JPS6341445A - Optically active liquid crystal compound and liquid crystal composition containing same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is 1-18C alkyl; C* is asymmetric C; R<1> is 4-18C alkyl or alkoxy; ring A is group of formula II or III; x is 0 or 1; y is 1-8). EXAMPLE:4-(2-n-Propoxypropyloxy)phenyl-4'-(4''-n-octyloxybenzoyloxy)be nzoate. USE:A liquid crystal element. Since the compound has ferroelectricity and spontaneous polarization, it has extremely quick response, gives a bistable state having memorizing property, has excellent view angle characteristic and is suitable for a large-capacity large-sized display. PREPARATION:The compound of formula I can be produced by converting an optically active alcohol of formula IV to the compound of formula V and acylating the product.

Description

DETAILED DESCRIPTION OF THE INVENTION 11 relates to a novel liquid crystal compound, a liquid crystal composition containing the same, and a liquid crystal 7Kr- using the liquid crystal composition.

1.For conventional LCD, for example, 1.
M, 5chadt) and Tableu Helfrich (W,
He1frieh) 'A,' Applied, Fizuix, Letters °゛ Volume 18, No. 4 ('Appli
ed Physics Letters”, Vol. I
8. No, 4) (+971.2.15),
P.

127-128 “Voltage-Dependent Optics of Nematic Liquid Crystals f) JJ (” Voltage-Depen
dent 0pticalActivit7 at
a Ti+1sjed Nematic Liquid
A device using TN (twisted nematic) liquid crystal described in Cr7stal°°) is known. However, this TN liquid crystal has a problem in that crosstalk occurs when driving at 113 hours using a matrix electrode structure with a high pixel density, so the number of pixels is limited. In addition, its use as a display has been limited because its electric field response and viewing angle characteristics are poor.

Furthermore, a display system that connects a switching element using a thin film transistor to each pixel and switches each image,
Although the 3-layer structure is known, there are problems in that the process of forming a thin film transistor on the board is extremely complicated, and it is difficult to create a large-area display element.

In order to overcome these drawbacks of conventional liquid crystal elements, the use of bistable liquid crystal elements is proposed by Clark (C
1ark) and Lagerwall (Japanese Unexamined Patent Publication No. 56-10721FI, U.S. Pat. No. 4,367,924, 1), etc.), the liquid crystal that exhibits bistability is generally chiral methic. A ferroelectric liquid crystal having a C phase (SmC") or an H phase (SmH") is used.

Because this ferroelectric liquid crystal has spontaneous polarization, it has an extremely fast response speed.Secondly, it can develop a bistable state with memory properties, and it can also be used for viewing purposes. It is a human world because of its excellent horn characteristics! Suitable as an IX dog screen display.

Colorful standing blood The present invention has been made in view of the above points.

The object of the present invention is to provide a liquid crystal compound useful for controlling a liquid crystal state, a liquid crystal composition containing the same, and a liquid crystal element using the liquid crystal composition.

LLΩ]L 亥 That is, the present invention is based on the general formula (I) (wherein R represents an alkyl group with an R prime number of 1 to 18,
C1 represents an asymmetric carbon atom; R1 represents a C4-C18 furkyl, (or alkoxy) group;
- or (N, X is 0 or 1, y is 1 to 8).

1 shot again at 7! II also provides a liquid crystal composition containing at least one optically active liquid crystal compound described in 1- above as a compounding component, and a liquid crystal M element using the liquid crystal M1 composition.

Summer 1-・LLi According to the present invention, a method for producing the liquid crystal compound of formula (I) will be explained.

First, starting D: [the following general formula (II) CH as a starting material.

嘗HO(C1-[2)-V CH(CH2)-xOR(I
I) (Here, R represents an alkyl group having 1 to 18 carbon atoms, C1 represents an asymmetric carbon atom, X is 0 or t, y is 1
-8) is used. This formula (1
The optically active alcohol represented by 1) has the general formula (b) (where Ro is lower alkynoleno,
represents a missing atom; X and Z represent O or 1; when X is 0, Z is O or 1; when X is 1, 2 is 0;

) is a compound represented by,! In terms of the L-isomer, from 2-hydroxypropionic acid alkyl ester, 3-hydroxybutyric acid alkyl ester and 3-hydroxy-2-methylpropionic acid alkyl ester, the following reaction step 2 G, l
) and (2) or by repeating the process formula (2).

Engineering-CH.

