CA1339649C - Liquid crystal composition for twist nematic mode - Google Patents
Liquid crystal composition for twist nematic modeInfo
- Publication number
- CA1339649C CA1339649C CA000583735A CA583735A CA1339649C CA 1339649 C CA1339649 C CA 1339649C CA 000583735 A CA000583735 A CA 000583735A CA 583735 A CA583735 A CA 583735A CA 1339649 C CA1339649 C CA 1339649C
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- liquid crystal
- formula
- compound
- cyclohexyl
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
Abstract
A liquid crystal composition for twist nematic mode having improved reduction in the threshold voltage and the temperature dependency of threshold voltage in the liquid crystal display element using the composition, and a liquid crystal display element are provided, which composition comprises a compound of the formula (see fig. I) wherein R1 is 1-8C alkyl, R2 is F or CN and n is 1 or 2;
or comprises the compound of the formula (I) as a first component and at least one member as a second component selected from compounds of the following formulas (II), (III) and (IV);
(see fig. II) wherein R3 is 1-8C alkyl and R4 is H or F, (see fig. III) wherein R5 is 1-8C alkyl, R6 is 1-8C alkoxy or F, m is 1 or 2 and X is single bond or -COO-, and (see fig. IV) wherein R7 is 1-8C alkyl, R8 is 1-8C alkyl or alkoxy, F or CN and (see fig. V) is (see fig. VI) or (see fig. VII).
or comprises the compound of the formula (I) as a first component and at least one member as a second component selected from compounds of the following formulas (II), (III) and (IV);
(see fig. II) wherein R3 is 1-8C alkyl and R4 is H or F, (see fig. III) wherein R5 is 1-8C alkyl, R6 is 1-8C alkoxy or F, m is 1 or 2 and X is single bond or -COO-, and (see fig. IV) wherein R7 is 1-8C alkyl, R8 is 1-8C alkyl or alkoxy, F or CN and (see fig. V) is (see fig. VI) or (see fig. VII).
Description
133~9649 This invention relates to a liquid crystal composition for twist nematic (hereinafter abbreviated to TN) mode and a liquid crystal display element of TN mode using the above-mentioned composition. More particularly it relates to a liquid crystal composition capable of reducing the threshold voltage (hereinafter abbreviated to Vth) of TN
mode liquid crystal display elements and improving the temperature dependency thereof.
In recent years, the performances of liquid crystal display devices have been improved and their application fields have been being broadened. At the initial period of liquid crystal display devices, the devices have been mainly used for handy type electronic calculators, watches, clocks, etc., making use of the specific feature of small power consumption thereof. Recently, however, the application fields of the devices, in combination with development of liquid crystal compositions, have come to be rapidly broadened toward those of large-size ~7~.
~L3396~9 devices such as outdoor display devices, instrument panels for automobiles, and further, display devices for hand-held computers, terminals of computers, etc.
From the viewpoint of the driving mode of display devices relative to the foregoing, since the information quantity has increased and the number of parts has been reduced, the 3V drive static mode at the initial period has come to be transferred into 3V drive, 1/2 duty in the case of watches, etc., 3V drive, 1/3 to 1/~ duty in the case of electronic calculators, and 4.5V drive, 1/16 duty and ten and several V drive, 1/64 duty or further, highly functional display having higher driv-ing voltage and multiplex number in the case of graphic displays such as those of word processors, computer terminals, etc. Further, in addition to these movements, need for low voltage drive as one more specific feature of liquid crystal display devices, has come to be intensified in order to realize making LCD smaller and more lightweight. For example, 1/2 to 1/4 duty in the case of watches, electronic calculators, etc. has been desired to be driven at 1.5 V, 1/16 duty in the case of word processors, etc., at 3 V, and 1/64 duty in the case of computer terminals, etc., at 10 V or lower. Namely, it has been desired to reduce the threshold voltage in the voltage-brightness characteristic of liquid crystal compositions, but it has been very difficult in the case 1~39649 of conventional materials to effect low voltage drive, while satisfying specific features for securing a display quality as mentioned later, i.e. a sufficiently low optical anisotropy value for securing a broad viewing angle and a small temperature-dependency value of threshold voltage.
Usually, in the case of multiplex drive mode employing a voltage-leveling method, there is an operational restriction which does not occur at all in principle in the case of static mode.
Namely, cross-talk is liable to occur in a half-selected element or unselected element. Furthermore, the higher the multiplex, the less the allowance of the operating voltage, in short, the operating margin;
hence cross-talk is more liable to occur.
The operating margin depends on the following three factors:
temperature dependency of threshold voltage, ~ viewing angle dependency of threshold voltage and ~ steepness of threshold voltage.
As to the factor ~ among these three, a product of the thickness of display cell (hereinafter abbreviated to d) by the optical anisotropy value (hereinafter abbreviated to ~n) i.e. a light path length of bire-fringence (hereinafter abbreviated to d-An) has a great influence upon the factor ~ . For example, it has I~39~g generally been carried out to obtain a display element of broad viewing angle, by satisfying the following conditional equation (1) derived from Gooch-Tarry's equation (J. Phys. D.: Appl. Phys.,-vol. 8, 1975) sin2 ~ +
T =
( l+u2) wherein T: light transmittance, e twist angle, u: ~d ~n/~, and ~: wavelength:
d-~n = 550 nm ... (1) In general, it is difficult in the aspects of cell preparation and product yield to make the cell thick-ness (d) 5 ~m or less; hence the ~n value of liquid crystal materials is preferred to be less than 0.11 in view of the above equation (1). The above factor is specific of TN mode liquid crystal display devices, and no notable difference in the factor (3) occurs depending on materials. The above factor ~ has a relation also with the operating temperature range, and is most affected by materials. In general, as a countermeasure to liquid crystal compositions in order to improve the above factor ~ , it has been carried out to increase the proportion of a material having a negative dielectric anisotropy value (herein-after abbreviated to ~~ ) to thereby reduce the temperature dependency of threshold voltage. However, increase in 13396~9 the proportion of a material having a negative ~ raises the threshold voltage; hence a sufficiently low voltage drive could not have been achieved.
Further, in the case of display devices, the response rate is a nonnegligible and important factor. It is well known that the response rate of liquid crystal display devices has a correlationship with the viscosity of liquid crystal compositions relative thereto.
The present invention provides a nematic liquid crystal composition which has a sufficiently low optical anisotropy a value and also a sufficiently low threshold voltage value for effecting a broad viewing angle, while keeping various characteristics required for liquid crystal display devices such as operating temperature range, response rate, etc. in well-balanced manner, and has an improved temperature dependency.
The present invention also provides a liquid crystal display element which can be driven at low voltages, has a broad viewing angle and has a small temperature dependency.
The present invention in a first aspect resides in a liquid crystal composition for twist nematic mode comprising a compound expressed by the formula 13~6 R~ n~R2 (I) wherein Rl represents an alkyl group of 1 to 8 carbon atoms, R2 represents F or CN and n represents 1 or 2;
as a preferred embodiment of the above composition, a liquid crystal composition comprising a first component comprising at least one member of the compound expressed by the above formula (I) and a second com-ponent comprising at least one member selected from the group consisting of a compound expressed by the formula R3{0~F (lD
wherein R3 re~resents an alkyl group of 1 to 8 carbon atoms and R4 represents H or F, a compound expressed by the formula Rs~ ( ~ m ~ R6 (IID
wherein R5 represents an alkyl group of 1 to 8 carbon atoms, R6 represents an alkoxy group of 1 to 8 carbon atoms or F, m represents 1 or 2 and X represents a single bond or -COO-, - 7 - 13396~9 and a comp'ound expressed by the formula R7 {~ Rs wherein R7 represents an alkyl group of 1 to 8 carbon atoms, R8 represents an alkyl group or alkoxy group each of 1 to 3 carbon atoms, F or C~J group and ~ -represents ~ or ~ -.
