissue from the tissue-engaging means. The tissue-engaging means may comprise a resilient hook.
Some embodiments of the invention may take the form of a kit for performing a procedure on a spine, in which the kit includes an insertion member for accessing the epidural space, and an expandable device adapted to be inserted into the epidural space by the insertion member and expanded so as to compress a portion of the thecal sac and provide a safety zone within the epidural space. The expandable device may comprise a volume of a contrast medium, such as a radio-opaque non-ionic myelographic contrast medium, and/or may comprise a volume of a medium that is injectable at ambient temperatures and more viscous at body temperature. The contrast medium may include a bioactive agent and/or a steroid.
The kit may further include a surgical device, which in turn may comprise a hollow cannulated scalpel or outer needle having a side aperture proximal its distal end, and an elongate body housed within the outer needle and comprising two radially extendable arms constructed such that radially extending the arms causes them to extend outward through the side aperture and retracting said arms causes them to close. In other embodiments, the kit may comprise means for engaging the ligamentum flavum and means for resecting a section of the ligamentum flavum and the means for resecting may in turn comprise a trocar, a barbed member coaxially received within the trocar, and a blade. In other embodiments, the surgical device may comprise means for engaging a first anatomical structure and means for affixing the first anatomical structure to a second anatomical structure. Alternatively, the surgical device may comprise means for engaging the ligamentum flavum and soft tissues in the Para spinal region of the patient so as to anchor the ligamentum flavum, and/or means for engaging and retracting the ligamentum flavum and means for anchoring the retracted ligamentum flavum.
In still other embodiments, a percutaneous tool for treating a stenosed spine by removing tissue therefrom, comprises an cannulated scalpel, a first tissue-engaging means housed within the cannulated scalpel, and a cutting element configured to resect a sample of tissue that is engaged by the first tissue-engaging means. The cannulated scalpel may include a side aperture through which the first tissue-engaging means engages the tissue and the tool may further include a second tissue-engaging device that is adapted to remove the resected tissue sample from the first tissue-engaging device. The second tissue-engaging device may comprise a keyhole slot.
In still other embodiments, a device for removing tissue from a stenosed spine may comprise a hollow outer needle having a side aperture proximal its distal end, an elongate body housed within the outer needle and comprising two radially extendable arms constructed such that radially extending the arms causes them to extend outward through said side aperture and retracting the arms causes them to close. Each arm may include an opposing edge and at least one opposing edge may include teeth or ridges or the opposing edges may comprise cutting blades.
In certain embodiments, the present percutaneous tissue excision system may include an inner needle having one or more barbs extending around 120 degrees of its circumference. The barb(s) may be directed toward the proximal end of the needle. The tool may further include an occluding member that closes a side aperture in the cannula may include a distal cutting edge adapted to cut tissue. The tool may further comprise an outer cutting member. The tissue-engaging components of the device preferably comprise a resilient metal that can withstand repeated elastic deflections.
In yet further other embodiments, a method for preventing leakage of cerebrospinal fluid from an opening in a thecal sac in a spine may comprise accessing the epidural space in the vicinity of the opening and inserting a volume of fluid into the epidural space, where the fluid thickens as it attains body temperature such that the fluid blocks the opening in the thecal sac.
In further embodiments, a bone cutting device can be used to access the ligamentum flavum and epidural space, to perform a laminotomy or to allow placement of a cannula. Using a cannula fixed within (extending through) the lamina, a cutting device can be inserted into and removed from the ligamentum flavum and/or epidural space. Real-time use of fluoroscopy or other imaging means during the subsequent MILD procedure can be minimized with the appropriate placement of tools following use of the bone cutting device. The laminotomy creates a portal and gives a steady purchase for instruments and instrument exchange. In addition, either the laminotomy site or the neighboring tissue, including bone and/or other tissue, can be used as an anchoring site for sutures or other tissue-engaging means.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the invention, reference is made to the accompanying drawings, wherein:
FIG. 1 is an illustration of a vertebra showing the spinal canal with the thecal sac and a normal (un-stenosed) ligamentum flavum therein;
FIG. 2 is an illustration of a vertebra showing the spinal canal with the thecal sac and a thickened ligamentum flavum therein;
FIG. 3 is an enlarged cross-section of the spine of FIG. 2 , showing a safety zone created by compression of the thecal sac;
FIG. 4 is the enlarged cross-section of FIG. 3 , showing a tissue removal tool positioned in the ligamentum flavum;
FIGS. 5-9 are a series of illustrations showing tissue excision by a tissue-excision tool constructed in accordance with a first embodiment of the invention;
FIGS. 10-14 are a series of illustrations showing tissue excision by a tissue-excision tool constructed in accordance with a second embodiment of the invention;
FIGS. 15 and 17 are sequential illustrations showing removal of tissue from a tissue-excision tool by a tissue-removal device constructed in accordance with an embodiment of the invention;
FIGS. 16 and 18 are end views of the tissue-removal device of FIGS. 15 and 17 , respectively;
FIG. 19 shows an alternative embodiment of a grasping needle with a corkscrew shape;
FIG. 20 is a perspective view of a tissue-excision tool constructed in accordance with a third embodiment of the invention;
FIGS. 21 and 22 are enlarged cross-sectional and perspective views, respectively, of the grasping device of FIG. 20 in its retracted position;
FIGS. 23 and 24 are enlarged cross-sectional and perspective views, respectively, of the grasping device of FIG. 20 in its extended position;
FIG. 25 is a schematic illustration of one embodiment of a double-ended ligament anchor being deployed in a ligamentum flavum;
FIG. 26 shows the device of FIG. 25 after full deployment;
FIG. 27 is a perspective view of an entire tool constructed in accordance with preferred embodiments;
FIG. 28 is an enlarged cross-sectional view of the distal tip of the tool of FIG. 27 with the aperture partially opened;
FIG. 29 is a cross-sectional view of the handle end of the tool of FIG. 27 ;
FIG. 30 is cross-section of a tissue-removal device constructed in accordance with an alternative embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The epidural space is the space between the ligamentum flavum and the thecal sac. This space is filled with blood vessels and fat. The nerves contained within the thecal sac are normally surrounded by cerebrospinal fluid (CSF). When the ligamentum flavum hypertrophies, the blood vessels that supply the nerves of the cauda equina are compressed. This results in ischemic pain termed spinal claudication. The nerve roots may also be compressed resulting in back and/or leg pain.
Referring again to FIG. 1 , the posterior border of the normal epidural space 30 is formed by the normally thin ligamentum flavum 26 and posterior epidural fat (not shown). Ligamentum flavum 26 extends from the lamina above the interspinous space to the lamina below the interspinous space. The dural sleeve (thecal sac) 32 contains nerve roots 34 surrounded by cerebrospinal fluid. The nerve roots 34 normally comprise only a small proportion of the thecal sac volume.
In FIG. 2 , spinal stenosis is present. Ligamentum flavum 26 is markedly thickened, compressing the posterior margin of dural sleeve 32 . As shown in FIG. 2 , the posterior margin of the dural sleeve 32 is apposed to the ligamentum flavum and the epidural space is only a potential space. Because more than 90% of the volume of the thecal sac in the lumbar region is filled by CSF, the thecal sac is highly compressible. Thus, even though stenosis may be causing compression of the thecal sac (and associated pain or discomfort), in most instances it will be possible to temporarily compress the thecal sac further. Thus, according to preferred embodiments of the invention, thecal sac 32 is compressed in a region of interest by applying pressure to the outside of the sac so that at least a portion of the CSF is forced out of the region of interest.
Creation of Safety Zone
According to certain embodiments, thecal sac 32 is compressed by injecting a standard radio-opaque non-ionic myelographic contrast medium or other imagable or non-imagable medium into the epidural space in the region of interest. This is preferably accomplished with a percutaneous injection. The result is illustrated in FIG. 3 . The presence of the fluid gently compresses and displaces the dural sleeve 32 in the region of interest, creating a safety zone 40 between thecal sac 32 and ligamentum flavum 26 . Sufficient injectable fluid is preferably injected to displace the CSF out of the region of interest and compress the thecal sac to at least a desired degree. The injected medium is preferably substantially contained within the confines of the epidural space extending to the margins of the nerve root sleeves. The epidural space is substantially watertight and the fatty tissues and vascularization in the epidural space, combined with the viscous properties of the preferred fluids, serve to substantially maintain the injected medium in the desired region of interest. This novel method for protecting the neural column may be referred to hereinafter as “contrast-guided dural protection.”
Once a safety zone 40 has been created, a tool 100 , such as the tissue excision devices and tissue retraction devices described below, can be inserted into the ligamentum flavum 26 , as illustrated in FIG. 4 . While it is preferred that the tip of the tool remain within the ligament as shown, the presence of safety zone 40 ensures that the thecal sac will not be damaged even if the tool breaks through the anterior surface of ligament 26 . For insertion of the tool, a fluoroscopic window of access (FWA) is defined by the inferior margin of the lamina (contra lateral to the point of instrument entry in the soft tissues) and the dorsal margin of the contrast material that defines the epidural space. This FWA is roughly orthogonal to the long axis of the cutting instrument, which parallels the inferior surface of the lamina as in FIG. 4 . The fluoroscopic plane of projection is preferably but not necessarily oriented 20-45 degrees from normal (AP projection).
Because the present techniques are preferably performed percutaneously, certain aspects of the present invention can be facilitated by imaging. In this context, the spine can be imaged using any suitable technology, including but not limited to 2D, 3D fluoroscopy, CT, MRI, ultrasound or with direct visualization with fiber optic or microsurgical techniques. Stereotactic or computerized image fusion techniques are also suitable. Fluoroscopy is currently particularly well-suited to the techniques disclosed herein. Fluoroscopic equipment is safe and easy to use, readily available in most medical facilities, relatively inexpensive. In a typical procedure, using direct biplane fluoroscopic guidance and local anesthesia, the epidural space is accessed adjacent to the surgical site as described above.
If the injected medium is radio-opaque, as are for example myelographic contrast media, the margins of the expanded epidural space will be readily visible using fluoroscopy or CT imaging. Thus, the safety zone created by the present contrast-guided dural compression techniques can reduce the risk of damage to the spinal cord during procedures to remove or displace portions of the ligamentum flavum and/or laminae in order to treat spinal stenosis.
Injectable Medium
If desired, the injected medium can be provided as a re-absorbable water-soluble gel, so as to better localize the safety zone at the site of surgery and reduce leakage of this protective layer from the spinal canal. An injectable gel is a significant improvement on prior epidural injection techniques. The gel is preferably substantially more viscid than conventional contrast media and the relatively viscid and/or viscous gel preferably tends to remain localized at the desired site of treatment as it does not spread as much as standard liquid contrast media that are used in epidurography. The injected gel is preferably sufficiently viscous that it remains substantially within the local epidural space. This results in more uniform compression on the thecal sac and less leakage of contrast out of the canal. In addition, preferred embodiments of the gel are re-absorbed more slowly than conventional contrast media, allowing for better visualization during the course of the surgical procedure.
In some embodiments, a contrast agent can be included in the gel itself, so that the entire gel mass is imagable. In other embodiments, an amount of contrast can be injected first, followed by the desired amount of gel, or an amount of gel can be injected first, followed by the desired amount of contrast. In this case, the contrast agent is captured on the surface of the expanding gel mass, so that the periphery of the mass is imagable.
Any standard hydrophilic-lipophilic block copolymer (Pluronic) gel such as are known in the art would be suitable and other gels may be used as the injectable medium. The gel preferably has an inert base. In certain embodiments, the gel material is liquid at ambient temperatures and can be injected through a small bore (such as a 27 gauge needle). The gel then preferably becomes viscous when warmed to body temperature after being injected. The viscosity of the gel can be adjusted through the specifics of the preparation. The gel or other fluid is preferably sufficiently viscid or viscous at body temperature to compress and protect the thecal sac in the manner described above and to remain sufficiently present in the region of interest for at least about 30 minutes. Thus, in some embodiments, the injected gel attains a viscosity that is two, three, six or even ten times that of the fluids that are typically used for epidurograms.
In certain embodiments, the injected medium undergoes a reversible change in viscosity when warmed to body temperature so that it can be injected as a low-viscosity fluid, thicken upon injection into the patient, and be returned to its low-viscosity state by cooling. In these embodiments, the injected medium is injected as desired and thickens upon warming, but can be removed by contacting it with a heat removal device, such as an aspirator that has been provided with a cooled tip. As a result of localized cooling, the gel reverts to its initial non viscous liquid state and can be easily suctioned up the cooled needle or catheter.
An example of a suitable contrast medium having the desired properties is Omnipaque® 240 available from Nycomed, New York, which is a commercially available non-ionic iodinated myelographic contrast medium. Other suitable injectable media will be known to those skilled in the art. Because of the proximity to the spinal nerves, it is preferred not to use ionic media in the injectable medium. The preferred compositions are reabsorbed relatively rapidly after the procedure. Thus any residual gel compression on the thecal sac after the MILD procedure resolves relatively quickly. For example, in preferred embodiments, the gel would have sufficient viscosity to compress the thecal sac for thirty minutes, and sufficient degradability to be substantially reabsorbed within approximately two hours.
The injected contrast medium further may further include one or more bioactive agents. For example, medications such as those used in epidural steroid injection (e.g. Depo medrol, Celestone Soluspan) may be added to the epidural gel to speed healing and reduce inflammation, scarring and adhesions. The gel preferably releases the steroid medication slowly and prolongs the anti-inflammatory effect, which can be extremely advantageous. Local anesthetic agents may also be added to the gel. This prolongs the duration of action of local anesthetic agents in the epidural space to prolong pain relief during epidural anesthesia. In this embodiment the gel may be formulated to slow the reabsorption of the gel.
The present gels may also be used for epidural steroid injection and perineural blocks for management of acute and chronic spinal pain. Thrombin or other haemostatic agents can be added if desired, so as to reduce the risk of bleeding.
In some embodiments, the gel may also be used as a substitute for a blood patch if a CSF leak occurs. The gel may also be used as an alternative method to treat lumbar puncture complications such as post-lumbar puncture CSF leak or other causes of intracranial hypotension. Similarly, the gel may be used to patch postoperative CSF leaks or dural tears. If the dural sac were inadvertently torn or cut, then gel could immediately serve to seal the site and prevent leakage of the cerebral spinal fluid.
Percutaneous Tissue Excision
After safety zone 40 has been created, the margins of the epidural space are clearly demarcated by the injected medium and can be visualized radiographically if an imagable medium has been used. As mentioned above, percutaneous procedures can now safely be performed on the ligamentum flavum and/or surrounding tissues without injuring the dural sac or nerves and the spinal canal can be decompressed using any of several techniques. Suitable decompression techniques include removal of tissue from the ligamentum flavum, laminectomy, laminotomy, and ligament retraction and anchoring.
In some embodiments, all or a portion of the ligamentum flavum and/or lamina are excised using a percutaneous tissue excision device or probe 100 , which may hereinafter be referred to as the MILD device. As shown schematically in FIG. 4 , a device 100 may be placed parallel to the posterior and lateral margin of the safety zone 40 with its tip in the ligamentum flavum 26 .
Preferred embodiments of the present tissue excision devices and techniques can take several forms. In the discussion below, the distal ends of the tools are described in detail. The construction of the proximal ends of the tools, and the means by which the various components disclosed herein are assembled and actuated, will be known and understood by those skilled in the art.
By way of example, in the embodiment shown in FIG. 4 and as illustrated in FIG. 5 , device 100 may be a coaxial excision system 50 with a sharpened or blunt tip that is placed obliquely into the thickened ligamentum flavum 26 posterior to safety zone 40 under fluoroscopic guidance. The needle is preferably placed parallel to the posterior margin of the canal. Excision system 50 is preferably manufactured from stainless steel, titanium or other suitable durable biocompatible material. As shown in FIGS. 5-10 , an outer needle or cannula 51 has an opening or aperture 52 on one side that is closed during insertion by an inner occluding member 54 . Aperture 52 is readily visible under imaging guidance. Once needle 51 is positioned in the ligamentum flavum or other tissue removal site, inner occluding member 54 is removed or retracted so that it no longer closes aperture 52 ( FIG. 6 ). Aperture 52 is preferably oriented away from the epidural space so as to further protect the underlying structures from injury during the surgical procedure. If it was not already present in the tool, a tissue-engaging means 56 is inserted through outer needle 51 to aperture 52 so that it contacts adjacent tissue, e.g. the ligamentum flavum, via aperture 52 .
Tissue-engaging means 56 may be a needle, hook, blade, tooth or the like, and preferably has at least one flexible barb or hook 58 attached to its shaft. The barb 58 or barbs may extend around approximately 120 degrees of the circumference of the shaft. Barbs 58 are preferably directed towards the proximal end of the tool. When needle 56 is retracted slightly, barbs 58 allow it to engage a segment of tissue. Depending on the configuration of barbs 58 , the tissue sample engaged by needle 56 may be generally cylindrical or approximately hemispherical. Once needle 56 has engaged the desired tissue, inner occluding means 54 , which is preferably provided with a sharpened distal edge, is advanced so that it cuts the engaged tissue section or sample loose from the surrounding tissue. Hence occluding means 54 also functions as a cutting means in this embodiment. In alternative embodiments, such as FIGS. 10-14 discussed below, a cylindrical outer cutting element 60 may extended over outer needle 51 and used in place of occluding member 54 to excise the tissue sample.
Referring still to FIGS. 5-9 , once the tissue sample has been cut, tissue-engaging needle 56 can be pulled back through outer needle 51 so that the segment of tissue can be retrieved and removed from the barbs ( FIG. 8 ). The process or engaging and resecting tissue may be repeated ( FIG. 9 ) until the canal is adequately decompressed.
Referring briefly to FIGS. 10-14 , in other embodiments, a tissue-engaging hook 64 can be used in place of needle 56 and an outer cutting member 60 can be used in place of inner occluding member 54 . Hook 64 may comprise a length of wire that has been bent through at least about 270°, more preferably through 315°, and still more preferably through about 405°. Alternatively or in addition, hook 64 may comprise Nitinol™, or any other resilient metal that can withstand repeated elastic deflections. In the embodiment illustrated, hook 64 includes at least one barb 58 at its distal end. In some embodiments, hook 64 is pre-configured in a curvilinear shape and is retained within tool 100 by outer cutting member 60 . When cutting member 60 is retracted, the curved shape of hook 64 urges its outer end to extend outward through aperture 52 . If desired, hook 64 can be advanced toward the distal end of tool 100 , causing it to extend farther into the surrounding tissue. In some embodiments, hook 64 is provided with a camming surface 66 . Camming surface 66 bears on the edge of opening 52 as hook 64 is advance or retracted and thereby facilitates retraction and retention of hook 64 as it is retracted into the tool. In these embodiments, hook 64 may not extend through aperture 52 until it has been advanced sufficiently for camming surface 66 to clear the edge of the opening. Hook 64 may alternatively be used in conjunction with an inner occluding member 54 in the manner described above. As above, hook 64 can be used to retrieve the engaged tissue from the distal end of the tool.
In still other embodiments, the tissue-engaging means may comprise a hook or tooth or the like that engages tissue via aperture 52 by being rotated about the tool axis. In such embodiments (not shown) and by way of example only, the tissue-engaging means could comprise a partial cylinder that is received in outer cannula 51 and has a serrated side edge. Such a device can be rotated via a connection with the tool handle or other proximal device. As the serrated edge traverses aperture 52 tissue protruding into the tool via the aperture is engaged by the edge, whereupon it can be resected and retrieved in the manner disclosed herein.
In preferred embodiments, the working tip of tool 100 remains within the ligamentum flavum and does not penetrate the safety zone 40 . Nonetheless, safety zone 40 is provided so that even an inadvertent penetration of the tool into the epidural space will not result in damage to the thecal sac. Regardless of the means by which the tissue is engaged and cut, it is preferably retrieved from the distal end of the tool so that additional tissue segments can be excised without requiring that the working tip of the tool be repositioned. A tissue-removal device such as that described below is preferably used to remove the tissue from the retrieval device between each excision.
Tissue Removal
Each piece of tissue may be removed from barbs 58 by pushing tissue-engaging means 56 through an opening that is large enough to allow passage of the flexible barbs and supporting needle but smaller than the diameter of the excised tissue mass. This pushes the tissue up onto the shaft, where it can be removed with a slicing blade or the like or by sliding the tissue over the proximal end of the needle. Alternatively, needle 56 can be removed and re-inserted into the tool for external, manual tissue removal.
It is expected that in some embodiments, approximately 8-10 cores or segments of tissue will be excised and pushed up the shaft towards the hub during the course of the procedure. Alternatively, a small blade can be used to split the tissue segment and thereby ease removal of the segment from the device. If desired, a blade for this purpose can be placed on the shaft of needle 56 proximal to the barbs.
In an exemplary embodiment, shown in FIGS. 15-18 , the tissue removal device may include a scraper 120 that includes a keyhole slot having a wide end 122 and a narrow end 124 . To remove a tissue sample from needle 56 or hook 64 , the tissue-engaging device with a mass of excised tissue 110 thereon can be retracted (pulled toward the proximal end of the tool) through wide end 122 of the slot and then re-inserted (pushed toward the distal end of the tool) through narrow end 124 of the slot. Narrow end 124 is large enough to allow passage of the barbed needle, but small enough to remove the tissue mass as the needle passes through. By shuttling the tissue-engaging device through scraper 120 in this manner, each excised segment of tissue 110 can be removed from the device, readying the device for another excision.
In an alternative embodiment (not shown) an alternative mechanism for removing the tissue segment from needle 56 includes an adjustable aperture in a disc. After the tissue-bearing needle is pulled back through the aperture, the aperture is partially closed. Needle 56 and flexible hooks 58 then can pass through the partially closed aperture but the larger cylinder of tissue cannot. Thus the tissue segment is pushed back onto the shaft. The tissue segment can either be pulled off the proximal end of the shaft or cut off of it. A small blade may be placed just proximal to the barbs to help cut the tissue segment off the shaft. The variable aperture can formed by any suitable construction, including a pair of metal plates with matching edges that each define one half of a central opening. The two pieces may be held apart by springs. The aperture may be closed by pushing the two edges together. In other embodiments, this process can be mechanically automated by using a disc or plate with an opening that is adjustable by a variety of known techniques, including a slit screw assembly or flexible gaskets.
Alternative Tissue Excision Devices
Other cutting and/or grasping devices can be used in place of the system described above. For example, embodiments of the grasping mechanism include but are not limited to: needles with flexible barbs, needles with rigid barbs, corkscrew-shaped needles, and/or retaining wires. The corkscrew-shaped needle shown in FIG. 19 works by screwing into the ligamentum flavum in the manner that a corkscrew is inserted in a cork. After the screw engages a segment of tissue, outer cutting element 60 slides over the needle, cutting a segment of tissue in a manner similar to that of the previous embodiment. In some embodiments, the cutting element can be rotated as it cuts.
In other embodiments, shown in FIGS. 20-22 , cannulated scalpel 51 houses a grasping device 70 that includes at least one pair of arcuate, closable arms 72 . Closable arms 72 may be constructed in any suitable manner. One technique for creating closable arms is to provide a slotted sleeve 74 , as shown. Slotted member 74 preferably comprises an elongate body 75 with at least one slot 76 that extends through its thickness but does not extend to either end of the body. Slot 76 is preferably parallel to the longitudinal axis of the sleeve. On either side of slot 76 , a strip 77 is defined, with strips 77 being joined at each end of sleeve 74 . It is preferred that the width of each strip 77 be relatively small. In some embodiments, it may be desirable to construct slotted member 74 from a portion of a hollow tube or from a rectangular piece that has been curved around a longitudinal axis. The inner edge of each strip that lies along slot 76 forms an opposing edge 78 . The width of the piece is the total of the width of strips 77 and slot 76 .
Advancing one end of sleeve 74 toward the other end of sleeve 74 causes each strip 77 to buckle or bend. If strips 77 are prevented from buckling inward or if they are predisposed to bend in the desired direction, they will bend outward, thereby forming arcuate arms 72 , which extend through aperture 52 of cannulated scalpel 51 , as shown in FIG. 21 . As they move away from the axis of body 75 , arms 72 move apart in a direction normal to the axis of body 75 . Likewise, moving the ends of sleeve 74 apart causes arms 72 to straighten and to move together and inward toward the axis of the device, as shown in FIG. 22 . As the arms straighten, opposing edges 78 close and a segment of tissue can be capture between them. Tissue within the grasping device may then be resected or anchored via the other mechanisms described herein.
Closable arms 72 may include on their opposing edges 78 ridges, teeth, or other means to facilitate grasping of the tissue. In other embodiments, edges 78 may be sharpened, so as to excise a segment of tissue as they close. In these embodiments, closable arms 72 may also be used in conjunction with a hook, barbed needle, pincers or the like, which can in turn be used to retrieve the excised segment from the device.
Once arms 72 have closed on the tissue, if arms 72 have not cut the tissue themselves, the tissue can be excised using a blade such as cutting element 60 above. The excised tissue can be removed from the inside of needle 51 using a tissue-engaging hook 64 or other suitable means. The process of extending and closing arms 72 , excising the tissue, and removing it from the device can be repeated until a desired amount of tissue has been removed.
If desired, this cycle can be repeated without repositioning the device in the tissue. Alternatively, the tool can be rotated or repositioned as desired between excisions. It is possible to rotate or reposition the tool during an excision, but it is expected that this will not generally be preferred. Furthermore, it is expected that the steps of tissue excision and removal can be accomplished without breaching the surface of the ligament, i.e. without any part of the device entering the safety zone created by the injected fluid. Nonetheless, should the tool leave the working zone, the safety zone will reduce the risk of injury to the thecal sac.
Ligament Retraction
In some embodiments, the spinal canal may also be enlarged by retracting the ligamentum flavum, either with or without concurrent resection. Retraction is preferably but not necessarily performed after dural compression has been used to provide a safety zone. In addition, the dural compression techniques described above have the effect of pressing the ligamentum flavum back out of the spinal canal and thereby making it easier to apply a restraining means thereto.
Thus, in preferred embodiments, after a safety zone is created by epidural injection of contrast medium or gel, a retraction device 90 as shown in FIG. 23 is used to retract and compress the thickened soft tissues around the posterior aspect of the spinal canal, thereby increasing the available space for the dural sac and nerves. In the embodiment shown, retraction device 90 is a double-headed anchor that includes at least one distal retractable tissue-engaging member 91 and at least one proximal tissue-engaging member 92 , each of which are supported on a body 94 . Retraction device 90 is preferably constructed from an implantable, non-biodegradable material, such as titanium or stainless steel, but may alternatively be polymeric or any other suitable material. In certain preferred embodiments, body 94 is somewhat flexible. In some instances, flexibility in body 94 may facilitate the desired engagement of barbs 91 , 92 . Barbs 91 , 92 may comprise hooks, arms, teeth, clamps, or any other device capable of selectively engaging adjacent tissue. Barbs 91 , 92 may have any configuration that allows them to engage the ligamentum flavum and/or surrounding tissue. Similarly, barbs 91 , 92 may be covered, sheathed, pivotable, retractable, or otherwise able to be extended from a first position in which they do not engage adjacent tissue to a second position in which they can engage adjacent tissue.
FIG. 23 shows schematically the distal and proximal retractable arms 91 , 92 of a preferred ligament anchor 90 . The proximal end of the anchor preferably includes a threaded connector 96 or other releasable mechanism that attaches to a support rod 100 . Ligament anchor 90 may be attached to a support shaft 112 and sheathed in a guide housing 114 . The distal and proximal barbs 91 , 92 are prevented by guide housing 114 from engaging surrounding tissue. Housing 102 is preferably a metal or durable plastic guide housing.
The distal end of the device is preferably positioned in the ligamentum flavum under fluoroscopic guidance. If desired, an accessway through the lamina may be provided using an anchored cannula or the like. The device is held in position by support shaft 112 . Distal barbs 91 are unsheathed and optionally expanded by pulling back guide housing 102 , as shown in FIG. 23 . Distal barbs 91 are secured in the ligamentum flavum by pulling back on the support shaft 112 . With barbs 91 engaging the tissue, the ligamentum flavum is retracted posteriorly by pulling back on support shaft 112 . While maintaining traction on the now-retracted ligament, proximal barbs 92 are uncovered and expanded by retracting guide housing 114 , as shown in FIG. 24 . Barbs 92 are preferably positioned in the soft tissues 116 in the para-spinal region so that the device is firmly anchored behind the posterior elements of the spinal canal. Once the proximal end of the anchor is engaged, support shaft 112 may be detached from body 94 as shown in FIG. 24 . In this manner, the posterior margin 95 of the ligamentum flavum can be held in a retracted position, thereby expanding the canal. The procedure can then be repeated on adjacent portions of the ligamentum flavum until it is sufficiently retracted.
In an alternative embodiment, the proximal end of ligament anchor 90 may be adapted to engage the lamina. This may be accomplished by having the arm posterior to the lamina or by using the laminotomy and suturing the device to the lamina there. A knotted or knotless system or a suture plate can be used.
A second embodiment of the present method uses a plurality of retraction devices 90 . In this embodiment, the retraction device is inserted through one lamina in an oblique fashion, paralleling the opposite lamina. After the distal anchor is deployed, the retraction device is pulled back and across the ligamentum flavum, thereby decompressing the opposite lateral recess of the spinal canal. This is repeated on the opposite side. This same device can also be deployed with a direct approach to the lateral recess with a curved guide housing.
While retraction device 90 is describe above as a double-headed anchor, it will be understood that other devices can be used. For example sutures, barbed sutures, staples or the like can be used to fasten the ligament in a retracted position that reduces stenosis.
Using the percutaneous methods and devices described herein, significant reductions of stenosis can be achieved. For example, a dural sac cross-sectional area less than 100 mm 2 or an anteroposterior (AP) dimension of the canal of less than 10-12 mm in an average male is typically considered relative spinal stenosis. A dural sac cross-sectional area less than 85 mm 2 in an average male is considered severe spinal stenosis. The present devices and techniques are anticipated to cause an increase in canal area of 25 mm 2 per anchor or 50 mm 2 total. With resection and/or retraction of the ligamentum flavum, the cross-sectional area of the dural sac can be increased by 10 mm 2 , and in some instances by as much as 20 mm 2 or even 30 mm 2 . Likewise, the present invention can result in an increase of the anteroposterior dimension of the canal by 1 to 2 mm and in some instances by as much as 4 or 6 mm. The actual amount by which the cross-sectional area of the thecal sac and/or the anteroposterior dimension of the canal are increased will depend on the size and age of the patient and the degree of stenosis and can be adjusted by the degree of retraction of the ligament.
MILD
The minimally invasive ligament decompression (MILD) devices and techniques described herein allow spinal decompression to be performed percutaneously, avoiding the pain and risk associated with open surgery. Through the provision of a safety zone, the present devices and techniques offer reduced risk of spinal cord damage. In addition to improving nerve function, it is expected that decompression of the spinal canal in the manner described herein will result in improved blood flow to the neural elements by reducing the extrinsic pressure on the spinal vasculature. For these reasons, it is believed that spinal decompression performed according to the present invention will be preferable to decompression operations performed using currently known techniques.
Dural Shield
In some embodiments (not shown), a mechanical device such as a balloon or mechanical shield can also be used to create a protective guard or barrier between the borders of the epidural space and the adjacent structures. In one embodiment a durable expandable device is attached to the outside of the percutaneous laminectomy device, preferably on the side opposite the cutting aperture. The cutting device is inserted into the ligamentum flavum with the expandable device deflated. With the aperture directed away from the spinal canal, the expandable device is gently expanded via mechanical means or inflated with air or another sterile fluid, such as saline solution, via a lumen that may be within or adjacent to the body of the device. This pushes the adjacent vital structures clear from the cutting aperture of the device and simultaneously presses the cutting aperture into the ligament. As above, the grasping and cutting needles can then be deployed and operated as desired. The balloon does not interfere with tissue excision because it is located on the side opposite the cutting aperture. The cutting needle may be hemispherical (semi-tubular) in shape with either a straight cutting or a sawing/reciprocating blade or may be sized to be placed within the outer housing that separates the balloon from the cutting aperture.
In another embodiment, a self-expanding metal mesh is positioned percutaneously in the epidural space. First the epidural space is accessed in the usual fashion. Then a guide catheter is placed in the epidural space at the site of the intended surgical procedure. The mesh is preferably compressed within a guide catheter. When the outer cover of the guide catheter is retracted, the mesh expands in the epidural space, protecting and displacing the adjacent dural sheath. At the conclusion of the surgical procedure, the mesh is pulled back into the guide sheath and the assembly removed. The mesh is deformable and compresses as it is pulled back into the guide catheter, in a manner similar to a self-expanding mesh stent. There are many commercially available self-expanding stents approved and in use in other applications. However, using a self-expandable mesh as a device within the epidural space to protect and displace the thecal sac is novel.
While preferred embodiments of this invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the scope or teaching of this invention. For example, the means by which the safety zone is formed may be varied, the shape and configuration of the tissue excision devices may be varied, and the steps used in carrying out the technique may be modified. Accordingly, the invention is not limited to the embodiments described herein, but is only limited by the claims that follow, the scope of which shall include all equivalents of the subject matter of the claims. Likewise, the sequential recitation of steps in a claim, unless explicitly so stated, is not intended to require that the steps be performed in any particular order or that a particular step be completed before commencement of another step. | A method for treating stenosis in a spine comprises percutaneously accessing the epidural space in a stenotic region of interest, compressing the thecal sac in the region of interest to form a safety zone, inserting a tissue removal tool into tissue in the working zone, using the tool to percutaneously reduce the stenosis; and utilizing imaging to visualize the position of the tool during at least a part of the reduction step. A tissue excision system for performing percutaneous surgery, comprises a cannula comprising a tissue-penetrating member having a distal end defining an aperture on one side thereof, an occluding member slidably received on or in the cannula and closing the aperture when the occluding member is adjacent the cannula distal end, means for engaging adjacent tissue via the aperture, and cutting means for resecting a section of the engaged tissue. | 0 |
FIELD OF THE INVENTION
The present invention relates to a disposable needle guide system for a medical imaging instrument, in particular an ultrasonic transducer, for guiding a needle into a selected location of a patient relative to the imaging instrument, for use in percutaneous interventional procedures, such as fine needle aspiration, core biopsy, amniocentesis, and drainage.
BACKGROUND OF THE INVENTION
A great number of needle guide systems for use with ultrasonic transducers and the like are known in the art. Most of them are confined to be used with a transducer of particular geometry which is a considerable drawback in consideration of the considerable number of ultrasonic transducers of differing geometry on the market.
Another problem with most known needle guide systems is that they accept only one diameter size of needle, and that, therefore, their use with needles of different size necessitates the change of one or several parts. Present systems also suffer from the drawback that the user has to assemble the system from a number of parts. In addition most known needle guide systems require some sort of adapter which may constitute a substantial investment on its own. Also, such adapters may be lost or mislaid between individual percutaneous interventions.
A further problem with many known needle guide systems is that they are not truly disposable, that is, they are not easy and cheap to manufacture and, therefore, tend to be re-used, even if not suited or designed to be repeatedly used. They thus may constitute a risk to patients when being re-used improperly.
The present invention seeks to avoid the aforementioned problems.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide a needle guide system of the aforementioned kind which can be adapted to transducers of varying shape, in particular ultrasound transducers.
It is another object of the present invention to provide a needle guide system of the aforementioned kind which has improved flexibility and functionality in comparison with needle guide systems presently in use.
It is an additional object of the invention to provide a needle guide system accepting needles of varying diameter without the need for exchanging parts.
It is a further object of the invention to provide a needle guide system which enables the user to choose between an adapter-based solution and a solution where a disposable device is directly fit to the transducer.
It is a particularly important object of the invention to provide a truly disposable needle guide system, that is, a system which cannot be re-used at all or with considerably difficulty only.
Further objects of the invention are evident from the following short description of the invention, the attached drawings illustrating a preferred embodiment, the detailed description thereof, and the appended claims.
SUMMARY OF THE INVENTION
According to the present invention is provided a needle guide system of the aforementioned kind, comprising a needle guide assembly and a mounting assembly for attaching the needle guide assembly to a transducer, the mounting assembly comprising self-destroying means effective on dismounting.
It is preferred for the needle guide assembly to comprise needle guide means accepting needles of different diameters, in particular needles from three to six different diameters.
It is also preferred for the needle guide means to comprise a revolver mounted in a stepwise lockable revolving manner on a journal clip.
The journal clip is mountable on the mounting assembly. According to the invention it is possible to provide a journal clip which can be mounted in two or more angular or height positions in respect of the mounting assembly.
According to a preferred aspect of the invention, the mounting assembly comprises an adapter mountable on a transducer, an attaching clip mountable on the adapter and a locking clip mountable on the attaching clip. It should be understood that the attaching clip is interposed between the adapter and the locking element on which the needle guide assembly is mountable.
It is however also possible for the attaching clip to be directly mountable the transducer; the portion of the transducer at which the attaching clip is mountable should be designed in a manner functionally corresponding to the mounting portion of the adapter. In such case no separate adapter will be needed. The variant of the needle guide assembly in which mounting portion of the adapter is comprised by the transducer is fully encompassed within the present invention.
It is preferred for the adapter to be of a generally abutable shape in respect of the transducer to which it is intended to be mounted in a transducer encircling position. The adapter preferably has two free ends provided with a cooperating snap connection which is closed on mounting and which is preferably not easily dismountable by hand.
According to a preferred second aspect of the invention the attaching clip comprises a base and first and second pairs of prehensile organs extending from the short or lateral ends of the base (or from positions close to the short ends) in opposite directions. A rough approximation of the general shape of a preferred attaching clip of the invention are two letters C joined back-to-back but not necessarily of the same size. The first pair of prehensile organs, such as claws, is designed in a manner to enable it to grip a U-formed portion of the adapter mounted on a transducer (or to directly grip a portion of the transducer of corresponding design) and to snap into position by its terminal portions interlocking with recesses provided in corresponding external faces of the adapter. Preferably further means for firmly attaching the adapter to the attaching clip are provided at facing faces of the attaching clip and the adapter, such as a transverse ridge disposed on an external face of the adapter insertable into a facing transverse recess disposed in the attaching clip.
According to a preferred aspect of the invention the claws of the second prehensile organ are adapted to grip opposite sides of the locking clip in a way so as to hold it against the attaching clip and locking it in this position. Once snapped into position the locking element is not easily removed by hand from the attaching clip.
The locking element preferably comprises a front and back support areas, such as support faces, grids or similar, tilting in respect to each other, the back face facing the attaching clip whereas the front face faces the needle is preferably selectable to fit a particular type of transducer or needle insertion depth.
The needle assembly is mountable on the mounting assembly by attaching the journal clip to the locking element. Preferably the journal clip is mounted in a manner making it difficult or impossible to remove it from the locking element in a mounted position, for instance by snap tongues inserted into through openings in the locking element into which they lock and/or by snap tongues which can grip edges of the locking element.
It is preferred for the needle guide system of the invention to be easily detachable from a position mounted on a transducer only by damaging (breaking) a weak point, such as a fracture zone or line, of the mounting assembly. Particularly preferred is for such a weak point, kerf or facture zone to be comprised by the second prehensile means, in particular by one claw thereof.
It is preferred for the attaching clip to comprise breaking means for such destructive dismounting, the breaking means comprising a twisting element and a fracture zone or line. It is preferred for the fracture zone or line to be easily broken by displacement of sections adjacent to the zone or line in the direction of the transducer axis. Particularly preferred is the removal of a support for one or both second prehensile means providing for release of the locking element. By making the dismounting of the attaching clip conditional on its destruction the unsafe re-use of the needle assembly is prevented.
It is preferred for the revolver to comprise a multitude of needle receiving slots, for instance, three to six slots, each slot being dimensioned to receive a needle of different diameter. The revolver has about cylindrical shape with the slots disposed in its mantle in parallel with the cylinder axis and in an about equidistant manner along its circumference corresponding to an exactly equidistant manner in regard of the axes of their respective needles. Whereas the width of each slot corresponds closely to the diameter of the needle which it is intended to receive, its depth is slightly less than said diameter. Thereby the needle protrudes somewhat in a radial direction from the slot.
It is furthermore preferred for the revolver to comprise a multitude of locking elements. The locking elements, for instance, radially extending locking ribs, are arranged for locking the revolver in a position in which the a needle disposed in the slot of corresponding diameter is made abut a recess in a wall of the angular clip facing away from the transducer. Thereby the displacement of the needle is restricted to be strictly axial.
According to the present invention is also provided a disposable needle guide system comprising a needle guide assembly and a mounting assembly mountable on a transducer, the mounting assembly comprising an attaching clip mountable on a mounting portion of the transducer or on an adapter mountable on the transducer, and a locking clip mountable on the attaching clip so as to be releaseably held at its opposite ends by holding portions of the attaching clip, the release means including a kerf or other indication of fracture comprised by a support portion of the attaching clip supporting one of said holding portions and being easily breakable by hand. It is preferred for the release function to comprise a handle which can be turned to break the kerf or other indication of fracture and thereby irreversibly release the locking clip.
If not indicated otherwise, in this specification the orientation of the various elements of the needle guide system of the invention is in relation to the transducer. Ultrasound and other transducers are normally of a cylindrical, rectangular, parallelepipedeal or similar configuration for which a longitudinal axis can be defined. Directions perpendicular to that axis are termed “transverse” or “lateral”. Faces facing the transducer are termed “interior” or “inwardly facing” or similar. Faces facing away from the transducer are termed “exterior” or “outwardly facing” or similar.
BRIEF DESCRIPTION OF THE DRAWINGS
In the following the invention will be explained in greater detail by reference to preferred embodiments illustrated in a raw drawing showing in
FIG. 1 a first embodiment of the needle guide system according to the invention mounted on an ultrasonic transducer, in a perspective view and with the transducer not shown;
FIG. 2 the embodiment of FIG. 1, in an exploded view;
FIGS. 3 a-e , the individual elements of the embodiment of FIG. 1, in substantially the same view as in FIG. 1;
FIG. 4 the adapter of the embodiment of FIG. 1 in an unmounted state, in a bottom view;
FIG. 5 the embodiment of FIG. 1 with the transducer shown and a hypodermic needle mounted, in a bottom view;
FIG. 6 a second embodiment of the needle guide system according to the invention, in the same view as in FIG. 5 .
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The first embodiment of the needle guide system of the invention shown in FIGS. 1-5 comprises five elements: a revolver 1 , an journal clip 2 , a locking clip 3 , an attaching clip 4 , and an adapter 5 . The elements 1 - 5 are preferably made of suitable polymer material(s).
The revolver 1 is mounted rotatably between lower 14 and upper 15 arms of the journal clip 2 extending from a base plate 13 and carrying bearing necks 17 and 18 , respectively, which extend into a central bore 6 of the revolver at its respective ends. Juts 7 are disposed in the bore 6 close to its lower and upper end for snapping interaction with catches 19 on the bearing necks 17 , 18 . Five such catches 19 are symmetrically arranged on each bearing neck 17 ; 18 allowing the revolver 1 to be displaced between five fixed positions by hand. These fixed positions correspond to five axial slots 8 - 12 on the revolver 1 , each slot being dimensioned to receive a hypodermic needle 70 of certain width. Thereby the needle guide of the invention can be used with needles of various (standard) dimensions. For mounting the needle 70 is placed in the slot 10 of corresponding width, and the revolver 1 with the needle 70 in the slot 10 is rotated until the needle 70 is locked in the slot 10 by the abutting the base plate 13 at a shallow indentation (not shown). The locking mechanism uses the resilient nature of the polymer materials of the revolver 1 and the journal clip 2 ; it does not prevent the needle from being moved in the direction of the slot 10 . The journal clip 2 comprises a stiffening rib 16 . It is useful to provide the journal clip 2 and the elements 3 and 4 with further stabilizing structures like the stiffening rib 16 but is not shown in the drawing for the sake of clarity. How the journal clip 2 with the revolver 1 is mounted on the remainder of the needle guide system by of upper 20 , 21 and lower 24 claws extending from the rear side of the base plate 13 (the side facing away from the revolver 1 ) will be explained later.
The needle guide assembly of the invention can be mounted on transducers of different geometry by an adapter 5 designed to fit the individual transducer. It is also possible to incorporate the portion of the adapter at which the remainder of the needle guide assembly is to be mounted in the transducer; in such case a separate adapter becomes superfluous. Only one external wall (a wall facing away from the transducer) of the adapter 5 (or the transducer, if no separate adapter is being used) need to be designed in a standard manner so as receive the remaining needle guide system elements 1 - 4 .
This wall is the facing wall of the base plate 51 in FIG. 3 e . The base plate 51 forms part of a belt structure comprising left 52 and right 53 arms provided with angular end portions 64 , 63 and joined to the base plate 51 by right 56 and left 57 thin flexible hinge sections. On mounting the base plate 51 on a transducer 71 its internal wall is pressed against the corresponding transducer wall, the arms 52 , 53 are folded towards each other so as to enclose the transducer 71 , and the adapter 5 is secured at the transducer 71 by a snap connection 65 , 66 , 67 disposed at the external walls of it angular end portions 63 , 64 comprising a tongue 65 with a head 66 integral with the right end portion 63 insertable into a catch 67 integral with the left end portion 64 . The snap connection 65 , 66 , 67 is of a self-locking sort that is not easily disassembled by hand.
The journal clip 2 with the revolver 1 is attached to and locked on the adapter 5 by means of an attaching clip and a locking clip.
The attaching clip 4 comprises a base plate separated into right 36 and left 38 sections by a thin-walled flexible bridge 40 which has a hinge function. To the right section 36 is joined a claw 37 at a right angle provided with an inwardly extending claw head 49 . To the left section 38 is joined a left claw 39 at a right angle provided with an inwardly extending claw head 48 .
The attaching clip 4 is placed with its left right base plate section 38 against the external face of the adapter base plate 51 so as to make a retainer key 72 disposed at the interior face of left section 36 fit into a recess 55 disposed on the exterior face of the adapter base plate and the right claw head 49 fit into a recess 54 disposed at the external face of the right arm 53 of the adapter 5 . Then the left section 38 is swiveled around the flexible bridge 40 which forms a sort of hinge until it abuts the adapter base plate 51 ; thereby the right claw head 48 is inserted in recess (not shown) disposed on the external face of the adapter left arm 52 corresponding to recess 54 . In FIGS. 2-4 the attaching clip 4 is shown in a state prior to it being clamped on adapter 5 .
The attaching clip 4 is locked on the adapter 5 by means of the locking clip 3 which comprises two faces, an outwardly facing first face identical with the exterior face of a base plate 25 and an inwardly facing second face defined by the internal face of a right locking flange 30 provided with a locking cylinder 31 and the internal face of a transverse stiffening rib 34 as well as the internal faces of vertical stiffening ribs (not shown) extending downwards from rib 34 . The first face is tilted in respect of the second face by an angle of about 15°. The internal face of the locking clip comprises a recess (not shown) which is engageable with a retainer key 47 disposed at the external face of the right base element section 36 .
For locking the locking 3 on the attaching clip 4 the former is provided with laterally extending left 28 and right 30 locking arms, the right locking arm comprising a cylindrical end portion 31 from which upper 32 and lower 46 projections extend and the left locking arm comprising a handle 29 . The left and right locking arms 28 , 30 are insertable into the gaps 68 , 69 of left 41 and right 45 locking clip holders arranged on the external faces of the left 38 and right 36 attaching clip base plate sections. The left locking clip holder comprises clamping flanges 42 , 43 and a rear support portion 44 . In combination with the cylindrical end portion 31 of the right locking arm 30 the right locking clip holder 45 provides a slight hinge function used on mounting: the cylinder portion 31 of locking clip 3 is first inserted into gap 69 of the right locking clip holder 45 ; then the left side of locking clip 3 is flipped towards clamp flange 42 of the left locking clip holder 41 to make it snap into its gap 68 from which position it is not easily dismounted by hand. The locking clip 3 furthermore is locked in this position by a retainer key 47 disposed on the external face of the right section 36 of the attaching clip base plate engaging with a grove and rib indentations (not shown) disposed on the internal face of the locking clip 3 .
The journal clip 2 with the revolver 1 is mounted on the locking clip by inserting a pair of lower claws 24 (only one shown) disposed on the interior face of base plate 13 of the journal clip 2 into claw ducts 26 , 27 penetrating the locking clip base plate 25 , the claws being retained in the ducts 26 , 27 by keyways (not shown) engaging with the base plate. Simultaneously a pair of upper claws 20 , 21 disposed on the interior face of base plate 13 of the journal clip 2 above said lower claws 24 are pushed over the top face 73 of the locking clip base plate 25 with which they engage by keyways 22 , 23 in two selectable positions providing for different angles of hypodermic needle orientation. Thereby the journal clip 2 is locked on the locking clip 3 in a irreversible manner since the snap connection provided by claws 20 , 21 , 24 is not easily dismounted by hand.
The various snap connections make use of the resiliency of selected polymer materials.
As already pointed out the various snap connections in combination with the design of the needle guide system according to the invention provide for the mounted system not being easily dismountable in its integrity, thus preventing unauthorized multiple use which might put the patient at risk.
The needle guide system according to the invention can be easily dismounted only by damaging an important component, the attaching clip. To this effect, the attaching clip is provided with an arrangement supporting the left locking clip holder 41 which is attached to the left base plate section 38 by a rather thin bridge 58 of material which is sufficiently stable to provide support (in a mounted position) in direction perpendicular to the base plate and parallel with grove (gap) 68 but not in a transverse direction indicated by arrow A in FIG. 5 . In that transverse direction the clip holder 41 is supported by a release grip 50 via supports 59 and, to a lesser degree, 60 . The clip holder 50 is attached to the external face of the left claw 39 by a hinge pin 62 and a further support 61 . The supports 59 , 60 , 61 are designed to be easily broken by relative displacement of the elements which they connect in a perpendicular direction. This capability is used when releasing the left locking clip holder 41 by turning the release grip around the hinge pin 62 . The hinge pin 62 is not and need not be a pin freely rotatable in a bearing or hinge, it is sufficient that the material constituting it allows the clip holder 50 to be rotated by hand while being sufficiently rigid to hold the clip holder 50 in position against the pressure exerted by the mounted locking clip 3 in normal use. The breaking of supports 59 , 60 on rotating clip holder 50 out of its plane allows the left locking clip holder 41 to flip away from the locking clip 3 in the direction of arrow A, thus allowing the locking clip 3 with the journal clip 2 and the revolver 1 to be removed. Thereby the attaching clip 4 can be folded away from the adapter 5 (in the direction of arrow B) and removed. The pressure exerted on the adapter 5 by claws 37 , 39 thus comes to an end which facilitates its dismounting.
The second embodiment of the needle guide system of the invention shown in FIG. 6 comprises four elements: a revolver 1 , an journal clip 2 , a locking clip 3 , and an attaching clip 4 . The four elements 1 , 2 , 3 , 4 of the second embodiment fully correspond to elements 1 , 2 , 3 , 4 of the first embodiment and are therefore identified by same reference numbers. In the second embodiment the mounting portion of the adapter 5 of the first embodiment is incorporated in the transducer 80 on which the attaching clip 4 is directly mounted. | A needle guide system for a medical imaging instrument comprises a needle guide assembly ( 1, 2 ) and a mounting assembly ( 3, 4 , optionally 5 ) for attaching the needle guide assembly to a transducer, the mounting assembly comprising self-destroying means effective on dismounting. The mounting assembly comprises an attaching clip ( 4 ) mountable on a transducer directly or via an adapter ( 5 ), and a locking clip ( 3 ) mountable on the attaching clip from which it can be dismounted easily only by breaking indications of fracture comprised by the attaching clip. The needle guide assembly ( 1, 2 ) comprises a revolver ( 1 ) capable of receiving needles of varying diameter and a journal clip ( 2 ) by which it is mounted on the locking clip ( 3 ). | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of International Patent Application No. PCT/CN2006/002359 with an international filing date of Sep. 12, 2006, designating the United States, now pending, and further claims priority benefits to Chinese Patent Application No. 200510019781.X filed Nov. 11, 2005. The contents of these specifications are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a highly effective method for removing and separating ammonia nitrogen from solutions.
2. Description of the Related Art
A number of industries produce ammonia waste, including ammonia plants in the petrochemical industry, coking plants in the steel industry, and fertilizer plants in the agrochemical industry. Ammonia is a dangerous water pollutant that adversely affects human health. Accordingly, much research has been focused on the development of methods for removal of ammonia from solutions.
These methods include microbial degradation, steam stripping, gas stripping, ion exchange, adsorption, electrolysis, membrane separation, precipitation, oxidation, breakpoint chlorination, wet oxidation, etc. Most of these methods work well in theory but in practice suffer from high operational cost and difficult implementation. Only the first three of the methods listed above, i.e., microbial degradation, steam stripping, and gas stripping, are used commercially, as illustrated below.
Flow
Conventional
Concentration
rate
treatment
Operational
Typical
Category
(mg/L)
(m 3 /h)
method
Efficiency
cost
industry
High
>10000
0-100
Steam
Good
High
Ammonia
stripping
plants
Mid-high
200-10000
0-500
Gas stripping
Low; very
High
Ammonia
low at low
plants;
temperatures
Catalyst
factories
Low
<200
0-1000
Biological
Good
Low
Sewage
and up
degradation
treatment
plants
Ammonia nitrogen at high concentrations is amenable to steam stripping. Based on the difference in solubility at different temperatures, ammonia present in high concentrations is removed from the liquid phase by increasing solution temperature by means of steam. Meanwhile, ammonia is recycled or converted into ammonium salt generating revenue.
Ammonia nitrogen at low concentrations (mainly domestic sewage at 30-50 mg/L) is usually removed via biological methods. However, with the increase of NH 3 —N concentration, the operational cost increases significantly. For example, since 4.73 kg of O 2 is theoretically required for removing 1 kg of ammonia nitrogen (while only 0.7-1.2 kg of O 2 is required for removing 1 kg of BOD 5 ), oxygen must be supplied by an air diffuser or an air fan, increasing energy consumption.
When NH 3 -N in waste water increases to about 70 mg/L, a carbon source concentration of 280 mg/L is required for removal of ammonia, while the BOD of regular domestic sewage is 150-250 mg/L. Therefore, extra carbon source (such as methanol) is required, which results in significant increase in operating costs. Hence, biological treatment works well only on NH 3 -N concentration of less than 100 mg/L. It should be pointed that when the NH 3 -N concentration is greater than 150 mg/L, the growth of common microbes is inhibited, which leads to poor removal of ammonia.
Mid-high concentration of ammonia often comes in waste water from waste leachate, and the petrochemical industry. There is no economical and effective conventional method of treatment for this type of waste water. If steam stripping is used, steam consumption is high relative to the value of recycled ammonia; if biological methods are employed, implementation is difficult and impracticable. Therefore, the gas stripping method is commonly used as the lesser of two evils.
The stripping method used to remove soluble ammonia from aqueous solutions is exemplified in FIG. 1 . An external gas (carrier gas) is fed into a stripping tower where it passes against finely dispersed particles of ammonia-containing solution. In this way the gas-liquid interface is increased and soluble ammonia transfers from the liquid phase into the gas phase. Air is usually used as the carrier gas and the pH value of the ammonia-containing solution is adjusted to about 11 or higher by adding an alkali base, so as to convert ammonium ions (NH 4 + ) dissolved in water to NH 3 molecules. In the stripping tower, the aqueous solution is dispersed into small droplets or water mist, NH 3 from the liquid phase is transferred into gas phase, and then carried away from the stripping tower with the carrier gas introduced by a blower.
The stripping tower is equipped with a packing layer having a certain height. Ammonia-containing solution is sprayed from the top of the tower, and flows downward along a surface of the packing. Air is blown from the bottom of the tower up, and continuously contacts with the solution. The disadvantages of the stripping method are include low efficiency (40-60% at normal temperature), and high operating cost due to the need to frequently replace the packing and clean the tower. Moreover, in winter when the temperature is low, the stripping method has very low removal efficiency due to a higher solubility of ammonia in colder water. Heating of waste water to remove ammonia in this process is not economical.
Since the gas-to-water ratio in the gas-stripping method is high, the energy consumption for this process is also relatively high. Normal cost for the gas stripping method of removal of ammonia nitrogen is about 1.5 USD or above per cubic meter. In addition, the concentration of residual ammonia nitrogen in waste water from which ammonia was removed by the gas stripping method is between 200-500 mg/L, and does not meet the discharge standard. Therefore, further treatment is often necessary.
GB Pat. Appl. Publ. No. GB2383034A describes a method for treating liquid containing ammonia, comprising the following steps: spraying an alkaline liquid from the center of a cylindrical vessel in the shape of an umbrella, allowing the water stream to hit the walls of the vessel, forcing air or nitrogen to flow in a tangential direction to the vessel walls, so as to form a cylindrical gas-liquid interface, allowing the gas to discharge from the top of the vessel, and the liquid to flow out downwardly from the bottom of the vessel. The GB application publication particularly emphasizes that the gas stream must enter in a tangential direction to form a spiral shape, and the vessel must be a cylinder without any obstacles therein.
However, the method does not use highly-dispersed micrometer- or nanometer-sized liquid particles. The nozzle of the stripping tower usually uses a reflective-I type, a reflective-II type or any other low water pressure nozzle with a water pressure of approximately 1 kg/cm 2 . To enlarge the gas-liquid contact surface, the stripping method relies on the generation of a liquid film (the liquid is liquid film or liquid drops with comparatively large particles instead of small particles), and the gas and the liquid form eddies in the cylinder to increase the contact surface. The efficiency is low and the operational costs are high.
SUMMARY OF THE INVENTION
One objective of the invention is to provide a highly dispersive method and device for removing ammonia nitrogen from solution, which feature high removal efficiency, low cost, and infrequent maintenance.
In one embodiment, the method for removing ammonia nitrogen from solution comprises: a) adjusting the pH of the ammonia-containing solution to above 10 by adding a base; b) atomizing the ammonia-containing solution to produce an ammonia-containing mist so as to increase the gas-liquid interface and allow ammonia to transfer from the ammonia-containing mist to an ambient gas yielding a clean mist; and c) re-aggregating the clean mist.
In a class of this embodiment, the pH value of the solution is adjusted to 10 or above with a base (such as calcium hydroxide, sodium hydroxide, etc.), and after being mixed and compressed, the solution is dispersed into a spray or mist via a liquid atomizer or a nozzle.
In a class of this embodiment, the particle size of the spray or mist is on the order of microns or nanometers.
In a class of this embodiment, the smaller the size of dispersed particles, the higher the removal efficiency. Any type of liquid atomization technique can be used as long as the solution is dispersed into micro-sized or nano-sized particles.
In a class of this embodiment, the process or a portion thereof is implemented in open air or in a vessel.
In a class of this embodiment, when the process or a portion thereof is implemented in a vessel, a carrier gas is additionally introduced to force out of the vessel ammonia transferred from the ammonia-containing mist to ambient gas, or removing ammonia transferred from the ammonia-containing mist to ambient gas out of the vessel by using vacuum. The externally-supplied gas has the function of forcing separated NH 3 particles to flow out of the system. The gas may be nitrogen, or any other suitable gas.
In a class of this embodiment, when the process or a portion thereof is implemented in open air, natural wind flow accelerates the transfer of ammonia from the liquid phase to the gas phase.
In a class of this embodiment, the position of the atomizer or the nozzle of the atomization device in the air or the atomization chamber, the angle of spraying may be freely adjusted as required to maximize efficiency.
In a class of this embodiment, multiple atomizers or nozzles may be employed.
In a class of this embodiment, the base is Ca(OH) 2 .
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram illustrating a gas stripping method of the prior art;
FIG. 2 is a process flow chart illustrating a method of removing ammonia nitrogen according to one embodiment of the invention;
FIG. 3 is a schematic diagram of the method of removing ammonia nitrogen where atomization is directly implemented in the air according to another embodiment of the invention;
FIG. 4 is a flowchart illustrating a method of removing ammonia nitrogen according to another embodiment of the invention;
FIG. 5 is a schematic diagram of the method of removing ammonia nitrogen where atomization is directly implemented in the air according to another embodiment of the invention;
FIG. 6 ( 1 ) is a process flow chart illustrating a method of removing ammonia nitrogen according to one embodiment of the invention wherein another kind of gas is utilized in the atomization chamber;
FIG. 6 ( 2 ) is a process flow chart illustrating a method of removing ammonia nitrogen according to one embodiment of the invention employing vacuum atomization chamber;
FIG. 7 illustrates one design of a vacuum atomization chamber used in the methods of the invention;
FIG. 8 illustrates another design of a vacuum atomization chamber used in the methods of the invention;
FIG. 9 illustrates yet another design of a vacuum atomization chamber used in the methods of the invention;
FIG. 10 illustrates still further design of a vacuum atomization chamber used in the methods of the invention;
FIG. 11 is illustrates one design of an atomizing nozzle used in the methods of the invention; and
FIG. 12 is a process flow chart illustrating a method of removing ammonia nitrogen according to yet another embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
Preferred embodiments of the invention will now be described in connection with FIGS. 2-12 . Referring specifically to FIG. 2 , in a process flowchart of a method for removing ammonia from a solution, the following elements are employed: 1 —adjustment of the pH value of a solution; 2 —pressure pump; 3 —atomization chamber; 4 —air-induction device; 5 —post treatment of gas containing ammonia; 6 —air, N 2 , or other gas medium; 7 —clean solution, 8 —base; 9 —gas-liquid separation.
The configuration of the pressure pump 2 depends on the working condition so as to ensure a certain pressure of the solution flowing into the atomization chamber.
Based on the concentration of ammonia-nitrogen in the solution to be treated and treating requirements, the atomization chamber 3 can be set to one or multiple levels.
FIG. 3 is a flowchart of atomization implemented in open air in a scenario where NH 3 is emitted in the air. In FIG. 3 , 11 indicates a nozzle.
FIG. 4 illustrates another embodiment of a method for removing ammonia from a solution. The adjustment of the pH value 1 may be performed in a solution circulating pool 10 . The method is applicable for a condition where water flows in and out discontinuously. In FIG. 4 , 10 indicates the solution circulating pool.
FIG. 5 is another flowchart of atomization implemented in open air combined with adjusting of pH in a solution circulating pool 10 . The method is applicable for a condition where water flows in and out discontinuously.
Referring to FIGS. 6 ( 1 ) and 6 ( 2 ), 12 indicates a blowing device, and 13 indicates a vacuum pump. The blowing device 12 supplies carrier gas to the atomization chamber 3 by blowing. Alternatively, carrier gas is passed through the atomization chamber 3 by means of vacuum pump 13 .
FIGS. 7-10 illustrate various alternative designs of the atomization chamber 3 . Referring to FIG. 11 , the atomizing nozzle may be oriented upward, downward, sideways, and any other direction. Referring to FIG. 12 , another embodiment for implementing gas-liquid separation is shown.
Implementing the apparatus and methods of the invention overcomes difficulties encountered in prior art.
Firstly, the invention has good applicability, is applicable to solutions with high, medium and low ammonia nitrogen concentration, and is capable of directly reducing ammonia nitrogen to meet an emission standard without using any other method.
Secondly, the removal efficiency of the method at any concentration of ammonia nitrogen is high.
Thirdly, unlike the gas stripping method which has low removal efficiency at lower temperatures (e.g., in winter), the method of this invention has no restrictive requirement on temperature.
Fourthly, the treatment process of the invention is simple and easily applied commercially.
Finally, the cost of operation is low. The base accounts for a large portion of cost. In the stream stripping method and the gas stripping method, the base is usually NaOH instead of Ca(OH) 2 (cost of the latter is ⅓ than that of the former) due to problems caused by Ca(OH) 2 such as block of packing in the tower and so on.
It was discovered in connection with this invention that better efficiency is obtained if Ca(OH) 2 is used to adjust the pH value.
Initially, the NH 3 in the solution is prone to escape from a liquid surface and transfer to the gas phase, and finally steady state is realized, namely the rate at which NH 3 transfers from the aqueous to the gas phase is the same as that from the gas phase to the aqueous phase.
In an unsteady state, the rate of NH 3 transfer to the gas phase depends on the temperature of liquid, nitrogen pressure in the gas phase, and the gas-liquid contact area. As the temperature is constant, escape of NH 3 may speed up by decreasing nitrogen pressure in the gas phase and increasing the gas-liquid contact area. That is, to improve the removal efficiency, the overall area of liquid per unit volume must be increased; and the nitrogen pressure in the gas phase should be decreased. Since fast transfer of NH 3 to the gas phase is effectively implemented, less gas is consumed, and higher efficiency is obtained.
The higher the dispersion is, the larger the surface area is, the more NH 3 escapes, and the higher the removal efficiency will be. The invention disperses liquid into micro-graded or nano-graded dewdrops in the atomization chamber as required and enables gas to quickly flow through, thus NH 3 on the surface of the mist quickly transfers into the gas phase and nitrogen is removed.
Gas-liquid separation may be further performed on the gas-liquid mixture. After separation, post-treatment of gas containing NH 3 may employ techniques known in the art, and a post-treatment method for gas containing NH 3 may be utilized.
EXAMPLES
Detailed description of the invention will be given below, but the invention is not to be limited to the following embodiments.
Example 1
Ammonia Nitrogen Removal Using Steam Stripping of Prior Art
Waste water from a chemical factory contained ammonia nitrogen at a concentration of 3.29×10 3 mg/L. If Ca(OH) 2 were used, the packing tower would be easily be blocked, therefore after NaOH was used to raise the pH value, steam was heated to 45° C. and then the waste water was treated by stripping two times. The total removal efficiency was less than 50%. Calculated operating cost were comparatively high and the treated water still did not meet the national emission standard. Therefore, the treated water was mixed with and diluted by waste water containing less ammonia nitrogen, and was transmitted to a municipal wastewater treatment plant for treating via biological methods.
Example 2
Ammonia Nitrogen Removal Using Methods of this Invention
Waste water from the above-mentioned plant was processed using methods of the invention. The treatment conditions were: water temperature 15° C., the lift of the pump 45 m, the flow rate 2.8 m 3 /h, the power 550 W; type of the nozzle WFCS-0.5-90-304SS, 0.5 T/h, the fan characteristics were: air volume 1000 m 3 /h, air pressure 700 Pa, power 250 W. To water sample of 25 kg 200 g of calcium oxide was added, raising the pH value to 12. A second treatment was performed after the first treatment, the ammonia nitrogen concentration was reduced to 47 mg/L. The removal efficiency of 99% was reached and the treatment cost was approximately ¼-½ that of the steam stripping method.
Example 2
Ammonia Nitrogen Removal Using Methods of this Invention
Conditions were similar to those in Example 2, except that the water temperature was 19° C., and ammonia nitrogen concentration was 3.30×10 3 mg/L. Calcium oxide was added to adjust the pH value to 13. A small atomizer was used and the waste water was processed in open air. The ammonia nitrogen concentration after the first treatment was 445 mg/L, the removal efficiency was 86.6%, and the water temperature was reduced to 17° C. After a second treatment, the ammonia nitrogen concentration is reduced to 54 mg/L, and the overall removal efficiency was 98.3%.
Example 3
Ammonia Nitrogen Removal Using Methods of this Invention
Conditions were similar to those in Example 2, except that water temperature was 20° C., and the waste water was diluted for ammonia nitrogen concentration to reach 53.0 mg/L. Calcium oxide was added, and the pH value was adjusted to 12. A small atomizer was used. The ammonia nitrogen concentration of the solution after spraying in open air was reduced to 9.0 mg/L, which meets the national standard. The removal efficiency was 85%.
Example 4
Ammonia Nitrogen Removal Using Methods of this Invention
Conditions were similar to those in Example 2, except that water temperature was 19° C., and the ammonia nitrogen concentration is 210 mg/L. Calcium oxide was added to the waste water to adjust the pH value to 10. A small sprayer was used and spaying processing is performed in open air. The ammonia nitrogen concentration after first pass was 82 mg/L. The removal efficiency was 61%. After a second treatment, the ammonia nitrogen concentration was reduced to 46 mg/L, and the overall removal efficiency was 78%. | Taught is a method for removing ammonia nitrogen from an ammonia-containing solution via atomization, comprising a) adjusting the pH of the ammonia-containing solution to above 10 by adding a base; b) after mixing, atomizing the ammonia-containing solution to produce an ammonia-containing mist so as to increase the gas-liquid interface and allow ammonia to transfer from the ammonia-containing mist to an ambient gas yielding a clean mist; and c) re-aggregating said clean mist. The method is applicable for treatment of liquids containing high, medium and low ammonia nitrogen concentration. | 2 |
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH
This invention was made with Government support under Grant Nos. 2007-35203-18274 and 2011-67015-20025 from the USDA National Institute of Food and Agriculture (USDA-NIFA). The Government has certain rights in the invention.
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the priority of U.S. Provisional Appl. Ser. No. 61/630,345, filed Dec. 9, 2011, the entire disclosure of which is incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to a composition and method of use for artificial insemination. More specifically, the invention relates to a sperm-stimulating additive to be employed in artificial insemination of farm animals and in vitro fertilization and embryo culture in human infertility clinics.
BACKGROUND OF THE INVENTION
Artificial insemination (AI) is a common technique in swine and cattle farming. Freshly ejaculated boar semen must be stored in extender solution for preservation at 15-18° C. or 4-5° C., and bull semen has to be extended prior to cryopreservation and storage in liquid nitrogen. Various types of extender solutions and compounds have been developed to reduce the metabolic activity of sperm and allow for extended preservation. However, new and improved culture media and/or sperm extenders are needed to improve artificial insemination in animals and in vitro fertilization and embryo culture in humans.
SUMMARY OF THE INVENTION
In one aspect, the invention provides a sperm preservation media comprising inorganic pyrophosphate (PPi). In one embodiment, the concentration of PPi is between about 1 μM and about 200 μM. In another embodiment, concentration of PPi is between about 1 μM and about 20 μM. In another embodiment, the concentration of PPi is about 10 μM. In still another embodiment, the preservation media is used to preserve sperm from a porcine.
In another aspect, the invention provides a media for sperm transfer comprising inorganic pyrophosphate (PPi). In one embodiment, the concentration of PPi is between about 1 μM and about 200 μM. In another embodiment, the concentration of PPi is between about 1 μM and about 20 μM.
Another aspect of the invention provides a media for in vitro fertilization (IVF) or artificial insemination (AI) comprising inorganic pyrophosphate (PPi). In one embodiment, the concentration of PPi is between about 1 μM and about 200 μM. In another embodiment, the concentration of PPi is between about 1 μM and about 20 μM.