HO(CH2)7XCH(CH2)z Coo-Re
([[I)↓AgzO/Rx CH.

RO4CHt )x CH(CH2)Z C00RO↓
LiAl84CH.

1104CH2) x CH(CH2) z CHx
Of((Iri -1 north?... ↓GHz (COOC2Hs) 2 CH.

■ R04CHt 3” X CH(CH2) z CH2
CH(COOC2Hs) 2'LH2S
o.

CH.

1AI84 CH.

Cloudy-0(CH2>-xCM(CHt)z CHt-Br
CH2 Gate CH.

1(CH2)-, CH(CI,)z cti, CH2C
RI in formula 15 can be selected from a wide range of carbon numbers, and examples include iodobutane, iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iododecane, and iodoundecane. , iodododecane, iodotridecane, iodotetradecane, iodopentadecane, iodohexadecane.

Linear saturated hydrocarbon iodides such as iodoheptadecane, iodooctadecane, iodononadecane, iodoeicosane; branched saturated hydrocarbons such as 2-iodobutane, 1-iodo-2-methylpropane, l-iodo-3-methylbutane, etc. Iodide; iodobenzyl, iodophenacyl,
Cyclic unsaturated hydrocarbon iodides such as 3-iodo-1-cyclohexene: iodocyclopentane, iodocyclohexane, 1-iodo-3-methylcyclohexane.

There are cyclic saturated hydrocarbon iodides such as iodocyclohebutane and iodocyclooctane.

A typical synthesis example of the optically active alcohol represented by formula (II) is shown below.

example".

Synthesis of 2-butoxypropanol (x=0.y=1.
R= n-C4N9-) L-(10)-ethyl lactate 31.5 g,! =107.3 g of 1-iodobutane was mixed into a four-meter flask, and newly synthesized Ag2O was added over 2 hours.

After a 4-hour period of 15 nNj at room temperature, the mixture was diluted with 2001-tel, filtered, and the ether was distilled off. The remaining amount is 5%K
Wash with 100 OH aqueous solution 1? After 'rl, anhydrous Na25
Dry at O* and evaporate under reduced pressure L 10°C 154mmHg
When the fractions were collected, 23 g of (-)-ethyl-2-butot
- Dipropionate was obtained. Optical rotation [α = -7
3°.

Add 42.0 g of LiAlH to 100 liters of ether,
After stirring for 3 hours, 12.7 g of (-)-ethyl-2-butoxypropionate was added dropwise.
I continued to wear it one by one. Its contact with water is 50m15J: 10%H
2So4 aqueous solution 501 was added. Separate the ether layer,
Dry with MgSO4. It was filtered and the ether was distilled off. Convergence: 7.4g, optical rotation [α]”: +24
, 4°.

Synthesis of 3-pentyloxybutanol (X=0, y=2
．． R=n-Cs Ho-) (R)-(-)-3-hydroxymethyl acetate 92.1g
and 389 g of pentyl iodide were added to the flask and mixed under a N2 stream. Add 271 g of newly synthesized Agzo, stir at 60-65°C for 26 hours, and add Ag2O5.
4.2 g was added and stirred at 60-65° for 58 hours. P connection, wash the filtrate thoroughly with ether, and remove the ether from the p solution with q.
1 After leaving, vacuum steaming! WL, 112~l 31'
64.6 g of methyl 3-pentyloxybutyrate was obtained as a fraction of C/59 monHg.

Next, add 4 g of L i A I Ha 9 to 310 m1
In addition to the ether, a solution of 63.6 g of methyl 3-pentyloxybutyrate in 61 ml of ether was added dropwise at a temperature below 10°C over a period of 21141 hours.
After stirring for 2.5 hours, the mixture was left to stand for 15 hours.

After that, 11! Make it acidic with an acid aqueous solution (pH 1).

Ether 8111 was released. The ether layer was mixed with water and 5% NaH.
It was washed with a COs aqueous solution and then with water, and dried with Mg5O. Filtered and distilled under reduced pressure, 127-131"C/50
3.4.2 g of 3-pentyloxybutanol was obtained as a m m Hg (7) fraction. About the product
The following IR data was tltted.

IR (cm-'): 3360.2970-2870.1370, LO90゜9'' Synthesis of 3-ethyloxy-2-methylpropanol (x
=1. y=l, R=C2H5)(R)-C-)-3-hydroxy-2-methylpropionate methyl loog and 331 g of ethyl iodide were added to the flask, and the
It was 84 matches.