The present invention in the second aspect resides in a liquid crystal display element using a liquid crystal composition for twist nematic mode comprising a compound expressed by the formula -( ~ ) n ~ R2 (I) wherein Rl represents an alkyl group of 1 to 8 carbon atoms, R2 represents F or CN and n represents 1 or 2;
and as an embodiment of the above element, a liquid crystal display element using a liquid crystal composition for twist nematic mode comprising a first component com rising at least one member of the a-bovecompound expressed by the formula (I) and a second component comprising at least one member selected from the group consisting of the above compounds expressed by the formulas (II), (III) and (IV).
13396~9 .
~c In the liquid crystal composition of the present invention, the content of the compound of the formula (I) wherein n=l, i.e. a two-ring compound is preferably 15 to 40% by weight and the content of the compound of the form-ula (I) wherein n=2, i.e. a three-ring compound is prefer-ably 15 to 60% by weight. The content of the compound ex-pressed by the formula (II) is preferably 25% by weight or less, that of the compound expressed by the formula (III) is preferably 30% by weight or less and that of the com-pound expressed by the formula (IV) is preferably 35~ by weight or less. The composition preferably comprises at least a 30 weight percent mixture of the compounds of formula (I).
Besides the above compounds of the formulas (I) to (IV), the liquid crystal composition of the present invent-ion may further contain other nematic liquid crystals or liquid crystalline compounds for adjusting threshold volt-age, mesomorphic range, viscosity, etc. in a suitable quantity, within a range where the object of the present invention is not damaged.
Preferred representative examples of such other com-pounds are as follows:
4-(trans-4-alkylcyclohexyl)benzonitriles, 4'-alkyl-4-cyanobiphenyls, trans-2-(4-cyanophenyl)-5-alkyl-1,3-dioxanes, 4-(trans-4-alkoxymethylcyclohexyl)benzonitriles, etc.
133964g In the liquid crystal composition of the present invention, compounds of the formula (I) wherein n=l, i.e.
4-(trans-4-alkylcyclohexyl)-1,2-difluorobenzenes and 4-(trans-4-alkylcyclohexyl)-2-fluorobenzonitriles mostly exhibit no liquid crystal phase at room tempera-ture, but these compounds have an effectiveness of increasing the ~ value of compositions obtained by using them, toward positive values and reducing the ~n value thereof. The content of these compounds are preferably 15 to 40% by weight. If it is less than about 15% by weight, contribution of ~ is small and reduction in the threshold voltage value is insufficient, whereas if it exceeds about 40% by weight, they mostly exhibit no liquid crystal phase at room temperature, as described above; thus the clearing point of the resulting composi-tion often lowers and hence such higher contents are undesirable.
Further, compounds of the formula (I) wherein n=2, i.e.
4-{trans-4-(trans-4-alkylcyclohexyl)cyclohexyl}-1,2-difluorobenzenes, exhibit a high nematic-isotropic liquid phase transition point (hereinafter referred to as clearing point) OL 85.4~C or higher, a small ~n value, a low viscosity and a positive ~ value.
Further, 4-{trans-4-(trans-4-alkylcyclohexyl)cyclo-hexyl}-2-fluorobenzonitriles exhibit a clearing point of 133964g 176.5~C or higher and a positive large ~~ value. These compounds contribute to a high clearing point and reduc-tion in the threshold voltage without increasing ~n, in the resulting composition. The content of these compounds is preferably 15 to 60% by weight. If it is less than 15% by weight, the above-mentioned contribution to ~n, clearing point and threshold voltage is small, whereas if it exceeds 60% by weight, the lower limit temperature of the nematic phase of the resulting com-position rises and the operation temperature range onthe lower temperature side is narrowed.
In the liquid crystal composition of the present invention, compounds expressed by the formula (II), i.e.
mode liquid crystal display elements and improving the temperature dependency thereof.
In recent years, the performances of liquid crystal display devices have been improved and their application fields have been being broadened. At the initial period of liquid crystal display devices, the devices have been mainly used for handy type electronic calculators, watches, clocks, etc., making use of the specific feature of small power consumption thereof. Recently, however, the application fields of the devices, in combination with development of liquid crystal compositions, have come to be rapidly broadened toward those of large-size ~7~.
~L3396~9 devices such as outdoor display devices, instrument panels for automobiles, and further, display devices for hand-held computers, terminals of computers, etc.
From the viewpoint of the driving mode of display devices relative to the foregoing, since the information quantity has increased and the number of parts has been reduced, the 3V drive static mode at the initial period has come to be transferred into 3V drive, 1/2 duty in the case of watches, etc., 3V drive, 1/3 to 1/~ duty in the case of electronic calculators, and 4.5V drive, 1/16 duty and ten and several V drive, 1/64 duty or further, highly functional display having higher driv-ing voltage and multiplex number in the case of graphic displays such as those of word processors, computer terminals, etc. Further, in addition to these movements, need for low voltage drive as one more specific feature of liquid crystal display devices, has come to be intensified in order to realize making LCD smaller and more lightweight. For example, 1/2 to 1/4 duty in the case of watches, electronic calculators, etc. has been desired to be driven at 1.5 V, 1/16 duty in the case of word processors, etc., at 3 V, and 1/64 duty in the case of computer terminals, etc., at 10 V or lower. Namely, it has been desired to reduce the threshold voltage in the voltage-brightness characteristic of liquid crystal compositions, but it has been very difficult in the case 1~39649 of conventional materials to effect low voltage drive, while satisfying specific features for securing a display quality as mentioned later, i.e. a sufficiently low optical anisotropy value for securing a broad viewing angle and a small temperature-dependency value of threshold voltage.
Usually, in the case of multiplex drive mode employing a voltage-leveling method, there is an operational restriction which does not occur at all in principle in the case of static mode.
Namely, cross-talk is liable to occur in a half-selected element or unselected element. Furthermore, the higher the multiplex, the less the allowance of the operating voltage, in short, the operating margin;
hence cross-talk is more liable to occur.
The operating margin depends on the following three factors:
temperature dependency of threshold voltage, ~ viewing angle dependency of threshold voltage and ~ steepness of threshold voltage.
As to the factor ~ among these three, a product of the thickness of display cell (hereinafter abbreviated to d) by the optical anisotropy value (hereinafter abbreviated to ~n) i.e. a light path length of bire-fringence (hereinafter abbreviated to d-An) has a great influence upon the factor ~ . For example, it has I~39~g generally been carried out to obtain a display element of broad viewing angle, by satisfying the following conditional equation (1) derived from Gooch-Tarry's equation (J. Phys. D.: Appl. Phys.,-vol. 8, 1975) sin2 ~ +
T =
( l+u2) wherein T: light transmittance, e twist angle, u: ~d ~n/~, and ~: wavelength:
d-~n = 550 nm ... (1) In general, it is difficult in the aspects of cell preparation and product yield to make the cell thick-ness (d) 5 ~m or less; hence the ~n value of liquid crystal materials is preferred to be less than 0.11 in view of the above equation (1). The above factor is specific of TN mode liquid crystal display devices, and no notable difference in the factor (3) occurs depending on materials. The above factor ~ has a relation also with the operating temperature range, and is most affected by materials. In general, as a countermeasure to liquid crystal compositions in order to improve the above factor ~ , it has been carried out to increase the proportion of a material having a negative dielectric anisotropy value (herein-after abbreviated to ~~ ) to thereby reduce the temperature dependency of threshold voltage. However, increase in 13396~9 the proportion of a material having a negative ~ raises the threshold voltage; hence a sufficiently low voltage drive could not have been achieved.
Further, in the case of display devices, the response rate is a nonnegligible and important factor. It is well known that the response rate of liquid crystal display devices has a correlationship with the viscosity of liquid crystal compositions relative thereto.
