JPH07179371A - Liquid crystal compound, liquid crystal composition containing the compound, liquid crystal element using the composition, displaying method and displaying apparatus using the element - Google Patents

Abstract

PURPOSE:To obtain a new compound useful for a ferroelectric liquid crystal display device having excellent switching characteristics, quick response and small temperature dependency of optical response speed. CONSTITUTION:This compound is expressed by the formula R-A-Y-X {R is a 1-20C alkyl, H or F; A is A1, A1-Z1-A2 or A1-Z1-A2-Z2-A3 (A1 to A3 each is a substituted 1,4-phenylene, pyrimidine-2,5-diyl, etc.; Z1 and Z2 are each single bond, COO, OCO, CH2O, CH=CH, CidenticalC, etc.); X is 2-bicyclo[2,2,1]heptyl, 1- tricyclo[3,3,1,1<3.7>]decyl, etc.}, e.g. 2-(1-tricyclo[3,3,1,1<3.7>]decylacetic acid 4-(5- decylpyrimidin-2-yl)phenyl ester. The compound of the formula is produced e.g. by reacting 4-(5-decylpyrimidin-2-yl)phenol with (1-tricyclo[3,3,1,1<3.7>]decyl) acetic acid, 1,3-dicyclohexylcarbodiimide and 4-pyrrolidinopyridine.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel liquid crystalline compound,
The present invention relates to a liquid crystal composition containing the same, a liquid crystal element and a display device using the liquid crystal composition, and more specifically, a novel liquid crystal composition having improved response characteristics to an electric field and a liquid crystal display element or liquid crystal using the same. The present invention relates to a liquid crystal element used for an optical shutter and the like and a display device using the liquid crystal element for display.

[0002]

2. Description of the Related Art Conventionally, liquid crystals have been applied as electro-optical elements in various fields. Most of the liquid crystal elements currently in practical use are, for example, M. Sch.
adt) and W. Helfri
ch) "Applied Physics Letters (Ap
"Plied Physics Letters)" Vo
l. 18, No. 4 (1971.2.15) P.I. 127
~ 128 "Voltage Dependent O"
optical Activity of a Twis
ted Nematic Liquid Crystal
TN (Twisted Nemati)
A liquid crystal of type c) is used.

These are based on the dielectric alignment effect of liquid crystals, and the average molecular axis is due to the dielectric anisotropy of liquid crystal molecules.
It uses the effect of directing in a specific direction by the applied electric field. The optical response speed limit of these devices is said to be milliseconds, which is too slow for many applications.

On the other hand, in the application to a large flat display, the simple matrix drive is the most effective in consideration of price, productivity and the like. The simple matrix method employs an electrode configuration in which a scan electrode group and a signal electrode group are arranged in a matrix, and in order to drive the scan electrode group, an address signal is sequentially and selectively selected and applied to the scan electrode group. Employs a time-division drive system in which a predetermined information signal is synchronized with an address signal and selectively applied in parallel.

However, when the above-mentioned TN type liquid crystal is adopted for the device of such a driving system, the scan electrode is selected and the signal electrode is not selected, or the scan electrode is not selected and the signal electrode is selected. The electric field is applied to a limited area (so-called “half-selection point”) in a finite manner.

If the difference between the voltage applied to the selection point and the voltage applied to the half selection point is sufficiently large and the voltage threshold value required to align the liquid crystal molecules perpendicularly to the electric field is set to an intermediate voltage value, The display element works normally,
When the number of scanning lines (N) is increased, the time (duty ratio) during which an effective electric field is applied to one selected point while scanning the entire screen (one frame) decreases at a rate of 1 / N. Resulting in.

For this reason, the voltage difference as the effective value applied to the selected point and the non-selected point in the case of repeating scanning is
As the number of scanning lines increases, the number becomes smaller, and as a result, deterioration of image contrast and crosstalk are inevitable drawbacks.

Such a phenomenon is caused by a liquid crystal having no bistability (a stable state in which liquid crystal molecules are aligned horizontally with respect to an electrode surface, and a vertical state only while an electric field is effectively applied). This is a problem that is essentially unavoidable when driving (i.e., orienting to) is driven (that is, repeated scanning) using the temporal accumulation effect.

In order to improve this point, the voltage averaging method,
The two-frequency driving method and the multi-matrix method have already been proposed, but none of them is sufficient, and the increase in the screen size and the density of the display element is stopped because the number of scanning lines cannot be increased sufficiently. It is the current situation.

In order to improve the drawbacks of the conventional liquid crystal device, the use of a liquid crystal device having bistability is explained by using Clark and Lagerwell.
1) (Japanese Patent Laid-Open No. 56-107216).
Gazette, U.S. Pat. No. 4,367,924).

Bistable liquid crystals are generally chiral smectic C phase (SmC ^* phase) or H phase (SmH).
Ferroelectric liquid crystal having ^* phase) is used.

This ferroelectric liquid crystal has a bistable state consisting of a first optical stable state and a second optical stable state with respect to an electric field, and therefore the optical modulation used in the above-mentioned TN type liquid crystal. Unlike the element, for example, the liquid crystal is aligned in the first optically stable state with respect to one electric field vector, and the liquid crystal is aligned in the second optically stable state with respect to the other electric field vector. In addition, this type of liquid crystal has a property (bistability) of taking one of the two stable states described above in response to an applied electric field and maintaining that state when no electric field is applied.

In addition to the above-mentioned characteristic of having bistability, the ferroelectric liquid crystal has an excellent characteristic of high-speed response. This is because the spontaneous polarization of the ferroelectric liquid crystal and the applied electric field act directly to induce the transition of the alignment state.
It is 3 to 4 orders faster than the response speed due to the effect of the dielectric anisotropy and the electric field.

As described above, the ferroelectric liquid crystal potentially has extremely excellent characteristics, and by utilizing such characteristics, many of the problems of the conventional TN type element described above are solved. A fairly substantial improvement is obtained. In particular, it is expected to be applied to high-speed optical optical shutters and high-density, large-screen displays. For this reason, there has been extensive research on liquid crystal materials with ferroelectric properties, but the ferroelectric liquid crystal materials developed to date are sufficient for use in liquid crystal elements, including low-temperature operating characteristics, high-speed response, contrast, and so on. It is hard to say that it has such characteristics.

Between the response time τ, the magnitude Ps of spontaneous polarization and the viscosity η, the following equation (1) is used.

[0016]

[Equation 1] There is a relationship of. Therefore, in order to increase the response speed, there are methods of (a) increasing the magnitude Ps of spontaneous polarization (b) decreasing the viscosity η (c) increasing the applied electric field E. However, the applied electric field has an upper limit because it is driven by an IC or the like, and it is desirable that the applied electric field be as low as possible. Therefore, it is actually necessary to reduce the viscosity η or increase the value of the spontaneous polarization magnitude Ps.

Generally, in a ferroelectric chiral smectic liquid crystal compound having a large spontaneous polarization, the internal electric field of the cell caused by the spontaneous polarization is also large, and there is a tendency that there are many restrictions on the device structure capable of assuming a bistable state. Moreover, even if the spontaneous polarization is unnecessarily increased, the viscosity tends to increase accordingly, and as a result, the response speed may not be so fast.

When the temperature range used as an actual display is, for example, about 5 to 40 ° C., the response speed generally changes by about 20 times, which exceeds the limit of adjustment by the drive voltage and frequency. The current situation.

