Liquid crystal composition and liquid crystal device containing same

Abstract: A ferroelectric chiral smectic liquid crystal composition is provided with a fast response speed and a less temperature dependency of the response speed by containing at least one mesomorphic compound represented by the formula (1) below: wherein R₁ denotes an alkyl group having 1 - 16 carbon atoms and capable of having a substituent; R₂ denotes an alkyl group, alkoxy group, alkoxycarbonyl group, acyloxy group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and respectively denotes each capable of having a substituent.

Description: FIELD OF THE INVENTION AND RELATED ART The present invention relates to a liquid crystal composition used in a liquid crystal display device, a liquid crystal-optical shutter, etc., and more particularly to a novel iquid crystal composition with improved responsiveness to an electric field. Hitherto, liquid crystal devices have been used as an electro-optical device in various fields. Most liquid crystal devices which have been put into practice use TN (twisted nematic) type liquid crystals, as shown in "Voltage-Dependent Optical Activity of a Twisted Nematic Liquid Crystal" by M. Schadt and W. Helfrich "Applied Physics Letters" Vol. 18, No. 4 (Feb. 15, 1971) pp. 127-128. These devices are based on the dielectric alignment effect of a liquid crystal and utilize an effect that the average molecular axis direction is directed to a specific direction in response to an applied electric field because of the dielectric anisotropy of liquid crystal molecules. It is said that the limit of response speed is on the order of milli-seconds, which is too slow for many uses. On the other hand, a simple matrix system of driving is most promising for application to a large-area flat display in view of cost, productivity, etc., in combination. In the simple matrix system, an electrode arrangement wherein scanning electrodes and signal electrodes are arranged in a matrix, and for driving, a multiplex driving scheme is adopted wherein an adress signal is sequentially, periodically and selectively applied to the scanning electrodes and prescribed data signals are selectively applied in parallel to the signal electrodes in synchronism with the address signal. When the above-mentioned TN-type liquid crystal is used in a device of such a driving system, a certain electric field is applied to regions where a scanning electrode is selected and signal electrodes are not selected or regions where scanning electrode is not selected and a signal electrode is selected (which regions are so called "half-selected points"). If the difference between a voltage applied to the selected points and a voltage applied to half-selected points is sufficiently large, and a voltage threshold level required for allowing liquid crystal molecules to be aligned or oriented perpendicular to an electric field is set to a value therebetween, display devices normally operate. However, in fact, as the number (N) of scanning lines increases, a time (duty ratio) during which an effective electric field is applied to one selected point when a whole image area (corresponding to one frame) is scanned decreases with a ratio of 1/N. Accordingly, the larger the number of scanning lines are, the smaller is the voltage difference of an effective value applied to a selected point and non-selected points when scanning is repeatedly effected. As a result, this leads to unavoidable drawbacks of lowering of image contrast or occurrence of interference or crosstalk. These phenomena are regarded as essentially unavoidable problems appearing when a liquid crystal having no bistability (i.e. liquid crystal molecules are horizontally oriented with respect to the electrode surface as stable state and is vertically oriented with respect to the electrode surface only when an electric field is effectively applied) is driven (i.e. repeatedly scanned) by making use of a time storage effect. To overcome these drawbacks, the voltage averaging method, the two-frequency driving method, the multiple matrix method, etc. has been already proposed. However, any method is not sufficient to overcome the above-mentioned drawbacks. As a result, it is the present state that the development of large image area or high packaging density in respect to display elements is delayed because it is difficult to sufficiently increase the number of scanning lines. To overcome drawbacks with such prior art liquid crystal devices, the use of liquid crystal devices having bistability has been proposed by Clark and Lagerwall (e.g. Japanese Laid-Open Patent Appln. No. 56-107216, U.S.P. No. 4367924, etc.). In this instance, as the liquid crystals having bistability, ferroelectric liquid crystals having chiral smectic C-phase (SmC*) or H-phase (SmH*) are generally used. These liquid crystals have bistable states of first and second stable states with respect to an electric field applied thereto. Accordingly, as different from optical modulation devices in which the above-mentioned TN-type liquid crystals are used, the bistable liquid crystal molecules are oriented to first and second optically stable states with respect to one and the other electric field vectors, respectively. Further, this type of liquid crystal has a property (bistability) of assuming either one of the two stable states in response to an applied electric and retaining in the absence of the resultant state in the absence of an electric field. In addition to the above-described characteristic of showing bistability, the ferroelectric liquid crystal has an excellent property, i.e., a high-speed responsiveness. This is because the spontaneous polarization of the ferroelectric liquid crystal and an applied electric field directly interact with each other to induce transition of orientation states. The resultant response speed is faster than the response speed due to the interaction between dielectric anistropy and an electric field by 3 to 4 digits. Thus, a ferroelectric liquid crystal potentially has very excellent characteristics, and by making use of these properties, it is possible to provide essential improvements to many of the above-mentioned problems with the conventional TN-type devices. Particularly, the application to a high-speed optical shutter and a display of a high density and a large picture is expected. For this reason, there has been made extensive research with respect to liquid crystal materials showing ferroelectricity. Furthermore, the use of ferroelectric liquid crystals having a chiral smectic C-phase has been suggested in DE-A-35 18 734 for improving the response speed and the temperature-dependency. However, ferroelectric liquid crystal materials developed heretofore cannot be said to satisfy sufficient characteristics required for a liquid crystal device including low-temperature operation characteristic, high-speed responsiveness, etc. Among a response time τ, the magnitude of spontaneous polarization Ps and viscosity η, the following relationship exists: τ = η/(Ps·E) , where E is an applied voltage. Accordingly, a large response speed can be obtained by (a) increasing the spontaneous polarization, (b) lowering the viscosity η, or (c) increasing the applied voltage. However, the driving voltage has a certain upper limit in view of driving with IC, etc., and should desirably be as low as