Add newly synthesized L ta A g 20 294 g, 6
Stirred at 0-65°C for 20 hours. After pi, wash the 7j filtrate with ether, and evaporate the gj solution with ether.

Decompression no.qt: R, 100-110℃/L 50m
m Hg fraction, 87 g of 3-ethyloxy-
Methyl 2-methylpropionate was obtained.

Next, L i A I Ha 18, 5 g to 610
In addition to the ether of 1111, a solution of 87 g of methyl 3-ethyloxy-2-methylpropionate in ether 1221 was added dropwise at 10"C or less over 6 hours. After 0 dropwise addition, 2
After stirring at 0 to 25°C for 2.5 hours, it was left to stand at room temperature for 15 hours. Thereafter, the mixture was acidified with a 5% aqueous hydrochloric acid solution and extracted with ether. Water the ether layer.

It was washed with 5% NaHCO, an aqueous solution, and water in this order, and dried with Mg5O. After distilling off the ether, it was distilled under reduced pressure and
As a fraction of 115°C/155mmHg, 39g of 3-
Ethyloxy-2-methylpropatool was obtained.

IR: (am-'): 3380.2980-2870.1380.1110.
1040゜4-n-octyloxypentanol (X=0.7=3
, R=n-C6H13-) L-(+)-ethyl lactate 98 g, octyl iodide 380
g and 1245 g of oxidized ff were added, and 1611 g was added at 60°C.
If ff-L, remove insoluble matter in old age, reduce pressure I
77 g of ethyl 2-octyloxypropionate as a fraction of W, tto-, t3oC/3 mm Hg.
I got it.

Next, LiAIH, 7,
After adding 5 g and stirring for a while, the ester form 56
A solution of 50 ml of diethyl ether was added dropwise at 5°C or lower over 2 hours. After adding 1 drop, the solution was stirred at room temperature for 2 hours, and then
After the 0 reaction was completed, 30 ml of 5% hydrochloric acid was added and further 6 N rg! 11 with acid! The mixture was acidified (PH-1) and extracted with ether. After washing with water, it was dried and the solvent was distilled off. Distilled under reduced pressure.

39.5 g of 2-octylreoxypropanol was added as a fraction of 107°C/3 +a++Hg.

Next, pyridine 2301 was added to 70 g of the alcohol, and while stirring, tosyl chloride 85 was added to 70 g of the alcohol at 30° C.
I added it over a period of time. After stirring at this temperature for 15 minutes, the temperature was raised to 2
Stirred at 0-24°C for 3.5 hours. After pouring into cold water, extract with benzene, 5% 11! Wash with acid and wood in that order tII + L
, dried. Benzene was distilled off to obtain 127 g of (2-octyloxypropyl)p-)luenesulfone.

95% sodium ethoxide 2 in ethanol 2201
Add 6.7 g of 98% diethyl malonate 73 while stirring.
．． 1 g was added dropwise at 36-38@ over 50 minutes. After further stirring for 30 minutes, 127 g of the tosylate compound was added to 36-3
The mixture was added dropwise at 8°C over 1 hour. After further stirring for 15 minutes, the temperature was raised and the mixture was refluxed for 18 hours. After the reaction, ice water was poured into the mixture, followed by extraction with benzene, washing with water, and drying. After distilling off the solvent, 149g
ethyl 4-year-old ctyloxy-2-ethoxycarbonylvalerate was obtained.

Next, 388.5 g of 85% KO was dissolved in 90 ml of wood, and 149 g of the above ester was added dropwise at 20 to 25° C. over 50 minutes. After stirring for 30 minutes, the mixture was refluxed for 2 hours. After cold sawing, 153 g of C sulfuric acid was dissolved in Wood 1961 while keeping the temperature below 15° C., and this was added dropwise over 1 hour. After stirring for 30 minutes, 3
Refluxed for an hour. After cooling to room temperature, the mixture was extracted with benzene. The benzene layer was washed with 5% NaOH aqueous solution and added to the aqueous layer. The aqueous layer was made acidic (pH 1) with 6N hydrochloric acid, extracted with benzene, washed with water, and dried over anhydrous Mg5O. The solvent was distilled off to obtain 54 g of 4-octyloxylic acid.