In addition, in the case of a liquid crystal element that generally utilizes the birefringence of liquid crystal, the transmittance under orthogonal Nicols is expressed by the following equation (2).

[0020]

[Equation 2]

In equation (2), I ₀ is the incident light intensity, I is the transmitted light intensity, Θ _a is the apparent tilt angle defined below,
Δn is the refractive index anisotropy, d is the thickness of the liquid crystal layer, and λ is the wavelength of incident light. The apparent tilt angle Θ _a in the above-mentioned non-helical structure appears as the angle in the average molecular axis direction of the twisted liquid crystal molecules in the first and second alignment states. According to the equation (2), the maximum transmittance is obtained when the apparent tilt angle Θ _a is 22.5 °, and the apparent tilt angle Θ _a in the non-helical structure which realizes the bistability is 22.5. It should be as close as possible to °.

However, when it is applied to the ferroelectric liquid crystal having a non-helical structure exhibiting the bistability announced by Clark and Lagerwall as described above, it has the following problems and causes a decrease in contrast. Has become.

First, the apparent tilt angle Θ _a in the non-helical ferroelectric liquid crystal obtained by orienting with a conventional rubbing-treated polyimide film (the angle between the two stable molecular axes is 1 / 2) is smaller than the tilt angle in the ferroelectric liquid crystal (angle Θ which is 1/2 of the apex angle of the triangular pyramid shown in FIG. 4 described later), so the transmittance is low.

Secondly, even if the contrast is high in the static state where no electric field is applied, when driving display is performed by applying a voltage, liquid crystal molecules fluctuate due to a minute electric field during a non-selection period in matrix driving, and thus black is pale. Become.

As described above, in order to put a ferroelectric liquid crystal device into practical use, a liquid crystal composition having a high-speed response, a small temperature dependence of response speed, and a high contrast chiral smectic phase. Is required.

Further, the liquid crystal composition has spontaneous polarization, chiral smectic C pitch, cholesteric pitch, and liquid crystal phase for uniform switching of the display, good viewing angle characteristics, low temperature storage stability, and reduction of load on the driving IC. It is necessary to optimize the temperature range, optical anisotropy, tilt angle, dielectric anisotropy and the like.

[0027]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a liquid crystal compound effective for making the above-mentioned ferroelectric liquid crystal device practical, a liquid crystal composition containing the same, and particularly a ferroelectric chiral smectic. A liquid crystal composition exhibiting a phase, and
It is intended to provide a liquid crystal element and a display device using the liquid crystal composition.

[0028]

MEANS FOR SOLVING THE PROBLEMS The present invention includes the following general formula (I) R-AYX (I) (wherein R in the formula (I) has 1 to 20 carbon atoms). linear is, branched or cyclic alkyl group (-CH ₂ in the alkyl group - is -O under the condition that heteroatoms are not adjacent -, -
S-, -CO-, -CH = CH-, -C≡C-, -C
^(*) H (CN)-may be replaced, and the hydrogen atom in the alkyl group may be replaced with a fluorine atom. ) Or a hydrogen atom or a fluorine atom. A is -A
_{1 -, - A 1 -Z 1} -A 2 -, - A 1 -Z 1 -A 2 -Z 2 -A 3
Represented by-, A ₁ , A ₂ and A ₃ each independently represent unsubstituted or 1,4 having 1 or 2 substituents selected from F, Cl, Br, CH ₃ , CF ₃ or CN. -Phenylene,
Pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-
Diyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,3-dithian-2,5-diyl, furan-2,5-diyl, thiadiazole-2,5
-Diyl, thiophene-2,5-diyl, thiazole-
2,5-diyl, benzothiazole-2,6-diyl,
Benzothiazole-2,5-diyl, benzoxazole-2,5-diyl, benzoxazole-2,6-diyl, indane-2,5-diyl, 2-alkylindan-2,5-diyl (where the alkyl group is carbon Number of atoms 1-18
Is a linear or branched alkyl group), indanone-2,6-diyl, 2-alkylindanone-2,6-
Diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms), coumaran-2,5-diyl, 2-alkylcoumaran-2,5-diyl (the alkyl group is a carbon atom) Which is a linear or branched alkyl group of 1 to 18), 2,6-naphthylene, quinoxaline-2,
It is selected from 6-diyl and quinoline-2,6-diyl. Z ₁ and Z ₂ are each independently a single bond, —COO—, —
_{OCO -, - CH 2 O -} , - OCH 2 -, - CH 2 CH
_2- , —CH≡CH—, —C≡C—. Y
Is an alkylene group having 1 to 10 carbon atoms, and —CH ₂ — in the alkylene group may be replaced with —O—, —COO—, or —OCO— under the condition that they are not adjacent. X is 2-bicyclo [2,2,1] heptyl, 1-
Tricyclo [3,3,1,1 ^3,7 ] decyl or 2-
It is tricyclo [3,3,1,1 ^3,7 ] decyl. ), A liquid crystal compound represented by
The present invention provides a liquid crystal composition containing a seed, and a liquid crystal element and a display device in which the liquid crystal composition is disposed between a pair of electrode substrates.

In the liquid crystal compound represented by the general formula (I), the following compound (Ia) is preferable as a preferable compound from the viewpoint of the temperature range of the liquid crystal phase, the response characteristics when it is used as a liquid crystal composition, the viscosity and the orientation. ~ (Ic) are mentioned.

(Ia) A represents -A _1- , wherein A ₁ is unsubstituted or has 1 or 2 substituents selected from F, Cl, Br, CH ₃ , CF ₃ or CN. 4-phenylene, 1,4-cyclohexylene, 2,6-naphthylene,
Quinoxaline-2,6-diyl, liquid crystalline compounds selected from among quinoline-2,6-diyl (Ib) A is -A ₁ -Z ₁ -A ₂ - indicates at least one of A _1, A ₂ Is unsubstituted or F, Cl, Br, C
1,4-phenylene having 1 or 2 substituents selected from H ₃ , CF ₃ or CN, pyrimidine-2,5-
A liquid crystal compound (Ic) A selected from diyl, pyridine-2,5-diyl and 1,4-cyclohexylene represents -A ₁ -Z ₁ -A ₂ -Z ₂ -A _3- ,
At least one of A ₁ , A ₂ and A ₃ is unsubstituted or F or C
1,4-phenylene having 1 or 2 substituents selected from 1, Br, CH ₃ , CF ₃ or CN, the rest being pyrimidine-2,5-diyl, pyridine-2,5-diyl , 1,4-cyclohexylene, thiadiazole-
A liquid crystalline compound selected from 2,5-diyl, thiazole-2,5-diyl, thiophene-2,5-diyl, indane-2,5-diyl and coumarane-2,5-diyl.

Further preferred compounds are the following (Iba)
To (Icb).

(Iba) A represents -A ₁ -Z ₁ -A _2- , and A ₁ and A ₂ are both unsubstituted or F, Cl, Br, C
1,4-phenylene having 1 or 2 substituents selected from H ₃ , CF ₃ or CN, Z ₁ is a single bond,
_{-CH 2 O -, - OCH 2} -, - CH 2 CH 2 -, - C≡C
-Is a liquid crystalline compound.