possible. Accordingly, it is actually necessary to lower the viscosity or increase the spontaneous polarization. A ferroelectric chiral smectic liquid crystal having a large spontaneous polarization generally provides a large internal electric field in a cell given by the spontaneous polarization and is liable to pose many constraints on the device construction giving bistability. Further, an excessively large spontaneous polarization is liable to accompany an increase in viscosity, so that a remarkable increase in response speed may not be attained as a result. Further, if it is assumed that the operation temperature of an actual display device is 5 - 40°C, the response speed changes by a factor of about 20, so that it actually exceeds the range controllable by driving voltage and frequency. As described hereinabove, commercialization of a ferroelectric liquid crystal device requires a ferroelectric chiral smectic liquid crystal composition having a low viscosity, a high-speed responsiveness and a small temperature-dependency of response speed. SUMMARY OF THE INVENTION An object of the present invention is to provide a chiral smectic liquid crystal composition having a high response speed and a smaller temperature-dependency of the response speed for providing a practical ferroelectric liquid crystal device and a liquid crystal device using the liquid crystal composition. According to a generic aspect of the present invention, there is provided a ferroelectric chiral smectic liquid crystal composition containing at least one mesomorphic compound represented by the formula (1) below: wherein R₁ denotes an alkyl group having 1 - 16 carbon atoms and capable of having a substituent; R₂ denotes an alkyl group, alkoxy group, alkoxycarbonyl group, acyloxy group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and respectively denotes each capable of having a substituent; and at least one mesomorphic compound represented by the formula (3) below: wherein R₃ denotes an alkyl group having 1 - 16 carbon atoms and capable of having a substituent; R₄ denotes an alkyl group, alkoxy group, alkoxycarbonyl group, acyloxy group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and respectively denotes each capable of having a substituent; and at least one of A and B being a pyrazine or pyrimidine ring and/or at least one of C and D being a pyrimidine ring; or at least one mesomorphic compound represented by the formula (5) below: wherein R₅ and R₆ respectively denote an alkyl group, alkoxy group, acyloxy group, alkoxycarbonyl group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and m and n are respectively 0, 1 or 2; and at least one of A and B being a pyrazine or pyrimidine ring. According to another generic aspect of the present invention, there is provided a liquid crystal device comprising a pair of electrode plates, and the above liquid crystal composition disposed between the electrode plates. These and other objects, features and advantages of the present invention will become more apparent upon a consideration of the following description of the preferred embodiments of the present invention taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic sectional view of a liquid crystal display device using a ferroelectric liquid crystal; Figures 2 and 3 are respectively a schematic perspective view of a ferroelectric liquid crystal device for illustrating the operation of the device; and DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, according to a generic aspect of the present invention, there is provided a ferroelectric chiral smectic liquid crystal composition containing at least one mesomorphic compound represented by the formula (1) below: wherein R₁ denotes an alkyl group having 1 - 16 carbon atoms and capable of having a substituent; R₂ denotes an alkyl group, alkoxy group, alkoxycarbonyl group, acyloxy group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and respectively denotes each capable of having a substituent. According to a preferred embodiment, the liquid crystal composition of the present invention contains at least one mesomorphic compound represented by the following formula (2): wherein R₁ and R₂ have the same meanings as in the formula (1). According to one aspect of the present invention, there is provided a liquid crystal composition comprising at least one mesomorphic compound of the above-mentioned formula (1), and at least one mesomorphic compound of the formula (3) below: wherein R₃ denotes an alkyl group having 1 - 16 carbon atoms and capable of having a substituent; R₄ denotes an alkyl group, alkoxy group, alkoxycarbonyl group, acyloxy group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and respectively denotes or each capable of having a substituent. According to a preferred embodiment of this aspect, the liquid crystal comprises at least one mesomorphic compound represented by the following formula (2): wherein R₁ and R₂ have the same meanings as in the formula (1); and at least one mesomorphic compound represented by the following formula (4): wherein R₃ and R₄ have the same meanings as in the formula (3). According to another aspect of the present invention, there is provided a liquid crystal composition comprising at least one mesomorphic compound of the above-mentioned formula (1), and at least one mesomorphic compound of the formula (5) below: wherein R₅ and R₆ respectively denote an alkyl group, alkoxy group, acyloxy group, alkoxycarbonyl group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and m and n are respectively 0, 1 or 2. In a particularly preferred embodiment of this aspect, the liquid crystal composition comprises at least one mesomorphic compound of the formula (2), and at least one mesomorphic compound of the formula (6) and/or at least one mesomorphic compound of the formula (7) respectively shown below: wherein R₁, R₂, R₅ and R₆ have the same meanings as defined above. A liquid crystal device comprising the liquid crystal composition between a pair of electrode plates, is also provided. Specific examples of the mesomorphic compounds represented by the above-mentioned general formula (1) are enumerated hereinbelow with their numbers and structural formulas: Example Compound No. Then, a representative example of synthesis of the mesomorphic compound represented by the above formula (1) is described. Synthesis Example 1 (Synthesis of the above-mentioned Example Compound No. 1-4) 1.0 g (2.94 mmol) of 5-dodecyl-2-(4′-hydroxyphenyl)pyrimidine was dissolved in a mixture of toluene 4 ml and pyridine 4 ml. While the solution was held at 5°C or below or an iced water bath, a solution of 0.55 g of trans-4-n-propylcyclohexanecarboxylic acid chloride (mfd. by Kanto Kagaku K.K.) in 4 ml of toluene was gradually added dropwise. After the addition, the mixture was stirred for 12 hours at room temperature and then poured into 100 ml of iced water. The mixture was acidified with 6N-hydrochloric acid and then extracted with benzene, followed by sequential washing with water, 5 % aqueous solution of sodium bicarbonate and water after drying with magnesium sulfate, the solvent was distille-off to obtain a cream-colored crude product. The crude product was further purified by column chromatography and recrystallized from a solvent mixture of ethanol/ethyl acetate to obtain 0.94 g (yield: 64.8 %) of the objective compound in white color, which