The present invention provides a nematic liquid crystal composition which has a sufficiently low optical anisotropy a value and also a sufficiently low threshold voltage value for effecting a broad viewing angle, while keeping various characteristics required for liquid crystal display devices such as operating temperature range, response rate, etc. in well-balanced manner, and has an improved temperature dependency.
The present invention also provides a liquid crystal display element which can be driven at low voltages, has a broad viewing angle and has a small temperature dependency.
The present invention in a first aspect resides in a liquid crystal composition for twist nematic mode comprising a compound expressed by the formula 13~6 R~ n~R2 (I) wherein Rl represents an alkyl group of 1 to 8 carbon atoms, R2 represents F or CN and n represents 1 or 2;
as a preferred embodiment of the above composition, a liquid crystal composition comprising a first component comprising at least one member of the compound expressed by the above formula (I) and a second com-ponent comprising at least one member selected from the group consisting of a compound expressed by the formula R3{0~F (lD
wherein R3 re~resents an alkyl group of 1 to 8 carbon atoms and R4 represents H or F, a compound expressed by the formula Rs~ ( ~ m ~ R6 (IID
wherein R5 represents an alkyl group of 1 to 8 carbon atoms, R6 represents an alkoxy group of 1 to 8 carbon atoms or F, m represents 1 or 2 and X represents a single bond or -COO-, - 7 - 13396~9 and a comp'ound expressed by the formula R7 {~ Rs wherein R7 represents an alkyl group of 1 to 8 carbon atoms, R8 represents an alkyl group or alkoxy group each of 1 to 3 carbon atoms, F or C~J group and ~ -represents ~ or ~ -.
The present invention in the second aspect resides in a liquid crystal display element using a liquid crystal composition for twist nematic mode comprising a compound expressed by the formula -( ~ ) n ~ R2 (I) wherein Rl represents an alkyl group of 1 to 8 carbon atoms, R2 represents F or CN and n represents 1 or 2;
and as an embodiment of the above element, a liquid crystal display element using a liquid crystal composition for twist nematic mode comprising a first component com rising at least one member of the a-bovecompound expressed by the formula (I) and a second component comprising at least one member selected from the group consisting of the above compounds expressed by the formulas (II), (III) and (IV).
13396~9 .
~c In the liquid crystal composition of the present invention, the content of the compound of the formula (I) wherein n=l, i.e. a two-ring compound is preferably 15 to 40% by weight and the content of the compound of the form-ula (I) wherein n=2, i.e. a three-ring compound is prefer-ably 15 to 60% by weight. The content of the compound ex-pressed by the formula (II) is preferably 25% by weight or less, that of the compound expressed by the formula (III) is preferably 30% by weight or less and that of the com-pound expressed by the formula (IV) is preferably 35~ by weight or less. The composition preferably comprises at least a 30 weight percent mixture of the compounds of formula (I).
Besides the above compounds of the formulas (I) to (IV), the liquid crystal composition of the present invent-ion may further contain other nematic liquid crystals or liquid crystalline compounds for adjusting threshold volt-age, mesomorphic range, viscosity, etc. in a suitable quantity, within a range where the object of the present invention is not damaged.
Preferred representative examples of such other com-pounds are as follows:
4-(trans-4-alkylcyclohexyl)benzonitriles, 4'-alkyl-4-cyanobiphenyls, trans-2-(4-cyanophenyl)-5-alkyl-1,3-dioxanes, 4-(trans-4-alkoxymethylcyclohexyl)benzonitriles, etc.
133964g In the liquid crystal composition of the present invention, compounds of the formula (I) wherein n=l, i.e.
4-(trans-4-alkylcyclohexyl)-1,2-difluorobenzenes and 4-(trans-4-alkylcyclohexyl)-2-fluorobenzonitriles mostly exhibit no liquid crystal phase at room tempera-ture, but these compounds have an effectiveness of increasing the ~ value of compositions obtained by using them, toward positive values and reducing the ~n value thereof. The content of these compounds are preferably 15 to 40% by weight. If it is less than about 15% by weight, contribution of ~ is small and reduction in the threshold voltage value is insufficient, whereas if it exceeds about 40% by weight, they mostly exhibit no liquid crystal phase at room temperature, as described above; thus the clearing point of the resulting composi-tion often lowers and hence such higher contents are undesirable.
Further, compounds of the formula (I) wherein n=2, i.e.
4-{trans-4-(trans-4-alkylcyclohexyl)cyclohexyl}-1,2-difluorobenzenes, exhibit a high nematic-isotropic liquid phase transition point (hereinafter referred to as clearing point) OL 85.4~C or higher, a small ~n value, a low viscosity and a positive ~ value.
Further, 4-{trans-4-(trans-4-alkylcyclohexyl)cyclo-hexyl}-2-fluorobenzonitriles exhibit a clearing point of 133964g 176.5~C or higher and a positive large ~~ value. These compounds contribute to a high clearing point and reduc-tion in the threshold voltage without increasing ~n, in the resulting composition. The content of these compounds is preferably 15 to 60% by weight. If it is less than 15% by weight, the above-mentioned contribution to ~n, clearing point and threshold voltage is small, whereas if it exceeds 60% by weight, the lower limit temperature of the nematic phase of the resulting com-position rises and the operation temperature range onthe lower temperature side is narrowed.
In the liquid crystal composition of the present invention, compounds expressed by the formula (II), i.e.
2-(4-fluorophenyl)-5-alkylpyrimidines and 2-(3,4-difluorophenyl)-5-alkylpyrimidines exhibit no liquid crystal phase at room temperature, but they contribute to increase in the ~~ value, reduc-tion in the ~n value and reduction in the viscosity in the compositions obtained by using these compounds.
Further, the content of these compounds is preferably about 25% by weight or less. If it exceeds 25% by weight, no liquid crystal phase is exhibited at room temperature; hence the clearing point of the resulting liquid crystal composition often lowers.
In the liquid crystal composition of the present invention,compounds expressed by the formula (III ), i, e.
13396~g 4"-(trans-4-alkylcyclohexyl)alkoxybenzenes, 4-alkoxyphenyl trans-4-alkylcyclohexanecarboxylates, 4-fluorophenyl trans-4-alkylcyclohexanecarboxylates, - 4-fluorophenyl trans-4-(trans-4-alkylcyclohexyl)-cyclohexanecarboxylates, etc., have a low viscosity and a small An value, but exhibit a positive or negative ~~ value close to zero; hence they often raise the threshold voltage of the resulting liquid crystal composition depending on blending thereof.
The content of these compounds is preferably 25% by weight or less.
In the liquid crystal composition of the present invention, compounds expressed by the formula (IV), i.e.
4-{trans-4-(trans-4-alkylcyclohexyl)cyclohexyl}-alkylbenzenes, 4-{trans-4-(trans-4-alkylcyclohexyl)cyclohexyl}-benzonitriles, 4'-(trans-4-alkylcyclohexyl)-4-alkylbiphenyls, etc.
exhibit a low viscosity for three-ring compounds, but exhibit a high clearing point of 146.3~C or higher; hence they contribute to viscosity reduction, retention of clearing point, etc. in the resulting liquid crystal composition, but the lower limit temperature of nematic phase rises depending on blending thereof with other compounds and the operation temperature range on the lower temperature side is narrowed; hence the content of these compounds is preferably 10% by weight or less.
13396~9 The present invention will be described in more detail by way of Examples, but it should not be construed to be limited thereto.
In order to show the effectiveness of the liquid crystal composition of the present invention and the display element using the composition, a manner express-ing the characteristic values of the composition will be described.