(Ibb) A represents -A ₁ -Z ₁ -A _2- , A ₁ is unsubstituted or F, Cl, Br, CH ₃ , CF ₃
Or 1,4-phenylene having 1 or 2 substituents selected from CN, A ₂ is pyrimidine-2,5
-Diyl, pyridine-2,5-diyl, pyrazine-2,
5-diyl, pyridazine-3,6-diyl, 1,4-cyclohexylene, thiadiazole-2,5-diyl, thiophene-2,5-diyl, thiazole-2,5-diyl, benzothiazole-2,6- Diyl, benzoxazole-2,5-diyl, indane-2,5-diyl,
A liquid crystalline compound selected from coumaran-2,5-diyl, 2,6-naphthylene, quinoxaline-2,6-diyl and quinoline-2,6-diyl, wherein Z ₁ is a single bond.

(Ibc) A represents -A ₁ -Z ₁ -A _2- , A ₁ is pyridine-2,5-diyl, A ₂ is 1,4-cyclohexylene, indane-2,5 -Diyl, coumarane-2,5-diyl, 2,6-naphthylene, a liquid crystal compound in which Z ₁ is a single bond.

(Ibd) A represents -A ₁ -Z ₁ -A _2- , A ₁ is pyrimidine-2,5-diyl, A ₂ is 1,4-cyclohexylene, indane-2,5 -Diyl, coumarane-2,5-diyl, 2,6-naphthylene, a liquid crystal compound in which Z ₁ is a single bond.

(Ica) A is -A ₁ -Z ₁ -A ₂ -Z ₂
-A _3- , wherein A ₁ , A ₂ and A ₃ are all unsubstituted or F,
1,4-phenylene having 1 or 2 substituents selected from Cl, Br, CH ₃ , CF ₃ or CN, and Z
_One of Z ₁ and Z ₂ is a single bond, and the other is a single bond, —CH _{2
O -, - OCH 2 -,} - CH 2 CH 2 -, - C≡C- liquid crystal compound is either.

(Icb) A is -A ₁ -Z ₁ -A ₂ -Z ₂
-A _3- , _{two of} A ₁ , A ₂ and A ₃ are unsubstituted or selected from F, Cl, Br, CH ₃ , CF ₃ or CN 1
1,4-phenylene having 1 or 2 substituents, the remaining one is pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,4-cyclohexylene, thiadiazole-2,5 -Diyl, thiazole-2,5-diyl, thiophene-2,5-diyl, indane-2,5
-Choose from Diyl and Kumaran-2,5-diyl,
Liquid crystal compounds in which Z ₁ and Z ₂ are single bonds.

When 1,4-phenylene having one or two substituents is present in the liquid crystal compound represented by the general formula (I), preferable substituents are F, Cl, Br and C.
F ₃ and more preferably F.

In the liquid crystal compound represented by the general formula (I), R is preferably selected from the following (1) to (6) and Y
Is preferably selected from (7) to (8).

[0040]

[Chemical 3] (However, a is an integer of 1 to 17, d and g are integers of 0 to 7,
b and e are integers of 1 to 9, f is 0 or 1, and h is an integer of 1 to 16. Y ₁ is a single bond —O—, —OCO—, —CO
O-, Y ₂ is -CH ₂ O -, - COO- represents any. C ^* represents an optically active asymmetric carbon atom, and
(2) and (3) may be optically active. )

[0041]

[Chemical 4] (However, n is an integer of 1 to 8.) More preferably, in the general formula (I), R is the following (9), A represents -A ₁ -Z ₁ -A _2- , and A A liquid crystal compound in which ₁ is pyrimidine-2,5-diyl, A ₂ is 1,4-phenylene, and Z ₁ is a single bond.

[0042] _{(9) n-C a H} 2a + 1 -Y 3 - (. Provided that, a represents an integer of 1 to 17, Y ₃ represents a single bond or -O-) is also preferable that the general The liquid crystal compound of formula (I) is non-optically active.

As a result of detailed examination of the liquid crystal compound represented by the general formula (I), the present inventors have found that a ferroelectric chiral smectic liquid crystal composition containing the liquid crystal compound of the present invention and a liquid crystal device using the same. However, it has been found that various characteristics such as good orientation, high-speed response, reduction of temperature dependence of response speed, and high contrast are obtained, and good display characteristics can be obtained.

Further, the liquid crystalline compound of the present invention has good compatibility with other compounds, and has a chiral smectic C pitch, a cholesteric pitch, a liquid crystal phase temperature range, a viscosity, an optical anisotropy and a tilt. It can also be used for adjusting the angle, dielectric anisotropy, and the like.

Next, an example of a method for synthesizing the liquid crystal compound represented by the general formula (I) will be shown.

[0046]

[Chemical 5]

(However, in the above formula, Y ₅ and Y ₆ are each a single bond or an integer having 1 to 8 carbon atoms, and the sum of the carbon atoms of Y ₅ and Y ₆ is 9 or less. In Although,
-CH ₂ in the alkylene group - is -O under conditions which are not adjacent
-May be replaced. R, A and X are as defined above.

Hal is a halogen atom, T _s is a p-toluenesulfonyl group, DCC is 1,3-dicyclohexylcarbodiimide, and 9-BBN is 9-borabicyclo [3,3,1] nonane. It is also possible to bond -Y-X to A in advance and then bond the group represented by R from the back.

Alternatively, it is possible to finally bond A by a ring-closing reaction, an etherification reaction, or an esterification reaction to obtain the desired compound. (Y is as defined above).

Next, the specific structural formula of the liquid crystalline compound represented by the general formula (I) will be shown. Hereinafter, the abbreviations used in the present invention represent the following groups.

[0051]

[Chemical 6]

[0052]

[Chemical 7]

[0053]

[Chemical 8]

[0054]

[Chemical 9]

[0055]

[Chemical 10]

[0056]

[Chemical 11]

[0057]

[Chemical 11]

[0058]

[Chemical 12]

[0059]

[Chemical 13]

[0060]

[Chemical 14]

[0061]

[Chemical 15]

[0062]

[Chemical 16]

The liquid crystal composition of the present invention can be obtained by mixing at least one liquid crystal compound represented by the general formula (I) with one or more other liquid crystal compounds in an appropriate ratio. The number of other liquid crystal compounds used in combination is 1
-50, preferably 1-30, more preferably 3-30
Is the range. The liquid crystal composition according to the present invention is preferably a ferroelectric liquid crystal composition, particularly a ferroelectric chiral smectic liquid crystal composition.

Other liquid crystalline compounds used in the present invention include those described in JP-A-4-272989, pages 23 to 39: Directly-attached ester-based liquid crystalline compound containing a pyrimidine ring (III). (IV) Formula-Phenyl-based liquid crystalline compound (V) Formula-Phenyl-cyclohexane-based liquid crystalline compound (VI) Formula-Naphthalene-based liquid crystalline compound (VII) Formula-Pyrazine-based liquid crystalline compound (VIII) Formula-Pyridazine-based liquid crystal Formula (IX) formula-Pyridine-based liquid crystal compound (IX)-(X)-(XI) formula-Thiadiazole-based liquid crystal compound (XII) formula and the like. Further, among the respective liquid crystal compound groups, liquid crystal compounds represented by the formulas (IIIa) to (XIId) are preferable. Still more preferably, liquid crystal compounds represented by formulas (IIIaa) to (XIIdb) can be mentioned.

Further, the following general formulas (XIII) to (XV
A liquid crystal compound such as represented by II) can also be used.