showed the following phase transition characteristic. Phase transition temperature (°C) Herein, symbols regarding the phase transition characteristic of a mesomorphic compound or liquid crystal composition denote the following phases: Cry.: crystal phase, SmC: smectic C phase, SmC*: chiral smectic C phase, SmA: smectic A phase, Ch.: cholesteric phase, N: nematic phase, Iso.: isotropic phase, Sm3: a smectic phase other than SmA and SmC (un-identified). Hereinbelow, an example of synthesis of a representative mesomorphic compound has been explained. The other compounds represent by the general formula (1) may also be prepared by reacting a corresponding para-substituted cyclohexanecarboxylic acid chloride (which may be obtained by reacting a corresponding para-substituted cyclohexanecarboxylic acid with thionyl chloride, etc., according to an ordinary method, if not commercially available) with a corresponding phenol in the presence of an alkali. These reactions may be summarized by the following reaction scheme: R₁, R₂, have the same meanings as defined above. The ferroelectric liquid crystal composition of the present invention may be obtained by mixing at least one mesomorphic compound represented by the general formula (1) (hereinafter sometimes referred to as "instant mesomorphic compound" with or without indication of the formula) with another at least one mesomorphic compound of formulae (3) and (5) in appropriate proportions. The mixture may be generally heated into isotropic phase and sealed up in a device cell in vacuo, followed by gradual cooling to form a liquid crystal and then recovery of normal pressure, whereby the liquid crystal composition of the present invention may be formed in situ as the preparation of the liquid crystal device according to the present invention. When the mesomorphic compound of the formula (1) is optically inactive, it may suitably be mixed with ferroelectric liquid crystal composition comprising a ferroelectric mesomorphic compound as another mesomorphic compound. Specific examples of such ferroelectric mesomorphic compounds are shown below with their Compound Nos. and structural formulas: Example Compound No. Among the instant mesomorphic compounds of the formula (1), those of the above-mentioned formula (2) provide a liquid crystal composition showing better performances. A mesomorphic compound of the formula (1) may suitably be combined with a mesomorphic compound of the formula (3) in a ratio of 100 wt. parts of the former with 1 - 300 wt. parts, preferably 2 - 200 wt. parts, of the latter. Further the mesomorphic compounds of the formulas (1) and (3) in combination may further be suitably mixed with another FLC material in a ratio of 1 - 500 wt. parts, preferably 10 - 100 wt. parts, of the former with 100 wt. parts of the latter. Specific examples of the mesomorphic compounds represented by the above-mentioned general formula (3) are enumerated hereinbelow with their numbers and structural formulas wherein C* denotes an asymmetric carbon atom showing optical activity. Example Compound No. Some representative examples of synthesis of the mesomorphic compound represented by the above formula (3) are described. Synthesis Example 2 (I) 10 g (53.6 mmol) of trans-4-n-propylcyclohexanecarboxylic acid chloride was dissolved in 30 ml of ethanol, and a small amount of triethylamine was added thereto, followed by 10 hours of stirring at room temperature. The reaction mixture was poured into 100 ml of riced water, acidified with addition of 6N-hydrochloric acid aqueous solution and then extracted with isopropyl ether. The organic layer was washed with water repeatedly until the washing liquid reached neutrality, and then dried with magnesium sulfate. After distilling off the solvent, the product was purified by silica gel column chromatography to obtain 9.9 g of trans-4-n-propylcyclohexanecarboxylic acid-ethyl-ester. (II) 0.73 g (19.1 mmol) of aluminum lithium hydride was added to 30 ml of dry ether, and the mixture was heat-refluxed for 1 hour. The mixture was cooled to about 10°C on an iced water bath, and a solution of 5 g (25.5 mmol) of trans-4-n-propylcyclohexanecarboxylic acid-ethyl-ester dissolved in 30 ml of dry ether was gradually added dropwise thereto. After the addition, the mixture was stirred for 1 hour at room temperature and further heat-refluxed for 1 hour. The reaction mixture was treated with ethyl acetate and 6N-hydrochloric acid aqueous solution and then poured into 200 ml of iced water. After the extraction with isopropyl ether, the organic layer was successively washed with water, sodium hydroxide aqueous solution and water, followed by drying with magnesium sulfate. After distilling off the solvent, the product was purified by silica gel column chromatography to obtain 3.5 g of trans-4-n-propylcyclohexylmethanol. (III) 3.4 g (22.4 mmol) of trans-4-n-propylcyclohexylmethanol was dissolved in 20 ml of pyridine, and 5.3 g of p-toluenesulfonyl chloride dissolved in 20 ml of pyridine was added thereto on an iced water bath for cooling below 5°C. The mixture was stirred for 10 hours at room temperature and then poured in 200 ml of iced water. The mixture was acidified with 6N-hydrochloric acid aqueous solution and extracted with isopropyl ether. The organic layer was washed with water repeatedly until the washing liquid reached neutralty and then dried with magnesium sulfate. Then, the solvent was removed by distillation to obtain trans-4-n-propylcyclohexylmethyl-p-toluenesulfonate. (IV) 6.3 g (20.2 mmol) of 5-decyl-2-(4′-hydroxyphenyl)pyrimidine was dissolved in 40 ml of dimethylformamide, and 1.5 g of 85 %-potassium hydroxide was added thereto, followed by stirring for 1 hour at 100°C. To the mixture was added 6.9 g of trans-4-n-propylcyclohexylmethyl-p-toluenesulfonate, followed by 4 hours of stirring at 100°C. After the reaction, the reaction mixture was poured into 200 ml of iced water and extracted with benzene. The organic layer was washed with water and dried with magnesium sulfate. After distilling off the solvent, the product was purified by silica gel column chromatography and recrystallized from a mixture solvent of ethanol/ethyl acetate to obtain the above-mentioned Example Compound No. 3-4. IR (cm⁻¹) 2920, 2840, 1608, 1584, 1438, 1258, 1164, 800. Phase transition temperature (°C) (Sm2: a smectic phase other than SmA and SmC (un-identified)) Synthesis Example 3 (I) 4.0 g (26.3 mmol) of trans-4-n-propylcyclohexylmethanol prepared in the same manner as in (I) and (II) of the above Synthesis Example 2 was dissolved in 25 ml of pyridine, and 6.0 g of p-toluenesulfonyl chloride dissolved in 25 ml of pyridine was added thereto on an iced water bath for cooling below 5°C. The mixture was stirred for 12 hours at room temperature and then poured in 200 ml of iced water. The mixture was acidified with 6N-hydrochloric acid aqueous solution and extracted with isopropyl ether. The organic layer was washed with water repeatedly until the washing liquid reached neutralty and then dried with magnesium sulfate. Then, the solvent was removed by distillation to obtain trans-4-n-propylcyclohexylmethyl-p-toluenesulfonate. (II) 9.3 g (26.3 mmol) of 4-decyloxycarbonyl-4′-hydroxybiphenyl was dissolved in 70 ml of dimethylformamide, and 2.1 g of 85 %-potassium hydroxide was added thereto, followed by stirring for 1.5 hours at 100°C. To the mixture was