L i A I H41 in dry ether 210s+l
Add 0g of ether 7 and add 54g of the above carboxylic acid while stirring.
0ml solution was added dropwise over 70 minutes while maintaining the temperature at 2-6°C. 'tF4, the temperature was raised to 23°C and stirred for 3 hours. Open at 12:00 2H & Add 5% hydrochloric acid while keeping the temperature below 15℃ to make it acidic, extract with ether, add water, 5%
% NaOH aqueous solution, the wood was washed in this order, and dried with anhydrous MgSO4. The solvent was distilled off, then distilled under reduced pressure, and heated to 150℃15
The log of (S)-4-octyloxypentanol was obtained as a fraction of -■H.

IR(am-'): 3360.2970~2860.1460°1370.
1340, toao.

By using the optically active alcohol represented by the general formula (11) and following the reaction scheme shown below, a large number of optically 11'i liquid crystalline compounds represented by the general formula (I) can be produced.

The liquid crystal composition of the present invention contains at least one optically active liquid crystal compound represented by the above general formula (I) as a compounding component.

Among the compositions listed in L, those containing ferroelectric liquid crystals as represented by the following formulas (1) to (13) can increase spontaneous polarization and further reduce viscosity. Combined with the effect, the response speed is increased; 3. In such a case, the optically active liquid crystal compound of the present invention represented by the general formula (I) is added in an amount of 001 to 99% by weight, particularly 1 to 90% by weight of the resulting liquid crystal composition. It is preferable to use it at a rate that is a false percentage.

Phenyl ester 42 43.5 58.5
62Cryst, −1→SaC” −−→S
mA-1→Ch, -→Iso.

phenyl ester Crygt, -La SmA -La Iso.

! 6 to 5IIIC", /43.5 Phenyl ester Cryst, ->5ell: "--→SmA-
-Larso.

Phenyl ester Sf'', /48 Phenyl ester 49 52 e5Cryst
, −1→SaC” −1→, S+aA−+rso
.

-Methylbutylcinnamate (DOBAMBC) CH.

-COOCHt CHC2Hs 4.4'-7Zoxycinnamic acid bis(2-
methylbutyl) ester octyloxybiphenyl-4
-Carboxylate biphenyl-4'-carboxylate crystal 83.4"C cholesteric phase (19 isotropic phase SmC'74.3"C2 S mA 81
．． A composition that can be used as a ferroelectric liquid crystal can be obtained by blending it with a smectic liquid crystal that is not chiral per se and as shown in the following formulas () to 5) at 0°C.

In this case, it is preferably used in an amount of 0.1 to 99% by weight, particularly 1 to 90% by weight of the liquid crystal composition from which the optically active liquid crystalline compound of the present invention represented by general formula CI) is obtained.

4.4゛-decyloxyazogicibenzene Cr7sL,
7 45 m 1 Δ4 N % I30 Phenyl) Pyrimidine Cryst, 120°C Si 189”CSaA
Once, I so ----Xie-ri 2-(4'-octyloxyphenyl)-5-nonylpyrimidine Cryst, 33℃ SmC60℃
SmA 75°C Iso.

−? (-1112ν 4'-pentyloxyphenyl-4-octyloxybenzoate C
ryst, 58℃ 5lIIC64℃ SwA
86°C N 85°C Iso.

−−ichi−=ri −duck −−ichi−ri −
----Here, the symbols indicate the following phases, respectively.

Crystal: crystalline phase, SaA: smectic A phase.

5IIIO=smectic B phase, 5lIC: smectic C phase, N: nematic phase, Iso, isotropic phase.

Further, the optically active liquid crystal compound of the general formula (1) is
By adding it to nematic liquid crystals, it is effective in preventing the occurrence of reverse domains in TN type cells.

In this case, 1 of the liquid crystal composition obtained by adding the optically active liquid crystal compound of formula (I) to the nematic liquid crystal.
．． It is preferable to use the optically active liquid crystalline compound of formula (I) in a proportion of 0.01 to 50% by weight.

In addition, by adding it to nematic liquid crystal or chiral nematic liquid crystal, it can be used as chiral nematic liquid crystal.
It can be used as a liquid crystal composition for phase change type liquid crystal elements and why-tiller type guest-host type liquid crystal elements.

Figure 1 is for explaining the operation of ferroelectric liquid crystal.