[0066]

[Chemical 17]

Here, R ′ and R ′ are a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, and one or two or more —CH ₂ in the alkyl group.
The -group is -O-, -CO under the condition that hetero atoms are not adjacent to each other.
-, -OCO-, -COO-, -CH (CN)-, -C
It may be replaced with (CH ₃ ) (CN)-. Further, the hydrogen atom in the alkyl group may be replaced with a fluorine atom.

[0068] Moreover R _'7, R' ₈ is preferably i) to vi
ii).

I) a straight-chain alkyl group having 1 to 15 carbon atoms ii)-(CH ₂ ) _p --CH (CH ₃ )-C _q H _{2q + 1} p is 0 to 5 and q is 2 to 11 Indicates an integer. It may also be optically active.

Iii)-(CH ₂ ) _r --CH (CH ₃ )
_{- (CH 2) s OC t} H 2t + 1 r is Less than six, t is an integer of 1 to 14, s is 0 or 1. It may also be optically active.

Iv) --CH (CH ₃ )-COOC _w H
_{2w +} 1w represents an integer of 1 to 15. It may also be optically active.

V)-(CH ₂ ) _A -CH (CN)-
C _B H _{2B + 1} A represents an integer of 0 to 2 and B represents an integer of 1 to 15. It may also be optically active.

Vi)-(CH ₂ ) _C --C (CN) (C
_{H 3) -C D H 2D +} 1 C is 0 to 2, D is an integer of 1 to 15. It may also be optically active.

Vii)-(CH ₂ ) _E --C _G F _{2G + 1} E represents an integer of 0 to 10, and G represents an integer of 1 to 15.

Viii) -H

N, Q, R and T are 0 or 1 respectively.
Show, R '₇, R ’₈R ’₉Indicates H or F respectively
You R ’₇, R ’₈Is a single bond, -COO-, -OCO
-, -CH₂O- or -OCH₂-Indicates. Z ’₁Is
Indicates -O- or -S-, A '_FourIs 1,4-pheny
Lene or naphthalene-2,6-diyl is shown.

Preferred compounds of the formula (XIII) include (XIIIa).

[0078]

[Chemical 18]

As a preferred compound of the formula (XVI), (XVI)
VIa) and (XVIb).

[0080]

[Chemical 19]

Preferred compounds of the formula (XVII) are:
(XVIIa) to (XVIIb) may be mentioned.

[0082]

[Chemical 20]

Preferred compounds of the formula (XVIII) include (XVIIIa) to (XVIIIc).

[0084]

[Chemical 21]

More preferable compounds of the formulas (XVIa) and (XVIb) include (XVIaa) to (XVIbb).

[0086]

[Chemical formula 22]

Ph, Py2, Tn, Tz1, Cy, N
Abbreviations for p, Boa2, and Btb2 are in accordance with the above definitions, and other abbreviations are the following groups.

[0088]

[Chemical formula 23]

When the liquid crystal compound of the present invention is mixed with one or more kinds of the above liquid crystal compounds or the liquid crystal composition, the liquid crystal compound of the present invention occupies in the liquid crystal composition obtained by mixing. Is 1% to 80% by weight, preferably 1% to 60% by weight, and even more preferably 1% by weight.
It is desirable to set the content to 40% by weight.

When two or more liquid crystal compounds of the present invention are used, the proportion of the mixture of two or more liquid crystal compounds of the present invention in the liquid crystal composition obtained by mixing is 1% by weight.
It is desired to be -80% by weight, preferably 1% -60% by weight, and even more preferably 1% -40% by weight.

Further, the liquid crystal layer exhibiting ferroelectricity in the ferroelectric liquid crystal device according to the present invention is prepared by heating the liquid crystal composition prepared as described above in a vacuum to an isotropic liquid temperature to obtain a device cell. It is preferable that the liquid crystal layer is sealed in the inside and gradually cooled to form a liquid crystal layer and returned to normal pressure.

FIG. 1 is a schematic cross-sectional view showing an example of a liquid crystal element having a chiral smectic liquid crystal layer of the present invention, for explaining the structure of a crystal element utilizing ferroelectricity.

In FIG. 1, reference numeral 1 is a liquid crystal layer, 2 is a glass substrate, 3 is a transparent electrode, 4 is an insulating alignment control layer, 5 is a spacer, 6 is a lead wire, 7 is a power supply, 8 is a polarizing plate, and 9 is The light source is shown.

The two glass substrates 2 were each coated with In ₂
A transparent electrode 3 made of a thin film of O ₃ , SnO ₂ or ITO (Indium Tin Oxide) is covered. An insulating alignment control layer 4 for arranging liquid crystals in the rubbing direction is formed on top of this by rubbing a polymer thin film such as polyimide with gauze or acetate flocking cloth.

As the insulating material, for example, silicon nitride, silicon carbide, silicon carbide containing hydrogen, silicon oxide, boron nitride, boron nitride containing hydrogen, cerium oxide, aluminum oxide, zirconium oxide. Thing, an inorganic material insulating layer such as titanium oxide or magnesium fluoride is formed, on which polyvinyl alcohol, polyimide, polyamideimide, polyesterimide, polyparaxylene, polyester, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyacetic acid. As an orientation control layer, an organic insulating substance such as vinyl, polyamide, polystyrene, cellulose resin, melamine resin, urea resin, acrylic resin or photoresist resin is used.
The insulating orientation control layer 4 may be formed of two layers, or may be an inorganic material insulating orientation control layer or a single organic material insulating orientation control layer.

If this insulating orientation control layer is an inorganic type, it can be formed by a vapor deposition method, and if it is an organic type, a solution in which an organic insulating substance is dissolved, or a precursor solution thereof (0.1 to 20% by weight in a solvent, (Preferably 0.2 to 10% by weight) is applied by a spinner coating method, a dip coating method, a screen printing method, a spray coating method, a roll coating method or the like, and cured under predetermined curing conditions (for example, under heating). Can be formed.

The layer thickness of the insulating orientation control layer 4 is usually 10Å
1 μm, preferably 10 Å to 3000 Å, more preferably 10 Å to 1000 Å are suitable.

The two glass substrates 2 are held by the spacer 5 at arbitrary intervals. For example, there is a method in which silica beads and alumina beads having a predetermined diameter are used as spacers and sandwiched between two glass substrates, and the periphery is sealed with a sealing material, for example, an epoxy adhesive material. Alternatively, a polymer film or glass fiber may be used as the spacer. A liquid crystal exhibiting ferroelectricity is enclosed between the two glass substrates.

The liquid crystal layer 1 in which the ferroelectric liquid crystal is enclosed is generally 0.5 to 20 μm, preferably 1 to 5 μm.

The transparent electrode 3 is connected to an external power source 7 by a lead wire.

A polarizing plate 8 is attached to the outside of the glass substrate 2.

Since FIG. 1 is a transmissive type, a light source 9 is provided.