In addition, the threshold voltage and the temper-ature dependency of the threshold voltage in the presentinvention are defined as follows:
In the voltage-brightness characteristic, a voltage at which the transmittance of a light in the light axis direction perpendicular to the display surface reaches 10% is referred to as threshold voltage and expressed by Vth. Further, when the respective threshold voltages at two different temperatures tl (~C) and t2 (~C) are expressed by Vth (tl) and Vth (t2), the temperature dependency of the threshold voltage dV/dt is determined by the following equation (1):
dV Vth ~tl) ~ V th ( tz) 1 0 0 X ~%~C
dt Vth(tl) +Vth(t2) t~ ~ t2 (1) Thus, this equation shows that the nearer the absolute value of the parameter dV/dt is to zero, the more the temperature dependency is improved. In thé following Examples and Comparative examples, the compositions are expressed in terms of % by weight.
Example 1 A liquid crystal composition consisting of the following 5 compounds of the formula (I) was prepared:
4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 20%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 20%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 20%
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 20% and 4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-2-fluorobenzonitrile 20%.
This liquid crystal composition exhibited a clearing point of 60.4~C, an optical anisotropy value of 0.111 and a viscosity at 20~C of 33.0 cp.
This liquid crystal composition was filled in a 90~
twist TN cell having a rubbed film of a polyimide on the respective opposed transparent electrodes under a condition of d-~n=550 nm, followed by measuring various characteristics. Here, d refers to the thick-ness of the cell i.e. a distance between the electrodes.
The threshold voltage at 25~C was 1.05 V and 13396~g the temperature dependency of the threshold voltages at from 0~C to 40~C (dV/dt) was -0.40~/~C.
Example 2 A liquid crystal composition consisting of three compounds of the formula (I), 4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 14.3%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 14.2% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-2-fluorobenzonitrile 14.2%;
two compounds of the formula (II), 2-(3,4-difluorophenyl)-5-propylpyrimidine 9.5% and 2-(4-fluorophenyl)-5-ethylpyrimidine 14.3%; and three compounds of the formula (IV), 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-toluene 9-5%
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-propylbenzene 19% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-kenzonitrile 5%
was prepared, followed by measuring its characteristics in the same manner as in Example 1. The results are shown in Table 1.
i339649 Example 3 A liquid crystal composition consisting of six compounds of the formula (I), 4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 15%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 10%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15%
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-~ 2-fluorobenzonitrile 15% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-2-fluorobenzonitrile 15%; and two other compounds, 4-(trans-4-ethylcyclohexyl)benzonitrile 10% and 4'-ethyl-4-cyanobiphenyl 5%
was prepared, followed by measuring its characteristics in the same manner as in Example 1. The results are shown in Table 1.
Example 4 A liquid crystal composition consisting of seven compounds of the formula (I), 4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 7%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 6%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-- 1,2-difluorobenzene 7%
54-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 7%
4-{trans-4-(trans-4-pentylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 3%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-102-fluorobenzonitrile 13% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-2-fluorobenzonitrile 13%;
a compound of the formula (II), 2-(3,4-difluorophenyl)-5-propylpyrimidine 11%;
three compounds of the formula (III), 4-ethoxyphenyl trans-4-propylcyclohexanecarboxylate 8%
4-ethoxyphenyl trans-4-butylcyclohexanecarboxylate 8% and 204-butoxyphenyl trans-4-butylcyclohexanecarboxylate 9%; and another compound, trans-2-(4-cyanophenyl)-5-propyl-1,3-dioxane 8%
was prepared, followed by measurin~ its characteristics in the same manner as in Example 1. The results are shown in Table 1.
Comparative example 1 A liquid crystal composition consisting of the following component A, component B and component C
(seven compounds in total)was prepared:
component A: cyanophenylmetadioxanes which, when dissolved in 15% by weight to a so far known composition of cyanophenylcyclohexanes (ZQi-1083, tradename of product made by Merck Company), the resulting compositions exhibit an exceptionally low ~n and an exceptionally large ~E, concretely a clearing point of 26.0~ to 41.3~C, a ~n value of 0.09 to 0.100 and a ~~ value of 25.6 to 26.9 in terms of extrapolated values:
trans-2-(4-cyanophenyl)-5-propyl-1,3-dioxane 19.6 trans-2-(4-cyanophenyl)-5-butyl-1,3-dioxane 19.6% and trans-2-(4-cyanophenyl)-5-pentyl-1,3-dioxane 19.6%;
component B: phenyl cyclohexanecarboxylates which exhibit specific characteirstic values of a An value of 0.087 and a ~~ value of -1.2 and have been generally known to persons skilled in the art to be suitable for reducing the temperature dependency of threshold voltage:
133964~
4-ethoxyphenyl trans-~-propylcyclohexanecarboxylate 10%
4-ethoxyphenyl trans-4-butylcyclohexanecarboxylate 10% and 4-butoxyphenyl trans-4-butylcyclohexanecarboxylate 13.3%; and Component C: a so far known biphenyl cyclohexane generally used by persons skilled in the art for securing transparent point, 4'-(trans-4-pentyl-cyclohexyl)-4-cyanobiphenyl 7.9%, followed by measuring its characteristics in the same manner as in Example 1. The results are shown in Table 1.
Table 1 ~ xample Example Coemxp.
Charac- ~ 1 2 3 4 Clearing poi)nt 60.4 65.8 71.0 63.7 . 60.7 anisotropy 0.110 0.110 0.110 0.096 0.110 (20~Y)(c~) 33.0 19-2 34.2 36 34 Vth(25~C)~V~ 1.0 5 1.13 1.12 1.1 5 1.15 ~ %~C ~ ~ 040 -037 - 0.2 9 - 0 34 -061 Example 5 A liquid crystal composition consistin~ of seven compounds of the formula (I):
4-(trans-4-pentylcyclohexyl)-1,2-~ifluorobenzene 10%
4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 10%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 10%
104-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15~
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-152-fluorobenzonitrile 10% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-2-fluorobenzonitrile 10%;
a compound of the formula (IV), 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-20propylbenzene 10%; and another compound, 4-(trans-4-methoxymethylcyclohexyl)benzonitrile 10%, was prepared, followed by measuring its characteristics in the same maDner as in Example 1. The results are shown in Table 2.
- 20 - 1339fi49 Example 6 - A liquid crystal composition consisting of six compounds of the formula (I "
4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 12.2%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 14.6%
4-(trans-4-pentylcyclohexyl)-2-fluorobenzonitrile 12.2%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 13.4%
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 13.4% and 4-{trans-4-(trans-4-pentylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 13.4%;
two compounds of the formula (III), 4-fluorophenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanecarboxylate 4.9% and 4-fluorophenyl trans-4-(trans-4-pentylcyclohexyl)-cyclohexanecarboxylate 4.9%; and two compounds of the formula (IV), 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-fluorobenzene 6.1% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-methoxybenzene 4 0%' 13396~9 was prepared, followed by measuring its characteristics in the same manner as in Example 1. The results are shown in Table 2.
- Example 7 A liquid crystal composition consisting of five compounds of the formula (I), 4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 12%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 12%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15%
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15% and 154-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-2-fluorobenzonitrile 8%;
one compound of the formula (II), 2-(4-fluorophenyl)-5-ethylpyrimidine 15%; and two compounds of the formula (IV), 204-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-toluene 9% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-propylbenzene 14%
was prepared, followed by measuring its characteristics in the same manner as in Example 1. The results are shown in Table 2.