In another aspect, the invention provides a semen sexing method, comprising: (a) seperating a mixed sperm suspension in a first culture medium into a population of x-bearing or y-bearing sperm with the aid of an elutant medium; (b) preserving the x-bearing or y-bearing sperm in a second culture medium, wherein, inorganic pyrophosphate (PPi) is added to the first culture medium, the elutant medium or the second culture medium.
In still another aspect, the invention provides a method of sperm preservation comprising storing sperm in a media comprising inorganic pyrophosphate (PPi). In one embodiment, the concentration of PPi is between about 1 μM to about 200 μM. In other embodiments, the concentration of PPi is between about 1 μM to about 20 μM or the concentration of PPi is about 10 μM. In still another embodiment, the sperm is stored in the media comprising PPi for up to 10 days.
Another aspect of the invention provides a method of in vitro fertilization (IVF) comprising contacting an oocyte with sperm in the presence of inorganic pyrophosphate (PPi). In one embodiment, the concentration of PPi is between about 1 μM to about 200 μM. In another embodiment, the concentration of PPi is between about 1 μM to about 20 μM. In another embodiment, the sperm is stored in the presence of PPi.
In another aspect, the invention provides a method of culturing an embryo comprising culturing an embryo in a media comprising inorganic pyrophosphate.
In still another aspect, the invention provides a method of artificial insemination comprising providing sperm and inorganic pyrophosphate (PPi) to the reproductive tract of a female. In an embodiment, the PPi is gradually released into the reproductive tract of the female.
Another aspect of the invention provides a method of maturing an oocyte in vitro comprising culturing the oocyte in a media comprising inorganic pyrophosphate.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 : Shows measurement of pyrophosphate (PPi) content by fluorometric assay. (A) Fluorescence intensity of PPi standards (final conc. 0-200 μM PPi). (B) PPi assay with boar seminal plasma (SP), porcine oviductal fluids (pOVF), rabbit sera, mouse sera (final conc. 10 μg/ml), boar spermatozoa (1×10 6 spermatozoa/ml) and 10 mM H 2 O 2 working solution (negative control). The fluorescence intensities were measured at multiple time points to follow the reaction kinetics (Excitation 530 nm; emission 590 nm). Experiments were repeated three times. Values are expressed as the mean of fluorescence intensity.
FIG. 2 : Shows generation of PPi. PPi is produced by the hydrolysis of ATP into AMP in cells. Inorganic pyrophosphatase (PPA1) catalyzes the hydrolysis of PPi to form 2 orthophosphates (2Pi), resulting in energy release.
FIG. 3 : Shows detection of inorganic pyrophosphatase (PPA1) by western blotting. Boar seminal plasma (SP; 20 μg/ml), porcine oviductal fluid (pOVF; 100 μg/ml), and boar, bull, mouse, and human spermatozoa (all at 1×10 6 spermatozoa/ml) were extracted to perform the protein analysis. Equal protein loads were used. Distinct band at ˜32 kDa was detected by rabbit polyclonal anti-PPA1 antibody. The purified PPA1 (extreme right lane; 1 μg/ml; Sigma I1643) from S. cerevisiae was used as a control protein.
FIG. 4 : Shows localization of inorganic pyrophosphatase (PPA1; red) in spermatozoa by immunofluorescence. (A, B) Whole-mount immunofluorescence of boar spermatozoa. Most prominent labeling is observed in the sperm tail connecting piece and in the postacrosomal sheath of the sperm head. (C) Identical labeling was observed in spermatozoa attached to oocyte zona pellucida at 30 min after gamete mixing during IVF. (D) Negative control with anti-PPA1 antibody immunosaturated with full-length PPA1 protein. DNA was counterstained with DAPI (blue). Epifluorescence micrographs were overlapped with parfocal transmitted light photographs acquired with DIC optics.
FIG. 5 : Shows sperm viability and mitochondrial membrane potential during sperm storage with/without PPi. (A) Percentages of viable spermatozoa based SYBR14 (live sperm) and PI (dead sperm) labeling. (B) Percentages of spermatozoa with polarized (live), depolarizing (dying) and depolarized (dead) mitochondrial membranes. Experiments were repeated three times. Values are expressed as the mean percentages±SEM. Different superscripts a & b in each group of columns denote a significant difference at p<0.05.
FIG. 6 : Shows the effect of PPi on proteasomal enzymatic activities of stored boar spermatozoa. Fresh boar spermatozoa were stored in BTS with and without 10 μM PPi for 3 or 10 days (No treat/PPi+BTS). Proteasomal proteolytic and deubiquitinating activities were measured using specific fluorometric substrates Z-LLE-AMC (A), Z-LLVY-AMC (B), Z-LLL-AMC (C) and ubiquitin-AMC (D). In a separate treatment, PPi was added before measurement to spermatozoa preserved without PPi (Add PPi). As a negative control, 10 μM MG132 (a proteasomal inhibitor) was added to “No treat” and “PPi+BTS” spermatozoa on day 3. Experiments were repeated three times. Values are expressed as the mean of fluorescence intensity.
FIG. 7 : Shows the effect of PPi on total and polyspermic fertilization during porcine IVF. Values are expressed as the mean percentages±SEM. □ % monospermic and ▪ % polyspermic oocytes. Different superscripts a-c in each group of columns denote a significant difference at p<0.05. Numbers of inseminated ova are indicated in parentheses. (A) Porcine oocytes matured in vitro were inseminated with a standard concentration of 1×10 6 spermatozoa/ml, in the presence of ascending concentrations of PPi. Experiments were repeated five times. (B) The polyspermy rates, reflective of sperm fertilizing ability in vitro (same as panel A) dramatically increased in the presence of PPi. (C) Fertilization rates of porcine oocytes inseminated with different concentrations of spermatozoa in the presence/absence of 10 μM PPi. Experiments were repeated three times. (D) Fertilization rates of oocytes inseminated with boar spermatozoa preserved for 3 days in BTS with/without 10 μM PPi. Other porcine oocytes were inseminated (sperm conc. 5×10 5 spermatozoa/ml) with and without 10 μM PPi, with spermatozoa stored with and without PPi. Experiments were repeated three times. (E) Effect of extrinsic PPA1 enzyme on porcine IVF. Oocytes were inseminated with different concentrations of purified PPA1 protein. Experiments were repeated twice. (F) Porcine oocytes were inseminated in the presence of rabbit polyclonal anti-PPA1 antibody or non-immune rabbit serum (a control of PPA1 antibody). Experiments were repeated twice.
FIG. 8 : (A) Shows the effect of PPi on sperm-zona binding. Porcine oocytes were inseminated (sperm conc. 5×10 5 spermatozoa/ml) with various concentrations of PPi for 30 min, fixed and stained with DNA stain DAPI. The numbers of spermatozoa bound per zona-pellucida (ZP) were counted under epifluorescence microscope. Values are expressed as the mean±SEM. Different superscripts a-c in each group of columns denote a significant difference at p<0.05. Numbers of inseminated ova are indicated in parentheses. (B) The percentage of acrosome-reacted spermatozoa of panel A (PNA-FITC stained). Values are expressed as the mean percentages±SEM. Different superscripts a & b in each group of columns denote a significant difference at p<0.05. (C) Effect of PPi supplementation on the viability of spermatozoa stored in commercial and custom made BTS extenders. Boar spermatozoa were preserved in BTS-IMV (IMV technologies, France) or BTS-HM (homemade) with and without 10 μM PPi for 7 days at room temperature. Sperm motilities were evaluated by observation under light microscopy at 37.5° C. Higher sperm motility was observed in BTS-IMV with PPi on day 6 than in any other group. Experiments were repeated twice. Different superscripts a, b in each group of columns denote a significant difference at p<0.05. (D) Excessive concentrations of PPi were added into IVF medium. Fertilization rates decreased with high concentrations of PPi. Experiments were repeated twice. Values are expressed as the mean percentages±SEM. □ % monospermic and ▪ % polyspermic oocytes. Numbers of inseminated ova are indicated in parentheses. (E) Effect of PPi on fertilization with spermatozoa stored in commercial extender, BTS-IMV. Nearly 100% fertilization was achieved using spermatozoa preserved in BTS-IMV with 10 μM PPi (day 3). Experiments were repeated twice. Values are expressed as the mean percentages±SEM. □ % monospermic and ▪ % polyspermic oocytes. Numbers of inseminated ova are indicated in parentheses.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides novel media and methods for sperm preservation, embryo culture, in vitro fertilization (IVF), artificial insemination (AI). In particular, the present invention represents an advance in the art in that it reports and confirms that inorganic pyrophosphate (PPi) exists in spermatozoa, seminal plasma (SP) and oviductal fluids (OVF) of mammalian species, though the previous studies have shown that the concentration of cytosolic PPi is precisely regulated in mammalian cells (Baykov et al., Prog Mol Subcell Biol 23:127-150, 1999; Sivula et al., FEBS Lett 454:75-80, 1999). In one aspect of the invention, PPi might therefore be used as an energy source for sperm viability.
In one embodiment, the present invention provides a new and improved sperm preservation media, also referred to as sperm extender that can extend semen storage period and maintain sperm viability, and thus improve AI in animals. The invention also provides a new and improved culture media for embryo transfer in animals.
In another embodiment, invention provides a new and improved method of IVF and AI as well as embryo culture media in an animal and human clinic.
In still another aspect of the invention, a new and improved method for semen sexing employing PPi is described. The present semen sexing method comprises the step of adding a certain amount of PPi in the media during a semen sexing procedure to enhance the sperm longevity and viability. For instance, according to certain embodiments of the invention, the present semen sexing method may comprise the step of adding PPi in the starting sperm processing media (with both x- and y-bearing sperm; before the conventional separation/sorting step), in the eluting media, or in the sex-separated sperm media.
Traditionally, Beltsville thawing solution (BTS) is added to frozen-thawed sperm as a thawing solution, and is also used for liquid storage for 3-5 days (Johnson et al., Zuchthygiene 23:49-55, 1988). Liquid semen extended by BTS has typically been utilized for AI due to its simple composition and developments of transportation. However, the motility of sperm preserved in extender gradually decreases during storage from natural aging, loss of ATP and cAMP, as well as reduced calcium uptake (Johnson et al., Anim Reprod Sci 62 143-172, 2000). Extended semen preserved for 5 days after collection shows a reduction in farrowing rates of approximately 50% compared to semen preserved for 2 days after collection, which shows a reduction in farrowing rates of approximately 65-70% (Johnson et al., Anim Reprod Sci 62 143-172; Johnson et al., Zuchthygiene 23:49-55, 1988; Johnson and Rath, (Eds), Proc. 2 nd Int. Conf. Deep Freezing Boar Semen. Reprod. Domest. Anim., Suppl. 1, p. 402, 1991; Rath et al., (Eds) Proc. Int. Conf. Deep Freezing of Boar Semen. Reprod. Domest. Anim. Suppl. 1. p. 342, 1996; Johnson, Proc. 15 th Int. Pig Vet. Sci. Congress 1, 225-229, 1998). Recently, Yeste et al. ( Anim Reprod Sci 108:180-195, 2008) suggested that addition of prostaglandin F 2α (PGF 2α ) to sperm diluted in BTS maintained better sperm viability and motility after 6 days of cooling.
Inorganic pyrophosphate (PPi) is a potent, mineral-binding small molecule inhibitor of crystal nucleation and growth (Fleisch et al., Nature 212:901-903, 1966), and presents in the extracellular matrix of most tissues and body fluids including plasma (Fleisch et al., Am J Physiol 203:671-675, 1962; Russell et al., J Clin Invest 50:961-969, 1971). PPi metabolism has been observed in cultured hepatocytes and chondrocytes (Davidson et al., Biochem J 254:379-384, 1988; Johnson et al., 1999; Rosen et al., Arthritis Rheum 40:1275-1281, 1997; Rosenthal et al., Calcif Tissue Int 59:128-133, 1996; Rosenthal et al., J Rheumatol 26:395-401, 1999; Ryan et al., Arthritis Rheum 42:555-560, 1999). The intracellular PPi is generated in the mitochondria, and intra- and extracellular PPi concentrations are regulated by mitochondrial energy metabolism (Davidson et al., Biochem J 254:379-384, 1988; Johnson et al., Arthritis Rheum 43:1560-1570, 2000). In prokaryotes, PPi provides “high energy” compound, and is able to substitute for ATP in glycolysis-related reactions under attenuated respiration (Chi et al., J Biol Chem 275:35677-35679, 2000). Moreover, PPi produces a mitochondrial membrane potential with PPA (Pereira-da-Silva et al., Arch Biochem Biophys 304:310-313, 1993), and ATP-derived PPi serves as a phosphate donor in protein phosphorylation in yeast mitochondria as well as in mammalian cells (da Silva et al., Biochem Biophys Res Commun 178:1359-1364, 1991; Terkeltaub et al, Am J Physiol Cell Physiol 281:C1-C11, 2001). Consequently, PPi may be used as an energy source for viability.
Cellular PPi is yielded by various biosynthetic processes, and hydrolyzed to two inorganic phosphates (Pi) by inorganic pyrophosphatase (PPA1). PPA1 is a ubiquitous metal-dependent enzyme providing a thermodynamic pull for many biosynthetic reactions, such as DNA, RNA, protein, polysaccharide synthesis and cell life (Chen et al. 1990, Lundin et al. 1991, Sonnewald 1992, Lahti 1983, Peller 1976). The PPA1 has been detected in bacteria (Chen et al. 1990) and yeast (Lundin et al. 1991), and the soluble PPA1 was identified and characterized in Mycoplasma suis , which belongs to hemotrophic bacteria that attach to the surface of host erythrocytes (Hoelzle et al.). However, the PPi has not been used in any media related to sperm preservation or AI or IVF procedures.
The present invention identifies the PPi pathway as an important component of mammalian sperm physiology. Referring to FIG. 2 , PPi (P 2 O 7 4− ) is formed by the hydrolysis of ATP into AMP in cells, then, hydrolyzed by inorganic pyrophosphatase (PPA1) into two molecules of inorganic orthophosphate (Pi). PPA1, an important enzyme for energy metabolism (Chen et al., J Bacteriol 172:5686-5689, 1990; Lundin et al., J Biol Chem 266:12168-12172, 1991), has been implicated in the regulation of metabolism, growth and development in plants (Sonnewald, Plant J 2:571-581, 1992), and even in the development and molting in the parasitic roundworm Ascaris (Islam et al., Infect Immun 73:1995-2004, 2005). During cell division of S. cerevisiae , PPA1 is essential for mitochondria genome replication (Lundin et al., Biochim Biophys Acta 1098; 217-223, 1992).
While PPA1 is detectable in the sperm tail connecting piece, harboring sperm centriole and anchoring flagellar outer dense fibers and microtubule doublets, the invention suggests that from these locations, the PPi-metabolizing pathway may convey energy for flagellar movement and for acrosomal function during sperm-zona penetration. In addition, the invention also suggests that the PPi pathway in the sperm head and flagellum may support protein phosphorylation during sperm capacitation that is observed both in vitro and in vivo, in the oviductal sperm reservoir.
The invention further describes the ability of mammalian spermatozoa to utilize PPi as an energy source during sperm transport and sperm-egg interactions, as the spermatozoa undergo capacitation, acrosome reaction and sperm-zona penetration. It is presently disclosed that PPi can be used as a stable, inexpensive energy source to improve sperm viability during semen storage and transfer for large animal biotechnology and to enhance sperm penetration and fertilization rates enhance for assisted reproductive therapy in mammalian species (including humans). The invention further provides the addition of PPi in the culture media, the sperm extender, the IVF media, or in media employed in sperm sexing to provide beneficial effects in sperm preservation and fertilization, such as increasing sperm longevity and viability during sperm preservations and transfers and maintaining and enhancing sperm viability, penetration and fertilization rates during fertilization procedures.
Media of the present invention may therefore comprise PPi, the concentration of which may vary depending on the animal species. In certain embodiments, media of the present invention may comprise about 1 to 200 μM of PPi. In another embodiment, media of the present invention may comprise about 1 to 20 μM. The present invention may be employed for various mammals, including farm animals, such as, boar and bull.
For IVF or AI, PPi may be directly added or gradually released into the media. If needed, PPi release can be exactly controlled/modulated during AI, especially when the PPi-containing slow release gel is employed as a part of AI catheter, to gradually release PPi into the female reproductive tract.
Unless otherwise defined, 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 invention belongs. All publications, patent application, patents, and other references mentioned herein are incorporated by reference in their entirety.
EXAMPLES
The following disclosed embodiments are merely representative of the invention which may be embodied in various forms. Thus, specific structural, functional, and procedural details disclosed in the following examples are not to be interpreted as limiting.
Example 1
Semen Collection and Processing
Semen was collected from proven fertile adult Duroc boars 15-22 months of age under the guidance of approved Animal Care and Use Committee (ACUC) protocols of the University of Missouri-Columbia (UM-C). The boars were placed on a routine collection schedule of one collection per week. The sperm-rich fraction of ejaculate was collected into an insulated vacuum bottle. Sperm-rich fractions of ejaculates with greater than 85% motile spermatozoa were used. Semen volumes were determined with a graduated cylinder. Sperm concentrations were estimated by a hemocytometer (Fisher Scientific, Houston, Tex.). The percentage of motile spermatozoa was estimated at 38.5° C. by light microscopy at 250× magnification. Semen was slowly cooled to room temperature (20-23° C.) by 2 h after collection and diluted with Beltsville thawing solution (BTS; 3.71 g glucose, 0.60 g trisodium citrate, 1.25 g ethylenediamine tetraacetic acid, 1.25 g sodium bicarbonate, 0.75 g potassium chloride, 0.06 g penicillin G, and 0.10 g streptomycin in 100.0 ml distilled water) (Pursel and Johnson 1975) diluent to a final concentration of 35×10 6 spermatozoa/ml in 100 ml of BTS diluent. The diluted semen was stored in Styrofoam™ boxes at room temperature for 10 days. Unless otherwise noted, all chemicals used in this study were purchased from Sigma Chemical Co. (St. Louis, Mo.).
Example 2
Collection and in Vitro Maturation (IVM) of Porcine Oocyte
Ovaries were collected from prepubertal gilts at a local slaughterhouse and transported to the laboratory in a warm box (25-30° C.). Cumulus oocyte complexes (COCs) were aspirated from antral follicles (3-6 mm in diameter), washed three times in HEPES-buffered Tyrode lactate (TL-HEPES-PVA) medium containing 0.01% (w/v) polyvinyl alcohol (PVA), and then washed three times with maturation medium (Abeydeera et al., Biol Reprod 58:1316-1320, 1998). Each time, a total of 50 COCs were transferred to a 4-well multidish (Nunc, Roskilde, Denmark) containing 500 μl of maturation medium that had been covered with mineral oil and equilibrated at 38.5° C. with 5% CO 2 in the air. The medium used for oocyte maturation was tissue culture medium (TCM) 199 (Gibco, Grand Island, N.Y.) supplemented with 0.1% PVA, 3.05 mM D-glucose, 0.91 mM sodium pyruvate, 0.57 mM cysteine, 0.5 μg/ml LH (L5269, Sigma), 0.5 μg/ml FSH (F2293, Sigma), 10 ng/ml epidermal growth factor (E4127, Sigma), 10% porcine follicular fluid, 75 μg/ml penicillin G, and 50 μg/ml streptomycin. After 22 h of culture, the oocytes were washed twice and cultured in TCM199 without LH and FSH for 22 h at 38.5° C., 5% CO 2 .
Example 3
In Vitro Fertilization (IVF) and Culture of Porcine Oocyte
After oocyte maturation, cumulus cells were removed with 0.1% hyaluronidase in TL-HEPES-PVA medium and washed three times with TL-HEPES-PVA medium and Tris-buffered (mTBM) medium (Abeydeera et al., Biol Reprod 58:1316-1320, 1998) containing 0.2% BSA (A7888, Sigma), respectively. Thereafter, 25-30 oocytes were placed into each of four 50 μl drops of the mTBM medium, which had been covered with mineral oil in a 35 mm polystyrene culture dish. The dishes were allowed to equilibrate in the incubator for 30 min until spermatozoa were added for fertilization. One ml of liquid semen preserved in BTS diluent was washed twice in PBS containing 0.1% PVA (PBS-PVA) at 800×g for 5 min. At the end of the washing procedure, the spermatozoa were resuspended in mTBM medium. After appropriate dilution, 50 μl of this sperm suspension was added to 50 μl of the medium that contained oocytes to give a final sperm concentrations of 1-10×10 5 spermatozoa/ml. Different concentrations of inorganic pyrophosphate (PPi; S6422, Sigma) were added to fertilization drops (final concentrations; 0-20 μM) at the time of sperm addition. Oocytes were co-incubated with spermatozoa for 6 h at 38.5° C., 5% CO 2 . At 6 h after IVF, oocytes were transferred into 100 μl NCSU23 containing 0.4% BSA (A6003, Sigma) for further culture during 16-20 h.
Example 4
Immunofluorescence and Evaluation of Fertilization Rates
Spermatozoa/oocytes were fixed in 2% formaldehyde for 40 min at room temperature, washed, permeabilized in PBS with 0.1% Triton-X-100 (PBS-TX), and blocked for 25 min in PBS-TX containing 5% normal goat serum. Spermatozoa/oocytes were incubated with rabbit polyclonal anti-pyrophosphatase 1 (PPA1) antibody (1:200 dilution; #ab96099, Abcam, San Francisco, Calif.) or rabbit polyclonal anti-ANKH antibody (1:200 dilution; #SAB1102581, Sigma) for 40 min, then incubated with goat-anti-rabbit (GAR)-IgG-TRITC (1/80 dilution; Zymed Inc., San Francisco, Calif.). For the evaluation of fertilization, oocytes/zygotes were fixed with 2% formaldehyde for 40 min at room temperature, washed three times with PBS, permeabilized with PBS-TX for 40 min at room temperature, and stained with 2.5 μg/ml DAPI (Molecular Probes, Eugene, Oreg.) for 40 min. Oocytes with two or more pronuclei and at least one sperm tail in the ooplasm were recorded as fertilized. In order to count the number of spermatozoa bound to zona pellucida or acrosome reacted spermatozoa, oocyte were fixed and stained with DAPI and acrosome-binding lectin PNA-FITC (Molecular Probes) after IVF 30 min (5×10 5 spermatozoa/ml). Image acquisition was performed on a Nikon Eclipse 800 microscope (Nikon Instruments Inc., Melville, N.Y.) with Cool Snap camera (Roper Scientific, Tucson, Ariz.) and MetaMorph software (Universal Imaging Corp., Downington, Pa.).
As shown in FIG. 4 , immunofluorescence detected a prominent labeling of PPA1 in the sperm tail connecting piece and in the postacrosomal sheath of boar spermatozoa. Identical labeling was found in spermatozoa attached to oocyte zona pellucida at 30 min of in vitro fertilization, while negative control with anti-PPA1 antibody immunosaturated with full length recombinant PPA1 protein showed no such fluorescence, and neither did labeling of non-permeabilized spermatozoa.
Example 5
Western Blotting and Immunofluorescence
For western blotting, extracts of 1×10 6 spermatozoa/ml were loaded per lane. Spermatozoa were washed in PBS and boiled with loading buffer (50 mM Tris [pH 6.8], 150 mM NaCl, 2% SDS, 20% glycerol, 5% β-mercaptoethanol, 0.02% bromophenol blue). Gel electrophoresis was performed on 4-20% gradient gels (PAGEr® Precast gels, Lonza Rockland Inc., Rockland, Me.), followed by transfer to PVDF membranes (Millipore) using an Owl wet transfer system (Fisher Scientific) at a constant 50 V for 4 h. The membranes were sequentially incubated with 10% non-fat milk for 1 h, then with anti-PPA1 or anti-ANKH antibodies (1:2,000 dilution) overnight. The membranes were then incubated with an HRP-conjugated goat anti-rabbit IgG (GAR-IgG-HRP; 1:10,000 dilution) for 1 h. The membranes were reacted with chemiluminiscent substrate (SuperSignal, Pierce, Rockford, Ill.) and visualized by exposing to Kodak BioMax Light film (Kodak, Rochester, N.Y.).
PPA1 was detected in mammalian seminal plasma, oviductal fluid and spermatozoa. As shown in FIG. 3 , a protein band corresponding to the calculated mass of PPA1 (32 kDa) was detected in boar seminal plasma, in porcine oviductal fluid, and in boar, bull, mouse and human spermatozoa by Western blotting with rabbit polyclonal anti-PPA1 antibody. Minor bands of higher (˜51 and 75 kDa) or lower mass (˜13 kDa in boar and ˜18 kDa in bull) were observed in each sperm sample, likely corresponding to posttranslational protein modification and degradation products of PPA1. The purified PPA1 from baker's yeast ( S. cerevisiae ), used as a positive control protein, also showed additional bands at 32 and 13 kDa.
Example 6
Pyrophosphate Assay
The measurement of pyrophosphate (PPi) was performed using PiPer™ Pyrophosphate Assay Kit (Cat. No. P22062, Molecular Probes), following manufacturer's protocol. The samples were prepared using 1× reaction buffer (Kit) with boar seminal plasma (SP), porcine oviductal fluids (OVF), rabbit sera, mouse sera (final conc. 10 μg/ml), boar spermatozoa (1×10 6 spermatozoa/ml) and 10 mM H 2 O 2 working solution (a negative control). The PPi standard was prepared by diluting the 50 mM PPi standard solution (final conc. 0-200 μM PPi). The working solution of 100 μM Amplex® Red reagent contains 0.02 U/ml inorganic pyrophosphatase (PPA1), 4 U/ml maltose phosphorylase, 0.4 mM maltose, 2 U/ml glucose oxidase and 0.4 U/ml HRP. In this reaction, PPA1 hydrolyzes PPi into two inorganic phosphates (Pi). In the presence of Pi, maltose phosphorylase converts maltose to glucose 1-phosphate and glucose. Glucose oxidase then converts glucose to gluconolactone and H 2 O 2 . In the presence of horseradish peroxidase (HRP), the H 2 O 2 reacts with the Amplex® Red reagent (10-acetyl-3,7-dihyroxyphenoxazine) to generate resorufin, which is detected by fluorescence. Fifty μl samples were loaded into black 96-well (Coster-Corning, Corning, N.Y.), and then 50 μl working solutions were added into sample, respectively. The 96-well was incubated at 37.5° C. for 30 min, and fluorescence was measured at multiple time points to follow the kinetics of the reaction. Fluorescence intensity was measured by Thermo Fluoroskan Ascent (ThermoFisher Scientific) using 530 nm excitation and 590 nm emission wavelengths.
Results for measurement of the content of PPi in boar SP, pOVF and boar spermatozoa by a fluorometric assay are shown in FIGS. 1A and 1B . Different concentrations of PPi were measured as standards (0-200 μM PPi), and the fluorescence intensities increased progressively with increasing concentrations of PPi ( FIG. 1A ). The fluorescence intensities also increased in pOVF, SP, spermatozoa, mouse sera and rabbit sera. As shown in FIG. 1B , the boar spermatozoa, mouse sera, and rabbit sera showed higher fluorescence intensities than SP or pOVF at 40 min of acquisition (98.2-101.1 vs. 83.8 & 85.5). However, the intensities of pOVF, mouse sera and rabbit sera decreased gradually. Only the SP and spermatozoa showed continuous increase of fluorescence intensity during measurement (fluorescence intensities: 111.5 & 117.7 at 60 min, p<0.05). A negative control, 10 mM H 2 O 2 , showed a decreasing pattern, most likely due to bleaching of fluorescence.
Example 7
Flow Cytometric Analysis of Sperm Viability and Mitochondrial Membrane Potential
Boar spermatozoa were washed twice with PBS-PVA, and sperm concentration was adjusted to 1×10 6 spermatozoa/ml in PBS-PVA. The sperm viability was assessed by LIVE/DEAD® Sperm Viability Kit (L-7011, Molecular Probes) which contains DNA dyes SYBR14 and propidium iodide (PI), following a manufacturer's protocol. Sperm samples (198 μl) were loaded onto a 96-well plate. SYBR14 (1 μl; final conc. 100 nM) and PI (1 μl; final conc. 12 μM) were added to sperm samples and incubated for 10 min at 37.5° C. in darkness. Flow cytometric analysis was performed using a Guava EasyCyte™ Plus flow cytometer (Guava Technologies, IMV Technologies, L'Aigle, France). For each sample, 5,000 events were analyzed by the Guava ExpressPro Assay program, using standard manufacturer settings. For assessment of sperm mitopotential, boar spermatozoa were stained with JC-1 (Cat. No. 4500-0250, MitoPotential Kit, IMV), and measured using manufacturer settings. For negative controls, DMSO or no staining solution was added to sperm samples.
Following an industry practice for boar semen storage, fresh boar semen was diluted in BTS extender and stored at room temperature (15-17° C.) for 10 days. The base extender is designed for short term storage (3-5 days); however, the storage period was prolonged up to 10 days to compare sperm viability and mitochondrial membrane potential between storage days 3 and 10 in the presence/absence of 10 μM PPi. As described above, sperm viability was assessed by flow cytometry using a SYBR14/PI viability kit and mitopotential was measured with JC-1 dye. Supplementation with PPi altered the histograms and scatter diagrams of fluorescence produced by the above probes a vehicle control, DMSO produced no fluorescence.
FIGS. 5A and 5B compare the sperm viabilities and mitochondrial membrane potentials during sperm storage with and without PPi. As shown in FIG. 5A , the percentage of live spermatozoa was higher on day 3 than on day 10 (p<0.05), but there was no significant difference between control spermatozoa and those supplemented with 10 μM PPi. Contrary to viability, PPi supplementation augmented the content of metabolically active spermatozoa with polarized mitochondrial membranes on day 3 ( FIG. 5B ). Similar tendency was observed in spermatozoa preserved with 10 μM PPi for 10 days ( FIG. 5B ).
Example 8
Measurement of Proteasomal-Proteolytic Activity
The proteasomal-proteolytic and deubiquitinating activities, which are essential for fertilization, were assayed using specific fluorometric substrates Z-LLL-AMC, Z-LLVY-AMC, Z-LLE-AMC and ubiquitin-AMCs in spermatozoa stored for 3 and 10 days, with or without PPi. Alternatively, 10 μM PPi+BTS was added to semen preserved without PPi at the time of assay (“Add PPi” treatment). As a negative control, 10 μM MG132 (a proteasomal inhibitor) was added to sperm samples before assay.
Spermatozoa preserved in BTS with and without 10 μM PPi were loaded into a 96-well black plate (final sperm conc. 1×10 6 spermatozoa/ml), and incubated at 37.5° C. with Z-LLE-AMC (a specific substrate for 20S chymotrypsin-like peptidyl-glutamylpeptide hydrolyzing [PGPH] activity not sensitive to MG132; final conc. 100 μM; Enzo Life Sciences, Plymouth, Pa.), Z-LLVY-AMC (a specific substrate for 20S proteasome and other chymotrypsin-like proteases, as well as calpains; final conc. 100 μM; Enzo), Z-LLL-AMC (a specific substrate for 20S chymotrypsin-like activity sensitive to proteasomal inhibitor MG132; final conc. 100 μM; BostonBiochem, Cambridge, Mass.) or ubiquitin-AMC (specific substrate for ubiquitin-C-terminal hydrolase activity; final conc. 1 μM; Enzo) for 1 h. Fluorogenic proteasomal core substrates are composed of a small peptide (LLL/LLE/LLVY) coupled to a fluorescent probe, aminomethylcoumarin (AMC). The intact AMC-coupled substrate does not emit fluorescence. In the presence of appropriate 20S core activity, the AMC molecule is cleaved off and becomes fluorescent. This emitted fluorescence was measured every 10 min for a period of 1 h, yielding a curve of relative fluorescence (no units). Fluorescence intensity was measured by Thermo Fluoroskan Ascent (Thermo Scientific), using a 380 nm excitation and 460 nm emission.
FIGS. 6A to 6D show the effects of PPi on proteasomal enzymatic activities of stored boar spermatozoa. As shown in FIG. 6A , higher chymotrypsin-like PGPH activity (Z-LLE-AMC substrate) was measured in Add PPi treatment on day 3 (relative fluorescence of 392.1; no units) and PPi+BTS on day 10 (relative fluorescence of 388), compared to other treatments (363.1-386.1; p<0.05). As shown in FIG. 6B , chymotrypsin-like proteasomal core activity (Z-LLVY-AMC substrate) gradually increased during measurement in all groups, and the PPi+BTS and Add PPi treatments showed higher fluorescence intensities with this substrate, compared to controls (110.8-121.5 vs. 85.7; p<0.05). The highest fluorescence intensity was observed in Add PPi at 10 min, but the intensity decreased progressively during measurement, and chymotrypsin-like activity showed no differences between treatments ( FIG. 6C ). On the contrary, a higher deubiquitinating activity (ubiquitin-AMC) was observed in PPi+BTS treatment on day 10, compared to other treatments (relative fluorescence of 138.9 vs. 98.4-122.7; FIG. 6D ). As anticipated, low chymotrypsin-like activity was detected in spermatozoa treated with proteasomal inhibitor MG132. Overall, supplementation with PPi increased the proteasomal-proteolytic and deubiquitinating activities in spermatozoa and showed beneficial effects during sperm preservation.
Example 9
PPi Enhances Sperm-Zona Penetration During Fertilization and Fertilizing Ability Following Extended Storage
FIGS. 7A to 7F and FIGS. 8A to 8E illustrate the effects of PPi on total and polyspermic fertilization during porcine IVF ( FIGS. 7A to 7F ), and the effects of PPi on sperm-zona binding ( FIGS. 8A to 8E ). Porcine oocytes were fertilized in the presence of PPi at different concentrations ( FIG. 7A ). The rates of total and polyspermic fertilization increased significantly and progressively (up to 10 μM PPi) with increasing concentrations of PPi (p<0.05). The highest polyspermy was observed after addition of 10 μM PPi (84.9% polyspermy; FIG. 7B ). The mean number of spermatozoa bound to ZP decreased slightly, but not significantly with increasing concentrations of PPi ( FIG. 8A ). However, the percentage of acrosome-reacted spermatozoa was significantly higher in the presence of 20 μM PPi than 0-15 μM PPi (p<0.05, FIG. 8B ). Since a reduction of an insemination dose is desirable in AI settings, porcine oocytes were also inseminated with reduced sperm concentrations with and without 10 μM PPi. Consistently, the percentage of total and polyspermic fertilization was augmented by PPi at 1, 2, and 5×10 5 spermatozoa/ml; the increase induced by PPi was statistically significant at 5×10 5 spermatozoa/ml concentration ( FIG. 7C ). To determine if sperm storage in PPi-supplemented BTS extender has a beneficial effect on sperm fertilizing ability, freshly ejaculated boar spermatozoa were stored in BTS with or without 10 μM PPi for 3-4 days, and used for IVF in the presence or absence of 10 μM PPi. The fertilization rates were higher, and the polyspermy was highest of all treatments with addition of PPi during IVF, in the absence of PPi in TBM ( FIG. 7D ; second column). However, the highest combined (mono+polyspermic) fertilization rate was observed with spermatozoa preserved with 10 μM PPi in BTS when used for IVF without PPi addition ( FIG. 7D ; third column), or with PPi in IVF medium ( FIG. 7D ; fourth column). Altogether, PPi showed statistically significant (p<0.05), beneficial effects on sperm preservation and sperm fertilizing ability.
Control experiments were conducted to deplete sperm PPi with extrinsic inorganic pyrophosphatase in the form of purified PPA1. To incapacitate sperm-borne PPA1, porcine oocytes were fertilized in the presence of anti-PPA1 antibody. The specificity of both reagents was established by western blotting (see FIG. 3 ). Both PPA and anti-PPA1 antibody decreased the fertilization rate in a dose-dependent manner ( FIGS. 7E & F). No significant differences in fertilization rates were observed when the anti-PPA1 antibody was replaced with normal serum during fertilization ( FIG. 7F ).
To assess possible variation between sperm storage media, boar sperm batches were preserved in commercial BTS (BTS-IMV, IMV Technologies, L'Aigle, France) or homemade BTS (BTS-HM) (Pursel et al., J Anim Sci 40:99-102, 1975) in the presence of 10 μM PPi for 7 days. Higher sperm motility was found in BTS-IMV+10 μM PPi on day 6 than in all other groups ( FIG. 8C ). Excess PPi added into IVF medium (100-500 μM PPi) decreased fertilization rates in a dose-dependent manner ( FIG. 8D ). In a separate trial, boar spermatozoa were stored in BTS-IMV with 10 μM PPi for 3 days, and used for IVF. Near 100% fertilization was observed with spermatozoa preserved with 10 μM PPi, compared to below 70% fertilization without PPi in BTS-IMV ( FIG. 8E ).
Example 10
Statistical Analysis
Analyses of variance (ANOVA) were carried out using the SAS package in a completely randomized design. Duncan's multiple range test was used to compare values of individual treatment when the F-value was significant (p<0.05).
While the invention has been described in connection with specific embodiments thereof, it will be understood that the inventive device is capable of further modifications. This patent application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains and as may be applied to the essential features herein before set forth. | The present invention provides a new and improved sperm stimulating additive comprising a certain amount of inorganic pyrophosphate (PPi). Addition of PPi in the media for human/animal in vitro fertilization (IVF) improves fertilization rate; addition of PPi in the semen extender for farm animal artificial insemination (AI) may improve pregnancy rates; furthermore, mammalian oocytes matured in vitro in a medium including PPi attain improved fertilization and developmental potential, while embryos cultured in medium supplemented with PPi have improved development to blastocyst. | 2 |
RELATED APPLICATIONS
[0001] The present application claims priority to U.S. provisional patent application Ser. No. 60/460,365 filed Apr. 3, 2003 the entire contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a process for passivating a metallic surface. Specifically, an oxidation treatment is described herein is capable of efficiently passivating a metallic medical device thereby improving the corrosion resistance of the treated device. In one embodiment of the present invention the medical device is a vascular stent.
BACKGROUND OF THE INVENTION
[0003] Devices manufactured from at least one metallic material are commonly implanted within the body of patient to treat a variety of conditions. For example, stents, shunts, or other mechanical scaffoldings may be inserted into an occluded region of a lumen or luminal structure to provide and maintain patency therethrough. In an alternate embodiment, metallic screws, braces, or plates may be positioned within or attached to skeletonal structures throughout the patient's body to provide support thereto. Recently, total joint replacement devices such as replacement hip prosthetics and replacement knee prosthetics have been used to replace incompetent natural joint systems.
[0004] Presently, implantable metallic devices are manufactured from a variety of materials, including, stainless steel, tantalum, titanium, Nickel-Titanium alloys, shape memory alloys, super elastic alloys, low-modulus Ti—Nb—Zr alloys, and colbalt-nickel alloy steel (MP-35N). While implantable metallic devices manufactured these materials have proven useful in treating a variety of physiological conditions, a number of shortcomings associated with implantable metallic devices have been identified. For example, the extended exposure of the implanted metallic devices to bodily fluids and biological materials may result in device corrosion. As a result, the performance of the implanted device may be compromised.
[0005] In response, the materials used in the manufacture of implantable metallic devices generally undergo a chemical passivation process during the manufacture of the implantable device. Typically, the device is coated with, submerged in, or otherwise exposed to an oxidizing agent or compound. For example, nitric acid is frequently used as an oxidizing agent when passivating stainless steel. As a result, free metals on the surface of the implantable device may be removed and a non-reactive protective oxide layer capable of reducing or preventing material corrosion may be formed thereon. While the chemical passivating process has been effective in passivating implantable metallic devices, a number of shortcomings have been identified. For example, the chemical passivating processes tend to be time intensive procedures typically requiring the implantable device be exposed to an oxidizing agent for 15 minutes or more. In addition, oxidizing agents are hazardous materials and pose a health risk to exposed workers and may result in the unwanted deposition of chemical residues on the treated device.
[0006] Thus, in light of the foregoing, there is a need oxidation treatment for metallic medical devices capable of quickly passivating a metallic device without leaving chemical residues thereon.
BRIEF SUMMARY OF THE INVENTION
[0007] The oxidation treatment described herein is capable of efficiently passivating a metallic medical device thereby improving the corrosion resistance of the treated device. In addition, the oxidation treatment disclosed herein reduces or eliminates the possibility of residual chemical impurities remaining on the treated device as a result of the passivating procedure.
[0008] In one embodiment, a method of treating a metallic medical device is disclosed and includes providing a metallic medical device, ionizing the media surrounding at least one electrode to produce an energized plasma proximate to the electrode, and exposing the metallic device to the plasma prior to use of the metallic device.
[0009] In an alternate embodiment, a method of passivating a medical device is described herein and includes providing a metallic medical device, positioning at least one electrode within an atmosphere containing at least oxygen, applying energy to the electrode, forming a plasma by ionizing the atmosphere proximate to the electrode, and exposing the metallic medical device to the plasma to produce an corrosion resistant oxidation layer thereon.
[0010] In another embodiment, an oxidation treatment for a metallic stent is disclosed and includes providing a metallic stent, forming a plasma within an atmosphere containing at least oxygen, and positioning the stent within the plasma.
[0011] In addition, a corrosion resistant medical device is described and comprises a metallic body and at least a corrosion resistant oxidation layer formed on the metallic body.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 shows a table detailing the surface composition of stents subjected to the oxidation treatment of the present invention as compared with the surface composition of untreated control stents;
[0013] FIG. 2 shows a table summarizing the test results of a cyclic potentiodynamic polarization tests performed on untreated control stents;
[0014] FIG. 3 shows a table summarizing the historical test results relating to cyclic potentiodynamic polarization tests performed on the untreated stents;
[0015] FIG. 4 shows a table summarizing the test results of a cyclic potentiodynamic polarization tests performed on stents treated with the oxidation treatment of the present invention;
[0016] FIG. 5 shows a graph illustrating the corrosion potential of the stents treated using an oxidation treatment disclosed herein as compared to the corrosion potential of untreated control stents;
[0017] FIG. 6 shows a graph illustrating the cyclic polarization of the treated stent sample numbers 1 , 2 , and 3 as compared to the cyclic polarization of untreated control stent sample numbers 6 and 7 ; and
[0018] FIG. 7 shows a graph illustrating the cyclic polarization of the treated stent sample numbers 4 and 5 as compared to the cyclic polarization of untreated stent sample number 8 .
DETAILED DESCRIPTION OF THE INVENTION
[0019] The oxidation treatment disclosed herein may be used to passivate metallic medical devices to be used within the body of a patient, thereby improving the ability of the device to resist corrosion once implanted. Generally, passivation may be described as the removal of exogenous contaminants or compounds from the surface of a metallic device. When passivating a stainless steel item, for example, exogenous iron or iron compounds may be removed from the surface of the item, thereby altering the surface chemistry thereof. In addition, the oxidation treatment disclosed herein results in formation of an oxidation layer on the surface of the item. In addition to passivating metallic devices, the oxidation treatment of the present invention provides a metallic device substantially free of organic residues, unlike conventional passivating procedures utilizing wet chemical techniques which may result in the deposition of an organic contaminants on the implantable device.
[0020] The oxidation treatment of the present invention may be used to passivate a variety of metallic devices used throughout the body of a patient. For example, a metallic vascular stent may be subjected to the oxidation treatment disclosed herein prior to implantation with the vasculature of a patient. In another embodiment, the metallic medical device may include components of a replacement joint such as a replacement ball and socket joint, a metallic heart valve, implantable screws, pins, bolts, plates, skeletonal fusion devices, spinal fusion devices, bone anchors, shunts, staples, fasteners, dental implants or devices including orthodontic braces and retainers, or other metallic devices capable of being implanted into the body of a patient. In an alternate embodiment, the oxidation treatment described herein may be used to passivate or otherwise treat a variety of medical devices used prior to, during, or following a surgical or therapeutic procedure. For example, the disclosed oxidation treatment may be used to improve the corrosion resistance of retractors, retainers, couplings, scalpels, needles, forceps, dental tools or devices, bone cutters, saws, and/or other surgical or dental tools or devices. In addition, the present oxidation treatment may be used to passive various metals, including, without limitation, stainless steel, tantalum, titanium, Nickel-Titanium alloys, shape memory alloys, super elastic alloys, low-modulus Ti-Nb-Zr alloys, and colbalt-nickel alloy steel (MP-35N).
[0021] The oxidation treatment of the present invention utilizes a commercially available corona discharge or corona treatment system to produce the electrochemical reaction resulting in the passivation of the metallic device. A voltage sufficient to ionize the surrounding environment is applied to at least one electrode. In one embodiment, approximately 18 kV of direct current (DC) may be applied to the electrode thereby generating a corona discharge proximate thereto, although any voltage or current capable of creating a corona discharge may be used. Similarly, any number of electrodes may be used in the present invention. For example, a first charged electrode may be positioned proximate to a second electrode. The first charged electrode may be separated from the second electrode by a separation gap. The electrodes may positioned within an air environment, although those skilled in the art will appreciate that the electrodes may be located within environments containing other materials or gases. For example, the electrodes may be positioned within a field containing argon, helium, neon, or xenon. The application of sufficient voltage to the first charged electrode ionizes the media surrounding the electrode, for example, oxygen, thereby forming ozone (O 3 ) and producing a plasma between or proximate to the first and second electrodes. Further, the Applicants theorize the Ozone forming the plasma is capable of chemically reacting with various metals of the metallic device and resulting in the oxidation thereof.
[0022] The metallic device may be subjected to or positioned within the ionized environment formed proximate to the electrode. For example, a stainless steel device (for example stainless steel 316L) may be subjected to the high energy plasma generated between or proximate to at least one electrode. As a result, the atoms of ozone forming the plasma react with atoms of iron, nickel, and chromium within the stainless steel substrate material thereby forming or depositing a corrosive resistant oxidation layer thereon. Those skilled in the art will appreciate that the metallic device undergoing the oxidation treatment disclosed herein is maintained at an ambient or near ambient temperature during the treatment procedure. Unlike wet oxidation procedures which may result in the deposition of residual materials on the metallic device and may require additional cleaning processes, the metallic device treated with the method disclosed herein may be sterilized and packaged for shipment. In addition, those skilled in the art will appreciate that the oxidation treatment disclosed herein results in the deposition of a corrosion resistant layer to the metallic device in substantially less time than presently required using a wet oxidation process. In one embodiment, the metallic device may be passivated by subjecting the metallic device to the corona discharge for about 3 seconds to several minutes, although those skilled in the art will appreciate that the metallic device may be subject to the corona discharge for a considerably less or more time as desired by the manufacturer. In contrast, the present wet passivating procedures using nitric acid typically require the metallic device be exposed to the oxiding agent for a period of 15 minutes or more.
[0023] A further, non-limiting illustration of the oxidation treatment disclosed herein is illustrated in the following examples.
EXAMPLE 1
[0024] Seven stainless steel S670 stents manufactured by Medtronic AVE were washed for three minutes within an ultrasound bath containing 99% isopropyl alcohol (IPA). Thereafter, the seven stents were removed from the IPA bath and dried within a gaseous flow of nitrogen.
[0025] Once dried, the scents were number 1 through 7. Sample number 1 was left untreated. Sample numbers 2 through 7 underwent passivation using the oxidation treatment disclosed herein. A corona discharge device included an electrode was positioned within an oxygen environment. Approximately 18 kV of direct current electrical energy was applied to the electrode, thereby ionizing the oxygen proximate to the electrode and resulting in the creation of a ionizing plasma. As Table 1 shows, sample numbers 2-7 were exposed to a plasma created from a corona discharge device for varying lengths of times.
TABLE 1 SAMPLE NO. CORONA EXPOSURE TIME 1 0 sec (control) 2 5 sec. 3 10 sec. 4 20 sec. 5 20 sec. (Dwell) 6 60 mm. (Dwell) 7 95 mm. (Dwell)
[0026] Following the oxidation treatment, sample number 1 (the untreated control sample) and treated sample numbers 2-7 underwent Electron Spectroscopy for Chemical Analysis (hereinafter ESCA) to determine the effects of the oxidation treatment on the surface composition of the stents. During the ESCA process, a small diameter x-ray beam is focused across an area of each stent, thereby causing electrons to be emitted from the of each stent. The emitted electrons are collected and examined to determine the surface composition of the device under test. FIG. 1 shows the results of the ESCA testing on samples 1-7.
[0027] As shown in FIG. 1 , the surface composition of sample number 1 (the untreated control sample) included significantly higher concentrations of carbon when compared with the surface composition of the treated samples (sample numbers 2-7). In addition, the treated sample numbers 2-7 exhibited higher surface concentrations of nitrogen and nickel than the untreated sample 1. Furthermore, the chromium to iron ratio in the treated samples sample number 2-7) was greatly reduced as a result of the oxidation treatment when compared with the untreated sample (sample number 1), thereby producing a more corrosion-resistant device than presently available.
EXAMPLE 2
[0028] Eight stainless steel S670 stents manufactured by Medtronic AVE were washed for three minutes within an ultrasound bath containing 99% isopropyl alcohol (IPA). Thereafter, the eight stents were removed from the IPA bath and dried within a gaseous flow of Nitrogen.
[0029] Once dried, the stents were number 1 through 8. Sample numbers 6-8 were left untreated. Sample numbers 1 through 5 underwent passivation using the oxidation treatment disclosed within. A corona discharge device included an electrode was positioned within an oxygen environment. Approximately 18 kV of direct current electrical energy was applied to the electrode, thereby ionizing the oxygen proximate to the electrode and resulting in the creation of a ionizing plasma. As Table 1 shows, sample numbers 1-5 were exposed to the plasma created from a corona discharge device for varying lengths of times between 5 seconds and 10 seconds.
TABLE 3 SAMPLE NO. CORONA EXPOSURE TIME 1 5-10 sec. 2 5-10 sec. 3 5-10 sec. 4 5-10 sec. 5 5-10 sec. 6 0 (control) 7 0 (control) 8 0 (control)
[0030] Thereafter, the stents were subjected to cyclic potentiodynamic corrosion testing to determine the corrosion resistance of each sample. FIG. 2 shows a table summarizing the cyclic potentiodynamic polarization test results for the untreated samples (sample numbers 6-8). FIG. 3 shows historical data of potentiodynamic polarization testing of similar S670 stents manufactured by Medtronic AVE. As illustrated, the corrosion potential for the untreated samples (sample numbers 6-8) was comparable with the historical data obtained by previous potentiodynamic polarization tests performed on untreated S670 stent samples. The corrosion potential of the untreated samples (sample numbers 6-8) averaged −108 mV, while the breakdown potential averaged 462 mV.
[0031] FIG. 4 shows a table summarizing the cyclic potentiodynamic polarization test results for the treated samples (sample numbers 1-5). As shown, the breakdown potential of the treated samples (sample numbers 1-5) was consistently higher than the untreated samples (sample number 6 - 8 ). In addition, the potential difference (i.e. the average difference between the corrosion potential and the breakdown potential (E b -Ecorr)) was greater in the treated samples (sample numbers 1-5) than the untreated samples (sample numbers 6-8), thereby suggesting that the oxidation treatment had improved the corrosion resistance of the treated samples (sample numbers 1-5).
[0032] FIGS. 5-7 graphically illustrate the effects of the oxidation treatment on the treated samples (sample numbers 1-5) as compared with the untreated samples (sample numbers 6-8). FIG. 5 shows the corrosion potential ((V pot /E ref )/t) of the treated samples (sample number 1 - 5 ) and the untreated samples (sample numbers 6-8). As shown, the corrosion potential of the treated samples (sample numbers 1-5)is considerably higher then the untreated samples (sample numbers 6-8). Further, FIGS. 6 and 7 show the cyclic polarization ((V pot /E ref )/(A/cm 2 )) of the treated samples (sample numbers 1-5) and the untreated samples (sample numbers 6-8), More specifically, FIG. 6 shows the cyclic polarization of treated sample numbers 1, 2, and 3 and untreated sample numbers 6 and 7. FIG. 8 shows the cyclic polarization of treated sample numbers 4 and 5, and untreated sample number 8. As shown in FIGS. 2 and 3 , the treated samples (sample numbers 1-5)exhibited a higher cyclic polarization than the untreated samples (sample numbers 6-8).
[0033] In light of the foregoing, cyclic potentiodynamic polarization test revealed a higher breakdown potential and an increased difference between the rest potential and the breakdown potential for the treated stents (sample numbers 1-5)than found in the untreated stents (sample number 6-8). As a result, the oxidation treatment disclosed herein reduced the treated stent's susceptibility to localized corrosion thereby improving the treated stent's resistance to corrosion.
[0034] In closing it is understood that the embodiments of the invention disclosed herein are illustrative of the principles of the invention. In addition, those skilled in the art will appreciate that the oxidation treatment described herein may be used to provide the user with a variety of corrosion resistant metallic medical device, including, for example, vascular stents, replacement joints, metallic heart valves, screws, pins, bolts, staples, fasteners, plates, skeletonal fusion devices, spinal fusion devices, bone anchors, shunts, staples, fasteners, dental implants, orthodontic braces, dental retainers, retractors, retainers, couplings, scalpels, needles, forceps, dental tools, surgical tools, bone cutters, and saws. Accordingly, the present invention is not limited to that precisely as shown and described in the present invention. | A method of treating a metallic medical device is disclosed and includes providing a metallic medical device, ionizing the media surrounding at least one electrode to produce an energized plasma proximate to the electrode, and exposing the metallic device to the plasma prior to use of the metallic device. In one embodiment a vascular stent is the medical device. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to injection devices and in particular, but not exclusively, to reusable autoinjector devices comprising a housing into which a disposable syringe may be inserted to effect the injection and then removed and replaced as required for the next injection.
2. Description of the Related Art
It is a common requirement that autoinjectors signal to the user when the injection is complete by means of an ‘injection complete’ signal. The term ‘injection complete’ is used to refer to a condition in which a satisfactory delivery of the drug has been achieved. It is also desirable that this indication is not only visual but also audible and/or tactile, to provide confirmation to the user when injection site is out of sight, or would require some straining to see, for example in the buttocks or upper arm.
It is desirable that at least some of the energy required to generate the audible signal is stored in an energy store associated with an indicator element so that a fast impact energetic movement can be released, that is essentially independent of the actual speed of plunger movement. Moreover it is desirable to provide an indicator arrangement which resets automatically for each injection cycle.
BRIEF SUMMARY OF THE INVENTION
Accordingly, in one aspect, this invention provides an injection device including an injection complete indicator for providing a kinetic impact indication, the device including:
a housing;
a plunger moveable in said housing between cocked and fired positions under the influence of a plunger drive source;
an indicator element biased towards an injection complete indicating position by an indicator bias;
a hold-release arrangement responsive to arrival of said plunger at or near its fired position to release said indicator element for movement under the influence of said indicator bias to move to said injection complete indicating position to impact a stop to create said kinetic impact.
By this arrangement, the energy to create the kinetic impact may be stored in the indicator bias which means that, once the indicator element is released its movement is generally independent of the plunger, which allows considerable flexibility in the design of the extent of movement, and energy delivered by the indicator.
Preferably said indicator element also provides a visual indication.
Conveniently, as said plunger moves towards its fired position, it energises said indicator bias. There are numerous ways which the bias may be energised, but in one arrangement, said plunger and said indicator element may have co-operating surfaces which engage to move the indicator element with the plunger during a part of the plunger stroke, thereby to energise said indicator bias. The hold-release arrangement may include a hold surface that co-operates with a complimentary surface on said indicator element to prevent movement thereof to said injection complete indicating position during energisation of said indicator bias. In this way, the energy tapped from the drive source is spread over a significant portion of the stroke of movement of the plunger so as to reduce the effect on the plunger movement. This allows an energy charging cycle in which charging is done slowly over an extended portion of the stroke, and discharging is done very quickly in a snap action.
In this arrangement, as said plunger arrives near or at its fired position, the plunger may move the complimentary surface on the indicator element out of co-operation with said hold surface, thereby releasing the indicator element for movement.
Preferably the indicator element moves angularly to its injection complete indicating position, optionally with an amount of longitudinal movement.
Preferably the indicator bias biases the indicator element linearly in a rearward direction generally opposed to that of the plunger as it moves towards its fired position and co-operating surfaces of said plunger and said indicator element are operable to act in a cammed manner to convert relative linear movement therebetween into angular movement of said indicator element upon release.
Preferably, the co-operating surfaces comprise an ear on said plunger and a repeating profile on said indicator element, the repeating profile comprising a plurality of ramp surfaces alternating with rising edge surfaces arranged such that a rising edge surface is adapted to impact a side of said ear as said indicator element reaches its injection complete indicating position.
Preferably said hold surface is provided on an element that includes a cam face that co-operates with one of said ramp surfaces on said indicator element to rotate the indicator element to a pre-firing position under the influence of said indicator bias as said drive plunger is returned to a cocked position.
In another aspect, this invention provides an injection device including an injection complete indicator, the device including:
a housing;
a plunger movable in said housing between cocked and fired positions under the influence of a plunger drive source;
an indicator element movable between a pre-firing position and an injection complete position;
the device being arranged such that, upon firing, as the plunger nears or reaches the end of its operating stroke, the indicator element is caused to move to its injection complete position and wherein subsequent re-cocking of the plunger returns said indicator element to its pre-firing position.
Whilst the invention has been described above it extends to any combination of the inventive features disclosed herein or in the following description or drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention may be performed in various ways and, by way of example only, an embodiment thereof will now be described, reference being made to the accompanying drawings in which:
FIG. 1 is a general perspective view of an autoinjection device in accordance with this invention;
FIG. 2 is an exploded view of the rear body assembly with the syringe removed;
FIGS. 3 ( a ) to ( h ) are perspective views of the rear body assembly showing the configuration of various components in sequence through a firing and cocking operation, and
FIGS. 4( a ) to ( h ) are corresponding side views of the rear body assembly during these operations.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring initially to FIG. 1 , a preferred embodiment of autoinjector comprises a separable body comprising a front body assembly 10 screwed or otherwise releasably coupled to a rear body 12 having an outer slideable cover 14 . The device is designed to be reusable with the user separating the front and rear body assembly, cocking a drive mechanism contained in the rear body assembly, inserting or replacing a syringe 22 housed in the front body assembly and connecting the front and rear body assemblies together ready for use. This is similar to a well known Autoject® II device and as described in WO2004/108194. As in the arrangement of WO2004/108194, the cover is biased rearwardly to a position in which it interlocks with a trigger 16 to prevent actuation thereof. The cover 14 also has two diametrically opposed windows 18 through which an indicator sleeve 20 is visible and which moves to change colour on satisfactory completion of an injection.
In order to operate the device, the user grasps the cover 14 and presses the front end of the front body assembly 10 against the injection site, thus shifting the cover forwardly to release the mechanical interlock. On firing the trigger, the drive mechanism inside the rear body housing moves a drive plunger forwardly which is in contact with the syringe plunger 25 and this initially advances the syringe 22 so that its needle 24 penetrates the injection site, and thereafter the plunger moves the syringe piston 23 to expel a dose. Upon nearing or reaching the forward end of its stroke, the plunger releases the indicator sleeve 20 which rotates to change colour under the window 18 and to create an internal impact which provides an audible and tactile signal. On removing the device from the injection site the reaction force is removed and so the cover 14 shifts rearwardly on the rear body to interlock with the trigger 16 .
Because of the accumulated tolerances on the syringe (typically of glass) it is known that there is a variation in the forwardmost position of the plunger and so the injection complete position is usually determined to be a short distance behind the final, forwardmost position of the plunger.
Referring now to FIGS. 2-4 , the rear body assembly will be described in more detail. In FIGS. 3 and 4 , the rear body assembly 12 is shown in side and perspective views respectively, with a portion of the cover 14 cut away to reveal the inner workings of the assembly. In this arrangement, the cover 14 is slideably mounted around the outside of an inner body housing 22 of generally cylindrical form. At its rear end, the trigger 16 is secured by means of an integral fitting 24 which clips over the rear end of the inner body housing and supports the trigger for resilient rocking release movement. At the forward end of the inner body housing 22 is secured an externally threaded collar fitting 26 which screws into a threaded bore in the rear end of the front body assembly 10 . Slideably disposed within the inner body housing 22 is a drive plunger 28 which is urged forwardly by a main drive spring 30 acting between the plunger and a rear inner wall of the rear body assembly. The plunger 28 has a forward end face 32 (visible in FIGS. 3( b ) to ( h )) which is designed to engage the plunger 25 of a syringe 22 . The drive plunger 28 has at its rear end a latch surface 31 which latches with a corresponding latch surface (not shown) on the forward underside end of the trigger 16 which holds the plunger in its rearward, cocked position against the force of the main spring 30 . The drive plunger 28 has a pair of transverse ears 34 that extend through opposed longitudinal slots 36 in the wall of the inner body housing 22 . Each ear 34 has an inclined cam surface 37 and a longitudinally extending impact surface 38 . Towards the front end of the slot and angularly spaced therefrom in a counter-clockwise direction when viewed from the front end, are two diametrically opposed body stops 40 each of which defines a longitudinally extending hold surface 42 and a cam surface 44 .
The plunger ears 34 and the body stops 40 each co-operate with a circumferentially extending, rearwardly facing saw tooth profile on the rear of the indicator sleeve 20 which is slideably and rotatably mounted on the front end of the inner body housing 22 . The saw tooth profile in this example is made up of four linear ramp surfaces 41 each subtending an angle of 90°, and four axial rising edges 43 , with valleys 45 and peaks 47 being defined where the ramps meet the rising edges 43 . The indicator sleeve 20 is biased rearwardly by a compression spring 46 that acts between a forward facing inner shoulder of the indicator 20 and the rearward facing edge of the collar fitting 26 . The compression spring 46 is much weaker than the main spring 30 . The indicator sleeve carries coloured patches 21 equispaced at 90° around the sleeve which provide a visual indication of when the injection is complete.
In operation, assuming the rear body assembly has been cocked, the components of the assembly will be as in the configuration shown in FIGS. 3( a ) and 4 ( a ). In this condition, the plunger 28 is latched in its cocked position with the main spring 30 fully compressed. The plunger ears 34 are at the rear of the slot 36 . The indicator sleeve 20 is at its rearmost position urged by the spring 46 so that diametrically opposed valleys 45 of the saw tooth profile are urged into contact with the forward ends of the body stops 40 , with the holding surfaces 42 of the body stops effectively urged into contact with the rising edges 43 of the saw tooth, by virtue of the cam surfaces 44 of the body stops 40 being in camming contact with the ramp surfaces 41 of the indicator sleeve 20 . In this condition, the plain, uncoloured, surfaces of the indicator sleeve 20 are visible through windows 18 .
Having prepared the device for injection and offered it up to an injection site and pressed the outer cover 14 to release the interlock with the trigger, the trigger 16 is pressed thereby releasing the drive plunger 28 so that it can shoot forward under the influence of the main drive spring 30 , initially extending the syringe 22 so that its needle 24 projects from the front end of the front body assembly and thereafter moving the syringe piston 23 to expel a dose.
FIGS. 3( b ) and 4 ( b ) show the plunger having moved forward to the point where the cam surfaces 37 on the ears 34 of the plunger have just contacted respective ramp surfaces 41 on the indicator sleeve 20 , but before any forward movement has been transmitted to the indicator sleeve. From this point, further forward movement of the plunger 28 shifts the indicator sleeve 20 against the bias of the spring 46 , with the sleeve being constrained against rotation by the sliding contact between the holding surface 42 of the body stops and rising edges 43 of the indicator 20 .
Beyond this point, as shown in FIGS. 3( d ) and 4 ( d ), the ramp surfaces 41 on the indicator 20 ride over the cam surfaces 37 and 44 on the plunger ears and body stops 40 respectively as the indicator sleeve 20 is now free to quickly rotate and move rearwardly under the influence of the expanding indicator spring 46 and the camming action of the ramps surfaces 41 on the cam surfaces 37 , until the rising edges 43 on the indicator sleeve 20 impact the impact surfaces 38 on the ears 36 , to generate an audible and tactile signal. At this point, the coloured region 21 on the indicator sleeve is now visible in the window 18 to indicate that the drive plunger 28 is at or near its forwardmost position. As noted above, due to the need to provide manufacturing tolerances due to the accumulated longitudinal tolerances in the syringe, the plunger continues moving forwardly a short distance to the position shown in FIGS. 3( e ) and 4 ( e ) which shifts the indicator sleeve 20 forwardly off the body stops 40 .
Referring now to the cocking sequence shown in FIGS. 3 and 4( e ) to ( h ), from a fully fired position, in order to cock the device, pressure is applied to the exposed end face 32 of the plunger to compress the main spring 30 e.g. using the forward end of the front body assembly 10 or other suitable tool and, as the plunger moves back, the indicator spring 46 expands to move the indicator sleeve 20 rearwardly with it.
When the indicator sleeve 20 reaches the position shown in FIGS. 3( f ) and 4 ( f ) the ramp surfaces 41 thereon engage the cam surfaces 44 on the body stops 40 , but rotational movement of the indicator sleeve 20 is prevented because of the sliding contact between the impact surface 38 of the ears 34 of the plunger and the rising edges 43 of the indicator sleeve 20 . However, as shown in FIGS. 3( g ) and 4 ( g ), once the sliding contact is lost, the indicator sleeve 20 is free to rotate and consequently move rearwardly under the influence of the indicator compression spring 46 as the ramp surfaces 43 slide over the cam surfaces 44 of the body stops 40 . This continues to the position shown in FIGS. 3( h ) and 4 ( h ), with the rising edges 43 of the indicator sleeve 20 abutting the holding surfaces 42 on the body stops 40 . In this position the sleeve is located with an uncoloured portion visible through the window 18 . Continued rearward movement of the plunger latches it against the trigger in the cocked position shown in FIGS. 3( a ) and 4 ( a ).
It will be noted that, in the embodiment described below, with each firing and cocking cycle, the indicator sleeve indexes through 90° (45° to move from the cocked, pre-firing state into the injection complete state and 45° in the same direction to move from the injection complete into the cocked state). | In an injection device a rotary indicator element ( 20 ) indexes angularly between a pre-firing position to an injection complete position to create a visual and audible/tactile signal as the drive plunger ( 28 ) arrives at or near its fired position. The indicator element ( 20 ) has a saw tooth profile which co-operates with respective abutments ( 34, 40 ) on the plunger and a housing part of the device to control and energise indicator movement. | 0 |
BACKGROUND OF THE INVENTION
1. Technical Field
The present invention—involving bookbinding units that form encased booklets by binding into coversheets inner-leaf sheets that have been collated into bundles—relates to improvements in cover-binding mechanisms for securely binding into booklets inner-leaf sheets having single leaves mixed with saddle-stitch folded sheets.
2. Description of the Related Art
Bookbinding units that in general collate into bundles sheets that have been printed in a digital printer or other printing machine and encase the bundles in coversheets to form booklets are widely known. With this scheme, inner-leaf sheets collated into a sheet bundle are set into a stack on an inner-leaf tray, and the bundled sheets are conveyed from the tray to an adhesive-application location, and an adhesive (such as a hot-melt adhesive) is applied to a spine-portion endface of the sheets. Meanwhile, a coversheet from a coversheet tray is fed to, and set into place at, a cover-binding location arranged downstream of the adhesive-application location; the spine portion of the inner-leaf sheets, where the adhesive has been applied, is joined to a cover-binding portion of the coversheet in its middle; and thereafter the coversheet is spine-creased and molded in a coversheet pressing means.
Conventionally, as disclosed in Japanese Unexamined Pat. App. Pub. No. 2003-025759, an inner-leaf tray is disposed on one end of the unit, and a cover tray is disposed on the other end. The inner-leaf tray stores collated and stacked inner-leaf sheets (bundles), and the coversheet tray stores a plurality of coversheets of predetermined sizes. The inner-leaf sheets are conveyed in bundle form to a bookbinding processing stage (cover-binding location) situated in the mid-portion of the device, and from the tray the coversheets are conveyed separated into single sheets. To the upstream side of the coversheet binding stage, adhesive tape (or a hot-melt adhesive) is attached to the spine-portion endface of the inner-leaf sheets. In addition, the coversheet binding stage is fitted out with spine-folding press members. Conventional bookbinding units of this sort are known to suffer from the device requiring scaled-up installation space in that, for example, as disclosed in the cited reference, the inner-leaf sheets in bundle form are conveyed with a conveyor mechanism from a sheet supply unit to the bookbinding processing stage. Furthermore, when the three sides (the head, foot and fore-edge portions) of a sheet bundle in booklet form that has been book-forming processed in a bookbinding unit of this sort are trimmed true, the bookbinding unit is equipped with a trimming device that is distinct from the unit, and the trim-finishing is carried out in the trimming device.
Meanwhile, the present applicants have proposed, in Japanese Unexamined Pat. App. Pub. No. 2005-305822 and elsewhere, a unit that continuously bookbinding-processes image-bearing sheets from an image-forming unit. In the publication, a unit is proposed wherein sheets printed with images are collated and stacked in a bookbinding unit connected to a discharge outlet of an image-forming unit. These inner-leaf sheets are conveyed to an adhesive application position by a gripping conveyance means. There a spine portion of the sheet bundle is coated with adhesive. A coversheet is fed from a cover path that is different from the conveyance path for the inner-leaf sheets and set into place in a cover-binding location.
In both of the publications above, the unit collates and stacks simple sheets of the sheet bundle; the unit disclosed in Japanese Unexamined Pat. App. Pub. No. 2003-025759 is configured to set in a feed stacker a sheet bundle composed of simple sheets (a stack of single-leaf sheets). Likewise, the unit disclosed in Japanese Unexamined Pat. App. Pub. No. 2005-305822 collates simple sheets conveyed from the image-forming unit by stacking and storing them in a stacking tray.
The conventional bookbinding unit stacks simple sheets to compose the inner-leaf sheets of the sheet bundle, applies adhesive to the sheet bundle, then joins the sheet bundle to a central spine-binding portion of a coversheet. However, in print-forming inner-leaf sheets in a printing unit or like device, in some cases signatures are created by folding over a plurality of printed sheets. The plurality of sheets is stacked and folded over along the middle, the spine portion is stapled or saddle-stitched to create a signature, and presumably a plurality of signatures is stacked together to be encased in a coversheet as a booklet.
With conventional bookbinding approaches of this sort, prior to forming the text block into a book in the above-described bookbinding unit, it is known to subject the block to a milling process that cuts (grinds) it into a serrated form, and then to set the block into the inner-leaf tray. A problem with in this way finishing into booklets inner-leaf sheets in which sets of sheets have been folded over has been that if the sheets are milling-processed and the adhesive does not penetrate to the inside of the folded sheets, they cannot be securely bound together.