FIG. 2 is a schematic drawing of an example of a cell for explaining the operation of a liquid crystal element utilizing ferroelectricity.
Reference numerals 21a and 21b respectively denote a substrate (glass plate) covered with a transparent electrode composed of a thin film of In ₂ O ₃ ; SnO ₂ or ITO (Indium Tin Oxide), and the liquid crystal molecular layer 22 is perpendicular to the glass surface therebetween. A liquid crystal of SmC ^* phase or SmH ^* phase oriented so as to be enclosed is enclosed. A thick line 23 represents a liquid crystal molecule, and this liquid crystal molecule 23 has a dipole moment (P⊥) 24 in a direction orthogonal to the molecule. When a voltage of a certain threshold value or more is applied between the electrodes on the substrates 21a and 21b, the helical structure of the liquid crystal molecules 23 is unraveled, and the dipole moment (P⊥) 24 is entirely oriented in the electric field direction. Can be changed. The liquid crystal molecules 23 have an elongated shape and exhibit refractive index anisotropy in the major axis direction and the minor axis direction thereof. Therefore, for example, if crossed Nicols polarizers are placed above and below the glass surface, the voltage application polarity It will be easily understood that the liquid crystal optical modulator has optical characteristics that change.

The thickness of the liquid crystal cell preferably used in the optical modulation liquid crystal element of the present invention can be made sufficiently thin (for example, 10 μm or less). As the liquid crystal layer becomes thinner in this way, as shown in FIG. 3, the helical structure of the liquid crystal molecules unwinds even when no electric field is applied, and the dipole moment Pa or Pb of the liquid crystal molecule is upward (34a) or downward (34b). Take either state. When an electric field Ea or Eb having different polarities equal to or higher than a certain threshold is applied to such a cell by the voltage applying means 31a and 31b, the dipole moment is directed upward corresponding to the electric field vector of the electric field Ea or Eb. 34a or the downward direction 34b, and the liquid crystal molecules are changed to the first stable state 33 accordingly.
a or the second stable state 33b.

As described above, there are two advantages of using such a ferroelectric liquid crystal element as an optical modulation element.

The first is that the response speed is extremely fast, and the second is that the alignment of the liquid crystal molecules has bistability. Explaining the second point further with reference to FIG. 3, for example, when the electric field Ea is applied, the liquid crystal molecules are aligned in the first stable state 33a, but this state is stable even when the electric field is cut off. When a reverse electric field Eb is applied, the liquid crystal molecules are oriented in the second stable state 33b and change their orientation.
After all, it remains in this state even when the electric field is turned off. Also, unless the applied electric field Ea or Eb exceeds a certain threshold value,
Each is also maintained in the previous orientation.

FIG. 5 shows an example of drive waveforms used in the present invention.

In FIG. 5A, S _S is the selected scan waveform to be applied to the selected scan line, S _N is the unselected scan waveform that is not selected, and I _S is the applied to the selected data line. I _N represents a non-selection information signal (white) applied to the unselected data lines. In the drawings, (I _S -S _S) and (I _N -S _S) is the voltage waveforms applied to pixels on a selected scanning line, the voltage (I _S -S _S) is pixels bites mark black , The voltage ( _IN −
The pixel to which S _S ) is applied has a white display state.

FIG. 5B shows the drive waveform shown in FIG.
7 is a time series waveform when the display shown in FIG. 6 is performed.

In the driving example shown in FIG. 5, the minimum application time Δt of the single polarity voltage applied to the pixel on the selected scanning line.
Corresponds to the time of the write phase t _{2, and} the time of the 1-line clear t ₁ phase is set to 2Δt.

The values of the parameters V _S , V _I and Δt of the drive waveform shown in FIG. 5 are determined by the switching characteristics of the liquid crystal material used.

Here, the bias ratio V _I / (V _I + V _S )
It is fixed at = 1/3.

Although it is possible to increase the width of the appropriate drive voltage by increasing the bias ratio, increasing the bias ratio means increasing the amplitude of the information signal, and the flicker in image quality increases. However, the contrast is lowered, which is not preferable. In our study, the bias ratio is 1/3 ~
About 1/4 was practical.

By using the liquid crystal device of the present invention in the display panel section and taking the communication format of the data format of the card information having the scanning line address information shown in FIGS. 4 and 5 and the SYNC signal, the liquid crystal display device is obtained. To realize.

In the figure, the symbols are as follows.

101 ferroelectric liquid crystal display device 102 graphic controller 103 display panel 104 scanning line driving circuit 105 information line driving circuit 106 decoder 107 scanning signal generating circuit 108 shift register 109 line memory 110 information signal generating circuit 111 driving control circuit 112 GCPU 113 Host CPU 114 VRAM Image information is generated by the graphic controller 102 on the main body side and transferred to the display panel 103 according to the signal transfer means shown in FIGS. 7 and 8. The graphic controller 102 has a CPU (central processing unit, abbreviated as GCPU 112 hereafter) and a VRAM (memory for storing image information) 114 as its core, and manages image information and communicates between the host CPU 113 and the liquid crystal display device 101. Therefore, the control method of the present invention is mainly realized on the graphic controller 102.

A light source is arranged on the back surface of the display panel.

[0118]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[Example 1] 2- (1-tricyclo [3,3,1,1 ^3,7 ] decyl)
Preparation of 4- (5-decylpyrimidin-2-yl) phenyl (I-12) acetate 1.5 g 4- (5-decylpyrimidin-2-yl) phenol, (1-tricyclo [3,3,1,1] ^3,7 ] decyl) acetic acid 0.95 g, 1,3-dicyclohexylcarbodiimide 1.0 g, 4-pyrrolidinopyridine 0.1 g
40 ml of dichloromethane was added to and stirred at room temperature for 5 hours. After completion of the reaction, insoluble matter was removed by filtration, and purification was performed by column chromatography and recrystallization. The yield was 1.94 g (yield 81.8 g).

[0120]

[Chemical formula 24]

[Example 2] 2- {4- (2-bicyclo [2,2,1] heptylmethyleneoxy) phenyl} -5-decylpyrimidine (I-
18) Production (Step 1) Production of 2-bicyclo [2,2,1] heptylmethyl p-toluenesulfonate 5 g of 2-bicyclo [2,2,1] heptylmethanol was dissolved in 9.5 g of pyridine, The mixture was stirred at 0 ° C for 30 minutes. 7.56 g of chlorinated p-toluenesulfonic acid was added to this reaction solution, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, the product was poured into water, acidified with dilute hydrochloric acid, and extracted with toluene. The obtained organic layer was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 8.52 g of the desired product (yield 76.4%).

(Step 2) 2- {4- (2-bicyclo [2,2,1] heptylmethyleneoxy) phenyl}-
Preparation of 5-decylpyrimidine 4- (5-decylpyrimidin-2-yl) phenol 6
After dissolving 00 mg and 0.16 g of potassium hydroxide in 6 ml of 1-butanol and stirring for 30 minutes, 549 mg of 2-bicyclo [2,2,1] heptylmethyl p-toluenesulfonate and 3 ml of 1-butanol were added at 110 ° C. It was stirred for 4 hours. After completion of the reaction, the composition was obtained by pouring into ice water, adding methanol and filtering. This was purified by silica gel column chromatography and recrystallization to obtain 267 mg of the desired product (yield 32.8%).

[0123]

[Chemical 25]

Example 3 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition A.

[0125]

[Chemical formula 26]

Further, the liquid crystal composition B was prepared by mixing the liquid crystal composition A with the compound produced in Example 1 in the following parts by weight.

[0127]

This shows the following phase transition temperature (° C.).

[0129]

[Chemical 27]

Prepare two 0.7 mm thick glass plates,
An ITO film was formed on each glass plate to form a voltage application electrode, and SiO ₂ was further vapor-deposited on this to form an insulating layer. A silane coupling agent [KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.] 0.2% isopropyl alcohol solution was spun on a glass plate at a rotation speed of 2000 r. p. 1 with m spinner
It was applied for 5 seconds and surface-treated. After that, heat drying treatment was performed at 120 ° C. for 20 minutes.