- 22 - 133964~
Example 8 A liquid crystal composition consisting of two compounds of the formula (I), 4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 518% and 4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 18%, five compounds of the formula (III), 4-ethoxyphenyl trans-4-propylcyclohexanecarboxylate 10 10%
4-ethoxyphenyl trans-4-butylcyclohexanecarboxylate 10%
4-butoxyphenyl trans-4-butylcyclohexanecarboxylate 7%
154-fluorophenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanecarboxylate 4.5% and 4-fluorophenyl trans-4-(trans-4-pentylcyclohexyl)-cyclohexanecarboxylate 4.5%;
three compounds of the formula (IV), 204-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-benzonitrile 5%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl~-benzonitrile 5% and 4'-(trans-4-pentylcyclohexyl)-4-ethylbiphenyl 259%; and ' - 23 - ~33961g another compound, trans-2-t4-cyanophenyl)-5-propyl-1,3-dioxane 9%
was prepared, followed by measuring its characteristics,in the same manner as in Example 1. The results are shown in Table 2.
Example 9 A liquid crystal composition consisting of five compounds of the formula (I), 4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 15%
104-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 15%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15%
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-151,2-difluorobenzene 15% and 4-{trans-4-(trans-4-pentylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 10%;
one compound of the formula (III), 4-(trans-4-propylcyclohexyl)ethoxybenzene 8%;
two compounds of the formula (IV), 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-benzonitrile 6% and 4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-benzonitrile 6%; and another compound, trans-2-(4-cyanophenyl)-5-propyl-1,3-dioxane 10%
- 133~6~9 was prepared, followed by measuring its characteristics in the same manner as in Example 1. The results are shown in Table 2.
Comparative example 2 A liquid crystal composition consisting of the following components A, B and C used in Comparative example 1 and further the following component D, that is, a so far known compound, 4'-(trans-4-pentylcyclo-hexyl)-4-cyanobiphenyl having a clearing point of 280.0~C
was prepared:
component A
trans-2-(4-cyanophenyl)-5-propyl-1,3-dioxane 19.6%
trans-2-(4-cyanophenyl)-5-butyl-1,3-dioxane 19.6% and trans-2-(4-cyanophenyl)-5-pentyl-1,3-dioxane 19.6%;
component B
4-ethoxyphenyl trans-4-propylcyclohexane-carboxylate 9%
4-ethoxyphenyl trans-4-butylcyclohexane-carboxylate 9% and 4-butoxyphenyl trans-4-butylcyclohexane-carboxylate 11.3%;
- 25- 1~396~9 component C
4'-(trans-4-pentylcyclohexyl)-4-cyanobiphenyl 7.9%; and component D
4'-cyano-4-biphenylyl trans-4-(trans-4-pentyl-cyclohexyl)cyclohexanecarboxylate 4%.
The characteristics of the composition was then measured in the same manner as in Example l. The results are shown in Table 2.
Table 2 \ exam- Comp. .
Ch~_ple Example ex.
acte~ 6 7 8 9 2 Clearing point 68.6 6 1.1 68.5 6 1.4 61.3 7 0.1 ( o C ) Optical aniso- 0.0 9 4 0.0 7 8 0.0 9 8 0.0 8 9 0.0 9 3 P.l 17 tropy Viscositv (20~C) 26.7 22.2 20.5 23.9 25.5 35 (cp) Vt~ V2~c) 1.2 2 1.3 6 1.2 8 1.1 6 1.18 1.3 8 dV/dt (O 40 C) 0.3 3 0.3 8 0.3 4 0.4 2 0.4 3 0.5 3 ~ %/~C ~
133964~
The liquid crystal composition and the liquid crystal display element of the present invention have various characteristics required for liquid crystal materials - used for twist nematic (TN) mode liquid crystal display elements, particularly multiplex drive TN elements, namely a sufficiently low viscosity for securing response properties, a sufficiently low an value for obtaining a broad viewing angle, particularly a low threshold voltage for low voltage drive and its low temperature dependency, and these various characteristics have been notably improved as compared with those of conventional compositions and display elements.
As to the temperature dependency of threshold voltage defined by the above equation (1), the nearer the dependency is to zero, the more it is desired, and in the present invention, a further less value has been achieved. It has been well known for persons skilled in the art that as the threshold voltage lowers, the temperature dependency thereof increases, that is, this has a bad influence upon display elements, but as directly shown in comparison of Comparative example 1 with Example l, the compound of the formula (I) of the present invention has almost the same clearing point and the same low ~n value as those of Comparative example 1 and nevertheless affords particularly a lower threshold voltage and a less temperature dependency of threshold voltage.
1339fi49 Further, as seen from comparisons of Comparative example 1 with Examples 2 to 4 and those of Comparative example 2 with Examples 5 to 9 in Table 2, particularly a lower threshold voltage and a less temperature dependency of threshold voltage are exhibited while clearing point, An and viscosity values are kept in well-balanced manner. It is considered that the com-pounds of the formulas (I) and (II) greatly contribute to the above facts and particularly the compound of the formula (I) does.
Since the nematic liquid crystal composition of the present invention has the above-mentioned charac-teristics, when the composition is used, a broad viewing angle and a low-voltage multiplex drive (e.g. 1.5 V, l/2 _ 1/3 duty drive) is possible.
Further, the content of these compounds is preferably about 25% by weight or less. If it exceeds 25% by weight, no liquid crystal phase is exhibited at room temperature; hence the clearing point of the resulting liquid crystal composition often lowers.
In the liquid crystal composition of the present invention,compounds expressed by the formula (III ), i, e.
13396~g 4"-(trans-4-alkylcyclohexyl)alkoxybenzenes, 4-alkoxyphenyl trans-4-alkylcyclohexanecarboxylates, 4-fluorophenyl trans-4-alkylcyclohexanecarboxylates, - 4-fluorophenyl trans-4-(trans-4-alkylcyclohexyl)-cyclohexanecarboxylates, etc., have a low viscosity and a small An value, but exhibit a positive or negative ~~ value close to zero; hence they often raise the threshold voltage of the resulting liquid crystal composition depending on blending thereof.
The content of these compounds is preferably 25% by weight or less.
In the liquid crystal composition of the present invention, compounds expressed by the formula (IV), i.e.
4-{trans-4-(trans-4-alkylcyclohexyl)cyclohexyl}-alkylbenzenes, 4-{trans-4-(trans-4-alkylcyclohexyl)cyclohexyl}-benzonitriles, 4'-(trans-4-alkylcyclohexyl)-4-alkylbiphenyls, etc.
exhibit a low viscosity for three-ring compounds, but exhibit a high clearing point of 146.3~C or higher; hence they contribute to viscosity reduction, retention of clearing point, etc. in the resulting liquid crystal composition, but the lower limit temperature of nematic phase rises depending on blending thereof with other compounds and the operation temperature range on the lower temperature side is narrowed; hence the content of these compounds is preferably 10% by weight or less.
13396~9 The present invention will be described in more detail by way of Examples, but it should not be construed to be limited thereto.
In order to show the effectiveness of the liquid crystal composition of the present invention and the display element using the composition, a manner express-ing the characteristic values of the composition will be described.
In addition, the threshold voltage and the temper-ature dependency of the threshold voltage in the presentinvention are defined as follows:
In the voltage-brightness characteristic, a voltage at which the transmittance of a light in the light axis direction perpendicular to the display surface reaches 10% is referred to as threshold voltage and expressed by Vth. Further, when the respective threshold voltages at two different temperatures tl (~C) and t2 (~C) are expressed by Vth (tl) and Vth (t2), the temperature dependency of the threshold voltage dV/dt is determined by the following equation (1):
dV Vth ~tl) ~ V th ( tz) 1 0 0 X ~%~C
dt Vth(tl) +Vth(t2) t~ ~ t2 (1) Thus, this equation shows that the nearer the absolute value of the parameter dV/dt is to zero, the more the temperature dependency is improved. In thé following Examples and Comparative examples, the compositions are expressed in terms of % by weight.
Example 1 A liquid crystal composition consisting of the following 5 compounds of the formula (I) was prepared:
4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 20%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 20%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 20%
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 20% and 4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-2-fluorobenzonitrile 20%.
This liquid crystal composition exhibited a clearing point of 60.4~C, an optical anisotropy value of 0.111 and a viscosity at 20~C of 33.0 cp.