BRIEF SUMMARY OF THE INVENTION
There, the inventors determined that binding without trimming is possible by setting the adhesive application amount and temperature (viscosity) when stacking a plurality of folded sheets (quire) and encasing a plurality of them in coversheet. The inventors came upon the idea of varying the adhesive application process, the spine folding process or the trimming process according to the configuration of the inner-leaf sheets to make bookbinding processes possible that conform to a variety of bundle constitutions.
An object of the present invention is to provide a bookbinding unit that securely binds printed or other inner-leaf sheets to a coversheet regardless of whether the inner-leaf sheets are unfolded or include a plurality of folded sheets.
Another object of the present invention is to provide a bookbinding unit that securely binds a variety of sheet bundles to a coversheet with a simple structure by increasing or decreasing the amount of adhesive according to the configuration of the sheet bundle.
It should be understood that in the present invention, “saddle-stitch folded sheets” means a bundle of a plurality of sheets that have been folded onto themselves and bound down the middle. To attain the aforementioned objects, the present invention provides input means for inputting the makeup (constitution) of a bundle of inner-leaf sheets set in a inner-leaf tray, and control means that varies the control of at least one of the means of sheet conveyance means, adhesive application means, and cover binding means to correspond to the bundle makeup from the input means.
The bookbinding unit that encases in a coversheet inner-leaf sheets collated into a bundle has a inner-leaf tray that sets the inner-leaf sheets in bundles and a coversheet tray that sets coversheets and is equipped with a bookbinding path that guides the sheet bundle from the inner-leaf tray to an adhesive application position and a cover-binding location; inner-leaf conveyance means for feeding the sheet bundle from the inner-leaf tray along the bookbinding path; coversheet conveyance means for feeding the coversheet from the coversheet tray to the cover-binding location; adhesive application means disposed in an adhesive application position for applying adhesive to a spine-portion endface of inner-leaf sheets; cover binding means for binding the inner-leaf sheets and coversheet; and control means for controlling the inner-leaf conveyance means, adhesive application means and the cover binding means. The control means has input means for inputting whether the sheet bundle makeup includes saddle-stitch sheets or only simple sheets, and varies the control of at least one of the means of sheet conveyance means, adhesive application means, and cover binding means based on the bundle makeup information from the input means
Trimming means is disposed downstream of the cover binding means to trim true edges of a bound sheet bundle; the control means varies the trimming speed of the trimming means based on the sheet bundle makeup information from the input means.
The control means compares when the input information from the input means includes saddle-stitch sheets and when the sheet bundle includes only simple sheets to (1) slow the conveyance speed of the inner-leaf conveyance means and/or (2) increase the adhesive amount of the adhesive application means, and/or (3) lengthen the adhesive cooling time of the cover binding means, and/or (4) slow down the trimming speed of the trimming means.
The control means controls the trimming means to trim at least the fore-edge of the sheet bundle conveyed from the cover-binding location when the input information from the input means include saddle-stitch sheets.
A first sensor means is disposed in the inner-leaf tray to detect the presence of paper, and a second sensor means is disposed in the coversheet tray to detect presence of the coversheet. The control means controls the inner-leaf conveyance means, adhesive application means, cover binding means, and the trimming means in a preset order when both the first and second sensors detect the presence of paper.
The inner-leaf tray and coversheet tray are disposed so that one is over the other above the bookbinding path. The length of the path from the inner-leaf tray to the cover-binding location is configured to be shorter than the length of the path from the coversheet tray to the cover-binding location.
The present invention has the following effects because the controls of the inner-leaf conveyance means, adhesive application means, and cover binding means are varied according to whether the inner-leaf sheets set in the inner-leaf tray include saddle-stitch sheets.
When the inner-leaf sheets are composed of only simple sheets, or unfolded and saddle-stitch sheets, or only saddle-stitch sheets, the bookbinding processes such as the paper conveyance speed, adhesive application amount, the adhesive cooling time and the trimming speed and the like are varied so the bookbinding process that is appropriate for each type of sheet bundle is possible.
Therefore, while sheet conveyance, the application of adhesive and cooling of the adhesive were performed conventionally in a uniform manner regardless of whether the inner-leaf sheets include saddle-stitch sheets, the present invention solves the problems of missing pages caused by an incomplete gluing and problems in the bookbinding quality where wrinkles or unevenness occur in the spine portion by varying the control conditions of those processes according to the configuration of the sheet bundle.
Furthermore, the present invention has the notable effects of a secure binding, and forming a good quality spine binding without the bundle becoming disorganized in the conveyance process by slowing down the conveyance speed to convey the inner-leaf sheets, increasing the amount of adhesive that is applied and extending the adhesive cooling time.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1 is an overall view of a bookbinding unit of the present invention;
FIG. 2 is an expanded explanatory view of the bookbinding unit in the unit shown in FIG. 1 ;
FIG. 3 is an explanatory drawing of a configuration of a bundle conveyance means in the unit shown in FIG. 1 ;
FIG. 4 is an overall view of adhesive application means in the unit shown in FIG. 1 ;
FIGS. 5A to 5D are explanatory views of applying adhesive using an adhesive application means shown in FIG. 4 ; FIG. 5A shows an outward movement state of adhesive container; FIG. 5B shows a return movement of the adhesive container; FIG. 5C is a sectional view of FIG. 5A ; FIG. 5D is a sectional view of FIG. 5B ;
FIG. 6 is an explanatory view of a configuration of bundle conveyance means in the unit shown in FIG. 1 ;
FIGS. 7A to 7D are explanatory views of a configuration of a bundle of saddle-stitch sheets in the unit shown in FIG. 1 ; FIG. 7A shows the status of applying adhesive; FIGS. 7B , C, D show the configuration of the sheet bundle;
FIGS. 8A to 8C are explanatory views of operations of coversheet binding procedures in the unit shown in FIG. 2 ; each drawing shows spine folding press members moving between idle positions and folding positions;
FIGS. 9A and 9B are explanatory views of essential portions of the unit shown in FIG. 1 ; FIG. 9A is an explanatory view of a state to set sheets in an inner-leaf tray; FIG. 9B shows a configuration of a first bundle thickness detection means disposed in the inner-leaf tray;
FIG. 10 is an explanatory view of a configuration of sheet width size detection means on the inner-leaf tray and coversheet tray in the unit shown in FIG. 1 ;
FIG. 11 is a block diagram of a configuration of control means in the unit shown in FIG. 2 ;
FIG. 12A is a flowchart showing operating procedures of cover binding means in the unit shown in FIG. 2 ; and
FIG. 12B is a flowchart showing operating procedures of cover binding means in the unit shown in FIG. 2 .
DETAILED DESCRIPTION OF THE INVENTION
Preferred embodiments of the present invention will now be explained with reference to the drawings provided. FIG. 1 is an explanatory view of the overall configuration of the bookbinding unit according to the present invention; and FIG. 2 is an expanded view of an essential portion thereof.
The present invention relates to a bookbinding unit A that applies hot-melt adhesive such as glue, or adhesive tape to a spine edge surface of a sheet bundle (inner-leaf sheets) set in a predetermined tray (inner-leaf tray 2 ) and encases the sheet bundle in a coversheet conveyed from a coversheet tray 31 . The bookbinding unit A shown in FIG. 1 is composed of the inner-leaf tray 2 that stores inner-leaf sheets that have been collated into a sheet bundle; adhesive application means 20 that apply adhesive to a spine-portion endface of the sheet bundle conveyed from the tray; coversheet conveyance means 30 that convey to and set a coversheet at the cover-binding location Y; and cover binding means 40 disposed at the cover-binding location. An adhesive application position (hereinafter referred to as the application position) X, a cover-binding location (hereinafter referred to as the binding position) Y, and trimming position Z are disposed in this order in the bookbinding process path (hereinafter referred to as the bookbinding path) 5 . Trimming means 50 that trims true three sides of the sheet bundle covered by the coversheet are disposed in the trimming position Z. The configuration of each of these will now be explained.
Inner-Leaf Tray Configuration
The inner-leaf tray 2 disposed in the bookbinding path 5 is composed of a tray that stacks sheets in a bundle; the tray shown in the drawing is substantially horizontally oriented. A trailing edge aligning member 3 that aligns the position of the trailing edge of the sheet and side guides 4 a , 4 b that align the positions of the sheet sides are provided in the inner-leaf tray 2 . It is acceptable for the inner-leaf tray 2 to be fastened to the apparatus frame. However, the drawing shows the tray attached to the apparatus frame to move in up and down directions between a stacking position and a conveyance out position of FIG. 1 . As shown in FIG. 2 , a gear rack 8 established on a bottom portion of the tray 2 is mated to a pinion 9 of a tray elevator motor Ma. The forward and reverse drives of the tray elevator motor Ma raise and lower the inner-leaf tray 2 between the stacking position (solid lines in FIG. 1 ) and the conveyance out position (dashed lines in FIG. 1 ). Therefore, sheets stacked on the inner-leaf tray 2 are lowered in the direction of the arrow a from the stacking position, then are moved in the direction of the arrow b to be transferred to the inner-leaf conveyance means (gripping conveyance means) 10 . Note that the symbol 7 in the drawing denotes an opening cover of the inner-leaf tray 2 ; the cover is openably linked to the apparatus casing by a hinge.
Configuration of Inner-Leaf Width Detection Means
The side guides 4 a , 4 b are composed of one or a pair of guide members to align sheets to a side or a center reference. The inner-leaf sheet width size detection means SS 1 is disposed on the side guides 4 a , 4 b shown in the drawing to detect the width size of aligned sheets. The configuration is shown in FIG. 10 . The right side guide 4 a and left side guide 4 b disposed on the top surface of the tray are connected by an interlock gear 4 g to mutually approach and separate from each other the same amount. A flag 4 f is provided on one of the side guides 4 a to detect its position. Positions of the flag 4 f are detected by a plurality of sensor arrays SS 1 to identify the inner-leaf sheet width size. Note that when using a side reference, it is acceptable to align the position of the sheets using one side guide and detect an opposite side edge of sheets aligned to position with this guide directly with a sensor.
Configuration of First Bundle Thickness Detection Means
The first sheet bundle thickness detection means St is disposed to detect the thickness of the sheet bundle stacked on the inner-leaf tray 2 . As shown in FIG. 9B , a paper contacting arm 3 a that rises and lowers along a sheet aligning surface of the trailing edge aligning member 3 is supported by a shaft 3 b on a guide member 3 e . The sheet bundle thickness detection means St 1 composed of a position detection sensor (hereinafter referred to as a “Slidac” sensor—Slidac being Toshiba Corp.'s registered trademark for a variable transformer) is provided on the paper contacting arm 3 a . Also, the paper contacting arm 3 a is constantly held at an idle position (the position shown in the drawing) over the tray via a transmission lever 3 d by magnetic force (holding torque) from an elevator motor Mi. Also, when the elevator motor Mi is rotated in a clockwise direction at the sheet conveyance out instruction signal (described below), the paper contacting arm 3 a lowers under its own weight or the force of an urging spring 3 c to the top of an uppermost sheet of paper on the tray. The first sheet bundle thickness detection sensor St 1 detects the position of the paper contacting arm 3 a to detect the thickness of the sheet bundle set on the tray.
Tray Sensor Configuration
A first sensor Se 1 is disposed on the inner-leaf tray 2 to detect the presence of sheets. (See FIG. 9B ). The configuration of the sensor is known. For example, it is possible to adopt an empty sensor and the like, so any detailed explanation thereof will be omitted. However, the sensor is composed to detect the existence of sheets on the tray.
Configuration of Sheet Conveyance Means
The inner-leaf conveyance means 10 that conveys the sheet bundle from the inner-leaf tray 2 to an downstream application position is composed as shown in FIGS. 2 and 3 . The inner-leaf conveyance means 10 is disposed in the bookbinding path 5 disposed in a longitudinal direction to intersect the device in up and down directions, as shown in FIG. 1 . The sheet bundle received from the inner-leaf tray 2 in a substantially horizontal orientation is turned 90° to become substantially vertically oriented. It is then conveyed to the downstream application position X. For that reason, the inner-leaf conveyance means 10 is composed of a pair of clampers 13 a , 33 b ( 13 a is movable; 13 b is fixed) that grip the sheet bundle, and a unit frame 12 that is equipped with both clampers 13 a , 13 b . Also, this unit frame 12 is rotatably supported on the apparatus frame by the rotating shaft 11 . By rotatingly driving a fan-shaped gear 35 by a turning motor Mb equipped on the apparatus frame, the unit frame 12 turns in clockwise and counterclockwise directions of FIG. 3 around the rotating shaft 11 .
As described above, the movable clamper 13 a and fixed clamper 13 b are risibly attached to the unit frame 12 rotatably supported on the apparatus frame. A movable frame 16 matingly supported by the guide rail (rod) 16 a (partially shown in FIG. 3 ) is provided on the unit frame 12 . The pinion 17 P connected to an elevator motor Mc provided on the unit frame 12 and the gear rack 17 R provided on the movable frame 16 are meshed. Therefore, the movable frame 16 is raised and lowered by the elevator motor Mc, and can convey sheets downstream along the bookbinding path 5 .
The movable and fixed clampers 13 a , 13 b are mounted on the movable frame 16 . The fixed side clamper 13 b is fastened to the left and right side frames that compose the movable frame 16 with a width size to grip sheets; a rod 18 is disposed on the movable side clamper 13 a , the rod 18 matingly supported by the bearing 14 provided on the movable frame 16 . A pinion of the grip motor Md is meshingly linked to the gear rack 18 R integrally formed on the rod 18 .
Therefore, the movable clamper 13 a approaches the fixed clamper 13 b with the grip motor Md thereby nipping (gripping) sheets with the fixed clamper 13 b . Conversely, when the movable clamper 13 a separates from the fixed clamper 13 b in an opposite direction, the nipping of the sheets is released (the grip on the sheets is freed). In this way, the clampers 13 a , 13 b are caused to grip the sheet bundle by the grip motor Md. The turning motor Mb changes the orientation of the sheet bundle from a horizontal orientation to a vertical orientation, then the elevator motor Mc moves the vertically oriented sheet bundle to the downstream application position X along the bookbinding path P 5 . Note that Sg in the drawing denotes the grip end sensor. The grip end sensor is disposed on the movable clamper 13 a to detect whether the sheet bundle has been securely gripped with the predetermined pressure.
Configuration of Second Bundle Thickness Detection Means
The second sheet bundle thickness detection means St 2 is disposed on the movable flapper 13 a to detect the thickness of the gripped sheet bundle. The movable clamper 13 a is caused to approach the fixed clamper 13 b as described above by the grip motor Md to grip the sheet bundle. This gripping action is detected by the grip end sensor Sg. This sensor detects the thickness of the sheet bundle being gripped when it detects the position of the movable clamper 13 a when the detection signal is issued. The sheets at this time are firmly compressed by an urging spring, not shown, so a highly precise detection of the sheet bundle thickness is possible. For that reason, the Slidac sensor that detects the position is disposed along with a bearing 14 on the rod integrated to the movable clamper 13 a . This sensor composes the second sheet bundle thickness detection means St 2 .
The sheet bundle thickness information detected by the second sheet bundle thickness detection means St 2 (1) sets the gap between the adhesive applicator roll, described below, and the sheet bundle according to the thickness of the sheet bundle; (2) adjusts the setting position of the coversheet and the amount it is fed to correspond to the thickness of the sheet bundle so that the sheet bundle matches the center of the coversheet; (3) adjusts the starting position (idle position) of the spine folding press means, described below, to correspond to the sheet bundle thickness; and (4) adjusts the starting position (idle position) of the trimming means, described below, to correspond to the sheet bundle thickness. That information is used in finishing processes.
Configuration of Adhesive Application Means
Adhesive application means 20 is composed of an adhesive container 21 that holds an adhesive, such as glue and the like; an applicator roller 22 rotatably installed in the container; a drive motor Me that rotatingly drives the applicator roller 22 ; and a drive motor Mf that reciprocates the adhesive container 21 along the sheet bundle. FIG. 4 is a conceptual view of the adhesive application means. The adhesive container 21 is formed to a shorter length (dimension) than the bottom side edge of the sheet bundle (the spine portion covered at the binding process). This is supported on a guide rail 24 (see FIG. 4 ) of the apparatus frame to move along the bottom side edge of the sheet bundle along with the applicator roller 22 installed in that container. The adhesive container 21 is connected to a timing belt 23 installed on the apparatus frame; a drive motor Mf is connected to the timing belt 23 .
The adhesive container 21 shown in the drawings is configured to move along the sheet bundle, but it is also acceptable to adopt a tray shape that is longer than the length of the sheet bundle, and to move only the applicator roller 22 in the left and right directions of the drawing. Note that the applicator roller 22 shown in the drawing is composed of a porous and heat resistant material and is configured to be impregnated with adhesive. This enable adhesive to form layer on the circumference of the applicator roller.
The drive motor MF reciprocates the adhesive container 21 between a home position HP and a return position RP where the return operation is started along the sheet bundle, and to a refilling position where adhesive can be charged to the container. Each position is set to the positional relationships shown in FIG. 4 ; the return position RP is set based on sheet width size information. The adhesive container 21 is set to the home position HP when the power is turned on (at device initialization). For example, this moves from the home position HP to the return position RP after a predetermined amount of time (estimated time for the sheet bundle to reach the adhesive application position) after a sheet grip signal of the grip end sensor Sg of the inner-leaf conveyance means 10 . At the same time as this movement, the drive motor Me starts rotating the applicator roller 22 . Note that Sp in the drawings denotes the home position sensor of the adhesive container 21 .
With the rotation of the drive motor Mf, the adhesive container 21 starts moving from the left side of FIG. 4 to the right side along the guide rail 24 . The amount of travel of the inner-leaf conveyance means 10 is adjusted by the elevator motor so that the applicator roller 22 pressingly contacts the sheet bundle to slightly separate the edges of the sheets (see FIGS. 5A and 5C ) in the advancing path, and forms a predetermined gap Ga with the sheet bundle edge in the return path (to return from the return position RP to the home position HP) to apply adhesive (see FIGS. 5B and 5D ). The adjustment of the amount of adhesive using the amount of travel of the sheet bundle is based on the sheet bundle thickness information from the second sheet bundle thickness detection means St 2 . If the sheet bundle is thick, the gap Ga is widened to increase the amount of adhesive applied. If the thickness is small, the gap Ga is narrowed to reduce the amount of adhesive applied. Instead of controlling the elevator motor Mc of the inner-leaf conveyance means 10 to adjust the amount of travel of the sheet bundle, it is also acceptable to equip roller position adjusting means that adjust the up/down position of the applicator roller 22 . When the drive motor Mf moves the adhesive container from the operating position where adhesive is applied to the sheet bundle to the idle position EP separated therefrom at the idle instruction signal, adhesive can be recharged from an adhesive tank 25 disposed in the idle position EP.
The unit shown in FIG. 1 has a feature to set the gap Ga based on the “bundle makeup” information of the inner-leaf sheets, described below, at the same time as the sheet bundle thickness information from the second sheet bundle thickness detection means St 2 , when setting the gap Ga. The bundle composition of the inner-leaf sheets is input using a control device B, described below. Input selections can be either “composed of only simple sheets in the state shown in FIG. 7B (hereinafter referred to as simple sheets),” “composed of simple sheets and saddle-stitch sheets in the state shown in FIG. 7D (hereinafter referred to as mixed sheets),” or “composed only of saddle-stitch sheets in the state shown in FIG. 7C (hereinafter referred to as folded sheets).” Here, the gap Ga is set so that the standard gap Ga 1 for simple sheets, and the non-standard gap Ga 2 for mixed sheets or folded sheets have a relationship of Ga 2 >Ga 1 . (See FIG. 7A ) Note that in this case, the differences in gaps are determined by experiment for the properties of the adhesive being used.
Coversheet Feeder Unit
The sheet bundle applied with adhesive at the adhesive application means 20 is bound to the coversheet, but the feeding of the coversheet will now be explained. The coversheet feeder unit B disposed over the bookbinding unit A is composed of one or a plurality of coversheet stacking trays 31 for stacking sheets (a drawing shows two tiers of stacking trays), pickup means 32 for separating sheets on the coversheet stacking tray 31 into single sheets, and a coversheet feeding path 6 for guiding a sheet from the pickup means 32 to the binding position Y.
Special sheets such as thick or coated sheets are prepared as coversheets in the coversheet tray 31 . A sheet on the stacking tray is conveyed to the coversheet conveyance path 6 at a control signal sent from the bookmaking unit A. The reason why there is a two-tiered approach to the coversheet stacking trays 31 is that it is possible to prepare different types of coversheets on the trays in advance, so the operator can select the type of coversheet to bind to the sheet bundle from the selected stacker.
Configurations of Coversheet Conveyance Path
The configuration of the coversheet conveyance path 6 will now be explained with reference to FIG. 2 . The coversheet conveyance path 6 conveys and sets a coversheet from the coversheet tray 31 to the binding position Y established at the intersection of the bookbinding path 5 . Particularly, a feature of the unit shown in the drawing is that the length of the coversheet conveyance path 6 , in other words the length of the path from the coversheet tray 31 to the binding position Y (L 1 , not shown) and the length of the path from the inner-leaf tray 2 of the bookbinding path 5 to the binding position Y (L 2 ; not shown) are set to a relationship of L 1 >L 2 . To make the unit more compact, the inner-leaf tray 2 and coversheet tray 31 are arranged one above the other, and the length (L 1 ) of the path of the coversheet tray is longer than the length (L 2 ) of the path of the inner-leaf tray 2 . This makes a more compact unit possible that conveys a coversheet requiring twice the length of the inner-leaf sheets to the binding position Y.
The conveyance roller that conveys the coversheet and an aligning mechanism 35 are disposed in the coversheet conveyance path 6 . A path guide that forms the coversheet conveyance path 6 is composed of movable guides 36 a , 36 b that move up and down between a guiding orientation and a retreated orientation upstream and downstream of the binding position Y. (See FIG. 2 ) This guide is positioned in the guiding orientation (see the state shown in FIG. 3 ) to guide the coversheet to the binding position Y, and is shifted to the retreated orientation (not shown) when the coversheet is being folded.
The aligning mechanism 35 is composed of nipping claw 35 a that engages a trailing edge of the coversheet, an aligning member 35 b that offsets in a direction perpendicular to the direction of conveyance the coversheet gripped by the nipping claw 35 a , and a forward and reverse drive roller 35 r that switches back the coversheet conveyed in the coversheet conveyance path 6 to abut the nipping claw 35 a , provided in the coversheet conveyance path 6 . The forward and reverse drive roller 35 r is composed to move up and down with regard to its retreated idle position above the coversheet.
Therefore, the coversheet conveyed into the coversheet conveyance path 6 is switched back and conveyed by the reverse drive of the forward and reverse drive roller 35 r at a predetermined timing after its trailing edge passes the aligning mechanism 35 . Then, the trailing edge of the sheet abuts the nipping claw 35 a which corrects any skewing of the sheet. In this state the nipping claw 35 a grips the trailing edge of the sheet and the aligning member 35 b equipped with this nipping claw 35 a moves in a direction perpendicular to the direction of sheet conveyance to align the sides of the sheet. This corrects any skewing the coversheet may have in the leading and trailing edge directions of sheet conveyance, and the position of the sheet in its width direction (a direction perpendicular to the direction of sheet conveyance) (in other words correction of the side edge positions). The coversheet that has been aligned is conveyed toward the downstream binding position Y by the forward and reverse drive roller 35 r . Conveying and setting the sheet at the binding position Y is performed by the coversheet conveyance means (roller) 30 conveying the coversheet from the aligning position a predetermined amount.
Configuration of Coversheet Size Detection Means
In the same way as the inner-leaf tray 2 , a second sensor Se 2 that detects the presence of sheets on the tray and coversheet width size detection means SS 2 that detects the width of the sheets on the tray are disposed in the coversheet tray 31 . The second sensor Se 2 has the same configuration as that in the inner-leaf tray 2 explained with reference to FIG. 9 , and the detection means SS 2 has the same configuration as that in the inner-leaf tray 2 explained with reference to FIG. 10 ; both sensors are disposed in the coversheet tray 31 .
A coversheet length size detection sensor SS 3 that detects a trailing edge of the conveyed coversheet is disposed in the coversheet conveyance path 6 . The length of the sheet is calculated using the time from when this sensor detects the leading edge of the coversheet to the time it detects the trailing edge of the coversheet and the sheet conveyance speed.
Configuration of Cover Binding Means
Adhesive is applied by the adhesive application means 20 to the bottom edge of the sheet bundle gripped by the inner-leaf conveyance means 10 at the sheet bundle conveyance path P 5 , and the adhesive container 21 is then retracted to its home position HP outside of the path. The inner-leaf conveyance means 10 moves the sheet bundle along the bookbinding path 5 from the application position X to the binding position Y. At the same time, a coversheet is conveyed to the binding position Y and set at the coversheet conveyance path 6 . Cover binding means 40 is provided at the binding position Y. This cover binding means 40 is composed of a spine rest plate 41 and spine-folding press members 42 .
Configuration of Spine Rest Plate
As shown in FIG. 6 , the shutter vane-shaped spine rest plate 41 that intersects the bookbinding path 5 is disposed in the binding position Y. This spine rest plate 41 is disposed directly under (at the downstream side) the spine-folding press members 42 a , 42 b at the binding position Y of the bookbinding path 5 . These spine-folding press members 42 a , 42 b cooperate to fold the coversheet. The spine rest plate is configured to move between an operating position positioned in the bookbinding path 5 , and is configured to be advanced and retreated by drive means (such as a solenoid and the like), not shown. Also, the spine rest plate 41 is formed by a metal plate with high coefficient of thermal conductivity and good heat dissipation effect, and can cool the adhesive (hot-melt adhesive is shown in the drawing) applied to the sheet bundle.
Control of Spine Press Members
The control of the spine press members 42 a , 42 b will now be explained. The spine press members 42 a , 42 b are controlled to be positioned at the spine folding position (see FIG. 8A ) when a coversheet is fed from the coversheet conveyance path 6 to the binding position Y, and to be positioned at their home positions (see FIG. 8B ) retracted from the bookbinding path 5 when the sheet bundle and coversheet from the bookbinding path 5 are being joined. Next, the spine press members 42 a , 42 b fold the coversheet in the process of moving from their home positions to the spine folding positions ( FIG. 8C ). A transmission mechanism such as a drive motor, and rack and pinion are installed on the left and right spine press members 42 a , 42 b.
Configuration of Bundle Posture-Reorienting Means
The following will now explain the finishing process for the sheet bundle formed into a booklet. The finishing process trims true three side edges of the sheet bundle in booklet form excluding the spine portion. Folding rollers 45 are disposed downstream of the cover binding means 40 . Further downstream, a bundle-posture reorienting means 46 that turns the sheet bundle over from top to bottom, and trimming means 50 that trims true the edges of the sheet bundle are disposed in the trimming position Z positioned further downstream. The bundle posture changing means 46 turns the covered sheet bundle fed from the binding position Y to a predetermined direction (or orientation) and conveys the sheet bundle to the downstream trimming means 50 or to the storage stacker 57 . The trimming means 50 trims the fringes of the sheet bundle to align the edges. Therefore, the bundle posture changing means 46 is equipped with swivel tables 47 a , 64 b that grip and turn the sheet bundle fed from the folding rollers 45 . As shown in FIG. 1 , the swivel tables 47 a , 47 b are furnished on the unit frame 48 installed on the apparatus frame to rise and lower. The pair of swivel tables 47 a , 47 b that sandwich the bookbinding path 5 are rotatably supported on bearings in the unit frame 48 ; one of the movable swivel tables 47 b is supported to move in a sheet bundle thickness direction (a direction orthogonal to the bookbinding path 5 ). Spinning motors, not shown, are furnished in the bookbinding path for the swivel tables 47 a , 47 b to change the posture (or orientation) of the sheet bundle.
Configuration of Trimming Means
Trimming means 50 are provided downstream of the bundle posture changing means 46 . As shown in FIG. 1 , the trimming means 50 is composed of a trimming edge pressing member 52 that pressingly supports the edge of the sheet bundle to be trimmed against a blade-edge bearing member 51 , and a trimming blade unit 53 . The trimming edge pressing member 52 is disposed in a position that opposes the blade-edge bearing member 51 disposed in the bookbinding path 5 , and is composed of a pressing member that is moved in a direction that is perpendicular to the sheet bundle by drive means, not shown. The trimming blade unit 53 is composed of a flat, blade-shaped trimming blade 54 and a cutter motor Mh that drives that blade. The trimming means 50 with this configuration cuts a predetermined amount around the edges, excluding the spine of the sheet bundle that has been made into a booklet, to align the edges.
A discharge roller 55 and storage stacker 57 are disposed downstream of the trimming position Z. This storage stacker 57 stores sheet bundles in an inverted manner as shown in FIG. 1 . This storage stacker 57 is disposed to be drawn from the unit as shown in FIG. 1 . The stacker can be drawn toward the front side of the apparatus (the front side of the sheet in FIG. 1 ). The operator can view it from the top direction when it is drawn to the front of the unit.
Configuration of Control Means
The following will now explain the control of the bookbinding unit A shown in FIG. 1 . FIG. 11 is a block diagram shown a configuration of the controls. The control is composed of a bookbinding control unit 65 furnished in the bookbinding unit A, and a controller 60 . The controller 60 in the drawing is composed of a computer device. As shown in the drawing, the controller 60 is composed of an input means 61 , display unit 62 and control CPU 60 P; the bookbinding control unit 65 is composed of a control CPU 65 P built-in to the bookbinding unit A.
The controller 60 performs the role of input means 61 for inputting processing conditions when binding a booklet, a memory means for storing inputted data, and the function of the display means 62 for displaying a jam or other states of the bookbinding process. Note that the controller 60 can also be integrated to the bookbinding control unit 65 .
Particularly, the “size of the saddle-stitch sheets,” “coversheet size,” and “inner-leaf sheet bundle makeup” are input with the unit shown in the drawing. This information is used as the control conditions for the bookbinding processes described below. Also, although not shown, it is possible to add functions to the controller 60 . For example, a layout function that adjusts the coversheet setting position so that the title formed on the spine of the coversheet is positioned in the center, or a function for setting the bookbinding process such as adjusting the amount of adhesive that is applied to the sheet bundle according to the properties of the adhesive being used can be added for the aspects of the bookbinding process. When using a computer as the controller 60 , it is simple to add these functions or create programs to correct them.
A ROM 75 that stores a program for executing the bookbinding operation, and a RAM 76 that stores data that sets the control conditions are connected to the bookbinding control unit 65 . The bookbinding control unit 65 is composed of the unit starting control unit 65 a , the inner-leaf conveyance control unit 65 b , the coversheet conveyance control unit 65 c , the adhesive application control unit 65 d , the coversheet binding process control unit 65 e , the trimming process control unit 65 f , and the stack control unit 65 g.
An appropriate size determining means 66 is incorporated in the bookbinding control unit 65 for determining whether the size of sheets prepared in the inner-leaf tray 2 and the coversheet tray 31 are capable of performing the predetermined bookbinding operation. This means is composed of a primary determining means 66 a for determining the size using the sheet width size, and a secondary determining means 66 b for determining the size using the sheet length. The primary determining means 66 a is incorporated in the unit starting control unit 65 a.
The unit starting control unit 65 a is equipped with a first sensor Se 1 disposed in the inner-leaf tray 2 ; a sheet presence determining means 67 for determining whether saddle-stitch sheets and coversheet have been set in the trays using signals from a second sensor Se 2 disposed in the coversheet tray 31 ; primary determining means 66 a of the appropriate size determining means; and the tray sheet bundle thickness comparison means 68 . Data 76 a of the maximum sheet bundle thickness that can be gripped by the inner-leaf conveyance means 10 is provided from the RAM 76 to the comparison means 68 .
The unit starting control unit 65 a configured as described above is configured to determine whether sheets have been set in the inner-leaf tray 2 and coversheet tray 31 , whether the widths of the sheets match, and whether the thickness of the sheet bundle set in the inner-leaf tray 2 exceeds the maximum permissible thickness of a sheet bundle.
The inner-leaf conveyance control unit 65 b controls the inner-leaf conveyance means 10 . If predetermined conditions are met at the unit starting control unit 65 a , the inner-leaf conveyance means 10 is started to convey inner-leaf sheets from the inner-leaf tray 2 into the unit. For that reason, the speed setting data 76 b to be set based on the “bundle makeup information” from the input means 61 is received from RAM 76 to set the speed to convey the inner-leaf sheets. The second sheet bundle thickness detection means St 2 detects the thickness of the sheet bundle gripped by the inner-leaf conveyance means 10 and that thickness information is stored in an internal memory.
The coversheet conveyance control unit 65 c starts the pick-up means disposed in the coversheet tray 31 and feeds one sheet from the tray at a time. The coversheet length detection means SS 3 disposed in the coversheet conveyance path 6 detects the length of the coversheet. The secondary determining means is provided to determine whether the length of the coversheet is able to perform the predetermined bookbinding process, based on the value of that detection. Operation data 76 c that calculates a length of the bookbinding process is supplied from the RAM 76 in the control unit. Also, a conveyance amount operation means (not shown) is provided in the coversheet conveyance control unit 65 c for positioning the coversheet in the binding position Y based on the sheet bundle thickness detected by the second sheet bundle thickness detection means St 2 .
The adhesive application control unit 65 d is composed of an adhesive amount setting means and temperature setting means. Adhesive amount setting data 76 d and adhesive temperature control data 76 e are provided from RAM 76 . Particularly, the adhesive amount setting means sets the adhesive amount based on bundle makeup information of the inner-leaf sheets, and sheet bundle thickness information detected by second bundle thickness detection means. This is configured to adjust the coating gap Ga between an edge of the sheet bundle in the inner-leaf conveyance means 10 and applicator roller according to that setting.
This coversheet binding control unit 65 e controls the spine rest plate 41 and spine-folding press members 42 a , 42 b . That control is configured to execute the operations explained with reference to FIG. 8 . Cooling time setting data 76 f for cooling adhesive is supplied from RAM 76 when the coversheet binding control unit 65 e touches the spine covering portion against the spine rest plate 41 after the binding process. This cooling time setting data selects one of a plurality of data based on the inner-leaf sheet thickness configuration information.
The trimming process control unit 65 f is composed of operation means that calculates the trimming amount using the trimming blade 54 , speed setting means for setting the trimming speed of the trimming blade 54 and stroke setting means for setting the movement stroke of the trimming blade 54 . Also, the trimming amount operation means is configured to calculate the trimming about using inner-leaf sheet size information, coversheet size information, and sheet bundle thickness information detected by the second sheet bundle thickness detection means St 2 . The speed setting means is configured to set the cutting speed using the inner-leaf sheet bundle makeup information. The stroke setting means sets the trimming starting position (the idle position) of the trimming blade using sheet bundle thickness information.
The stack control unit 65 g controls the discharge roller 55 and is configured to store sheet bundles conveyed from the bookbinding path 5 in the storage stacker.
Explanation of Bookbinding Operation
The bookbinding procedures in the unit shown in FIG. 1 will now be explained with reference to the flowchart shown in FIG. 12 . The unit shown in FIG. 1 is configured to perform the following bookbinding operations using the bookbinding control unit 65 disposed in the bookbinding unit A and the controller 60 disposed in the computer device connected to the bookbinding control unit 65 .
Initial Operations
First, the bookbinding control unit 65 executes an initialization operation when the unit power is turned ON. (St 01 ). When the unit power is turned ON, the control unit composed of the control CPU 65 P detects whether there are any sheets remaining in the bookbinding path 5 and coversheet conveyance path 6 . If there is a sheet existing in either of the paths, the control CPU 65 P issues a “jam” warning. Along with this, the adhesive application means 20 , the cover binding means 30 and the trimming means 50 are set to their initial states (home positions).
Sheet-Setting Operation
Next, the controller 60 detects whether there is a sheet in the inner-leaf tray 2 and coversheet tray 31 . The first and second sensors Se 1 and Se 2 disposed in each tray detect (determine) whether there are sheets (St 02 ). When both sensor means Se 1 and sensor means Se 2 are ON, the system waits for sheets to be prepared in the trays and when both are ON, the system shifts to the next step.
Size Information Input
The controller 60 then prompts for input of the coversheet size information, inner-leaf sheet size information and inner-leaf sheet bundle makeup information from the input device (means) 61 . That information can be selected or directly input via a computer. In such a case, sensors can be provided in each tray to detect sheet sizes using inner-leaf sheet size information and coversheet size information. However, the drawing shows only the inner-leaf sheet width size detection means SS 1 disposed to detect the size of the inner-leaf sheet, and the coversheet width size detection means SS 2 that detects the size of the coversheet is positioned in the coversheet tray 31 ; the coversheet length size detection means SS 3 that detects the length of the sheet is disposed in the coversheet conveyance path 6 . The system is configured to make a primary determination of whether the inner-leaf sheets and coversheet can perform the predetermined bookbinding operation using the width size information, and then a secondary determination using the coversheet length information.
Sheet-Bundle-Makeup Information Input
Further, for “inner-leaf sheet bundle makeup information” a user is prompted to input, using the input means 61 of the controller 60 , the structural makeup of a bundle of inner-leaf sheets set on the inner-leaf tray 2 . The user inputs whether the inner-leaf sheets collated into a sheet bundle are: constituted from simple sheets only (“simple-sheet makeup” hereinafter), constituted from simple sheets and saddle-stitch folded sheets (“mixed-sheet makeup” hereinafter), or constituted from saddle-stitch folded sheets only (“folded-sheet makeup” hereinafter). This bundle makeup information is used to set the control conditions, described below, of the bookbinding process that follows.
Suitable Size Primary Determination
The controller 60 performs the primary determination of whether the predetermined bookbinding process is possible with each sheet using a conforming sheet determination means 66 a based on detection results from the inner-leaf sheet width detection means SS 1 disposed in the inner-leaf tray 2 and the coversheet width detection means SS 3 disposed in the coversheet tray 31 . (Step St 04 ) Determining whether the inner-leaf sheet width and coversheet width (the length in the top to bottom direction after the bookbinding process) match determines whether the predetermined bookbinding process is possible. Also, the bookbinding control unit 65 prohibits shifting to the later processes (St 05 ) when both sheet widths do not match, and issues a “size mis-match” warning to the operator at the same time. If the operator inputs in instruction to “continue process with unmatched sizes,” this is cleared and the system shifts to the next step.
Operation of First Bundle Thickness Detection Means
Next, the controller 60 issues an “inner-leaf conveyance out” command to convey out the inner-leaf sheet set in the inner-leaf tray 2 toward the inner-leaf conveyance means 10 . When this command is received (when sizes match in the primary determination), the bookbinding control unit 65 detects the thickness of the inner-leaf sheet bundle set in the inner-leaf tray 2 . This is detected using the first sheet bundle thickness detection means St 1 disposed in the inner-leaf tray 2 . (First sheet bundle thickness detection; St 05 ) This sheet bundle thickness is canceled by rotating the paper contacting arm 3 a held magnetically at its initial position (the uppermost position) in advance with the rotation of the elevator motor Mi. The paper contacting arm 3 a is lowered by an urging spring 3 c to touch the uppermost sheet on the tray. At this time, the position of the paper contacting arm detects the sheet bundle thickness by detection using the Slidac sensor.
The controller 60 determines whether the sheet bundle can be conveyed based on detection values for the first sheet bundle thickness detection means St 1 . (St 06 ) The detection value and the preset maximum permissible sheet bundle thickness of the inner-leaf conveyance means 10 are compared for this determination. The controller 60 then determines whether the detection value exceeds the maximum permissible sheet bundle thickness. When it is determined that the maximum permissible sheet bundle thickness has been exceeded, the saddle-stitch sheet conveyance out is prohibited. The controller 60 warns the operator by displaying on a display unit that the maximum sheet bundle thickness permissible for bookbinding has been reached.
Operations for Conveying Out Inner-Leaf Sheets
When the number of inner-leaf sheets is determined to be less than the maximum permissible sheet bundle thickness in the first sheet bundle thickness determination, the bookbinding control unit 65 hands the inner-leaf sheets to the downstream inner-leaf conveyance means 10 . For that reason, the unit in the drawing lowers the inner-leaf tray 2 from the setting position to the conveyance out position. After the tray is lowered, the inner-leaf conveyance means 10 grips the sheet bundle on the tray using the fixed clamper 13 b and the movable clamper 13 a . A sheet feeding means, not shown, is installed in the inner-leaf tray 2 . This pushes the sheet bundle along the tray to the inner-leaf conveyance means 10 . The sheet bundle on the tray is conveyed out to the downstream inner-leaf conveyance means 10 (St 07 ).
Second Sheet-Bundle Thickness Detection
The inner-leaf conveyance means 10 that transfers the inner-leaf sheets as described above changes the orientation of the sheet bundle simultaneous to the sheet bundle thickness being detected. The inner-leaf conveyance means 10 nips the sheet bundle between the fixed clamper 13 b and movable clamper 13 a with a strong pressure. The second sheet bundle thickness detection sensor St 2 and gripping sensor Sg are provided on the movable clamper 13 a ; the second sheet bundle thickness detection means St 2 detects the sheet bundle thickness. (St 08 ) These detection values are used to set control conditions such as the amount of adhesive to apply using the adhesive application means 20 , the coversheet setting position of the coversheet conveyance means 30 , the idle position of the cover binding means 40 , and the trimming blade idle position of the trimming means 50 and the like.
Changing Bundle Orientation
At the same time as the second sheet bundle thickness detection, the bookbinding control unit 65 receives the gripping end signal from the gripping end sensor Sg, then rotatingly drives the turning motor Mb to turn the sheet bundle substantially 90°. Then, the inner-leaf sheets handed over in a horizontal orientation from the inner-leaf tray 2 are turned substantially vertically to be conveyed along the bookbinding path 5 which is also vertically oriented.
Setting Application Position of Inner-Leaf Sheets
The bookbinding control unit 65 conveys the inner-leaf sheets and sets them at a predetermined adhesive application position using the elevator motor Mc of the inner-leaf conveyance means 10 . (St 09 ). At that time, the bookbinding control unit 65 varies the speed to convey the inner-leaf sheets to the application position X using the inner-leaf conveyance means 10 according to the bundle makeup information. For that purpose, the bookbinding control unit 65 , in an instance of a “mixed-sheet makeup” or a “folded-sheet makeup” that includes saddle-stitch folded sheets, compares the instance with the case of a “simple-sheet makeup” and sets the speed of the elevator motor Mc for the inner-leaf conveyance means 10 to a lower rate.
Next, the bookbinding control unit 65 is equipped with inner-leaf sheet setting position operation means that calculate a setting position of the inner-leaf sheets based on the bundle makeup information and the bundle thickness information. As described above, the inner-leaf sheet setting position operation means sets the inner-leaf sheets at the adhesive application position so that the adhesive application amount is standard when the bundle makeup of the inner-leaf sheets is (1) configured of simple sheets, and so that the application amount is greater compared to the standard amount when the bundle makeup of the inner-leaf sheets is (2) configured of mixed sheets or folded sheets. At the same time as this, this sets the inner-leaf sheets at the adhesive application position to increase or decrease the amount of adhesive to apply according to the bundle thickness detected by the second bundle thickness detection means St 2 . (St 09 )
For that reason, the inner-leaf conveyance means 10 adjusts the gap Ga (see FIG. 6 ) between the applicator roller 21 and edges of the sheets disposed in the adhesive application position when using the elevator motor Mc to set the inner-leaf sheets at the application position X. This position adjustment is achieved by the varying the amount of rotation of the elevator motor Mc. However, operation means are configured to calculate the amount of rotation using the bundle makeup information and sheet bundle thickness information. A data table that sets the amount of motor rotation according to the inner-leaf sheet bundle thickness for the operation means is provided on RAM 76 . Rotation amounts are set in this table to correspond to bundle thickness with standard and non-standard. Compared to standard, the adhesive application amount is greater for non-standard. The differences in the adhesive application amounts for standard and non-standard are determined by testing according to the adhesive properties and application temperature (viscosity). When the inner-leaf sheet bundle makeup only has simple sheets, the adhesive application amount is set to standard. For the other sheet bundle constitutions, the adhesive application amount is set to non-standard.
Coversheet Conveyance
Next, almost in tandem to setting the sheet bundle at the adhesive application position, the bookbinding control unit 65 conveys the coversheet from the coversheet tray 31 to the cover-binding location Y. (St 10 ) For that reason, the bookbinding control unit 65 rotatingly drives the pickup means 32 of the coversheet tray 31 at a signal from the gripping end sensor Sg of the inner-leaf conveyance means 10 , for example, to separate coversheets into single sheets. The coversheet is fed to the coversheet conveyance path 6 and to the aligning mechanism 35 . The coversheet size that reaches the aligning mechanism 35 is detected by the coversheet length detection means SS 3 . In other words, the sensor detects the leading and trailing edge of the coversheet conveyed through the coversheet conveyance path 6 . The time for the sheet to pass therethrough is used to calculate the length of the sheet in its direction of conveyance to detect the length of the coversheet.
Suitable Size Secondary Determination
The controller 60 recognizes the length of the coversheet using the detection signal from the length detection means of the coversheet, and determines whether the coversheet is twice the length of the coversheet input using the input means 61 (St 11 ). In other words, the controller 60 determines whether the length of the coversheet conforms to the predetermined bookbinding process. The controller 60 prohibits application of adhesive by the adhesive application means 20 and processes a jam when the length is determined to be non-conforming at the secondary determination.
The jam process is either for the operator to remove the non-conforming coversheet that is in the coversheet conveyance path 6 , or to convey it out of the unit from an ejection outlet (discharge outlet). Also, the inner-leaf sheets are conveyed out from the bookbinding path 5 to the stacker 57 by the inner-leaf conveyance means 10 . At this time can be bound (top binding) by adhesive to prevent the sheet bundle from becoming in disarray.
Setting Coversheet into Binding Location
At the determination above, when the coversheet size conforms to the bookbinding process, the bookbinding control unit 65 controls a coversheet conveyance roller 30 to convey the coversheet from the aligning mechanism 35 and sets it at the cover-binding location Y. (St 12 ) The positioning of the coversheet at the cover-binding location is set so that the coversheet spine binding portion is positioned at the reference position shown in FIG. 8 , considering the bundle thickness detected by the second bundle thickness detection means St 2 . In other words, the coversheet is fed to the cover-binding location Y so that the fore-edge of the coversheet is aligned after the spine is bound, according to the thickness of the sheet bundle.
Adhesive Application Operation
The bookbinding control unit 65 receives the signal that the coversheet is set at the cover-binding location Y, and coats the spine portion of the sheet bundle set at the adhesive application position with adhesive at step St 09 . (St 13 ) The adhesive application is executed by the adhesive application means 20 reciprocating the adhesive container 21 along an edge of the sheet bundle. In other words, with the outward movement of the adhesive container 21 , the edge of the sheet bundle is caused to separate (the states of FIGS. 5A and 5C ) and applies adhesive in the return movement ( FIGS. 5B and 5D ).
Coversheet Binding Operation
Next, the bookbinding control unit 65 the inner-leaf sheets in the inner-leaf conveyance means 10 to the cover-binding location Y and touches the sheet bundle to the preset spine binding portion of the coversheet in an upside-down T shape. The coversheet at this time is supported by the spine rest plate 41 and the spine-folding press members 42 retreat from the spine folding position. In this way, after abutting and joining the inner-leaf sheets to the coversheet, the bookbinding control unit 65 moves the spine-folding press members 42 to the spine folding position. The amount of movement of the spine-folding press members is set according to the sheet bundle thickness detected by the second sheet bundle thickness detection means St 2 . The coversheet is bound to the sheet bundle at this cover-binding location Y. (St 14 )
Adhesive Cooling
After the coversheet is bound to the sheet bundle, the bookbinding control unit 65 waits for a predetermined cooling time to pass while pressing the coversheet against the spine rest plate 41 . (St 15 ) When the cooling time has passed, the adhesive (hot-melt adhesive) coated on the spine portion of the inner-leaf sheets hardens and forms the spine portion of the booklet. The bookbinding control unit 65 is configured to set the cooling time according to the sheet bundle makeup information. In other words, depending on the bundle makeup, the adhesive application amount is set to a standard cooling time when the sheet bundle is standard or when it is non-standard, it is set to a non-standard cooling time, the latter, non-standard cooling time set to be longer than the standard cooling time.
Trimming
After the cooling time has passed, the bookbinding control unit 65 feeds the sheet bundle encased in the coversheet to the downstream folding rollers 45 where they fold the coversheet to completely fold the coversheet. The trimming means 50 is disposed downstream of the folding rollers 45 . At the trimming position Z, the trimming means trims true three sides of the sheet bundle, excluding the spine portion. (St 16 ) The swivel tables 47 a , 47 b change the orientation of the sheet bundle so that the trimming means 50 can trip the top, bottom and fore-edge portions in that order. At this time, the bookbinding control unit 65 changes the speed of the movement of the trimming blade 54 based on the bundle makeup information of the inner-leaf sheets. In other words, if the sheet bundle is composed of simple sheets the speed is high, and if the sheet bundle is composed of folded sheets, the speed is low.
Stacking Storage Operation
The bookbinding control unit 65 feeds the sheet bundle to the discharge roller when the trimming process is completed and stores the sheet bundle in the stacker 57 . (St 17 )
As described above, the present invention is equipped with a controller 60 and bookbinding control unit 65 to vary the adhesive application amount using the adhesive application means, the adhesive cooling amount using the cover binding means, and/or the trimming speed using the trimming means according to when the bundle makeup of the sheet bundle set on the inner tray is (1) composed only of simple sheets, (2) composed of a mix of saddle-stitch and simple sheets, and (3) composed of only saddle-stitch sheets.
For that reason, the control conditions are set so that the adhesive application amount is greater for (2) and (3) that include saddle-stitch sheets, the adhesive cooling time is longer and the trimming speed is slower. Only the outermost sheet of saddle-stitch sheets that have been folded over each other is coated with adhesive and bound, and a gap (gap d in FIGS. 7C and D) is formed at the spine portion between separate sheet bundles. However, the adhesive impregnates this gap portion and hardens the folded sheet bundle to bind them to the coversheet. At the same time as this, there is no wrinkling or unevenness caused by the gap d (because of the adhesive filing the gaps) when the spine portion is folded and pressed.
Also, by lengthening the cooling time setting when the sheet bundle makeup includes saddle-stitch sheets, there is no worry of adhesive leaking out when trimming the sheet bundle later, and by slowing down the trimming speed, trimming can be performed without wear on the trimming blade.
The present application claims priority from Japanese Pat. App. No. 2007-244303, which is herein incorporated by reference. | Bookbinding unit enabling, in encasing inner-leaf sheets in coversheets to form booklets, secure book-forming binding regardless of whether the inner-leaf sheets constitute a simple-sheet bundle or are made up of a plurality of folded-over signature sheets. Constituent components are: inner-leaf sheet tray; coversheet tray; bookbinding process path for guiding sheets from the inner-leaf sheet tray to successive adhesive-application and cover-binding locations; inner-leaf conveyor; coversheet conveyor for conveying coversheets to the cover-binding location; bundle-spine adhesive applicator in the adhesive-application location; and cover binder in the cover-binding location. Components' controller is configured to receive input as to whether inner-sheet-bundle makeup includes saddle-stitch sheets or is of simple sheets only, and, based on the bundle makeup information, varies its control of at least one of the coversheet conveyor, adhesive applicator, and cover binder. | 1 |
BACKGROUND OF THE INVENTION
This invention is directed towards alkylene oxide adducts, especially polyether polyols, suitable for use in the preparation of flexible slabstock polyurethane foam and the manufacture of such alkylene oxide adducts from initiators comprising polymerized ethylene oxide.
When preparing polyurethane polymers, particularly flexible slabstock foam the nature of the polyol employed can be important for conferring the desired physical properties to the foamed product. Generally speaking, polyether polyols suitable for the preparation of slabstock foam will have an average functionality of from about 2 to about 4 and an equivalent weight of typically from about 800 to about 3000. Such polyether polyols can be prepared by reacting one or more alkylene oxide compounds with an initiator containing active hydrogen atoms in the presence of a basic, alkoxylation catalyst. Typically, the alkylene oxide compounds used usually include ethylene oxide and propylene oxide. Frequently an ethylene oxide content of at least 10 weight percent or more of the resulting polyether polyol is necessary if the product is to be commercially useful. The ethylene oxide content of the polyol serves a number of purposes including minimizing unsaturation and enhancing inherent surfactancy and thus ease of preparing good quality polyurethane foams. Physical properties of resulting foams including, for example, elongation properties are also improved by having an ethylene oxide content. A disadvantage of such a high ethylene oxide content is that it provides the polyol with an inherently high reactivity which consequently in manufacturing of foams permits only for narrow tin catalyst processing ranges.
Handling of, and use of alkylene oxide compounds in reactions to prepare polyether polyols requires care with respect to minimizing and preventing exposure of workers to these potentially harmful chemicals. In addition such alkylene oxide compounds by nature of their structure and oxygen content are often flammable liquids or gases, requiring further care and attention to minimize the risks of fire and/or explosion when being handled. These precautionary measures are required more so when handling ethylene oxide than other alkylene oxide compounds.
It is therefore desirable to find a means of producing polyether polyols which minimizes or eliminates the direct handling and use of ethylene oxide, and yet obtains polyether polyols which possess or confer desirable foam processing and/or foam properties
One possible way of avoiding the direct use of ethylene oxide is to use for example ethylene carbonate. When ethylene carbonate is contacted under the appropriate reaction and catalyst conditions with an active hydrogen-containing initiator it functions as ethylene oxide would do, allowing for the alkoxylation, ethoxylation, of the initiator. However, the type of catalyst and reaction conditions required are not the most favorable with respect to obtaining a polyether polyol of good quality for use in manufacturing flexible polyurethane foam. Polyether polyols so prepared can contain high levels of undesirable color, unsaturation and residues of catalyst not necessarily compatible with a polyurethane-forming reaction.
It is therefore desirable to find a means of providing a polyether polyol with an ethylene oxide content by a process which avoids the direct use of ethylene oxide as an alkoxylating agent and yet can provide products of acceptable quality which can be used to prepare polyurethane foams having commercially acceptable performance properties.
SUMMARY OF THE INVENTION
In a first aspect, this invention is a hydroxyl-terminated alkylene oxide adduct suitable for use in preparing flexible polyurethane foams which is a product having an average hydroxyl equivalent weight of from about 800 to about 3000 and containing up to about 20 weight percent polymerized ethylene oxide and which is obtained by reacting a C 3 , or higher, alkylene oxide with an initiator characterized in that the initiator comprises at least one component (a), having from about 2 to about 4 active hydrogen atoms per molecule, an average hydroxyl equivalent weight of from about 50 to about 750 and comprising from at least 50 percent by weight, polymerized ethylene oxide.
In a second aspect, this invention is a polyurethane foam prepared by reacting a hydroxyl-terminated alkylene oxide adduct with an organic polyisocyanate in the presence of a blowing agent, a surfactant and a catalyst wherein the alkylene oxide adduct is the adduct as described in the first aspect.
In a third aspect, this invention is a polyol composition for use in preparing a flexible polyurethane foam that comprises from about 1 to about 99 percent by weight of a hydroxyl-terminated alkylene oxide adduct wherein the alkylene oxide adduct comprises the adduct as described in the first aspect.
Surprisingly, it has been found that the alkylene oxide adducts of this invention, when used to prepare flexible polyurethane foam, provide for foams having equivalent physical properties to foams prepared with comparative alkylene oxide adducts containing a significantly higher ethylene oxide content. Comparative alkylene oxide adducts are prepared through direct reaction of an initiator with ethylene oxide. In addition, the tin processing range available when manufacturing foam is improved when employing alkylene oxide adducts of this invention.
This invention offers the distinct advantage of preparing competitive alkylene oxide adducts and polyurethane foams therefrom, where the availability or possibility of conducting alkoxylation reactions with ethylene oxide is restricted or not at all feasible.
DETAILED DESCRIPTION OF THE INVENTION
As already described above, this invention is a process for preparing an alkylene oxide adduct by reacting an initiator with an alkylene oxide compound
The initiator is characterized in that it comprises at least one component, component (a) having an average of from about 2 to about 4, preferably from about 2 to about 3, and more preferably about 2 active hydrogen atoms per molecule, an average hydroxyl equivalent weight of from about 50 to about 750, and comprising from at least 50 percent by weight, polymerized ethylene oxide. Component (a) is further characterized in that it has an average hydroxyl equivalent weight preferably from about 100, more preferably from about 175, and up to about 500 and more preferably up to about 400. As stated above, component (a) comprises at least in part, polymerized ethylene oxide, preferably from at least 60, more preferably from at least 70, and most preferably from at least 80 percent by weight. The remaining part when not polymerized ethylene oxide is another polymerized alkylene oxide or the residue of the initiator.
For the purpose of this invention active hydrogen atoms are defined as those hydrogens which react positively in the well-known Zerewitinoff test. See Kohler, Journal of the American Chemical Society, p. 3181, Vol. 49 (1927). Representative of groups containing active hydrogen atoms are --OH, --COOH, --SH and --NHR where R can be hydrogen, alkyl, cycloalkyl, aryl aromatic and the like. Preferred for component (a) are initiators where the active hydrogen-containing group is --COOH, or --NHR where R can be hydrogen, and especially preferred where the active hydrogen-containing group is --OH.
Suitable initiators for use as component (a) include the alkoxylated products of water, ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerine, butylene glycol, trimethylolpropane, pentaerythritol, hexane triol and its various isomers, ethylenediamine, aminoethylpiperazine, aniline, diaminotoluene, and other aromatic compounds such as 2,2-bis(4-hydroxylphenyl)propane and its halogenated derivatives and condensation products of aniline and formaldehyde, or mixtures thereof. Alkoxylated products of these compounds are adducts of the compound with one or more alkylene oxides comprising ethylene oxide. The above-mentioned compounds may also be used in combination with additional compounds, which may be non-alkoxylated, containing more than 4 active hydrogen atoms per molecule providing that in combination, as component (a), they contain a molar average of from about 2 to about 4 active hydrogen atoms per mole. Suitable additional compounds include carbohydrate compounds such as lactose, α-methylglucoside, α-hydroxyethylglucoside, hexitol, heptitol, sorbitol, dextrose, mannitol, sucrose, or mixtures thereof.
Preferred compounds for use as component (a) include the alkoxylated products of water, ethylene glycol, propylene glycol, butylene glycol, glycerine or mixtures thereof, especially preferred are the ethoxylated products of these compounds having average hydroxyl equivalent weights from about 100 to about 400.
Advantageously the initiator used in the preparation of the alkylene oxide adducts of this present invention further comprises a second component, component (b). Use of a second component can provide for alkylene oxide adducts that are more suitable for preparing flexible polyurethane foams.
When the alkylene oxide adducts of this invention are prepared where the initiator comprises components (a) and (b), component (a) is present in a quantity sufficient to provide the alkylene oxide adduct with good processing characteristics for polyurethane foam formation. Advantageously, component (a) is present in from about 5 to about 50, preferably from about 10 to about 40, and more preferably from about 10 to about 30 percent by weight based upon the combined weights of components (a) and (b) present.
Component (b) is a compound having from about 2 to about 4 active hydrogen atoms per molecule, an average hydroxyl equivalent weight of less than about 500 and comprising less than about 25 percent by weight polymerized ethylene oxide. Preferably component (b) comprises no polymerized ethylene oxide.
Advantageously, component (b) has an average hydroxyl equivalent weight from about 50, preferably from about 75, and more preferably from about 125, up to about 300, preferably up to about 200. The equivalent weight of component (b) can be outside these limits, but for reasons of equipment productivity and economics with respect to preparing the alkylene oxide adduct of this invention it is desirable to remain within these limits
Examples of organic compounds suitable as component (b) include water, ethylene glycol, propylene glycol, glycerine, butylene glycol, trimethylolpropane, pentaerythritol, hexane triol and its various isomers, α-methylglucoside, ethylenediamine, aminoethylpiperazine, aniline or condensation adducts of aniline with, for example, formaldehyde, diaminotoluene, or alkoxylated products thereof, or mixtures thereof. The above-mentioned compounds may also be used in combination with additional organic compounds containing active hydrogen atoms providing that in combination, as component (b), they contain a molar average of from about 2 to about 4, preferably from about 2 to about 3 active hydrogen atoms. Other additional compounds include those such as lactose, α-hydroxyethylglucoside, hexitol, sorbitol, dextrose, mannitol, sucrose, or their alkoxylated products, and the like.
Preferred compounds for use as component (b) are water, glycerine, trimethylolpropane, pentaerythritol, hexane triol and its various isomers, ethylenediamine, aminoethylpiperazine, or mixtures thereof, and especially preferred is glycerine. Particularly preferred as component (b) are the alkoxylated adducts of these compounds, especially propoxylated adducts of glycerine or trimethylolpropane.
Suitable alkylene oxides that can be employed for preparing the alkylene oxide adduct of this present invention are the C 3 , or higher, alkylene oxides and include the α- and β-alkylene oxides and halogenated and aryl-substituted derivatives thereof, glycidyl ethers having from about 3 to about 20 carbon atoms, cyclic ethers such as tetrahydrofuran, mixtures thereof and the like.
Exemplary of these alkylene oxides are 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, glycidol, epichlorohydrin, allyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether, mixtures thereof and the like. The preferred alkylene oxides for use in the process according to this invention include 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and mixtures thereof.
The quantity of alkylene oxide reacted with the initiator depends upon the desired equivalent weight of the alkylene oxide adduct. Advantageously, the quantity of alkylene oxide reacted with the initiator is such so as to provide a resulting adduct having an average hydroxyl equivalent weight from about 800 to about 3000, preferably from about 1000 to about 2500, and more preferably from about 1000 to about 2000.
The alkylene oxide adducts of this invention can be further characterized in that they contain polymerized ethylene oxide introduced by component (a) of the initiator. The polymerized ethylene oxide content of the adduct is up to about 20, preferably from about 1 to about 10, more preferably from about 1 to about 7, and most preferably from about 1 to about 5 weight percent of the average hydroxyl equivalent weight of the adduct. Alkylene oxide adducts of this invention having average equivalent weights and proportions of polymerized ethylene oxide outside these limits can be prepared, but when employed to prepare flexible polyurethane foam, such resulting foam may not exhibit the desired characteristics and properties.
Suitable processes for the preparation of alkylene oxide adducts have been disclosed in The Encyclopaedia of Chemical Technology, Vol. 7, pp. 257-266, published by Interscience Publishers Inc. (1951), and U.S. Pat. No. 1,922,459.
When preparing the alkylene oxide adducts of this present invention, advantageously the reaction of alkylene oxide with initiator is conducted in the presence of a catalytic amount of an alkoxylation catalyst.
The choice of alkoxylation catalyst used in the preparation of the alkylene oxide adduct is well-known to those skilled in the art of preparing polyether polyols. Preferred catalysts are compounds of the group I and group II metals of the Periodic Table comprising, for example, sodium hydroxide, potassium hydroxide, barium hydroxide, strontium hydroxide, caesium hydroxide, potassium methoxide and the like. In a preferred embodiment of this process the catalyst of choice is barium hydroxide, as this allows for the preparation of adducts with a minimized unsaturation level.
Unsaturation is the formation of adducts containing a double bond. Such adducts can form through rearrangement reactions of any alkylene oxide compound containing hydrogen atom(s) on a tertiary center of the oxirane ring. Propylene oxide is especially prone to such rearrangement.
When preparing the alkylene oxide adducts of this invention, the initial concentration of the catalyst is such so as to provide for the preparation of the product in an acceptable time. Advantageously, at least 100 ppm, and preferably at least 500 ppm of metal cation based upon the weight of initiator present is suitable for catalyzing the reaction. Preferably, the catalyst is present in an amount from about 0.01 to about 50 percent by weight based upon the weight of the initiator to be reacted.
The quantity of catalyst used to catalyze the reaction should be such that the resulting crude product, prior to neutralization or treatment to remove residual catalyst, contains less than about 20,000, preferably less than about 10,000 and most preferably less than about 5,000 ppm of the metal based on the weight of the end product present.
The reaction of alkylene oxide with initiator is advantageously conducted at a temperature within the range of 60° C. to 180° C., and preferably within the range of 75° C. to 130° C. The reaction is normally conducted in a closed system at a pressure normally not exceeding 150 pounds per square inch gauge (psig), preferably not exceeding 120 psig and most preferably not exceeding 75 psig. These pressures are maintained by controlling the feed rates of the alkylene oxides and thus the quantity of oxide in the gaseous phase at the reaction temperature. Temperatures and pressures over and above these ranges are generally not beneficial to the quality of resultant product obtained, and products with a high level of color or unsaturation may be produced
The residual catalyst in the resulting alkylene oxide adduct may be neutralized and/or removed by any of the procedures well-known to those skilled in the art, for example, neutralization of the catalyst by acids such as phosphoric acid, sulfuric acid, acetic acid and solid organic acids as described in U.S. Pat. No. 3,000,963. The catalyst may also be removed by the carbon dioxide finishing procedure as described in the Japanese Patent 55/092,733-A, or removed by adsorption on activated clay such as, for example, magnesium silicate.
After removal and/or neutralization of the catalyst, the metal cation content of the alkylene oxide adduct advantageously is less than about 200 ppm, preferably less than 80 ppm, and more preferably less than 40 ppm. Catalyst concentrations greater than this in the end product are generally not beneficial to the use of the product in the preparation of polyurethanes.
The alkylene oxide adducts prepared by the process of this invention may be blended with other compounds containing active hydrogen groups. Such blends are referred to hereinafter as polyol compositions. Polyol compositions when prepared can comprise from 1 to 99 weight percent by total weight of the composition, of the alkylene oxide adduct. Polyol compositions are of value for manufacturing polyurethane polymers.
The alkylene oxide adducts of the invention may be contacted under reaction conditions with polyisocyanates to produce polyurethane polymers The alkylene oxide adducts can be reacted with the polyisocyanates optionally in the presence of other active hydrogen-containing compounds, blowing agents, catalysts, surfactants, stabilizers, fillers, dyes, flame retardants and other additives.
Polyisocyanates which may be used in preparing the polyurethane foam include aromatic, aliphatic and cycloaliphatic polyisocyanates and combination thereof. Representative examples are diisocyanates such as m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, 1,4-cyclohexane diisocyanate, hexahydrotoluene diisocyanate, 1,5-naphthalene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate.
Polyisocyanates and prepolymers, including those modified prior to reacting with the alkylene oxide adduct may also be employed. Especially useful, and preferred, due to their availability and properties are the toluene diisocyanates, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate, commonly referred to as "crude MDI." The preferred polyisocyanates can be used alone or in combinations when being reacted with the alkylene oxide adduct of this invention.
The polyisocyanate reacting with the alkylene oxide adduct is present in such a quantity to provide a ratio of isocyanate groups to total active hydrogen atoms present, including those of the alkylene oxide adduct and any other compounds present containing active hydrogen atoms, of from about 0.8:1 to about 1.3:1 and preferably from about 0.9:1 to about 1.1:1.
Suitable catalysts that may be used alone or in a mixture include for example, tertiary amines, such as triethylenediamine, N-methylmorpholine, N-ethylmorpholine, triethylamine, 2-methyltriethylenediamine, mixtures thereof, and the like. Also organic tin compounds can be used such as, for example, stannous octoate, stannous oleate, stannous laurate, dibutyltin dilaurate, dibutyltin di-2-ethylhexoate and dibutyltin dibutoxide. Advantageously, a combination of tertiary amine and organic tin compounds can be employed.
The optimum concentration of the organotin catalyst must be determined experimentally, and will depend on a number of factors including the reactivity of the alkylene oxide adduct and/or the polyol composition and the isocyanate. Typically the concentration of the organotin catalyst is from about 0.05 to 3.0 parts by weight per 100 parts of alkylene oxide adduct or polyol composition comprising the alkylene oxide adduct, and preferably from 0.05 to 2.0 parts by weight.
The reaction mixture may also contain a surfactant or stabilizer or other cell size control agent. Such materials are well-known in the art and reference is made thereto for the purpose of the present invention. In general, representative of such foam surfactants are alkoxysilanes, polysilylphosphonates, polydimethylsiloxanes, the condensates of ethylene oxide with a hydrophobic base formed by condensing propylene oxide with propylene glycol, the alkylene oxide adducts of ethylenediamine, and the polyoxyalkylene esters of long chain fatty acids and sorbitan, and (siloxaneoxyalkylene) block copolymers Preferred of such materials are the siloxaneoxyalkylene block copolymers. Such block copolymers are described in U.S. Pat. Nos. 2,834,748; 2,917,480; 3,505,377; 3,507,815; 3,563,924 and 4,483,894.
Examples of suitable surfactants are the products sold by, for example, Goldschmidt under the trademark "Tegostab" including Tegostab B-4113, B-4380, and B-8681 and the surfactant DC-5043, sold by Dow Corning Corporation Examples of suitable stabilizers are Tegostab BF-2270, BF-2370, BF-4900 and B-3136 sold by Goldschmidt and the Dow Corning Corporation products DC-190 and DC-198. The foam stabilizer, surfactant is generally employed in amounts from about 0.05 to about 5.0, preferably from about 0.1 to about 2.0, parts by weight per one hundred parts of alkylene oxide adduct.
In addition to the above described components, the foaming mixture can optionally contain any of a variety of additives commonly employed in the preparation of flexible urethane foams. Representative additives include fire-retardant agents, fillers, dyes, pigments, anti-oxidizing agents, fungicides and the like. Cross-linkers used to modify foam properties can also be incorporated in the reacting mixture Representative cross-linkers are alkylamines, diamines, glycerine, diethanolamine and the like.
Suitable blowing agents for preparing a polyurethane foam are those organic compounds having a boiling point of from about -40° C. to about 90° C. and include the chlorinated and/or the fluorinated hydrocarbons such as tetrafluoromethane, bromotrifluoromethane, chlorotrifluoromethane, dibromodifluoromethane, dichlorodifluoromethane, trichlorofluoromethane, hexafluoroethane, 1,2,2 -trichloro-1,1,2-trifluoroethane, 1,1,2,2-tetrachloro-1,2-difluoroethane, 1,2-dibromo-1,1,2,2-tetrafluoroethane, 1,2,2-tribromo-1,1,2-trifluoroethane, octafluoropropane, decafluorobutane, hexafluorocyclopropane, 1,2,3-trichloro-1,2,3-trifluorocyclopropane, octafluorocyclobutane, 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane, 1,2,3,4-tetrachloro-1,2,3,4-tetrafluorocyclobutane, trichloroethylene, trichloroethane, chloroform, dichloromethane, carbon tetrachloride and low boiling hydrocarbons including alkanes and/or alkenes such as butane, pentane, and hexane.