added 7.4 g of trans-4-n-propylcyclohexylmethyl-p-toluenesulfonate, followed by 5 hours of stirring at 100°C. After the reaction, the reaction mixture was poured into 200 ml of iced water and extracted with benzene. The organic layer was washed with water and dried with magnesium sulfate. After distilling off the solvent, the product was purified by silica gel column chromatography and recrystallized from a mixture solvent of ethanol/ethyl acetate to obtain the above-mentioned Example Compound No. 3-12. IR (cm⁻¹) 2920, 2840, 1710, 1604, 1288, 1198, 1110, 830, 772 Phase transition temperature (°C) Hereinabove, some examples of synthesis of representative mesomorphic compounds have been explained. The other compounds represented by the general formula (3) may also be prepared by tosylating or halogenating a corresponding para-substituted cyclohexylmethanol and then reacting the product with a corresponding phenol. Principal reaction paths therefore may be represented by the following scheme: R₃, R₄, have the same meanings as defined above. Further, a mesomorphic compound of the formula (1) may suitably be combined with a mesomorphic compound of the formula (5) in a ratio of 100 wt. parts of the former with 50 - 800 wt. parts, preferably 100 - 600 wt. parts, of the latter. Further, the mesomorphic compounds of the formulas (1) and (5) in combination may further be suitably mixed with another FLC material in a ratio of 1 - 500 wt. parts, prereferably 50 - 400 wt. parts, of the former with 100 wt. parts of the latter. Specific examples of the mesomorphic compounds represented by the above-mentioned general formula (5) are enumerated hereinbelow with their numbers and structural formulas: Example Compound No. Among the mesomorphic compounds represented by the general formula (5), those also represented by the following formula, for example, may be synthesized along the reaction scheme shown below. wherein R′₆ denotes an alkyl group having 1 - 16 carbon atoms and capable of having a substituent. R₅, m and n have the same meanings as defined hereinabove. The liquid crystal composition comprising a mesomorphic compound represented by the formula (1) and a mesomorphic compound represented by the formula (5) may show a further improved performance where it comprises a combination of a mesomorphic compound of the formula (2) below and a mesomorphic compound of the formula (6), or further a mesomorphic compound of the formula (7) below: By using the ferroelectric liquid crystal composition, there is provided a ferroelectric liquid crystal device which shows excellent responsive characteristics inclusive of high speed responsiveness, low-temperature operation characteristic and temperature-dependency of the response speed; and shows excellent threshold characteristics with respect to electric field response, thus giving a good contrast while preventing crosstalk. Figure 1 is a schematic sectional view of an embodiment of the ferroelectric liquid crystal device for explanation of the structure thereof. Referring to Figure 1, the ferroelectric liquid crystal device includes a ferroelectric liquid crystal layer 1 disposed between a pair of glass substrates 2 each having thereon a transparent electrode 3 and an insulating alignment control layer 4. Lead wires 6 are connected to the electrodes so as to apply a driving voltage to the liquid crystal layer 1 from a power supply 7. Outside the substrates 2, a pair of polarizers 8 are disposed so as to modulate incident light I₀ from a light source 9 in cooperation with the liquid crystal 1 to provide modulated light I. Each of two glass substrates 2 is coated with a transparent electrode 3 comprising a film of In₂O₃, SnO₂ or ITO (indium-Tin-Oxide) to form an electrode plate. Further thereon, an insulating alignment control layer 4 is formed by rubbing a film of a polymer such as polyimide with gauze or acetate fiber-planted cloth so as to align the liquid crystal molecules in the rubbing direction. Further, it is also possible to compose the alignment control layer of two layers, e.g., by first forming an insulating layer of an inorganic material, such as silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide, boron nitride, boron nitride containing hydrogen, cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, or magnesium fluoride, and forming thereon an alignment control layer of an organic insulating material, such as polyvinyl alcohol, polyimide, polyamide-imide, polyester-imide, polyparaxylylene, polyester, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin, melamine resin, urea resin, acrylic resin, or photoresist resin. Alternatively, it is also possible to use a single layer of inorganic insulating alignment control layer or organic insulating alignment control layer. An inorganic insulating alignment control layer may be formed by vapor deposition, while an organic insulating alignment control layer may be formed by applying a selection of an organic insulating material or a precursor thereof in a concentration of 0.1 to 20 wt.%, preferably 0.2 - 10 wt. %, by spinner coating, dip coating, screen printing, spray coating or roller coating, followed by curing or hardening under prescribed hardening condition (e.g., by heating). The inorganic insulating layer may have a thickness of ordinarily 50 Å - 1 µ, preferably 100 Å - 5000 Å, further preferably 500 Å - 3000 Å. The two glass substrates 2 with transparent electrodes 3 (which may be inclusively referred to herein as "electrode plates") and further with insulating alignment control layers 4 thereof are held to have a prescribed (but arbitrary) gap with a spacer 5. For example, such a cell structure with a prescribed gap may be formed by sandwiching spacers of silica beads or alumina beads having a prescribed diameter with two glass plates, and then sealing the periphery thereof with, e.g., an epoxy adhesive. Alternatively, a polymer film or glass fiber may also be used as a spacer. Between the two glass plates, a ferroelectric liquid crystal is sealed up to provide a ferroelectric liquid crystal layer in a thickness of generally 0.5 to 20 µ, preferably 1 to 5 µ. It is desired that the ferroelectric liquid crystal shows SmC* phase (chiral smectic C phase) over a wide temperature range (particularly on the lower temperature side) including room temperature and shows a low viscosity and a high-speed response characteristic when incorporated in a device. Further, it is desired to have a small temperature-dependency of the response speed. Further, so as to show a uniform alignment characteristic to form a monodomain, the ferroelectric liquid crystal may desirably show a phase transition series of isotropic phase - Ch (cholesteric) phase - SmA (smectic A) phase - SmC* (chiral smectic C) phase. The transparent electrodes 3 are connected to the external power supply 7 through the lead wires 6. Further, outside the glass substrates 2, polarizers 8 are applied. The device shown in Figure 1 is of a transmission type. Figure 2 is a schematic illustration of a ferroelectric liquid crystal cell (device) for explaining operation thereof. Reference numerals 21a and 21b denote substrates (glass plates) on which a transparent electrode of, e.g., In₂O₃, SnO₂, ITO (Indium Tin Oxide), etc., is disposed, respectively. A liquid crystal of an SmC*-phase (chiral smectic C phase) in which liquid crystal molecular layers 