This liquid crystal composition was filled in a 90~
twist TN cell having a rubbed film of a polyimide on the respective opposed transparent electrodes under a condition of d-~n=550 nm, followed by measuring various characteristics. Here, d refers to the thick-ness of the cell i.e. a distance between the electrodes.
The threshold voltage at 25~C was 1.05 V and 13396~g the temperature dependency of the threshold voltages at from 0~C to 40~C (dV/dt) was -0.40~/~C.
Example 2 A liquid crystal composition consisting of three compounds of the formula (I), 4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 14.3%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 14.2% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-2-fluorobenzonitrile 14.2%;
two compounds of the formula (II), 2-(3,4-difluorophenyl)-5-propylpyrimidine 9.5% and 2-(4-fluorophenyl)-5-ethylpyrimidine 14.3%; and three compounds of the formula (IV), 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-toluene 9-5%
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-propylbenzene 19% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-kenzonitrile 5%
was prepared, followed by measuring its characteristics in the same manner as in Example 1. The results are shown in Table 1.
i339649 Example 3 A liquid crystal composition consisting of six compounds of the formula (I), 4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 15%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 10%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15%
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-~ 2-fluorobenzonitrile 15% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-2-fluorobenzonitrile 15%; and two other compounds, 4-(trans-4-ethylcyclohexyl)benzonitrile 10% and 4'-ethyl-4-cyanobiphenyl 5%
was prepared, followed by measuring its characteristics in the same manner as in Example 1. The results are shown in Table 1.
Example 4 A liquid crystal composition consisting of seven compounds of the formula (I), 4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 7%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 6%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-- 1,2-difluorobenzene 7%
54-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 7%
4-{trans-4-(trans-4-pentylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 3%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-102-fluorobenzonitrile 13% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-2-fluorobenzonitrile 13%;
a compound of the formula (II), 2-(3,4-difluorophenyl)-5-propylpyrimidine 11%;
three compounds of the formula (III), 4-ethoxyphenyl trans-4-propylcyclohexanecarboxylate 8%
4-ethoxyphenyl trans-4-butylcyclohexanecarboxylate 8% and 204-butoxyphenyl trans-4-butylcyclohexanecarboxylate 9%; and another compound, trans-2-(4-cyanophenyl)-5-propyl-1,3-dioxane 8%
was prepared, followed by measurin~ its characteristics in the same manner as in Example 1. The results are shown in Table 1.
Comparative example 1 A liquid crystal composition consisting of the following component A, component B and component C
(seven compounds in total)was prepared:
component A: cyanophenylmetadioxanes which, when dissolved in 15% by weight to a so far known composition of cyanophenylcyclohexanes (ZQi-1083, tradename of product made by Merck Company), the resulting compositions exhibit an exceptionally low ~n and an exceptionally large ~E, concretely a clearing point of 26.0~ to 41.3~C, a ~n value of 0.09 to 0.100 and a ~~ value of 25.6 to 26.9 in terms of extrapolated values:
trans-2-(4-cyanophenyl)-5-propyl-1,3-dioxane 19.6 trans-2-(4-cyanophenyl)-5-butyl-1,3-dioxane 19.6% and trans-2-(4-cyanophenyl)-5-pentyl-1,3-dioxane 19.6%;
component B: phenyl cyclohexanecarboxylates which exhibit specific characteirstic values of a An value of 0.087 and a ~~ value of -1.2 and have been generally known to persons skilled in the art to be suitable for reducing the temperature dependency of threshold voltage:
133964~
4-ethoxyphenyl trans-~-propylcyclohexanecarboxylate 10%
4-ethoxyphenyl trans-4-butylcyclohexanecarboxylate 10% and 4-butoxyphenyl trans-4-butylcyclohexanecarboxylate 13.3%; and Component C: a so far known biphenyl cyclohexane generally used by persons skilled in the art for securing transparent point, 4'-(trans-4-pentyl-cyclohexyl)-4-cyanobiphenyl 7.9%, followed by measuring its characteristics in the same manner as in Example 1. The results are shown in Table 1.
Table 1 ~ xample Example Coemxp.
Charac- ~ 1 2 3 4 Clearing poi)nt 60.4 65.8 71.0 63.7 . 60.7 anisotropy 0.110 0.110 0.110 0.096 0.110 (20~Y)(c~) 33.0 19-2 34.2 36 34 Vth(25~C)~V~ 1.0 5 1.13 1.12 1.1 5 1.15 ~ %~C ~ ~ 040 -037 - 0.2 9 - 0 34 -061 Example 5 A liquid crystal composition consistin~ of seven compounds of the formula (I):
4-(trans-4-pentylcyclohexyl)-1,2-~ifluorobenzene 10%
4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 10%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 10%
104-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15~
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-152-fluorobenzonitrile 10% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-2-fluorobenzonitrile 10%;
a compound of the formula (IV), 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-20propylbenzene 10%; and another compound, 4-(trans-4-methoxymethylcyclohexyl)benzonitrile 10%, was prepared, followed by measuring its characteristics in the same maDner as in Example 1. The results are shown in Table 2.
- 20 - 1339fi49 Example 6 - A liquid crystal composition consisting of six compounds of the formula (I "
4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 12.2%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 14.6%
4-(trans-4-pentylcyclohexyl)-2-fluorobenzonitrile 12.2%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 13.4%
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 13.4% and 4-{trans-4-(trans-4-pentylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 13.4%;
two compounds of the formula (III), 4-fluorophenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanecarboxylate 4.9% and 4-fluorophenyl trans-4-(trans-4-pentylcyclohexyl)-cyclohexanecarboxylate 4.9%; and two compounds of the formula (IV), 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-fluorobenzene 6.1% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-methoxybenzene 4 0%' 13396~9 was prepared, followed by measuring its characteristics in the same manner as in Example 1. The results are shown in Table 2.
- Example 7 A liquid crystal composition consisting of five compounds of the formula (I), 4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 12%
4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 12%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15%
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15% and 154-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-2-fluorobenzonitrile 8%;
one compound of the formula (II), 2-(4-fluorophenyl)-5-ethylpyrimidine 15%; and two compounds of the formula (IV), 204-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-toluene 9% and 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-propylbenzene 14%
was prepared, followed by measuring its characteristics in the same manner as in Example 1. The results are shown in Table 2.
- 22 - 133964~
Example 8 A liquid crystal composition consisting of two compounds of the formula (I), 4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 518% and 4-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 18%, five compounds of the formula (III), 4-ethoxyphenyl trans-4-propylcyclohexanecarboxylate 10 10%
4-ethoxyphenyl trans-4-butylcyclohexanecarboxylate 10%
4-butoxyphenyl trans-4-butylcyclohexanecarboxylate 7%
154-fluorophenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanecarboxylate 4.5% and 4-fluorophenyl trans-4-(trans-4-pentylcyclohexyl)-cyclohexanecarboxylate 4.5%;
three compounds of the formula (IV), 204-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-benzonitrile 5%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl~-benzonitrile 5% and 4'-(trans-4-pentylcyclohexyl)-4-ethylbiphenyl 259%; and ' - 23 - ~33961g another compound, trans-2-t4-cyanophenyl)-5-propyl-1,3-dioxane 9%
was prepared, followed by measuring its characteristics,in the same manner as in Example 1. The results are shown in Table 2.