In a preferred embodiment for the preparation of polyurethane foam with alkylene oxide adducts of this invention the blowing agent is carbon dioxide generated from the reaction of isocyanate with water. The water is generally used in an amount of 1 to 10 parts by weight per 100 parts polyol composition. Sufficient amounts of blowing agent are used to give foams of the desired densities. The water-generated carbon dioxide accounts for the major portion of the blowing agent required to produce foam of the desired density. At least 50 percent, preferably at least 60 percent and more preferably at least 75 percent of the total blowing agent requirement needed for the production of the foam can be derived from the reaction of water with isocyanate to generate carbon dioxide If necessary, the remainder of the blowing agent requirement for the production of the foam can be provided by one or more of the above-listed suitable blowing agents.
In any event, the polyurethane polymers prepared with the alkylene oxide adduct of this invention are flexible products advantageously having densities of from about 6 to about 500, preferably from about 6 to about 200, more preferably from about 6 to about 100, and most preferably from about 10 to about 60 kilograms per cubic meter. These densities can be achieved by preparing the polymer in the presence of an appropriate quantity of blowing agent and/or blowing agent precursor.
Suitable processes for the preparation of polyurethane polymers are discussed in U.S. Pat. Nos. 24514, 3,821,130, and G.B. Patent 1,534,258. Suitable equipment, material and processes for the preparation of polyurethane polymers is further discussed by J. H. Saunders and K. C. Frisch in "Polyurethanes Chemistry and Technology," Volumes I and II, R. E. Krieger Publishing Company, Inc., ISBN 0-89874-561-6.
Generally, flexible foams can be prepared in a one-step process by reacting all the ingredients together at once or alternatively, foams can be made by the so-called "quasi-prepolymer method." In the one-shot process, where foaming is carried out in machines, the active hydrogen-containing products, catalysts, surfactants, blowing agents and optional additives may be introduced through separate pipes to the mixing head where they are combined with the polyisocyanate to give the polyurethane-forming mixture. The mixture may be poured or injected into a suitable container or mold as required. For use of machines with a limited number of component lines into the mixing head, a premix of all the components except the polyisocyanate (and blowing agent when a gas is used) to give a polyol formulation, can be advantageously employed This simplifies the metering and mixing of the reacting components at the time the polyurethane-forming mixture is prepared.
Alternatively, the foams may be prepared by the so-called "quasi-prepolymer method." In this method a portion of the polyol component is reacted in the absence of catalysts with the polyisocyanate component in proportion so as to provide from about 10 percent to about 40 percent of free isocyanato groups in the reaction product based on the weight of prepolymer. To prepare foam, the remaining portion of the polyol is added and the components are allowed to react together in the presence of catalysts and other appropriate additives such as blowing agent, surfactant, etc. Other additives may be added to either the prepolymer or remaining polyol or both prior to the mixing of the components, whereby at the end of the reaction a flexible polyurethane foam is provided.
The alkylene oxide adducts of this invention are useful for the manufacture of polyurethane polymers in a variety of application areas. Areas include flexible slabstock and molded foam, carpet backing and rigid foams for laminate and insulative applications. Non-cellular polyurethane polymers may also be prepared including elastomers suitable for use as coatings, moldings, and shoe soles.
It is found that the alkylene oxide adducts of this invention when used to prepare flexible polyurethane foam provide acceptable foam properties and further allow for good tin catalyst processing ranges and flexibility within foam-forming compositions. The tin catalyst processing ranges are improved and generally become wider as the inherent reactivity of the adduct to isocyanate apparently is reduced through incorporating polymerized ethylene oxide via the initiator as opposed to introducing such ethylene oxide as part of the alkylene oxide feed during preparation of the adduct.
In addition, the alkylene oxide adducts of this invention may also be used to modify polyisocyanates in the preparation of isocyanate-terminated prepolymers.
Illustrative Embodiments
The following examples are given to illustrate the invention and should not be interpreted as limiting it in any way. Unless stated otherwise, all parts and percentages are given by weight.
In the following examples relating to the preparation of the alkylene oxide adduct hydroxyl number of the adduct is observed according to procedure ASTM E-326-69 and unsaturation content according to procedure D-2849-69.
In the following examples relating to the preparation of polyurethane foams, the properties of the foams can be determined in accordance with the following standard test procedures; resilience - ASTM D 3574-81, modulus and compressive load deflection (CLD) - DIN 53577, tensile strength and elongation - DIN 53571, tear resistance - DIN 53515.
EXAMPLE 1
An initiator is prepared in a reactor by mixing 191 parts by weight of a propoxylated glycerine, component (b), adduct having an equivalent weight of about 150 with 13.1 parts by weight of 45 percent aqueous potassium hydroxide. The resulting mixture is heated at about 115° C. and at a pressure less than one atmosphere until the concentration of the water within the mixture is less about 0.05 percent. To this resulting mixture is added 75 parts by weight of a component (a), a polyoxyethylene glycol having an equivalent weight of 300 and containing about 97 percent by weight polymerized ethylene oxide. The new resulting mixture is further heated and maintained at a temperature of about 115° C. and at a pressure less than one atmosphere until the concentration of the water within the mixture is less than about 0.074 percent. The resulting initiator contains 28 percent by weight of component (a), based on the combined weights of components (a) and (b).
To the resulting initiator is added, over a period of 8 to 10 hours at 120° C., 1308 parts by weight of 1,2-propylene oxide. After addition of the propylene oxide is completed, the contents of the reactor are maintained at about 120° C. for a further 4 hours to allow for complete reaction of the propylene oxide. After this period the potassium hydroxide is removed from the resulting alkylene oxide adduct by use of magnesium silicate, and then the adduct dried by use of reduced pressures below one atmosphere and at 115° C.
The so-obtained alkylene oxide adduct has a hydroxyl number of 57.4, a water content of 0.023 percent, an unsaturation level of 0.039 meq/gram, viscosity 222 centistokes at 37.7° C., a pH of 8.9, and theoretically contains 4.6 percent by weight polymerized ethylene oxide introduced by component (a) of the initiator.
EXAMPLE 2
This example, a 1000 equivalent weight alkylene oxide adduct, is prepared from an initiator having the same component (a) and component (b) as described for Example 1. Component (a) of the initiator is present in 30 percent by weight based on the combined weights of components (a) and (b).
The alkylene oxide adduct is prepared following the procedure given in Example 1, using 79 parts by weight component (a), 185 parts by weight component (b), 13.0 parts by weight 45 percent aqueous potassium hydroxide and 1262 parts by weight propylene oxide.
The so-obtained alkylene oxide adduct has a hydroxyl number of 54.5, viscosity 223 centistokes at 25° C., a pH of 8.7, and theoretically contains 6.0 percent by weight polymerized ethylene oxide introduced by component (a) of the initiator.
EXAMPLE 3
This example illustrates the preparation of an alkylene oxide adduct having an average hydroxyl equivalent weight of 1000 using a different initiator.
The alkylene oxide adduct is prepared from an initiator which consists of component (a) an ethoxylated monopropylene glycol having an average hydroxyl equivalent weight of 300 and containing about 87 percent by weight of its total weight, polymerized ethylene oxide, and component (b) a propoxylated glycerine adduct having an equivalent weight of 150. Component (a) of the initiator is present in 20 percent by weight based on the combined weights of components (a) and (b).
The alkylene oxide adduct is prepared following the procedure given in Example 1, using 51 parts by weight component (a), 202 parts by weight component (b), 12.5 parts by weight 45 percent aqueous potassium hydroxide and 1265 parts by weight propylene oxide.
The so-obtained alkylene oxide adduct has a hydroxyl number of 57.4, a water content of 0.026 percent, an unsaturation level of 0.041 meq/gram, viscosity 232 centistokes at 37.7° C., a pH of 8.8, and theoretically contains 2.9 percent by weight polymerized ethylene oxide introduced by component (a) of the initiator.
EXAMPLE 4
This example is prepared by the procedure given in Example 1 and using an initiator having the components (a) and (b) as described for Example 3. However, for this example component (a) of the initiator is present in 10 percent by weight based on the combined weights of components (a) and (b).
The alkylene oxide adduct is prepared using 24 parts by weight component (a), 212 parts by weight component (b), 12.5 parts by weight 45 percent aqueous potassium hydroxide and 1263 parts by weight propylene oxide.
The so-obtained alkylene oxide adduct has a hydroxyl number of 55.4, a water content of 0.017 percent, an unsaturation level of 0.041 meq/gram, viscosity 241 centistokes at 37.7° C., a pH of 8.6, and theoretically contains 1.4 percent by weight polymerized ethylene oxide introduced by component (a) of the initiator.
EXAMPLE 5
This example illustrates the preparation of an alkylene oxide adduct having an average hydroxyl equivalent weight of 1167.
The alkylene oxide adduct is prepared from an initiator which consists of component (a) a polyoxyethylene glycol having an equivalent weight of 400 and containing about 97.8 percent by weight polymerized ethylene oxide, and component (b) a propoxylated glycerine adduct having an equivalent weight of 150. Component (a) of the initiator is present in 25 percent by weight based on the combined weights of components (a) and (b).
The alkylene oxide adduct is prepared following the procedure given in Example 1, using 60 parts by weight component (a), 180 parts by weight component (b), 13.5 parts by weight 45 percent aqueous potassium hydroxide and 1343 parts by weight propylene oxide.
The so-obtained alkylene oxide adduct has a hydroxyl number of 48.0, a pH of 8.3, and theoretically contains 3.7 percent by weight polymerized ethylene oxide introduced by component (a) of the initiator.
EXAMPLE 6
This example illustrates the preparation of an alkylene oxide adduct having an average hydroxyl equivalent weight of 1230.
The alkylene oxide adduct is prepared from an initiator having an average hydroxyl equivalent weight of 300 and containing a polymerized ethylene oxide content of 72 percent by weight. The initiator itself is obtained by reacting ethylene oxide with glycerine and ethylene glycol present in an 80:20 weight ratio.
Following the alkoxylation procedure of Example 1,200 parts by weight of initiator is reacted with 620 parts by weight propylene oxide in the presence of 9.5 parts by weight 45 percent aqueous potassium hydroxide.
The so-obtained alkylene oxide adduct has a hydroxyl number of 45.6, a water content of 0.03 percent, an unsaturation level of 0.053 meq/gram, viscosity 321 centistokes at 37.7° C., a pH of 9.1, and theoretically contains 17.6 percent by weight polymerized ethylene oxide introduced by the initiator.
EXAMPLE 7
Flexible slabstock polyurethane foams, samples 1 to 4 are prepared from the alkylene oxide adduct as obtained in Example 2. Comparative foam samples A to D are prepared from a comparative alkylene oxide adduct (C-1) having a hydroxyl equivalent weight of 1000 and being the product of reacting propylene oxide and ethylene oxide as a heterofeed with glycerine. The comparative alkylene oxide adduct contains 12 percent by weight ethylene oxide.
The foams are prepared according to the formulations given in Table I, and the properties of the resulting foams is given in Table II.
Foams prepared with the alkylene oxide adduct of this invention show properties equivalent to those prepared with the comparative alkylene adduct. Significantly, such properties are obtained with an alkylene oxide adduct containing substantially less polymerized ethylene oxide, 6 percent compared to 12 percent by weight. As can be seen from Table I, the tin octoate catalyst levels are higher when using alkylene oxide adducts of this invention. The higher levels reflect the wider tin catalyst processing ranges available and hence greater processing flexibility when preparing open-celled flexible polyurethane foam.
TABLE I__________________________________________________________________________ Comparative Comparative Comparative Comparative Sample Sample Sample Sample Sample Sample Sample Sample 1 2 3 4 A* B* C* D*__________________________________________________________________________TDI .sup.1 Index 107 107 107 107 107 107 107 107Alkylene Oxide 100 100 100 100 -- -- -- --Adduct (Ex-2)Comparative -- -- -- -- 100* 100* 100* 100*Alkylene OxideAdduct C-1*Water 4.7 4.7 3.5 3.5 4.7 4.7 3.5 3.5Surfactant .sup.2 1.1 1.1 1.0 1.0 1.1 1.1 1.0 1.0DMEA .sup.3 0.12 0.12 0.18 0.18 0.12 0.12 0.18 0.18Niax Al .sup.4 0.06 0.06 0.09 0.09 0.06 0.06 0.09 0.09Stannous Octoate 0.35 0.30 0.35 0.30 0.25 0.20 0.25 0.20__________________________________________________________________________ *Not an example of this invention .sup.1 Toluene diisocyanate 80:20 ratio of 2,4 and 2,6isomer .sup.2 Silicone Surfactant, Tegostab BF 2370 sold by Th Goldschmidt Ag .sup.3 Dimethylethanolamine .sup.4 Niax Al 70% bis(dimethylaminoethyl) ether, 30% dipropylene glyco sold by Union Carbide.
TABLE II__________________________________________________________________________ Comparative Comparative Comparative Comparative Sample Sample Sample Sample Sample Sample Sample Sample 1 2 3 4 A* B* C* D*__________________________________________________________________________Density (Kg/M.sup.3) 20 20 25 25 20 21 26 27CLD (40%) (KPa) 3.48 3.54 3.68 3.68 3.87 3.55 4.21 3.95Tensile Strength 115 114 113 111 119 120 115 113(KPa)Elongation (%) 200 190 184 202 199 176 181 172Resilience (%) 38 42 43 47 43 42 46 47Modulus 2.13 2.17 2.07 2.04 2.11 2.07 2.01 2.04(65/25 CLD)__________________________________________________________________________ *Not an example of this invention.
EXAMPLE 8
Flexible slabstock polyurethane foams, samples 5 to 7, are prepared from the alkylene oxide adduct as obtained in Example 4. Comparative foam samples E and F are prepared from a comparative alkylene oxide adduct (C-2) having a hydroxyl equivalent weight of 1170 and being the product of reacting propylene oxide and ethylene oxide as a heterofeed with glycerine. The comparative alkylene oxide adduct contains 12 percent by weight ethylene oxide compared to the 1.4 percent of Example 4.
Foams are prepared according to the formulations given in Table III, properties of the resulting foams are reported in Table IV.
TABLE III______________________________________ Compar- Compar- ative ative Sample Sample Sample Sample Sample 5 6 7 E* F*______________________________________TDI Index .sup.1 110 100 100 100 100Alkylene Oxide 100 100 100 -- --Adduct (Ex-4)Comparative -- -- -- 100* 100*Alkylene OxideAdduct (C-2)*Water 4.5 3.5 2.5 4.5 2.5Surfactant-1 .sup.2 1.8 1.0 -- 1.8 --Surfactant-2 .sup.3 -- -- 1.0 -- 1.0Dabco 33LV .sup.4 0.1 0.25 -- 0.1 --DMEA .sup.5 0.2 -- 0.8 0.2 0.08Niax Al .sup.6 -- -- 0.04 -- 0.04Methylene 15.0 -- -- 15.0 --ChlorideStannous Octoate 0.55 0.30 0.18 0.45 0.18______________________________________ *Not an example of this invention .sup.1 Toluene diisocyanate 80:20 ratio of 2,4 and 2,6isomer .sup.2 Niax L540, silicone surfactant sold by Union Carbide .sup.3 Tegostab B3136, silicone surfactant sold by Th Goldschmidt Ag .sup.4 33% solution of triethylene diamine in dipropylene glycol sold by Air Products .sup.5 Dimethylethanolamine .sup.6 Niax Al 70% bis(dimethylaminoethyl) ether, 30% dipropylene glyco sold by Union Carbide
TABLE IV______________________________________ Compar- Compar- ative ative Sample Sample Sample Sample Sample 5 6 7 E* F*______________________________________Density (Kg/M.sup.3) 14.7 26.1 34.2 14.3 34.7Tensile Strength 83 130 102 69 76(KPa)Elongation (%) 222 200 140 184 174Resilience (%) 41 50 57 45 53Modulus 1.83 2.00 2.06 1.82 2.33(65/25 CLD)______________________________________ *Not an example of this invention
The foams prepared with the alkylene oxide adduct of the invention exhibit equivalent modulus, load bearing properties, and display improved tensile strengths and elongation properties. In addition, they have also been discovered to have improved dynamic flexural fatigue properties. | This invention relates to alkylene oxide adducts prepared by alkoxylating an initiator, containing polymerized ethylene oxide, with a C 3 or higher alkylene oxide, and polyurethane foams prepared therefrom. The invention offers the advantage of preparing alkylene oxide adducts and polyurethane foams with acceptable properties, where the availability or the possibility of conducting an alkoxylation reaction with ethylene oxide is restricted or not at all feasible. | 2 |
This is a division of application Ser. No. 893,557, filed Apr. 4, 1978, now U.S. Pat. No. 4,207,109, issued June 10, 1980.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to polymeric materials. More particularly, it relates to a polymeric material which is crosslinked at low pH with conventional gelatin crosslinking agents. The crosslinked polymers of the present invention can be coated on various supports to provide useful elements, particularly photographic elements.
2. Description of the Prior Art
It is well known that certain units can be included in a copolymer to provide for the later crosslinking of the polymer. Typically, conventional units which provide for the crosslinking of the polymer have had activated methylene groups, amine groups or hydroxyl groups. Unfortunately, known units of these types do not provide for crosslinking at low pH. Because of this deficiency, a large number of copolymers cannot be crosslinked using conventional crosslinking units. For example, polymers of acid comonomers containing conventional crosslinking groups must be neutralized before they can be crosslinked.
Frequently, it is desirable to disperse various components which are sensitive to pH in crosslinkable polymers. Thus, in addition to the fact that the polymer itself might hydrolyze at high pH (about 5 or higher), a component that is dispersed in the polymer might also be affected if the polymer dispersion was crosslinked at high pH. For example, photographic silver halide is usually coated in a polymeric binder and is optimally coated in the range of pH 4.5 to 6.5. The higher pH that is sometimes necessary to initiate crosslinking with conventional crosslinking units can adversely affect the silver halide. In addition to silver halide, other pH sensitive components can be coated in polymeric binders to form, for example, useful integral bio-analytical elements. Typical integral analytical elements are described, for example, in U.S. Pat. No. 3,992,158 to Pryzbylowicz and Millikan and the reference cited therein.
Typically, the active methylene group of a crosslinkable polymer is located in a side chain and is linked to the main chain of the polymer through an ester group. In one patent relating to active methylene group-containing polymers, namely, U.S. Pat. No. 3,904,418, crosslinked polymers which are particularly resistant to hydrolysis are described. The patent does discuss the disadvantages of hydrolysis of crosslinked polymers at high pH; however, since the crosslinking reaction itself must be carried out at pH values above about 5, hydrolysis of other components included with the polymer can occur.
One area where conventional crosslinking polymers are extremely useful is as extenders for gelatin in photographic elements. Due to its unique properties, including its ability to disperse silver halide and its excellent protective colloid properties, gelatin has been used as a binding agent in layers of photographic elements for many years. Gelatin is, however, vulnerable to dimensional change when subjected to varying conditions, such as temperature and humidity. Gelatin can also hydrolyze to amino acid fragments when subjected to extremely acidic or basic conditions. Crosslinking polymers have been proposed as substitutes or partial substitutes for gelatin in one or more layers of photographic elements to improve dimensional stability. As mentioned above, however, conventional crosslinking polymers must be crosslinked with care when used with silver halide emulsions, due to the fact that the silver halide is sensitive to pH. Some silver halide emulsions cannot be directly used with these conventional crosslinking polymers. This complicates, and therefore makes more expensive, the photographic film manufacturing process.
It is readily apparent that there is a continuing need for crosslinkable polymers which can be crosslinked with conventional gelatin hardening agents at relatively low pH.
SUMMARY OF THE INVENTION
We have found that a particular addition copolymer can be crosslinked with conventional gelatin crosslinking agents over a wide pH range. The copolymer is an acrylamidophenol comprising:
A. from about 0.5 to 50 percent by weight of a unit having the formula: ##STR2## wherein:
x is 1 or 0,
R represents hydrogen or methyl,
L is a linking group such as alkylene and cycloalkylene having from 1 to 6 carbon atoms or arylene having from 6 to 10 carbon atoms, and
R 1 through R 5 are independently selected from the group consisting of hydrogen, hydroxy, alkyl from 1 to 6 carbon atoms such as methyl, ethyl, isopropyl, butyl, hexyl and the like and aryl from 6 to 10 carbon atoms such as phenyl, naphthyl and the like, with the proviso that at least one of R 1 through R 5 is hydroxy and at least one of the positions ortho or para to said hydroxy has a hydrogen atom attached thereto; and
B. from about 50 to 99.5 percent by weight of units of at least one additional polymerized ethylenically unsaturated monomer. Particularly preferred polymers according to the present invention are those wherein the acrylamidophenol has the hydroxy of the phenol in the meta position. The copolymers described above can be crosslinked at a pH as low as 1.0. Polymers according to the present invention can take a wide variety of forms, and the crosslinking unit described above can be used with numerous polymeric units which could otherwise not be crosslinked. Thus, in another aspect of the present invention, there is provided a crosslinked polymer comprising the addition copolymer described above which has been crosslinked with 0.1 to 25 percent by weight based on the total weight of the uncrosslinked polymer with a crosslinking agent. Preferably, the crosslinking agent is an aldehyde or an organic compound having at least two activated double bonds.
It is noted here that throughout the specification and claims the terms "alkyl" and "aryl" include alkyl and aryl substituted with a variety of substituents which have no effect on the crosslinking properties of the polymer, including halo (such as chloro and bromo), nitro, cyano, oxo and the like.
Portion B of the addition copolymers described above can provide a wide variety of useful properties to a coating composition. For example, portion B can be an antistatic unit, a dye mordanting unit, an acid buffering unit and the like. Thus, in another aspect of the present invention, there is described an element comprising a support having coated thereon either the uncrosslinked or crosslinked addition copolymer described above.
The acrylamidophenol crosslinking unit described above is compatible with gelatin. By compatible, it is meant that when certain polymers containing the unit are mixed with gelatin, a substantially clear mixture results. Thus, in another aspect of the present invention, there is provided a photographic element comprising a support having coated thereon at least one photographic silver halide emulsion layer with or without gelatin and, either in the same or adjacent layer, the crosslinked or uncrosslinked addition copolymer described above. In preferred embodiments, the addition copolymer described above is in the same layer as the photographic silver halide.
DETAILED DESCRIPTION OF THE INVENTION
The acrylamidophenol monomers that are used to make the polymers of the present invention can easily be made by one of ordinary skill in the art. One convenient method is to form a suspension of the selected aminophenol and add it dropwise to a solution of acrylic or methacrylic anhydride. The reaction mixture is then stirred until the reaction is complete and the product precipitated by pouring the reaction mixture onto ice. Exemplary monomers prepared in this manner include:
N-(3-hydroxyphenyl)methacrylamide
N-(4-hydroxyphenol)methacrylamide
N-(3-hydroxyphenyl)acrylamide
N-(4-hydroxyphenyl)acrylamide
The polymers according to the present invention are made using the acrylamidophenol monomer by techniques which are well known to those skilled in the art. Typically, the polymers are made by simply dissolving the acrylamidophenol monomer and the other ethylenically unsaturated monomer in a suitable solvent in the presence of catalyst. The temperature at which the polymers described herein are prepared is subject to wide variation, since this temperature depends upon such variable features as the specific monomer used, duration of heating, pressure employed and like considerations. However, the polymerization temperature generally does not exceed about 110° C., and most often it is in the range of about 50 to about 100° C. The pressure employed in the polymerization is usually only sufficient to maintain the reaction mixture is liquid form, although either superatmospheric or subatmospheric pressures can be used where such is advantageous. The concentration of polymerizable monomers in the polymerization mixture can be varied widely with concentrations up to about 100 percent by weight, and preferably from about 20 to about 70 percent by weight, based on the weight of the polymerization mixture being satisfactory. Suitable catalysts for the polymerization reaction include, for example, the free radical catalysts, such as hydrogen peroxide, cumene hydroperoxide, water-soluble azo-type initiators and the like. In redox polymerization systems, conventional ingredients can be employed. If desired, the polymer can be isolated from the reaction vehicle by freezing, salting out, precipitation or any other procedure suitable for this purpose.
The acrylamidophenol monomer can be copolymerized with 50 to 99.5 percent by weight of a large variety of other ethylenically unsaturated monomers. The acrylamidophenol monomer can be copolymerized with monomers which would be unstable at high pH, such as cyanomethyl methacrylate, phenol acrylate and vinylbenzyl chloride. Thus, the range of useful comonomers is extremely wide. Exemplary monomers include: vinyl esters, amides, nitriles, ketones, halides, ethers, alpha-beta unsaturated acids or esters thereof, olefins, diolefins and the like, as exemplified by acrylonitrile, methacrylonitrile, styrene, alpha-methyl styrene, acrylamide, methacrylamide, vinyl chloride, methyl vinyl ketone, fumaric, maleic and itaconic esters, 2-chloroethyl vinyl ether, acrylic acid, sodium methacryloyloxyethyl sulfate, methacrylic acid, dimethylaminoethyl methacrylate, sodium 2-acrylamido-2-methylpropane-1-sulfonate, 2-hydroxyethyl methacrylate, 4,4,9-trimethyl-8-oxo-7-oxa-4-azonia-9-decene-1-sulfonate, N-vinylsuccinamide, N,N-dimethyl-N-2-hydroxypropylamine methacrylimide, N-vinylphthalimide, 1-vinyl-2-pyrrolidinone, butadiene, isoprene, vinylidene chloride, ethylene and the like. Sulfoacrylate salts are particularly useful as comonomers in the practice of this invention. For example, sodium 3-methacryloyloxypropane-1-sulfonate, sodium 3-acryloyloxypropane-1-sulfonate and others, as described in Dykstra, U.S. Pat. No. 3,411,911, issued Nov. 19, 1968, are particularly useful.
The acrylamidophenol unit can be incorporated primarily to provide for the crosslinking of the polymer. The other comonomer may provide other desirable properties and functions. For example, where the other ethylenically unsaturated comonomer is a quaternary ammonium salt or other charged group, the crosslinkable or uncrosslinked polymer can form an antistatic polymer which is useful in antistatic layers on fibers and other elements such as photographic elements and the like. Where the other ethylenically unsaturated comonomer contains a color coupler group such as active methylene, phenolic and pyrazolone groups, the copolymer can provide for the formation of a colored image by reaction of the color coupler group with oxidized developer. The other ethylenically unsaturated comonomer can also provide a mordanting function, with the acrylamidophenol being present only in sufficient amount to crosslink the mordant. In another useful embodiment, the copolymers of the present invention can be used in acid buffering layers. The other ethylenically unsaturated comonomer can include groups which hydrolyze at high pH. These copolymers can be formed and coated at low pH and, when subsequently subjected to a high pH environment, provide a buffering action through hydrolysis. It will be readily appreciated that copolymers containing conventional crosslinkable groups which must be crosslinked at high pH would be less suited to these embodiments.
As mentioned previously, the acrylamidophenol unit is present in the polymer typically in an amount that is sufficient to crosslink the polymer. At excessively high proportions of the crosslinking acrylamidophenol, the desirable properties of the other ethylenically unsaturated monomer are diluted. Conversely, at excessively low proportions or crosslinking acrylamidophenol, there are insufficient crosslinking sites to adequately crosslink the polymer. A useful crosslinking range is from about 0.5 to about 50 percent by weight of the acrylamidophenol unit, based on the total amount of copolymer. A preferred range is between about 1 percent and about 20 percent by weight of the acrylamidophenol crosslinking monomer.
Copolymers containing the acrylamidophenol crosslinking site described above can be crosslinked with any of an extremely wide variety of crosslinking agents. The useful crosslinking agents include those which are generally known to crosslink gelatin. Particularly preferred crosslinking agents include aldehydes and organic compounds having at least two activated double bonds. Useful crosslinking agents for the polymers of the present invention include aldehydes such as formaldehyde, succinaldehyde, glutaraldehyde and alpha-methyl glutaraldehyde. Activated double-bond crosslinking agents include vinylsulfone methanes, triazines such as triallyl cyanurate and N,N-diallyl-melamine, and bis(vinylsulfonyl) compounds such as those disclosed in U.S. Pat. Nos. 3,490,911; 3,539,644 and 3,841,872.
To crosslink the copolymers containing the acrylamidophenol crosslinking unit of the present invention, the crosslinking agent is simply added to the solution of the polymer at room temperature. Crosslinking of the polymer will take place at a pH of the polymer solution as low as 1.0. Generally, the amount of crosslinking agent that is used depends upon the proportion of the acrylamidophenol crosslinking site in the interpolymer. Typically, the crosslinking agent is used in an amount between about 0.1 to about 10 percent by weight of the copolymer. Of course, the lower end of the useful range of the amount of crosslinking agent would be most useful with the lower end of the range of acrylamidophenol crosslinking unit. The optimum amount can easily be determined by one of ordinary skill in the art.
Exemplary polymers of the present invention include:
poly(methyl methacrylate-co-m-methacrylamidophenol) 80:20
poly(acrylamide-co-1 vinylimidazole-co-m-methacrylamidophenol) 90:5:5
poly[2-acrylamido-2-methylpropane-1-sulfonic acid, sodium salt-co-4'-chloro-3'-[α-4(4-methoxycarbonylphenoxy)-α-pivaloylacetamido]acrylanilide-co-m-methacrylamidophenol] 50:45:5
poly[2-acrylamido-2-methylpropane-1-sulfonic acid, sodium salt-co-1-(2,4,6-trichlorophenyl)-3-(3-acrylamidobenzamido)-2-pyrazoline-5-one-co-m-acrylamidophenol] 48:47:5
poly[2-acrylamido-2-methylpropane-1-sulfonic acid, sodium salt-co-1-(2,4,6-trichlorophenyl)-3-(3-acrylamidobenzamide)-2-pyrazoline-5-one-co-p-methacrylamidophenol] 51:45:5
poly[2-acrylamido-2-methylpropane-1-sulfonic acid, sodium salt-co-1-(2,4,6-trichlorophenyl)-3-(3-acrylamidobenzamido)-2-pyrazoline-5-one-co-p-acrylamidophenol] 48:47:5
poly(acrylic acid-co-m-methacrylamidophenol) 95:5, and
poly(methacrylic acid-co-m-methacrylamidophenol) 95:5
The elements of the present invention may have a wide variety of uses, depending upon the properties of the specific copolymer that is coated on the support. For example, where the acrylamidophenol crosslinking unit is used with an antistatic monomer, the resulting copolymer can be coated on fibers, cloth webs, photographic supports and the like to provide useful static-resistant elements. Where the acrylamidophenol crosslinking unit is included with a dye mordant monomer, the resulting copolymer can be coated on a suitable support and the element used as a dye receiver in a diffusion transfer photographic process. Where the other ethylenically unsaturated monomer is ionizable at a particular pH, the copolymer can serve as a pH buffer. Layers of the polymers of the present invention can, therefore, be used in a wide number of environments requiring such a buffer. For example, photographic elements, typically diffusion transfer elements, require a specific pH for optimum performance, and these polymers could be used as neutralizing layers in image transfer units. Similarly, many bio-analytical elements require a specific pH environment.
Depending upon the specific use of the element, the copolymer of the present invention can be coated on a wide variety of supports. For example, the copolymers can be coated on a wide variety of fibers, such as polyester fibers and the like. The copolymers of the present invention may also be coated on conventional photographic supports, such as poly(ethylene terephthalate), cellulose acetate butyrate, polycarbonate, polyolefins and the like. The support can be an opaque support, such as paper, or polyolefin-coated paper, such as polyethylene- or polypropylene-coated paper, which can be pigmented with TiO 2 , for example, and electron bombarded to promote emulsion adhesion.
The support has a layer thereon which contains either the crosslinked or uncrosslinked polymer of the present invention. Supports with a layer thereon containing the uncrosslinked copolymer are useful, for example, where it is desirable to harden, i.e., crosslink the layer at some time after manufacture. In silver halide elements, for example, it is sometimes desirable to coat the silver halide emulsion in a not fully hardened binder, so as to facilitate penetration of the layer by processing solutions. The silver halide emulsion layer can then be hardened in a process step after development, thereby providing desirable properties to the processed element. The uncrosslinked copolymer of the invention can be crosslinked in situ on the element by simply exposing the element to the crosslinking agent, such as by immersing the element in a solution of the agent. It is preferred, however, that the copolymers of the present invention be mixed with the crosslinking agent before coating.
The polymers of the present invention are particularly useful in photographic elements where they can be used to perform a variety of functions, such as antistatic layers, acid buffering layers and the like, as described above. The polymers can be used in a variety of photographic elements, such as silver halide, diazo, diffusion transfer, vesicular, photothermographic and like elements. Since the acrylamidophenol unit is compatible with gelatin, the polymers of the present invention are particularly useful with silver halide elements with a gelatin binder. The silver halide employed in the preparation of lightsensitive coatings and elements described herein includes any of the photographic silver halide as exemplified by silver bromide, silver chloride, and silver iodide, or mixed silver halides such as silver chlorobromide, silver bromoiodide and the like. Very good results are obtained with high-contrast silver halide emulsions in which the halide comprises at least 50 mole percent chloride. Preferred emulsions of this type contain at least 60 mole percent chloride; less than 40 mole percent bromide and less than 5 mole percent iodide. The polymers can be used in various kinds of photographic emulsions. For example, they can be used in direct positive silver halide emulsions, x-ray and other non-spectrally sensitized emulsions, as well as in orthochromatic, panchromatic and infrared sensitive emulsions, particularly those sensitized with merocyanine dyes, cyanine dyes, carbocyanine dyes and the like. Furthermore, these polymers can be used in emulsions intended for color-forming couplers or emulsions to be developed by solutions containing couplers or other color-generating materials. In addition, these polymers can be used in photographic emulsions containing developers, e.g., polyhydroxybenzenes, as well as in emulsions intended for use in diffusion transfer processes which use the non-developed silver halide in the non-image areas of the negative to form a positive by dissolving the under-developed silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer. Such processes are described in Rott, U.S. Pat. No. 2,352,014; Land, U.S. Pat. No. 2,543,181 and Yackel et al, U.S. Pat. No. 3,020,155.
A detailed description of various emulsions in which the polymers can be used can be found in Product Licensing Index, publication 9232, December 1971, pages 107 through 110.
The copolymers of the present invention are particularly useful to modify the properties of silver halide emulsion layers having gelatin binders. Dispersions of the photographic silver halide containing addition copolymers containing acrylamidophenol groups, in combination with photographic binding agents, such as gelatin, can be made in a variety of ways. For example, an aqueous gelatin dispersion of the photographic silver halide can be mixed with an aqueous dispersion or solution of the polymer. Alternatively, the photographic silver halide can be precipitated in an aqueous dispersion or solution of the polymer with or without colloid, depending upon the dispersion characteristics of the polymer. In this case, a water-soluble salt, such as silver nitrate, is admixed with a water-soluble halide, such as potassium bromide, in the presence of the mixture. In still another procedure, the photographic silver halide is precipitated in an aqueous gelatin solution and digested in the conventional manner known to the art. After digestion, but prior to coating, there is added to the emulsion an aqueous dispersion of the copolymer containing the acrylamidophenol unit. The bulk of the resulting dispersion can be increased by the addition of more of the polymer and/or natural or synthetic colloids or other binding agents suitable for use in photographic silver halide emulsions. Satisfactory colloids include, for example, gelatin, protein derivatives, e.g., carboxy methylated proteins, colloidal albumin, cellulose derivatives, synthetic resins such as polyvinyl compounds, e.g., polyacrylamide and the like.
The gelatin substitutes described herein can be employed as the binder agent in one or more layers of a photographic silver halide element. However, photographic silver halides are generally precipitated in the presence of binding agents, such as gelatin or other colloids, which exhibit very good peptizing action. Therefore, the photographic silver halide emulsions or layers according to this invention will generally contain some binding agent, such as gelatin, which exhibits this very good peptizing action. Generally, the concentration of the polymers described herein as gelatin substitutes will be in the range of about 20 to about 100 percent, more preferably in the range of about 50 to 80 percent by weight, based on total binding agent (dry weight), employed in any layer of a photographic element. In the preferred case, the remainder of the binding agent is gelatin, because it provides the advantage of allowing the coated layers to be chill-set, instead of heat dried.
In certain preferred embodiments, the polymers of this invention are used in photographic image-transfer film units, such as in image-transfer film units as described, for example, in U.S. Pat. Nos. 2,543,181; 2,983,606; 3,227,550; 3,227,552; 3,415,645; 3,415,644; 3,415,646 and 3,635,707; Canadian Pat. No. 674,082; Belgian Pat. Nos. 757,959 and 757,960, both issued Apr. 23, 1971, and British Pat. Nos. 904,364 and 840,731. The polymers of this invention are generally useful in image-transfer film units which comprise:
(1) a photosensitive element comprising a support having thereon at least one layer containing a silver halide emulsion preferably having associated therewith an image dye-providing material, and more preferably at least three of said layers which contain, respectively, a blue-sensitive silver halide emulsion, a green-sensitive silver halide emulsion and a red-sensitive silver halide emulsion;
(2) an image-receiving layer which can be located on a separate support and superposed on said support containing said silver halide emulsion layers or, preferably, it can be coated on the same support adjacent to the photosensitive silver halide emulsion layers; and
(3) an alkaline processing composition and means adapted to discharge said alkaline processing composition within said film unit.
Where the receiver layer is coated on the same support as the photosensitive silver halide layers, the support is preferably a transparent support. An opaque layer is preferably positioned between the image-receiving layer and the photosensitive silver halide layer. The alkaline processing composition preferably contains an opacifying substance, such as carbon or a pH-indicator dye, which is discharged into the film unit between a dimensionally stable support or cover sheet and the photosensitive element.
As mentioned previously, the polymers containing the acrylamidophenol crosslinking group are particularly useful in forming crosslinkable and crosslinked polymers that are sensitive to high pH. This feature makes these polymers particularly useful in various layers in photographic image-transfer film units and in various layers in elements for analyzing blood chemistry. For example, acid layers for neutralizing base may be formed using the acrylamidophenol unit containing polymers of the present invention wherein the acrylamidophenol is polymerized with an acid-providing monomer. Acidic polymers are unstable and ineffective using conventional active methylene groups containing crosslinkable units because the high pH necessary to crosslink the polymer also neutralizes the acid-providing monomer. The present polymers can be crosslinked at low pH, thereby avoiding this problem. Details regarding the use of such a layer for analyzing blood chemistry can be found in commonly assigned copending U.S. Application Ser. No. 880,828, entitled "Method Composition and Element for the Detection of Nitrogen-Containing Compounds" of Figueras et al., filed Feb. 24, 1978, now U.S. Pat. No. 4,176,008.
The following examples are presented for a further understanding of the invention and not to limit its scope in any way.
PREPARATION OF M-METHACRYLAMIDOPHENOL
To a suspension of 47 g (0.43 moles) of m-aminophenol in 100 ml of acetone at 0° to 5° C. was added dropwise a solution of 66.2 g (0.43 moles) of methacrylic anhydride in 150 ml of acetone. After the addition, the reaction was stirred for 0.5 hours at room temperature and was then poured onto ice to precipitate the product. The solid was collected by filtration and recrystallized from 400 ml of 50 percent aqueous ethanol to give 65.6 g of product melting at 171° to 173° C. The yield was 86.6 percent.
EXAMPLE 1
Poly(methyl methacrylate-co-m-methacrylamidophenol) 80:20
To 300 g dimethylformamide (DMF) was added 80.0 g methyl methacrylate and 20 g m-methacrylamidophenol in a 500 ml round-bottom flask equipped with reflux condenser and stirrer. After sparging the solution for 20 minutes with nitrogen at room temperature, the flask was immersed in a 60° C. constant temperature water bath. The solution was sparged with nitrogen for an additional 10 minutes, at which time 0.50 g 2,2'-azobis[2-methylpropionitrile], dissolved in 5 ml DMF, was added. The solution was kept at 60° C. for 22 hours, resulting in a very slightly viscous amber solution. Percent solids=25.25.
A small amount of polymer was isolated by adding the 10 ml polymer solution to 100 ml water, obtaining hard white polymer. The polymer was washed with two 50-ml portions of water, dried for 3 hours at 95° C., and dissolved in 10 ml of acetone. The polymer was reprecipitated in water, washed and dried. η inh (DMF)=0.19.
The title polymer was confirmed by elemental analysis.
EXAMPLE 2
Poly(acrylamide-co-1-vinylimidazole-co-m-methacrylamidophenol) 90:05:05
In a 3-liter, 3-neck round bottom flask was added 405 g of water, 69 g of acrylamide and 100 g of acetone containing 3.75 g of 1-vinylimidazole and 3.75 g of m-methacrylamidophenol. The pH of the solution was adjusted from 7.2 to 3.25 with 10 percent H 2 SO 4 and then 20 g of ethanol was added. The flask containing the hazy solution was placed in a 60° C. constant temperature bath and the solution sparged with nitrogen for 20 minutes. Hydrogen peroxide (1.0 ml, 27.7 percent) was added and the solution remained at 60° C. for 21 hours. The resultant clear, viscous solution was slightly amber. Percent solids=17.25.
The polymer was precipitated in acetone, washed with acetone and dried. η inh (H 2 O)=3.39.
The title polymer was confirmed by elemental analysis.
EXAMPLE 3
Poly[2-acrylamido-2-methylpropane-1-sulfonic acid, sodium salt-co-4'-chloro-3'-[α-(4-methoxycarbonylphenoxy)-α-pivaloylacetamido]acrylanilide-co-m-methacrylamidophenol] 50:45:5
A round-bottom flask was charged with 30.0 g of 2-acrylamido-2-methylpropane-1-sulfonic acid, sodium salt, 27.0 g of 4'-chloro-3'-[α-(4-methoxycarbonylphenoxy-α-pivaloylacetamido]acrylanilide, 3.00 g m-methacrylamidophenol, 0.30 g of 2,2'-azobis(2-methylpropionitrile) and 240 ml of dimethylformamide. The clear pale orange solution which resulted after swirling for a few minutes was immersed in a 60° C. bath and bubbled with high purity nitrogen for 16 minutes. The solution was then stoppered and kept at 60° C. for an additional 6 hours. The resulting viscous, clear, pale red dope was placed in a cellulosic dialysis bag (Union Carbide) and tumbled overnight in a vat of flowing distilled water. Upon freeze-drying the retentate, a fluffy light tan solid was obtained which was found to contain 1.1 percent volatiles.
The title polymer was confirmed by elemental analysis.
EXAMPLE 4
Coating a Polymer of the Invention
A solution of 1.00 g of the polymer of Example 3 in 9 ml of distilled water was brought to pH 6 with a small amount of dilute aqueous sodium hydroxide. It was subsequently treated with 8 drops of a 10 percent solution of bis(vinylsulfonylmethyl) ether in methanol and 11 drops of a 2.5 percent solution of Surfactant 10G (a non-ionic surfactant manufactured by Rohm and Haas) in water. The resulting dope was coated with a 6-mil coating blade onto subbed 4-mil poly(ethylene terephthalate) film base. Upon drying, a clear, non-tacky, smooth coating was obtained.
The coating was found to be effectively crosslinked. It could not be washed off or easily rubbed off in water, and required scraping to remove it from the film base. The scrapings were found to be insoluble in water.
EXAMPLE 5
This is a comparative example.
A copolymer (essentially the same as the copolymer of Example 3, except that it did not contain the m-methacrylamidophenol) poly[2-acrylamido-2-methylpropane-sulfonic acid, sodium salt-co-4'-chloro-3'-[α-(4-methoxycarbonylphenoxy)-α-pivaloylacetamido]-acrylanilide], weight ratio 49:51, failed to crosslink either when coated or examined in the same manner as described in Example 4 or when coated with formaldehyde as the crosslinking agent. The resulting films readily washed off and dissolved in water.
EXAMPLE 6
Poly[2-acrylamido-2-methylpropane-1-sulfonic acid, sodium salt-co-1-(2,4,6-trichlorophenyl)-3-(3-acrylamidobenzamido)-2-pyrazoline-5-one-co-m-acrylamidophenyl] 48:47:5
The title polymer was prepared and examined in essentially the same manner as the title polymer in Example 3. Its behavior on coating and crosslinking was also virtually identical. The polymer was effectively crosslinked, forming a coating which could not be washed off or easily rubbed off in water. Scraping was required to remove the wet coating from the film base. The scrapings were found to be insoluble in water.
EXAMPLE 7
Poly[2-acrylamido-2-methylpropane-1-sulfonic acid, sodium salt-co-1-(2,4,6-trichlorophenyl)-3-(3-acrylamidobenzamido)-2-pyrazoline-5-one-co-p-methacrylamidophenol] 51:44:5
The title polymer was prepared and examined in essentially the same manner as the title polymer in Example 3. Coatings prepared as in Example 4 failed to wash off in water, although they could be removed by vigorous rubbing.
EXAMPLE 8
Poly[2-acrylamido-2-methylpropane-1-sulfonic acid, sodium salt-co-1-(2,4,6-trichlorophenyl)-3-(3-acrylamidobenzamido)-2-pyrazoline-5-one-co-p-acrylamidophenol] 48:47:5
The title polymer was prepared and examined in essentially the same manner as the title polymer in Example 3. Coatings prepared as in Example 4 failed to wash off in water, although they could be removed by vigorous rubbing.
EXAMPLE 9
Poly(acrylic acid-co-m-methacrylamidophenol) 95:5
In a 2-liter flask equipped with stirrer, reflux condenser and nitrogen inlet was added 95 g of acrylic acid in 705 g of distilled water and 5 g of m-methacrylamidophenol in 200 ml of alcohol. The solution was sparged for 20 minutes with nitrogen and 0.5 g of 2,2'-azobis[2-methylpropionitrile], dissolved in 20 ml of acetone, was added. The reaction mixture was brought to 60° C. and remained at that temperature for 17 hours. The resultant polymer solution had a bulk viscosity of 145 cps at 11.1 percent solids.
EXAMPLE 10
Poly(methacrylic acid-co-m-methacrylamidophenol) 80:20
The title polymer was prepared using methacrylic acid according to the procedure of Example 9, except that the weight ratio of acid to phenol was 80:20. The resulting solution of polymer had a bulk viscosity of 486 cps at 11.1 percent solids.
EXAMPLE 11
Crosslinking of Acid Copolymer
A. Acrylic Acid Copolymer
To 1 g of the acrylic acid copolymer of Example 9 in 10 ml H 2 O was added 1 percent bis-vinylsulfonylmethyl) ether (BVSME) plus 1 ml of 2.5 percent Surfactant 10G. The pH was 1.5. Coating of this polymer melt on 4-mil gel-subbed poly(ethylene terephthalate) at 6 mil wet thickness resulted in a clear, transparent, smooth film upon drying at 130° F. for 10 minutes. After 3 days at room temperature, the polymer film was insoluble in water.
The experiment was repeated with the pH adjusted to 6 before coating. The results were the same.
B. Methacrylic Acid Copolymer
To 10 ml of a 4.8 percent by weight solution of the methacrylic acid polymer of Example 10 (pH 6) was added 0.02 g of 1 percent BVSME. After coating as in A at 8 mil wet thickness and drying, the film was insoluble in water but soluble in a photographic developer solution (pH 12). It was also insoluble in a photographic fix (about pH 4).
A coating of a 1:1 mixture of the polymer and Type IV gelatin gave a clear continuous film useful in photographic materials.
EXAMPLE 12
Analytical Element for Urea Assay
This example corresponds to Example 2 of the commonly assigned copending U.S. Application Ser. No. 880,828 entitled "Method Composition and Element for the Detection of Nitrogen Containing Compounds" cited earlier. Layer 1 of the element contains a copolymer of the present invention, and this layer is responsible for the relative insensitivity of the element to serum pH, as indicated below.
An analytical element for the analysis of urea was prepared by coating the following solutions and dispersing on a cellulose acetate film support at the following coverage.
______________________________________Layer 1 Copoly(acrylic acid-co-N-(m-hydroxy- phenyl)methacrylamide), 95 weight percent acrylic acid 10.8 g/m.sup.2 bis(vinylsulfonylmethyl) ether 0.11 g/m.sup.2 (melt adjusted to pH 6.0 prior to coating)Layer 2 agarose 5.40 g/m.sup.2- Na.sub.2 HPO.sub.4 1.62 g /m.sup.2 citric acid 1.08 g/m.sup.2 methylenebis(acetoacetic ester) 3.24 g/m.sup.2 copoly[styrene-co-N-vinylbenzyl-N,N- dimethyl-N-benzylammonium chloride- co-divinylbenzene] 2.16 g/m.sup.2 octylphenoxy polyethoxy ethanol 0.13 g/m.sup.2 urease 22,680 μ/m.sup.2 (pH adjusted to 6.0 prior to coating)Layer 3 poly(n-isopropylacrylamide) 0.32 g/m.sup.2Layer 4 cellulose acetate 6.6 g/m.sup.2 titanium dioxide 46.0 g/m.sup.2 polyurethane 1.38 g/m.sup.2 octylphenoxy polyethoxy ethanol 2.69 g/m.sup.2______________________________________
To evaluate the coated element, a series of aqueous standards varying in concentration from 20 to 300 mg/dl of urea and a series of spiked serum standards varying in concentration from 50 to 300 mg/dl of urea were prepared.
The element was spotted with 10 μl drops of the above-described urea solutions and the results monitored in a filter fluorimeter standardized to 250 mv vs. BaSO 4 and held at a temperature of 42° C. Plots of the slope of the straight line portions of the output curves against urea concentration demonostrate excellent linearity up to 100 mg/dl urea with the aqueous standards and good linearity up to 300 mg/dl added urea with the spiked serum.
The coated element was then evaluated for change in response with change in serum pH over a range of 6.7 to 8.4 using spiked serum at 200 mg/dl urea concentration. In terms of slope and in terms of urea concentration read from a calibration curve, there was little change in response with change in serum pH over the given range.
______________________________________Serum pH Slope Urea Equivalents______________________________________6.7 5.58 2047.8 5.70 2088.4 5.60 204______________________________________
The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. | Copolymers containing an acrylamidophenol as a crosslinking site and the corresponding crosslinked polymers are disclosed. The acrylamidophenol unit can be copolymerized with a wide variety of other monomers to provide crosslinkable and crosslinked polymers with useful properties. The acrylamidophenol unit provides for crosslinking at low pH with conventional crosslinking agents. The acrylamidophenol monomer unit is present in the copolymer from about 0.5 to 50 percent by weight and has the formula: ##STR1## wherein: x is 1 or 0,
L is a linking group,
R represents hydrogen or methyl, and
R 1 through R 5 are independently selected from the group consisting of hydrogen, hydroxy, alkyl from 1 to 6 carbon atoms and aryl from 6 to 10 carbon atoms; with the proviso that at least one of R 1 through R 5 is hydroxy and at least one of the positions ortho or para to said hydroxy has a hydrogen atom attached thereto. The remainder of the polymer can comprise from 50 to 99.5 percent by weight of at least one additional polymerized ethylenically unsaturated monomer. Elements, particularly photographic elements, comprising a support having coated thereon either the crosslinked or uncrosslinked polymer are also disclosed. | 2 |
This invention relates to flexible wing sails for motive power, particularly to sails having reversible shape to form a lifting thick section airfoil in either direction. A reversable sail is one in which the leading edge becomes the trailing edge after tacking.
BACKGROUND OF THE INVENTION
The efficiency of sails and sail systems depend upon the relation of two forces namely lift and drag. All attempts to increase the performance of sails have been aimed at increasing the lift force to drag force ratio. By increasing the lift through better aerodynamic shape, or decreasing the drag by streamlining better sails have been developed. In addition to the drag associated with the airfoil section of the sail there is an additional drag from the supporting structure that will typically reduce the efficiency of the entire sail system. Supporting structures include masts, booms, spars and cables which all cause additional drag and tend to lower the lift to drag ratio of the sail system.
Various attempts have been made to lower the drag imparted to the sail system by the supporting structures. Masts, normally attached to the leading edge, cause a turbulent wake that disturbs the airflow to the sail and reduces aerodynamic lift and causes drag. One method used on many high performance sailboats has been to streamline the mast and allow rotation so that the narrowest section is across the impinging air flow. The extreme of this approach is called the wing mast, a rigid mast section, having up to 25% of the total sail area, has a flexible fabric sail cloth attached at its trailing edge to form the remaining portion of the sail. The increased efficiency is a result of having thickness in the airfoil section much the same as on an airplane wing, the intersection between the wing mast and the fabric portion however is not a smooth junction and thus some drag is still inherent. Other improvements extending from the wing mast approach has been the development of total rigid airfoil sails, (ex. Barkla U.S. Pat. No. 2,804,038 and Smith U.S. Pat. No. 3,295,487).
Another approach has been to have a freely hanging sail away from the mast, as are conventional jibs and genoas, and eliminate the mast turbulent effect on the airfoil, (eg. Darby "Popular Science" August 1965 pages 138-141 and Jamieson U.S. Pat. No. 4,044,702). The mast drag still remains although drag reduction can be accomplished by covering the mast with a rotatable streamlined fairing.
These developments have succeeded to reduce the drag effect of the supporting structures however they all have inherent disadvantages. The wing mast and solid wing structure is the airfoil and is very heavy and thus causes additional drag on the vehicle or craft being propelled. The triangular freely hanging sails are relatively high for sails having areas equal to sails with masts at the forward edge because of the inward curves of the edge tension and support elements, hence the masts to support such must be even higher than the sails they suspend and therefore add a considerable amount of drag to the sail system.
It is my invention to "eliminate" the drag associated with the sail support structure and to increase the airfoil lift by enclosing the structure within a double fabric high lift airfoil section.
SUMMARY OF THE INVENTION
It is the object of this invention to provide sail for vehicles such as ice boats, sailboats, multihull boats, land craft, and sailboards for increased speed and upwind performance.
The sail comprises two symetric fabric sections attached together at the edges and supported by an internal arrangement of a mast and curved boom. Cables run through pockets at the edge attachment points to hold the fabric out stretched and are terminated at the head and foot of the sail. A mast head device connects the internal mast and edge tension cables at the top of the sail, this device also forms the desired elliptic airfoil tip. The cables are attached at the tack and clew of the sail to fittings on the ends of the internal curved boom and terminate at the foot of the sail to the lower mast end. A control rope is attached to the mast at the internal mast boom connection, the boom is slideably connected to the mast, and runs to each end of the internal boom. This control rope is tensioned and the mast moves either direction along the boom to set up a differential between the cable tensions in one edge of the sail relative to the other edge. The curve of the leading edge becomes taught while the curve of the trailing edge slackens to form direction to the airfoil shape. The control rope is pulled to either end of the boom in sequence with tacking to provide the optimum airfoil shape in either direction.
In the preferred embodiment the sail is adapted for windsurfing by providing a spar attached to the end of the internal boom for hand holding. This spar is external and to windward of the sail. The foot of the mast is connected to a universal or flexible joint attached to the modified surfboard. The shape control rope runs along the external spar and is cleated to a convenient location near each end of the spar. A symetric airfoil that has flexibility will take on a non symetric airfoil shape due to the leeside pressure distribution of the sail and for simplicity the airfoil shape will reverse to some degree without differential cable adjustment.
This arrangement the boom forms a familiar wishbone boom with the spar, the boom internal within the airfoil section and the spar external to windward of the sail and is the only element outside of the sail and subjected to aerodynamic drag.
Another embodiment includes the sail attached to a double ended proa. The mast is rotatably stepped on the long hull that is always to leeward of the shorter, outrigger, hull. The ends of the internal boom are attached to control spars that slideably attach to the cross beams between the hulls. The control spars support the sail and control the sheeting angle. On larger versions a stay or set of stays are hooked to the head piece of the sail along the center line of rotation. The boat is sailed in the usual manner for a reversible proa. In addition, as in the preferred embodiment, a differential cable tension control can be used to directionalize the airfoil shape of the sail.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the preferred embodiment of the invention flexibly mounted on a sail board with a curved spar used as a hand holding device for stand up sailing.
FIG. 2 is a sectional drawing on line 2--2 of FIG. 1 showing a crossection of the sail encompassing the mast.
FIG. 3 is a sectional drawing on line 3--3 of FIG. 1 showing the internal mast boom arrangement and attachment to the external spar used for hand holding control of the sail.
FIG. 4 is a sectional drawing on line 4--4 of FIG. 1 showing a crossection of the mast head device used for supporting the top of the sail.
FIG. 5 is an edge on perspective view showing the leeward deflection of the sail and the position of the external boom for hand holding control.
FIG. 6 is a diagrammatical illustration showing the preferred airfoil shape due to wind pressure distribution along the arc of the sail and the leading and trailing edge angle differential as a result.
FIG. 7 is a perspective view of the sail showing the edge curves of the sail due to differential edge tensioning.
FIG. 8 is a perspective view of the invention mounted on a double ended proa for providing efficient motive power.
DETAILED DESCRIPTION OF THE INVENTION
In the preferred embodiment the sail is connected to a sailboard, large modified surfboard, through a universal or flexible joint, the sail is free to fall in any direction. In this preferred embodiment the greatest advantage of a high lift sail is utilized. When the sail is angled to windward the lift vector has an upward component. This upward component counteracts the weight of the sailor and the sailboard and as a result reduced drag and enhanced plaining increase the speed of the sailboard.
The sail as shown in FIG. 1 is flexibly mounted to a sailboard 28 by a universal or flexible joint 29. A curved spar 16 is attached to the ends of curved boom 18 by a boom connector 25 and is used for hand holding control. The uphaul line 19 serves for erecting the sail, especially after it has fallen in the water.
The sailboard is equipped with a centerboard 30 centerboard well 29 and skeg 31 for hydrodynamic stability while underway. The universal joint can be mounted on the centerboard as in FIG. 1 or as preferred forward of the centerboard. Directional control is achieved by positioning the sail fore and aft longitudinally with respect to the centerboard.
A windward flexible sail section 10 is constructed of polyester or sailcloth and is located to windward of the internal boom 18 and internal mast 14 and is attached to a cable, or tension device 13 at the fore and aft edges of the sail section. The cable 13 is attached to the internal boom 18 near the outer ends. The attachment comprise a ring 43 attached to the edge tension cables 13 and an outhaul line 32. The outhaul line connects to the spar 16 and boom end 25 through a turning block 44 and jam cleat 42 for adjustable outhaul control to set the airfoil section for various wind conditions.
At the head or top of the sail the edge cables 13 are connected to the lower corners of a rigid mast head piece 20 in addition the sail forms a boot over and is supported by the mast head piece 20. The mast head piece is a spreader for the edge tension cables 13 and is supported by the mast 14. The sail forms an arch around the tip or top of the mast and thus a larger sail area and a lower mast is achieved. The vertical tension of the sail is adjusted by a pair of downhaul lines 56, one attached to an eye, cable loop, at the lower end of the edge cables 13 and is tied to the downhaul cleat 58 the other line through a grommet 54 at the base of the sail also tied off to the downhaul cleat 58, see FIG. 5.
The mast head piece, FIG. 4, has a foam core 48 for light weight and flotation, and a reinforced plastic skin 52 to add strength. A tube 46 is attached to the edge of the mast head piece 20. The edge cables 13 run in the tube and are fixed on either end to prevent sliding through the tube. A socket 50 within the lower end of the head piece 20 accomodates the upper end of the internal mast 14.
A second flexible section sailcloth is attached along its edge perimeter 45 to the edge cable pocket 12 of the windward sail 10 and has greater curvature than the windward sail 10. This second sail 11 hereby referred to as the leeward section, is located to leeward of the windward sail and encompasses the mast 14 and curved boom 18 is slideably attached to the mast 14 (see FIG. 3) and a control line 22 is used to adjust the mast position along the boom. The mast centrally located within the sail slides along the boom within a bracket 21 and is pulled by a control rope towards either end, the edge tension cables 13 attached to ends of the internal curved boom 18 are tensioned and loosened by the control of the mast position within the bracket 21 similar to the action of a bow and arrow. The leading edge has greater tension and the trailing edge has the lesser tension to form a more preferable airfoil section with the maximum curvature forward. The control line 22 effects the differential tension between the edge tension cables, the line is attached to the mast cleat 23 runs around block 24 and hand holding spar 16. The mast position is fixed by connecting the control line 22 through a jam cleat 26 at either end. Pulling the control line towards one side or the other and cleated off to form a preferred airfoil in either direction to control the reversal of the airfoil. The control device is not necessary for most flexible airfoils since the pressure distribution along the arc of the airfoil forces the maximum curvature forward, (see FIG. 6). Once the sail takes the preferred shape the control device will adjust the edge positions to compensate for the differing edge cable deflection angles, α and β, in FIG. 6. so that all twist of the sail is removed. The edges of the sail deflect along the leading and trailing angles of the airfoil, since the leading angle is greater than the trailing angle when the maximum curvature of the airfoil is forward, as in the preferred airfoil shape, then the leading edge should be tensioned to deflect less and the trailing edge slackened to deflect more in order to match the sidewards deflections so that there is no twist imparted to the airfoil, (see FIG. 6 & 7).
In another embodiment the sail as described is rotatably mounted on a double ended proa, this could be of much greater size than as described for boardsailing. A proa having a long hull 64 and a short hull 66 connected to the long hull by cross beams 68 to form an outrigger. The sail is mounted near the center of the long hull 64. A stay or guy wire 62 is attached to the windward side of the head piece 20 along the centerline of rotation and extends downward to a location on the outrigger hull 66 to increase the support for the sail. Control spars 60 are attached to the ends of the internal boom 18 on one end and is slideably attached to the cross beams 68 on the lower end. The position of the control spars 60 along the beams 68 is adjustable to effect sheeting angle control over the sail. The proa is sailed in the usual manner for reversing proas except the sail reverses airfoil direction without swinging the boom end to end. This embodiment is illustrative of one additional use for this invention. It is understood that this wing sail can be easily adapted to most any craft and the scope of this invention is not to be limited to the particular examples given.
METHOD OF OPERATION
To describe the use of the preferred embodiment reference is made to FIG. 1. and FIG. 5.
While sailing on one tack the operator holds on to the spar 16 with one hand forward and one hand aft and leans to windward to counter balance the wind force. By adjusting the inclination fore and aft directional control is achieved. This mode of operation is not unfamiliar to boardsailors. The distinction for reversible sails is in the area of tacking. Unlike the use of the conventional wishbone boom sail the operator always remains on the same side of the sail. Once the board is turned into the wind the sail is spun around by releasing the forward hand and pulling forward the after part of the sail with the aft hand while transfering in front of the mast to the other side of the board, the aft hand now being forward. In strong winds it is necessary to actually push the forward end of the sail off the wind to make the sail spin faster. Once this maneuver is completed the sail is inclined forward to head the board off the wind on the new tack.
Although the invention has been described with respect to particular illustrative embodiments, variations and modifications are possible within the inventive concept. In the first place, the term "universal joint", used with respect to the juncture of the foot of the mast with a sailboard, is used broadly, including a ball-and-socket joint or a gimbal joint, as well as the more common forms of universal joints. In other words, what is essential is that the attachment of the foot of the mast to a sailboard should permit variation of the inclination in any direction. Likewise, what has been referred to as the tension cable for the edges of the sail can be any kind of strong, flexible low-stretch strand. Thus, a braided prestretched polyester line would be useful, as would also a highly flexible wire cable. Furthermore, instead of separate cables for the two sets of edges at opposite ends of the airfoil chord of the sail and differential tensioning by shifting the boom, other systems are usable, the essential feature being that it should be possible to increase the tension on the edges of the sail at one end of the airfoil chord while reducing it for the edges of the sail at the other end of the airfoil chord. Conceivably, this might be done by slipping the corner of the sail on one side outward on the boom and on the other side, inward. There is even a possibility that the tension strands' effect could be provided by weaving-in stretched elastic strands lengthwise of the sail edges, rather than by fitting a line to run inside the joined edges of the windward and leeward webs of the sail. | A low drag and high lift sail has a fabric skin suspended by an edge tension device able to control forward and trailing edge tension to tune and reverse the airfoil section. The fabric skin is double, with a windward and lee section of different curvatures giving the airfoil section thickness. The sail is supported by a mast and a curved boom located between the two fabric sections and thus is out of the impinging air stream. The ends of the boom are used for the sail support, usually with an additional external spar or spars on the windward side. The mast includes a foot which is either fixed or attached by a universal joint to a craft for motive power. | 1 |
This application is a continuation of application Ser. No. 07/968,531 filed Oct. 29, 1992, now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to adsorbents for efficiently removing nitrogen oxides (NOx) which are contained in low concentrations in gases discharged by ventilation from various highway tunnels, mountain tunnels, underwater tunnels, underground roads, sheltered roads and the like (hereinafter referred to collectively as "highway tunnels").
Highway tunnels, especially those having a large length and a great vehicular traffic volume, must be ventilated at a considerable rate in order to assure the health of drivers and passengers and increase the least distance of distinct vision. Air is withdrawn also from tunnels of relatively short length for ventilation to control air pollution due to carbon monoxide (CO), NOx and the like which are concentrically released from the inlet and outlet of the tunnel when the tunnel is located in an urban or suburban area.
However, if the gas discharged by ventilation is released as it is in the neighborhood, the environment of the area concerned will not be improved. Exactly the same problem as above will be encountered in the case where roadway tunnels or sheltered tunnels are to be constructed as a pollution control measure for existing roads.
The present invention relates to adsorbents for efficiently removing NOx which is present in low concentrations in gases removed from highway tunnels by ventilation.
PRIOR ART
The gas released from highway tunnels by ventilation is characterized in that it has a low NOx concentration of about 5 ppm and ordinary temperature, and varies greatly in quantity with the volume of traffic.
Processes have heretofore been investigated for removing NOx produced from fixed sources in order to purify the combustion exhaust gas from boilers. These processes are divided generally into the following three types.
(1) Catalytic Reduction Process
In this process, NOx in the exhaust gas is selectively reduced to harmless nitrogen and water vapor using ammonia as a reducing agent. This process is most generally used for denitrating exhaust gases from boilers. However, the gas to be treated by the process must be heated to at least 200° C., so that the process is not economical for treating gases from highway tunnels since the gas, having ordinary temperature and being large in quantity, needs to be heated with a large amount of energy.
(2) Wet Absorption Process
This process utilizes the fact that nitrogen dioxide (NO 2 ) and nitrogen trioxide (N 2 O 3 ) can be readily absorbed by a liquid absorbent such as water or an aqueous alkali solution. Nitrogen monoxide is oxidized using the liquid absorbent with an oxidation catalyst or ozone injected into the absorbent, and the resulting NO 2 and N 2 O 3 are caused to be absorbed by the absorbent, or the absorbent is used with an oxidizing agent added thereto. However, this process is complex because NOx is accumulated in the absorbent in the form of nitrates and nitrites, necessiating the maintanance and aftertreatment of the absorbent. The process further has an economical problem since the cost of the oxidizing agent per mole is higher than that of ammonia for use in the catalytic reduction process.
(3) Dry Adsorption Process
This process removes NOx from the exhaust gas with use of a suitable adsorbent. Several processes of this type had been investigated before the catalytic reduction process was placed into wide use for denitrating boiler exhaust gases. Nevertheless, since the boiler exhaust gas has (a) a high NOx concentration, (b) a high temperature, and (c) a high water content, the dry adsorption process is economically inferior to the catalytic reduction process and has not been introduced into use.
However, when the dry adsorption process was evaluated for purifying the gas resulting from the ventilation of highway tunnels, the process was found simple but economical, and entirely different from the same process as applied to the treatment of boiler exhaust gases.
We have already proposed adsorbents intended to efficiently adsorb and remove NOx present in a low concentration of 5 ppm, i.e., a low-concentration NOx adsorbent which comprises at least one copper salt supported on natural or synthetic zeolite and selected from among copper chloride, double salts of copper chloride and amine complex salt of copper chloride (see Unexamined Japanese Patent Publication No. 299642/1989), and an adsorbent which comprises vanadium supported on a carrier of anatase-type titania (see the specification of Japanese Patent Application No. 340627/1990).
However, these adsorbents have the problem of exhibiting an impaired adsorbing property (deterioration) when used at an increased water (or moisture) content as shown in FIG. 24. (FIG. 24 shows the influence of the moisture content on the adsorbing property of the above-mentioned Cu-supporting zeolite and V-supporting titania. The reaction conditions are 5 ml of adsorbent, 2.5 NL/min of reactive gas, NOx concentration of 3.8 to 4.1 ppm, moisture content of about 60 ppm or about 500 ppm and reaction temperature of 24° to 26° C.)
Accordingly, to enable these adsorbents to exhibit a satisfactory adsorbing property, the moisture content of gases needs to be not higher than about -35° C. in terms of dew point (up to about 200 ppm), so that the gas to be treated must be dehumidified by a dehumidifying step before the removal of NOx.
An object of the present invention is to provide an adsorbent which is free of the influence of moisture for removing NOx.
Another object of the invention is to provide such an adsorbent which is free of poisoning with SOx present in the gas to be treated.
Still another object of the invention is to provide such an adsorbent which comprises a ruthenium halide and which retains high activity for a prolonged period of time without permitting the separation of the halogen.
SUMMARY OF THE INVENTION
The present invention provides a first agent for removing low-concentration NOx by adsorption. (Such agents will hereinafter be referred to merely as "adsorbers.") The first adsorbent comprises a carrier comprising gamma-alumina, and ruthenium supported on the carrier.
The invention provides a second adsorbent which comprises a carrier comprising anatase-type titania, and ruthenium supported on the carrier.
The invention provides a third adsorbent which comprises ceramic paper holding thereto a carrier comprising anatase-type titania, and ruthenium supported on the ceramic paper.
The invention provides a fourth adsorbent which comprises ceramic paper holding thereto a carrier comprising anatase-type titania, and a ruthenium halide and a halide of at least one addition metal co-supported on the ceramic paper, the addition metal being selected from the group consisting of potassium, sodium, magnesium, calcium, manganese, copper, zinc, rubidium, zirconium, barium, cerium and molybdenum. (The halide of addition metal will hereinafter be referred to as an "addition metal halide.")
The first to fourth adsorbents are not affected by moisture, so that the dehumidifying step which must be executed conventionally before the removal of NOx with use of a large amount of energy can be dispensed with or carried out to a diminished extent. This achieves great savings in energy and savings in the space needed (reduction in the size of equipment) unlike the conventional process. The NOx adsorbed by the adsorbent can be readily desorbed by heating to facilitate regeneration of the adsorbent. Accordingly, the adsorbents of the invention are suited for use with NOx adsorption rotors for continually and repeatedly adsorbing NOx and desorbing NOx (for regeneration).