22 are aligned perpendicular to surfaces of the glass plates is hermetically disposed therebetween. Full lines 23 show liquid crystal molecules. Each liquid crystal molecule 23 has a dipole moment (P⊥) 24 in a direction perpendicular to the axis thereof. The liquid crystal molecules 23 continuously form a helical structure in the direction of extension of the substrates. When a voltage higher than a certain threshold level is applied between electrodes formed on the substrates 21a and 21b, a helical structure of the liquid crystal molecule 23 is unwound or released to change the alignment direction of respective liquid crystal molecules 23 so that the dipole moments (P⊥) 24 are all directed in the direction of the electric field. The liquid crystal molecules 23 have an elongated shape and show refractive anisotropy between the long axis and the short axis thereof. Accordingly, it is easily understood that when, for instance, polarizers arranged in a cross nicol relationship, i.e., with their polarizing directions crossing each other, are disposed on the upper and the lower surfaces of the glass plates, the liquid crystal cell thus arranged functions as a liquid crystal optical modulation device of which optical characteristics vary depending upon the polarity of an applied voltage. Further, when the liquid crystal cell is made sufficiently thin (e.g., about 1 µ), the helical structure of the liquid crystal molecules is unwound to provide a non-helical structure even in the absence of an electric field, whereby the dipole moment assumes either of the two states, i.e., Pa in an upper direction 34a or Pb in a lower direction 34b as shown in Figure 3, thus providing a bistable condition. When an electric field Ea or Eb higher than a certain threshold level and different from each other in polarity as shown in Figure 3 is applied to a cell having the above-mentioned characteristics, the dipole moment is directed either in the upper direction 34a or in the lower direction 34b depending on the vector of the electric field Ea or Eb. In correspondence with this, the liquid crystal molecules are oriented in either of a first stable state 33a and a second stable state 33b. When the above-mentioned ferroelectric liquid crystal is used as an optical modulation element, it is possible to obtain two advantages. First is that the response speed is quite fast. Second is that the orientation of the liquid crystal shows bistability. The second advantage will be further explained, e.g., with reference to Figure 3. When the electric field Ea is applied to the liquid crystal molecules, they are oriented in the first stable state 33a. This state is stably retained even if the electric field is removed. On the other hand, when the electric field Eb of which direction is opposite to that of the electric field Ea is applied thereto, the liquid crystal molecules are oriented to the second stable state 33b, whereby the directions of molecules are changed. This state is similarly stably retained even if the electric field is removed. Further, as long as the magnitude of the electric field Ea or Eb being applied is not above a certain threshold value, the liquid crystal molecules are placed in the respective orientation states. Hereinbelow, the present invention will be explained more specifically with reference to Examples. Preparation Example 1 A liquid crystal composition A was prepared by mixing the following compounds in the respectively indicated amounts. Example Compound No. Weight parts 1 56 8 14 130 7.5 131 22.5 The liquid crystal composition A showed the following phase transition series (the numerals denote phase transition temperatures (°C). The same as in the Examples appearing hereinafter.) Preparation Example 2 Two 0.7 mm-thick glass plates were provided and respectively coated with an ITO film to form an electrode for voltage application, which was further coated with an insulating layer of vapor-deposited SiO₂. On the insulating layer, a 0.2 %-solution of silane coupling agent (KBM-602, available from Shinetsu Kagaku K.K.) is isopropyl alcohol was applied by spinner coating at a speed of 2000 rpm for 15 second and subjected to hot curing treatment at 120°C for 20 min. Further, each glass plate provided with an ITO film and treated in the above described manner was coated with a 2 %-solution of polyimide resin precursor (SP-510, available from Toray K.K.) in dimethylacetoamide by a spinner coater rotating at 2000 rpm for 15 seconds. Thereafter, the coating film was subjected to heat curing at 300°C for 60 min. to obtain about 250 Å-thick film. The coating film was rubbed with acetate fiber-planted cloth. The thus treated two glass plates were washed with isopropyl alcohol. After alumina beads with an average particle size of 2.0 µm were dispersed on one of the glass plates, the two glass plates were applied to each other with a bonding sealing agent (Lixon Bond available from Chisso K.K.) so that their rubbed directions were parallel to each other and heated at 100°C for 60 minutes to form a blank cell. The cell gap was found to be about 2 µm as measured by a Berek compensator. Then, a liquid crystal composition prepared according to one of the following Examples was heated into an isotropic liquid, and injected into the above prepared cell under vacuum and, after sealing, was gradually cooled at a rate of 5°C/hour to 25°C to prepare a ferroelectric liquid crystal device. The ferroelectric liquid crystal device was subjected to measurement of a spontaneous polarization Ps and an optical response time (time from voltage application until the transmittance change reaches 90 % of the maximum under the application of a peak-to-peak voltage Vpp of 20 V in combination with right-angle cross-nicol polarizers). Comparative Example 1 A ferroelectric liquid crystal device was prepared in the same manner as in Preparation Example 2 using the liquid crystal composition A prepared in Example 1 was injected into a cell. The measured values of Ps and the response time of the device were as follows: 25°C 35°C 45°C Response time 430 µsec 150 µsec 60 µsec Ps 36.5 nC/cm² 26.2 nC/cm² 13.3 nC/cm² Comparative Example 2 80 wt. parts of the liquid crystal composition A was mixed with Example Compounds 1-19, 1-46 and 1-50 in amounts of 5, 10 and 5 wt. parts, respectively, to prepare a liquid crystal composition C. A ferroelectric liquid crystal device was prepared in the same manner as in Example 2 except for using the composition C. In the ferroelectric liquid crystal device, a monodomain of a uniform alignment characteristic was observed. The ferroelectric liquid crystal device was subjected to measurement of response time and spontaneous polarization Ps in the same manner as in Example 2, whereby the following results were obtained. 25°C 35°C 45°C Response time 385 µsec 175 µsec 95 µsec Ps 25.3 nC/cm² 18.1 nC/cm² 10.2 nC/cm² Example 1 80 wt. parts of the liquid crystal composition A was mixed with Example Compounds 5-23, 1-46 and 5-93 in amounts of 6, 10 and 4 wt. parts, respectively, to prepare a liquid crystal composition D. A ferroelectric liquid crystal device was prepared in the same manner as in Preparation Example 2 using the composition D. In the ferroelectric liquid crystal device, a monodomain of a uniform alignment characteristic was observed. The ferroelectric liquid crystal device was subjected to measurement of response time and spontaneous polarization Ps in the same manner as in Example 2, whereby the following results were obtained. 