This is a schematic drawing of an example of a cell. 11a and ll
b is I n203.5 n02 or I
Substrate (glass plate) covered with a transparent Ij+ electrode made of a thin film of T O (Indium -Tin 0w1de)i
A liquid crystal of Smc" phase or SmH" phase, in which the liquid crystal molecules 12 are oriented perpendicularly to the glass surface, is sealed between them. Shown with a bold line! i13 represents a liquid crystal molecule, and this liquid crystal molecule 13 has a dipole moment (P) 14 in a direction perpendicular to the molecule. Nof board 2
When a voltage higher than a certain dark value is applied between the electrodes 1 and ttb, the helical structure of the liquid crystal molecules 13 is unraveled, and the liquid crystal molecules 13 are aligned in the direction such that all the dipole moments (P) 14 are directed in the direction of the electric field. can be changed. liquid crystal molecule 1
3 has an elongated shape and exhibits refractive index anisotropy in the long axis direction and the short axis direction. Therefore, for example, if crossed Nicol polarizers are placed above and below the glass surface, ? It is easily understood that this is a liquid crystal optical modulation element whose optical properties change depending on the polarity of the applied voltage.

The thickness of the liquid crystal cell preferably used in the optical modulation element of the present invention can be made sufficiently thin (for example, 10 mm or less).As the liquid crystal layer becomes thinner, as shown in FIG. Even when no electric field is applied, the helical structure of the liquid crystal molecules is unraveled, and the dipole moment (Pa or Pb) is either upward (24a) or downward (24b). When an electric field Ea or Eb of different polarity above a certain dark value is applied to such a cell by the voltage applying means 21a and 21b as shown in FIG. 2, the dipole moment changes to the electric field vector of the electric field Ea or Eb. Correspondingly, the liquid crystal molecules change direction upwards 24a or downwards 24b.

Either the first stable state 23a or the second stable state 23b
Orient in one direction.

As mentioned earlier, there are two advantages to using such ferroelectricity as an optical modulation element.

The first is that the response speed is extremely fast, and the second is that the alignment of liquid crystal molecules has bistability. To further explain the second point with reference to FIG. 2, for example, the electric field Ea
When the voltage is applied, the liquid crystal molecules are aligned in the first stable state 23a, and this state remains stable even when the electric field is turned off. Further, when an electric field Eb in the opposite direction is applied, the liquid crystal molecules are oriented to the second stable state 23b and change their orientation, but they remain in this state even after the electric field is turned off. or.

As long as the applied electric field Ea or Eb does not exceed a certain darkness value, the previous orientation state is maintained. In order to effectively realize such fast response speed and bistability, it is preferable for the cell to be as thin as possible, and generally 0.51L to 20mm, especially 1μ to 5#L is suitable. There is.

Next, specific examples of the driving method of ferroelectric liquid crystal are shown in Figures t53 to 5.
This will be explained using figures.

FIG. 3 is a schematic diagram of a cell 31 having a matrix electrode structure in which a ferroelectric liquid crystal compound (not shown) is sandwiched between. 32 is a scanning electrode group, and 33 is a signal electrode group. First, the case where scan electrode SI is selected will be described. FIG. 4(a) and FIG. 4(b) are scanning signals, and are electrical signals applied to the selected scanning electrode Sl and the other scanning electrodes (unselected scanning type J4).
) S2 , St , S4 ・fist・ shows the electrical signals applied to it. Figure 4(C) and Figure 4(d) are
lI signal, respectively selected signal electrodes I, , I
, , I, and the unselected signal electrode I2. It shows the electrical signal applied to I.

In FIGS. 4 and 5, the horizontal axis represents time and the vertical axis represents voltage. For example, when displaying a moving image, the scanning electrode group 32 is sequentially moved.

Selected periodically. Now, in order to provide the first stable state of the liquid crystal cell having bistability for a predetermined voltage application time 1 or t2, the 1-value voltage is -v th,
2 stable condition! The jump 1/I voltage to give E is +v
Assuming th2, the electrode signal given to the selected scanning electrode 32 (S+) is 2V at phase (time) 1+ and − at phase (time) t2, as shown in FIG. 4(a).
This is an alternating voltage of 2V. When electrical signals having multiple phase intervals with different voltages are applied to the scanning electrodes selected in this way, optical "darkness" or "
An important effect can be obtained in that the state of the liquid crystal can be rapidly changed between the hl l or the second stable state corresponding to the "bright" state.

On the other hand, the other scan electrodes S2 to S,... are in a grounded state as shown in Figure i4 (b), and receive the electrical signal O.
It is. Also, the selected signal electrode I4.13. The electrical signal sent to Is.

v as shown in FIG. 4(C), and the unselected signal electrodes I2.1. The electrical signal given to is <-V as shown in FIG. 4(d).