A polyimide resin precursor [S manufactured by Toray Industries, Inc.] was applied on a glass plate with an ITO film that had been further surface treated.
P-510] 1.5% dimethylacetamide solution was rotated at 2000 rpm. p. m spinner for 15 seconds. After the film formation, the film was subjected to heat condensation baking treatment at 300 ° C. for 60 minutes. At this time, the film thickness of the coating film was about 250Å.

The film after firing was rubbed with an acetate flocked cloth, washed with an isopropyl alcohol solution, sprayed with silica beads having an average particle diameter of 2 μm on one glass plate, and then rubbed. The axes were made parallel to each other, the glass plates were bonded together using an adhesive sealant [Rixon Bond (manufactured by Chisso Corporation)], and dried by heating at 100 ° C. for 60 minutes to prepare a cell.

The liquid crystal composition B mixed in Example 5 was injected into this cell in an isotropic liquid state and gradually cooled from the isotropic phase to 25 ° C. at 20 ° C./h to obtain a ferroelectric liquid crystal element. Created. When the cell thickness of this cell was measured with a Berek phase plate, it was about 2 μm.

Using this ferroelectric liquid crystal element, the magnitude Ps of spontaneous polarization and the peak-to-peak voltage Vpp = 20V
The voltage was applied to detect the optical response under the crossed Nicols (change in the amount of transmitted light 0 to 90%), and the response speed (hereinafter referred to as the optical response speed) was measured. The results are shown below.

30 ° C. 40 ° C. 50 ° C. Response speed 91 μsec 57 μsec 44 μsec Ps 12 nC / cm ² 10 nC / cm ² 7 nC / cm ²

Example 4 Liquid crystal composition C was prepared by mixing the following exemplary compounds in the following parts by weight in place of the exemplary compounds used in Example 3.

[0137]

It exhibits the following phase transition temperatures (° C.).

[0139]

[Chemical 28]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that the liquid crystal composition C mixed in Example 3 was injected into the cell, and the chemical response speed was measured.

The measurement results are shown below.

30 ° C. 40 ° C. 50 ° C. Response speed 81 μsec 58 μsec 39 μsec Ps 12 nC / cm ² 10 nC / cm ² 6 nC / cm ²

Example 5 A liquid crystal composition D was prepared by mixing the following compounds in the following parts by weight.

[0144]

[Chemical 29]

Further, with respect to the liquid crystal composition D, the following exemplary compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition E.

[0146]

[Chemical 30]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that the liquid crystal composition E was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

10 ° C. 20 ° C. 30 ° C. Response speed 602 μsec 321 μsec 174 μsec

Comparative Example 1 A ferroelectric liquid crystal device was prepared in the same manner as in Example 5 except that the liquid crystal composition D mixed in Example 5 was injected into the cell, and the optical response speed was measured. .

The measurement results are shown below.

10 ° C. 25 ° C. 40 ° C. Response speed 668 μsec 340 μsec 182 μsec

Example 6 Instead of the exemplary compound used in Example 5, the following exemplary compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition F.

[0153]

[Chemical 31]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that the liquid crystal composition F was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

10 ° C. 20 ° C. 30 ° C. Response speed 543 μsec 295 μsec 165 μsec

Example 7 A liquid crystal composition G was prepared by mixing the following compounds in the following parts by weight.

[0157]

[Chemical 32]

Further, with respect to this liquid crystal composition G, the following exemplary compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition H.

[0159]

[Chemical 33]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that the liquid crystal composition H was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

10 ° C. 20 ° C. 30 ° C. Response speed 525 μsec 275 μsec 150 μsec

Comparative Example 2 A ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that the liquid crystal composition G mixed in Example 7 was injected into the cell, and the optical response speed was measured. The switching state was observed. The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained.
The measurement results are shown below.

10 ° C. 20 ° C. 30 ° C. Response speed 653 μsec 317 μsec 159 μsec

Example 8 A liquid crystal composition J was prepared by mixing the exemplified compounds shown below instead of the exemplified compound used in Example 7 in the weight parts shown below.

[0165]

[Chemical 34]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that the liquid crystal composition J was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

10 ° C. 20 ° C. 30 ° C. Response speed 513 μsec 266 μsec 142 μsec

Example 9 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition K.

[0169]

[Chemical 35]

Further, with respect to this liquid crystal composition K, the following exemplified compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition L.

[0171]

[Chemical 36]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that the liquid crystal composition L was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

10 ° C. 20 ° C. 30 ° C. Response speed 662 μsec 335 μsec 182 μsec

Comparative Example 3 A ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that the liquid crystal composition K mixed in Example 9 was injected into the cell, and the optical response speed was measured. The switching state was observed. The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained.
The measurement results are shown below.

10 ° C. 20 ° C. 30 ° C. Response speed 784 μsec 373 μsec 197 μsec

Example 10 A liquid crystal composition M was prepared by mixing the following exemplary compounds in the following parts by weight instead of the exemplary compound used in Example 9.

[0177]

[Chemical 37]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that the liquid crystal composition M was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

10 ° C. 20 ° C. 30 ° C. Response speed 592 μsec 318 μsec 178 μsec

(The abbreviations in the examples are as defined above.) As is clear from Examples 5 to 10, the liquid crystal compositions E, F, H, J, L and M according to the present invention are contained. Ferroelectric liquid crystal elements have improved operating characteristics at low temperatures and have reduced temperature dependence of response speed.

Example 11 In place of the polyimide resin precursor 1.5% dimethylacetamide solution used in Example 5, a polyvinyl alcohol resin [P manufactured by Kuraray Co., Ltd. was used.
VA-117] A ferroelectric liquid crystal device was prepared by the same method except that a 2% aqueous solution was used, and the optical response speed was measured by the same method as in Example 5.

The measurement results are shown below.

10 ° C. 20 ° C. 30 ° C. Response speed 573 μsec 302 μsec 164 μsec

Example 12 SiO used in Example 5
_A ferroelectric liquid crystal device was prepared in the same manner as in Example 5 except that the alignment control layer was formed only with a polyimide resin without using ₂ , and the optical response speed was measured in the same manner as in Example 5. .

The measurement results are shown below.

10 ° C. 25 ° C. 40 ° C. Response speed 543 μsec 284 μsec 154 μsec

As is apparent from Examples 11 and 12, even when the element structure was changed, the element containing the ferroelectric liquid crystal composition according to the present invention had much improved low-temperature operating characteristics as in Example 5. In addition, the temperature dependence of the response speed is reduced.