25°C 35°C 45°C Response time 330 µsec 155 µsec 85 µsec Ps 24.2 nC/cm² 16.5 nC/cm² 8.6 nC/cm² Example 2 80 wt. parts of the liquid crystal composition A was mixed with Example Compounds 1-46 and 5-23 in amounts of 10 and 10 wt. parts, respectively, to prepare a liquid crystal composition E. A ferroelectric liquid crystal device was prepared in the same manner as in Example 2 using the composition E. In the ferroelectric liquid crystal device, a monodomain of a uniform alignment characteristic was observed. The ferroelectric liquid crystal device was subjected to measurement of response time and spontaneous polarization Ps in the same manner as in Example 2, whereby the following results were obtained. 25°C 35°C 45°C Response time 260 µsec 125 µsec 65 µsec Ps 22.8 nC/cm² 14.9 nC/cm² 7.4 nC/cm² As is understood from the results of Comparative Examples 1 and 2 and Examples 1 and 2, the ferroelectric liquid crystal devices containing a mesomorphic compound of the formula (1) and one of formula (5) showed improved dynamic characteristic and high-speed responsiveness at a low temperature, and particularly showed a remarkably improved temperature dependency of response speed compared with one containing no mesomorphic compound of the formula (1) or only a mesomorphic compound of formula (1). Further, comparison between Comparative Example 2 and Example 1 shows that the use of a compound of the formula (2) in combination with the compounds of the formulas (6) and (7) provided an improved (higher) response speed as a whole than when the compound of the formula (2) alone was used. Further, some improvement in temperature-dependency of response speed was also observed. Further, in the case of Example 2 where the compounds of the formulas (2) and (6) were used in combination, the temperature dependency of response speed was remarkably improved to realize a faster response over the whole temperature range, which might be attributable to a decrease in viscosity. Comparative Example 3 A liquid crystal composition F was prepared by mixing the following components in the respectively indicated amounts. Example Compound No. wt. parts 20 15 21 15 58 10 89 20 120 13 129 7 1-4 15 1-7 5 The liquid crystal composition F showed the following phase transition series. A ferroelectric liquid crystal device was prepared in the same manner as in Example 2 using the liquid crystal composition F. In the ferroelectric liquid crystal device, a monodomain of a uniform alignment characteristic was observed. The ferroelectric liquid crystal device was subjected to measurement of response time and spontaneous polarization Ps in the same manner as in Example 2, whereby the following results were obtained. 15°C 25°C 35°C Response time 195 µsec 125 µsec 85 µsec Ps 23.4 nC/cm² 19.0 nC/cm² 15.2 nC/cm² Further, the device was driven at 25°C with a contrast of 14 and a clear switching action was observed. Good bistability was also observed when the voltage application was stopped. Comparative Example 4 A liquid crystal composition G was prepared in the same mixing proportions as the liquid crystal composition F in Comparative Example 3 except that only Example Compounds 1-4 and 1-7 were removed. The composition D showed the following phase transition series: A ferroelectric liquid crystal device was prepared in the same manner as in Comparative Example 3 except for injecting the liquid crystal composition G in the cell and was observed with respect to the switching action, etc., whereby the alignment in the cell was not uniform and clear switching action was not observed. The remarkable difference in alignment state between the devices of Comparative Example 3 and Comparative Example 4 may be attributable to a difference in phase transition series of the liquid crystals used that the liquid crystal composition F showed Iso → Ch → SmA → SmC* from the higher temperature side whereas the liquid crystal composition G showed Iso → SmA → SmC* and did not show cholesteric phase. Thus, it is understood that the liquid crystal composition F containing the mesomorphic compounds 1-4 and 1-7 showed an improved alignment characteristic in the device due to introduction of Ch phase in addition to an enlarged temperature region for SmC* phase. Example 3 A liquid crystal composition H was prepared in the same manner as the liquid crystal composition F in Comparative Example 3 except that the Example Compound 1-4 was replaced by 5 wt. parts of Example Compound 3-30. A ferroelectric liquid crystal device was prepared in the same manner as in Example 2 using the composition H. In the ferroelectric liquid crystal device, a monodomain of a uniform alignment characteristic was observed. The ferroelectric liquid crystal device was subjected to measurement of response time and spontaneous polarization Ps in the same manner as in Example 2, whereby the following results were obtained. 15°C 25°C 35°C Response time 155 µsec 100 µsec 80 µsec Ps 24.2 nC/cm² 19.8 nC/cm² 15.7 nC/cm² Further, the device was driven at 25°C with a contrast of 17 and a clear switching action was observed. Good bistability was also observed when the voltage application was stopped. Compared with the liquid crystal composition F in Comparative Example 3, the liquid crystal composition H containing the mesomorphic compounds of the formulas (2) and (4) in combination showed a better response speed and also a remarkably improved temperature-dependency thereof. Further, the contrast has been remarkably increased to 17 compared with 14 of the liquid crystal composition F. Comparative Example 5 A liquid crystal composition I was prepared in the same manner as the liquid crystal composition F in Comparative Example 3 except that the Example Compounds 1-4 and 1-7 were replaced by 20 wt. parts of Example Compound 3-30. A ferroelectric liquid crystal device was prepared in the same manner as in Example 2 using the composition I. In the ferroelectric liquid crystal device, a monodomain of a uniform alignment characteristic was observed. The ferroelectric liquid crystal device was subjected to measurement of response time and spontaneous polarization Ps in the same manner as in Example 2, whereby the following results were obtained. 15°C 25°C 35°C Response time 240 µsec 135 µsec 75 µsec Ps 26.3 nC/cm² 21.1 nC/cm² 16.5 nC/cm² Compared with the liquid crystal composition H in Example 3, the liquid crystal composition I obtained by the addition of only a mesomorphic compound of the formula (4) showed a lower response speed, particularly at a low temperature, and also a remarkably worse temperature dependency of response speed. Comparative Example 6 A liquid crystal composition J was prepared in the same manner as the liquid crystal composition F in Comparative Example 3 except that the Example Compounds 1-4 and 1-7 were replaced by 20 wt. parts of the compound of the formula: A ferroelectric liquid crystal composition device was prepared in the same manner as in Example 2 using the composition J. In the ferroelectric liquid crystal device, a monodomain of a uniform alignment characteristic was observed. The ferroelectric liquid crystal device was subjected to measurement of response time and spontaneous polarization Ps in the same manner as in Example 2, whereby the following results were obtained. 