Example 9 A liquid crystal composition consisting of five compounds of the formula (I), 4-(trans-4-ethylcyclohexyl)-2-fluorobenzonitrile 15%
104-(trans-4-propylcyclohexyl)-2-fluorobenzonitrile 15%
4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 15%
4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-151,2-difluorobenzene 15% and 4-{trans-4-(trans-4-pentylcyclohexyl)cyclohexyl}-1,2-difluorobenzene 10%;
one compound of the formula (III), 4-(trans-4-propylcyclohexyl)ethoxybenzene 8%;
two compounds of the formula (IV), 4-{trans-4-(trans-4-propylcyclohexyl)cyclohexyl}-benzonitrile 6% and 4-{trans-4-(trans-4-ethylcyclohexyl)cyclohexyl}-benzonitrile 6%; and another compound, trans-2-(4-cyanophenyl)-5-propyl-1,3-dioxane 10%
- 133~6~9 was prepared, followed by measuring its characteristics in the same manner as in Example 1. The results are shown in Table 2.
Comparative example 2 A liquid crystal composition consisting of the following components A, B and C used in Comparative example 1 and further the following component D, that is, a so far known compound, 4'-(trans-4-pentylcyclo-hexyl)-4-cyanobiphenyl having a clearing point of 280.0~C
was prepared:
component A
trans-2-(4-cyanophenyl)-5-propyl-1,3-dioxane 19.6%
trans-2-(4-cyanophenyl)-5-butyl-1,3-dioxane 19.6% and trans-2-(4-cyanophenyl)-5-pentyl-1,3-dioxane 19.6%;
component B
4-ethoxyphenyl trans-4-propylcyclohexane-carboxylate 9%
4-ethoxyphenyl trans-4-butylcyclohexane-carboxylate 9% and 4-butoxyphenyl trans-4-butylcyclohexane-carboxylate 11.3%;
- 25- 1~396~9 component C
4'-(trans-4-pentylcyclohexyl)-4-cyanobiphenyl 7.9%; and component D
4'-cyano-4-biphenylyl trans-4-(trans-4-pentyl-cyclohexyl)cyclohexanecarboxylate 4%.
The characteristics of the composition was then measured in the same manner as in Example l. The results are shown in Table 2.
Table 2 \ exam- Comp. .
Ch~_ple Example ex.
acte~ 6 7 8 9 2 Clearing point 68.6 6 1.1 68.5 6 1.4 61.3 7 0.1 ( o C ) Optical aniso- 0.0 9 4 0.0 7 8 0.0 9 8 0.0 8 9 0.0 9 3 P.l 17 tropy Viscositv (20~C) 26.7 22.2 20.5 23.9 25.5 35 (cp) Vt~ V2~c) 1.2 2 1.3 6 1.2 8 1.1 6 1.18 1.3 8 dV/dt (O 40 C) 0.3 3 0.3 8 0.3 4 0.4 2 0.4 3 0.5 3 ~ %/~C ~
133964~
The liquid crystal composition and the liquid crystal display element of the present invention have various characteristics required for liquid crystal materials - used for twist nematic (TN) mode liquid crystal display elements, particularly multiplex drive TN elements, namely a sufficiently low viscosity for securing response properties, a sufficiently low an value for obtaining a broad viewing angle, particularly a low threshold voltage for low voltage drive and its low temperature dependency, and these various characteristics have been notably improved as compared with those of conventional compositions and display elements.
As to the temperature dependency of threshold voltage defined by the above equation (1), the nearer the dependency is to zero, the more it is desired, and in the present invention, a further less value has been achieved. It has been well known for persons skilled in the art that as the threshold voltage lowers, the temperature dependency thereof increases, that is, this has a bad influence upon display elements, but as directly shown in comparison of Comparative example 1 with Example l, the compound of the formula (I) of the present invention has almost the same clearing point and the same low ~n value as those of Comparative example 1 and nevertheless affords particularly a lower threshold voltage and a less temperature dependency of threshold voltage.
1339fi49 Further, as seen from comparisons of Comparative example 1 with Examples 2 to 4 and those of Comparative example 2 with Examples 5 to 9 in Table 2, particularly a lower threshold voltage and a less temperature dependency of threshold voltage are exhibited while clearing point, An and viscosity values are kept in well-balanced manner. It is considered that the com-pounds of the formulas (I) and (II) greatly contribute to the above facts and particularly the compound of the formula (I) does.
Since the nematic liquid crystal composition of the present invention has the above-mentioned charac-teristics, when the composition is used, a broad viewing angle and a low-voltage multiplex drive (e.g. 1.5 V, l/2 _ 1/3 duty drive) is possible.
Claims (6)
1. A liquid crystal composition for a twist nematic mode comprising at least 30 weight percent of a mixture of compounds of general formula:
wherein: R1 represents C1-8 alkyl, R2 represents F or CN, and n is one or 2;
with the proviso that: when n is one, said mixture contains 15 to 40 weight percent of a compound of formula (I), and when n is 2, said mixture contains 15 to 60 weight percent of a compound of formula (I).
wherein: R1 represents C1-8 alkyl, R2 represents F or CN, and n is one or 2;
with the proviso that: when n is one, said mixture contains 15 to 40 weight percent of a compound of formula (I), and when n is 2, said mixture contains 15 to 60 weight percent of a compound of formula (I).
2. The composition of claim 1, further comprising at least one compound selected from the group consisting of general formulae:
wherein:
R3 represents C1-8 alkyl, and R4 represents H or F;
R5 represents C1-8 alkyl, R6 represents C1-8 alkoxy or F, X represents a single bond or -COO-, and m is one or 2;
and R7 represents C1-8 alkyl, R8 represents C1-8 alkoxy, F
or CN, and represents or ;
said composition comprising a maximum of 25 weight percent, 30 weight percent and 35 weight percent of a compound of formulae (II), (III) and (IV), respectively.
wherein:
R3 represents C1-8 alkyl, and R4 represents H or F;
R5 represents C1-8 alkyl, R6 represents C1-8 alkoxy or F, X represents a single bond or -COO-, and m is one or 2;
and R7 represents C1-8 alkyl, R8 represents C1-8 alkoxy, F
or CN, and represents or ;
said composition comprising a maximum of 25 weight percent, 30 weight percent and 35 weight percent of a compound of formulae (II), (III) and (IV), respectively.
3. The composition of claim 2, comprising at least one compound of formula (II) and at least one compound of formula (III).
4. The composition of claim 2, comprising at least one compound of formula (II) and at least one compound of formula (IV).
5. The composition of claim 2, comprising at least one compound of formula (III) and at least one compound of formula (IV).