Example 13 Preparation of 2- {4- (2-bicyclo [2,2,1] heptylmethyleneoxy) phenyl} -5-octyloxypyrimidine (I-253) (Step 2 of Example 2) In 4) except that 4- (5-decylpyrimidin-2-yl) phenol is replaced with 4- (5-octyloxypyrimidin-2-yl) phenol to give the title compound by the same operation as in Example 2. Obtained. (Yield 40%) [Example 14] 5- {6- (2-bicyclo [2,2,1] heptylmethyleneoxy) naphthalen-2-yl} -2-hexyl-
Production of 1,3-thiazole (I-257) 6- (2-hexyl-1,3-thiazole-in place of 5- (5-decylpyrimidin-2-yl) phenol in (Step 2) of Example 2 5-yl) naphthalene-2
The title compound was obtained by performing the same operations as in Example 2 except that -ole was used. (Yield 34%) [Example 15] 2- {4- (2-bicyclo [2,2,1] heptylmethyleneoxy) phenyl} -5- (1-fluoroheptyl) -1,3,4-thiadiazole Production of (I-258) In (Step 2) of Example 2, 4- {5- (1 was used instead of 4- (5-decylpyrimidin-2-yl) phenol.
-Fluoroheptyl) -1,3,4-thiadiazole-
The title compound was obtained by the same procedures as in Example 2 except that 2-yl} phenol was used. (Yield 21
%) [Example 16] 4-perfluorooctylphenylbenzoic acid 4- (2-
Preparation of Bicyclo [2,2,1] heptylmethyleneoxy) phenyl (I-259) In Example 1, 4- (2-decylpyrimidin-2-yl) phenol was replaced by 4- (2-bicyclo [2,2]).
2,1] heptylmethyleneoxy) phenol} and (1-tricyclo [3,3,1,1 ^3,7 ] decyl)
The title compound was obtained by the same procedure as in Example 1 except that 4-perfluorooctylphenylbenzoic acid was used instead of acetic acid. (Yield 58%) The phase transition temperatures of the liquid crystalline compounds produced in Examples 13 to 16 are shown below.

[0189]

[Table 1]

[0190]

The liquid crystal composition containing the liquid crystalline compound of the present invention can be operated by utilizing the ferroelectricity of the liquid crystal composition. The ferroelectric liquid crystal element of the present invention that can be used in this manner can be a liquid crystal element having excellent switching characteristics and excellent characteristics such as high-speed response and reduction of temperature dependence of optical response speed. .

A display device in which the liquid crystal element of the present invention is used as a display element in combination with a light source, a drive circuit, etc. is a good device.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of an example of a liquid crystal element using liquid crystal exhibiting a chiral smectic phase.

FIG. 2 is a perspective view schematically showing an example of an element cell for explaining the operation of a liquid crystal element utilizing the ferroelectricity of liquid crystal.

FIG. 3 is a perspective view schematically showing an example of an element cell for explaining the operation of a liquid crystal element utilizing the ferroelectricity of liquid crystal.

FIG. 4 is an explanatory diagram showing a tilt angle.

FIG. 5 is a waveform diagram of a driving method of a liquid crystal element used in the present invention.

6 is a schematic diagram of a display pattern when actual driving is performed with the time-series driving waveform shown in FIG.

FIG. 7 is a block configuration diagram showing a liquid crystal display device having a liquid crystal element utilizing ferroelectricity and a graphics controller.

FIG. 8 is a timing chart of image information communication between the liquid crystal display device and the graphics controller.

[Explanation of symbols]

 1 Liquid Crystal Layer 2 Glass Substrate 3 Transparent Electrode 4 Insulating Alignment Control Layer 5 Spacer 6 Lead Wire 7 Power Supply 21a, 21b Substrate 22 Liquid Crystal Sublayer 23 Liquid Crystal Molecule 24, 34a, 34b Dipole Moment 33a, 33b Stable State 101 Ferroelectric Liquid crystal display device 102 Graphics controller 103 Display panel 104 Scan line drive circuit 105 Information line drive circuit 106 Decoder 107 Scan signal generation circuit 108 Shift register 109 Line memory 110 Information signal generation circuit 111 Drive control circuit 112 GCPU 113 Host CPU 114 VRAM

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 10, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Correction content]

Title: Liquid crystal compound, liquid crystal composition containing the same, liquid crystal element using the liquid crystal composition, display method using the same, and liquid crystal display device

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 43/21 43/225 C 7419-4H 69/75 A 9279-4H 69/753 Z 9279-4H 69/757 C 9279-4H 69/76 A 9279-4H 69/773 9279-4H 69/92 9279-4H 69/94 9279-4H 255/46 255/49 321/12 323/00 C09K 19/32 9279- 4H 19/34 9279-4H G02F 1/13 500 (72) Inventor Goji Kadono 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Shinichi Nakamura 3-chome, Shimomaruko, Ota-ku, Tokyo No. 30-2 Canon Inc. (72) Inventor Ikuo Nakazawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (27)