The second, third and fourth adsorbents comprise a carrier of anatase-type titania, are therefore unlikely to be poisoned with SOx in the gas to be treated and exhibit excellent durability.
The third adsorbent is superior to adsorbents comprising a granular titania carrier in NOx adsorbing property relative to the weight of TiO 2 and also to the amount of Ru supported, and is more advantageous in that the NOx adsorbed can be removed at a lower temperature for facilitated regeneration. The fourth adsorbent is more superior in these features.
The fourth adsorbent retains full activity even when exposed to an atmosphere having a high temperature of 250° C. for 100 hours. The adsorbent is therefore especially suited for use with the NOx adsorbing rotor.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 2 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 3 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 4 is a graph showing a relation between the amount of Ru supported and the breakthrough time;
FIG. 5 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 6 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 7 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 8 is a graph showing a relation between the amount of Ru supported and the 10% breakthrough time;
FIG. 9 is a perspective view showing an adsorbent of flat sheet-corrugated sheet multilayer structure;
FIG. 10 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 11 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 12 is a graph showing a relation between the amount of TiO 2 supported and the 10% breakthrough time;
FIG. 13 is a graph showing a relation of the time with the NOx concentration and with the temperature;
FIG. 14 is a graph showing a relation of the time with the NOx concentration and with the temperature;
FIG. 15 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 16 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 17 is a graph showing a relation between the amount of Ru supported and the 10% breakthrough time;
FIG. 18 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 19 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 20 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 21 is a graph showing a relation of the time with the NOx concentration and with the temperature;
FIG. 22 is a graph showing a relation between the time and the breakthrough ratio;
FIG. 23 is a graph showing a relation between the amount of Ru supported and the 10% breakthrough time; and
FIG. 24 is a graph showing relations between the time and the breakthrough ratio as established by conventional adsorbers.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The first adsorbent of the present invention comprises a carrier comprising gamma-alumina, and ruthenium supported thereon.
When desired, the carrier may contain, in addition to gamma-alumina, organic auxiliary forming agents, inorganic forming agents (serving as binders or diluents) such as silica sol and silica-alumina, and inorganic fibrous substances such as ceramic fibers.
The carrier is prepared by kneading the alumina with such an auxiliary forming agent and fibrous substance which are used as required, then forming the mixture into a desired shape, and drying and baking the shaped mixture.
The gamma-alumina carrier may be a commercial alumina carrier, or an alumina carrier prepared from alumina sol.
Ruthenium is supported on the carrier preferably in an amount, calculated as ruthenium metal, of at least about 0.01 wt. %, more preferably about 0.1 to about 5 wt. % based on the adsorbent. The amount of ruthenium to be supported is adjusted generally by varying the ruthenium concentration of the immersion bath to be used, temperature of the bath, immersion time or the like.
The carrier is caused to support ruthenium thereon generally by dissolving or dispersing ruthenium chloride (RuCl 3 ) or like ruthenium compound in a suitable medium to obtain an immersion bath, and immersing the alumina carrier in the bath, although this method is not limitative.
The immersed carrier is thereafter withdrawn from the bath, washed with water and dried in air at about 100° to about 120° C. The dried product is baked at about 300° to about 500° C. when so required. When the adsorbent is to be used continuously by repeating adsorption and desorption for regeneration, it is sometimes desirable to treat the dried product at a temperature slightly higher than the highest temperature at which the adsorbent is to be used.
The shape of the adsorbent is not limited specifically. Preferably it is shaped to have a large contact area and permit smooth passage of gases therethrough, as is the case with solid cylinders, balls, Raschig rings or a honeycomb structure.
The second adsorbent of the present invention comprises a carrier comprising anatase-type titania, and ruthenium supported on the carrier.
Examples of anatase-type titanias useful as carriers are commercial titania carriers, titania prepared from hydrated titania (titanic acid slurry) which is an intermediate product from the sulfuric acid process for producing titania, and titania prepared from titania sol obtained by deflocculating and stabilizing the titanic acid slurry.
When desired, the carrier may contain, in addition to anatase-type titania, organic auxiliary forming agents, inorganic forming agents (serving as binders or diluents) such as alumina sol, alumina, silica sol, silica-alumina and the like, and inorganic fibrous substances such as ceramic fibers.
The carrier is prepared by kneading the titania with such an auxiliary forming agent and fibrous substance which may be used as required, then forming the mixture into a desired shape, and drying and baking the shaped mixture.
The second adsorbent is the same as the first adsorbent with respect to the amount of ruthenium to be supported, supporting method, shape of the adsorbent, drying and baking conditions to be employed after immersion.
The third adsorbent of the invention comprises ceramic paper holding thereto a carrier comprising anatase-type titania, and ruthenium supported on the ceramic paper.
The third adsorbent is prepared by impregnating ceramic paper with anatase-type titania sol, drying or baking the impregnated ceramic paper, subsequently impregnating the carrier-holding ceramic paper with ruthenium, and drying or baking the resulting ceramic paper.
The ceramic paper is prepared from ceramic fibers by the papermaking process. Ceramic papers commercially available are also usable.
The anatase-type titania for use in the third adsorbent is the same as the one for use in the second adsorbent.
The adsorbent tends to exhibit a higher NOx adsorbing property as the amount of anatase-type titania retained thereon increases. If the amount of anatase-type titania is less than 20 g/m 2 , a markedly impaired NOx adsorbing property will result, so that the amount is preferably at least 20 g/m 2 , more preferably 25 to 500 g/m 2 .
The third adsorbent is the same as the first adsorbent with respect to the amount of ruthenium to be supported, supporting method, drying and baking conditions to be employed after immersion, etc.
The fourth adsorbent of the present invention comprises ceramic paper holding thereto a carrier comprising anatase-type titania, and a ruthenium halide and the above-mentioned addition metal halide which are co-supported on the ceramic paper.
The fourth adsorbent is prepared by impregnating ceramic paper with anatase-type titania sol to cause the paper to retain the sol, drying or baking the impregnated ceramic paper, subsequently impregnating the carrier-holding ceramic paper with the ruthenium halide and addition metal halide, and drying or baking the resulting paper.
The fourth adsorbent is the same as the third adsorbent with respect to the ceramic paper, anatase-type titania and the amount thereof to be held to the paper.
The amount of ruthenium to be supported is preferably at least about 0.01 wt. %, more preferably about 0.1 to about 5 wt. %, calculated as ruthenium metal and based on the adsorbent.
The amount of addition metal halide to be supported is preferably at least about 0.1 wt. %, more preferably about 1 to about 10 wt. %, calculated as the metal and based on the adsorbent.
The ruthenium halide and the addition metal halide are caused to be co-supported on the ceramic paper generally by dissolving or dispersing the ruthenium halide, such as ruthenium chloride (RuCl 3 ), and the addition metal halide, such as the chloride of the above-mentioned metal, in a suitable medium to obtain an immersion bath of the mixture, and immersing the carrier in the bath. This method, however, is not limitative.
The drying or baking conditions to be employed after the immersion, etc. are the same as those described for the first adsorbent.
In treating large quantities of gases such as ventilation gases from highway tunnels, it is required that the adsorbent be diminished in the resistance to the gas flow to ensure a minimized pressure loss. The first adsorbent preferable for use in this case is an adsorbent which comprises a flat sheet-corrugated sheet multilayer structure having a honeycomb cross section, and ruthenium supported thereon, the multilayer structure being composed of alternately arranged flat sheets of ceramic paper retaining a carrier of gamma-alumina thereon and corrugated sheets of ceramic paper retaining the same carrier thereon. Also preferred as the second and third adsorbents are those which comprise a flat sheet-corrugated sheet multilayer structure having a honeycomb cross section, and ruthenium supported-thereon, the multilayer structure being composed of alternately arranged flat sheets of ceramic paper retaining a carrier of anatase-type titania thereon and corrugated sheets of ceramic paper retaining the same carrier thereon. Further preferred as the fourth adsorbent is one comprising a flat sheet-corrugated sheet multilayer structure having a honeycomb cross section, and a ruthenium halide and an addition metal halide co-supported on the structure, the multilayer structure being composed of alternately arranged flat sheets of ceramic paper retaining a carrier of anatase-type titania thereon and corrugated sheets of ceramic paper retaining the same carrier thereon.
The first to fourth adsorbents embodying the present invention are used for removing NOx present in a low concentration in the ventilation gas of highway tunnels by contact with the gas. The adsorbent having NOx adsorbed thereto can be heated for the desorption of NOx, and the regenerated adsorbent is exposed to the ventilation gas for a continuous treatment.
EXAMPLE 1
Commercial gamma-alumina (brand name, Sanbido-AN, product of Shokubai Kagakukogyo Co., Ltd.) as comminuted and sieved to 8- to 14-mesh sizes was immersed in an amount of 7 ml in 10 ml of an aqueous solution of ruthenium chloride (RUCl 3 ), 0.38 wt. % in Ru concentration, at room temperature for 20 hours. The alumina was then washed with water and thereafter dried at about 110° C. for 2 hours to obtain a Ru-supporting alumina adsorbent (amount of Ru supported: 0.6 wt. %).
A 5-ml quantity (3.5 g) of the adsorbent was packed in a stainless steel reactor tube having an inside diameter of 22 mm, treated at about 300° C. for 1 hour while passing dry air (moisture content: about 50 ppm) through the tube at a rate of 2.5 NL/min and then allowed to cool to room temperature. After cooling, the passage of dry air was discontinued, and air adjusted to a moisture content of 500 ppm and containing 3.5 ppm of NOx was introduced into the adsorbent layer at a rate of 2.5 NL/min. Immediately after the start of introduction, the outlet gas of the reactor tube was checked for NOx concentration by a chemiluminescent detector. FIG. 1 shows variations in the NOx concentration of the outlet gas with time. Plotted as ordinate in FIG. 1 is a value obtained by dividing the NOx concentration of the outlet gas by the NOx concentration of the inlet gas. (The value will hereinafter be referred to as a "breakthrough ratio.")
The drawing, showing the result of Example 1, indicates that the time taken for the NOx concentration of the outlet gas to reach 10% of the concentration at the inlet (breakthrough ratio: 0.1), i.e., 0.35 ppm, is 30.0 minutes. (The time will be referred to as "10% breakthrough time.")
COMPARATIVE EXAMPLES 1 AND 2
An adsorbent comprising vanadium (V) supported on titania was prepared by heating a titanic acid slurry (TiO 2 content: about 30 wt. %) in air at 400° C. for 5 hours to obtain anatase-type titanium oxide (titania) for use as a carrier, and impregnating the carrier with ammonium metavanadate (NH 4 VO 3 ). The adsorbent was used under the same conditions as in Example 1 to measure the outlet NOx concentration similarly. FIG. 1 also shows variations in this concentration with time as the result of Comparative Example 1.
Further a Cu-supporting zeolite adsorbent was prepared by impregnating commercial Y-type zeolite serving as a carrier with cupric chloride (CuCl 2 ). This adsorbent was used under the same conditions as in Example 1 to measure the outlet NOx concentration similarly. FIG. 1 shows variations in the NOx concentration with time thus determined as the result of Comparative Example 2.
The drawing reveals that at a moisture content of 500 ppm, the Ru-supporting alumina adsorbent (Example 1) exhibits an exceedingly higher property than the V-supporting titania adsorbent (Comparative Example 1) and the Cu-supporting zeolite adsorbent (Comparative Example 2).
EXAMPLE 2
An adsorbent was prepared in the same manner as in Example 1 using a gamma-alumina carrier which was obtained by pelletizing "Colloidal Alumina 200," manufactured by Nissan Chemical Industries, Ltd, drying the pelletized alumina at about 110° C. for 44 hours and thereafter baking the alumina in air at 400° C. for 24 hours. This adsorbent was used under the same conditions as in Example 1 to measure the outlet NOx concentration similarly. FIG. 2 shows variations in the NOx concentration with time thus determined as the result of Example 2.
The diagram reveals that the alumina carrier prepared from colloidal alumina (alumina sol, Example 2) and the commercial alumina carrier are both usable as such with no noticeable difference found therebetween in the NOx adsorbing property.
EXAMPLE 3
A 5-ml quantity (3.5 g) of an adsorbent prepared in the same manner as in Example 2 was packed in a stainless steel reactor tube having an inside diameter of 22 mm, treated at about 300° C. for 1 hour while passing dry air (moisture content: about 50 ppm) through the tube at a rate of 2.5 NL/min and then allowed to cool to room temperature. After cooling, the passage of dry air was discontinued, and air (temperature: 24.5° C., relative humidity: 49%, moisture content: about 15,000 ppm) containing 3.5 ppm of NOx was introduced into the adsorbent layer at a rate of 2.5 NL/min. Immediately after the start of introduction, the gas from the outlet of the reactor tube was checked for NOx concentration. FIG. 3 shows variations in the NOx concentration of the outlet gas with time as the result of Example 3 along with the result achieved in Example 2 (moisture content: 500 ppm).
The diagram reveals that the adsorbent retains its NOx adsorbing property even at an increased water content, ensuring efficient removal of NOx at the moisture content of the atmosphere.
EXAMPLE 4
The same carrier as used in Example 2 was crushed and sieved to 8- to 14-mesh sizes, then immersed in an aqueous ruthenium chloride solution of specified concentration at room temperature for 20 hours, washed with water and thereafter dried. In this way, adsorbents were prepared with varying amounts of Ru supported on the carrier.
A 5-ml quantity (3.5 g) of each of these adsorbents was packed in a stainless steel reactor tube having an inside diameter of 22 mm and used under the same conditions as in Example 1 to measure the outlet NOx concentration and determine 10% breakthrough time. FIG. 4 shows the relation between the amount of Ru supported and the 10% breakthrough time thus established.
The diagram reveals that as the amount of Ru supported increases, the 10% breakthrough time increases to result in a higher NOx adsorbing property. It is seen, however, that when the amount of Ru exceeds about 3 wt. %, the 10% breakthrough time becomes almost definite.
EXAMPLE 5
A 7-ml quantity of commercial anatase-type titania (product of Shokubai Kagakukogyo Co., Ltd., 144.4 m 2 /g in specific surface area) as crushed and sieved to 8- to 14-mesh sizes was immersed in 10 ml of an aqueous solution of ruthenium chloride (RuCl 3 ), 0.38 wt. % in Ru concentration, at room temperature for 20 hours. The titania was then washed with water and thereafter dried at about 110° C. for 2 hours to obtain a Ru-supporting anatase-type titania adsorbent (amount of Ru supported: 0.24 wt. %).
A 5-ml quantity (4.2 g) of the adsorbent was packed in a stainless steel reactor tube having an inside diameter of 22 mm, treated at about 300° C. for 1 hour while passing dry air (moisture content: about 50 ppm) through the tube at a rate of 2.5 NL/min and then allowed to cool to room temperature. After cooling, the passage of dry air was discontinued, and air adjusted to a moisture content of 500 ppm and containing 3.5 ppm of NOx was introduced into the adsorbent layer at a rate of 2.5 NL/min. Immediately after the start of introduction, the gas at the outlet of the reactor tube was checked for NOx concentration by a chemiluminescent detector. FIG. 5 shows variations in the NOx concentration of the outlet gas with time.
The diagram, showing the result of Example 5, indicates that the time (10% breakthrough time) taken for the NOx concentration of the outlet gas to reach 10% of the concentration at the inlet (breakthrough ratio: 0.1), i.e., 0.35 ppm, is 24.0 minutes.
EXAMPLE 6
A titania sol (TiO 2 content: about 30 wt. %) was heated in air at 400° C. for 3 hours to obtain anatase-type titania (specific surface area: 99.3 m 2 /g), which was comminuted and sieved to obtain an 8- to 14-mesh fraction. A Ru-supporting anatase-type titania adsorbent (amount of Ru supported: 0.21 wt. % was prepared by the same procedure as in Example 5 with the exception of using the anatase-type titania powder obtained as a carrier.
The adsorbent was used under the same conditions as in Example 5 to measure the outlet NOx concentration similarly. FIG. 5 shows variations in the NOx concentration with time thus measured as the result of Example 6. The drawing shows that the breakthrough time determined for Example 6 was 31.3 minutes.
COMPARATIVE EXAMPLE 3
The same commercial anatase-type titania as used in Example 5 was crushed and sieved to obtain an 8- to 14-mesh fraction, which was used as it was as an adsorbent to measure the outlet NOx concentration under the same conditions as in Example 5. FIG. 5 shows variations in the NOx concentration with time thus measured as indicated as Comparative Example 3. With Comparative Example 3 illustrated, the breakthrough time was 2.2 minutes. This shows that the adsorbent is almost unable to adsorb NOx for removal at a high moisture content of 500 ppm.
COMPARATIVE EXAMPLE 4
A Ru-supporting gamma-alumina adsorbent (amount of Ru supported: 0.68 wt. %) was prepared by the same procedure as in Example 5 except that the carrier used was commercial gamma-alumina (Sanbido AN, product of Shokubai Kagakukogyo Co., Ltd.) as crushed and sieved to 8- to 14-mesh sizes.
The adsorbent was used under the same conditions as in Example 5 to measure the outlet NOx concentration similarly. FIG. 5 shows variations in the NOx concentration with time thus measured as indicated as Comparative Example 4. With Comparative Example 4, the breakthrough time was 30.0 minutes as illustrated.
Evaluation of the Property
The curves shown in FIG. 5 reveal that the adsorbents of Examples 5 and 6 are comparable to the Ru-supporting gamma-alumina adsorbent of Comparative Example 4 in NOx adsorbing property and serve the function even at a high moisture content of 500 ppm. A comparison between Examples 5 and 6 shows a slight difference therebetween in NOx adsorbing property due to differences involved in the conditions for preparing the titania carriers. However, it is seen that the adsorbents having different titania carriers both efficiently adsorb NOx.
EXAMPLES 7, 8 AND 9
A Ru-supporting titania adsorbent (amount of Ru supported: 0.16 wt. %) was prepared by the same procedure as in Example 5 except that the carrier used was prepared in the same manner as in Example 6 by heating a titania sol (TiO content: about 30 wt. %) in air at 400° C. for 3 hours to obtain anatase-type titania, and comminuting and sieving the titania to 8- to 14-mesh sizes.
A portion of this adsorbent was used under the same conditions as in Example 5 to measure the outlet NOx concentration similarly. FIG. 6 shows variations in the NOx concentration with time thus measured as indicated as Example 7.
A 5-ml quantity (4.2 g) of the same adsorbent as used in Example 7 was packed in a stainless steel reactor tube having an inside diameter of 22 mm, and dry air was passed through the tube under the same conditions as in Example 5, followed by cooling and interruption of the passage of the dry air. Air adjusted to a moisture content of 1,000 ppm, containing 3.5 ppm of NOx and serving as a reactive gas was introduced into the adsorbent layer at a rate of 2.5 NL/min, and checked for NOx concentration at the outlet of the reactor tube. FIG. 6 shows variations in this concentration with time thus measured, as indicated as Example 8.
Further the same procedure as in Example 8 was repeated with the exception of introducing air (temperature: 26° C., relative humidity: 56% moisture content: about 25,000 ppm) containing 3.5 ppm of NOx into the adsorbent layer at a rate of 2.5 NL/min as a reactive gas. FIG. 6 shows the measurements obtained, as indicated as Example 9.
Evaluation of the Property
FIG. 6 reveals that the adsorbent exhibits a high NOx adsorbing property free of deterioration even at higher moisture contents, efficiently removing NOx even at the moisture content of the atmosphere.
EXAMPLE 10
The adsorbent used for adsorbing NOx by the procedure of Example 6 was treated at about 350° C. for 1 hour in a stream of air (2.5 NL/min) adjusted to a moisture content of 500 ppm to remove the adsorbed NOx from the adsorbent, which was then allowed to cool to room temperature. After cooling, the supply of the air with the moisture content of 500 ppm was discontinued, and air adjusted to a moisture content of 500 ppm and containing 3.5 ppm of NOx was introduced into the adsorbent layer at 2.5 NL/min. Immediately after the start of introduction, the outlet gas was checked for NOx concentration. FIG. 7 shows variations in the NOx concentration of the outlet gas with time thus measured, as indicated as Example 10.
Evaluation of the Property
FIG. 7 shows that the NOx adsorbed by the adsorbent can be desorbed by heating the adsorbent in an air stream to readily regenerate the adsorbent. This suggests that the adsorbent is continuously usable through repetitions of adsorption and regeneration. The adsorbent is therefore usable with an NOx adsorption rotor for use in the apparatus proposed by the present inventors for purifying the ventilation gas from highway tunnels (see Unexamined Japanese Patent Publication No. 26616/1990).
Amount of Ru Supported
The same titania as used in Example 6 was crushed and sieved to 8- to 14-mesh sizes, then immersed in an aqueous ruthenium chloride solution of specified concentration at room temperature for 20 hours, washed with water and thereafter dried. In this way, adsorbents were prepared which were different from 0 to 5 wt. % in the amount of Ru supported on the carrier.
A 5-ml quantity (4.2 g) of each of these adsorbents was packed in a stainless steel reactor tube having an inside diameter of 22 mm and used under the same conditions as in Example 5 to measure the outlet NOx concentration and determine 10% breakthrough time. FIG. 8 shows the relation between the amount of Ru supported and the 10% breakthrough time thus established.
The diagram reveals that as the amount of Ru supported increases, the 10% breakthrough time increases to result in a higher NOx adsorbing property. It is seen, however, that when the amount of Ru exceeds about 2 wt. %, the 10% breakthrough time becomes almost definite.
EXAMPLE 11
Commercial ceramic paper (manufactured by Japan Radio Co., Ltd., composed of silica and alumina (50:50), having a thickness of 0.25 mm and weighing 46 g/m 2 ) was cut to a predetermined size, and the cut sheet was immersed in an anatase-type titania sol (TiO 2 content: about 30 wt. %) at room temperature. The ceramic paper was thereafter immediately placed onto a flat plate, treated with a roller or the like to remove an excess of titania sol and thereby made uniform in thickness, and dried in hot air at the same time. The ceramic paper impregnated with the titania sol and thus prepared in the form of a flat sheet was placed into an electric oven and baked in air at 400° C. for 3 hours to obtain a flat sheet of titania-retaining ceramic paper.
The same ceramic paper as above and immersed in the anatase-type titania sol was withdrawn from the sol, placed on a corrugated plate and thereafter treated in the same manner as above to obtain a corrugated sheet of titania-retaining ceramic paper.
The amount of TiO 2 retained on the paper was determined from the difference between the weight of paper before the immersion in the titania sol and the weight thereof after baking, with the result that 85 g/m 2 of TiO 2 was found retained on the paper.
The same procedure as above was repeated to prepare flat sheets of titania-retaining ceramic paper having varying widths and corrugated sheets of titania-retaining ceramic paper also having varying widths. Subsequently the flat sheets 1 and corrugated sheets 2 of predetermined widths were alternately arranged in layers into a cylindrical assembly as seen in FIG. 9 and temporarily held together with ceramic paper bands to obtain a flat sheet-corrugated sheet multilayer structure having a honeycomb cross section, externally measuring 22 mm in diameter and 50 mm in length, having a geometric surface area of 0.0385 m 2 and weighing 4.3 g (TiO 2 content: 3.3 g).
The multilayer structure was immersed in 100 ml of an aqueous solution of ruthenium chloride (RuCl 3 ), 0.38 wt. % in Ru concentration, at room temperature for 30 minutes, then washed with water and thereafter dried at about 110° C. for 2 hours to obtain a Ru-supporting titania honeycomb adsorbent (amount of Ru supported: 0.55 wt. %).
The adsorbent was fitted into a stainless steel reactor tube 3 having an inside diameter of 22 mm with the holding bands removed. The adsorbent was subsequently treated at about 300° C. for 1 hour while passing dry air (moisture content: about 50 ppm) through the tube at 2.5 NL/min and then allowed to cool to room temperature. After cooling, the passage of dry air was discontinued, and air adjusted to a moisture content of 500 ppm and containing 3.5 ppm of NOx was introduced into the honeycomb adsorbent at 2.5 NL/min. Immediately after the start of introduction, the gas at the outlet of the reactor tube 3 was checked for NOx concentration by a chemiluminescent detector. FIG. 10 shows variations in the NOx concentration of the outlet gas thus measured with time, as indicated as Example 11.
As will be apparent from the drawing, the time (10% breakthrough time) taken for the NOx concentration of the outlet gas to reach 10% of the concentration at the inlet (breakthrough ratio: 0.1), i.e., 0.35 ppm, was 24.0 minutes.
With the adsorbent of Example 11 wherein ruthenium is supported on ceramic paper retaining an anatase-type titania carrier thereon, fine particles of titania are supported as uniformly dispersed over the entire wide area of the paper. FIG. 10 therefore shows that the adsorbent has a higher adsorbing property relative to the weight of titania than the adsorbent of Example 6 wherein granular titania carrier is used, effectively serving the function not only over the surface of the titania carrier but also in its interior.
EXAMPLE 12
Flat sheets and corrugated sheets of titania-retaining ceramic paper, 20 g/m 2 in the amount of TiO 2 retained thereon, were prepared in the same manner as in Example 11 except that the paper material was immersed in the anatase-type titanium sol a different number of times for an altered period of time.
By the same procedure as in Example 11, these flat sheets and corrugated sheets were made into a flat sheet-corrugated sheet multilayer structure externally measuring 22 mm in diameter and 50 mm in length and having a geometic surface area of 0.0417 m 2 and a weight of 4.2 g (TiO 2 content: 0.8 g).
The multilayer structure was caused to support ruthenium thereon in the same manner as in Example 11 to obtain Ru-supporting titania honeycomb adsorbent (amount of Ru supported: 0.13 wt. %).
As in Example 11, the adsorbent was fitted into a reactor tube, and the outlet NOx concentration was measured under the same conditions. FIG. 11 shows the measurements, as indicated as Example 12.
FIG. 12 further shows the relation between the amount of TiO 2 retained on the ceramic paper and the 10% breakthrough time.
EXAMPLE 13
Flat sheets and corrugated sheets of titania-retaining ceramic paper, 100 g/m 2 in the amount of TiO 2 retained thereon, were prepared in the same manner as in Example 11 except that the paper material was immersed in the anatase-type titanium sol a different number of times for an altered perod of time.
By the same procedure as in Example 11, these flat sheets and corrugated sheets were made into a flat sheet-corrugated sheet multilayer structure externally measuring 22 mm in diameter and 50 mm in length and having a geometric surface area of 0.0375 m 2 and a weight of 4.4 g (TiO 2 content: 3.8 g).
The multilayer structure was caused to support ruthenium thereon in the same manner as in Example 11 to obtain Ru-supporting titania honeycomb adsorbent (amount of Ru supported: 0.66 wt. %).
As in Example 11, the adsorbent was fitted into a reactor tube, and the outlet NOx concentration was measured under the same conditions. FIG. 11 shows the measurements, as indicated as Example 13.
FIG. 12 further shows the relation between the amount of TiO 2 retained on the ceramic paper and the 10% breakthrough time.
FIGS. 11 and 12 show that an increase in the amount of TiO 2 retained tends to result in a higher NOx adsorbing property. The amount of TiO 2 to be retained is preferably not smaller than 20 g/m 2 since amounts less than 20 g/m 2 entail markedly impaired NOx adsorbing properties.
Adsorbent Regeneration Temperature
After NOx was removed by the procedure of Example 11, the temperature of the adsorbent was raised while passing air adjusted to a moisture content of 500 ppm through the reactor tube at 2.5 NL/min. FIG. 13 shows the resulting variations in the NOx concentration of the outlet gas of the tube.
As will be apparent from the drawing, a rise in the temperature of the adsorbent increases the amount of NOx desorbed, consequently increasing the outlet NOx concentration greatly. As the amount of NOx remaining in the adsorbent thereafter decreases owing to desorption, the amount of NOx desorbed decreases to lower the outlet NOx concentration. Accordingly, the outlet NOx concentration is represented by a curve having a peak (desorption peak). In the case of the adsorbent of Example 11 used for the removal of NOx, the desorption peak after the removal was about 240° C.
In the case where the adsorbent of Example 6 was used for removing NOx and thereafter treated by the same desorption procedure as above, the desorption peak was about 290° C. as shown in FIG. 14.
This demonstrates that-the adsorbent of Example 11 which comprises titania-retaining ceramic paper permits removal of adsorbed NOx at a lower temperature and is easier to regenerate.
EXAMPLE 14
The adsorbent as regenerated in Example 13 was allowed to cool to room temperature while passing air adjusted to a moisture content of 500 ppm through the reactor tube at 2.5 NL/min. With the passage of air thereafter discontinued, the NOx concentration of the reactor tube outlet gas was measured under the same condition as in Example 11. FIG. 15 shows the resulting variations in the NOx concentration with time, as indicated as Example 14.
FIG. 15 shows that the NOx adsorbed by the adsorbent can be desorbed by heating the adsorbent in an air stream to readily regenerate the adsorbent. This suggests that the adsorbent is continuously usable through repeated adsorption and desorption. The adsorbent is therefore usable with NOx adsorption rotors for use in the apparatus proposed by the present inventors for purifying the ventilation gas from highway tunnels (see Unexamined Japese Patent Publication No. 26616/1990).
EXAMPLE 15
A Ru-supporting titania adsorbent prepared by the same method as in Example 11 was fitted into a reactor tube as in Example 11, dried under the same condition and then allowed to cool. With the pasage of dry air thereafter discontinued, air adjusted to a moisture content of about 22,000 ppm (temperature: 26.0° C., relative humidity: 51%) and containing 3.5 ppm of NOx was introduced into the adsorbent at 2.5 NL/min as a reactive gas to measure the NOx concentration in the reactor tube outlet gas. FIG. 15 shows the resulting variations in the concentration with time, as indicated as Example 16, along with the result of Example 11 (moisture content: 500 ppm).
FIG. 16 reveals that the adsorbent retains a high NOx adsorbing property even at an increased moisture content and is useful for efficiently removing NOx even at the moisture content of the atmosphere.
Amount of Ru Supported
Flat sheet-corrugated sheet multilayer structures were prepared by the procedure of Example 11. Each of the structures was immersed in an aqueous ruthenium chloride solution of specified concentration at room temperature for a predetermined period of time, then washed with water and thereafter dried. Honeycomb adsorbents were thus prepared which were different in the amount of Ru supported.
These adsorbents were each fitted into a reactor tube in the same manner as in Example 11 and checked for the NOx concentration of the outlet gas under the same condition to determine 10% breakthrough time. FIG. 17 shows the relation between the amount of Ru supported and the 10% breakthrough time estabilished.
As will be apparent from the drawing, an increase in the amount of Ru supported results in an increased 10% breakthrough time, i.e., a higher NOx adsorbing property. However, when the amount of Ru exceeds about 2 wt. %, the 10% breakthrough time becomes approximately definite.
The same procedure as above was repeated except that the carriers used were granular titania carriers. FIG. 17 also shows the relation between the amount of Ru supported and the 10% breakthrough time.
A comparison between the two types of adsorbents reveals that the honeycomb adsorbents were superior to the granular adsorbents in adsorbing property.
EXAMPLE 16
By the same procedure as in Example 11, flat sheets 1 and corrugated sheets 2 were fabricated into a multilayer structure externally measuring 22 mm in diameter and 50 mm in length and having a geometric surface area of 0.0385 m 2 and a weight of 4.3 g (TiO 2 content: 3.3 g) as shown in FIG. 9.
The flat sheet-corrugated sheet multilayer structure was immersed in an aqueous mixture solution of ruthenium chloride (RuCl 3 ) and manganese chloride (MnCl 2 ) in an amount of 100 ml (Ru concentration: 0.38 wt. % Mn concentration: 2.07 wt. %) at room temperature for 30 minutes. The structure was then washed with water and thereafter dried at about 110° C. for 2 hours to obtain Ru-Mn co-supporting titania honeycomb adsorbent (amount of Ru supported: 0.55 wt. %, amount of Mn supported: 3.00 wt. %).
The adsorbent was fitted into a stainless steel reactor tube 3 having an inside diameter of 22 mm and checked for the NOx concentration of the outlet gas of the reactor tube by the same procedure as in Example 11. FIG. 18 shows the resulting variations in the NOx concentration of the outlet gas with time in terms of breakthrough ratio, as indicated as Example 16.
In the case of Example 16 (before heat treatment) shown in the drawing, the time (breakthrough time) taken for the NOx concentration of the outlet gas to reach 5% of the inlet concentration (breakthrough ratio: 0.05), i.e., 0.175 ppm, was 33.0 minutes.
Next, the adsorbent was heat-treated in the atmosphere at 250° C. for 100 hours and thereafter checked for NOx adsorption characteristics by the same procedure and under the same condition as above. FIG. 18 shows the resulting variations in the NOx concentration of the outlet gas, as indicated as Example 16 (after heat treatment). In the case of Example 16 (after heat treatment), the breakthrough time was 27 minutes for the breakthrough ratio of 0.05.
Evaluation of the Property
The adsorbent of Example 11 was checked for NOx adsorption characteristics by the same procedure and under the same condition as in Example 16. FIG. 18 shows the resulting variations in the NOx concentration of the outlet gas, as indicated as Example 11. With Example 11 shown, the breakthrough time was 40 minutes for the breakthrough ratio of 0.05.
Next, the adsorbent of Example 11 was heat-treated under the same condition as in Example 16, and therafter checked for NOx adsorption characteristics by the same procedure and under the same condition as in Example 16. FIG. 18 shows the resulting variations in the NOx concentration of the outlet gas, as indicated as Example 11 (after heat treatment). With Example 11 (after heat treatment) shown in the drawing, the breakthrough time was 5 minutes for the breakthrough ratio of 0.05.
EXAMPLE 17
The same procedure as in Example 16 was repeated except that the immersion solution used was 100 ml of an aqueous mixture solution of ruthenium chloride (RuCl 3 ) and cerium chloride (CeCl 3 ) (Ru concentration: 0.38 wt. % Ce concentration: 5.32 wt. %) to prepare a Ru-Ce co-supporting titania adsorbent (amount of Ru supported: 0.55 wt. %, amount of Ce supported: 7.70 wt. %).
The adsorbent was checked for NOx adsorption characteristics by the same procedure and under the same condition as in Example 16. FIG. 19 shows the resulting variations in the NOx concentration of the outlet gas with time, as indicated as Example 17 (before heat treatment). With Example 17 (before heat treatment), the breakthrough time was 14 minutes for the breakthrough ratio of 0.05.
Next, the adsorbent was heat-treated under the same condition as in Example 16, and thereafter checked for NOx adsorption characteristics by the same procedure and under the same condition as above. FIG. 19 shows the resulting variations in the NOx concentration of the outlet gas with time, as indicated as Example 17 (after heat treatment). In the case of Example 17 (after heat treatment) shown in the drawing, the breakthrough time was 35 minutes for the breakthrough ratio of 0.05.
EXAMPLE 18
A Ru-K co-supporting titania adsorbent (amount of Ru supported: 0.55 wt. %, amount of K supported: 0.42 wt. %) was prepared by the same procedure as in Example 16 except that the immersion solution used was 100 ml of an aqueous mixture solution of ruthenium chloride (RuCl 3 ) and potassium chloride (KCl) (Ru concentration: 0.38 wt. % K concentration: 0.29 wt. %)
The adsorbent was checked for NOx adsorption characteristics by the same procedure and under the same condition as in Example 16. FIG. 20 shows the resulting variations in the NOx concentration of the outlet gas with time, as indicated as Example 18 (before heat treatment). In the case of Example 18 (before heat treatment) shown in the drawing, the breakthrough time was 14 minutes for the breakthrough ratio of 0.05.
Next, the adsorbent was heat-treated under the same condition as in Example 16, and thereafter checked for NOx adsorption characteristics by the same procedure and under the same condition as above. FIG. 20 shows the resulting variations in the NOx concentration of the outlet gas with time, as indicated as Example 18 (after heat treatment). With Example 18 (after heat treatment) shown in the drawing, the breakthrough time was 20 minutes for the breakthrough ratio of 0.05.
EXAMPLES 19-27 AND COMPARATIVE EXAMPLES 5-7
In these examples and comparative examples, titania adsorbents each having co-supported Ru and addition metal were prepared by the same procedure as in Example 16 with the exception of using the aqueous mixture solutions listed in Table 1 below for immersion.
These adsorbents were checked for NOx adsorption characteristics by the same procedure and under the same condition as in Example 16. Table 1, the column "Breakthrough time before heat treatment" shows the periods of breakthrough time thus determined for the adsorbents at the breakthrough ratio of 0.05.
Next, these adsorbents were heat-treated under the same condition as in Example 16 and thereafter checked for NOx adsorption characteristics under the same condition as above. The breakthrough time determined for the adsorbents at the breakthrough ratio of 0.05 is given in the corresponding column of Table 1.
TABLE 1__________________________________________________________________________ Amount of Amount of Breakthrough Breakthrough Ru sup- addition time before time after Immersion soln. ported metal sup- heat treat- heat treat- (of chlorides) (wt. %) ported (wt. %) ment (min) ment (min)__________________________________________________________________________Example 16 RuCl.sub.3 + MnCl.sub.2 0.55 3.00 33 27Example 17 RuCl.sub.3 + CeCl.sub.3 0.55 7.70 14 35Example 18 RuCl.sub.3 + KCl 0.55 0.42 14 20Example 19 RuCl.sub.3 + NaCl 0.55 1.25 32 24Example 20 RuCl.sub.3 + MgCl.sub.2 0.55 1.32 34 26Example 21 RuCl.sub.3 + CaCl.sub.2 0.55 2.18 29 22Example 22 RuCl.sub.3 + CuCl.sub.2 0.55 3.46 35 25Example 23 RuCl.sub.3 + ZnCl.sub.2 0.55 3.56 31 23Example 24 RuCl.sub.3 + RbCl 0.55 4.66 26 24Example 25 RuCl.sub.3 + ZrCl.sub.4 0.55 4.97 24 21Example 26 RuCl.sub.3 + BaCl.sub. 2 0.55 7.48 28 22Example 27 RuCl.sub.3 + MoCl.sub.5 0.55 5.22 26 20Comp. Ex. 5 RuCl.sub.3 + BiCl.sub.3 0.55 11.38 36 2Comp. Ex. 6 RuCl.sub.3 + SnCl.sub.2 0.55 6.46 32 3Comp. Ex. 7 RuCl.sub.3 + SbCl.sub.5 0.55 6.63 35 2__________________________________________________________________________
Evaluation of the Property
FIGS. 18 to 20 and Table 1 showing the NOx adsorption characteristics of the adsorbents reveal the following. The adsorbents of Examples 16 to 27 retain satisfactory activity even when exposed to a high-temperature atmosphere of 250° C. for 100 hours. This suggests that these adsorbents are continuously usable through repeated adsorption and regeneration.
In contrast, the adsorbents of Comparative Examples 5 to 7 exhibited a markedly impaired property when exposed to a high-temperature atmosphere of 250° C. for 100 hours although comparable to the adsorbents of Examples in the initial property.
Adsorbent Regeneration Temperature
After NOx was desorbed from the adsorbent of Example 16 by the procedure of Example 16, the temperature of the adsorbent was raised while passing air as adjusted to a moisture content of 500 ppm through the reactor tube at 2.5 NL/min. FIG. 21 shows the resulting variations in the NOx concentration of the outlet gas of the tube.
As will be apparent from the drawing, the amount of NOx desorbed increases as the temperature of the adsorbent rises, consequently increasing the outlet NOx concentration greatly. As the amount of NOx remaining in the adsorbent thereafter decreases owing to desorption, the amount of NOx desorbed decreases to lower the outlet NOx concentration. Accordingly, the outlet NOx concentration is represented by a curve having a desorption peak. In the case of the adsorbent of Example 16 used for the removal of NOx, the desorption peak after the removal was about 190° C.
In the case where the adsorbent of Example 11 was used for removing NOx and thereafter treated by the same desorption procedure as above, the desorption peak was about 240° C. as shown in FIG. 13.
This indicates that the adsorbent of Example 16 permits removal of adsorbed NOx at a lower temperature and is easier to regenerate.
EXAMPLE 27
A Ru-supporting titania adsorbent prepared by the same method as in Example 16 was fitted into a reactor tube as in Example 16, dried under the same condition and then allowed to cool. With the passage of dry air thereafter discontinued, air adjusted to a moisture content of about 22,000 ppm (temperature: 26.0° C., relative humidity: 51%) and containing 3.5 ppm of NOx was introduced into the adsorbent at 2.5 NL/min as a reactive gas to measure the NOx concentration in the reactor tube outlet gas. FIG. 22 shows the resulting variations in the concentration with time, as indicated as Example 27, along with the result of Example 16 (moisture content: 500 ppm).
FIG. 22 reveals that the adsorbent retains a high NOx adsorbing property even at an increased moisture content and is useful for efficiently removing NOx even at the moisture content of the atmosphere.
Amount of Ru Supported
Flat sheet-corrugated sheet multilayer structures were prepared by the same procedure as in Example 16. Each of the structures was immersed in an aqueous mixture solution containing ruthenium chloride and manganese chloride in specified concentrations (Ru concentration: 0.2 to 0.3 wt. %, Mn concentration: 2.07 wt. %) at room temperature for a predetermined period of time, then washed with water and thereafter dried. Honeycomb adsorbents were thus prepared which were different in the amount of Ru supported.
These adsorbents were each fitted into a reactor tube in the same manner as in Example 16 and checked for the NOx concentration of the outlet gas under the same condition to determine 10% breakthrough time (the time taken for the NOx concentration of the outlet gas to reach 10% of the inlet concentration). FIG. 23 shows the relation between the amount of Ru supported and the 10% breakthrough time established.
As will be apparent from the drawing, an increase in the amount of Ru supported results in an increased 10% breakthrough time, i.e., a higher NOx adsorbing property. However, when the amount of Ru exceeds about 2 wt. %, the 10% breakthrough time becomes approximately definite. | The invention provides first to fourth adsorbents for removing low-concentration nitrogen oxides. The first adsorbent comprises a carrier of gamma-alumina, and ruthenium supported thereon. The second adsorbent comprises a carrier of anatase-type titania, and ruthenium supported thereon. The third adsorbent comprises ceramic paper retaining a carrier of anatase-type titania thereon, and ruthenium supported on the ceramic paper. The fourth adsorbent comprises ceramic paper retaining a carrier of anatase-type titania thereon, and a ruthenium halide and a halide of addition metal which are co-supported on the ceramic paper. These adsorbents are free of the influence of moisture and therefore usable without necessitating energy-consuming dehumidification or only with dehumidification on a reduced scale. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates to pharmaceutical compounds for use in the management of pain. More particularly, it relates to histogranin-like peptides and non-peptides.
BACKGROUND OF THE INVENTION
[0002] Histogranin (HN, Scheme 1) (SEQ ID NO. 1), a pentadecapeptide whose structure presents 80% and 73% homologies with those of fragment-(86-100) of histone H4 (SEQ ID NO. 2) and osteogenic growth peptide (OGP) (SEQ ID NO. 3), respectively, was first isolated from extracts of bovine adrenal medulla (Lemaire, Eur. J. Pharmacol., 1993, 245; 247-256), a tissue recognized to contain various pain reducing substances, including the endogenous opioid peptides Met- and Leu-enkephalins and catecholamines (Boarder et al. J. Neurochem., 1982, 39, 149-154; Liston et al. Science, 1984, 225, 734-737).
[0003] I.c.v. administration of HN (SEQ ID NO. 1) and related peptides in mice dose-and structure-dependently blocked writhing induced by i.p. administration of acetic acid and tail-flick induced by radiant heat (Lemaire et al., Soc. Neurosci. 1997, 23, 674., Ruan, Prasad and Lemaire, Pharmcol. Biochem. Behav. 2000, 66, 1-9). In addition, [Ser 1 ]HN, a chemically stable analog of HN (SEQ ID NO. 1) (Shukla and Lemaire, Pharmcol. Biochem. Behav. 1995, 50, 49-54), blocked tonic pain in the rat formalin assay (Siegen and Sagan, Neuroreport. 1997, 8 1379-81) and attenuated hyperalgesia and allodynia caused by sciatic nerve injury (Siegan and Sagen, Brain Res. 1997, 755, 331-334) and intrathecal (i.t.) administration of N-methyl-D-aspartate (NMDA; Hama and Sagen, Pharmacol. Biochem. Behav., 1999, 62, 67-74).
[0000] Scheme 1:
[0000]
Histogranin (HN) (SEQ ID NO. 1): Met-Asn-Tyr-Ala-Leu-Lys-Gly-Gln-Gly-Arg-Thr-Leu-Tyr-Gly-Phe
H4-(86-100) (Histone H4 fragment) (SEQ ID NO. 2): Val-Val-Tyr-Ala-Leu-Lys-Arg-Gln-Gly-Arg-Thr-Leu-Tyr-Gly-Phe
OGP (Osteogenic Growth Peptide) (SEQ ID NO. 3): Ala-Leu-Lys-Arg-Gln-Gly-Arg-Thr-Leu-Tyr-Gly-Phe-Gly-Gly
Histogranin(7-15) (SEQ ID NO. 4):
[0008] In the mouse writhing tail-flick assays, the analgesic effects of i.c.v. administration of HN (SEQ ID NO. 1) and related peptides are not mediated by opioid receptors and may involve a participation of dopamine D2 sites (Ruan, Prasad and Lemaire, Pharmcol. Biochem. Behav. 2000, 66, 1-9). A hypothesis is that HN (SEQ ID NO. 1) and related peptides bind to a specific receptor present in the brain (Roger et Lemaire, J. Pharmacol. Exp. Ther., 1993, 267, 350-356) and on peripheral cells (Lemaire et al., Biochem Biophys Res Commun. 1993, 194, 1323-9) and modulate processes involved in the pathophysiology of pain.
[0009] Among various HN related peptides and fragments, the C-terminal peptide HN-(7-15) (SEQ ID NO. 1) (Scheme 1) was shown to be particularly potent in the mouse writhing test with an AD 50 of 8.5 nmol/mouse as compared with 23 nmol/mouse for HN (SEQ ID NO. 1) (Ruan, Prasad and Lemaire, Pharmcol. Biochem, Behav. 2000, 66, 1-9; Canadian patent application 2,219,437).
SUMMARY OF THE INVENTION
[0010] There is provided a compound of general formula I, II or III, or pharmaceutically acceptable salt thereof:
wherein:
[0011] is A is -hydrogen, —(C 1 -C 8 )alkyl or —(C 1 -C 8 )alkyl substituted by hydroxy;
[0012] B is —(C 1 -C 6 )alkylguanidino, —(C 1 -C 6 s)alkyl(4-imidazolyl), —(C 1 -C 6 )alkylamino, p-aminophenylalkyl(C 1 -C 6 )—, p-guanidinophenylalkyl(C 1 -C 6 )— or 4-pyridinylalkyl (C 1 -C 6 )—;
[0013] D is —(CO)—, —(CO)—(C 1 -C 6 )alkylene or —(C 1 -C 6 )alkylene;
[0014] E is a single bond or —(C 1 -C 6 )alkylene;
[0015] Z is —NH 2 , —NH—(C 1 -C 6 )alkylcarboxamide, —NH—(C 1 -C 6 )alkyl, —NH-benzyl, —NH-cyclo(C 5 -C 7 )alkyl, —NH-2-(1-piperidyl)ethyl, —NH-2-(1-pyrrolidyl)ethyl, —NH-2-(1-pyridyl)ethyl, —NH-2-(morpholino)ethyl, -morpholino, -piperidyl, —OH, —(C 1 -C 6 )alkoxy, —O-benzyl or —O-halobenzyl;
[0016] R 1 , R 2 and R 3 are, independent of one another, -hydrogen, -arylcarbonylamino, —(C 1 -C 6 )alkoylamino, —(C 1 -C 6 )alkylamino, —(C 1 -C 6 )alkyloxy, —(C 1 -C 6 )alkylaminocarbonyl, -carboxy, —OH, -benzoyl, -p-halogenobenzoyl, -methyl, —S-(2,4-dinitrophenyl), —S-(3-nitro-2-pyridinesulfenyl), -sulfonyl, -trifluoromethyl, —(C 1 -C 6 )alkylaminocarbonylamino, -halo or -amino;
[0017] R 4 and R 5 are, independent of one another, -hydrogen, —(C 1 -C 6 )alkyl, -methyloxy, -nitro, -amino, -arylcarbonylamino, —(C 3 -C 6 )alkoylamino, —(C 1 -C 6 )alkylamino, -halo or —OH.
[0018] There are also provided methods for synthesizing compounds of Formulae I, II and III.
[0019] There are also provided pharmaceutical compositions comprising a compound of Formulae I, II or III, or a pharmaceutically acceptable salt thereof, together with a pharmaceutically acceptable carrier, diluent or excipient.
[0020] In addition, there is provided a method for managing pain comprising administering a pain managing effective amount of a compound of Formulae I, II or III, or a pharmaceutically acceptable salt thereof, to a subject in need of pain management.
[0021] Furthermore, there is provided the use of a compound of Formulae I, II or III, or a pharmaceutically acceptable salt thereof, for managing pain or for manufacturing a medicament for managing pain.
[0022] There is also provided commercial packages comprising a compound of Formulae I, II or III, or a pharmaceutically acceptable salt thereof, or a composition comprising a compound of Formulae I, II or III, or a pharmaceutically acceptable salt thereof, together with instructions for their use for managing pain.
[0023] There is also provided a method of modulating COX-2 induction comprising administering an effective amount of a COX-2 induction modulating compound of Formulae I, II or III, or a pharmaceutically acceptable salt thereof, or a composition comprising a compound of Formulae I, II or III, or a pharmaceutically acceptable salt thereof, to a subject.
[0024] Compounds of Formulae I, II and III were invented according to the unifying hypothesis that compounds containing basic, hydroxyphenyl and phenyl groups (or homologues) with proper spatial arrangements display HN-like biological activities.
DETAILED DESCRIPTION OF THE INVENTION
[0025] The radical A is preferably hydrogen, CH 3 CH(OH)— or (CH 3 ) 2 CHCH 2 —. The CH 3 CH(OH)— or (CH 3 ) 2 CHCH 2 — groups may be bonded to the molecule in such a way as to provide either the R- or S-configuration at the carbon atom to which the group is bonded. As one skilled in the art will recognize, the hydrogen radical corresponds to the amino acid glycine, he group CH 3 CH(OH)— has the same structure as the side-chain from the amino acid threonine while (CH 3 ) 2 CHCH 2 — has the same structure as the side-chain from the amino acid leucine.
[0026] The radical B is preferably H 2 N—C(NH)—NH—C—CH 2 CH 2 — or H 2 N—(CH 2 ) 4 —. The H 2 N—C(NH)—NH—CH 2 CH 2 CH 2 — or H 2 N—(CH 2 ) 4 — groups may be bonded to the molecule in such a way as to provide either the R- or S-configuration at the carbon atom to which the group is bonded. As one skilled in the art will recognize, the group H 2 N—C(NH)—NH—CH 2 CH 2 CH 2 — has the same structure as the side-chain from the amino acid arginine while H 2 N—(CH 2 ) 4 — has the same structure as the side-chain from the amino acid lysine.
[0027] Generally, chiral carbon atoms in the compounds of Formula I, II or III may be in either optically active R- of S-configuration. Therefore, where amino acid moieties are present in the compounds, they may have either the L- or D-configurations. Optically pure compounds, racemic mixtures, and diastereomeric mixtures are all contemplated within the scope of the invention.
[0028] Pharmaceutically acceptable salts encompass any salts of the active compounds which are suitable for the formulation of a pharmaceutical composition and which are compatible with the animal to which the compound is being administered. Such salts include, but are not limited to, salts of acids (e.g. hydrochlorides and sulphates) and salts of bases (e.g. sodium and ammonium salts).
[0029] For the synthesis of cyclic peptides (Formula I), Kaiser's oxime-resin may be used following the procedures of Nishino et al. ( J. Chem. Soc., Perkin Trans. 1, 1996, 939-946) and Osapay et al. ( Tetrahedron Lett. 1990, 31, 6121-6124), the disclosures of which are hereby incorporated by reference.
[0030] The solid-phase synthesis of the compounds of Formula II or III (Schemes 2a and 2b) may be achieved by starting with MBHA Resin (i.e. modified Merrifield resin, which is a polystyrene based resin having bound thereto a 4-methylbenzhydrylamine hydrochloride moiety) or with Rink-Amide Resin. The method may begin with neutralization of the amine hydrochloride group in MBHA resin (1) with 10% N,N′-diisopropylethylamine/CH 2 Cl 2 (DIEA/DCM) or with the removal of the Fmoc-protecting group from Rink-Amide resin (2) with 20% piperidine in DMF. Protected N-amino acids may then be attached to the resultant amino-resin (method A or method B) or to 4-sulfamylbutyryl AM resin (3) (method C) using benzotriazole-1-yl-oxy-tris-pyrrolidino-phosphonium hexafluorophosphate (PyBOP/DIEA). The intermediates 4, 5, 6 are ninhydrin negative by the Kaiser test (Kaiser et al. Anal. Biochem. 1970, 34, 595-598).
[0031] Incorporation of specific groups may be achieved by reacting the deprotected resin 4, 5, 6 with a variety of substituted o-fluoro-nitroarens (preferably about 10 equiv.) and DIEA (preferably about 5 equiv.) in DMF or DMSO, preferably for about 2 days (Scheme 2b). The completion of the reaction leading to substituted o-nitro-aniline resin (7) may be monitored by the ninhydrin test.
[0032] In the next step, the aryl nitro group (intermediate resin product 7) may be reduced by a solution (preferably at a concentration of about 1 M) of tin(II) chloride dihydrate (SnCl 2 .2H 2 O) in N-methylpyrrolidine-2-one (NMP) in the presence of N-methylmorpholine (NMM), preferably overnight at room temperature. The resin may be washed and then immediately acylated by using symmetric anhydride generated in situ from N′,N′-dicyclohexylcarbodiimide (DCC) and corresponding carboxylic acids (path a in scheme 2b) or treated with aldehydes in NMP, preferably for about 8 hr at room temperature, followed by heating, preferably at about 50° C. for about 8 hr (path b in scheme 2b).
[0033] Resin-bound o-(N-acyl)-phenylenediamine (8) or benzimidazole (9) may be washed with DMF, MeOH, DCM and Et 2 O and then dried in vacuo overnight at room temperature. The compounds may then be cleaved from the MBHA resin with liquid hydrogen fluoride (HF) under standard cleaving conditions (Matsueda et al. Peptide, 1981, 2, 45-50, the disclosure of which is hereby incorporated by reference). Substituted-Rink-Amide resin may be treated with CF 3 COOH (TFA/H 2 O (95:5)), preferably for 1 hour at ice-bath temperature (Lee et al. J. Org. Chem. 1997, 62, 3874-3879, the disclosure of which is hereby incorporated by reference). For the removal of the compounds from the resin, the 4-sulfamylbutyryl AM resin may first be N-methylated with ICH 2 CN/DIEA in NMP and then treated with either hydroxide at room temperature or an amine in THF or dioxane at elevated temperature (Backes et al. J. Am. Chem. Soc., 1996, 118, 3055-3056, the disclosure of which is hereby incorporated by reference).
wherein B, D, E, R 1 , R 2 , R 3 , R 4 , R 5 and Z represent the groups described above and the spherical element in Schemes 2a and 2b represents the remainder of the MBHA resin, Rink-Amide resin or 4-sulfamylbutyryl AM resin, as appropriate.
[0034] Particularly preferred compounds that may be prepared by the procedures described above are:
[0035] (A) Cyclic tetrapeptides of Formula I (see Scheme 3):
(SEQ ID NO. 5) Cyclo(-Gly-(p-chloro)Phe-Tyr-D-Arg-) [Compound I-1] (SEQ ID NO. 6) Cyclo(-Gly-(p-chloro)Phe-Tyr-(p-amino)Phe-) [Compound I-2] (SEQ ID NO. 7) Cyclo(-Gly-(p-chloro)Phe-Tyr-(p-guanidino)Phe-) [Compound I-3] (SEQ ID NO. 8) Cyclo(-Gly-(p-amino)Phe-Tyr-D-Arg-) [Compound I-4] (SEQ ID NO. 9) Cyclo(-Thr-(p-chloro)Phe-Tyr-D-Arg-) [Compound I-5]
(B) Non-peptides of Formula II (see Scheme 4):
N-5-guanidinopentanamide-(2S)-yl-2-N-(p-hydroxyphenylacetyl) phenylenediamine [Compound II-1] N-5-guanidinopentanamide-(2S)-yl-2-N-(p-hydroxyphenylacetyl)-4-trifluorometyl-phenylenediamine [Compound II-2] N-5-guanidinopentanamide-(2R)-yl-2-N-(p-hydroxyphenylacetyl)-4-carboxy-phenylenediamine [Compound II-3] N-5-guanidinopentanamide-(2R)-yl-2-N-(p-hydroxyphenylacetyl)-4-(p-chlorobenzoyl)-phenylenediamine [Compound II-4]
(C) A non-peptide of Formula III (see Scheme 4):
N-5-guanidinopentanamide-(2R)-yl-2-(p-hydroxybenzyl)-5-carboxybenzimidazole [Compound III-1]
[0041] Pharmaceutical compositions comprising a compound of the present invention, or a pharmaceutically acceptable salt thereof, in admixture with a pharmaceutically acceptable carrier, diluent or excipient may be formulated by methods generally known in the art. The preparation and administration of pharmaceutical compositions are generally known in the art, for example as described in U.S. Pat. No. 5,169,833, the disclosure of which is hereby incorporated by reference.
[0042] Thus, the active compounds of the invention may be formulated for oral, buccal, transdermal (e.g., patch), intranasal, parenteral (e.g., intravenous, intramuscular or subcutaneous) or rectal administration or in a form suitable for administration by inhalation or insufflation.
[0043] For oral administration, the pharmaceutical compositions may take the form of, for example, tablets or capsules prepared by conventional means with pharmaceutically acceptable excipients such as binding agents (e.g., pregelatinised maize starch, polyvinylpyrrolidone or hydroxypropyl methylcellulose); filters (e.g., lactose, microcrystalline cellulose or calcium phosphate); lubricants (e.g., magnesium stearate, talc or silica); disintegrants (e.g., potato starch or sodium starch glycollate); or wetting agents (e.g., sodium lauryl sulphate). The tablets may be coated by methods well known in the art. Liquid preparations for oral administration may take the form of, for example, solutions, syrups or suspensions, or they may be presented as a dry product for constitution with water or other suitable vehicle before use. Such liquid preparations may be prepared by conventional means with pharmaceutically acceptable additives such as suspending agents (e.g., sorbitol syrup, methyl cellulose or hydrogenated edible fats); emulsifying agents (e.g., lecithin or acacia); non-aqueous vehicles (e.g., almond oil, oily esters or ethyl alcohol); and preservatives (e.g., methyl or propyl p-hydroxybenzoates or sorbic acid).
[0044] For buccal administration the composition may take the form of tablets of lozenges formulated in conventional manner.
[0045] The active compounds of the invention may be formulated for parenteral administration by injection, including using conventional catheterization techniques or infusion. Formulations for injection may be presented in unit dosage form, e.g., in ampules or in multi-dose containers, with an added preservative. The compositions may take such forms as suspensions, solutions or emulsions in oily or aqueous vehicles, and may contain formulating agents such as suspending, stabilizing and/or dispersing agents. Alternatively, the active ingredient may be in powder form for reconstitution with a suitable vehicle, e.g., sterile pyrogen-free water, before use.
[0046] The active compounds of the invention may also be formulated in rectal compositions such as suppositories or retention enemas, e.g., containing conventional suppository bases such as cocoa butter or other glycerides.
[0047] For intranasal administration or administration by inhalation, the active compounds of the invention are conveniently delivered in the form of a solution or suspension from a pump spray container that is squeezed or pumped by the patient or as an aerosol spray presentation from a pressurized container or a nebulizer, with the use of a suitable propellant, e.g., dichlorodifluoromethane, trichlorofluoromethane, dichlorotetrafluoroethane, carbon dioxide or other suitable gas. In the case of a pressurized aerosol, the dosage unit may be determined by providing a valve to deliver a metered amount. The pressurized container or nebulizer may contain a solution or suspension of the active compound. Capsules and cartridges (made, for example, from gelatin) for use in an inhaler or insufflator may be formulated containing a powder mix of a compound of the invention and a suitable powder base such as lactose or starch.
[0048] The active compounds or pharmaceutical compositions thereof are generally administered to or used in animals, for example in humans for medical purposes or in domestic animals or farm animals for veterinary purposes. Preferably, the animal is a mammal, particularly a human. Selection of appropriate doses would depend on the particular patient and on the compound being used and is ultimately decided by a medical practitioner. Generally, doses may range, depending on the compound, from 200 times less to 500 times more than would be used for morphine, which could be administered, for example, 1 to 4 times per day.
[0049] The active compounds of the present invention are analgesic in various animal pain assays, particularly after central (i.c.v., i.t.) or peripheral (oral, i.p. and/or i.v.) administrations. They also potentiate the action of morphine, therefore, pharmaceutical compositions comprising the active compounds of the present invention in admixture with morphine are contemplated within the scope of the invention. The active compounds may be administered in conjunction with morphine to enhance the effectiveness of morphine.
[0050] The active compounds also block morphine tolerance and, particularly in isolated rat alveolar macrophages, they inhibit the induction of COX-2 and the secretion of PGE 2 in response to lipopolysaccharide (LPS).
[0051] The active compounds show potent analgesic activity (1.4 to 135 fold as potent as HN (SEQ ID NO. 1)) in the mouse writhing test. Significant analgesic activity is observed after both central (i.c.v.) and peripheral (oral, i.p.) administrations of compounds I-1 (SEQ ID NO. 5), II-1 and III-1. The various compounds also display high analgesic activity in the mouse tail-flick (i.c.v.) pain assay. None of the compounds (i.c.v.) induce motor dysfunction at analgesic doses as assessed by the mouse rotarod assay. In addition, compound II-1 potentiates the analgesic effects of morphine in the mouse writhing test and inhibits morphine tolerance in the mouse tail-flick assay. In isolated rat alveolar macrophages, the active compounds potently inhibit the induction of COX-2 and the secretion of PGE 2 in response to LPS.
BRIEF DESCRIPTION OF THE DRAWINGS
[0052] The invention will now be particularly described by non-limiting examples having reference to the appended drawings in, which:
[0053] FIG. 1 is a graph showing the dose-dependent analgesic effects of morphine and Histogranin-like peptides and non-peptides (i.c.v.) in the mouse writhing assay.
[0054] FIGS. 2A and 2B are graphs showing the antinociceptive effects of oral and intraperitoneal administrations of HN-like peptides and non-peptides in the mouse writhing test.
[0055] FIG. 3 is a graph showing the dose-dependent analgesic effects of morphine and Histogranin-like peptides and non-peptides in the mouse tail-flick assay.
[0056] FIGS. 4A and 4B are graphs showing the potentiation (A) and prolongation (B) of the analgesic effect of morphine (i.c.v.) in the mouse writhing test by coadministration of a subanalgesic dose (3 nmol) of compound
[0057] FIG. 5 is a graph showing blockade of morphine tolerance by compound II-1 in mice (* P<0.05 as compared with control).
[0058] FIG. 6 is a graph showing the inhibitory effects of HN (SEQ ID NO. 1) and related peptides and non-peptides on PGE 2 release from LPS-stimulated rat alveolar macrophages.
[0059] FIG. 7 is a graph showing the inhibitory effects of HN (SEQ ID NO. 1), related peptides and non-peptides on the expression of COX-2 in LPS-stimulated rat alveolar macrophages.
EXAMPLES
[0060] The purity and identity of the synthetic products were confirmed by thin-layer chromatography, analytical HPLC on μ-Bondapak™ C-18 (Waters™) and FAB mass spectroscopy.
Example I
Cyclo(-Gly-(p-chloro)Phe-Tyr-D-Arg-) (I-1) (SEQ ID NO. 5).
[0061] Boc-Gly-oxime-resin was first prepared by mixing oxime-resin (available--from Novabiochem™) (1.5 g, 0.57 meq/g) with Boc-Gly-OH (1.3 g, 9 eq) in the presence of DCC (9.9 ml of DCC 8%, 4.5 eq), 4-dimethylaminopyridine (DMAP), (0.3 g, 3 eq), N-hydroxybenzotriazole hydrate (HOBt), (0.4 g, 3 eq) in 50 ml of DCM at room temperature for 12 hr. The resin was submitted to three washes with 50 ml of DCM, one wash with 50 ml of propanol-2 and two washes with 50 ml of DCM. The free oxime groups were capped by acetylation with acetic anhydride (0.4 ml, 5 eq) for 30 min. The peptide chain was then assembled according to the following coupling steps: (i) one wash with 25% trifluoroacetic acid (TFA)-DCM; (ii) deprotection with 25% TFA-DCM (30 min); (iii) two washes with DCM; (iv) one wash with propanol-2; (v) three washes with DCM; (vi) one wash with dimethylformamide (DMF); (vii) coupling of Boc-amino-acids (consecutively Boc-D-Arg(Tos)-OH (1.1 g, 3 eq), Boc-Tyr(2,6-di-Cl-Bzl)-OH (1.1 g, 3 eq) and Boc-Phe (pCl)—OH (0.8 g, 3 eq)) in presence of PyBOP, (1.3 g, 3 eq), HOBt (0.13 g, 1 eq) and DIEA (0.95 ml, 6.5 eq) in DMF (45 min); (viii) three washes with DMF; (ix) two washes with DCM. Solvent volumes were 15 cm 3 g −1 resin. Coupling efficiency was checked at each coupling cycle by the Kaiser test. The peptide was cleaved from the resin by intrachain aminolysis in the presence of AcOH (0.097 ml, 2 eq) and DIEA (0.293 ml, 2 eq,) in 30 ml DMF at room temperature for 24 hr. The product was obtained from the solution phase by filtration. Protecting groups were removed with anhydrous hydrogen fluoride (HF) at 0° C. for 30 min. The product was purifed by chromatography on Sephadex™ G-10 (1.5×30 cm column) and preparative reversed-phase HPLC on μ-Bondapak C18 column (25∴100 mm) with a gradient of 0%-50% acetonitrile in 0.1% TFA and a flow rate of 5 ml/min over 65 min. The procedure yielded 50 mg of I-1 (SEQ ID NO. 5) (Scheme 3; 11% based on starting resin).
[0062] Other cyclic peptides (Scheme 3) were prepared according to this technique with the following yields: cyclo(-Gly-(p-chloro)Phe-Tyr-(p-amino)Phe-) (I-2 (SEQ ID NO. 6); 45 mg, 9%), cyclo(-Gly-(p-chloro)Phe-Tyr-(p-guanidino)Phe-) (I-3 (SEQ ID NO. 7); 15 mg, 2%), cyclo(-Gly-(p-amino)Phe-tyr-D-Arg-) (I-4 (SEQ ID NO. 8); 40 mg, 9%), cyclo(-Thr-(p-chloro)Phe-Tyr-D-Arg-) (I-5 (SEQ.ID NQ. 9); 40 mg, 9%).
Example II
Synthesis of N-5-guanidinopentanamide-(2S)-yl-2-N-(p-hydroxyphenylacetyl)phenylenediamine (II-1).
[0063] Attachment of Boc-L-Arg(Tos)-OH to MBHA-resin. The MBHA-resin (1 g. 0.67 mmol, Novabiochem™) was first neutralized with 10% DIBA in DCM (two 5 min washes with 50 ml each) and washed six times with six 50 ml fractions of DCM. The first amino acid was attached by mixing the resin for 1 hr at room temperature with 1.1 g (2.68 mmol) of Boc-L-Arg(Tos)-OH, 1.4 g (2.68 mmol) of PyBOP, 0.2 g (1.34 mmol) of HOBt, H 2 O and 0.9 ml (5.36 mmol) of DIEA in 50 ml of DMF/DCM (1:1). At the end of the coupling reaction, the resin was ninhydrin negative by the Kaiser test. The resulting mixed Boc-Arg)Tos)-MBHA-resin was washed three times with 50 ml of DMF, three times with 50 ml of DCM and then acetylated for 30 min with 0.6 ml (6.7 mmol) of Ac 2 O and 0.6 ml (3.35 mmol) of DIEA in 50 ml of DCM. The resin was washed 4 times with 50 ml of DCM, 2 times with 50 ml of Me OH, 2 times with 50 ml of DCM and dried.
[0064] Incorporation of 1-fluoro-2-nitrobenzen to Boc-L-Arg(Tos)-MBHA-resin. One g of the above-described resin (approximately 0.67 mmol) was washed with 50 ml of TFA/DCM (4:6) and subsequently deprotected for 15 min with 5.0 ml of. TFA/DCM (4:6). The resin was washed 4 times with 50 ml of DCM, neutralized twice for 2 min each with 50 ml portions of DIEA/DCM (5:95) and washed six times with 50 ml of DCM. The next reaction was conducted by addition of 0.7 ml (6.7 mmol) of 1-fluoro-2-nitrobenzene, 0.6 ml (3.35 mmol) of DIEA and 20 ml of DMF. The suspension was allowed to mix at room temperature for 24 hr, the reagents were changed and a novel suspension was made and mixed for another 24 hr. The completion of the reaction was verified by the Kaiser test. The resin then was washed 4 times with 50 ml of DMF, 2 times with 50 ml of MeOH, 2 times with 50 ml of DCM and acetylated for 30 min with 0.6 ml (6.7 mmol) of Ac 2 O and 0.6 ml (3.35 mmol) of DIEA in 50 ml of DCM. The o-nitroaniline-resin was washed 4 times with 50 ml of DCM, 2 times with 50 ml of MeOH, 2 times with 50 ml of DCM and dried.