In the above, the voltage value of each )/ is set to a desired value i16 that satisfies the following relationship.

V < V th 2 < 3 V -3V <-Vth, <-V When such an electric signal is received, one of each l1Ti element, for example, is applied to pixels A and B in FIG. 3, respectively. The voltage waveforms are shown in FIGS. 5(a) and 5(b). That is, as is clear from FIGS. 5(a) and 5(b), at the pixel A on one selected scanning line, at phase t2, Threshold value v th
A voltage 3■ exceeding 2 is applied. In addition, the phase of pixel B existing on the same scanning line is different from that of (+fj −V
A voltage of -3V exceeding th is applied. Therefore, depending on whether or not a signal electrode is selected on the selected scanning electrode line, if the signal electrode is selected, the liquid crystal molecules are aligned in the first stable state. Align the orientation to the stable state of 2.

On the other hand, as shown in FIGS. 5(C) and (d), on the unselected scanning lines, all Ii! The voltage applied to the i element is V or 1, and neither exceeds the dark value '+1Z pressure.Therefore, the liquid crystal molecules in each pixel other than on the selected scanning line remain the same as the previous one without changing their alignment state. Signal shape when scanned! The orientation corresponding to E is maintained as is. In other words, scanning? As soon as a pole lj is selected, the signal is aged for l life, and the signal state can be maintained until the next selection after one frame ends. Therefore, even if the number of scanning electrodes increases, the actual duty ratio does not change and the contrast does not deteriorate at all.

Next, let us consider the problems that may actually occur when the device is driven as a display device.

In Fig. 3, among the pixels formed at the intersections of the scanning electrodes SL"S5... and the signal electrodes 1 to I,..., the pixels in the shaded areas are in the "bright" state and are shown in white. The pixel shall correspond to the "r dark" state. Now, the signal electrode in Figure 3■□
Pay attention to the display above.

The pixel (A) corresponding to the scanning electrode S1 is in the "bright" state, and all other pixels (B) are r l1llt J
state. As an example of the driving method in this case, FIG. 6 shows a time-series representation of the scanning signal, the information signal applied to the signal electrode I, and the voltage applied to the II'ri element A.

For example, when boat A is driven in the sixth manner, when the scanning signal S1 is scanned, at time L2, boat A has the following:
Since a voltage of 3V exceeding the threshold value v th2 is applied, one pixel A transitions (switches) to a stable state in one direction, +ai, that is, a "bright" state, regardless of the previous history, and thereafter, S2
~S,... While the fist is being scanned, as shown in Figure 6 (-
The voltage of V continues to be applied, but this is IM(〆i −V
One pixel A should be able to maintain a "bright" state because it does not exceed th, but in reality, one signal (corresponding to "dark" in this case) is given on one signal electrode. When displaying continuous information, the number of scanning lines is extremely large and high-speed driving is required, causing an inversion phenomenon. , such a reversal phenomenon is completely prevented.

Furthermore, in the present invention, in order to prevent the above-mentioned reversal phenomenon, it is preferable to provide an insulator 11 made of an insulating material on at least one of the opposing electrodes constituting the liquid crystal cell.

The insulating material used in this case is not particularly limited, but silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon 1 containing hydrogen
Inorganic insulating materials such as chloride, silicon oxide, boron nitride, hydrogen-containing boron nitride, cerium oxide, aluminum oxide, zirconium oxide, titanium oxide and magnesium fluoride, or polyvinyl alcohol,
Polyimide, polyamideimide, polyesterimide,
polyparaxylene, polyester, polycarbonate,
Organic insulating materials such as polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin, melamine resin, urea resin, acrylic resin, and photoresist resin are used as the insulating film. The thickness of these insulating films is 5000 Å or less, preferably 10
0 to 1000 people, especially 500 to 3000 people is suitable.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Practical JL Example 2 Synthesis of 4-(2-n-7'lopoxypropyloxy)phenyl-4'-(4''-n-octyloxybenzoyloxy)benzonitono.

(Step) l Synthesis of P-hydroquinone mono(2-propoxypropyl) ether.

140 ml of dry pyridine and 27.5 g of 2-propyloxypropanol were mixed, and 53.5 g of P-toluenesulfonic acid chloride l-' was added over 30 minutes to the mixture, which was cooled with water. After returning to room temperature, the mixture was stirred for 6 hours. 15 more
I left it for a while. The reaction mixture was added to cold water, extracted with benzene, and dried over anhydrous Na2SO4. Benzene was distilled off to obtain 59 g of oily (2'-propoxypropyl)-P-toluenesulfonate.