[Claims] 1. A liquid crystalline compound represented by the following general formula (I): R-A-Y-X ( I) ( In the formula (I), R is, -CH ₂ in a linear, branched or cyclic alkyl group (the alkyl group carbon atoms is 1 to 20 - Is -O-,-under the condition that heteroatoms are not adjacent.
S-, -CO-, -CH = CH-, -C≡C-, -C
^(*) H (CN)-may be replaced, and the hydrogen atom in the alkyl group may be replaced with a fluorine atom. ) Or a hydrogen atom or a fluorine atom. A is -A
_{1 -, - A 1 -Z 1} -A 2 -, - A 1 -Z 1 -A 2 -Z 2 -A 3
Represented by-, A ₁ , A ₂ and A ₃ each independently represent unsubstituted or 1,4 having 1 or 2 substituents selected from F, Cl, Br, CH ₃ , CF ₃ or CN. -Phenylene,
Pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-
Diyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,3-dithian-2,5-diyl, furan-2,5-diyl, thiadiazole-2,5
-Diyl, thiophene-2,5-diyl, thiazole-
2,5-diyl, benzothiazole-2,6-diyl,
Benzothiazole-2,5-diyl, benzoxazole-2,5-diyl, benzoxazole-2,6-diyl, indane-2,5-diyl, 2-alkylindan-2,5-diyl (where the alkyl group is carbon Number of atoms 1-18
Is a linear or branched alkyl group), indanone-2,6-diyl, 2-alkylindanone-2,6-
Diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms), coumaran-2,5-diyl, 2-alkylcoumaran-2,5-diyl (the alkyl group is a carbon atom) Which is a linear or branched alkyl group of 1 to 18), 2,6-naphthylene, quinoxaline-2,
It is selected from 6-diyl and quinoline-2,6-diyl. Z ₁ and Z ₂ are each independently a single bond, —COO—, —
_{OCO -, - CH 2 O -} , - OCH 2 -, - CH 2 CH
₂ —, —CH═CH—, —C≡C—. Y
Is an alkylene group having 1 to 10 carbon atoms, and —CH ₂ — in the alkylene group may be replaced with —O—, —COO—, or —OCO— under the condition that they are not adjacent. X is 2-bicyclo [2,2,1] heptyl, 1-
Tricyclo [3,3,1,1 ^3,7 ] decyl or 2-
It is tricyclo [3,3,1,1 ^3,7 ] decyl. ) 2. The liquid crystal compound according to claim 1, wherein the liquid crystal compound represented by the general formula (I) is any one of the following (Ia) to (Ic). (Ia) A represents -A _1- , A ₁ is unsubstituted or F,
1,4-phenylene having 1 or 2 substituents selected from Cl, Br, CH ₃ , CF ₃ or CN, 1,4-
A liquid crystal compound (Ib) A selected from cyclohexylene, 2,6-naphthylene, quinoxaline-2,6-diyl and quinoline-2,6-diyl represents -A ₁ -Z ₁ -A _2- , At least one of A ₁ and A ₂ is unsubstituted or F, Cl, Br, C
1,4-phenylene having 1 or 2 substituents selected from H ₃ , CF ₃ or CN, pyrimidine-2,5-
A liquid crystal compound (Ic) A selected from diyl, pyridine-2,5-diyl and 1,4-cyclohexylene represents -A ₁ -Z ₁ -A ₂ -Z ₂ -A _3- ,
At least one of A ₁ , A ₂ and A ₃ is unsubstituted or F or C
1,4-phenylene having 1 or 2 substituents selected from 1, Br, CH ₃ , CF ₃ or CN, the rest being pyrimidine-2,5-diyl, pyridine-2,5-diyl , 1,4-cyclohexylene, thiadiazole-
A liquid crystalline compound selected from 2,5-diyl, thiazole-2,5-diyl, thiophene-2,5-diyl, indane-2,5-diyl and coumarane-2,5-diyl. 3. The liquid crystal compound according to claim 1, wherein the liquid crystal compound represented by the general formula (I) is any one of the following (Iba) to (Icb). (Iba) A is, -A ₁ -Z ₁ -A ₂ - indicates, A _1, A
₂ are both unsubstituted or have 1 or 2 substituents selected from F, Cl, Br, CH ₃ , CF ₃ or CN 1,
4-phenylene, Z ₁ is a single bond, —CH ₂ O—,
_{-OCH 2 -, - CH 2 CH} 2 -, - C≡C- a is a liquid crystal compound (Ibb) A is -A ₁ -Z ₁ -A ₂ - indicates, A ₁ is unsubstituted or F, Cl, 1,4-phenylene having 1 or 2 substituents selected from Br, CH ₃ , CF ₃ or CN, A ₂ is pyrimidine-2,5-diyl, pyridine-2,5-diyl, Pyrazine-2,5-diyl, pyridazine-3,6-diyl, 1,4-cyclohexylene,
Thiadiazole-2,5-diyl, thiophene-2,5
-Diyl, thiazole-2,5-diyl, benzothiazole-2,6-diyl, benzoxazole-2,5-
Jiru, Indane-2,5-jiiru, Kumaran-2,5
-Diyl, 2,6-naphthylene, quinoxaline-2,6
-Diyl, quinoline-2,6-diyl,
Liquid crystalline compound (Ibc) A in which Z ₁ is a single bond represents -A ₁ -Z ₁ -A _2- , A ₁ is pyridine-2,5-diyl, and A ₂ is 1,4-cyclohexyl. Siren, indane-2,5-diyl, kumaran-
Selected from 2,5-diyl and 2,6-naphthylene,
Liquid crystalline compound (Ibd) A in which Z ₁ is a single bond represents —A ₁ —Z ₁ —A ₂ —, A ₁ is pyrimidine-2,5-diyl, and A ₂ is 1,4-cyclohexene. Siren, indane-2,5-diyl, kumaran-
Selected from 2,5-diyl and 2,6-naphthylene,
Z ₁ is a single bond, and the liquid crystal compound (Ica) A represents -A ₁ -Z ₁ -A ₂ -Z ₂ -A _3- , and A ₁ , A ₂ and A ₃ are both unsubstituted or F, Cl, B
1,4-phenylene having 1 or 2 substituents selected from r, CH ₃ , CF ₃ or CN, one of Z ₁ and Z ₂ is a single bond, the other is a single bond, − CH ₂ O-,-
A liquid crystal compound (Icb) A which is any of OCH ₂ —, —CH ₂ CH ₂ —, and —C≡C— represents —A ₁ —Z ₁ —A ₂ —Z ₂ —A ₃ — _{Two of 1} , A ₂ and A ₃ are unsubstituted or F, Cl,
1,4-phenylene having 1 or 2 substituents selected from Br, CH ₃ , CF ₃ or CN, and the remaining 1
One is pyrimidine-2,5-diyl, pyridine-2,5-
Diyl, 1,4-cyclohexylene, thiadiazole-
2,5-diyl, thiazole-2,5-diyl, thiophene-2,5-diyl, indane-2,5-diyl, coumarane-2,5-diyl, Z ₁ and Z ₂ are single Liquid crystal compound that is a bond 4. The liquid crystal compound according to claim 1, wherein in the general formula (I), R is any of the following (1) to (6). [Chemical 1] (However, a is an integer of 1 to 17, d and g are integers of 0 to 7,
b and e are integers of 1 to 9, f is 0 or 1, and h is an integer of 1 to 16. Y ₁ is a single bond —O—, —OCO—, —CO
O-, Y ₂ is -CH ₂ O -, - COO- represents any. C ^* represents an optically active asymmetric carbon atom, and
(2) and (3) may be optically active. ) 5. The liquid crystal compound according to claim 4, wherein R in the general formula (I) is optically active. 6. The liquid crystal compound according to claim 4, wherein R in the general formula (I) is non-optically active. 7. The liquid crystal compound according to claim 1, wherein in the general formula (I), Y is any one of the following (7) and (8). [Chemical 2] (However, n is an integer of 1 to 8.) 8. In the general formula (I), R is the liquid crystal compound according to claim 1 characterized in that the following (9) (9) n- C a H 2a + 1 -Y 3 - ( However, a is an integer of 1 to 17, Y ₃ represents a single bond or -O-.) 9. In the general formula (I), A is -A ₁
The liquid crystal according to claim 8, wherein -Z ₁ -A ₂ -is shown, A ₁ is pyrimidine-2,5-diyl, A ₂ is 1,4-phenylene, and Z ₁ is a single bond. Sex compounds. 10. In the general formula (I), X is 1-
The liquid crystalline compound according to claim 9, which is either tricyclo [3,3,1,1 ^3,7 ] decyl or 2-tricyclo [3,3,1,1 ^3,7, ] decyl. . 11. In the general formula (I), Y is —O.
The liquid crystal compound according to claim 9, which is CH ₂ —. 12. In the general formula (I), X is 2-
The liquid crystalline compound according to claim 11, which is bicyclo [2,2,1] heptyl. 13. The liquid crystal compound according to claim 12, wherein the liquid crystal compound represented by the general formula (I) is non-optically active. 14. A liquid crystal composition comprising at least one liquid crystal compound according to any one of claims 1 to 13. 15. A liquid crystal composition according to claim 14, wherein the liquid crystal compound according to any one of claims 1 to 13 is contained in an amount of 1 to 80% by weight. 16. A liquid crystal composition according to claim 14, which contains 1 to 60% by weight of the liquid crystal compound according to any one of claims 1 to 13. 17. A liquid crystal composition according to claim 14, wherein the liquid crystal compound according to any one of claims 1 to 13 is contained in an amount of 1 to 40% by weight. 18. The liquid crystal composition according to claim 14, which has a chiral smectic phase. 19. A liquid crystal device comprising the liquid crystal composition according to claim 14 disposed between a pair of electrode substrates. 20. The liquid crystal device according to claim 19, further comprising an alignment control layer provided on the electrode substrate. 21. The liquid crystal device according to claim 20, wherein the alignment control layer is a layer subjected to a rubbing treatment. 22. The liquid crystal device according to claim 19, wherein the pair of electrode substrates are arranged with a film thickness in which the spiral formed by the alignment of liquid crystal molecules is released. 23. A display device comprising the liquid crystal element according to claim 19. 24. The display device according to claim 23, further comprising a drive circuit for the liquid crystal element. 25. The display device according to claim 24, further comprising a light source. 26. A display method using the liquid crystal composition according to claim 14. 27. A display method using the liquid crystal element according to any one of claims 19 to 22.