[0065] N-5-guanidinopentanamide-(2S)-yl-2-N-(p-hydroxyphenylacetyl)phenylenediamine (I-1). One g (approximately 0.67 mmol) of the o-nitroaniline-resin was reduced with 1 M of SnCl 2 , 2H 2 O (4.5 g) and 1 M of NMM (2.2 ml) in 20 ml of NMP overnight at room temperature. The resin was washed 4 times with 50 ml of NMP, 2 times with 50 ml of DCM, 2 times with 50 ml of MeOH, 2 times with 50 ml of DCM and then immediately acylated with 0.18 M of carboxylic anhydride prepared in situ from 1 g (6.7 mmol) of 4-hydroxyphenylacetic acid, 17.3 ml (6.7 mmol) of 8% DCC/DCM, 0.5 g (3.35 mmol) of HOBt. H 2 O and 0.4 g (3.35 mmol) of DMAP in 20 ml DCM overnight at room temperature. The resin was washed with 50 ml portions of DMF (×4), DCM (×2), MeOH (×2), DCM (×2), Et 2 O (×2) and dried in vacuum. Compound (II-1) was cleaved from the resin by treatment with 15 ml of anhydrous liquid HF and 1 ml of anisole as scavenger for 1 hr at 0° C. HF and scavenger were evaporated in vacuo. The compound was extracted from the dried resin with 50 ml of DMF (×4), and then concentrated in vacuo. It was purified by gel filtration on Sephadex™ G-10 followed by preparative reversed-phase HPLC using a 25×200 mm column (Water, μ-Bondapak C18, 10 μm, 125 Å), operating at a flow 5 ml/min. The chromatography was achieved using a gradient of acetonitrile in 0.1% TFA, increasing from 15% to 65% over 1 hr. The purified compound was detected by UV at 280 nm. Yield: 120 mg (45%) (based on the substitution of the starting resin).
Example III
[0066] N-5-guanidinopentanamide-(2S)-yl-2-N-(p-hydroxyphenylacetyl)-4-trifluorometyl-phenylenediamine (II-2). The preparation of compound II-2 was performed as described above. 4-fluoro-3-nitrobenzotrifluoride was used instead of 1-fluoro-2-nitrobenzen in the 2 nd step. 1 g of the deprotected H-L-Arg(Tos)-MBHA-resin (approximately 0.67 mmol) was added 0.9 ml (6,7 mmol) of 4-fluoro-3-nitrobenzotrifluoride, 0.6 ml (3.35 mmol) of DIEA and 20 ml of DMF. The suspension was allowed to mix at room temperature for 24 hr, followed by a change of the reagents and another 24 hr of mixing. The completion of the reaction was verified by the Kaiser test. The other steps were accomplished using the same reaction conditions as those described for compound 11-1. Yield: 96 mg (31%).
Example IV
N-5-guanidinopentanamide-(2R)-yl-2-N-(p-hydroxyphenylacetyl)-4-carboxyphenylene-diamine (II-3).
[0067] Compound II-3 was obtained following a procedure similar to that used for the preparation of compound II-1. Boc-D-Arg(Tos)-OH was used instead of Boc-L-Arg(Tos)-OH in the 1 st step and 4-fluoro-3-nitrobenzoic acid was used in the 2 nd step. One g of the MBHA-resin (0.67 mmol) was coupled with 1.1 g (2.68 mmol) of Boc-D-Arg(Tos)-OH, 1.4g (2.68 mmol) of PyBOP, 0.2 g (1.34 mmol) of HOBt.H 2 O and 0.9 ml (5.36 mmol) of DIEA in 50 ml of DMF/DCM (1:1) for 1 hr at room temperature. In the 2 nd step, 1 g of the deprotected H-L-Arg(Tos)-MBHA-resin (approximately 0.67 mmol) was added 1.2 g (6.7 mmol) of 4-fluoro-3-nitrobenzoic acid, 0.6 ml (3.35 mmol) of DIEA and 20 ml of DMF. The suspension was allowed to mix at room temperature for two 24 hour periods as described above. The other steps were accomplished in the same reaction conditions as those for compound II-1. Yield: 90 mg (30%).
Example V
[0068] N-5-guanidinopentanamide-(2R)-yl-2-N-(p-hydroxyphenylacetyl)-4-(p-chlorobenzoyl)-phenylenediamine (II-4). Compound II-4 was obtained following a procedure similar to that used for the preparation of compound II-3. Following acetylation of amino group with 4-hydroxyphenylacetic anhydride prepared in situ from DCC and corresponding carboxylic acid, 1 g (approximately 0.67 mmol) of the resin-bound o-(N-acyl)phenylenediamine was treated with 1.1 g (6.7 mmol) of 1,1′-carbonyldiimidazole and 0.4 g (3.35 mmol) of DMAP in 20 ml of tetrahydrofuran (THF) overnight at 4° C. then immediately coupled with 6.7 ml (6.7 mmol) of 4-chlorophenylmagnesium bromide (1.0 M solution in diethyl ether) in 20 ml of THF overnight at 4° C. The other steps were accomplished using the same reaction conditions as those described for compound II-3. Yield: 49 mg (14%).
Example VI
[0069] N-5-guanidinopentanamide-(2R)-yl-2-(p-hydroxybenzyl)-5-carboxybenzimidazole (III-1). Compound III-1 was obtained by a modification of the procedure for the preparation of compound II-3. Following the reduction of nitro group with SnCl 2 .2H 2 O, 1 g (approximately 0.67 mmol) of the o-aminoaniline-resin was immediately treated with 0.8 g (6.7 mmol) of p-hydroxybenzaldehyde in NMP with stirring for 8 hr at room temperature, followed by heating at 50° C. for 8 hr. The resultant resin was transferred to a 25 ml filter tube, washed with the following schedule (50 ml each): NMP (×3), DCM (×2), MeOH (×3), Et 2 O (×3). It was then dried overnight in vacuo at room temperature. Finally, the cleavage and purification steps were accomplished using the same conditions as those described for compound II-3. Yield: 94 mg (34%).
[0070] The purity and identity of the synthetic compounds were assessed by thin layer chromatography (TLC), high performance liquid chromatography (HPLC) and mass spectrometry (ES-MS or FAB-MS) (Table 1).
TABLE 1 Analytical properties of Histogranin-like peptides and non-peptides. TLC HPLC ES-MS or Compounds (Rf) a (k′) b FAB-MS (MH+) Peptides I-1 (SEQ ID NO. 5) 0.77 4.47 558 I-2 (SEQ ID NO. 6) 0.86 4.00 580 I-3 (SEQ ID NO. 7) 0.58* — 622 I-4 (SEQ ID NO. 8) 0.52 4.19 538 I-5 (SEQ ID NO. 9) 0.65 0.83 602 Non-peptides II-1 0.66 2.02 399 II-2 0.70 2.18 467 II-3 0.68 0.70 443 II-4 0.70 1.54 538 III-1 0.59 2.50 411 a BAWP (v/v), 1-butanol-acetic acid-water-pyridine (15/3/10/12). b by analytical reversed-phase HPLC using a 3.9 × 300 mm column (Water, μBondapak ™ C18), operating at a flow 1 ml/min. Separations were achieved using a water/acetonitrile/TFA gradient, increasing from 0% to 50% (I-1, I-2), 0% to 65% (I-4, I-5), 15% to 65% (compounds II-1 and II-2) and from 15% to 80% (compounds II-3, II-4 and III-1) over 50 min and UV detection at 280 and 350 nm. *R f (v/v, CH 2 Cl 2 /MeOH, 8/2).
Example VII
Analgesia, morphine potentiation and blockade of morphine tolerance
[0000] Materials and Methods:
[0071] Animals. Mice (male 20-25 g, Swiss Webster) were obtained from Charles River (Canadian Breeding Farm, St. Constant, Quebec). They were housed five per cage in a room with controlled temperature (22±2° C.), humidity and artificial light (06.30-19 h). The animals had free access to food and water and were used after a minimum of 4 days of acclimation to housing conditions. Experiments were carried out between 10:00 a.m. and 4:00 p.m. in an air-regulated and soundproof laboratory (23±1 20 C., 40% humidity), in which mice were habituated at least 30 min before each experiment. The experiments were authorized by the animal care committee of the University of Ottawa in accordance with the guidelines of the Canadian Council on Animal Care.
[0072] Drugs and peptides. Morphine, raclopride, naloxone, SCH-23390 were products of ENDO laboratory Inc (Garden City, N.Y.). HN (SEQ ID NO. 1), [Ser 1 ]HN, HN-(7-15) (SEQ ID NO. 4) and H4-(86-100) (SEQ ID NO. 2) were synthesized by the solid-phase procedure (Lemaire et al. Int. J. Peptide Protein Res. 1986, 27, 300-305). Cyclic tetrapeptides and non-peptides were synthesized as described above.
[0073] Administration of compounds. The i.c.v. administrations of the peptides and non-peptides in mice were performed as described by Shukla et al. (Shukla et al., Brain Res. 1992, 591,176). Peptides are dissolved in double-distilled sterile water (vehicle) and 10 μl of the peptide solution or vehicle are delivered gradually within approximately 3 sec, mice exhibiting normal behaviour within 1 min after injection. The administration site is confirmed by injecting Indian ink in preliminary experiments.
[0074] Mouse writhing test. Antinociceptive activity of HN (SEQ ID NO. 1) and related compounds were evaluated using the acetic acid-induced writhing test according to a modification (Shukla et al., Brain Res. 1992, 591,176) of the method of Hayashi and Takemori (Eur. J. Pharmacol. 1971, 16, 63). Male swiss webster [(SW)f BR] mice are injected intraperitoneally (i.p.) with 1.0% acetic acid (10 ml/kg) 5 min after i.c.v. injection of 0 (saline), 0.1, 0.5, 1 ,10 25, 50, 75 and 100 nmol of HN (SEQ ID NO. 1) or related peptides or non-peptides. The number of writhes displayed by each mouse is counted for a period of 10 min after the injection of the acetic acid solution. An abdominal stretch is characterized by the contraction of the abdominal muscles, the arching of the back ventrally such as the abdomen touches the bedding surface and the extension of one or both hind limbs. Mice are used once and then killed immediately. Groups of 10 mice are used for each dose. The analgesic activity of the peptides is assessed by the percent analgesia displayed by a test group of 10 mice. The percentage of analgesia is calculated for each dose by the formula: [(mean number of writhes in control group—mean number of writhes for the test group)/(mean number of writhes in control group)×100]. The doses producing 50% analgesia (AD 50 ) with 95% confidence limits (95% CL) and potency ratios with 95% CL are measured by the method of Lichfield and Wilcoxon (J. Pharmacol. Exp. Ther. 1949, 96, 99-104) using procedure 47 of the computer program of Tallarida and Murray (in “Manual of pharmacological calculations with computer programs”. 2nd ed., Springer, New York, 1987).
[0075] In order to determine the length of action of the compounds, the acetic acid solution is administered at different times after the administration of the drug, as indicated. The experiments for the assessment of the peripheral antinociceptive activity of the compounds are performed by administration of 10 or 20 μmol/kg i.p or i.v. or 0.5 or 1 mg /mouse oral of the tested compounds 30 and 60 min prior to the injection of the acetic acid solution. Data are analyzed by the Wilcoxon's paired non-parametric test. The criterion for statistical significance was P<0.05.
[0076] Mouse tail flick assay. Antinociception was also determined using the radiant heat tail-flick technique (D'Amour and Smith, J. Pharmacol. Exp. Ther. 1941, 72: 74). Briefly, the latency to withdraw the tail from a focused light stimulus was determined using a photocell. The light intensity was set to give a control reading of about 3 sec. Baseline latencies were determined before experimental treatment as the mean of two trials and a maximal latency of 12 s was used to minimize tissue damage. Post-treatment latencies were determined 5 min after i.c.v. injection. The antinociceptive effect was expressed as the percentage of the maximum possible effect, as calculated by the formula: % MPE=[(post-injection latency-baseline latency)/(cutoff latency-baseline latency)]×100. The use of % MPEs takes into account differences in baseline latencies so that these differences do not bias the quantification of antinociception. Group % MPE means were compared using one-way ANOVAs and P≦0.05 was considered significant.
[0077] The induction of tolerance to morphine was obtained as described by Verma and Kulkarni (Eur. J. Neuropsychopharmacol. 1995, 5, 81-87). Briefly, groups of 10 mice were injected i.p. for 8 consecutive days twice a day at 9.00 and 17.00 hr with saline, morphine (10 mg/kg), II-1 (4 mg/kg) or a combination of II-1 (4 mg/kg) 30 min prior to morphine (10 mg/kg). Tail-flick latency to thermal pain was recorded 30 min after the i.p. administration(s) in the morning session of days 1, 3, 6 and 8 as indicated in the figure.
[0078] Mouse rotarod assay. The rotarod treadmill (model 7600, UGO Basile, Italy) for mice was used to assess the motor side-effects of antinociceptive agents. The method used is derived from the procedure described by Dunham and Miya (J. Am. Pharmac. Assoc. 1957, 46: 208). The apparatus is constituted of a rod with a diameter of 2.5 cm suspended horizontally 50 cm above a plane working area. The rod is turning at a speed of 8 revolutions per min. Circular perpex separators are placed at regular intervals along the rod so that five mice can be tested at the same time. Before administering any compound, all animals are placed on the turning rod for one min in two consecutive rounds. Mice that fall from the rod during these conditioning experiments are excluded from the assay. For the assay, the test compounds were administered i.c.v. and the animals were placed on the turning rod for two min. The % of mice in groups of 10 mice which fell during this latter two min-experiment was recorded as the % of mice showing motor effects. Rotarod assays were conducted at different times (up to 60 min) after the administration of peptides. Statistical calculation were made using Student t-test.
[0000] Results:
[0079] Mouse writhing pain assay. Histogranin (HN) (SEQ ID NO. 1) and related peptides and non-peptides were tested for their abilities to block writhing in mice induced by intraperitoneal administration of acetic acid. All compounds (i.c.v.) blocked writhing in a dose-dependent manner ( FIG. 1 ), I-1 (SEQ ID NO. 5) being 135 and 3.9 fold more potent than HN and morphine, respectively (Table 2). The non-peptides displayed potencies that were comparable to that of morphine (in the nmol range). The lengths of action of the various compounds were evaluated by measuring the time (T 1/2 ) it took after injection of a specific dose of a compound to produce half-maximal effect. T 1/2 of HN (SEQ ID NO. 1) (50 nmol/mouse, i.c.v.) was 22.1 min (Table 2). T 1/2 of the cyclic tetrapeptides were longer than 60 min, I-1 (SEQ ID NO. 5) displaying the longest T 1/2 (>90 min at a dose of 10 nmol/mouse). T 1/2 -of the non-peptides (10 nmol) ranged between 15 and 58 min, compound II-3 showing the longest T 1/2 (58 min).
[0080] Analgesic effects of peripheral administrations. Compounds I-1 (SEQ ID NO. 5), II-1 and III-1 were shown to display dose-dependent analgesic activity in the mouse writhing test after oral and i.p. administrations ( FIG. 2 ). Compounds I-1 (SEQ ID NO. 5), I-4, and I-1 also showed 84%, 71% and 35% analgesia, respectively, after i.v. administration (1 μmol/kg, not shown).
[0081] Mouse tail-flick assay. In the mouse tail-flick assay, HN related compounds of Formulae I, II and III displayed dose-dependent analgesia ( FIG. 3 ). All HN related compounds including compounds I-1 (SEQ ID NO. 5), II-1 and III-1 were more potent than HN (SEQ ID NO. 1) (Table 3). Compound I-1 (SEQ ID NO. 5) (10 nmol/mouse, i.c.v.) had a T 1/2 of >120 min as compared with 45 min for [Ser 1 ]HN (50 nmol/mouse, i.c.v.).
TABLE 2 Relative potencies of Histogranin (HN) (SEQ ID NO. 1) and related peptides and non-peptides (i.c.v.) in the mouse writhing assay AD 50 Potency (nmol/mouse) ratio b T 1/2 [dose] c Compounds (95% CL) a (95% CL) a (min) (nmol) Morphine 0.72 34.8 22 [0.5] (0.66-0.78) (16.0-71.2)* HN 23.0 1.0 22.1 [50] (SEQ ID NO. 1) (12.5-47.0) HN-(7-15) 8.5 2.71 (SEQ ID NO. 4) (1.9-15.4) (0.81-34.7)* I-1 0.17 135 >90 [10] (SEQ ID NO. 5) (0.06-0.46) (27.2-783)* I-2 6.79 3.39 (SEQ ID NO. 6) (3.18-14.49) (0.86-14.8)* I-3 1.08 21.3 >60 [10] (SEQ ID NO. 7) (0.30-3.6) (3.47-157)* I-4 2.52 9.14 (SEQ ID NO. 8) (2.02-3.50) (3.57-23.3)* I-5 10.7 2.14 (SEQ ID NO. 9) (10.1-11.3) (1.16-4.65)* II-1 6.5 3.54 15 [10] (4.55-9.29) (1.82-6.87)* II-2 16.1 1.40 19 [10] (9.91-26.3) (0.54-3.63) II-3 3.16 7.27 58 [10] (1.79-5.62) (3.26-16.2)* II-4 2.61 8.87 36 [10] (1.53-4.48) (4.06-19.1)* III-1 4.14 5.56 36 [10] (32.3-7.38) (2.40-12.4)* a CL: confidence limit. b Potency ratio relative to Histogranin (HN) (SEQ ID NO. 1). c The time after injection of the compound at which half-maximal response was observed for the indicated dose. *P < 0.05 in comparison with HN (SEQ ID NO. 1).
[0082] TABLE 3 Relative potency of Histogranin (HN) (SEQ ID NO. 1) and related peptides and non-peptides (i.c.v.) in the mouse tail-flick assay AD 50 Potency (nmol/mouse) ratio b T 1/2 [dose] Compounds (95% CL) a (95% CL) a (min) (nmol) Morphine 1.57 72.6 (1.28-1.93) (47.6-10)* [Ser 1 ]HN 114 1 45.0 [50] (92-141) I-1 9.1 12.5 >120 [10] (SEQ ID NO. 5) (3.7-22.3) (4.1-38.1)* I-5 38.5 2.96 45.0 [20] (SEQ ID NO. 9) (32.5-45.4) (2.02-4.3)* II-1 14.2 8.0 21.3 [10] (11.5-17.4) (5.2-12.2)* II-2 98.6 1.16 18.5 [10] (70.0-138.8) (0.66-2.01) II-3 31.7 3.59 28.9 [10] (22.9-43.8) (2.10-6.16)* II-4 13.1 8.70 16.7 [10] (10.6-16.1) (5.71-13.3)* III-1 9.6 11.9 28.5 [10] (0.1-800) (0.12-1400) a CL: confidence limit. b Relative to [Ser 1 ]HN. *P < 0.05 in comparison with [Ser 1 ]HN.
Potentiation and Prolongation of Morphine Analgesia.
[0083] Coadministration (i.c.v.) of a subanalgesic dose of compound II-1 with morphine induced a left shift in the dose-response curve of morphine in the mouse writhing test ( FIG. 4A ). Similar effects were also observed with I-1 (SEQ ID NO. 5) on the dose-response curve of morphine (i.v.; not shown). The analgesic effects of morphine (0.5 nmol, i.c.v.) were also slightly prolongated by the coadministration of compound II-1 ( FIG. 4B ).
[0084] Blockade of morphine tolerance. Morphine, injected twice a day (10 mg/kg, i.p.) for 8 consecutive days in mice, produced an increase in the tail-flick latency that remained significant as compared to the control group (saline) for only 3 days, tolerance being developed at days 6 and 8 ( FIG. 5 ). Compound II-1 (4 mg/kg, twice a day, i.p. in mice) produced a small increase in the tail-flick latency that was significant only on days 1 and 8. Compound II-1 administered 30 min prior to morphine (10 mg/kg) potentiated the analgesic effect of morphine and, on days 6 and 8, inhibited morphine tolerance ( FIG. 7 ; * P<0.05 as compared with control).
[0085] Lack of motor effect. All cyclic peptides (compounds I-1 (SEQ ID NO. 5), I-2 (SEQ ID NO. 6), I-3 (SEQ ID NO. 7), I-4 (SEQ ID NO. 8) and I-5 (SEQ ID NO. 9); 10 nmol; i.c.v.) and non-peptides (compounds I-1, I-2, II-3, II-4 and III-1, 10 nmol, i.c.v.) did not cause any motor effect in the mouse rotarod assay.
Example VIII
Inibition of cyclooxygenase-2 induction and prostaglandin-2 formation
[0086] Animals and Reagents. Lung pathogen-free male Wistar rats weighing 250-275 g were purchased from Harlan—Sprague Dawley (Indianapolis, USA). These animals were shipped behind filter barriers and housed in isolated temperature-controlled quarters in an animal isolator unit (John's Scientific Inc., Toronto, Ont.). Roswell Park Institute medium-(RPMI) 1640, Dulbecco's phosphate buffered saline (PBS) and dialysed fetal bovine serum (FBS) were purchased from Wisent Inc. (St-Bruno, Que.). Lipopolysaccharide (LPS, E. coli , serotype 0127:B8) was from Sigma Chemical Co. (St-Louis, Mo.).
[0087] Isolation of rat Alveolar Macrophages (AM). Animals received a lethal dose of pentobarbital sodium (100 mg/kg, MTC Pharmaceuticals Canada Packers, Cambridge, Ont.), the abdominal aorta was severed, and the trachea was canulated. The lungs were lavaged with six 8-ml aliquots of sterile phosphate-buffered saline (PBS, pH 7.4) with gentle massage of the lungs during the washings as described (Lemaire I. Am. Rev. Respir. Dis. 1985, 131, 144-149). Bronchoalveolar (BAL) cells were obtained by centrifugation at 200 g at 4° C. for 5 min, and resuspended in RPMI supplemented with 0.5% dialysed FBS and 0.8% N-2-hydroxyethylpiperazine-N′-2-ethanesulfonic acid (HEPES), which will henceforth be referred to as complete culture medium (CM). Cells were counted in a hemacytometer chamber and viability (99-100%) was determined by trypan blue exclusion. Differential analysis of cytocentrifuge smears of lavage cells (Shandon, 2.5×10 4 cells) stained with Wright-Giemsa indicated that the BAL cell population is essentially composed of macrophages (99% AM) in normal rats.
[0088] Culture and Stimulation of AM. AM (2×10 5 ) were plated into 96-well plates in 200 μl of CM alone or with LPS (1 μg/ml) in the presence and absence of HN (SEQ ID NO. 1) and related compounds at various concentrations as indicated. Cells were incubated for 20 h at 37° C. in 5% CO 2 . Following incubation, the culture supernatants were collected and frozen at −20° C., and their prostaglandin E 2 (PGE 2 ) content was measured within 2 days.
[0089] Prostaglandin E 2 Determination. Prostaglandin E 2 (PGE 2 ) was determined from cell-free supernatants using a competitive enzymeimmunoassay system (Biotrack™, Amersham Pharmacia Biotech). Following dissociation of PGE 2 from soluble receptors and interfering binding proteins present in culture media, the assay is based on competition between unlabelled PGE 2 and a fixed quantity of peroxidase-labelled PGE 2 for a limited number of binding sites on a PGE 2 specific antibody. It was performed according to the manufacturer's instruction using two different dilutions of culture media. At least 4 different experiments were performed for each compound and results are expressed as mean±SEM.
[0090] COX-1 and COX-2 Immunoblotting. Macrophages were cultured at 10 6 /ml in 24-wells for 20 h in complete medium in the presence or absence of LPS (1 μg/ml). Cells were collected with a rubber policeman, pooled and centrifuged (5 min, 200×g). The pellet was washed with PBS (pH 7.4) and frozen at −80° C. The cell pellet from each sample was resuspended in 100 mM Tris, pH 7.4 and sonicated for 15 sec twice with an Ultrasonics™ cell disrupter to lyse the cells. Cell lysates were assayed for protein content by the Bradford method (Bio-Rad Laboratories). Protein from each sample (5 μg-20 μg) was denatured in Laemmli buffer for 5 min and resolved by SDS-gel electrophoresis on a polyacrylamide gel (4% stacking and 10% resolving layer) using an apparatus for minigels (Hoefer Scientific Instruments). After electrophoresis, the proteins were transferred to nitrocellulose membranes with a Transfor™ electrophoresis unit (Hoefer Scientific Instruments). The membranes were blocked overnight at 4° C. in Tris-buffered saline-0.1% Tween™ 20 (TBS-T) supplemented with 3% fat-free dried milk. After rinsing away the blocking solution with TBS-T-1% milk, the membranes were incubated for 90 minutes with primary antibody against COX-2 (1:1000, Cayman) or COX-1 (1:100, Cayman) and against actin (1:250 or 1:2000 for COX-2 and COX-1 detection respectively, Sigma). The specificity of the COX isoform-specific antibodies was tested by Western blotting of purified COX-2 (Song) and COX-1 (500 ng) electrophoresis standards per lane (Cayman). After washes with TBS-T-l% milk, the membranes were incubated with HRP-conjugated goat anti-rabbit IgG (Santa Cruz) (1:1000 for COX-2 and 1:100 for COX-1) for 1 hr at room temperature. Excess secondary antibody was washed away with TBS-T-1% milk (3×) followed by TBS (5×). The results were visualized after developing with BM chemiluminescence blotting POD substrate (Boehringer) according to the manufacturer's instructions. Scanning densitometry was performed using a Kodak™ digital science Image Station and software. COX-2 and COX-1 signal density was normalized to actin density. Results are expressed as percent of control and represent mean±SEM of at least 3 different experiments.
[0000] Results:
[0091] Decrease of PGE 2 release through inhibition of inducible COX-2 expression. Prostaglandins are known to play an important role in inflammation and transmission of pain. Macrophages stimulated with lipopolysaccharide (LPS, the archetype of bacterial antigen), produce significant amounts of prostaglandins such as PGE 2 . LPS-stimulated release of PGE 2 from isolated rat alveolar macrophages was potently (10 −12 M-10 −7 M) and significantly (up to 50%) inhibited by HN (SEQ ID NO. 1) and related compounds. FIG. 6 represents the inhibition observed with 10 −8 M of HN (SEQ ID NO. 1), H4-(86-100) (SEQ ID NO. 2) and compounds of the three Formulae.
[0092] Inhibition of LPS-induced COX-2. Cyclooxygenase (COX), the enzymatic system responsible for the formation of PGE 2 exists under two isoforms: COX-1 and COX-2. In macrophages, COX-1 is expressed constitutively while COX-2 expression is induced by appropriate stimuli including LPS. The effects of HN (SEQ ID NO. 1) and related compounds were determined on both isoenzymes. HN (SEQ ID NO. 1), H4-(86-100) (SEQ ID NO. 2) and compounds of the three Formulae did not alter the basal level of constitutively expressed COX-1 (not shown) but significantly inhibited LPS induction of COX-2 as assessed by immunoblot analyses ( FIG. 7 ).
[0093] Having thus described the invention, it is apparent to one skilled in the art that modifications can be made without departing from the spirit and scope of the claims that now follow. | The invention relates to new basic amino acid derivatives of general formulae I, II and III, and the preparation and use thereof in treatment of pain. The compounds have histogranin-like antinociceptive, morphine potentiating and COX-2 induction modulating activities.
wherein:
A is -hydrogen, —(C 1 -C 8 )alkyl or —(C 1 -C 8 )alkyl substituted by hydroxy;
B is —(C 1 -C 6 )alkylguanidino, —(C 1 -C 6 )alkyl(4-imidazolyl), —(C 1 -C 6 )alkylamino, p-aminophenylalkyl(C 1 -C 6 )—, p-guanidinophenylalkyl(C 1 -C 6 )— or 4-pyridinylalkyl(C 1 -C 6 )—;
D is —(CO)—, —(CO)—(C 1 -C 6 )alkylene or —(C 1 -C 6 )alkylene;
E is a single bond or —(C 1 -C 6 )alkylene;
Z is —NH 2 , —NH—(C 1 -C 6 )alkylcarboxamide, —NH—(C 1 -C 6 )alkyl, —NH—(N-benzyl), —NH-cyclo(C 5 -C 7 )alkyl, —NH-2-(1-piperidyl)ethyl, 13 NH-2-(1-pyrrolidyl)ethyl, —NH-2-(1-pyridyl)ethyl, —NH-2-(morpholino)ethyl, -morpholino, -piperidyl, —OH, —(C 1 -C 6 )alkoxy, —O-benzyl or —O-halobenzyl;
R 1 , R 2 and R 3 are, independent of one another, -hydrogen, -arylcarbonylamino, —(C 3 -C 6 )alkoylamino, —(C 1 -C 6 )alkylamino, —(C 1 -C 6 )alkyloxy, —(C 1 -C 6 )alkylaminocarbonyl, -carboxy, —OH, -benzoyl, -p-halogenobenzoyl, -methyl, —S-(2,4-dinitrophenyl), —S-(3-nitro-2-pyridinesulfenyl), -sulfonyl, -trifluoromethyl, —(C 1 -C 6 )alkylaminocarbonylamino, -halo or -amino;
R 4 and R 5 are, independent of one another, -hydrogen, —(C 1 -C 6 )alkyl, -methyloxy, -nitro, -amino, -arylcarbonylamino, —(C 1 -C 6 )alkoylamino, —(C 1 -C 6 )alkylamino, -halo or —OH. | 2 |
TECHNICAL FIELD
[0001] The present invention relates to a diagnostic service providing system and a diagnostic service providing method, and is suitably applied to a diagnostic service providing system and a diagnostic service providing method in which a diagnosis is performed with a diagnostic apparatus using a disposable device.
BACKGROUND ART
[0002] The present invention relates to a service method for diagnosing an analyte sample such as blood, urine, or exhalation collected by a user himself/herself with a diagnostic apparatus using a disposable device, and more particularly to a diagnostic service method using electronic commerce.
[0003] When it is intended to live a healthy life, it is required to find a disease before onset of the disease or at an initial stage of the disease and receive appropriate treatment in a medical institution. However, even today, where a medical system is established, there is a case where a disease is left without receiving diagnosis in a medical institution and symptoms of a disease become serious, due to the burden of visiting a medical institution or the like.
[0004] In recent years, there has been a disease diagnostic method using a simple inspection kit as a method for receiving a diagnosis of a disease without visiting a medical institution. In the diagnostic method, a user purchases the inspection kit, collects an analyte such as blood, urine, or feces using the inspection kit, and then sends the collected analyte to an inspection institution. The user can receive an inspection result via mail or the Internet after several days from the date when the analyte was sent. Such an inspection kit for use at home targets a cancer inspection for colon cancer or the like and a disease, which requires a long period of time for treatment, for example, lifestyle-related diseases such as AIDS, hepatitis C, and diabetes.
[0005] For example, PTL 1 discloses a diagnostic service using an inspection kit installed in an inspection kit installation facility. Specifically, the user brings the inspection kit installed in the inspection kit installation facility home and then, collects the analyte such as blood or urine by himself/herself. Then, the user sends the collected inspection kit to the inspection institution directly or through the inspection kit installation facility and thus, obtains a result of an inspection conducted in the inspection institution over the Internet.
CITATION LIST
Patent Literature
[0006] PTL 1: JP-A-2007-47856
SUMMARY OF INVENTION
Technical Problem
[0007] The inspection using the simple kit and the Internet described in PTL 1 has an advantage that the user is capable of being inspected without visiting a medical institution or an inspection institution. However, there is a problem that the collected analyte cannot be immediately inspected and the analyte is changed with time, or it takes a long time to receive a diagnostic result in a case where treatment should be made immediately after the onset of a disease.
[0008] The present invention has been made in consideration of the problem described above and provides a diagnostic service providing system and a diagnostic service providing method capable of immediately presenting a diagnostic result using a diagnostic apparatus installed in a diagnostic apparatus installation facility.
Solution to Problem
[0009] In the present invention for solving the problem described above, there is provided a diagnostic service system which includes a diagnostic apparatus installed in a diagnostic apparatus installation facility and performing a diagnosis using a disposable device, a user terminal owned by a user of the diagnostic apparatus, an information processing apparatus connected with the diagnostic apparatus and the user terminal and gathering a diagnostic result of the diagnostic apparatus, in which the information processing apparatus manages information of the diagnostic result diagnosed by the diagnostic apparatus and information of the user by associating the both with each other and provides the diagnostic result in accordance with an access from the user terminal of the user.
[0010] In the present invention for solving the problem described above, there is provided a diagnostic service providing method in a diagnostic service system including a diagnostic apparatus installed in a diagnostic apparatus installation facility, a user terminal owned by a user of the diagnostic apparatus, an information processing apparatus connected with the diagnostic apparatus and the user terminal and gathering a diagnostic result of the diagnostic apparatus, and the diagnostic service providing method includes a step of, by the diagnostic apparatus, sending the diagnostic result and contact information of the user to the information processing apparatus of an information manager, a step of, by the information management apparatus, sending an address in which information of the diagnostic result is written, a step of, by the user terminal, accessing the address in which the diagnostic result is written in accordance with an input by the user to obtain information of the diagnostic result, a lot number of the diagnostic result, and the medical institution, a step of providing the lot number of the diagnostic result to an information processing terminal of the medical institution through the user terminal in a case where the user has consultation in the medical institution, a step of, by the information processing terminal of the medical institution, sending the lot number of the diagnostic result to the information processing apparatus to acquire the information of the diagnostic result, and a step of, by the information processing terminal of the medical institution, sending a diagnostic result of the medical institution to the information processing apparatus.
Advantageous Effects of Invention
[0011] According to the present invention, it is possible to immediately present a diagnostic result using a diagnostic apparatus installed in a diagnostic apparatus installation facility and find a disease of a user at an early stage without visiting a medical institution.
BRIEF DESCRIPTION OF DRAWINGS
[0012] [ FIG. 1 ] FIG. 1 is a diagram conceptually illustrating a configuration of a diagnostic service system according to an embodiment of the invention.
[0013] [ FIG. 2 ] FIG. 2 is a diagram conceptually illustrating a configuration of a disposable device according to the embodiment.
[0014] [ FIG. 3 ] FIG. 3 is a diagram conceptually illustrating an example of display of a simple diagnostic result according to the embodiment.
[0015] [ FIG. 4 ] FIG. 4 is a diagram conceptually illustrating a flow of information between an information managing company and a contracted institution according to the embodiment.
DESCRIPTION OF EMBODIMENTS
[0016] As described above, for the prevention of a disease from becoming serious, it is important to find a disease before the onset of the disease or at an initial stage and receive appropriate treatment in a medical institution. To do this, it is preferable that a user simply conducts a diagnosis by himself/herself even without visiting a medical institution. The inventors of the invention have studied various methods and systems for self-diagnosis and reached the invention.
[0017] In the following drawings, an embodiment of the present invention will be described in detail. In the meantime, the embodiment which will be described later is an example, and it is needless to say that other aspects by a combination of respective embodiments with each other, a combination or replacement with well-known art or frequently used art may be made.
[0018] (1) Summary of the Present Embodiment
[0019] As described above, the inspection using the simple kit and the Internet has an advantage that the user is capable of conducting the inspection without visiting the medical institution or the inspection institution. However, since it takes time for sending a simple kit which has collected the analyte to the inspection institution, it is difficult to immediately inspect the collected analyte and is unsuitable for inspection of substance which is contained in the analyte and easily changed with time. Further, since it is a method having difficulty in acquiring the diagnostic result immediately after the analyte is collected, it is an inspection method unsuitable for a disease which requires treatment immediately after the onset of a disease such as infectious diseases of the respiratory system such as influenza.
[0020] Furthermore, when the user who acquires the inspection result intends to receive a diagnosis and treatment of the medical institution, the user needs to look for a medical institution suitable for symptoms of the disease, and there is also a case where the necessity of receiving the same inspection again is caused in a case where the user has consultation in the medical institution which does not use a result of an inspection by the simple kit as a diagnostic material. When the user presents the inspection result of the simple kit to the medical institution, it is necessary to prevent the inspection result from being leaked to a third person.
[0021] In the present embodiment, the user conducts a simple diagnosis by himself/herself by the diagnostic apparatus installed in the diagnostic apparatus installation facility and thus, it is possible to immediately present the diagnostic result to the user and select an optimum medical institution for treatment. With this, the user can receive the simplified diagnostic result by the diagnostic apparatus immediately over the Internet and can find the disease of the user at an early stage without visiting the medical institution.
[0022] (2) Configuration of Diagnostic Service System
[0023] Next, a configuration of a diagnostic service system 1 according to the present embodiment will be described with reference to FIG. 1 . As illustrated in FIG. 1 , the diagnostic service system 1 is constituted with an information processing apparatus 101 which is able to access the Internet, a diagnostic apparatus 201 , an information processing apparatus 301 for simple diagnosis which receives information from the diagnostic apparatus 201 using a disposable device 202 and stores the information, and an information processing apparatus 401 for a medical institution which saves diagnostic records by the medical institution, and these apparatuses are connected to each other over the Internet.
[0024] The information processing apparatus 101 (user terminal of the invention) is owned by a user 100 who wants to make a simple diagnosis. The diagnostic apparatus 201 is installed in a diagnostic apparatus installation facility 200 . The information processing apparatus 301 is owned by an information managing company 300 which is an operator and an administrator of the diagnostic service system 1 . The information processing apparatus 401 for a medical institution is owned by a contracted medical institution 400 which has concluded a contract with the information managing company 300 .
[0025] As illustrated in FIG. 1 , in order to provide the user 100 with a diagnostic service, the information managing company 300 lends out the diagnostic apparatus 201 for a fee or free to the diagnostic apparatus installation facility 200 and supplies the disposable device 202 for a fee or free (O 101 ). In a case where the diagnostic apparatus 201 is lent out for a fee or the disposable device 202 is a device for a fee, the administrator of the diagnostic apparatus installation facility 200 pays a lending fee or a fee of an article of consumption of the disposable device 202 to the information managing company 300 (M 101 ).
[0026] The diagnostic apparatus installation facility 200 is a retail store such as a drug store or a convenience store, a staying facility such as a hotel, or an educational facility such as a school or a day-care center. The information managing company 300 is a company, which handles a large quantity of customer information, such as an insurance company.
[0027] The disposable device 202 is a disposable device having a function necessary for detecting a specific substance related to a specific case from blood, urine, exhalation, or the like of the user 100 . The diagnostic apparatus 201 automates a detection process performed in the disposable device 202 and specifies an amount of the specific substance detected by the disposable device 202 . Information about the specific substance is transmitted from the diagnostic apparatus 201 to the information processing apparatus 301 via the network. The information processing apparatus 301 diagnoses the presence or absence or a degree of progress of the disease of the user 100 on the basis of the transmitted information.
[0028] (3) Procedural Sequence of Diagnostic Service
[0029] Next, a procedural sequence of a diagnostic service will be described.
[0030] (3-1) Simple Diagnostic Processing
[0031] The user 100 who wants to make a simple diagnosis visits the diagnostic apparatus installation facility 200 , pays a fee for an apparatus diagnosis (M 102 ), and purchases the disposable device 202 .
[0032] The disposable device 202 is essential for the diagnosis of the diagnostic apparatus 201 . Therefore, the diagnostic apparatus 201 maybe allowed to be used even without a usage ticket or a usage card for using the diagnostic apparatus 201 . The user 100 collects the analyte such as the blood, urine, or exhalation into the disposable device 202 by himself/herself and sets the disposable device 202 which has collected the analyte in the diagnostic apparatus 201 .
[0033] After the disposable device 202 is set, an email address (I 101 ) and a password (I 102 ) of the user 100 are transmitted to the information processing apparatus 301 through the diagnostic apparatus 201 .
[0034] The diagnostic apparatus 201 which has received the email address and the password of the user reads a lot number 2012 of the disposable device 202 and selects an optimum process from a plurality of detection processes recorded previously. Thereafter, the diagnostic apparatus 201 automatically conducts the selected detection process and detects the specific substance contained in the collected analyte.
[0035] The information about a kind or an amount of the detected specific substance (I 104 ) and the lot number 2022 (I 103 ) of the disposable device 202 are transmitted to the information processing apparatus 301 through a network. The information processing apparatus 301 diagnoses the symptoms of the user 100 on the basis of the information about the kind or the amount of the detected specific substance sent.
[0036] (3-2) Provision of Simple Diagnostic Result
[0037] The information processing apparatus 301 writes the obtained simple diagnostic result into an electronic medical chart of the user 100 prepared in the information processing apparatus 301 in advance. In this case, personal information such as an age of the user 100 and information such as a place of a diagnostic apparatus installation facility 200 or a diagnosis date in addition to the simple diagnostic result are written into the electronic medical chart.
[0038] After the completion of writing into the information processing apparatus 301 , the information processing apparatus 301 sends information of an address in which the simple diagnostic result is described to the user 100 (I 105 ). Since the address in which the simple diagnostic result is described is prepared from the lot number 2022 of the disposable device 202 and the email address of the user 100 , even though a third person obtains the lot number 2022 of the disposable device 202 or the email address of the user 100 , it is impossible to obtain the address in which the simple diagnostic result is described.
[0039] Further, in a case where the user 100 uses the diagnostic service system 1 for the first time, the information processing apparatus 301 prepares an electronic medical chart having the email address input by the user 100 as an ID number. Since the electronic medical chart is not prepared in the diagnostic apparatus 201 but in the information processing apparatus 301 , even in a case where the user 100 visits another diagnostic apparatus installation facility 200 and uses the diagnostic apparatus 201 of the diagnostic apparatus installation facility 200 , the user 100 inputs the email address and the password and thus, another simple diagnostic result is written into the electronic medical chart of the user 100 .
[0040] Further, only the newest diagnostic result of information recorded in the electronic medical chart may be provided to the user 100 . With this, even in a case where the user 100 visits a plurality of medical institutions, it is possible to always input and output the newest diagnostic result.
[0041] (3-3) Provision of Contracted Medical Institution Information or the Like
[0042] The user 100 accesses the address sent from the information processing apparatus 301 through the information processing apparatus 101 , inputs the password set in advance, and obtains the simple diagnostic result (I 104 ) and the lot number of diagnostic result (I 107 ). Information obtained by the user 100 is only the simple diagnostic result and the lot number of diagnostic result among the information described in the electronic medical chart.
[0043] The user 100 can receive information (I 108 ) of the contracted medical institution 400 which has concluded a contract with the information managing company 300 and information of the article that the diagnostic apparatus installation facility 200 handles as an advertisement in accordance with the result of a simple diagnostic result (I 109 ).
[0044] Selection of the article handled by the contracted medical institution 400 or the diagnostic apparatus installation facility 200 is performed by the information processing apparatus 301 using contents of the simple diagnostic result, personal information such as an address or age of the user 100 , or a business state of the contracted medical institution 400 as the determination basis. The individualized advertisement is provided to the user 100 and thus, it is possible to enhance interest in the diagnosis in the contracted medical institution 400 or the article handled by the diagnostic apparatus installation facility 200 .
[0045] (3-4) Sending of Information to Contracted Medical Institution
[0046] In a case where the above-described simple diagnostic result is positive, the information of the contracted medical institution 400 is sent to the user 100 . The user 100 visits the contracted medical institution 400 and receives a diagnosis and treatment from the contracted medical institution 400 and thus, it is possible to prevent deterioration of a user due to disease symptoms of a disease at an early stage.
[0047] The contracted medical institution 400 receives the password (I 110 ) which was input to the information processing apparatus 301 at the time of concluding the contract with the information managing company 300 . The contracted medical institution 400 can receive the lot number of the simple diagnostic result (I 107 ) from the user 100 at the time of clinical consultation and input the password (I 110 ) so as to obtain the simple diagnostic result from the electronic medical chart of the user 100 within the information processing apparatus 301 .
[0048] In this case, the contracted medical institution 400 can also obtain information (I 111 ) such as a place of the diagnostic apparatus installation facility 200 , a diagnosis time, and a past diagnostic history in addition to the diagnostic result obtained by the user 100 . The contracted medical institution 400 can predict a period and a place of onset of the disease for the user 100 from the diagnostic result for the medical institution (I 111 ).
[0049] (3-5) Diagnosis of Contracted Medical Institution
[0050] The user 100 can pay a consultation fee to the contracted medical institution 400 so as to receive the diagnosis from the contracted medical institution 400 . Since the diagnosis of symptoms becomes easy by obtaining the information of the simple diagnostic result, the contracted medical institution 400 can reduce the time and labor required for clinical consultation of a user. Then, the user 100 may be allowed to receive a discount on the consultation fee by presenting the lot number of the simple diagnostic result to the contracted medical institution 400 .
[0051] The contracted medical institution 400 may receive an amount of discount for the clinical consultation from the information managing company 300 . Specifically, the contracted medical institution 400 pays the amount of discount for the clinical consultation fee (M 103 ) to the user 100 who has performed payment of the consultation fee M 104 . Thereafter, the contracted medical institution 400 transmits a clinical consultation result of the medical institution I 112 and the lot number of diagnostic result I 107 to the information managing company 300 and receives the amount of discount for the clinical consultation fee (M 103 ) corresponding to the amount paid to the user 100 from the information managing company 300 .
[0052] As described above, when the diagnostic result by the contracted medical institution 400 is transmitted to the information processing apparatus 301 , the simple diagnostic result for the disease of the user 100 and the diagnostic result by the contracted medical institution are gathered in the information processing apparatus 301 . Performance of the diagnostic apparatus 201 can be evaluated by collating the simple diagnostic result with the diagnostic result of the contracted medical institution and the performance of the diagnostic apparatus 201 can be improved on the basis of an evaluation result.
[0053] (3-6) Provision of Insurance Product
[0054] In a case where a POS system (point-of-sales information management diagnosis) 203 is provided in the diagnostic apparatus installation facility 200 , the personal information such as the age or sex of the user 100 (I 150 ) and the simple diagnostic result may be provided to the information managing company 300 by making the diagnostic apparatus 201 cooperate with the POS system 203 . With this, the information managing company 300 can estimate an age group or sex with a lot of patients.
[0055] In a case where the information managing company 300 has a function as an insurance company, it is possible to provide the user 100 with individualized information of the insurance product (I 151 ) on the basis of the above-described personal information (I 150 ). Since the user 100 who conducts the self-diagnosis using the diagnostic apparatus 201 can be determined as a customer who is highly conscious about his/her health by the information managing company 300 , the insurance product for which an insurance fee is discounted can be provided with lower risk (M 150 , M 151 ).
[0056] (3-7) Provision of Health and Infection Information
[0057] Information of the simple diagnostic results aggregated from the diagnostic apparatus 201 installed in a plurality of the diagnostic apparatus installation facilities 200 is gathered in the information processing apparatus 301 of the information managing company 300 . The information of the simple diagnostic results is arranged for each group of an area, age, sex, or the like and thus, an occurrence state of a disease can be clarified in each group.
[0058] Information about the occurrence state of the disease can be appropriately transmitted to the user 100 or the contracted medical institution 400 by the information managing company 300 and the user 100 can take appropriate preventive measures from the transmitted information. The user 100 receives the health and infection information I 160 from the information managing company 300 can take measures such as precautions in advance. The contracted medical institution 400 receives the health and infection information I 160 from the information managing company 300 and can predict the number or medical examination item of the user 100 who receives the clinical consultation of the contracted medical institution 400 from the transmitted information and arrange a consultation system in advance.
[0059] Next, descriptions will be made on a disposable device 202 with reference to FIG. 2 . FIG. 2 illustrates the disposable device 202 immediately after being opened. As illustrated in FIG. 2 , the disposable device 202 is stored in a box 2021 in which a diagnostic disease name is described, the box 2021 is opened immediately before being used, and the disposable device 202 is taken out.
[0060] In order to protect diagnostic performance of the disposable device 202 , it is preferable that the box 2021 is sealed or has light shielding performance. The lot number 2022 is printed in the disposable device 202 . The diagnostic apparatus 201 is caused to read the lot number 2022 and thus, the diagnostic apparatus 201 can automatically conduct a diagnostic process corresponding to each disease. With this, it is possible to prevent a failure occurring due to erroneous selection of the diagnostic process by the user 100 .
[0061] FIG. 3 is an example of display of a simple diagnostic result 1011 displayed on the information processing apparatus 101 by accessing the information processing apparatus 301 through the information processing apparatus 101 by the user 100 . A lot number 1012 for identifying the diagnostic result is allocated to the diagnostic result of the simple diagnostic result 1011 . The lot number 1012 is associated with the lot number 2022 of the disposable device 202 , an installed place or a use time of the diagnostic apparatus 201 , and information of the user 100 , and can check the information as necessary.
[0062] It is possible to display a banner 1013 and a simple diagnostic result 1012 . As described above, it is possible to change the contents such as information of the contracted medical institution 400 or an advertisement to be displayed in the banner 1013 according to the contents of the diagnostic result of the simple diagnostic result 1011 .
[0063] For example, in a case where it is expected that a possibility of infection is high and a disease will occur in the near future, information of the contracted medical institution 400 is displayed on the banner. With this, it is possible to urge the user 100 to receive the diagnosis and treatment at an early stage.
[0064] Further, it is possible to promote purchase intention by causing a cold medicine or energy drink handled by the diagnostic apparatus installation facility 200 to be displayed. When the diagnostic result is determined as negative, it may be allowed to display the advertisement of a product or service having a high possibility of being preferred by the user 100 on the basis of the information of the POS system 203 without displaying the information described above.
[0065] FIG. 4 illustrates information exchange between the information managing company 300 and a contracted institution 500 which has concluded a contract related to provision of information with the information managing company 300 . As described above, it is possible to gather information of the simple diagnostic results aggregated from the diagnostic apparatus 201 installed in a plurality of the diagnostic apparatus installation facilities 200 to clarify an occurrence state of a disease in each group of an area, age, sex, or the like.
[0066] The information can be provided to a party other than the user 100 or the contracted medical institution 400 . The information managing company 300 provides a password for a contracted institution at the time of concluding a contract with the contracted institution 500 . The contracted institution 500 can access the information processing apparatus 301 and input the password to obtain information about an occurrence state of a disease. The contracted institution 500 can rapidly take preventive measures for a target group on the basis of the obtained information.
REFERENCE SIGNS LIST
[0067] 1 diagnostic service system
[0068] 100 user
[0069] 101 information processing apparatus
[0070] 200 diagnostic apparatus installation facility
[0071] 201 diagnostic apparatus
[0072] 202 disposable device
[0073] 300 information managing company
[0074] 301 information processing apparatus
[0075] 400 contracted medical institution
[0076] 500 contracted institution | A diagnostic result is immediately presented using a diagnostic apparatus installed in a diagnostic apparatus installation facility. Provided is a diagnostic service system which includes a diagnostic apparatus installed in a diagnostic apparatus installation facility and performing a diagnosis using a disposable device, a user terminal owned by a user of the diagnostic apparatus, and an information processing apparatus connected with the diagnostic apparatus and the user terminal and gathering a diagnostic result of the diagnostic apparatus, in which the information processing apparatus manages information of the diagnostic result diagnosed by the diagnostic apparatus and information of the user by associating the both with each other, and provides the diagnostic result in accordance with an access from the user terminal of the user. | 0 |
FIELD OF THE INVENTION
[0001] The present invention relates to a double-axis double-speed linear motor mechanism, applicable especially to machines demanding fast feed rate between the work pieces and the tools, such as high speed sculpturing machines, PCB drill machines, rapid prototyping machines, electric discharge machine (EDM) and other electronics production equipments.
BACKGROUND OF THE INVENTION
[0002] In order to increase the work efficiency of machine, each movement time of the machine needs to be reduced, that is to say that the movement speed and acceleration of the moving mechanism need to be increased. The relative speed and acceleration between the tools and the work pieces especially need to be increased because they are the key points of efficiency improvement.
[0003] Nevertheless, there is a limitation to increase the movement speed of the mechanism. Using a high-speed servomotor with a belt pulley transmission mechanism to increase revolutions per minute, using a high-lead screw shaft, or using high-speed linear motor to drive the mechanism is one of the ways to increase the speed and acceleration. There are shortcomings for those conventional ways which will be explained as follows:
[0004] In order to operate at high speed, not only the speed but the acceleration have to be increased; otherwise, the speed of the mechanism begins to slow down before the maximum speed is reached. Even if the maximum speed is reached, the travel distance for the mechanism running at the maximum speed is pretty short, in this case, the maximum speed can only be kept for a short period of time, as a result, not much time can be saved and the mechanism contributes little to improving the work efficiency.
[0005] Accordingly, not only the maximum speed has to be increased, the high acceleration is also important. In those ways to increase the speed, the linear motor can make the fastest maximum speed and acceleration. The maximum acceleration for high-speed linear motor is about 4G (G represents the gravity acceleration). The platform usually has a huge mass so that it is difficult to accelerate the heavy platform to 4G and normally it only can be accelerated to 1 G. Some prior arts use one motor to drive two moving objects to move in opposite direction, however, the more objects one motor drives, the greater the resistance will be, but the slower the acceleration rate of the moving objects will be. Because the acceleration is not high enough, the platform starts to reduce its speed before a maximum speed is reached. Accordingly, the distance that the platform travels at the maximum speed is very limited. The conventional high-speed moving mechanism needs to be improved.
[0006] The present invention intends to provide a double-axis double-speed linear motor mechanism. It has inherited the advantage of linear motors, that is, high speed and acceleration characteristics. And it has increased the relative speed and acceleration between the work piece and the tool by the simultaneous motion in both axes. When both axes move at the same speed but in the opposite direction, the relative speed is doubled compared to the conventional design. This allows the machining speed and acceleration of the present invention to be increased and meets the requirement of saving machining time.
SUMMARY OF THE INVENTION
[0007] An object of the present invention is to provide an electric discharge machine that has a more reliable drive mechanism for machining.
[0008] Another object of the present invention is to provide an electrical discharge machine that is able to perform high speed and yet stable and precise “jump” procedure than existing embodiment.
[0009] The present invention proposes a double-axis double-speed linear motor mechanism that has a base on which a work piece platform assembly and a tool fixture assembly resides. The work piece platform moves along the first axis on the base. The tool fixture assembly moves along the second axis parallel to the first axis. The tools used to process the work piece are installed in the tool fixture. In order to increase both relative speed and acceleration between the tools and the work pieces so as to save the machining time, when the work piece platform in accordance with the present invention moves along the first axis, the tool moves in a parallel but opposite direction along the second axis, such that the speed between the work piece platform and the tool fixture is the sum of the speed of the work piece platform relative to the base and the speed of the tool fixture relative to the base. When both speeds equal to the conventional mechanism's speed, the speed between the work piece platform and the tool fixture is twice as much as that of the conventional mechanism, the acceleration between the work piece platform and the tool fixture is also twice as much as that of the conventional mechanism. This is the benefit of increasing one more linear motor set for reducing the moving time. In order to prevent the problem of acceleration slowing down caused by one motor driving two objects, each axis in accordance with the present invention can be driven by an independent motor. Linear motors are employed to drive the work piece platform and the tool so as to increase the desired speed of the double-axis double-speed linear motor mechanism. In a typical linear motor application, the speed between the work piece platform and the base can exceed 120 meters per minute, and the acceleration can exceed 1G. In the present invention, the speed and acceleration of the tool relative to the base can be the same as that in the conventional case, and the speed and acceleration of the work piece relative to the base can be the same, too. Since the work piece platform and the tool in accordance with the present invention are designed to move in opposite direction, the relative speed between them can reach 240 meters per minute, and the relative acceleration can reach 2G.
[0010] The speed and the acceleration can reach the desired value so that the speed and the acceleration of the double-axis double-speed linear motor mechanism are double compared to the conventional ones.
[0011] For the present invention, one might think that one more motor is needed for driving the additional axis so that the cost will be increased. However, the motor cost is just a portion of the total cost of the mechanism. The slightly increase for the motor is worthy. The axis driven in only one direction is changed into two axes driven in opposite directions; the stroke of the moving axis is reduced to half. This space-saving reduces the cost so that the final cost varies slightly and the efficiency is increased dramatically, which is worthy.
[0012] The present invention will become more obvious from the following description when taken in connection with the accompanying drawings which show, for purpose of illustration only, a preferred embodiment in accordance with the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] [0013]FIG. 1 shows a double-axis double-speed linear motor mechanism in accordance with the present invention, and
[0014] [0014]FIG. 2 shows a right side view of the double-axis double-speed linear motor mechanism in accordance with the present invention;
[0015] [0015]FIG. 3 shows a cross sectional view of a double-axis double-speed linear motor mechanism in accordance with a second embodiment of an electric discharge machine of the present invention;
[0016] [0016]FIG. 4 shows a side view of a double-axis double-speed linear motor mechanism in accordance with a second embodiment of an electric discharge machine of the present invention;
[0017] [0017]FIG. 5 shows a stereographic view of a double-axis double-speed linear motor mechanism in accordance with a second embodiment of an electric discharge machine of the present invention;
[0018] [0018]FIG. 6 shows a cross sectional view of a double-axis double-speed linear motor mechanism in accordance with a third embodiment of an electric discharge machine of the present invention;
[0019] [0019]FIG. 7 shows a longitudinal cross-sectional view of the linear motor mechanism for driving the tool electrode in accordance with present invention;
[0020] [0020]FIG. 8 shows a lateral cross-sectional view of the linear motor mechanism for driving the tool electrode in accordance with present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] Referring to FIG. 1 which shows a double-axis double-speed linear motor mechanism of the present invention and comprises a base 3 to which a work piece platform 21 for carrying work pieces and a work piece drive axis 22 for driving the work piece platform 21 are connected, wherein the work piece platform 21 and the work piece drive axis 22 are called as a work piece platform assembly. A tool fixture 11 for fixing a tool and a tool drive axis 12 for driving the tool fixture 11 are also connected to the base 3 . The tool fixture 11 and the tool drive axis 12 are called as a tool fixture assembly. The tool drive axis 12 is connected to the base 3 and parallel to one surface of the base 3 . The work piece platform 21 is connected to the work piece drive axis 22 and movable along the work piece drive axis 22 . For convenience of description, the work piece drive axis 22 is named as a first axis. The tool fixture 11 is connected to the tool drive axis 12 and movable along the tool drive axis 12 . The tool drive axis 12 and the work piece drive axis 22 move parallel to each other. When the work piece platform 21 moves along the first axis, the tool fixture 11 in the second axis is driven to move in the opposite direction to the work piece platform. The relative speed between the work piece platform 21 and the tool fixture 11 is therefore the sum of the speed of the work piece platform 21 relative to the base 3 and the speed of the tool fixture 11 relative to the base 3 . Similarly, the relative acceleration between the work piece platform 21 and the tool fixture 11 is the sum of the acceleration of the work piece platform 21 relative to the base 3 and the acceleration of the tool fixture 11 relative to the base 3 . The relative speed between the work piece platform 21 and the tool fixture 11 is twice as much as that of the conventional mechanism, and the relative acceleration between the work piece platform 21 and the tool fixture 11 is twice as much as that of the conventional mechanism.
[0022] In order to achieve the desired speed and acceleration, the mechanism of the present invention employs linear motors to drive the work piece platform 21 and the tool fixture 11 . The driving mechanisms for driving the work piece platform 21 and the tool fixture 11 are independent from each other, and the weight of the object to be driven in accordance with the present invention is also no heavier than that of the conventional mechanism, thereby the relative speed and relative acceleration between the work piece platform 21 and the tool fixture 11 in accordance with the present invention can be doubled as compared to the conventional mechanism.
[0023] [0023]FIG. 2 shows a right side view of the double-axis double-speed linear motor mechanism of the present invention and what is disclosed in an embodiment of the present invention. In this embodiment, the work piece fixing base 23 is assembled to the work piece platform 21 and the work piece 4 is fixed to the work piece fixing base 23 . The tool fixture 11 has a tool axis 5 which drives the tool 6 to access to or move away from the work piece in left and right direction as shown in FIG. 2. This is an application embodiment of the mechanism as shown in FIG. 1 and which is used for those which have slower moving speed but require rapid positioning, such as the PCB drill. The tool 6 and the work piece 4 in this embodiment can move at a high relative speed while each axis is moving at the speed of the conventional mechanism. Since an effect of double axis and double speed can be achieved in the direction of the work piece drive axis 22 in accordance with the embodiment of the present invention, such that the work efficiency of the mechanism of the present invention is substantially increased.
[0024] To better under the present invention, please refer to FIGS. 3-8, which show another embodiment of Z-axis an electric discharge machine (EDM) of the present invention. The EDM comprise a base 3 ′, a tool fixture assembly 11 ′ mounted on the base 3 ′, and work piece platform assembly 2 ′ on which the work piece is fixed. The tool fixture assembly 11 ′ comprises a linear motor assembly 111 ′, which drives the tool electrode 112 ′ whose moving axis parallel to the surface of the base 3 ′, and an air cylinder 113 ′, which compensates weight of the motor linear assembly 111 ′ and the tool electrode 112 ′. The work piece platform assembly 2 ′ comprises a work piece platform 21 ′ carrying the workpiece, an air cylinder 20 ′ compensating weight of the work piece platform 21 ′, and linear motor assembly 23 ′, which is mounted on the same motion axis of the linear motor assembly 111 ′ and moves the work piece platform 21 ′.
[0025] In comparison with conventional ballscrews whose driving force is generated by physical contact between nut and spindle, linear motors are non-contact and maintenance-free. It performs higher speed positioning since there is no ball circulation wear problem inherited in ballscrews.
[0026] During machining, when the linear motor assembly 111 ′ drives the tool electrode 112 ′ in one direction, another linear motor assembly 23 ′ moves the work piece platform 21 ′ in the opposite direction. Through this way, the relative speed between the tool electrode 112 ′ and the work piece platform 21 ′ is increased, and a high effective jump operation can be realized. In addition, the reaction force created by the highly repetitive movement of work piece platform assembly 2 ′ is canceled, and a stable and precise “jump” procedure can be ensured.
[0027] [0027]FIG. 6 shows another embodiment of an electric discharge machine of the present invention where hollow cylindrical linear motors are used. Inside the linear motor assembly 111 ′ the air cylinder 113 ′ for counter-balance is mounted. On one end of the linear motor assembly 111 ′ the tool electrode 112 ′ is attached. On the same motion axis, another linear motor assembly 23 ′ with air cylinder 20 ′ drives the work piece platform 21 ′ in opposite moving direction of the tool electrode 112 ′.
[0028] [0028]FIGS. 7 and 8 illustrates details of the hollow cylindrical linear motor assembly 111 ′ shown in FIG. 2. The linear motor assembly 111 ′ comprises a hollow cylindrical forcer 114 ′, circular permanent magnets 115 ′ mounted on the outer cylindrical surface of the forcer 111 ′, a hollow cylindrical stator 116 ′ with motor windings surrounded by cooling module 117 ′, 2 linear guide ways 117 ′ on which slide blocks 118 ′ connected with the stator 116 ′ through the bracket 119 ′, a linear encoder read head 120 ′ which is mounted inside the slide block 118 ′ and detects tool electrode's position from a linear scale 121 ′ glued on guide way surface.
[0029] In the second embodiment driving forces generated by hollow cylindrical linear motor pass through the center of mass of the tool fixture assembly as well as the work piece platform assembly. This saves equipment space, eliminates disturbance torque moments created by non-co-centric driving, and ensures higher speed and yet very stable machining.
[0030] In sum, the present invention has the following advantages as compared to the conventional mechanism:
[0031] 1. Maintenance-free and more reliable operations.
[0032] 2. Higher speed jump operation, and thus higher productivity and
[0033] 3. More stable positioning of the tool electrode, and thus superior surface machining quality
[0034] 4. Space saving through using direct drive motors, without intermediate power transmission elements, such as nuts and couplings.
[0035] While we have shown and described the embodiment in accordance with the present invention, it should be clear to those skilled in the art that further embodiments may be made without departing from the scope of the present invention. | The present invention provides an electrical discharge machine (EDM) with double-axis double-speed linear motor mechanism for fast machining operation. In this EDM the tool fixture assembly is driven by a linear motor, whiles the work piece platform assembly is driven by another linear motor in the opposite direction. Applying no contact direct drive, such as linear motors, eliminates wear problem in ballscrews in conventional embodiments and enhances availability of the machine. Opposite and double motors drive configuration not only increases relative speed between the tool electrode and the work piece, but also stabilize the speedy jump operation by canceling reaction force of tool electrode movement. | 1 |
FIELD OF THE INVENTION
The present invention relates to inlet flue systems for banks of electrostatic precipitator chambers which greatly reduce or eliminate particulate settling and, therefore, several problems that result from particulate settling in conventional inlet flue systems.
BACKGROUND OF THE INVENTION
The inlet flue systems of most conventional electrostatic precipitators have many horizontal or nearly horizontal lower surfaces onto which particulates in the gases flowing to the precipitator chambers settle and accumulate. Often, the weight of the accumulated particulates builds to a level several times that of the flues themselves and requires the flues and the structures supporting them to be strong and heavy, and correspondingly costly. The settled particulates increasingly disrupt normal gas distribution by changing, usually unpredictably, the internal shapes and dimensions of the flow passages in the flues and between turning vanes. Some flow passages may even become plugged.
The tons and tons of accumulated particulates must be removed periodically. Often, removal can be accomplished only by manual shovelling, which is costly and time consuming and requires extended shutdown of an entire plant.
It is common practice in designing precipitator inlet flue systems to maintain relatively high gas flow velocities (about 50 feet per second) in order to minimize particulate settling. Reducing the gas flow from conveying velocity to precipitation velocity complicates the structures of transition sections to provide reasonably uniform distribution at the entrance to each precipitator chamber and generally involves providing multiple stages of perforated plates with attendant draft losses.
SUMMARY OF THE INVENTION
The present invention is a flue system for conducting particulate-containing gases to the inlet nozzles of a multiplicity of electrostatic precipitator chambers. The principal component of the system is an elongated plenum which is located generally above the chamber inlet nozzles. The plenum has top and side walls but is substantially entirely open at the bottom. Generally downwardly directed branch ducts lead from the bottom of the plenum to the inlet nozzles, the inlet ends of the walls of each branch duct defining an outlet opening from the plenum. The plenum, therefore, has an open bottom subdivided by the branch duct inlets into a row of longitudinally adjacent outlet openings.
The system may take numerous forms, depending upon the available ground space, size, number and arrangement of the precipitator chambers, and similar factors. One advantageous layout comprises two banks of at least two side-by-side precipitator chambers each, one bank being laterally on one side of and below the plenum and the other bank being laterally on the other side and below the plenum. With this layout of chambers the plenum may have either one or two longitudinal rows of outlet openings in the bottom. With one row of outlet openings it is advantageous to stagger the chambers of one bank longitudinally with respect to those of the other bank and to connect the outlet openings alternately, moving in the downstream direction, with the chambers of the two banks. The upstream portion of each branch duct where it leads away from the plenum outlet opening is oriented obliquely to the horizontal, adjacent branch ducts being of opposite orientations with respect to the vertical. Each branch duct then turns downwardly, preferably through an expansion section, and is connected to the inlet nozzle of the corresponding chamber.
With two longitudinal rows of outlet openings, the outlet openings of each row are connected exclusively to the chambers of one bank. Preferably, this layout will involve a symmetrical arrangement of the chambers and the outlet openings and back-to-back vertical branch ducts.
The system can be used with banks of precipitator chambers stacked one above the other, known as a "double-decked" arrangement. Preferably, the chambers of the upper deck register vertically with the chambers of the lower deck. Plenum outlet openings arranged longitudinally adjacent each other in one row are connected by branch ducts to the inlet nozzles of each chamber of the upper deck and plenum outlet openings in a second row are connected to the chambers of the lower deck. Two double-decked arrangements of opposite orientations can be installed in tandem, preferably arranged symmetrically on opposite sides of a vertical-longitudinal bisector plane of the plenum. In such a double-decked, tandem arrangement, the open bottom of the plenum is subdivided by the inlet ends of the branch ducts into four side-by-side longitudinal rows of outlet openings.
With double-decked arrangements, either single or tandem, weight and expense can be saved by providing a contraction section at the inlet end and an expansion section at the outlet end of each branch duct, particularly the branch ducts communicating the plenum with the lower deck chambers. The intermediate section of each such duct is of reduced size, weight and cost.
The lower edges of the side walls of the plenum (which define the longitudinal edges of the laterally outermost plenum outlet openings) are, preferably, parallel and lie in a horizontal plane, thereby permitting the branch ducts to be of rectangular cross section. To minimize the sizes of the walls (sides and top) of the plenum, for given cross-sectional areas along the length, the lower portions of each side wall may be oblique to the horizontal plane of the bottom edges and diverge upwardly from the bottom edges, thus to widen the plenum and reduce the height. The upper portion of the plenum may be of rectangular or "balloon" cross section. The plenum is of varying cross-sectional area along its length to provide a desired, usually a substantially uniform, distribution of gas and particulates among the several chambers.
A flue system embodying the present invention has the following advantages:
1. The most important advantage, of course, is the lack of any horizontal surfaces in the plenum where particulates might settle--the invention has, quite literally, a bottomless plenum.
2. The elimination of particulate settling and accumulation in the plenum reduces the weight and cost of the inlet plenum and duct system and the structures which support them because there is no weight of settled dust--often many times that of the plenum and ducts themselves--to be supported.
3. Elimination of particulate settling prevents gas-flow mal-distribution due to flue blockage and unpredictable changes in internal effective flue shapes and dimensions, including distorted and/or plugged turning vanes, etc.
4. Because particulate settling, which is normally kept to a minimum in conventional precipitator inlet flue systems by keeping gas velocities high (i.e., conveying velocities of about 50 fps), is eliminated, a lower gas velocity can be used in the inlet system.
5. Using lower gas velocities within the inlet plenum and flue system saves costly energy due to draft loss, which loss increases as the second power of the velocity of the gas.
6. Elimination of particulate settling within the inlet plenum and duct system saves the costs of removing tons and tons of dust. Often, such removal in conventional inlet systems can be accomplished by manual shovelling only, which is costly and time consuming requiring extended outages of whole plants.
7. The use of lower gas velocities within the inlet system improves the inherent capability of the system to divide the total gas flow equally among many outlets.
8. The use of lower gas velocities within the inlet system, combined with the opportunity to increase the size of the plenum outlet openings, enables lower gas velocities entering the ESP inlet nozzles. This earlier reduction of gas velocities from conveying velocity (about 50 fps) toward precipitation velocity (about 5 fps) can reduce draft loss due to the reduction in the need for multiple stages of perforated plates.
9. The simple geometry of the inlet plenum provides an uncomplicated and economic base on which to design, and optimize through modeling, a flow-control system of equal gas distribution and equal particulate distribution to numbers of parallel precipitator chambers.
10. The elimination of particulate settling on horizontal surfaces enables designing a flue system optimized for gas flow alone. Previous designs had to be compromised to prevent or minimize particulate settling.
11. Since all plenum outlet openings are grouped in a row or rows along the bottom of the plenum and since each outlet is fed by a simple, ninety-degree turn downward, the equal and even distribution of both gas and dust is controlled by the gas velocity at each plane of entry. This gas velocity in turn is inherently controlled by the taper of the plenum, by the heights and shapes of the baffles and by the areas of the outlets. Optimization of these inherent gas-flow-control dimensions is possible by means of three-dimensional modeling. Should modeling or subsequent field measurement indicate the need for design modification, the generous size and unencumbered interior of the plenum provide practical bases for upgrading.
12. The downward flow of gas and particulate into each ESP chamber inlet nozzle is one of the most favorable for gas-flow and particulate-flow control across the inlet plane of each ESP chamber.