Next, 35.9g of hydroquinone and 85% KOH14,9
318 g of ethanol and 621 g of methanol were added thereto, and the mixture was stirred for 5 hours. To this, 59 g of 2'-propoxypropyl-P-)J reninsulfonate obtained in Section 2.
and heated at 60°C for 2 hours.

The reaction mixture was allowed to react under reflux at 76-78°C for 5 hours, and then cooled.

+1 after adding anti-I5 to water cooling! Made resistant to acid. After extraction with n-hexane, the mixture was washed successively with a 5% aqueous NaOH solution and water, and then n-hexane was distilled off to obtain crystals. Further, recrystallization was performed using n-hexane to obtain 13.6 g of p-hydroquinone mono(2-propoxypropyl) ether.

(Step 2) 4-(2-n-propoxypropyloxy)phenyl-
Synthesis of 4'-hydroxybenzony 1.

5 g of p-hydroquinone mono(2-propoxypropyl) ether and 2.7 g of p-hydroxybenzoic acid were dissolved in 100a+I of toluene, and concentrated acids MO, Lg,
Add 0.06g of boric acid and heat to 110-115℃,
The reaction was carried out by reflux dehydration for 18 hours. It was then cooled and poured into cold water. Extracted with ether, 5% N
After washing with an aOH aqueous solution and water, the ether was distilled off, and the resulting oil was dissolved in benzene, treated with an activated carbon column, and then the benzene was removed.
．． 5 g of 4-(2-n-propoxypropyloxy)phenyl-4'-hydroxybenzoate was obtained.

(Step 3) 4-(2-n-propoxypropyloxy)phenyl-
Synthesis of 4'-(4'''-n-octyloxybenzoyloxy)benzoate.

4-(2-n-propoxypropyloxy)phenyl-
1.5 g of 4-hydroxybenzoate was added to 15 g of pyridine.
Dissolve in 5 ml of p-n-octyloxyammonium (7), 9. A solution of 10 ml of toluene of fragrant chloride (based on p-n-octyloxy, synthesized from 1.2 g of fragrant acid) was added, and the mixture was stirred at room temperature for 1 hour, then at 90-95°C for 2 hours, and cooled. The reaction solution was added to cold water, extracted with ether, and diluted with 5% li! Acid, water, 5% NaOH aqueous solution,
After sequential washing with water, the ether was distilled off, and the resulting crystals were subjected to ILT crystallization with ethanol to obtain 0.8 g of white crystals. The phase transition temperature of the product is shown below.

The following compounds are synthesized in the same manner.

4-(2-methyloxypropyloxy)phenyl-
4'-(4''-n-decyloxybenzoyloxy)benzony), 4-(2-ethyloxypropyloxy)phenyl-4'-(4''-n-hexyloxybenzoyloxy)benzoate.

4-(2-Butyloxypropyloxy)phenyl-
4'-(4''-n-hebutyloxybenzyloxy)
Benzony 1-,4-(2-pentyloxypropyloxy)phenyl-4'-(4''-n-octylbenzoyl)benzoate, 4-(2-octyloxypropyloxy)phenyl-4'-(4 "-) lance-propyl #xychlorohexylcarponyloxy)benzoate, 4-(3-hebutyloxybutyloxy)phenyl-4'-(4"-n-7'yloxybenzoyloxy)benzoate, 4- (4- probyloxypentyloquine) phenyl-4'-(4'-trans-n-
Hexylene chlorhexyl (propyloxy)benzoate, 4-(6-butyloxy,butyloxy)phenyl-4'-(4''-propylbenzoyloxy)benzoate, 4(2-methyl-3-ethyloxypropyloxy)phenyl-4 '-(4''-n-hexyloxybenzoyloxy)benzoate.

Look 1-? Rixon GR-63 (biphenyl liquid crystal mixture made by Chisso)
99 weight 1? A TN cell using a liquid crystal mixture in which 1 part by weight of 4-(2-n-propoxypropyloxy)phenyl-4'-(4''-n-octyloxybenzoyloxy)benzoate is added to a portion of the liquid crystal mixture is based on this optically active It was observed that the reverse domain was significantly reduced compared to the TN cell manufactured without adding any liquid crystalline compound.