6. A liquid crystal display element comprising a composition according to any one of claims 1 to 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62295906A JP2832349B2 (en) | 1987-11-24 | 1987-11-24 | Liquid crystal composition for twisted nematic mode |
| JP295906/1987 | 1987-11-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1339649C true CA1339649C (en) | 1998-02-03 |
Family
ID=17826680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000583735A Expired - Fee Related CA1339649C (en) | 1987-11-24 | 1988-11-22 | Liquid crystal composition for twist nematic mode |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4923632A (en) |
| EP (1) | EP0318003B1 (en) |
| JP (1) | JP2832349B2 (en) |
| KR (1) | KR0132677B1 (en) |
| AT (1) | ATE96161T1 (en) |
| CA (1) | CA1339649C (en) |
| DE (1) | DE3885065T2 (en) |
| NO (1) | NO176325C (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8712464D0 (en) * | 1987-05-27 | 1987-07-01 | Merck Patent Gmbh | Liquid crystal phase |
| US5286410A (en) * | 1988-03-10 | 1994-02-15 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Supertwist liquid-crystal display |
| US6004479A (en) | 1988-07-13 | 1999-12-21 | Merck Kgaa | Matrix liquid crystal display |
| US5387369A (en) * | 1988-10-20 | 1995-02-07 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Supertwist liquid crystal display |
| DE3835804B4 (en) | 1988-10-20 | 2006-12-28 | Merck Patent Gmbh | Nematic liquid-crystal mixture |
| ES2058433T3 (en) * | 1988-10-20 | 1994-11-01 | Merck Patent Gmbh | LIQUID CRYSTAL MATRIX INDICATOR. |
| US5178794A (en) * | 1989-03-01 | 1993-01-12 | Dainippon Ink And Chemicals, Inc. | Alkylene glycol derivative and liquid crystal mixture containing the same |
| JP2917286B2 (en) * | 1989-03-28 | 1999-07-12 | セイコーエプソン株式会社 | Liquid crystal device |
| JPH02274794A (en) * | 1989-04-17 | 1990-11-08 | Chisso Corp | Liquid crystal composition and liquid crystal display element prepared therefrom |
| WO1991013947A2 (en) * | 1990-03-09 | 1991-09-19 | MERCK Patent Gesellschaft mit beschränkter Haftung | Liquid crystalline medium |
| US5389289A (en) * | 1990-03-09 | 1995-02-14 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Liquid-crystalline medium |
| US5185098A (en) * | 1990-04-05 | 1993-02-09 | Hoffmann-La Roche Inc. | Liquid crystalline mixtures containing 3,4-difluorophenyl-substituted bicyclohexyls |
| EP0477329B1 (en) * | 1990-04-13 | 1996-03-20 | MERCK PATENT GmbH | Liquid crystalline medium |
| DE4112001B4 (en) * | 1990-04-13 | 2007-06-06 | Merck Patent Gmbh | Liquid crystalline medium |
| DE59108187D1 (en) * | 1990-04-13 | 1996-10-24 | Merck Patent Gmbh | Liquid crystalline medium |
| DE59108017D1 (en) * | 1990-04-13 | 1996-08-29 | Merck Patent Gmbh | LIQUID CRYSTAL MEDIUM |
| US5746941A (en) * | 1990-04-13 | 1998-05-05 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Liquid-crystalline medium |
| JP3544207B2 (en) * | 1990-04-13 | 2004-07-21 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Liquid crystal medium |
| WO1991016394A1 (en) * | 1990-04-13 | 1991-10-31 | MERCK Patent Gesellschaft mit beschränkter Haftung | Liquid crystalline medium |
| JPH05500682A (en) * | 1990-04-13 | 1993-02-12 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | liquid crystal medium |
| DE4107119A1 (en) * | 1990-08-03 | 1992-02-06 | Merck Patent Gmbh | LIQUID CRYSTAL MEDIUM |
| DE69120245T2 (en) * | 1990-10-02 | 1996-11-28 | Merck Patent Gmbh | LIQUID CRYSTAL MEDIUM |
| EP0525144B1 (en) * | 1991-02-20 | 1996-12-27 | MERCK PATENT GmbH | Nematic liquid-crystal composition |
| JP2732335B2 (en) * | 1992-05-28 | 1998-03-30 | チッソ株式会社 | Liquid crystal composition and liquid crystal display device using the composition |
| JP3579698B2 (en) * | 1994-09-06 | 2004-10-20 | チッソ株式会社 | Liquid crystal composition and liquid crystal display device using the same |
| DE19528104B4 (en) * | 1995-08-01 | 2008-05-15 | Merck Patent Gmbh | Electro-optical liquid crystal medium |
| GB2329391A (en) * | 1997-09-17 | 1999-03-24 | Sharp Kk | Liquid crystal composition containing fluorinated phenylpyrimidines with SmC phase and fluorinated terphenyl(s), and use thereof in a liquid crystal shutter |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD105701A1 (en) * | 1973-07-02 | 1974-05-05 | ||
| DE2636684C3 (en) * | 1976-08-14 | 1980-06-19 | Merck Patent Gmbh, 6100 Darmstadt | Phenylcyclohexane derivatives and their use in liquid-crystalline dielectrics |
| JPS56135445A (en) * | 1980-03-27 | 1981-10-22 | Chisso Corp | 4"-halogenophenyl ester of trans-4-(trans-4'-substituted cyclohexyl)-cyclohexanecarboxylic acid |
| US4405488A (en) * | 1980-10-09 | 1983-09-20 | Chisso Corporation | Liquid-crystalline halogenobenzene derivatives |
| US4422951A (en) * | 1981-04-02 | 1983-12-27 | Chisso Corporation | Liquid crystal benzene derivatives |
| DE3223637C2 (en) * | 1981-07-09 | 1983-09-01 | Chisso Corp., Osaka | Cyano-mono- or -diphenylbicyclohexane derivatives and their use in liquid crystal compositions |
| US4536321A (en) * | 1983-02-18 | 1985-08-20 | Chisso Corporation | Fluorobenzene derivatives and liquid crystal compositions containing the same |
| US4581155A (en) * | 1983-03-31 | 1986-04-08 | Chisso Corporation | Halogenopyrimidine derivatives |
| DE3500897A1 (en) * | 1985-01-12 | 1986-07-17 | Merck Patent Gmbh, 6100 Darmstadt | LIQUID CRYSTALLINE PHASE |
| JPS61207347A (en) * | 1985-03-12 | 1986-09-13 | Chisso Corp | Cyclohexane derivative |
| JPS62127384A (en) * | 1985-11-28 | 1987-06-09 | Matsushita Electric Ind Co Ltd | Active matrix liquid crystal display element |
| JPH0781141B2 (en) * | 1986-01-20 | 1995-08-30 | チッソ株式会社 | Nematic liquid crystal composition |
| US4640795A (en) * | 1986-03-21 | 1987-02-03 | Chisso Corporation | 5-alkyl-2-(3,4-difluorophenyl)pyrimidine and nematic liquid crystal composition containing same |
| JPH07100790B2 (en) * | 1986-09-01 | 1995-11-01 | チッソ株式会社 | Nematic liquid crystal composition |
| JPS63196685A (en) * | 1987-02-10 | 1988-08-15 | Seiko Instr & Electronics Ltd | Liquid crystal device |
| JPH0765043B2 (en) * | 1987-03-03 | 1995-07-12 | チッソ株式会社 | Liquid crystal composition |
| JPH0684339B2 (en) * | 1987-11-16 | 1994-10-26 | チッソ株式会社 | Cyclohexane derivative |
| DE4035792C1 (en) * | 1990-11-10 | 1992-04-23 | Loehr & Herrmann Gmbh, 7531 Neuhausen, De | Printed circuit board panel de-edging device - has two saw-blades mounted in bearingblockings which can be positionally adjusted |
-
1987
- 1987-11-24 JP JP62295906A patent/JP2832349B2/en not_active Expired - Fee Related
-
1988
- 1988-11-18 US US07/272,942 patent/US4923632A/en not_active Expired - Lifetime
- 1988-11-21 NO NO885180A patent/NO176325C/en unknown
- 1988-11-22 CA CA000583735A patent/CA1339649C/en not_active Expired - Fee Related
- 1988-11-24 KR KR1019880015458A patent/KR0132677B1/en not_active IP Right Cessation
- 1988-11-24 AT AT88119588T patent/ATE96161T1/en not_active IP Right Cessation
- 1988-11-24 DE DE88119588T patent/DE3885065T2/en not_active Expired - Fee Related
- 1988-11-24 EP EP88119588A patent/EP0318003B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| NO176325B (en) | 1994-12-05 |
| EP0318003A2 (en) | 1989-05-31 |
| JP2832349B2 (en) | 1998-12-09 |
| NO176325C (en) | 1995-03-15 |
| EP0318003B1 (en) | 1993-10-20 |
| DE3885065T2 (en) | 1994-04-21 |
| EP0318003A3 (en) | 1990-10-31 |
| NO885180D0 (en) | 1988-11-21 |
| ATE96161T1 (en) | 1993-11-15 |
| KR0132677B1 (en) | 1998-04-14 |
| KR890008295A (en) | 1989-07-10 |
| NO885180L (en) | 1989-05-25 |
| DE3885065D1 (en) | 1993-11-25 |
| US4923632A (en) | 1990-05-08 |
| JPH01138290A (en) | 1989-05-31 |
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