13. The downward flow of gas and particulate into nested and touching ESP inlet nozzles provides an exceptionally compact arrangement of precipitators which conserves ground or other site area.
14. The location of the plenum above the precipitator casings enables economic structural support from the precipitator casing structures.
15. Since all plenum outlets are (preferably) grouped in a row or parallel rows symmetrical about the center line of the bottom of the plenum, and since all outlets require the same, simple ninety-degree turn downward, the dampering of any single chamber has a minimal effect on the distribution of gas and particulate to the parallel precipitator chambers remaining in service.
For a better understanding of the invention, reference may be made to the following description of exemplary embodiments, taken in conjunction with the figures of the accompanying drawings, all of which are schematic in form.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of an electrostatic precipitator having one embodiment of inlet flue system;
FIG. 2 is an end view of the installation of FIG. 1 taken generally along the lines 2--2 of FIG. 1 and in the direction of the arrows, a portion of the inlet system being shown in cross section;
FIG. 3 is a partial pictorial view of the branch ducts, inlet nozzles and inlets of the chambers of the system shown in FIGS. 1 and 2;
FIG. 4 is a top view of the plenum shown in FIGS. 1 to 3, a portion of the top wall being broken away;
FIG. 5 is a side elevational view of the plenum shown in FIG. 4;
FIG. 6 is a bottom view of the plenum shown in FIGS. 4 and 5;
FIGS. 7, 8 and 9 are end (and end cross-sectional) views of the plenum taken along the lines 7--7, 8--8 and 9--9 of FIG. 5 and in the direction of the arrows;
FIG. 10 is a bottom view of another embodiment of a plenum;
FIG. 11 is an end elevational view of a double-decked, tandem installation;
FIG. 12 is a bottom view of the plenum of the FIG. 11 precipitator;
FIG. 13 is an end elevational view of another double-decked, tandem precipitator; and
FIGS. 14, 15 and 16 are side, bottom and end cross-sectional views, respectively, of the plenum and parts of the branch ducts of the precipitator shown in FIG. 13.
DESCRIPTION OF EXEMPLARY EMBODIMENTS
The electrostatic precipitator shown in FIGS. 1 to 9 comprises 12 precipitator chambers arranged side by side in two banks of six each. The chambers are oriented with the inlet nozzles N of the chambers of one bank back-to-back to the inlet nozzles of the chambers of the other bank, and the chambers of one bank are evenly staggered longitudinally with respect to the chambers of the other bank. Particulate-containing gases are conducted from a source, as indicated by the arrow labelled "I," to an elongated plenum P, are distributed among branch ducts D leading from the open bottom of the plenum P to the inlet nozzles N and flow through the chambers, out through outlet nozzles O to an outlet flue system F which conducts them to a stack S. Each electrostatic precipitator chamber C may be of any suitable design and will normally consist of a supporting structure 10, a casing 11, a penthouse 12, a number of electrostatic precipitation fields 14 and hoppers 16 for accumulating particulates collected in the fields.
It is desirable to provide a damper or dampers somewhere in the path of gas flow between the plenum outlet opening to the branch duct D and the outlet opening from the outlet nozzle O of each chamber so that gas flow can be interrupted by closing the damper during electrode cleaning (rapping). The stoppage of gas flow reduces rapping losses to a negligible level, increases hopper catch per rapping cycle and improves overall collection efficiency. "Dampering off" each precipitator chamber for rapping may also be done according to the present inventor's U.S. Pat. No. 3,988,127 by using two dampers to create an isolated zone into which clean gas (such as air or gas from the outlet flue) is introduced under a pressure above the ambient pressure in the chamber. The "air-lock" effect prevents even the small losses that would otherwise occur due to damper leakage. The double-dampered, pressured air-lock is conveniently installed at the outlet throat of each outlet nozzle, as indicated by the letter A ("Air-lock").
The plenums P of all four embodiments shown in the drawings are similar in that they are tapered along their entire length to reduce the cross-sectional area from a maximum at the inlet end to a minimum at the closed end. The cross-sectional area at any plane along the length of the plenum is approximately proportional to the gas flow through that plane, thereby maintaining the gas velocity within the plenum approximately constant at any selected value. The degree of taper can, however, be varied such that the gas velocity is either increased or decreased moving from the inlet toward the closed end. The selection of taper for any particular installation is a matter of design evaluation taking into account many variables, such as quantity and characteristics of the gas, quantity and characteristics of the entrained particulates, number of precipitator chambers, and the ground or other site space available. The width of the plenum outlets can be selected to provide any desired outlet gas velocity. In many cases, as is common practice in the industry, the final design selected for the precipitator installation will be optimized by a three-dimensional scale model study.
The effective taper of the plenum P is, preferably, accomplished by varying both height and width of a rectangular cross section and also varying the height of baffles 20 which separate the open bottom of the plenum into a series of outlet openings.
More particularly, as best shown in FIGS. 4 to 9, the plenums P used in the four embodiments of the drawings comprise a tapered, trapezoidal top wall 22 which slopes downwardly from the inlet end (to the left in FIGS. 4 to 6) to the closed end, a pair of upper trapezoidal side walls 24 and 26 which lie vertically, are tapered toward the closed end, and lie obliquely at a small angle to the longitudinal-vertical center plane, and a pair of lower side walls 28 and 30 which lie obliquely to a horizontal plane and taper toward the closed end. The lower side walls 28 and 30 form an elongated trough-like hopper of truncated triangular transverse cross section along the lower portion of the plenum. The lowermost edges of the side walls 28 and 30 are parallel along the entire length of the plenum, lie in a horizontal plane and thus define an open bottom 32 on the plenum that is of uniform width and extends continuously along the entire length of the plenum. As mentioned above, the width of that opening can be varied to accommodate outlet openings of the desired shapes and sizes. The downstream end of the plenum is closed by an end wall 34.
The open bottom 32 of the plenum P is subdivided into a series of outlet openings by the inlet ends of the branch ducts D which communicate the plenum with the nozzles N of the chambers C. In the embodiment shown in FIGS. 1 to 9 there is a single row of plenum outlet openings 36. Each branch duct D consists of an upper section 38 having a rectangular upper edge that is oblique to its axis and is oriented with its axis oblique to the plane of the plenum bottom, such axis lying in a transverse plane perpendicular to the axis of the plenum. Adjacent branch ducts D are right and left handed so that the lower ends of adjacent sections 38 are offset on either side of the longitudinal-vertical center plane of the plenum, thus to register longitudinally and laterally with the nozzles N. The lower end of each oblique upper inlet section 38 is connected to the upper end of an expansion section 40 of the duct D, the lower end of which opens to the upper end of a corresponding nozzle.
The positioning of the two banks of chambers with the nozzles attached back to back, the staggered relation of the chambers of the two banks, and the delivery of gas and particulates alternately to the chambers of the two banks from longitudinally adjacent outlet openings provide the advantages of using a minimum of ground or other site space, an efficient structural system of reduced weight and complexity and a simple system of ducting in which identical duct parts can be used correspondingly for all branch ducts. As described above, the gas flow characteristics can be optimized for a desired, preferably uniform, distribution of gas and particulates to the individual chambers. The baffles 20 installed between the adjacent outlet openings 36 defined by the inlet sections 38 are relatively simple components, which can be designed and optimized by modeling--such as by varying the heights and shapes--to provide the desired distribution and can be field modified relatively easily if initial operation of the precipitator suggests that changes would be beneficial. A small deflector 41 (see FIGS. 5 and 6) is installed in front of the first baffle at the inlet end of the plenum. Generally, suitable gas-flow-control vaning (not shown) will be provided at the inlet to the plenum.
FIG. 10 shows the bottom of a modified plenum P which, though virtually identical to the plenum shown in FIGS. 1 to 9, differs in that the open bottom 32 is subdivided into two longitudinal, side-by-side rows of individual plenum outlet openings defined by the inlet ends of branch ducts. The plenum P shown in FIG. 10 is suitable for use with a symmetrical arrangement of two banks of six side-by-side chambers each on either side of a longitudinal-vertical center plane. Each outlet opening 42 in one row communicates through a corresponding branch duct to a chamber of one bank, and each outlet opening 44 in the other row communicates with a chamber of the other bank. Such an arrangement has all of the advantages of the arrangement shown in FIGS. 1 to 9, except that the cross section of each branch duct, though simpler, provides a higher ratio of cross-section perimeter to area and may be slightly less efficient in terms of duct metal work and weight.
The electrostatic precipitator shown in FIGS. 11 and 12 includes a tandem arrangement of double-decked units. Each double-decked unit comprises a lower bank 50 and an upper bank 52 of three side-by-side chambers each stacked in vertical register. The overall construction and geometry of the plenum P are the same as those of the plenum of FIGS. 1 to 9, except that the open bottom 32 is much wider and the plenum is shorter. The outlet openings are arranged in four longitudinal, side-by-side rows of three openings each, as defined by the back-to-back upper ends of branch ducts; to wit, the laterally outermost rows of branch ducts 54 and 56 lead straight down to the corresponding nozzles of the upper banks of chambers 52, and the remaining two rows of branch ducts 58 and 60 lead downwardly from the plenum, are offset laterally and then lead down the rest of the way to the corresponding nozzles of the chambers of the lower banks 50. The longitudinal dimension of each duct (longitudinal with respect to the axis of the plenum) may be uniform throughout the height of the duct and may be equal to the longitudinal dimension of the opening to the nozzle, as shown in FIGS. 11 and 12.
The precipitator shown in FIGS. 13 to 16 has an arrangement of upper and lower banks 52 and 50, respectively, of chambers in double-decked, tandem relationship that is identical to the arrangement shown in FIGS. 11 and 12, and the plenum is very similar to the plenum shown in FIGS. 11 to 12. However, each branch duct includes a contraction section 70 at the inlet end, an expansion section 72 at the lower end, and in the case of the branch ducts leading to the lower banks 50, a "downcomer" section 74 connected between the contraction and expansion sections 70 and 72. This embodiment is exemplary of modifications that can be made in the design of the branch ducts to provide flow control or achieve economy, or both. In this instance, the reduced cross section of each "downcomer" section 74 significantly reduces the weight and cost of the duct system.
The above-described embodiments of the invention are merely exemplary, and numerous variations and modifications will be readily apparent to those skilled in the art without departing from the spirit and scope of the invention. | An inlet flue system for conducting particulate-containing gases to the inlet nozzles of a multiplicity of electrostatic precipitator chambers comprises an elongated plenum located generally above the nozzles. The plenum is substantially entirely open at the bottom, and the inlet ends of the perimeter walls of branch ducts leading from the open bottom define a series of outlet openings from the plenum. The open bottom construction leaves the plenum substantially free of upwardly facing surfaces where particulates can settle. | 1 |
BACKGROUND
[0001] This invention relates to pressure swing adsorption (PSA) processes, and more particularly to such processes employing multiple adsorbent beds.
[0002] PSA processes are well-known for the separation of gas mixtures that contain components with different adsorbing characteristics. The pressure swing adsorption process may be used for separating a primary gas component from a feed gas mixture comprising the primary gas component and one or more secondary gas components. The primary gas component may be H 2 and the secondary gas components may be gases such as N 2 , CO, CO 2 , and CH 4 , such as a reformate from a steam methane reformer or other hydrocarbon reforming process. The primary gas component may be H 2 and the secondary gas components may be gases such as CH 4 , C 2 H 6 , C 3 H 8 , and/or higher alkanes, alkenes, and aromatics associated with refinery off gas streams. The primary gas component may be He and the secondary gas components may be gases such as N 2 , CH 4 , CO, and/or CO 2 . The primary gas component may be N 2 and the secondary gas components may be gases such as C 2 H 4 , C 2 H 6 , C 3 H 6 , and/or C 4 H 8 .
[0003] Hydrogen production via pressure swing adsorption (H 2 PSA) is an established industry practice for supplying high purity hydrogen for petroleum refiners, chemical producing industries, metals refining, and other related industries. The feed gas mixture may be a reformate from a steam-hydrocarbon reforming process or an autothermal reforming process. The reformate may have been shifted in a shift reactor. The feed gas mixture may be a properly treated effluent stream from a gasification unit.
[0004] In a typical PSA system, a multicomponent gas is passed to at least one of multiple adsorption beds at an elevated pressure to adsorb at least one strongly sorbed component while at least one component passes through the adsorption bed. In the case of H 2 PSA, H 2 is the most weakly adsorbed component and passes through the adsorption bed.
[0005] Industry desires to reduce compression requirements for PSA cycles.
[0006] Industry desires improved PSA processes and cycles which increase H 2 production and/or H 2 recovery in a multiple bed system.
[0007] Industry desires improved PSA processes and cycles that reduce capital and/or operating costs to produce hydrogen.
[0008] Pressure swing adsorption cycles comprise a number of well-known steps. The skilled person can combine the known steps in any suitable manner to achieve desired objectives. Determining a suitable combination of known steps follows rules known in the art and computer programs are available to assist with development and evaluation of any combination of known steps. Furthermore, many suitable pressure swing adsorption cycles are known and published, and modification of those known cycles with other well-known steps is straightforward and can be readily evaluated.
[0009] For example Mehrotra et al. in a paper titled “Arithmetic approach for complex PSA cycle scheduling,” Adsorption (2010) 16: 113-126, incorporated herein by reference, describe an algebraic model derived for obtaining complex pressure swing adsorption cycle schedules. The approach uses a priori specified cycle steps, their sequence and any constraints, and then solving a set of analytical equations. The solution identifies all the cycle schedules for a given number of beds, the minimum number of beds required to operate the specified cycle step sequence, the minimum number and location of idle steps to ensure alignment of coupled cycle steps, and a simple screening technique to aid in identifying the best performing cycles that deserve further examination. Overall, the methodology for complex PSA cycle scheduling can be applied to any number of cycle steps, any corresponding cycle step sequence, and any number of constraints, with the outcome being the complete set of cycle schedules for any number of beds greater than or equal to the minimum number it determines.
[0010] As pressure swing adsorption (PSA) processes are well-known, one of ordinary skill in the art can construct an adsorption system suitable for carrying out the process described herein. Suitable equipment for carrying out the process is well-known in the art. Operating conditions not specifically disclosed herein that are suitable for use in the process described herein may be determined by one skilled in the art without undue experimentation.
[0011] The process may be carried out in axial adsorbent beds or radial adsorbent beds.
[0012] Number of Beds
[0013] Pressure swing adsorption processes are carried out in adsorption beds. Any suitable number of adsorption beds may be used. In general, the PSA process is designed to meet required product purity and H 2 product recovery.
[0014] For a required product purity, the number of beds can be a trade-off between capital and hydrogen recovery. For example, increasing the number of beds allows the PSA process to utilize a greater number of pressure equalization steps. Pressure equalization steps are hydrogen saving steps. Increasing the number will reduce the pressure at which gas is discharged from the bed to the waste stream, decreasing hydrogen losses. If the pressure equalization steps are conducted through co-current depressurization of the high pressure bed, the impurity front advances farther when more pressure equalization steps are used. To maintain the desired production, the size of each bed increases in addition to the number of beds.
[0015] Alternatively, the number of beds may be increased to lengthen the time available to individual steps that may be limiting the efficiency of the overall process. For example, increasing the number of beds allows the PSA process to increase the number of beds that will process feed gas or process purge gas. Sending gas to more beds on feed or more beds on purge decreases the velocity of the gas passing over the adsorbent particles, which in turn increases the efficiency of the process step.
[0016] Generally more than one adsorption bed is used so that at least one adsorption bed can be producing product gas while another bed is regenerating. In this way, product gas can be produced on a continuous basis.
[0017] The skilled person can readily select the number of adsorption beds to use.
[0018] Number of Adsorbents
[0019] The adsorption beds may contain a single adsorbent or multiple adsorbents. In the case of multiple adsorbents, the adsorbents may be interspersed, layered, or a combination thereof. Adsorbent beds may comprise multiple layers as described, for example, in U.S. Pat. No. 7,179,324, incorporated herein by reference.
[0020] Suitable adsorbents may be readily selected by those skilled in the art. Activated alumina, silica gel, activated carbon, molecular sieves, and naturally occurring zeolites are common.
[0021] FIG. 1 shows a schematic of an example adsorption system with adsorption beds 10 A, 20 A, 30 A, 40 A, 50 A, 10 B, 20 B, 30 B, 40 B, and 50 B, suitable for the PSA process. An adsorption system may be constructed with pairs, or other multiples of beds, operating in parallel (i.e. on the same step). For example adsorption beds 10 A and 10 B could be configured to always be on the same step, adsorption beds 20 A and 20 B on the same step, etc. Alternatively, an adsorption system may be constructed without beds operating in parallel.
[0022] An adsorption bed is a grouping of adsorption material which undergoes each of the cycle steps contemporaneously. An adsorption bed may be contained in a single containment vessel or contained within multiple containment vessels. For example, with reference to the 4 bed cycle in FIGS. 2 a / 2 b , and the adsorption system schematic in FIG. 1 , all of the adsorption material in adsorption bed 10 A undergoes the production step (P) contemporaneously, then all of the adsorption material in adsorption bed 10 A undergoes the production/supply product step (P/SP) contemporaneously, then all of the adsorption material in adsorption bed 10 A undergoes the first pressure decreasing equalization (DEQ1) step contemporaneously, then all of the adsorption material in adsorption bed 10 A undergoes the supply purge (SPG) step contemporaneously, then all of the adsorption material in adsorption bed 10 A undergoes the blowdown (BD) step contemporaneously, then all of the adsorption material in adsorption bed 10 A undergoes the purge step (PRG) contemporaneously, then all of the adsorption material in adsorption bed 10 A undergoes the first pressure increasing equalization step (PEQ1) step contemporaneously, then all of the adsorption material in adsorption bed 10 A undergoes the product pressurization (PP) step contemporaneously.
[0023] Various known PSA cycle steps are described below. The length of a step may be quantized (discretized) (i.e. an integer number of cycle time segments). However the step may be a fractional value of a cycle time segment with the balance as an idle step as shown in FIG. 3 . Furthermore the steps do not need to align with each other exactly as shown in FIG. 3 . In FIG. 3 , for example, the timing of the change from the SPG step to BD step does not align with the timing of the change from the DEQ p 2 step to DEQ p 3 step.
[0024] The cycle time of the PSA cycle is the length of time when the feed gas mixture is first conducted to the first bed in the repetitive cycle to the time when the gaseous mixture is again first conducted to the first bed in the cycle immediately following.
[0025] Production Step (P)
[0026] The production step is abbreviated herein as “P”. The production step is also called the feed step and/or adsorption step in the literature. While this step is sometimes referred to as the feed step and/or adsorption step, the term “production step” is used herein instead of “feed step” since it is possible to have feed introduced into an adsorption bed without a product gas being produced, and the term “adsorption step” is not used because adsorption and desorption are occurring in many of the different steps.
[0027] The production step comprises introducing a feed gas mixture (e.g. a reformate) at a feed gas pressure into an adsorption bed undergoing the production step and adsorbing the secondary gas components (e.g. CO, CO 2 , and/or CH 4 ) on the adsorbent in the adsorption bed undergoing the production step while simultaneously withdrawing a product gas (e.g. H 2 product gas) from the adsorption bed undergoing the production step. The product gas contains a higher concentration of the primary gas component than the feed gas mixture and is depleted of the secondary gas components. The duration of the production step may be any suitable duration, for example from 1 second to 300 seconds, or from 30 seconds to 300 seconds. The skilled person can readily determine a suitable duration for any of the known PSA cycle steps.
[0028] For hydrogen production the feed gas pressure may range, for example, from 0.5 MPa to 7.0 MPa or from 1.0 MPa to 3.6 MPa (absolute pressure).
[0029] The term “depleted” means having a lesser mole % concentration of the indicated gas than the original stream from which it was formed. “Depleted” does not mean that the stream is completely lacking the indicated gas. The product gas withdrawn during the feed step therefore has a higher mole % concentration of the primary gas component than the feed gas mixture due to adsorption of the secondary gas components on the adsorbent.
[0030] At the end of the production step, the adsorption bed contains what is called a void space gas which is a combination of both gas phase and adsorbed phase molecules. The void space gas has a higher average concentration of the more strongly adsorbable components than the feed gas mixture since the less adsorbable components were withdrawn as the product stream. The concentration of the various components of the void space gas mixture will generally vary as a function of distance from the feed end to the product end of the adsorption bed. The void space gas near the product end will generally have a higher concentration of weakly adsorbable components and non-adsorbable components. The void space gas near the feed end will generally have a higher concentration of the more strongly adsorbable components.
[0031] In terms of pressure, the bed pressure during the feed step is typically substantially maintained at a constant pressure that corresponds with the highest pressure (P H ) in the Pressure Swing Adsorption (PSA) cycle.
[0032] As shown in U.S. Pat. No. 7,179,324, it is possible to have a PSA cycle where there is a time segment where there are no beds in a production step or hybrid form thereof. It means that during this time segment, no product gas is being withdrawn from the PSA system.
[0033] Multiple production steps at different feed gas pressures are also known and can be incorporated by the skilled person if desired. Kumar et al., “A new concept to increase recovery from H 2 PSA: processing different pressure feed streams in a single unit,” Gas Sep. Purif . Vol, 9, No. 4, pp. 271-276, 1995, incorporated herein by reference, discloses a PSA cycle with a low pressure production step and a high pressure production step. Three or more production step pressure levels are possible if desired.
[0034] Co-Current and Countercurrent
[0035] Each of the adsorption beds has a “feed end” and a “product end,” so termed because of their function during the production step of the adsorption cycle. A feed gas mixture is introduced into the “feed end” of the adsorption bed and a product gas is withdrawn from the “product end” during the production step of the cycle. During other steps of the adsorption cycle, gas may be introduced or withdrawn from “feed end.” Likewise, during other steps of the adsorption cycle, gas may be introduced or withdrawn from the “product end.”
[0036] The direction of flow during other steps is typically described with reference to the direction of flow during the production step. Thus gas flow in the same direction as the gas flow during the production step is “co-current” (sometimes called “concurrent”) and gas flow that is in the opposite direction to the gas flow during the production step is “counter-current.” Co-currently introducing a gas into an adsorption bed means to introduce the gas in the same direction as the feed gas introduced during the production step (i.e. introducing into the feed end). Counter-currently introducing a gas into an adsorption bed means to introduce the gas in a direction opposite to the direction of the feed gas flow during the feed step (i.e. introducing into the product end). Co-currently withdrawing a gas from an adsorption bed means to withdraw the gas in the same direction as the product gas during the production step (i.e. withdrawing from the product end). Counter-currently withdrawing a gas from an adsorption bed means to withdraw the gas in a direction opposite to the direction of the product gas flow during the production step (i.e. withdrawing from the feed end).
[0037] Gas may be simultaneously co-currently introduced to the feed end and counter-currently introduced to the product end. Gas may be simultaneously co-currently withdrawn from product end and counter-currently withdrawn from the feed end. Gas may be simultaneously co-currently introduced into the feed end and co-currently withdrawn from the product end. Gas may be simultaneously counter-currently introduced to product end and counter-currently withdrawn from the feed end.
[0038] When gas is withdrawn from an intermediate position to the feed end and the product end, a portion of the gas is co-currently withdrawn and a portion of the gas is counter-currently withdrawn. When gas is introduced to an intermediate position to the feed end and the product end, a portion of the gas is co-currently introduced and a portion is counter-currently introduced.
[0039] Feed gas introduction and product gas withdrawal at intermediate positions of the adsorption bed is disclosed by Grande, “Advances in Pressure Swing Adsorption for Gas Separation,” International Scholarly Research Network Chemical Engineering , Vol. 2012, Article ID 982934, 2012, incorporated herein by reference.
[0040] Production/No Feed Step (P/NF)
[0041] Kleinberg et al. (U.S. Pat. No. 6,585,804), incorporated herein by reference, discloses a step where product gas is produced without the introduction of feed gas to the adsorption bed. This step is abbreviated herein as “P/NF.” This step generally follows a production step and is stated to be useful when the adsorption system is operated at turndown conditions. The production/no feed step may be added to any known PSA cycle and/or substituted for the production step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0042] Co-Current Depressurizing Equalization Step (DEQ p #)
[0043] The co-current depressurizing equalization step has also been termed the “equalization down step” and the “pressure decreasing equalization step.” The depressurizing equalization step is abbreviated herein as “DEQ p ” or “DEQ p #”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0044] A co-current depressurizing (pressure decreasing) equalization step comprises co-currently withdrawing a pressure equalization gas from an adsorption bed undergoing the co-current depressurizing equalization step, and passing the pressure equalization gas to an adsorption bed undergoing a complementary pressurizing (pressure increasing) equalization step (e.g. PEQ, PEQ f or PEQ d ) or a hybrid step thereof thereby equalizing the pressure between the adsorption bed undergoing the co-current depressurizing equalization step and the adsorption bed undergoing the pressurizing equalization step at the end of the respective steps. The various forms of pressurizing equalization steps (PEQ, PEQ f or PEQ d ) including hybrid forms thereof are discussed below.
[0045] The phrase “equalizing the pressure” generally means that the pressure difference between the adsorption beds at the end of the co-current pressure equalization step is less than 250 kPa (36 psi). Then, at the end of the co-current depressurizing equalization step (DEQ) and the complementary pressurizing (pressure increasing) equalization step, the pressure in the adsorption bed at the end of the co-current depressurizing equalization step is no greater than 250 KPa more than the pressure in the adsorption bed at the end of the pressurizing equalization step.
[0046] The duration of the co-current depressurizing equalization step may be any suitable duration, for example from 1 second to 150 seconds, or from 10 seconds to 150 seconds, while shorter or longer times are possible. The skilled person can readily determine a suitable duration for a co-current depressurizing equalization step.
[0047] Multiple DEQ p steps may be used in the same PSA cycle. A DEQ p step may be used in the same PSA cycle with one or more DEQ f steps, one or more DEQ d steps, and/or one or more hybrid forms of the various depressurizing equalization steps (each described below).
[0048] As used herein, the term “depressurizing equalization step” is the generic term for the various depressurizing equalization steps, i.e. DEQ p , DEQ f , DEQ d , and hybrid forms thereof.
[0049] Multiple depressurizing equalization steps, in one form or another (i.e. DEQ p , DEQ f , and DEQ d ), may be facilitated by increasing the number of adsorption beds.
[0050] The first co-current depressurizing equalization step is designated herein as DEQ p 1. The second co-current depressurizing equalization step is designated herein as DEQ p 2. The third co-current depressurizing equalization step is designated herein as DEQ p 3. Additional co-current depressurizing equalization steps are similarly designated.
[0051] Co-current depressurizing equalization steps are ubiquitous in pressure swing adsorption processes. Co-current depressurizing equalization steps are shown, for example, as “EQ1DN” and “EQ2DN” in Table 2 of U.S. Pat. No. 7,537,742, incorporated herein by reference. U.S. Pat. No. 7,537,742 illustrates a PSA cycle using two co-current depressurizing equalization steps for a cycle using 4 adsorption beds.
[0052] Table 2 of US 2012/0174776, incorporated herein by reference, discloses a 6 adsorption bed PSA cycle having 3 co-current depressurizing equalization steps shown therein as “E1”, “E2”, and “E3”. US 2012/0174776 also discloses a hybrid depressurizing equalization step shown as “E4/BD1”. Hybrid depressurizing equalization steps are described in more detail later below.
[0053] Additional co-current depressurization equalization steps have the effect of improving recovery of the desired product gas, i.e. hydrogen recovery can be increased by increasing the number of co-current pressure equalization steps. Additional depressurization equalization steps may also help to concentrate the more adsorbable component(s) in the by-product gas (tail gas) stream(s). However, the trade off may be to reduce the productivity of the system, i.e. the total amount of adsorbent required may become larger. More co-current depressurization equalization steps cause the impurities within the bed to advance closer to the product end of the adsorbent bed. This means that the volume of each bed must increase to maintain the desired production at the desired product purity. Each additional co-current depressurizing equalization step usually requires that another adsorption bed be added to the PSA system.
[0054] A co-current depressurization equalization step may be used in addition in any known PSA cycle and/or substituted for any depressurization equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0055] Counter-Current Depressurizing Equalization Step (DEQ f #)
[0056] A counter-current depressurizing (pressure decreasing) equalization step is a depressurizing equalization with equalization gas withdrawn from the feed end and is abbreviated herein by “DEQ f ” or “DEQ f #”, where # is an integer number depending on its arrangement in the PSA cycle and how many depressurizing equalization steps are present in the PSA cycle.
[0057] The counter-current depressurizing equalization step comprises counter-currently (i.e. from the feed end) withdrawing a pressure equalization gas from an adsorption bed undergoing the counter-current depressurizing equalization step, and passing the pressure equalization gas to an adsorption bed undergoing a complementary pressurizing (pressure increasing) equalization step (e.g. PEQ, PEQ f or PEQ d ) or a hybrid pressurizing equalization step thereby equalizing the pressure between the adsorption bed undergoing the counter-current depressurizing equalization step and the adsorption bed undergoing the pressurizing equalization step at the end of the step.
[0058] The duration of any DEQ f steps may be any suitable duration, for example from 1 second to 150 seconds, or from 10 seconds to 150 seconds, while shorter or longer times are possible. The skilled person can readily determine a suitable duration for DEQ f steps.
[0059] Multiple DEQ f steps may be used in the same PSA cycle. A DEQ f step may be used in the same PSA cycle with one or more DEQ p steps, one or more DEQ d steps, and/or one or more hybrid forms of the various DEQ steps (described below). Multiple depressurizing equalization steps, in one form or another (i.e. DEQ p , DEQ f , DEQ d and hybrid forms thereof), may be facilitated by increasing the number of adsorption beds. DEQ f steps may be numbered similarly to the DEQ p steps.
[0060] A DEQ f step is generally less effective at saving product gas (H 2 ) than a DEQ p step. DEQ p steps tend to sharpen the mass transfer zone of impurities within the adsorbent bed because the impurities desorbed from the feed end of the mass transfer zone are brought into contact with available adsorption sites in the mass transfer zone. DEQ f steps tend to spread the mass transfer zone because the impurities at the product end of the mass transfer zone tend to remain in place.
[0061] A counter-current depressurizing equalization step “DEQ f 1” is shown in FIGS. 5 a and 5 b.
[0062] Yoshida et al., Ind. Eng. Chem. Res ., Vol. 45, No. 18, pp. 6243-6250 (2006), incorporated herein by reference, also discloses a counter-current depressurizing equalization step.
[0063] A counter-current depressurization equalization step may be added to any known PSA cycle and/or substituted for any depressurization equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0064] Dual Depressurizing Equalization Step (DEQ d #)
[0065] A dual depressurizing (pressure decreasing) equalization step is a depressurizing equalization step with equalization gas withdrawn from both the feed end and the product end of the bed and is abbreviated herein by “DEQ d ”, or “DEQ d #”, where # is an integer number depending on its arrangement in the PSA cycle and how many depressurizing equalization steps are present in the PSA cycle.
[0066] The dual depressurizing equalization step comprises counter-currently and co-currently withdrawing a pressure equalization gas from an adsorption bed undergoing the dual depressurizing equalization step, and passing the pressure equalization gas to an adsorption bed undergoing a complementary pressurizing (pressure increasing) equalization step (PEQ p , PEQ f , or PEQ d , described below) or hybrid version of a pressurizing equalization step thereby equalizing the pressure between the adsorption bed undergoing the dual depressurizing equalization step and the adsorption bed undergoing the complementary pressurizing equalization step.
[0067] The duration of any DEQ d steps may be any suitable duration, for example from 1 second to 150 seconds, or from 10 seconds to 150 seconds, while shorter or longer times are possible. The skilled person can readily determine a suitable duration for DEQ d steps.
[0068] Multiple DEQ d steps may be used in the same PSA cycle. A DEQ d step may be used in the same PSA cycle with one or more DEQ p steps, one or more DEQ f and/or one or more hybrid forms of the various DEQ steps. Multiple depressurizing equalization steps, in one form or another (i.e. DEQ p , DEQ f , and DEQ d ), may be facilitated by increasing the number of adsorption beds. DEQ d steps may be numbered similarly to the DEQ p steps.
[0069] As disclosed in U.S. Pat. No. 4,783,203, incorporated herein by reference, a dual end depressurization creates a point of zero flow in the adsorbent-containing vessel. If this point of zero flow is advantageously located at the bulk mass transfer front of the controlling impurity, transfer of the less adsorbable gas to the bed receiving the effluent occurs with little or no advancement of the impurity front. Recovery of the less adsorbable gas can increase without requiring an increase in the amount of adsorbent that is required with the DEQ p step. This benefit comes at the cost of additional valves, gas handling, manifolds, and overall system complexity.
[0070] A dual depressurizing equalization step “DEQ d 1” is shown in FIGS. 5 a and 5 b.
[0071] A dual depressurizing equalization step is described in U.S. Pat. No. 4,783,203 as “double-ended depressurization and is also described, for example, in U.S. Pat. No. 8,545,601, incorporated herein by reference, as “two-end equalization depressurization, 2ED” (col. 6, line 43).
[0072] A dual depressurization equalization step may be added to any known PSA cycle and/or substituted for any depressurization equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0073] Parallel Depressurizing Equalization Step (PDEQ#)
[0074] A parallel depressurizing (pressure decreasing) equalization is abbreviated herein as “PDEQ” or “PDEQ#”, where # is an integer number depending on how many depressurizing equalization steps are present in the PSA cycle.
[0075] A parallel depressurizing equalization step comprises transferring gas from the adsorption bed undergoing the parallel depressurizing equalization step from one or more axial positions along the adsorption bed into an adsorption bed undergoing a pressurizing equalization step thereby equalizing the pressure between the adsorption bed undergoing the parallel depressurizing equalization step and the adsorption bed undergoing the pressurizing equalization step at the end of the respective steps. Normally, an adsorption bed undergoing the parallel depressurizing equalization step will be paired with an adsorption bed undergoing a complementary parallel pressurizing equalization step, described below, but could be paired with any pressurizing equalization step.
[0076] The duration of the parallel depressurizing equalization step may be any suitable duration, for example from 1 second to 150 seconds, or from 10 seconds to 150 seconds, while shorter or longer times are possible. The skilled person can readily determine a suitable duration for a parallel depressurizing equalization step.
[0077] Multiple PDEQ steps may be used in the same PSA cycle. A PDEQ step may be used in the same PSA cycle with one or more DEQ p steps, with one or more DEQ f steps, one or more DEQ d steps, and/or one or more hybrid forms of the various DEQ steps (each described below). Multiple depressurizing equalization steps, in one form or another (i.e. DEQ p , DEQ f , DEQ d , and PDEQ), may be facilitated by increasing the number of adsorption beds. PDEQ steps may be numbered similarly to the DEQ p steps. Generally, the PDEQ# step is numbered according to its complementary PPEQ# step, e.g. PDEQ1 with PPEQ1, PDEQ2 with PPEQ2, etc.
[0078] The parallel depressurizing equalization step and parallel pressurizing equalization step are described, for example, in Yoshida et al., Ind. Eng. Chem. Res ., Vol. 45, No. 18, pp. 6243-6250 (2006).
[0079] A parallel depressurizing equalization step and a parallel pressurizing equalization step may be added to any known PSA cycle and/or substituted for any corresponding depressurizing and pressurizing equalization steps in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0080] Counter-Current Pressurizing Equalization STEP (PEQ p #)
[0081] The counter-current pressurizing equalization step has also been termed the “equalization up step” and the “pressure increasing equalization step.” The counter-current pressurizing equalization step is abbreviated herein as “PEQ p ” or “PEQ p #”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0082] A counter-current pressurizing (pressure increasing) equalization step comprises counter-currently introducing the pressure equalization gas from the adsorption bed undergoing a complementary depressurizing (pressure decreasing) equalization step (e.g. DEQ, DEQ f , or DEQ d ) or hybrid version of a depressurizing equalization step into the adsorption bed undergoing the counter-current pressurizing (pressure increasing) equalization step thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization step and the adsorption bed undergoing the counter-current pressurizing equalization step at the end of the respective steps.
[0083] The duration of the counter-current pressurizing equalization step may be any suitable duration, for example from 1 second to 150 seconds, or from 10 seconds to 150 seconds, while shorter or longer times are possible. The skilled person can readily determine a suitable duration for a counter-current pressurizing equalization step.
[0084] Multiple PEQ p steps may be used in the same PSA cycle. A PEQ p step may be used in the same PSA cycle with one or more PEQ f steps, one or more PEQ d steps, and/or one or more hybrid forms of the various PEQ steps (each described below).
[0085] As used herein, the term “pressurizing equalization step” is the generic term for the various pressurizing equalization steps, i.e. PEQ p , PEQ f , PEQ d , and hybrid forms thereof.
[0086] Multiple pressurizing equalization steps, in one form or another (i.e. PEQ p , PEQ f , and PEQ d , including hybrid forms thereof), may be facilitated by increasing the number of adsorption beds. PEQ steps may be numbered similarly to the DEQ p steps. Generally, the PEQ p # step is numbered according to its complementary DEQ# step, e.g. PEQ p 1 with DEQ1, PEQ p 2 with DEQ2, etc.
[0087] Counter-current pressurizing equalization steps are ubiquitous in pressure swing adsorption processes. Counter-current pressurizing equalization steps are shown, for example, as “EQ1UP” and “EQ2UP” in Table 2 of U.S. Pat. No. 7,537,742, which illustrates a PSA cycle using two counter-current pressurizing equalization steps for a cycle using 4 adsorption beds.
[0088] Table 2 of US 2012/0174776, discloses a 6 adsorption bed PSA cycle having 4 counter-current pressurizing equalization steps shown as “E1′”, “E2′, “E3′”, and “E4′”. The E4′ step is complementary to a hybrid depressurizing equalization step, discussed later below.
[0089] A counter-current pressurizing equalization step may be added to any known PSA cycle and/or substituted for any pressurization equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0090] Co-Current Pressurizing Equalization (PEQ f #)
[0091] The co-current pressurizing (pressure increasing) equalization step is abbreviated herein as “PEQ f ” or “PEQ f #”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0092] The co-current pressurizing equalization step comprises co-currently introducing the pressure equalization gas from an adsorption bed undergoing a complementary depressurizing (pressure decreasing) equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid form thereof) into the feed end of the adsorption bed undergoing the co-current pressurizing equalization thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization step and the adsorption bed undergoing the co-current pressurizing equalization step at the end of the respective steps.
[0093] The duration of any PEQ f steps may be any suitable duration, for example from 1 second to 150 seconds, or from 10 seconds to 150 seconds, while shorter or longer times are possible. The skilled person can readily determine a suitable duration for PEQ f steps.
[0094] Multiple PEQ f steps may be used in the same PSA cycle. A PEQ f step may be used in the same PSA cycle with one or more PEQ p steps, one or more PEQ d steps (described below) and/or one or more hybrid forms of the various PEQ steps (described below). Multiple pressurizing equalization steps, in one form or another (i.e. PEQ p , PEQ f , and PEQ d ), may be facilitated by increasing the number of adsorption beds. PEQ f steps may be numbered similarly to the PEQ steps.
[0095] A co-current pressurizing equalization step is shown in FIGS. 4 a and 4 b as “PEQ f 1.”
[0096] A PSA cycle employing co-current pressurizing equalization steps is described, for example in US 2005/0098034, incorporated herein by reference.
[0097] A co-current pressurizing equalization step may be added to any known PSA cycle and/or substituted for any pressurization equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0098] Dual Pressurizing Equalization Step (PEQ d #)
[0099] A dual pressurizing (pressure increasing) equalization step is a pressurizing equalization step with equalization gas introduced into both the feed end and the product end of the bed and is abbreviated herein by “PEQ d ”, or “PEQ d #”, where # is an integer number depending on its arrangement in the PSA cycle and how many pressurizing equalization steps are present in the PSA cycle.
[0100] The dual pressurizing equalization step comprises co-currently and counter-currently introducing a pressure equalization gas from an adsorption bed undergoing a complementary depressurizing (pressure decreasing) equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) into the feed end and the product end of the adsorption bed undergoing the dual pressurizing equalization step thereby equalizing the pressure between the adsorption bed undergoing the complementary depressurizing equalization step and the adsorption bed undergoing the dual pressurizing equalization step at the end of the respective steps.
[0101] The duration of any PEQ d steps may be any suitable duration, for example from 1 second to 150 seconds, or from 10 seconds to 150 seconds, while shorter or longer times are possible. The skilled person can readily determine a suitable duration for PEQ d steps.
[0102] Multiple PEQ d steps may be used in the same PSA cycle. A PEQ d step may be used in the same PSA cycle with one or more PEQ p steps, one or more PEQ f steps (described above) and/or one or more hybrid forms of the various PEQ steps. Multiple pressurizing equalization steps, in one form or another (i.e. PEQ p , PEQ f , and PEQ d ), may be facilitated by increasing the number of adsorption beds. PEQ d steps may be numbered similarly to the PEQ p steps.
[0103] A dual pressurizing equalization step is shown in FIGS. 5 a and 5 b as “PEQ d 1.”
[0104] A dual pressurizing equalization step is also described, for example, in U.S. Pat. No. 8,545,601, as “two-end equalization repressurization, 2ER′” (col. 8 line 22).
[0105] A dual pressurizing equalization step may be added to any known PSA cycle and/or substituted for any pressurization equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0106] Parallel Pressurizing Equalization Step (PPEQ#)
[0107] A parallel pressurizing (pressure increasing) equalization is abbreviated herein as “PPEQ” or “PPEQ#”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0108] A parallel pressurizing equalization step comprises transferring gas from an adsorption bed undergoing a depressurizing equalization step into one or more axial positions along the adsorption bed undergoing the parallel pressurizing equalization step thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization step and the adsorption bed undergoing the parallel pressurizing equalization step at the end of the respective steps. Normally, an adsorption bed undergoing the parallel pressurizing equalization step will be paired with an adsorption bed undergoing a complementary parallel depressurizing equalization step, but could be paired with any depressurizing equalization step.
[0109] The duration of the parallel pressurizing equalization step may be any suitable duration, for example from 1 second to 150 seconds, or from 10 seconds to 150 seconds, while shorter or longer times are possible. The skilled person can readily determine a suitable duration for a parallel pressurizing equalization step.
[0110] Multiple PPEQ steps may be used in the same PSA cycle. A PPEQ step may be used in the same PSA cycle with one or more PEQ p steps, with one or more PEQ f steps, one or more PEQ d steps, and/or one or more hybrid forms of the various PEQ steps (each described below). Multiple pressurizing equalization steps, in one form or another (i.e. PEQ p , PEQ f , PEQ d , and PPEQ), may be facilitated by increasing the number of adsorption beds. PPEQ steps may be numbered similarly to the DEQ steps. Generally, the PPEQ# step is numbered according to its complementary PDEQ# step, e.g. PDEQ1 with PPEQ1, PDEQ2 with PPEQ2, etc.
[0111] A parallel pressurizing equalization step may be added to any known PSA cycle and/or substituted for any pressurization equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0112] Partial Equalization Steps (pPEQ, pDEQ)
[0113] Any of the equalization steps (pressurizing and depressurizing) or hybrid forms thereof may be partial equalization steps. In a partial equalization step, the pressure difference between the adsorption beds that are exchanging gas is greater than 250 kPa (36 psi) at the end of the partial equalization step. The transfer of equalization gas between the adsorption beds is stopped before the pressure is equalized. In H 2 PSA processes halting the transfer of gas between beds prior to complete pressure equalization for PEQ steps will keep the impurities farther from the product end of the column, allowing the system to process more feed gas at the expense of hydrogen recovery.
[0114] Partial equalization is disclosed, for example, in U.S. Pat. No. 6,565,628, incorporated herein by reference.
[0115] Partial equalization steps may be added to any known PSA cycle and/or substituted for any equalization steps in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0116] Compressor-Enhanced Equalization Steps
[0117] Any of the equalization step (pressurizing and depressurizing) or hybrid forms thereof may be compressor-enhanced equalization steps. In compressor-enhanced equalization steps, a compressor is used to assist the movement of gas between adsorption beds, from intermediate storage tanks to adsorption beds, and/or from adsorption beds to intermediate storage tanks. For example, after two adsorption beds have pressure equalized, a compressor could be used to continue the transfer of gas so that that pressure of the adsorption bed receiving the gas can exceed the pressure of the bed supplying the gas.
[0118] Compressor-enhanced equalization steps may be added to any known PSA cycle and/or substituted for any equalization steps in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0119] Supply Purge Gas Step (SPG)
[0120] The supply purge gas step, abbreviated “SPG” herein, has also been termed the “provide purge gas step.”
[0121] The supply purge gas step comprises co-currently withdrawing a purge gas from an adsorption bed undergoing the supply purge gas step, and passing the purge gas from the adsorption bed undergoing the supply purge gas step to an adsorption bed undergoing a purge step (PRG), described below. During a standard supply purge gas step, no gas is introduced into the adsorption bed undergoing the supply purge gas step.
[0122] The purge gas may be stored temporarily in an intermediate storage tank before the purge gas is used to purge the vessel undergoing the purge step. Use of an intermediate storage tank allows for the cycle to be asynchronous and provides flexibility in the duration of the various steps. For example, in U.S. Pat. No. 4,461,630, incorporated herein by reference, a portion or all of the purge gas is stored in a storage vessel prior to use as purge gas.
[0123] The purge gas may be stored temporarily in an intermediate storage tank that is designed to spatially “hold” the exiting impurity profile, and then reverse the profile when used in a purge step. Inversion of the exiting impurity profile adds the purist purge gas at the end of the purge step, ensuring that the adsorbent at the product end of the adsorbent bed is less contaminated by impurities than if the supplied purge gas were sent directly to the adsorbent bed undergoing its purge step. For example, in U.S. Pat. No. 4,512,779, incorporated herein by reference, external tanks are designed and employed within the cycle to reverse the impurity front profile of co-current depressurization gases before use as purge or counter-current equalization repressurization.
[0124] An adsorption bed undergoing a supply purge gas step may supply purge gas to one or more adsorption beds. For example, in U.S. Pat. No. 6,379,431 (EP1486245), incorporated herein by reference, two beds receive purge gas from the bed that is supplying purge gas.
[0125] Supply purge gas steps are ubiquitous in the art. A supply purge gas step is shown in FIGS. 2a, and 2b of US2013/0239807 A1 as “pp.”
[0126] Purge Step (PRG)
[0127] The purge step, abbreviated “PRG” herein, comprises counter-currently introducing the purge gas from the adsorption bed undergoing a complementary supply purge gas step (SPG) or hybrid version thereof (e.g. production/supply purge gas step (P/SPG) described later), into an adsorption bed undergoing the purge step and counter-currently withdrawing a purge gas effluent from the adsorption bed undergoing the purge step. The purge gas effluent has a concentration of the secondary gas components that is higher than the concentration of the secondary gas components in the feed gas mixture. Performing the purge step at as low a pressure as economically possible increases the effectiveness of the step and the overall efficiency of the process.
[0128] A portion of the purge gas effluent may be compressed and used as a rinse gas. The purge gas effluent may be removed from the PSA process as a waste or tail gas stream. The tail gas from a PSA as part of a hydrogen production plant with a steam methane reformer is frequently used as a fuel in the steam methane reformer.
[0129] Purge steps are ubiquitous in the art. A purge step is shown, for example in FIGS. 2a, and 2b of US2013/0239807 A1 as “purge.”
[0130] Counter-Current Blowdown Step (BD f )
[0131] The counter-current blowdown step, abbreviated “BD f ” herein, comprises counter-currently withdrawing a blowdown gas from an adsorption bed undergoing the blowdown step. The blowdown gas has a concentration of the secondary gas components that is higher than the concentration of the secondary gas components in the feed gas mixture. The blowdown gas may be withdrawn from the adsorption bed undergoing the counter-current blowdown step until the pressure in the adsorption bed undergoing the counter-current blowdown step reaches a blowdown pressure ranging from 100 kPa to 500 kPa. The blowdown pressure is the pressure in the adsorption bed at the end of the counter-current blowdown step.
[0132] The counter-current blowdown step is ubiquitous in the art. A counter-current blowdown step is shown in FIGS. 2a and 2b of US2013/0239807 as “bd.”
[0133] Co-Current Blowdown Step (BD p )
[0134] The co-current blowdown step, abbreviated “BD p ” herein, comprises co-current withdrawal of a blowdown gas from the product end of an adsorption bed undergoing the co-current blowdown step. The blowdown gas has a concentration of the secondary gas components that is higher than the concentration of the secondary gas components in the feed gas mixture. The blowdown gas may be withdrawn from the adsorption bed undergoing the co-current blowdown step until the pressure in the adsorption bed undergoing the co-current blowdown step reaches a blowdown pressure ranging from 100 kPa to 500 kPa. The blowdown pressure is the pressure in the adsorption bed at the end of the co-current blowdown step.
[0135] A co-current blowdown step is shown in FIG. 4 a and FIG. 4 b as “BD p .”
[0136] A co-current blowdown step is also described, for example, in U.S. Pat. No. 7,550,030, incorporated herein by reference, as the “fuel” step (cf. FIGS. 2 , 5 , and 6 ).
[0137] Dual Blowdown Step (BD d )
[0138] The dual blowdown step, abbreviated “BD d ” herein, comprises simultaneous counter-current and co-current withdrawal of a blowdown gas from an adsorption bed undergoing the dual blowdown step. The overall blowdown gas (i.e. the combined blowdown gas from the feed end and the product end of the adsorption bed) has a concentration of the secondary gas components that is higher than the concentration of the secondary gas components in the feed gas mixture. The effluent gas withdrawn from the product end of the adsorption bed may not have a concentration of secondary gas components that is higher than the concentration of the secondary gas components in the feed gas mixture. The blowdown gas may be withdrawn from the adsorption bed undergoing the dual blowdown step until the pressure in the adsorption bed undergoing the dual blowdown step reaches a blowdown pressure ranging from 100 kPa to 500 kPa. The blowdown pressure is the pressure in the adsorption bed at the end of the dual blowdown step.
[0139] A dual blowdown step is shown in FIG. 5 a and FIG. 5 b as “BD d.”
[0140] A dual blowdown step is also described, for example, in U.S. Pat. No. 4,783,203, incorporated herein by reference, as “double-end depressurization” which immediately precedes a counter-current purge step (col. 7, lines 26-41).
[0141] The advantage of a dual blowdown step is that the pressure drop during evacuation is reduced.
[0142] As used herein, the term “blowdown step” is the generic term for the various blowdown steps, i.e. B Dp , B Df , B Dd , and hybrid forms thereof. A portion of the blowdown gas may be compressed and used as a rinse gas in the rinse step.
[0143] A counter-current blowdown step may be added to any known PSA cycle and/or substituted for any blowdown step in any known PSA cycle. A co-current blowdown step may be added to any known PSA cycle and/or substituted for any blowdown step in any known PSA cycle. A dual blowdown step may be added to any known PSA cycle and/or substituted for any blowdown step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0144] Evacuation Steps (EV)
[0145] In addition to or in place of the various blowdown steps, the PSA cycle may include one or more evacuation steps. Evacuation steps are similar to the various blowdown steps or hybrid forms thereof, with the addition of using a compressor, vacuum pump, or the like, to draw the pressure down below atmospheric pressure. The pressure of the purge step may be lowered using a compressor, vacuum pump or the like. When multiple adsorption beds undergo evacuation steps at the same time but starting at different time and multistage vacuum equipment is used, it will be economically favorable to direct the effluent from the adsorption bed at the lowest to the first stage of the compressor and combine the effluent of the first stage of the compressor with the effluent of an adsorption bed at a higher pressure.
[0146] Evacuation from both ends of the adsorption bed (i.e. dual evacuation), has the advantage of reduced pressure drop during evacuation. In case of using a vacuum pump to assist with evacuation, a dual evacuation step reduces the size and cost of the vacuum pump and pumping power required compared to co-current and counter-current evacuation.
[0147] An evacuation step may be added to any known PSA cycle and/or substituted for any of the blowdown steps. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0148] Rinse Step (R)
[0149] The rinse step is abbreviated “R”. The rinse step comprises co-currently introducing a rinse gas into an adsorption bed undergoing the rinse step while simultaneously co-currently withdrawing a rinse gas effluent from the adsorption bed undergoing the rinse step. The rinse gas effluent, or portion thereof, may be combined with the product gas. The rinse gas effluent, or portion thereof, may be used to pressurize another adsorption bed. The rinse gas may be formed by compressing at least a portion of at least one of the blowdown gas from the adsorption bed undergoing a blowdown step and/or at least a portion of the purge gas effluent from the adsorption bed undergoing a purge step. A compressor compresses the blowdown gas and/or purge gas effluent to form the rinse gas. During a rinse step, the more strongly adsorbed components displace the less strongly adsorbed components from the adsorbent and void spaces, providing a means to increase the recovery of the less strongly adsorbed components.
[0150] The rinse gas may be formed from a portion of the blowdown gas and none of the purge gas effluent, all of the blowdown gas and none of the purge gas effluent, a portion of the blowdown gas and a portion of the purge gas effluent, all of the blowdown gas and a portion of the purge gas effluent, none of the blowdown gas and a portion of the purge gas effluent, or none of the blowdown gas and all of the purge gas effluent. The rinse gas may be passed directly to the adsorption bed undergoing the rinse step or stored temporarily in an intermediate storage tank before being passed to the adsorption bed undergoing the rinse step.
[0151] When the repetitive cycle includes a rinse step, any of the repressurization steps may further comprise counter-currently introducing at least a portion of the rinse gas effluent from the adsorption bed undergoing the rinse step into the adsorption bed undergoing the repressurization step. In addition or alternatively, at least a portion of the rinse gas effluent may be co-currently or counter-currently introduced into an adsorption bed undergoing a pressurizing equalization step or counter-currently introduced into an adsorption bed undergoing a purge step.
[0152] The rinse gas may also come from a source of gas that does not come from the PSA process itself. A secondary gas supply stream, preferably leaner in H 2 than the feed gas mixture, can be used advantageously as the rinse gas.
[0153] A rinse step is shown in FIGS. 4a and 4b of US2013/0239807 as “rinse.”
[0154] Idle Step (I)
[0155] As the name suggests, in the idle step, abbreviated “I”, the adsorption bed is idle and no gases flow into or out of the adsorption bed.
[0156] An idle step is shown in FIGS. 11a and 11b of US2013/0239807 as “idle.”
[0157] An idle step may be added to any known PSA cycle.
[0158] Counter-Current Product Pressurization Step (PP p )
[0159] The counter-current product pressurization step, abbreviated “PP p ”, comprises counter-currently introducing product gas into the bed to pressurize the vessel. Product gas may be introduced into the adsorption bed undergoing the counter-current product pressurization step until the adsorption bed undergoing the counter-current product pressurization step is substantially at the feed gas pressure. “Substantially at the feed gas pressure” means within 10% of the feed gas pressure.
[0160] A counter-current product pressurization step is shown in FIGS. 2a and 2b of US2013/0239807 as “repr.” Product gas 103 is introduced (excluding the optional introduction of feed gas 81 ) into the adsorption bed undergoing the “repr” step.
[0161] Co-Current Product Pressurization Step (PP f )
[0162] The co-current product pressurization step, abbreviated “PP f ” comprises co-currently introducing product gas into the feed end of the bed to pressurize the vessel. Product gas may be introduced into the adsorption bed undergoing the co-current product pressurization step until the adsorption bed undergoing the co-current product pressurization step is substantially at the feed gas pressure.
[0163] A co-current product pressurization step is shown in FIG. 5 a and FIG. 5 b as “PP f .”
[0164] Dual Product Pressurization Step (PP d )
[0165] The dual product pressurization step, abbreviated “PP d ” comprises co-currently and counter-currently introducing product gas into the adsorption bed to pressurize the vessel. Product gas may be introduced into the adsorption bed undergoing the dual product pressurization step until the adsorption bed undergoing the dual product pressurization step is substantially at the feed gas pressure.
[0166] A dual product pressurization step is shown in FIG. 4 a and FIG. 4 b as “PP d .”
[0167] As used herein, the term “product pressurization step” is the generic term for the various product pressurization steps, i.e. PP p , PP f , PP d , and hybrid forms thereof.
[0168] Co-Current Feed Pressurization Step (FP f )
[0169] The co-current feed pressurization step, abbreviated “FP f ” comprises co-currently introducing feed gas into the adsorption bed to pressurize the vessel. Feed gas may be introduced into the adsorption bed undergoing the co-current feed pressurization step until the adsorption bed undergoing the co-current feed pressurization step is substantially at the feed gas pressure.
[0170] Co-current feed gas pressurization is disclosed, for example, in paragraph [0050] of US 2003/0015091, incorporated herein by reference, where it discloses that the repressurization step proceeds by introducing pressurized feed gas into the feed end of the bed, introducing product gas into the product end of the bed, or by simultaneously introducing pressurized feed gas into the feed end of the bed and introducing product gas into the product end of the bed.
[0171] A feed pressurization step is also disclosed, for example, in U.S. Pat. No. 5,082,474, incorporated herein by reference.
[0172] Counter-Current Feed Pressurization Step (FP p )
[0173] The counter-current feed pressurization step, abbreviated “FP p ” comprises counter-currently introducing feed gas into the adsorption bed to pressurize the vessel. Feed gas may be introduced into the adsorption bed undergoing the feed pressurization step until the adsorption bed undergoing the counter-current feed pressurization step is substantially at the feed gas pressure.
[0174] A counter-current feed pressurization step is disclosed, for example, in U.S. Pat. No. 5,232,473, incorporated herein by reference.
[0175] As used herein, the term “feed pressurization step” is the generic term for the various feed pressurization steps, i.e. FP p , FP f , and hybrid forms thereof.
[0176] Rinse Gas Effluent Pressurization Step (REP)
[0177] The rinse gas effluent pressurization step, abbreviated “REP” comprises counter-currently introducing rinse gas effluent (i.e. effluent from adsorption bed undergoing the rinse step) into the adsorption bed undergoing the rinse gas effluent pressurization step to pressurize the vessel. Rinse gas effluent may be introduced into the adsorption bed undergoing the rinse gas effluent pressurization step until the adsorption bed undergoing the rinse gas effluent pressurization step is substantially at the feed gas pressure.
[0178] A rinse gas effluent pressurization step is shown in FIGS. 4a, 4b, 11a and 11b of US2013/0239807 as “repr,” but without the optional feed gas pressurization. The rinse gas effluent 92 from the adsorption bed on the rinse step is divided, where a portion of the rinse gas effluent is passed to the bed undergoing the rinse gas effluent pressurization step and another portion is combined with product gas 103 from an adsorption bed on the production step.
[0179] As used herein, the term “repressurization step” is the generic term that includes the various product pressurization steps, i.e. PP p , PP f , PP d , and hybrid forms thereof, the various feed pressurization steps, i.e. FP p , FP f , and hybrid forms thereof, and the rinse gas effluent pressurization step and hybrid forms thereof.
[0180] Any of the various feed pressurization steps, product pressurization steps and rinse gas effluent pressurization step may be added to any known PSA cycle and/or substituted for any repressurization step in any known PSA cycle, if desired. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0181] Hybrid Steps
[0182] Many of the basic PSA cycle steps may be combined with others to form hybrid steps as described below. The concurrent combination of PSA cycles steps can allow the process to be completed with fewer adsorption beds often with a small or no impact on the efficiency of the process.
[0183] Depressurizing Equalization/Rinse Step (DEQ/R)
[0184] Depressurizing equalization may be combined with rinse in a hybrid depressurizing equalization/rinse step, abbreviated “DEQ/R” or “DEQ#/R”, where # is an integer number depending on how many depressurizing equalization steps are present in the PSA cycle.
[0185] The depressurizing equalization/rinse step comprises co-currently introducing rinse gas simultaneous with co-currently withdrawing a pressure equalization gas from an adsorption bed undergoing the depressurizing equalization/rinse step, and passing the pressure equalization gas to an adsorption bed undergoing a complementary pressurizing (pressure increasing) equalization step (e.g. PEQ, PEQ f or PEQ d ) or a hybrid step thereof, thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization/rinse step and the adsorption bed undergoing the complementary pressurizing equalization step (PEQ, PEQ f or PEQ d including hybrid forms thereof).
[0186] The characteristics and options disclosed for the depressurizing equalization step and the characteristics and options disclosed for the rinse step apply to the hybrid depressurizing equalization/rinse step.
[0187] A depressurizing equalization/rinse step is shown in FIGS. 2a and 2b of US2013/0239807 as “eq1d.” Rinse gas 91 is introduced into the adsorption bed undergoing the “eq1d” step while equalization gas 83 is simultaneously withdrawn and equalized with the adsorption bed undergoing the pressurizing equalization step “eq1r.”
[0188] A depressurizing equalization/rinse step is also shown in FIGS. 6 a and 6 b as DEQ p 1/R.
[0189] A depressurizing equalization/rinse step may be added to any known PSA cycle and/or substituted for any depressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0190] Production/Rinse (P/R)
[0191] Production may be combined with rinse in a hybrid production/rinse step, abbreviated “P/R.”
[0192] The production/rinse step comprises simultaneously introducing a feed gas mixture and rinse gas into the adsorption bed undergoing the production/rinse step while simultaneously withdrawing a product gas from the adsorption bed undergoing the production/rinse step.
[0193] The characteristics and options disclosed for the production step and the characteristics and options disclosed for the rinse step apply to the hybrid production/rinse step.
[0194] A production/rinse step “P/R” is shown in FIGS. 6 a and 6 b.
[0195] A production/rinse step may be added to any known PSA cycle and/or substituted for any production step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0196] A production/rinse step is shown in FIG. 5b of US2013/0239807 as “rinse.” Rinse gas effluent 91 is combined with the effluent of an adsorbent bed undergoing the production step (“feed”), a portion of the effluent 91 exits the system as product (stream 103 ), and a portion is combined for counter-current repressurization of another adsorbent bed (“repr”).
[0197] Production/Supply Product Step (P/SP)
[0198] Production may be combined with supplying product to another bed in a hybrid production/supply product step, abbreviated “P/SP.”
[0199] In a production/supply product step, a portion of the product gas withdrawn from adsorption bed undergoing the production/supply product step is passed to an adsorption bed undergoing a product pressurization step or a hybrid product pressurization step.
[0200] The characteristics and options disclosed for the production step apply to the hybrid production/supply product step.
[0201] A production/supply product step is shown in FIGS. 2a and 2b of US2013/0239807 as “feed.” A portion of the product gas withdrawn from the adsorption bed undergoing the “feed” step is passed to the adsorption bed undergoing the product pressurization step “repr” thereby pressurizing the adsorption bed with product gas.
[0202] Production while supplying product to another adsorption bed for product pressurization is also disclosed, for example, as A2/PP1 and A3/PP2 in Table 2 of US 2012/0174776, incorporated herein by reference.
[0203] A production/supply product step “P/SP” is shown in FIGS. 2 a , 2 b , 4 a , 4 b , 5 a , and 5 b.
[0204] A production/supply product step may be added to any known PSA cycle and/or substituted for any production step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0205] Production/Rinse/Supply Product Step (P/R/SP)
[0206] Production may be combined with rinse and supply product in a hybrid production/rinse/supply product step, abbreviated “P/R/SP.”
[0207] The production/rinse/supply product step comprises simultaneously introducing a feed gas mixture and rinse gas into the adsorption bed undergoing the production/rinse step while simultaneously withdrawing a product gas from the adsorption bed undergoing the production/rinse step. A portion of the product gas withdrawn from adsorption bed undergoing the production/rinse/supply product step is passed to an adsorption bed undergoing a product pressurization step or a hybrid product pressurization step.
[0208] The characteristics and options disclosed for the production step and the characteristics and options disclosed for the rinse step apply to the hybrid production/rinse step.
[0209] A production/rinse/supply product step “P/R/SP” is shown in FIGS. 7 a and 7 b.
[0210] Simultaneous production/rinse with supply product is disclosed, for example, in FIG. 1 and col. 1, lines 1-6 of U.S. Pat. No. 5,254,154, incorporated herein by reference.
[0211] A production/rinse/supply product step may be added to any known PSA cycle and/or substituted for any production step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0212] Production/Supply Purge Gas Step (P/SPG)
[0213] Production may be combined with supplying purge gas to another bed in a hybrid production/supply purge gas step, abbreviated “P/SPG.”
[0214] In a production/supply purge gas step, a portion of the product gas withdrawn from adsorption bed undergoing the production/supply purge gas step is passed to an adsorption bed undergoing a purge step or a hybrid purge step.
[0215] An advantage of a production/supply purge gas step is that a separate supply purge gas step can be avoided. For a given number of adsorption beds, this may provide the opportunity to increase the number of equalization steps. Compared to a supply purge gas step (SPG), a production/supply purge step uses a gas containing a higher concentration of the less strongly adsorbed component as the purge gas, which in turn can decrease the recovery of the less strongly adsorbed component.
[0216] The production/supply purge gas step may be part of a PSA cycle with production steps at multiple pressure levels. The production/supply purge gas step may be combined with any of the multiple pressure level production steps in a hybrid step. The supply purge gas step may be conveniently combined with a lower pressure production step in a hybrid low pressure production/supply purge gas step. The production/supply gas purge step may precede, occur concurrently with, or follow the supply purge gas step (SPG).
[0217] The characteristics and options disclosed for the production step and supply purge gas step apply to the hybrid production/supply purge gas step.
[0218] Production while supplying product to another adsorption bed undergoing a purge step is disclosed, for example, in FIG. 7 and paragraph [0060] of US2005/0268780, incorporated herein by reference.
[0219] A production/supply purge gas step may be added to any known PSA cycle and/or substituted for any production step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0220] Supply Purge Gas/Feed Step (SPG/F)
[0221] Supplying purge gas may be combined with introduction of feed gas in a hybrid supply purge gas/feed step, abbreviated as SPG/F.
[0222] A supply purge gas/feed step comprises co-current withdrawal of purge gas to supply purge gas to another vessel undergoing the purge step (PRG) with contemporaneous co-current introduction of feed gas into the bed. The feed gas may be introduced into the bed undergoing the supply purge gas/feed step at a lower pressure than the feed gas is introduced into the bed undergoing the production step.
[0223] The supply purge gas/feed step (SPG/F) is distinguished from the production/supply purge gas step (P/SPG) in that the production/supply purge gas step, only a portion of the product gas is passed to a bed undergoing the purge step whereas in the supply purge gas/feed step, all of the effluent from the adsorption bed is passed to a bed undergoing the purge step.
[0224] A supply purge gas/feed step may be added to any known PSA cycle and/or substituted for any supply purge gas step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0225] Supply Purge Gas/Rinse Step (SPG/R)
[0226] Supplying purge gas may be combined with rinse in a hybrid supply purge gas/rinse step, abbreviated as “SPG/R.”
[0227] A supply purge gas/rinse step comprises co-current withdrawal of gas to supply purge gas to another vessel undergoing the purge step (PRG) with contemporaneous co-current introduction of rinse gas.
[0228] The characteristics and options disclosed for the supply purge gas and the rinse step apply to the hybrid supply purge gas/rinse step.
[0229] A supply purge gas/rinse step is shown in FIG. 2b of US 2013/0239807 as “pp” where the optional introduction of rinse gas is included.
[0230] A supply purge gas/rinse step may be added to any known PSA cycle and/or substituted for any supply purge gas step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0231] Counter-Current Pressurizing Equalization/Feed Pressurization Step (PEQ p /FP)
[0232] Counter-current pressurizing equalization may be combined with feed pressurization in a hybrid counter-current pressurizing equalization/feed pressurization step, abbreviated “PEQ p /FP” or “PEQ p #/FP”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0233] A counter-current pressurizing equalization/feed pressurization step comprises simultaneous co-current introduction of feed gas and counter-current introduction of pressure equalization gas from an adsorption bed undergoing a complementary depressurizing (pressure decreasing) equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization step and the adsorption bed undergoing the counter-current pressurizing equalization/feed pressurization step at the end of the respective steps.
[0234] The characteristics and options disclosed for the counter-current pressurizing equalization step and the feed pressurization step apply to the hybrid counter-current pressurizing equalization/feed pressurization step.
[0235] A counter-current pressurizing equalization/feed pressurization step is shown in FIGS. 2a and 2b of US2013/0239807 as “eq1r” when the optional introduction of feed gas 81 is included and optional introduction of product gas 103 is excluded.
[0236] A counter-current pressurizing equalization/feed pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0237] Co-Current Pressurizing Equalization/Feed Pressurization Step (PEQ f /FP)
[0238] The co-current pressurizing equalization step may be combined with feed pressurization in a hybrid co-current pressurizing equalization/feed pressurization step, abbreviated herein as “PEQ f /FP” or “PEQ f #/FP”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0239] The co-current pressurizing equalization step comprises simultaneous co-current introduction of feed gas and co-current introduction of a pressure equalization gas from an adsorption bed undergoing a complementary depressurizing (pressure decreasing) equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization step and the adsorption bed undergoing the co-current pressurizing equalization/feed pressurization step at the end of the respective steps.
[0240] The characteristics and options disclosed for the co-current pressurizing equalization step and the feed pressurization step apply to the hybrid co-current pressurizing equalization/feed pressurization step.
[0241] A co-current pressurizing equalization/feed pressurization step is shown in FIG. 8 a and FIG. 8 b as “PEQ f 1/FP.” Equalization gas 83 from the bed undergoing a depressurizing equalization and feed gas 81 are both co-currently introduced the adsorption bed undergoing the co-current pressurizing equalization/feed pressurization step.
[0242] A co-current pressurizing equalization/feed pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0243] Dual Pressurizing Equalization/Feed Pressurization Step (PEQ d /FP)
[0244] The dual pressurizing equalization step may be combined with feed pressurization in a hybrid dual pressurizing equalization/feed pressurization step, abbreviated herein as “PEQ d /FP” or “PEQ d #/FP”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0245] The dual pressurizing equalization/feed pressurization step comprises co-current introduction of feed gas and co-current and counter-current introduction of a pressure equalization gas from an adsorption bed undergoing a complementary depressurizing equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) thereby equalizing the pressure between the adsorption bed undergoing the complementary depressurizing equalization step and the adsorption bed undergoing the dual pressurizing equalization step at the end of the respective steps.
[0246] The characteristics and options disclosed for the dual equalization step and the feed pressurization step apply to the hybrid dual pressurizing equalization/feed pressurization step.
[0247] A dual pressurizing equalization/feed pressurization step is shown in FIGS. 9 a and 9 b as PEQ d 1/FP. Feed gas 81 is introduced co-currently and equalization gas 83 from the bed undergoing a dual depressurizing equalization is introduced both co-currently and counter-currently into the bed undergoing the dual pressurizing equalization/feed pressurization step.
[0248] A dual pressurizing equalization/feed pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0249] Counter-Current Pressurizing Equalization/Product Pressurization Step (PEQ p /PP)
[0250] Counter-current pressurizing equalization may be combined with product pressurization in a hybrid pressurizing equalization/product pressurization step, abbreviated “PEQ p /PP” or “PEQ p #/PP”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0251] A counter-current pressurizing equalization/product pressurization step comprises simultaneous counter-current introduction of product gas and counter-current introduction of pressure equalization gas from an adsorption bed undergoing a complementary depressurizing equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization step and the adsorption bed undergoing the counter-current pressurizing equalization/product pressurization step at the end of the respective steps.
[0252] The characteristics and options disclosed for the pressurizing equalization step and the product pressurization step apply to the hybrid pressurizing equalization/product pressurization step.
[0253] A counter-current pressurizing equalization/product pressurization step is shown in FIGS. 2a and 2b of US2013/0239807 as “eq1r” when the optional introduction of product gas 103 is included and optional introduction of feed gas 81 is excluded.
[0254] A counter-current pressurizing equalization/product pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0255] Co-Current Pressurizing Equalization/Product Pressurization Step (PEQ f /PP)
[0256] Co-current pressurizing equalization may be combined with product pressurization in a hybrid co-current pressurizing equalization/product pressurization step, abbreviated herein as “PEQ f /PP” or “PEQ f #/PP”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0257] A co-current pressurizing equalization/product pressurization step comprises simultaneous counter-current introduction of product gas and co-current introduction of pressure equalization gas from an adsorption bed undergoing a complementary depressurizing equalization step (e.g. DEQ, DEQ f , or DEQ d or hybridized version thereof) thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization step and the adsorption bed undergoing the co-current pressurizing equalization step at the end of the respective steps.
[0258] The characteristics and options disclosed for the co-current pressurizing equalization step and the product pressurization step apply to the hybrid co-current pressurizing equalization/product pressurization step.
[0259] A co-current pressurizing equalization/product pressurization step is shown in FIGS. 10 a and 10 b as PEQ f 1/PP, where product gas 103 is counter-currently introduced and pressure equalization gas 83 is co-currently introduced into the adsorption bed undergoing the co-current pressurizing equalization/product pressurization step.
[0260] A co-current pressurizing equalization/product pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0261] Dual Pressurizing Equalization/Product Pressurization Step (PEQ d /PP)
[0262] Dual pressurizing equalization may be combined with product pressurization in a hybrid dual pressurizing equalization/product pressurization step, abbreviated as “PEQ d /PP” or “PEQ d #/PP”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0263] A dual pressurizing equalization/product pressurization step comprises simultaneous counter-current introduction of product gas and co-current and counter-current introduction of a pressure equalization gas from an adsorption bed undergoing a complementary depressurizing equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) thereby equalizing the pressure between the adsorption bed undergoing the complementary depressurizing equalization step and the adsorption bed undergoing the dual pressurizing equalization/product pressurization step at the end of the respective steps.
[0264] The characteristics and options disclosed for the dual equalization step and the product pressurization step apply to the hybrid dual pressurizing equalization/feed pressurization step.
[0265] A dual pressurizing equalization/product pressurization step is shown in FIGS. 11 a and 11 b as PEQ d 1/PP. Product gas 103 is introduced counter-currently and equalization gas 83 from the bed undergoing a dual depressurizing equalization is introduced both co-currently and counter-currently into the bed undergoing a dual pressurizing equalization/product pressurization step.
[0266] A dual pressurizing equalization/product pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0267] Counter-Current Pressurizing Equalization/Product Pressurization/Feed Pressurization Step (PEQ 2 /PP/FP)
[0268] Counter-current pressurizing equalization may be combined with product pressurization and feed pressurization in a hybrid counter-current pressurizing equalization/product pressurization/feed pressurization step, abbreviated as PEQ p /PP/FP or PEQ p #/PP/FP, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0269] A counter-current pressurizing equalization/product pressurization/feed pressurization step comprises simultaneous co-current introduction of feed gas, counter-current introduction of product gas, and counter-current introduction of pressure equalization gas from an adsorption bed undergoing a complementary depressurizing equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization step and the adsorption bed undergoing the counter-current pressurizing equalization/product pressurization/feed pressurization step at the end of the respective steps.
[0270] The characteristics and options disclosed for the counter-current pressurizing equalization step, the product pressurization step, and feed pressurization step apply to the hybrid counter-current pressurizing equalization/product pressurization step.
[0271] A counter-current pressurizing equalization/product pressurization/feed pressurization step is shown in FIGS. 2a and 2b of US2013/0239807 as “eq1r” when the optional introduction of product gas 103 and optional introduction of feed gas 81 are included. Paragraph [0116] of US2013/0239807 discloses that the first pressure increasing equalization step may further comprise co-currently introducing the feed gas mixture and/or counter-currently introducing product gas into the adsorption bed undergoing the first pressure increasing equalization step simultaneous with the counter-current introduction of the pressure equalization gas from the adsorption bed undergoing the first pressure decreasing equalization step.
[0272] A counter-current pressurizing equalization/product pressurization/feed pressurization step is also disclosed in US 2003/0015091 as “1′/R”, for example in FIG. 1 and as described in paragraphs [0050] and [0056]. In paragraphs [0056] US 2003/0015091 discloses that 1′/R is the optional combined step of pressure equalization at increasing pressure and repressurization. In paragraph [0050], US 2003/0015091 discloses that the repressurization step proceeds by introducing pressurized feed gas into the feed end of the bed, introducing product gas into the product end of the bed, or by simultaneously introducing pressurized feed gas into the feed end of the bed and introducing product gas into the product end of the bed.
[0273] A counter-current pressurizing equalization/product pressurization/feed pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0274] Co-Current Pressurizing Equalization/Product Pressurization/Feed Pressurization Step (PEQ f /PP/FP)
[0275] Co-current pressurizing equalization may be combined with product pressurization and feed pressurization in a hybrid co-current pressurizing equalization/product pressurization/feed pressurization step, abbreviated as “PEQ f /PP/FP” or “PEQ f #/PP/FP,” where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0276] A co-current pressurizing equalization/product pressurization/feed pressurization step comprises simultaneous co-current introduction of feed gas, counter-current introduction of product gas, and co-current introduction of pressure equalization gas from an adsorption bed undergoing a complementary depressurizing equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization step and the adsorption bed undergoing the co-current pressurizing equalization/product pressurization/feed pressurization step at the end of the respective steps.
[0277] The characteristics and options disclosed for the pressurizing equalization step, the product pressurization step, and feed pressurization step apply to the hybrid pressurizing equalization/product pressurization step.
[0278] A co-current pressurizing equalization/product pressurization/feed pressurization step is shown in FIGS. 12 a and 12 b as PEQ f 1/PP/FP. Product gas 103 is introduced counter-currently and both feed gas and equalization gas 83 from the bed undergoing a counter-current depressurizing equalization is introduced co-currently into the bed undergoing a co-current pressurizing equalization/product pressurization/feed pressurization step.
[0279] A co-current pressurizing equalization/product pressurization/feed pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0280] Dual Pressurizing Equalization/Product Pressurization/Feed Pressurization Step (PEQ d /PP/FP)
[0281] Dual pressurizing equalization may be combined with product pressurization and feed pressurization in a hybrid dual pressurizing equalization/product pressurization/feed pressurization step, abbreviated as “PEQ d /PP/FP” or “PEQ d #/PP/FP”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0282] A dual pressurizing equalization/product pressurization/feed pressurization step comprises simultaneous counter-current introduction of product gas, co-current introduction of feed gas, and co-current and counter-current introduction of a pressure equalization gas from an adsorption bed undergoing a complementary depressurizing equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) thereby equalizing the pressure between the adsorption bed undergoing the complementary depressurizing equalization step and the adsorption bed undergoing the dual pressurizing equalization/product pressurization/feed pressurization step at the end of the respective steps.
[0283] The characteristics and options disclosed for the dual equalization step and the product pressurization step apply to the hybrid dual pressurizing equalization/feed pressurization step.
[0284] A dual pressurizing equalization/product pressurization/feed pressurization step is shown in FIGS. 13 a and 13 b as PEQ d 1/PP/FP. Product gas 103 is introduced counter-currently, feed gas is introduced co-currently, and equalization gas 83 from the bed undergoing a dual depressurizing equalization is introduced both co-currently and counter-currently into the bed undergoing a dual pressurizing equalization/product pressurization step.
[0285] A dual pressurizing equalization/product pressurization/feed pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
Pressurizing Equalization/Rinse Gas Effluent Pressurization Step (PEQ/REP)
[0286] Pressurizing equalization may be combined with rinse gas effluent pressurization in a hybrid pressurizing equalization/rinse gas effluent pressurization step, abbreviated “PEQ/REP” or “PEQ#/REP”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0287] A pressurizing equalization/rinse gas effluent pressurization step comprises simultaneous counter-current introduction of rinse gas effluent from an adsorption bed undergoing a rinse step and counter-current introduction of pressure equalization gas from an adsorption bed undergoing a complementary depressurizing equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization step and the adsorption bed undergoing the pressurizing equalization/rinse gas effluent pressurization step at the end of the respective steps.
[0288] The characteristics and options disclosed for the pressurizing equalization step and the rinse gas effluent pressurization step apply to the hybrid pressurizing equalization/rinse gas effluent pressurization step.
[0289] The pressurizing equalization/rinse gas effluent pressurization step is a variant shown in FIGS. 15a and 15b of US2013/0239807 where the bed on “eq1r” is pressurized with pressure equalization gas from the bed on eq1d along with rinse gas effluent 92 (but without introduction of the optional feed gas 81 ). The rinse gas effluent 92 from the adsorption bed on the rinse step is divided, where a portion of the rinse gas effluent is passed to the bed undergoing the rinse gas effluent pressurization step and another portion is combined with product gas 103 from an adsorption bed on the production step.
[0290] A pressurizing equalization/rinse gas effluent pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0291] Counter-Current Pressurizing Equalization/Rinse Gas Effluent Pressurization/Feed Pressurization Step (PEQ p /REP/FP)
[0292] Counter-current pressurizing equalization may be combined with rinse gas effluent pressurization and feed pressurization in a hybrid counter-current pressurizing equalization/rinse gas effluent pressurization/feed pressurization step, abbreviated “PEQ p /REP/FP” or “PEQ p #/REP/FP”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0293] A counter-current pressurizing equalization/rinse gas effluent pressurization/feed pressurization step comprises simultaneous co-current introduction of feed gas, counter-current introduction of rinse gas effluent from an adsorption bed undergoing a rinse step, and counter-current introduction of pressure equalization gas from an adsorption bed undergoing a complementary depressurizing equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization step and the adsorption bed undergoing the pressurizing equalization/rinse gas effluent pressurization step at the end of the respective steps.
[0294] The characteristics and options disclosed for the counter-current pressurizing equalization step, the rinse gas effluent pressurization step, and feed pressurization step apply to the hybrid counter-current pressurizing equalization/rinse gas effluent pressurization/feed pressurization step.
[0295] The counter-current pressurizing equalization/rinse gas effluent pressurization/feed pressurization step is a variant shown in FIGS. 15a and 15b of US2013/0239807 where the bed on “eq1r” is pressurized with pressure equalization gas from the bed on eq1d along with rinse gas effluent 92 , and with introduction of the optional feed gas 81 . The rinse gas effluent 92 from the adsorption bed on the rinse step may be divided, where a portion of the rinse gas effluent is passed to the bed undergoing the rinse gas effluent pressurization step and another portion is combined with product gas 103 from an adsorption bed on the production step.
[0296] A counter-current pressurizing equalization/rinse gas effluent pressurization/feed pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0297] Co-Current Pressurizing Equalization/Rinse Gas Effluent Pressurization/Feed Pressurization Step (PEQ f /REP/FP)
[0298] Co-current pressurizing equalization may be combined with rinse gas effluent pressurization and feed pressurization in a hybrid co-current pressurizing equalization/rinse gas effluent pressurization/feed pressurization step, abbreviated as “PEQ f /REP/FP” or “PEQ f #/REP/FP,” where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0299] A co-current pressurizing equalization/rinse gas effluent pressurization/feed pressurization step comprises simultaneous co-current introduction of feed gas, counter-current introduction of rinse gas effluent gas from an adsorption bed undergoing a rinse step, and co-current introduction of pressure equalization gas from an adsorption bed undergoing a complementary depressurizing equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization step and the adsorption bed undergoing the co-current pressurizing equalization/product pressurization/feed pressurization step at the end of the respective steps.
[0300] The characteristics and options disclosed for the pressurizing equalization step, the rinse gas effluent pressurization step, and feed pressurization step apply to the hybrid co-current pressurizing equalization/rinse gas effluent pressurization/feed pressurization step.
[0301] A co-current pressurizing equalization/rinse gas effluent pressurization/feed pressurization step is shown in FIGS. 14 a and 14 b as PEW/REP/FP. Rinse gas effluent 92 is introduced counter-currently and both feed gas 81 and equalization gas 83 from the bed undergoing a hybrid counter-current depressurizing equalization DEQ1/R is introduced co-currently into the bed undergoing a co-current pressurizing equalization/rinse gas effluent pressurization/feed pressurization step.
[0302] A co-current pressurizing equalization/rinse gas effluent pressurization/feed pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0303] Dual Pressurizing Equalization/Rinse Gas Effluent Pressurization/Feed Pressurization Step (PEQ d /REP/FP)
[0304] Dual pressurizing equalization may be combined with rinse gas effluent pressurization and feed pressurization in a hybrid dual pressurizing equalization/rinse gas effluent pressurization/feed pressurization step, abbreviated as “PEQ d /REP/FP” or “PEQ d #/REP/FP”, where # is an integer number depending on how many pressurizing equalization steps are present in the PSA cycle.
[0305] A dual pressurizing equalization/rinse gas effluent pressurization/feed pressurization step comprises simultaneous counter-current introduction of rinse gas effluent gas, co-current introduction of feed gas, and co-current and counter-current introduction of a pressure equalization gas from an adsorption bed undergoing a complementary depressurizing equalization step (e.g. DEQ, DEQ f , or DEQ d or hybrid version thereof) thereby equalizing the pressure between the adsorption bed undergoing the complementary depressurizing equalization step and the adsorption bed undergoing the dual pressurizing equalization/product pressurization/feed pressurization step at the end of the respective steps.
[0306] The characteristics and options disclosed for the dual equalization step and the rinse gas effluent pressurization step apply to the hybrid dual pressurizing equalization/feed pressurization step.
[0307] A dual pressurizing equalization/rinse gas effluent pressurization/feed pressurization step is shown in FIGS. 15 a and 15 b as PEQ d 1/REP/FP. Rinse gas effluent gas 92 is introduced counter-currently, feed gas is introduced co-currently, and equalization gas 83 from the bed undergoing a hybrid depressurizing equalization DEQ1/R is introduced both co-currently and counter-currently into the bed undergoing a dual pressurizing equalization/rinse gas effluent pressurization/feed pressurization step.
[0308] A dual pressurizing equalization/rinse gas effluent pressurization/feed pressurization step may be added to any known PSA cycle and/or substituted for any pressurizing equalization in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0309] Product Pressurization/Feed Pressurization Step (PP/FP)
[0310] Product pressurization may be combined with feed pressurization in a hybrid product pressurization/feed pressurization step, abbreviated as “PP/FP.” The hybrid product pressurization/feed pressurization step may be added to any known PSA cycle and/or substituted for any product pressurization or feed pressurization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0311] A product pressurization/feed pressurization step comprises counter-current introduction of product gas with contemporaneous co-current introduction of feed gas.
[0312] The characteristics and options disclosed for the product pressurization step and the feed pressurization step apply to the hybrid product pressurization/feed pressurization step.
[0313] A product pressurization/feed pressurization step is shown in FIGS. 2a and 2b of US2013/0239807 as “repr” when the optional introduction of feed gas 81 is included.
[0314] A product pressurization/feed pressurization step may be added to any known PSA cycle and/or substituted for any product pressurization step and/or feed pressurization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0315] Rinse Gas Effluent Pressurization/Feed Pressurization (REP/FP) Step
[0316] Rinse gas effluent pressurization may be combined with feed pressurization in a hybrid rinse gas effluent pressurization/feed pressurization step, abbreviated as “REP/FP.”
[0317] A rinse gas effluent pressurization/feed pressurization step comprises counter-current introduction of rinse gas effluent with contemporaneous co-current introduction of feed gas.
[0318] The characteristics and option disclosed for the rinse gas effluent pressurization step and the feed pressurization step apply to the hybrid rinse gas effluent pressurization/feed pressurization step.
[0319] A hybrid rinse gas effluent pressurization/feed pressurization step is shown in 15a and 15b of US2013/0239807 as “repr” when the optional introduction of feed gas 81 is included and all of the product gas from the feed step is withdrawn as product with none used for repressurization.
[0320] A hybrid rinse gas effluent pressurization/feed pressurization step may be added to any known PSA cycle and/or substituted for any feed pressurization step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0321] Depressurizing Equalization/Supply Purge Gas Step (DEQ/SPG)
[0322] Depressurizing equalization may be combined with supplying purge gas in a hybrid depressurizing equalization/supply purge gas step, abbreviated “DEQ/SPG,” or “DEQ#/SPG”, where # is an integer number depending on how many depressurizing equalization steps are present in the PSA cycle.
[0323] A depressurizing equalization/supply purge gas step comprises co-currently withdrawing a gas from the adsorption bed undergoing the depressurizing equalization/supply purge gas step and passing a first portion of the gas to an adsorption bed undergoing a complementary pressurizing equalization step (e.g. PEQ, PEQ f or PEQ d ) or a hybrid step thereof, thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization/rinse step and the adsorption bed undergoing the complementary pressurizing equalization step (PEQ, PEQ f or PEQ d including hybrid forms thereof), and passing a second portion of the gas as a purge gas to an adsorption bed undergoing a purge step (PRG).
[0324] A depressurizing equalization/supply purge gas step is shown, for example, as eq5d* in FIG. 16b of US2013/0239807, where gas 94 is passed both to a bed undergoing a purge step (purge) and another undergoing a pressurizing equalization step, (eq5r).
[0325] U.S. Pat. No. 6,379,431 (EP1486245) also shows a hybrid DEQ/SPG step in Table 3. Gas is withdrawn from a bed undergoing the hybrid DEQ/SPG step (identified as P′ in Table 3) and a first portion is passed to an adsorption bed as pressure equalization gas for equalization therewith (identified as 4′ in Table 3) and a second portion is passed as purge gas to another adsorption bed undergoing the purge step (identified as G in Table 3).
[0326] The supply purge step, SPG, may also be combined with a counter-current depressurization equalization step, DEQ f , or a dual depressurizing equalization step, DEQ d , in corresponding hybrid steps.
[0327] A depressurizing equalization/supply purge gas step may be added to any known PSA cycle and/or substituted for any depressurizing equalization and/or supply purge gas step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0328] Depressurizing Equalization/Blowdown Step (DEQ/BD)
[0329] Depressurizing equalization may be combined with blowdown in a hybrid depressurizing equalization/blowdown step, abbreviated “DEQ/BD” or “DEQ#/BD”, where # is an integer number depending on how many depressurizing equalization steps are present in the PSA cycle.
[0330] The depressurizing equalization/blowdown step comprises counter-current blowdown with contemporaneous co-current withdrawal of pressure equalization gas to an adsorption bed undergoing a complementary pressurizing equalization step (e.g. PEQ, PEQ f or PEQ d ) or a hybrid step thereof, thereby equalizing the pressure between the adsorption bed undergoing the depressurizing equalization/rinse step and the adsorption bed undergoing the complementary pressurizing equalization step (PEQ, PEQ f or PEQ d including hybrid forms thereof).
[0331] A depressurizing equalization/blowdown step is shown for example in Table 2 of US 2012/0174776. Bed B1 at step 9 is undergoing an E4/BD1 step where the bed is undergoing a blowdown while simultaneously equalizing with the adsorption bed undergoing the E4′ step.
[0332] Various blowdown steps, BD, BD p , BD d , may also be combined with a counter-current depressurization equalization step, DEQ f , or a dual depressurizing equalization step, DEQ d , in corresponding hybrid steps.
[0333] A depressurizing equalization/blowdown step may be added to any known PSA cycle and/or substituted for any depressurizing equalization and/or blowdown step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0334] Supply Purge Gas/Blowdown (SPG/BD)
[0335] A supply purge gas step may be combined with blowdown in a supply purge gas/blowdown step, abbreviated “SPG/BD”.
[0336] The hybrid supply purge gas/blowdown step comprises counter-current blowdown where blowdown gas is withdrawn along with contemporaneous co-currently withdrawing a purge gas from an adsorption bed undergoing the supply purge gas/blowdown step, and passing the purge gas from the adsorption bed undergoing the hybrid supply purge gas/blowdown step to an adsorption bed undergoing a purge step (PRG).
[0337] A supply purge gas/blowdown step is shown, for example, in U.S. Pat. No. 8,496,733, incorporated herein by reference, in Table 2 as PPG3/BD1, and is described in the text as the third provide purge gas/first blowdown.
[0338] A hybrid supply purge gas/blowdown step may be added to any known PSA cycle and/or substituted for any supply purge gas and/or blowdown step in any known PSA cycle. The cycle changes may be evaluated using methods, software, and techniques like those described by Mehrotra et al.
[0339] Intermediate Storage Tanks
[0340] Any of the steps where gas is passed from one adsorption bed to another adsorption may be augmented through the use of one or more intermediate storage tanks. Use of an intermediate storage tank allows for the cycle to be asynchronous and provides flexibility in the duration of the various steps. Intermediate storage tanks may be designed to spatially hold the impurity profile of the gas exiting an adsorption bed, then introducing the profile in reverse order to the adsorption bed receiving the gas.
[0341] In some literature, a particular PSA cycle step is described as being multiple steps, while in others it is described as a single step. For example, the 4 bed PSA cycle described in Table 2 of U.S. Pat. No. 7,537,742 is shown to have multiple production steps (i.e. AD1, AD2, and AD3 in Table 2 and reproduced in FIG. 16 a as P1, P2, and P3) and multiple product pressurization steps PP1, PP2. This same PSA cycle can also be described as having a single production step and a single product pressurization step. FIG. 16 b shows the equivalent PSA cycle for a 4 bed system represented in different ways depending on the convention used.
[0342] The same 4 bed cycle can be further abbreviated simply as P, DEQ1, SPG, DEQ2, BD, PRG, PEQ2, PEQ1, PP. The skilled person can readily determine the relation of the steps between the 4 beds.
[0343] A pressure swing adsorption system may be operated using multiple pressure swing adsorption cycles to control the buildup of secondary components on the adsorbent as described in U.S. Pat. No. 8,394,171, incorporated herein by reference.
BRIEF SUMMARY
[0344] The present invention relates to a process for separating a primary gas component from a feed gas mixture comprising the primary gas component and secondary gas components in a plurality of twelve adsorption beds in total, each adsorption bed containing an adsorbent selective for the secondary gas components.
[0345] There are several aspects of the invention as outlined below. In the following, specific aspects of the invention are outlined below.
[0346] Aspect 1. A process comprising subjecting each of the plurality of adsorption beds to at least one of a first repetitive cycle and a second repetitive cycle, the first repetitive cycle comprising, in sequence, (a) a production step or hybrid step thereof, (b) a plurality of five depressurizing equalization steps, (c) a supply purge gas step, (d) a blowdown step, (e) a purge step, (f) a plurality of five pressurizing equalization steps, and (g) a repressurization step, and the second repetitive cycle comprising, in sequence, (a) a production step or hybrid step thereof, (b) a plurality of five depressurizing equalization steps, (c/d) a hybrid supply purge gas/blowdown step, (e) a purge step, (f) a plurality of five pressurizing equalization steps, and (g) a repressurization step.
[0347] Aspect 2. The process of aspect 1 wherein:
(i) the duration of the production step is 23% to 27% of the cycle time of the first repetitive cycle or the duration of the purge step is 23% to 27% of the cycle time of the first repetitive cycle when the adsorption beds are subjected to the first repetitive cycle; and (ii) the duration of the purge step is 23% to 27% of the cycle time of the second repetitive cycle when the adsorption beds are subjected to the second repetitive cycle.
[0350] Aspect 3. The process of aspect 1 or aspect 2 wherein the primary gas component is H 2 and the secondary gas components comprise at least two of CO, CO 2 , CH 4 , and N 2 .
[0351] Aspect 4. The process of any one of the preceding aspects wherein the first pressurizing equalization step further comprises at least one of (i) co-currently introducing the feed gas mixture into the adsorption bed undergoing the first pressurizing equalization step simultaneous with the counter-current introduction of the pressure equalization gas from the adsorption bed undergoing the first depressurizing equalization bed, and (ii) counter-currently introducing product gas from at least one of the adsorption beds undergoing the feed step into the adsorption bed undergoing the first pressurizing equalization step simultaneous with the counter-current introduction of the pressure equalization gas from the adsorption bed undergoing the first depressurizing equalization bed.
[0352] Aspect 5. The process of any one of the preceding aspects wherein the purge step (e) comprises counter-currently introducing the purge gas from the adsorption bed undergoing the fifth depressurizing equalization step into the adsorption bed undergoing the purge step and the fifth depressurizing equalization step further comprises passing a second portion of the effluent gas from the adsorption bed undergoing the fifth depressurizing equalization step to at least one of the adsorption beds undergoing the purge step as the purge gas.
[0353] Aspect 6. The process of any one of aspects 1-5 wherein the process comprises subjecting each of the plurality of adsorption beds to the first repetitive cycle.
[0354] Aspect 7. The process of aspect 6 wherein the first repetitive cycle further comprises an idle step between the fifth depressurizing equalization step of the plurality of five pressurizing equalization steps and the supply purge gas step.
[0355] Aspect 8. The process of any one of aspects 1-5 wherein the process comprises subjecting each of the plurality of adsorption beds to the second repetitive cycle.
[0356] Aspect 9. The process of aspect 8 wherein the second repetitive cycle further comprises an idle step between the fifth depressurizing equalization step of the plurality of five pressurizing equalization steps and the hybrid supply purge gas/blowdown step.
[0357] Aspect 10. The process of any one of aspects 1-9 wherein at least one of the plurality of five depressurizing equalization steps is a parallel depressurizing equalization step and at least one of the plurality of five pressurizing equalization steps is a parallel pressurizing equalization step.
[0358] Aspect 11. The process of any one of aspects 1-9 wherein at least one of the plurality of five pressurizing equalization steps is a hybrid pressurizing equalization/feed pressurization step.
[0359] Aspect 12. The process of any one of aspects 1-9 wherein at least one of the plurality of five pressurizing equalization steps is a hybrid pressurizing equalization/product pressurization step.
BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS
[0360] FIG. 1 is a process flow diagram for an adsorption system.
[0361] FIG. 2 a is a pressure swing adsorption cycle chart for a 4 adsorption bed cycle having a single co-current depressurizing equalization step with complementary counter-current pressurizing equalization step. FIG. 2 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 2 a.
[0362] FIG. 3 is a pressure swing adsorption cycle chart for a 6 adsorption bed cycle showing that the timing of the cycle steps do not need to align with each other exactly.
[0363] FIG. 4 a is a pressure swing adsorption cycle chart for a 4 adsorption bed cycle having a counter-current depressurizing equalization step with complementary co-current pressurizing equalization step, a co-current blowdown step, and a dual product pressurization step. FIG. 4 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 4 a.
[0364] FIG. 5 a is a pressure swing adsorption cycle chart for a 4 adsorption bed cycle having a dual depressurizing equalization step with complementary dual pressurizing equalization step, a dual blowdown step, and a co-current product pressurization step. FIG. 5 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 5 a.
[0365] FIG. 6 a is a pressure swing adsorption cycle chart for a 4 adsorption bed cycle having a hybrid production/rinse step, and a feed pressurization step. FIG. 6 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 6 a.
[0366] FIG. 7 a is a pressure swing adsorption cycle chart for a 4 adsorption bed cycle having a hybrid production/rinse/supply product step, and a product pressurization step. FIG. 7 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 7 a.
[0367] FIG. 8 a is a pressure swing adsorption cycle chart for a 4 adsorption bed cycle having a hybrid production/supply product step, a hybrid co-current pressurizing equalization/feed pressurization step, and a hybrid product pressurization/feed pressurization step. FIG. 8 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 8 a.
[0368] FIG. 9 a is a pressure swing adsorption cycle chart for a 4 adsorption bed cycle having a hybrid production/supply product step, a dual depressurizing equalization step, a dual blowdown step, a hybrid dual pressurizing equalization/feed pressurization step, and a product pressurization step. FIG. 9 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 9 a.
[0369] FIG. 10 a is a pressure swing adsorption cycle chart for a 4 adsorption bed cycle having a hybrid production/supply product step, a counter-current depressurizing equalization step, a hybrid co-current pressurizing equalization/product pressurization step, and a hybrid product pressurization/feed pressurization step. FIG. 10 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 10 a.
[0370] FIG. 11 a is a pressure swing adsorption cycle chart for a 4 adsorption bed cycle having a hybrid production/supply product step, a dual depressurizing equalization step, a supply purge gas step, a dual blowdown step, a purge step, a hybrid dual pressurizing equalization/product pressurization step, and a product pressurization step. FIG. 11 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 11 a.
[0371] FIG. 12 a is a pressure swing adsorption cycle chart for a 4 adsorption bed cycle having a counter-current depressurizing equalization step, and a hybrid co-current pressurizing equalization/product pressurization/feed pressurization step. FIG. 12 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 12 a.
[0372] FIG. 13 a is a pressure swing adsorption cycle chart for a 4 adsorption bed cycle having a dual depressurizing equalization step, and a hybrid dual pressurizing equalization/product pressurization/feed pressurization step. FIG. 13 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 13 a.
[0373] FIG. 14 a is a pressure swing adsorption cycle chart for a 10 adsorption bed cycle having a hybrid co-current depressurizing equalization/rinse step, and a hybrid co-current pressurizing equalization/rinse gas effluent pressurization/feed pressurization step. FIG. 14 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 14 a.
[0374] FIG. 15 a is a pressure swing adsorption cycle chart for a 10 adsorption bed cycle having a hybrid co-current depressurizing equalization/rinse step, and a hybrid dual pressurizing equalization/rinse gas effluent pressurization/feed pressurization step. FIG. 15 b is a schematic illustrating the direction of gas flows for the cycle chart of FIG. 15 a.
[0375] FIG. 16 a is a pressure swing adsorption cycle chart for a 4 adsorption bed cycle where the production step is shown as 3 steps according to one nomenclature convention and FIG. 16 b is an equivalent pressure swing adsorption cycle chart where the production step is shown as a single step according to another nomenclature convention.
[0376] FIG. 17 is a pressure swing adsorption cycle chart for a 12 adsorption bed cycle having 5 depressurizing equalization steps and 5 pressurizing equalization steps according to the present invention.
[0377] FIG. 18 is another pressure swing adsorption cycle chart for a 12 adsorption bed cycle having 5 depressurizing equalization steps and 5 pressurizing equalization steps according to the present invention.
[0378] FIG. 19 is another pressure swing adsorption cycle chart for a 12 adsorption bed cycle having 5 depressurizing equalization steps and 5 pressurizing equalization steps according to the present invention.
[0379] FIG. 20 is another pressure swing adsorption cycle chart for a 12 adsorption bed cycle having 5 depressurizing equalization steps and 5 pressurizing equalization steps according to the present invention.
[0380] FIG. 21 is another pressure swing adsorption cycle chart for a 12 adsorption bed cycle having 5 depressurizing equalization steps and 5 pressurizing equalization steps according to the present invention.
[0381] FIG. 22 is another pressure swing adsorption cycle chart for a 12 adsorption bed cycle having 5 depressurizing equalization steps and 5 pressurizing equalization steps according to the present invention.
[0382] FIG. 23 is another pressure swing adsorption cycle chart for a 12 adsorption bed cycle having 5 depressurizing equalization steps and 5 pressurizing equalization steps according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0383] The ensuing detailed description provides preferred exemplary embodiments only, and is not intended to limit the scope, applicability, or configuration of the invention. Rather, the ensuing detailed description of the preferred exemplary embodiments will provide those skilled in the art with an enabling description for implementing the preferred exemplary embodiments of the invention, it being understood that various changes may be made in the function and arrangement of elements without departing from scope of the invention as defined by the claims.
[0384] The articles “a” and “an” as used herein mean one or more when applied to any feature in embodiments of the present invention described in the specification and claims. The use of “a” and “an” does not limit the meaning to a single feature unless such a limit is specifically stated. The article “the” preceding singular or plural nouns or noun phrases denotes a particular specified feature or particular specified features and may have a singular or plural connotation depending upon the context in which it is used.
[0385] The adjective “any” means one, some, or all indiscriminately of whatever quantity.
[0386] The term “and/or” placed between a first entity and a second entity means one of (1) the first entity, (2) the second entity, and (3) the first entity and the second entity. The term “and/or” placed between the last two entities of a list of 3 or more entities means at least one of the entities in the list including any specific combination of entities in this list.
[0387] The term “plurality” means “two or more than two.” The phrase “a plurality of three or more” means three or more. The phrase “a plurality of three” means three in total, i.e. three and no more than three.
[0388] The phrase “at least a portion” means “a portion or all.” The at least a portion of a stream may have the same composition with the same concentration of each of the species as the stream from which it is derived. The at least a portion of a stream may have a different composition to that of the stream from which it is derived. The at least a portion of a stream may include specific components of the stream from which it is derived.
[0389] As used herein a “divided portion” of a stream is a portion having the same chemical composition and species concentrations as the stream from which it was taken.
[0390] As used herein a “separated portion” of a stream is a portion having a different chemical composition and different species concentrations than the stream from which it was taken.
[0391] As used herein, “first,” “second,” “third,” etc. are used to distinguish from among a plurality of steps and/or features, and is not indicative of the total number, or relative position in time and/or space unless expressly stated as such.
[0392] In order to aid in describing the invention, directional terms may be used in the specification and claims to describe portions of the present invention (e.g., upper, top, lower, bottom, left, right, etc.). These directional terms are merely intended to assist in describing and claiming the invention and are not intended to limit the invention in any way. In addition, reference numerals that are introduced in the specification in association with a drawing figure may be repeated in one or more subsequent figures without additional description in the specification in order to provide context for other features.
[0393] In the claims, letters may be used to identify claimed steps (e.g. (a), (b), and (c)). These letters are used to aid in referring to the method steps and are not intended to indicate the order in which claimed steps are performed, unless and only to the extent that such order is specifically recited in the claims.
[0394] The term “depleted” means having a lesser mole % concentration of the indicated gas than the original stream from which it was formed. “Depleted” does not mean that the stream is completely lacking the indicated gas.
[0395] The terms “rich” or “enriched” means having a greater mole % concentration of the indicated gas than the original stream from which it was formed.
[0396] The present invention relates to a process for separating a primary gas component from a feed gas mixture comprising the primary gas component and secondary gas components in a plurality of twelve adsorption beds (in total), each adsorption bed containing an adsorbent selective for the secondary gas components. The primary gas component may be H 2 and the secondary gas components may comprise at least two of CO, CO 2 , CH 4 , and N 2 .
[0397] The process comprises subjecting each of the plurality of adsorption beds to at least one of a first repetitive cycle and a second repetitive cycle. The first repetitive cycle comprises, in sequence, (a) a production step or hybrid step thereof, (b) a plurality of five depressurizing equalization steps, (c) a supply purge gas step, (d) a blowdown step, (e) a purge step, (f) a plurality of five pressurizing equalization steps, and (g) a repressurization step. The second repetitive cycle comprises, in sequence, (a) a production step or hybrid step thereof, (b) a plurality of five depressurizing equalization steps, (c/d) a hybrid supply purge gas/blowdown step, (e) a purge step, (f) a plurality of five pressurizing equalization steps, and (g) a repressurization step.
[0398] Each of the steps is described in the background section. Preferred embodiments are summarized in FIGS. 17 to 23 .
[0399] The first repetitive cycle may have a cycle time to execute one complete cycle of the first repetitive cycle. The second repetitive cycle may have a cycle time to execute one complete cycle of the second repetitive cycle.
[0400] The production step or hybrid step thereof may comprise introducing the feed gas mixture at a feed gas pressure ranging from 1.0 MPa to 7.0 MPa into an adsorption bed undergoing the production step or hybrid step thereof and adsorbing the secondary gas components on the adsorbent in the adsorption bed undergoing the production step or hybrid step thereof while simultaneously withdrawing a product gas from the adsorption bed undergoing the production step or hybrid step thereof.
[0401] As shown in FIG. 23 , the duration of the production step may be about 25% (e.g. 23% to 27%) of the total cycle time of the cycle.
[0402] The plurality of five depressurizing equalization steps may comprise, in sequence, a first depressurizing equalization step, a second depressurizing equalization step, a third depressurizing equalization step, a fourth depressurizing equalization step, and a fifth pressure decreasing equalization step.
[0403] The first depressurizing equalization step may comprise co-currently withdrawing a pressure equalization gas from an adsorption bed undergoing the first depressurizing equalization step, and passing the pressure equalization gas to an adsorption bed undergoing a first pressurizing equalization step thereby equalizing the pressure between the adsorption bed undergoing the first depressurizing equalization step and the adsorption bed undergoing the first pressurizing equalization step.
[0404] The second depressurizing equalization step may comprise co-currently withdrawing a pressure equalization gas from an adsorption bed undergoing the second depressurizing equalization step, and passing the pressure equalization gas from the adsorption bed undergoing the second depressurizing equalization step to an adsorption bed undergoing a second pressurizing equalization step thereby equalizing the pressure between the adsorption bed undergoing the second depressurizing equalization step and the adsorption bed undergoing the second pressurizing equalization step.
[0405] The third depressurizing equalization step may comprise co-currently withdrawing a pressure equalization gas from an adsorption bed undergoing the third depressurizing equalization step, and passing the pressure equalization gas from the adsorption bed undergoing the third depressurizing equalization step to an adsorption bed undergoing a third pressurizing equalization step thereby equalizing the pressure between the adsorption bed undergoing the third depressurizing equalization step and the adsorption bed undergoing the third pressurizing equalization step.
[0406] The fourth depressurizing equalization step may comprise co-currently withdrawing a pressure equalization gas from an adsorption bed undergoing the fourth depressurizing equalization step, and passing the pressure equalization gas from the adsorption bed undergoing the fourth depressurizing equalization step to an adsorption bed undergoing a fourth pressurizing equalization step thereby equalizing the pressure between the adsorption bed undergoing the fourth depressurizing equalization step and the adsorption bed undergoing the fourth pressurizing equalization step.
[0407] The fifth depressurizing equalization step may comprise co-currently withdrawing an effluent gas from an adsorption bed undergoing the fifth depressurizing equalization step, and passing at least a portion of the effluent gas from the adsorption bed undergoing the fifth depressurizing equalization step as pressure equalization gas to an adsorption bed undergoing a fifth pressurizing equalization step thereby equalizing the pressure between the adsorption bed undergoing the fifth depressurizing equalization step and the adsorption bed undergoing the fifth pressurizing equalization step.
[0408] The supply purge gas step may comprise co-currently withdrawing a purge gas from an adsorption bed undergoing the supply purge gas step, and passing the purge gas from the adsorption bed undergoing the supply purge gas step to the adsorption beds undergoing the purge step.
[0409] The first repetitive cycle may further comprise an idle step between the fifth depressurizing equalization step of the plurality of five pressurizing equalization steps and the supply purge gas step as shown in FIG. 17 .
[0410] The blowdown step may comprise counter-currently withdrawing a blowdown gas from an adsorption bed undergoing the blowdown step, the blowdown gas having a concentration of the primary gas component that is lower than the concentration of the primary gas component in the feed gas mixture.
[0411] The hybrid supply purge gas/blowdown step may comprise co-currently withdrawing a purge gas from an adsorption bed undergoing the hybrid supply purge gas/blowdown step, and passing the purge gas from the adsorption bed undergoing the hybrid supply purge gas/blowdown step to an adsorption bed undergoing the purge step while simultaneously counter-currently withdrawing a blowdown gas from the adsorption bed undergoing the hybrid supply purge gas/blowdown step, the blowdown gas having a concentration of the primary gas component that is lower than the concentration of the primary gas component in the feed gas mixture. The hybrid supply purge gas/blowdown step is shown in FIG. 19 and FIG. 21 .
[0412] The second repetitive cycle may further comprise an idle step between the fifth depressurizing equalization step of the plurality of five pressurizing equalization steps and the hybrid supply purge gas/blowdown step as shown in FIG. 19 .
[0413] The purge step may comprise counter-currently introducing at least one of (i) the purge gas from the adsorption bed undergoing the supply purge gas step ( FIGS. 17 , 18 , 20 , 21 , 22 , and 23 ), (ii) the purge gas from the hybrid supply purge gas/blowdown step ( FIGS. 19 , and 21 ), and (iii) a purge gas from the adsorption bed undergoing the fifth depressurizing equalization step ( FIGS. 18 , 20 , 22 , and 23 ) into an adsorption bed undergoing the purge step and counter-currently withdrawing a purge gas effluent from the adsorption bed undergoing the purge step, the purge gas effluent having a concentration of the secondary gas components that is higher than the concentration of the secondary gas components in the feed gas mixture.
[0414] As shown in FIGS. 18 and 19 , the duration of the purge step may be about 25% (e.g. 23% to 27%) of the total cycle time of the cycle.
[0415] The plurality of five pressurizing equalization steps may comprise, in sequence, the fifth pressurizing equalization step, the fourth pressurizing equalization step, the third pressurizing equalization step, the second pressurizing equalization step, and the first pressurizing equalization step.
[0416] The first pressurizing equalization step may comprise counter-currently introducing the pressure equalization gas from the adsorption bed undergoing the first depressurizing equalization step into the adsorption bed undergoing the first pressurizing equalization step.
[0417] The second pressurizing equalization step may comprise counter-currently introducing the pressure equalization gas from the adsorption bed undergoing the second depressurizing equalization step into the adsorption bed undergoing the second pressurizing equalization step.
[0418] The third pressurizing equalization step may comprise counter-currently introducing the pressure equalization gas from the adsorption bed undergoing the third depressurizing equalization step into the adsorption bed undergoing the third pressurizing equalization step.
[0419] The fourth pressurizing equalization step may comprise counter-currently introducing the pressure equalization gas from the adsorption bed undergoing the fourth depressurizing equalization step into the adsorption bed undergoing the fourth pressurizing equalization step.
[0420] The fifth pressurizing equalization step may comprise counter-currently introducing the pressure equalization gas from the adsorption bed undergoing the fifth depressurizing equalization step into the adsorption bed undergoing the fifth pressurizing equalization step.
[0421] The repressurization step may comprise increasing the pressure in an adsorption bed undergoing the repressurization step until the adsorption bed undergoing the repressurization step is substantially at the feed gas pressure, by at least one of co-currently introducing the feed gas mixture into the adsorption bed undergoing the repressurization step, and counter-currently introducing a portion of the product gas from the adsorption bed undergoing the production step into the adsorption bed undergoing the repressurization step.
[0422] The fifth depressurizing equalization step may comprise passing a second portion of the effluent gas from the adsorption bed undergoing the fifth depressurizing equalization step to at least one of the adsorption beds undergoing the purge step as the purge gas from the adsorption bed undergoing the fifth depressurizing equalization step when the purge step comprises counter-currently introducing the purge gas from the adsorption bed undergoing the fifth depressurizing equalization step.
[0423] The duration of the production step may be 23% to 27% of the cycle time of the first repetitive cycle or the duration of the purge step may be 23% to 27% of the cycle time of the first repetitive cycle when the adsorption beds are subjected to the first repetitive cycle.
[0424] The duration of the purge step may be 23% to 27% of the cycle time of the second repetitive cycle when the adsorption beds are subjected to the second repetitive cycle.
[0425] The first pressurizing equalization step may further comprise at least one of (i) co-currently introducing the feed gas mixture into the adsorption bed undergoing the first pressurizing equalization step simultaneous with the counter-current introduction of the pressure equalization gas from the adsorption bed undergoing the first depressurizing equalization bed, and (ii) counter-currently introducing product gas from at least one of the adsorption beds undergoing the feed step into the adsorption bed undergoing the first pressurizing equalization step simultaneous with the counter-current introduction of the pressure equalization gas from the adsorption bed undergoing the first depressurizing equalization bed.
[0426] The purge step may comprise counter-currently introducing the purge gas from the adsorption bed undergoing the fifth depressurizing equalization step into the adsorption bed undergoing the purge step and the fifth depressurizing equalization step may further comprise passing a second portion of the effluent gas from the adsorption bed undergoing the fifth depressurizing equalization step to at least one of the adsorption beds undergoing the purge step as the purge gas. | A pressure swing adsorption process for an adsorption system having 12 adsorption beds, the process having a cycle with 5 pressure equalization steps. Background is provided for the various pressure swing adsorption cycle steps. | 2 |
This is a 371 of PCT/GB93/01109 filed May 27, 1995.
FIELD OF INVENTION
This invention relates to the treatment of diseases caused by herpesviruses, especially by varicella zoster virus.
PRIOR ART
Viruses modify the polypeptides they synthesize in a number of ways. These modifications may result in glycoproteins or lipoproteins which have a wide variety of functions within the virus lifecycle. Lipoproteins are known to play a significant role in infection with many viruses, but their mode of action is poorly understood.
Lipoproteins may arise by the post- or co-translational addition of fatty acids such as palmitic acid and myristic acid. Myristic acid is conjugated to the polypeptide by the enzyme N-myristoyl transferase. Inhibitors of this enzyme have been suggested as being of use as anti-viral agents (R. A. J. McIlhinney, Trends in Biochemical Sciences (1990), 15, 387-391 and L. A. Paige et al., Biochemistry (1990), 29, 10566-10573).
Recently several myristic acid analogue inhibitors of N-myristoyl transferase have been shown to be effective in inhibiting the release of the human immunodeficiency virus (HIV) from HIV infected cells (T. Saermark et al., AIDS (1991), 5, 951-958 and M. L. Bryant et al., Proc. Natn. Acad. Sci. USA (1989), 86, 8655-8659). The analogues shown to be effective are 13-oxamyristic acid and other derivatives wherein a methylene group between C 4 and C 13 is substituted by an oxygen or sulphur atom. Although effective, the best of these derivatives has been shown to be toxic to the infected cells. In all cases described the infective virus has been a retrovirus such as HIV or Rashid sarcomavirus (RSV). A non-toxic inhibitor of myristoylation would therefore be of value. The activity in HIV is in no way indicative of activity in other viruses. Viruses are categorised into a wide range of groups and retroviruses, such as HIV, have a unique replication strategy. HIV is a particularly diverse virus especially in that it is an RNA virus. Thus, few generalities can be brought from data originating from HIV experiments.
SUMMARY OF THE INVENTION
It has now been found that certain other derivatives of myristic acid are effective in inhibiting herpesviruses with minimal cytotoxic effect on the infected cells. These derivatives are also of use in inhibiting retroviruses such as HIV when dissolved in an appropriate solvent. This is the first non-retroviral effect of any myristic acid analogue to be demonstrated.
Accordingly the invention provides the use of a compound of general formula (I) ##STR2## wherein n is 11, 12 or 13 and R is bromine or hydroxy, and physiologically acceptable salts thereof, for the manufacture of a medicament for use in the treatment of herpesvirus infections, with the proviso than when n is 11, R is not bromo.
The term "herpesvirus infections" includes any infection or disease caused by a virus classified as a herpesvirus, especially herpes simplex virus (HSV), varicella zoster virus (VZV), cytomegalovirus (CMV) and Epstein-Barr virus (EBV).
The compounds of general formula (I) when dissolved in a suitable solvent are also of use for the manufacture of a medicament for use in the treatment of retroviral infections, for example HIV.
Although the prior art discloses the use of 13-oxamyristic acid and other related derivatives of myristic acid, the compounds of use in the present invention differ in preserving the natural alkyl chain backbone of the fatty acid and placing substituents on that backbone chain. This results in compounds that are effective and non-toxic against non-retroviruses as well as retroviruses.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWING
FIG. 1 shows the effect of 2-hydroxymyristic acid on VZV (line with boxes) and HSV (line with triangles) over a range of concentrations.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred compounds of use in the present invention are 2-bromopalmitic acid, 2-hydroxymyristic acid and 2-hydroxypalmitic acid, especially 2-hydroxymyristic acid and 2-hydroxypalmitic acid. All these compounds may exist as stereoisomeric enantiomers. It is preferable that the compound of use is the (--) or laevrorotatory isomer. These compounds are effective against herpesviruses, especially varicella zoster virus (VZV) when dissolved in a variety of commonly used pharmaceutical solvents. They are also of use against retroviruses such as HIV, but in both cases show a preference for non-dimethylsulphoxide-like solvents. A suitable solvent for their use against HIV would be ethanol and similar solvents.
The activity against non-retroviruses is also improved by the presence of a non-dimethylsulphoxide-like solvent such as ethanol.
The compounds of formula (I) in the present invention are available from recognised chemical suppliers, e.g. Aldrich, Sigma. The compounds may be used in their free form or when as a salt, particularly as a salt with a base, suitable bases are the alkali metal hydroxides, for example, sodium hydroxide, quaternary ammonium hydroxides and amines such as tris (tris representing 2-amino-2-hydroxymethyl propane 1,3-diol).
The use of the invention may be described as a method of treating a patient suffering from a herpesvirus or retroviral infection, which comprises administering to the patient a therapeutically effective dosage of the compounds of general formula (I) or a physiologically acceptable salt thereof.
The compound is administered in any pharmaceutically acceptable form but preferably takes the form of a topical formulation.
A range of dosage for the compounds of general formula (I) in the above treatment is similar to the dosages of Acyclovir (Wellcome UK) used in the treatment of those infections as set out in the ABPI Data Sheet Compendium 1991-1992.
The compounds of general formula (I) may be formulated with a physiologically acceptable diluent or carrier for use as pharmaceuticals particularly for human use by a variety of methods. For instance, it may be applied as a composition incorporating a liquid diluent or carrier, for example an aqueous or oily solution, suspension or emulsion, which may often be employed in injectable form for parenteral administration and therefore may conveniently be sterile and pyrogen free. Oral administration may also be used, although compositions for this purpose may incorporate a liquid diluent or carrier, it is more usual to use a solid, for example a conventional solid carrier material such as starch, lactose, dextrin or magnesium stearate. Such solid compositions may conveniently be of a formed type, for example as tablets, capsules (including spansules), etc.
Other forms of administration than by injection or through the oral route may also be considered in both human and veterinary contexts, for example the use of suppositories or pessaries. Another form of pharmaceutical composition is one for buccal or nasal administration, for example lozenges, nose drops or an aerosol spray, or alternatively drops for administration into the eye which may conveniently contain a sterile liquid diluent or carrier.
It may be desired that the compound is administered topically in the form of creams, lotions or drops including shampoos.
EXAMPLES
Example 1
Effect of 2-hydroxymyristic acid on Varicella zoster virus (VZV)
2-Hydroxymyristic acid, 13-oxamyristic acid and N-myristoyl glycinol diethylacetal (GoA) were assayed for activity against VZV.
The assay system used was the Mewo cell plaque reduction assay of VZV, C. Grose and P. A. Brunell, Infection & Immunity, 19, 199-203 (1978). (The Mewo cell line is available from C. Grose, University of Iowa, Iowa, USA.) VZV does not form clearly defined plaques in MRC5 cells, and for this reason the Mewo cell line was used to allow plaque assay. Compounds were tested at levels from 2 to 200 μM. After staining, it was apparent that 13-oxamyristic acid was toxic to cells at 200 μM, while GoA did not cause 50% inhibition of virus at any concentration tested. In contrast, 2-hydroxymyristic acid showed inhibition at 20 and 200 μM, with an apparent 50% inhibitory concentration (IC 50 ) of 8 μM. FIG. 1 shows the effect of 2-hydroxymyristic acid on VZV (line joined by boxes). The concentration of 2-hydroxymyristic acid is shown on the abscissa and the reduction in plaque forming unit (PFU) as compared to the control having no test compound present. At the highest concentration of 2-hydroxymyristic acid, crystalline deposits were observed. The IC 50 of 8 μM is comparable with the range of 1.6-5.1 μM reported for acyclovir in VZV assay 12 .
In order to characterise the nature of the antiviral effect, the effect of 2-hydroxymyristic acid on the synthesis of viral antigen was assayed by immunoblotting. With an inoculum of one infected cell to four uninfected cells, harvested at three days post-infection (70-80% cytopathic effect), no reduction in antigen synthesis was apparent even with 2-hydroxymyristate present at 80 μM (10×IC 50 ). However, when the initial inoculum was reduced, and the time of harvest correspondingly increased, inhibition was apparent, and this was inversely proportional to the inoculum used. VZV spreads in MRC5 monolayers by the formation of syncytia, and these results strongly suggest that the effect of 2-hydroxymyristate was to inhibit syncytium formation rather than viral protein synthesis in the initially infected cell.
Cytotoxicity was assessed by the incorporation of radiolabelled precursors to assay protein synthesis and myristoylation in the infected cell. A high (1:4) inoculum was used so as to prevent any overall decrease in virus infection of the MRC5 monolayer, and 2-hydroxymyristic acid was again assayed from 0.1 to 10×IC 50 . It was clear that total protein synthesis (measured by incorporation of 35 S methionine) was unaffected at any concentration tested, further suggesting that 2-hydroxymyristic acid was not toxic to cells.
From the above data, it is clear that 2-hydroxymyristic acid is producing a non-specific inhibition of myristoylation, and that this is resulting in a specific antiviral effect without producing significant cellular toxicity even at levels ten times greater than the IC 50 .
Example 2
Effect of 2-hydroxymyristic acid on herpes simplex virus (HSV)
The Vero cell plaque assay was performed on HSV as described in C. S. Crumpacker et al., N. Eng. J. Med (1982), 306, 343-346, and using 2-hydroxymyristic acid over the range 0.8 μM to 80 μM. FIG. 1 shows the effect of 2-hydroxymyristic acid on HSV (line joined by triangles).
Example 3
The VZV plaque assay of Example 1 was repeated using a variety of myristic acid analogues. Briefly, sub-confluent Mewo monolayers (Grose and Brunell, 1978, supra) in 24 well plates were infected with approximately 40 P.F.U. (Plaque Forming Units) of cell-free varicella zoster virus (VZV) strain H-551. After an adsorption period of 2 hours the cells were overlaid with 750 μl of MEM (Minimum Essential Medium (Eagle)) supplemented with 2% fetal calf serum and 1% non-essential amino acids. The anti-viral compounds to be tested were solubilized in ethanol, added to final concentrations of 0, 2, 20 or 200 μM and the wells then overlaid with a further 750 μl of MEM supplemented with 2% fetal calf serum, 1% non-essential amino acids and 0.3% agarose. Mock infected wells were also included as controls to test for cytotoxicity. All plates were incubated at 32° C. with 5% CO 2 . Eight days post infection the monolayers were fixed in 4% formaldehyde and stained with crystal violet. Plaques were counted and the IC 50 values (the concentration causing a 50% reduction in plaque numbers) were calculated by interpolation. The IC 50 values and an index of cytotoxicity is presented in Table 1 below.
TABLE 1______________________________________ IC.sub.50 Toxicity Against inTest Compound VZV (μM) Mewo Cells______________________________________a) 2-azidotetradecanoic acid IC.sub.50 ++++ unobtainableb) 2-bromotetradecanoic acid 14.75 +++c) 9-(butylamino)nonanoic acid 164.2 -d) 11-(ethylamino)undecanoic acid IC.sub.50 - unobtainablee) 2-(ethyloxy)undecanoic acid 14.4 ++f) glycidic acid 4.5 +++g) 2-hydroxypalmitic acid 14.2 -h) myristoylmethylamide 56.6 +i) 2-hydroxytetradecanoic acid 21.5 -j) 2-hydroxytetradecanoic acid (-) 11.5 -k) 2-hydroxytetradecanoic acid (+) 48.7 -l) 11-(ethylthio)undecanoic acid IC.sub.50 +++ unobtainablem) 12-(methyloxy)dodecanoic acid 17.3 +++n) N-myristoylglycinaldiethylacetal (GoA) IC.sub.50 - unobtainableo) 2-bromopalmitic acid 0.89 +++______________________________________ Key - no apparent cytotoxicity + thinning of monolayer at high concentration ++ pronounced thinning of monolayer at high concentration +++ destruction of monolayer at 200 μM concentration ++++ destruction of monolayer at 20 μM concentration
The most effective myristic acid derivatives in the assay that failed to be cytotoxic were 2-hydroxymyristic acid racemic mixture and the isomers thereof, i), j) and k). 2-Bromopalmitic acid, although toxic at 200 μM is included in the present invention as the difference between is IC 50 and its toxic level is sufficient that it is unlikely to be toxic at a therapeutic level. It therefore possesses the advantages of the claimed invention.
The discrepancy in the IC 50 values of 2-hydroxymyristic acid in Examples 1 and 3 points towards a range of IC 50 from 8 μM at the lower end to 33 μM at the upper end. Both these figures are comparable to the performance of acyclovir in the described VZV assay (Boyd M. R. et al., Antimicrob. Agents & Chemotherapy (1987), 31, 1238-1242.
Example 4
The effect of 2-hydroxymyristic acid (2-HM) on VZV or HIV when solubilized in a variety of solvents was observed using the methods approved for the Medical Research Council AIDS Directed Programme as described in H. C. Holmes et al., Antiviral Chem. & Chemother. (1991), 2(5), 287-293, using concentrations of 2 HM from 0.08to 1000 μM. Additionally, back titration assays of HIV were carried out by adding supernatants from treated infected cells to uninfected C8166 cells at increasing dilutions. Assays were scored by recording the presence or absence of syncytium formation.
Preparation and assay of VZV was carried out as described previously in Examples 1 and 3.
The HIV assays were performed at three of the MRC approved laboratories (Mill Hill, Cambridge and St. Bartholomew's Hospital).
Stocks of 2-HM were prepared from crystalline solid by dissolving in ethanol or in dimethyl sulphoxide (DMSO) to a concentration of 20 mM to 100 mM, and were stored at -20° C. prior to addition to culture media. Concentrations of 2-HM greater than 80 to 100 μM are imprecise, since 2-HM crystallises from aqueous solutions at such levels.
As shown in Table 2 below, 2-HM inhibits the replication of both VZV (St. Bartholomew's Hospital) and HIV (Mill Hill) when solubilised in ethanol. However, when the results from the different test centres for HIV were compared, it was clear that solubilisation of 2-HM in DMSO (as initially used at St. Bartholomew's Hospital) resulted in a lack of any significant anti-viral effect despite apparent solubility of 2-HM in this solvent. In the light of the results obtained for VZV, 2-HM was re-tested against HIV at St. Bartholomew's Hospital using ethanol as the solvent. In this assay, a clear anti-viral effect was apparent, although at levels somewhat higher than those observed at Mill Hill. In both the St. Bartholomew's Hospital and the Mill Hill assay, toxicity of 2-HM to C8166 cells was detected, but only at levels above those at which 2-HM would crystallise from aqueous solution.
Experiments comparing the anti-viral activity of 2-HM against VZV using ethanol and DMSO solvents showed a similar effect, with no significant anti-viral effect produced by 2-HM solubilised in DMSO.
TABLE 2______________________________________Anti-viral efects of 2-hydroxymyristic acid Ethanol DMSOVirus Assay IC.sub.50 TC.sub.50 IC.sub.50 TC.sub.50______________________________________VZV Plaque reduction.sup.1 33.1 >200 >200 >200HIV Antigen assay.sup.1 31.4 168 220 >400 Antigen assay.sup.2 2.0 192 ND ND Virus titration.sup.2 3.9 192 ND ND______________________________________ .sup.1 Medical College of St. Bartholomew's Hospital, London. .sup.2 Medical Research Council Collaborative Centre, Mill Hill.
This example shows the importance that should be attached to the choice of solvent for anti-viral agents. The improved IC 50 value observed for 2-HM in ethanol was surprising and shows that this compound and similar ones, when solubilised in the appropriate solvent, are effective against HIV. | Compounds of general formula (I) ##STR1## wherein n is 11, 12 or 13 and R is bromine or hydroxy, and physiologically acceptable salts thereof, with the proviso than when n is 11, R is not bromo, have been found to be effective as non-toxic agents against herpesviruses and retroviruses. | 2 |
RELATED DOCUMENTS
This application is based upon information filed under the Disclosure Document Program on Feb. 9, 2001 as Disclosure Document Number 488491.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to carts for moving a variety of goods and more particularly to a cart which is readily folded for transport and storage.
2. Prior Art and Objects of the Invention
Skis are notably difficult to handle being long and awkward to carry. Along with the skis, ski boots and poles, an equipment bag is also essential to carry such items as goggles, caps and gloves. With all of this equipment to carry, the trip from the parking lot to the lodge of a ski center can be difficult and precarious.
In playing golf, carts have long been an essential part of golf equipment. However, carts which are pulled to carry equipment including golf clubs and golf bag, are not easily transportable in an automobile.
A cart on which all the equipment could be securely stowed and which could be easily pulled with all the necessary sports equipment on it would fill a long felt need. Such a cart would need to be light and compact. Of greatest importance, it would have to be capable of being folded so as to require minimal space when not in use and when being transported in an automobile. While skiing the cart could be compactly stored while with golf, the cart would be used during the playing of the game. In both situations, the cart could be easily carried and readily stored when not being used.
It should be understood that many other uses for a compact cart, besides golf and skiing, are possible and in fact are almost unlimited. However, skiing and golf provide two areas of use encompassing both winter and summer. Such a cart is not known or available.
Accordingly, it is an object of the present invention to provide a cart for carrying a variety of equipment.
It is another object of the present invention to provide a cart for carrying ski and snow board and golf equipment.
It is another object of the present invention safely to retain articles to prevent others from falling over the articles if placed to one side.
It is another object of the present invention to provide a cart that is light and is easily folded into a compact unit for storage.
These and other objects will be apparent to those skilled in the art based upon the description of the preferred embodiment.
SUMMARY OF THE INVENTION
A cart is provided for transporting various items most particularly sports equipment such as ski and snow board and golf equipment. The structural base for the cart is a frame which includes a cross bar and two wheel bars generally parallel to one another and extending substantially at right angles from the ends of the cross bar. Journals are mounted to rotate on the wheel bars and wheel plates extend from the journals to which the wheel plates are secured. The wheel plates taper from the journal to an outside end which is generally rounded. An axle is secured to each of the wheel plates at the outside end and a wheel is mounted on each axle to rotate. On these two wheels, the cart can be readily pulled.
To use the cart, the wheel plates are placed parallel to one another and locked into position. For storage purposes, the wheels can be rotated toward one another against the frame and are then locked in that position.
A handle extends from the frame and the handle folds downwardly and backwardly for storage. A cradle is mounted on the handle to retain items in place and the cradle may be modified to accommodate different items. Straps may be used to secure the various items to the handle and on the shelf.
A shelf is mounted on the cart on the opposite side of the cart from the wheels to rotate generally ninety degrees from a vertical position to a horizontal position with the cart in an upright position. A locking means is used to retain the shelf in its lower or operating position.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of the cart being used to transport ski equipment with the handle extended and the shelf down and the cart tipped back to be pulled.
FIG. 2 is a pictorial view from the side and front of the cart with the cart in an upright position but with the handle extended and showing in exploded form an modification member which can be added to the cradle so as to make the cart more suitable for use in carrying a snow board.
FIG. 3 . is a pictorial view from the side and rear showing the wheels in their stored position but with one wheel shown in italics in its operating position and also showing the handle folded down for storage with the handle in its upright position shown in italics.
FIG. 4 is a pictorial view partially exploded showing the journal and the outer collar with the lugs and indentations used to lock the wheels in selected positions.
FIG. 5 is a side elevation of the shelf view showing the locking mechanism for the shelf and for limiting the movement of the shelf.
FIG. 5A is an enlarged pictorial view of the locking mechanism shown in FIG. 5 .
FIG. 6 is a plan view of the underside of the shelf showing the plates affixed to the shelf and the locking mechanism.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIGS. 1, 2 and 3 , the cart is shown and the cart includes a frame 11 , a handle 13 , a platform or shelf 15 and a wheel assembly 19 including wheels 21 . The handle 13 is secured to the frame 11 at the center point of the frame 11 between the two wheels 21 . The frame 11 is an inverted U-shaped member including a cross bar 23 and two wheel bars 25 , each wheel bar 25 is attached at its upper end 27 to opposite ends of the cross bar 23 generally at right angles to the cross bar 23 and substantially parallel to one another. The opposite end of each wheel bar 25 is the lower end 29 of the wheel bar 25 . The handle 13 is securely affixed to the cross bar 23 , as stated, midway between the two wheel bars 25 .
For purposes of reference, the back of the frame 11 is where the wheels 21 are located and the front of the frame 11 is where the shelf 15 is located.
The wheel assembly 19 is mounted on each of the two wheel bars 25 . Each wheel assembly 19 includes a journal 31 mounted on each wheel bar 25 so as to rotate on the wheel bar 25 . The journal 31 has a lower end 33 adjacent the lower end 29 of the wheel bar 25 and an upper end 35 opposite from the lower end 33 . An end collar 37 is secured to the lower end 29 of each wheel bar 25 by a set screw 38 . A spring 39 is placed between each end collar 37 and the journal 31 to force the journal 31 away from the end collar 37 . An upper collar 41 is secured to the upper end 27 of the wheel bars 25 . The upper collar 41 has lugs or projections 43 , as shown in FIG. 4, and the upper end 35 of the journal 31 has indentations 45 which mate with the lugs 43 causing the journal 31 to lock to the upper collar 41 at ninety degree intervals thus preventing rotation of each journal 31 . However, when each journal 31 is pressed toward its respective end collar 37 against the spring 39 , each entire wheel assembly 19 including the wheel 21 may be rotated and then may be locked in a different position by the same lugs 43 and indentations 45 .
A wheel plate 47 , which is part of the wheel assembly 19 , is secured to each of the two journals 31 . The wheel plate 47 generally tapers from the journal 31 , to which it is secured, to a rounded end 49 . At the rounded end 49 , an axle 51 is secured to the wheel plate 47 on which the wheel 21 is mounted to rotate. The two wheels 21 so mounted serve to roll the cart by pulling. When the wheels 21 are set to serve as a basis to roll the cart, the two wheel plates 47 are parallel as shown in FIG. 2 . When the cart is being stored, the wheels 21 are folded against the frame 11 as seen in FIG. 3 . and are aligned with one another. The wheels 21 may be moved from the operation position, to the storage position as has been previously explained, by depressing the journal 31 against the spring 39 to release the lugs 43 from the indentations 45 .
The shelf or platform 15 is centrally mounted on the handle 13 slightly forward of the two wheel bars 25 . A hinge 55 is used to secure the shelf 15 to the handle so that the shelf 15 can be rotated up against the handle 13 and down approximately ninety degrees when in use. The shelf 15 may be mounted to rotate on the cart in any number of ways.
When the shelf 15 is its lowered position and particularly when is use, it is important that the shelf 15 not rotate back up toward the frame 11 as might occur if the shelf 15 struck a curb. To assure that the shelf 15 will not improperly rotate when is use, a lock 57 is provided as seen in FIGS.5, 5 A and 6 . A pair of tapered plates 59 on the underside 61 of the shelf 15 are located generally parallel to the side edges 63 of the shelf 15 and extend past the rear edge 65 of the shelf 15 to slide along the sides of the handle 13 in close proximity to the handle 13 . A pair of spring-loaded projections 67 engage openings 69 in the tapered plates 59 securing the shelf 15 in its lowered position. A stop bar 71 across the tapered plates 59 strikes the handle 13 to stop the shelf 15 in its desired lowered position, generally at ninety degrees from the upright position of the shelf 15 when not in use.
The handle 13 in its operating position can best be seen in FIG. 1 . The handle 13 has a lower section 73 and an upper section 75 . The lower end 77 of the upper section 75 is secured to the upper end 79 of the lower section 73 by a retaining assembly 81 . The upper section 75 and the lower section 73 are aligned with one another but are offset from one another. A hinge member 83 is secured to lower section 73 of the handle 13 towards the upper end 79 of the lower section 73 . The upper section 75 of the handle 13 is mounted to pivot on the hinge member 83 . A retaining member 85 is mounted to slide on the upper section 75 of the handle 13 and the retaining member 85 includes a socket 87 . The retaining member 85 , with the upper section 75 of the handle 13 in the operating position, slides downwardly so that the socket fits over the upper end 79 of the lower section 73 of the handle 13 thereby retaining the upper section 75 as a rigid extension of the lower section 73 . By lifting the retaining member 85 upwardly, the upper section 75 of the handle 13 may be folded over the back of the cart as seen in FIG 3 .
The upper section 75 of the handle 13 at its upper end 89 , most remote from the lower section 73 , includes a hand grip 91 . The lower section 73 is secured to the frame 11 as has been previously described and, as seen in FIGS. 2 and 5, the lower section 73 extends to a lower end 93 beneath the cross bar 23 below the shelf 15 and serves, as also previously discussed, to permit the lock 57 to secure the shelf 15 in its lowered position.
Again referring to FIG. 1, a cradle 95 is secured to the lower section 73 of the handle 13 but above the hinge member 83 . The cradle 95 , as seen in FIG. 3, is designed to retain articles such as skis, as shown in FIG. 1 . When used for larger articles such as a snow board, a broader support is preferable and, seen in FIG. 2, a cradle modifier 97 , that is a flat and elongated plate is placed on the cradle 95 . The cradle modifier 97 includes hooks 99 at each end to retain the snow board in place by means of hooked expansible straps (not shown). A hook 101 (FIG. 1) on the back of the upper section 75 of the handle 13 provides a means to hold a bag. Straps 103 affixed to the cart are provided to retain articles being transported, to secure the articles in place when in transit.
It is to be understood that the drawings and description matter are in all cases to be interpreted as merely illustrative of the principles of the invention, rather than as limiting the same in any way, since it is contemplated that various changes may be made in various elements to achieve like results without departing from the spirit of the invention or the scope of the appended claims. | A cart for transporting various articles, most particularly sporting goods such as ski and golf equipment, that folds into a compact package for storage including a handle folds down and a shelf that folds up and wheels that can be rotated so as to be aligned in a common plane against the frame of the cart. | 1 |
Subsets and Splits