15°C 25°C 35°C Response time 285 µsec 170 µsec 105 µsec Ps 27.5 nC/cm² 23.1 nC/cm² 18.6 nC/cm² Compared with the liquid crystal compositions H and F in Example 3 and in Comparative Example 3 containing mesomorphic compounds having a cyclohexane ring, the liquid crystal composition J containing a mesomorphic compound in the form of a benzoic acid ester having a benzene ring instead of the cyclohexane showed a show response speed and also a remarkably worse temperature-dependecy thereof. Further, the viscosity value calculated from the above equation remarkably increased to about 1.7 times. Comparative Example 7 A liquid crystal composition K was prepared by mixing the following components in the respectively indicated amounts. Example Compound No. wt. parts 1 64 8 16 9 22.5 43 22.5 63 15 87 15 130 6.75 131 18.75 1-4 20 1-18 20 The liquid crystal composition K showed the following phase transition series: A ferroelectric liquid crystal device was prepared in the same manner as in Example 2 except for using the composition K. In the ferroelectric liquid crystal device, a monodomain of a uniform alignment characteristic was observed. The ferroelectric liquid crystal device was subjected to measurement of response time in the same manner as in Example 2, whereby the following results were obtained. 10°C 25°C 35°C 890 µsec 340 µsec 230 µsec Further, the device was driven at 25°C with a contrast of 12 and a clear switching action was observed. Good bistability was also observed when the voltage application was stopped. Comparative Example 8 A liquid crystal composition L was prepared in the same mixing proportions as the liquid crystal composition K in Comparative Example 7 except for omitting the Example Compounds 1-4 and 1-8. The composition L showed the following phase transition series: A ferroelectric liquid crystal device was prepared in the same manner as in Comparative Example 7 except for injecting the liquid crystal composition G in the cell, and the response time was measured in the same manner, whereby the following results are obtained. 10°C 25°C 35°C 1400 µsec 450 µsec 250 µsec Comparative Example 9 A liquid crystal composition M was prepared in the same manner as the liquid crystal composition K in Comparative Example 7 except that the Example Compounds 1-4 and 1-18 were replaced by Example Compounds 1-7 and 1-15 in 30 wt. parts and 10 wt. parts, respectively. The liquid crystal composition M showed the following phase transition series: A ferroelectric liquid crystal device was prepared in the same manner as in Example 2 using the liquid crystal composition M. In the liquid crystal device, a monodomain of a uniform alignment characteristic was observed. The response time of the device was measured in the same manner as in Example 2, whereby the following results were obtained: 10°C 25°C 35°C 950 µsec 370 µsec 240 µsec Further, the device was driven at 25°C with a contrast of 15, and a clear switching was observed. Good bistability was also observed when the voltage application was stopped. Comparative Example 10 A liquid crystal composition N was prepared in the same manner as the liquid crystal composition K in Comparative Example 7 except that the Example Compounds 1-4 and 1-18 were replaced by Example Compounds 1-7, 1-8 and 1-9 in 20 wt. parts, 10 wt. parts and 10 wt. parts, respectively. The liquid crystal composition N showed the following phase transition series: A ferroelectric liquid crystal device was prepared in the same manner as in Example 2 using the liquid crystal composition N. In the liquid crystal device, a monodomain of a uniform alignment characteristic was observed. The response time of the device was measured in the same manner as in Example 2, whereby the following results are obtained: 10°C 25°C 35°C 910 µsec 350 µsec 240 µsec Further, the device was driven at 25°C with a contrast of 14 and a clear switching was observed. Good bistability was also observed when the voltage application was stopped. Example 4 A liquid crystal composition P was prepared in the same manner as the liquid crystal composition K in Comparative Example 7 except that the Example Compound 1-18 was replaced by Example Compounds 5-46 and 5-53 in 10 wt. parts and 10 wt. parts, respectively. A ferroelectric liquid crystal device was prepared in the same manner as in Example 2 using the liquid crystal composition P. In the liquid crystal device, a monodomain of a uniform alignment characteristic was observed. The response time of the device was measured in the same manner as in Example 2, whereby the following results were obtained: 10°C 25°C 35°C 635 µsec 270 µsec 195 µsec Further, the device was driven at 25°C with a contrast of 16 and a clear switching was observed. Good bistability was also observed when the voltage application was stopped. Comparative Example 11 A liquid crystal composition Q was prepared in the same manner as the liquid crystal composition K in Comparative Example 7 except that the Example Compound 1-18 was replaced by Example Compounds 1-61 and 1-63 in 10 wt. parts and 10 wt. parts, respectively. A ferroelectric liquid crystal device was prepared in the same manner as in Example 2 using the liquid crystal composition Q. In the liquid crystal device, a monodomain of a uniform alignment characteristic was observed. The response time of the device was measured in the same manner as in Example 2 whereby the following results were obtained: 10°C 25°C 35°C 1050 µsec 385 µsec 250 µsec Further, the device was driven at 25°C with a contrast of 16 and a clear switching was observed. Good bistability was also observed when the voltage application was stopped. As is understood from Example 4 and from Comparative Examples 7 to 11, a liquid cristal composition comprising both a mesomorphic compound of formula (1) and of formula (5) shows a remarkably improved low temperature operation characteristic and a smaller temperature dependency of response speed than compositions comprising none or only a mesomorphic compound of formula (1). A ferroelectric chiral smectic liquid crystal composition is provided with a fast response speed and a less temperature dependency of the response speed by containing at least one mesomorphic compound represented by the formula (1) below: wherein R₁ denotes an alkyl group having 1 - 16 carbon atoms and capable of having a substituent; R₂ denotes an alkyl group, alkoxy group, alkoxycarbonyl group, acyloxy group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and respectively denotes each capable of having a substituent; and at least one mesomorphic compound represented by the formula (3) below: wherein R₃ denotes an alkyl group having 1 - 16 carbon atoms and capable of having a substituent; R₄ denotes an alkyl group, alkoxy group, alkoxycarbonyl group, acyloxy group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and respectively denotes each capable of having a substituent; and at least one of A and B being a pyrazine or pyrimidine ring and/or at least one of C and D being a pyrimidine ring; or at least one mesomorphic compound represented by the formula (5) below: wherein R₅ and R₆ respectively denote an alkyl group, alkoxy group, acyloxy group, alkoxycarbonyl group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and m and n are respectively 0, 1 or 2; and at least one of A and B being a pyrazine or pyrimidine ring.

Claims: A ferroelectric chiral smectic liquid crystal composition, comprising: at least one mesomorphic compound represented by the formula (1) below: wherein R₁ denotes an alkyl group having 1 - 16 carbon atoms and capable of having a substituent; R₂ denotes an alkyl group, alkoxy group, alkoxy carbonyl group, acyloxy group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and respectively denotes each capable of having a substituent; at least one mesomorphic compound represented by the formula (3) below: wherein R₃ denotes an alkyl group having 1 - 16 carbon atoms and capable of having a substituent; R₄ denotes an alkyl group, alkoxy group, alkoxycarbonyl group, acyloxy group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and respectively denotes each capable of having a substituent; and at least one of A and B being a pyrazine or pyrimidine ring and/or at least one of C and D being a pyrimidine ring. The composition according to claim 1, wherein the mesomorphic compound represented by the formula (3) is free from an asymmetric carbon atom and is optically inactive. The composition according to claim 1, wherein at least one of R₃ and R₄ in the formula (3) has an asymmetric carbon atom and is optically active. The composition according to claim 1, wherein the mesomorphic compound represented by the formula (1) is one also represented by the following formula (2): wherein R₁ and R₂ have the same meanings as in the formula (1); and the mesomorphic compound represented by the formula (3) is one also represented by the following formula (4): wherein R₃ and R₄ have the same meanings as in the formula (3). A ferroelectric chiral smectic liquid crystal composition comprising: at least one mesomorphic compound represented by the formula (1) below: wherein R₁ denotes an alkyl group having 1 - 16 carbon atoms and capable of having a substituent; R₂ denotes an alkyl group, alkoxy group, alkoxycarbonyl group, acyloxy group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and respectively denotes each capable of having a substituent; at least one of A and B being a pyrazine or pyrimidine ring; and at least one mesomorphic compound represented by the formula (5) below: wherein R₅ and R₆ respectively denote an alkyl group, alkoxy group, acyloxy group, alkoxycarbonyl group or alkoxycarbonyloxy group each having 1 - 16 carbon atoms and capable of having a substituent; and m and n are respectively 0, 1 or 2. The composition according to claim 5, wherein the mesomorphic compound represented by the formula (5) is free from an asymmetric carbon atom and is optically inactive. The composition according to claim 5, wherein at least one of R₅ and R₆ in the formula (5) has an asymmetric carbon atom and is optically active. The composition according to claim 5, wherein the mesomorphic compound represented by the formula (1) is one also represented by the following formula (2): wherein R₁ and R₂ have the same meanings as in the formula (1), and the mesomorphic compound represented by the formula (5) is one also represented by the following formula (6): wherein R₅ and R₆ have the same meanings as in the formula (5). The composition according to claim 8, which further contains at least one mesomorphic compound represented by the following formula (7): wherein R₅ and R₆ have the same meanings as in the formula (5). The composition according to claim 1, wherein the mesomorphic compound represented by the formula (1) is free from an asymmetric carbon atom and is optically inactive. The composition according to claim 1, wherein at least one of R₁ and R₂ in the formula (1) has an asymmetric carbon atom and is optically active. The composition according to claim 1, which comprises 1-500 wt. parts in combination of the compounds of the formula (1) and (3) and 100 wt. parts of another liquid crystal material. The composition according to claim 1, which comprises 10-100 wt. parts in combination of the compounds of the formulae (1) and (3) and 100 wt. parts of another liquid crystal material. The composition according to claim 5, wherein the mesomorphic compound represented by the formula (1) is free from an asymmetric carbon atom and is optically inactive. A composition according to claim 5, wherein at least one of R₁ and R₂ in the formula (1) has an asymmetric carbon atom and is optically active. The composition according to claim 5, which comprises 1-500 wt. parts in combination of the compounds of the formulae (1) and (5) and 100 wt. parts of another liquid crystal material. The composition according to claim 5, which comprises 50-400 wt. parts in combination of the compounds of the formulae (1) and (5) and 100 wt. parts of another liquid crystal material. A liquid crystal device comprising a pair of electrode plates and a ferroelectric chiral smectic liquid crystal composition according to any preceding claims disposed between the electrode plates. The device according to claim 18, wherein said ferroelectric chiral smectic liquid crystal composition shows a phase transition series of isotropic phase, cholesteric phase, smectic A phase and chiral smectic C phase. The device according to claim 18, wherein at least one of the electrode plates has a face having a function of aligning the axis of liquid crystal molecules preferentially in one direction.

Inventors: ASAOKA MASANOBU, IWAKI TAKASHI, SHINJO KENJI, TERADA MASAHIRO, TOGANO TAKESHI, UCHIMI TOSHIHARU, YOSHIDA AKIO, ASAOKA, MASANOBU, IWAKI, TAKASHI, SHINJO, KENJI, TERADA, MASAHIRO, TOGANO, TAKESHI, UCHIMI, TOSHIHARU, YOSHIDA, AKIO
Applicants: CANON KK, CANON KABUSHIKI KAISHA
Application year: 1988
Main classification: C09K19
IPC codes: C09K19, G02F1