Mitate 1” Crossed Se 1? Polyimide II+2 (poly7 minic acid resin consisting of a combination of pyromellitic anhydride and 4,4'-diaminodiphenyl ether) was applied to each of the facing matrix electrodes formed of ITO with a thickness of 1000 mm. Apply ball amount% N-methylpyrrolidone solution,
250'C! A cell was prepared by rubbing the polyimide film 08 surfaces so that they were parallel to each other to make the cell thickness 1=.

Next, the following composition A was injected into the above-mentioned cell by a vacuum injection method under an isotropic phase, and the cell was sealed. After cooling, slow cooling (
A liquid crystal cell of "SmC" was prepared using 1"C/hour).

12 degrees) I36 18 nail amount % A crossed Nicol polarizer and an analyzer were placed on both sides of this liquid crystal cell, and a signal having the waveform shown in FIGS. 4 and 5 was applied between the opposing matrix electrodes. At this time, the scanning signal is ft54
The alternating waveforms of +8 volts and 18 volts shown in Figure (a) were used, and the illumination information was set to +4 volts and 14 volts, respectively. Further, one frame period was set to 30 mφsec.

As a result, even when this liquid crystal element was subjected to the above-mentioned memory-driven time-division driving, the written state was not reversed and a normal moving image display was obtained.

The following comparative liquid crystal B is obtained by omitting the optical l, η liquid crystalline compound represented by the general formula (I) in the liquid crystal composition used to create the liquid crystal element of Example 3. was prepared, and a liquid crystal element was created using the comparative liquid crystal. Although these liquid crystal elements were driven in the same manner as described above, a normal moving image was not displayed because a one-inversion phenomenon occurred.

[Brief explanation of the drawing]

1 and 2 are perspective views schematically showing the time-division drive liquid crystal element used in the present invention, FIG. 3 is a cross-sectional view of the matrix electrode structure used in the present invention, and FIG. 4(a) ~(d
) is an explanatory diagram representing the electric signal applied to the matrix electrodes, FIGS. 5(a) to (d) are explanatory diagrams representing the waveform of the voltage applied between the matrix electrodes, and FIG. Theory I of the time chart representing the electrical signal applied to the liquid crystal element of ! Figure 1. 11a, llb... one board. 12...Liquid crystal molecular layer. 13...Liquid crystal molecules. 14...Dipole moment (r'i), 23a...
First stable state! island. 23b...Second stable state, 24a...Upward dipole moment, 24b...Downward dipole moment. 31...Cell, 32...(S+, S2.s3,...)...Scanning electrode group. 33...(Il, I2.Il,...)...Signal electrode group. Sheep I Fig. 2 Fig. 33 Signal electrode group It 12 13 1415 ---- 3rd day (a) Product 4 Fig. (4) Name 5th

Claims (1)

[Claims] 1. The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (However, R represents an alkyl group having 1 to 18 carbon atoms, and C
^* indicates an asymmetric carbon atom. R^1 indicates an alkyl group or an alkoxy group having 4 to 18 carbon atoms, and ▲ has a mathematical formula, chemical formula, table, etc. ▼ means ▲ has a mathematical formula, chemical formula, table, etc. ▼ or ▲ has a mathematical formula, chemical formula, table, etc. Indicates ▼. x represents 0 or 1, and y represents 1-8. ) An optically active liquid crystal compound represented by 2. General formula (I) below ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (However, R represents an alkyl group having 1 to 18 carbon atoms, and C
^* indicates an asymmetric carbon atom. R^1 indicates an alkyl group or an alkoxy group having 4 to 18 carbon atoms, and ▲ has a mathematical formula, chemical formula, table, etc. ▼ means ▲ has a mathematical formula, chemical formula, table, etc. ▼ or ▲ has a mathematical formula, chemical formula, table, etc. Indicates ▼. x represents 0 or 1, and y represents 1-8. ) A liquid crystal composition comprising at least one optically active liquid crystal compound represented by the following. 3. The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (However, R represents an alkyl group having 1 to 18 carbon atoms, and C
^* indicates an asymmetric carbon atom. R^1 indicates an alkyl group or an alkoxy group having 4 to 18 carbon atoms, and ▲ has a mathematical formula, chemical formula, table, etc. ▼ means ▲ has a mathematical formula, chemical formula, table, etc. ▼ or ▲ has a mathematical formula, chemical formula, table, etc. Indicates ▼. x represents 0 or 1, and y represents 1-8. ) A liquid crystal element using a liquid crystal composition containing at least one type of optically active liquid crystal compound represented by: