JPS62209044A - Lactic acid derivative and liquid crystal composition containing said derivative - Google Patents

Abstract

NEW MATERIAL:An optically active substance expressed by formula I (R is 1-18C straight-chain, branched chain or cyclic saturated or unsaturated hydro carbon group; n is 1 or 2; C* is asymmetric carbon atom; X is detachable substit uent group selected from OH, halogen, benzyloxy, phenoxy, toluenesulfonic acid, OCOCH3 and OCOCF3). EXAMPLE:(2-Ethoxy)propyl p-hydroxybenzoate. USE:A liquid crystal substance capable of linking to a functional material intermediate having a moderate intermolecular force without impairing optical activity and freely carrying out molecular design, producing large spontaneous polarization in use as a ferroelectric liquid crystal and controlling the kind of temperature range of the liquid crystal phase developed in a liquid state. PREPARATION:A compound expressed by formula II is reacted with a compound expressed by formula III to afford the aimed compound expressed by formula I (X is OCOCH3).

Description

[Detailed Description of the Invention] The present invention relates to a lactic acid derivative whose molecular structure can be easily changed and which has optical activity, and a liquid crystal composition containing the same.More specifically, it relates to an optically active lactic acid derivative. The present invention relates to a liquid crystal compound intermediate, a liquid crystal compound derived therefrom, a liquid crystal composition containing the same, and a liquid crystal element using the liquid crystal composition.

1. As a conventional liquid crystal element, 1, for example, M shaft (M,
5chadt) and W Helfrich (W, He
Applied Physi, Volume 18, No. 4, Applied Physi.
csLetters”, Vol. 18. No.
4) (19?1.2.15), P, 127-12
Voltage-dependent optical behavior of twisted nematic liquid crystals J (
” Voltage-Dependent 0ptic
alActivit7 of a Twist
d Nematic Liquid Cr7st
A device using a TN (twisted nematic) liquid crystal described in ``alpa'' is known. However, this TN liquid crystal has a problem in that crosstalk occurs during time-division driving using a matrix electrode structure with a high pixel density, so the number of pixels is limited. Also,? I!
Its use as a display has been limited due to its slow field response and poor viewing angle characteristics.

Furthermore, a display element is known in which a switching element using a Vj film transistor is connected to each pixel, and each pixel is switched. However, the process of forming the thin film transistor on the substrate is extremely complicated, and the display requires a large area. There is a problem that it is difficult to create the device.

To improve the drawbacks of conventional liquid crystal devices, the use of bistable liquid crystal devices has been proposed by Clark (C
1ark) and Lagerwall
) (Japanese Unexamined Patent Publication No. 56-107218, U.S. Pat. No. 4,387,924, etc.), liquid crystals having bistability generally include chiral smectic phase (SmC") or H phase (SmH"). ) is used.

Because this ferroelectric liquid crystal has spontaneous polarization, it has an extremely fast response speed, can express a bistable state with memory properties, and has excellent viewing angle characteristics, so it can be used for large-capacity, large-screen displays. Suitable as a display.

Liquid crystal compounds used in ferroelectric liquid crystals have asymmetric carbon, so in addition to being used as ferroelectric liquid crystals using their chiral smectic phase, they can also be used in the following optical elements: can be used.

1) Those that utilize the cholesteric-nematic phase transition effect in the liquid crystal state (J, J, W7soki, A,
Adams and W, Haag; Phys-Rev
20.1024 (1968)), 2) Utilizing the White-Tiller type guest-host effect in the liquid crystal state (D, LJhite6nd
G, N, Taylor; J, App, 1. Phys.
, 45.4718 (1974)), 3) By fixing a cholesteric phase in a liquid crystal state into a matrix, its selective scattering properties can be utilized to utilize it as a notch filter or a bandpass filter (F, 1Kahn, Appl, Phy
S, Lett, , 18,231 (197+)) A circularly polarized beam splitter that utilizes circular polarization characteristics and one that utilizes 17 (S, [1, Jacobs, 5PIE, 3
7.98 (1981)); etc.

Although a detailed explanation of each method will be omitted, all of them are important as display elements and modulation elements.

Conventionally, optically active intermediates for synthesizing functional materials required for optical elements characterized by having optical activity include 2-methylbutanol, secondary octyl alcohol,
Secondary butyl alcohol, P-(2-methylbutyl) chloride
Benzoic acid, secondary phenethyl alcohol, amine m, derivatives, camphor derivatives, cholesterol derivatives, etc. are known.

However, these have the following drawbacks. It is difficult to change the structure of optically active chain hydrocarbon derivatives and, with the exception of some, they are very expensive. Amino a?
A conductor is relatively inexpensive and its structure can be easily changed, but the hydrogen group of the amine is chemically active and tends to cause hydrogen bonds and chemical reactions, which tends to limit the properties of functional materials. It is difficult to change the structure of , camphor derivatives, and cholesterol derivatives, and they tend to adversely affect the properties of functional materials due to steric hindrance.

The above drawbacks have been a major constraint on the development of various materials.

In view of the above circumstances, the main object of the present invention is to provide an optically active compound that is not only useful as a suitable optically active intermediate but also useful for controlling the liquid crystal state, and a liquid crystal composition containing the same. It's about providing things.

More specifically, the present invention is capable of bonding with a functional material intermediate having an appropriate intermolecular force and shape to form liquid crystals, LB films, bilayer films, etc. without impairing optical activity. The purpose of this invention is to provide compounds whose molecular design can be carried out freely.

Another object of the present invention is to provide a compound that exhibits large spontaneous polarization when used as a ferroelectric liquid crystal due to the presence of an ugly atom adjacent to an asymmetric carbon atom.

In addition, in the present invention, it is easy to change the length of the alkyl group, which allows H, Arnold, Z, Ph7g
.

Chem., 22614B (1984), a liquid crystal compound capable of controlling the M class and temperature range of the liquid crystal phase developed in the liquid crystal state, and a liquid crystal composition containing at least one compounded compound thereof. The purpose is to provide.

Further, the present invention provides LB (Langsuir-Blodgst)
t) The purpose of the present invention is to provide a compound whose hydrophobic groups can be easily controlled and which can be stably formed into a film when a monomolecular cumulative film is produced by the 112 method.

Sakitate 1” That is, the present invention provides general formula CI) (In the above general formula, R is a linear chain having 1 to 18 carbon atoms.

represents a branched or cyclic saturated or unsaturated hydrocarbon group, n is 1 or 2, Cm represents an asymmetric carbon atom, X is OHM, halogen, benzyloxy group, phenoxy group, toluenesulfonic acid group, acetyloxy group, a removable substituent selected from trifluoroacetyloxy group); The present invention provides a liquid crystal composition containing the above compound as a compounding component.

In addition, the present invention particularly provides that in the above general formula (I), R is an alkyl group having 1 to 18 carbon atoms, and X is R'& CO
O (wherein L R' is an alkyl group or alkoxy group having 4 to 18 carbon atoms, and m is 1 or 2)), and at least LM
The present invention provides a liquid crystal composition containing the compound as a component of type i, and a liquid crystal element using the liquid crystal composition.

[,; In the general formula (I) representing the above-mentioned optically active substance, R is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms; This is not preferable because it increases the viscosity and molar volume when used as a final functional material, and the preferable number of carbon atoms in R is 4 to 1.
It is 6.

Specific examples of R include linear alkyl groups, monobranched alkyl groups, cycloalkyl groups, linear alkenyl groups, branched alkenyl groups, cycloalkenyl groups, linear alkabuenyl groups, and branched alkabuenyl groups. , cycloalkabuenyl group, linear alkatrienyl group, branched alkatrienyl group, linear alkynyl group, monobranched alkynyl group, and aralkyl group. In order to provide the liquid crystalline compound described later, an alkyl group is particularly preferable, and C1 represents an asymmetric carbon atom; , trifluoroacetyloxino,! li
Under appropriate reaction conditions, a removable substituent selected from the group can be reacted with one reactant and easily replaced by another group. In this case, liquid crystalline compounds and other functional compounds can be obtained by variously changing the reaction reagents.

As an example of such a liquid crystal compound, X is
r COO- (where RL is an alkyl group or alkoxy group having 4 to 18 carbon atoms, and m is 1 or 2); in this case, the particularly preferable number of carbon atoms in R1 is 6
~16.

In order to synthesize a functional material suitable for uses such as optical elements and modulation elements other than those mentioned above, 1. The optically active lactic acid derivative provided by the present invention and an appropriate intermolecular force that allows molecular control. It is effective to combine with a functional material intermediate having a shape without impairing optical activity. Examples of functional material intermediates that can be effectively combined with the lactic acid derivative of the present invention include azo or azoxy derivatives, Ring assembled hydrocarbon derivatives, fused polycyclic hydrocarbon derivatives, heterocyclic derivatives, fused heterocyclic derivatives, ring assembled heterocyclic derivatives, etc., specifically, azobenzene derivatives, azoxybenzene derivatives,
Biphenyl derivatives, terphenyl derivatives, phenylcyclohexane derivatives are cheap.

These include aromatic acid derivatives, pyrimidine derivatives, pyrazine derivatives, pyridine derivatives, stilbene derivatives, tolan derivatives, chalcone derivatives, bicyclohexane derivatives, and cinnabar derivatives.

Next, an example of a method for synthesizing a compound in which X is a removable chemically active substituent among the optically active lactic acid derivatives represented by the general formula (I) of the present invention will be shown.

(a) Su (C) U (X=F, CI, Br, I)'' - In the reaction formula, RI can be selected from a wide range of carbon numbers, and specifically includes iodobutane, iodohentane, , iodohexane, iodohebutane,
Linear saturated hydrocarbon iodides such as iodooctane, iodononane, iododecane, iodoundecane, iodododecane, iodotridecane, iodotetradecane, iodopentadecane, iodohexadecane, iodoheptadecane, iodooctadecane, iodononadecane, iodoeicosane; 2 - Branched saturated carbonized true iodides such as iodobutane, 1-iodo-2-methylpropane, and l-iodo-3-methylbutane; cyclic unsaturated hydrocarbon iodides such as iodobenzyl, iodophenacil, and 3-iodo-1-cyclohexene; Compounds: iodocyclopenkune, iodocyclohexane, 1-iodo-3-methylcyclohexane,
There are cyclic saturated hydrocarbon iodides such as iodocyclohebutane and iodocyclooctane.

By freely selecting from the above iodides, optically active lactic acid derivatives 41) can be obtained.

Table 1 shows the optical rotation of the optically active lactic acid derivative thus obtained.

From various lactic acid derivatives obtained by such methods,
The liquid crystal compound shown below can be obtained by the following synthetic route.

(In L, R, R', m and n are as defined above.) Table 2 shows examples of the liquid crystalline lactic acid derivatives thus obtained.

(2) The liquid crystal composition of the present invention is represented by the above general formula (I). It contains at least one optically active substance or a liquid crystalline lactic acid derivative as a compounding component.

Among the above compositions, those containing ferroelectric liquid crystals as represented by the following formulas (1) to (13) can increase spontaneous polarization and further reduce viscosity. In such a case, the optically active substance which is the milk spJ conductor of the present invention represented by the general formula (I) is preferably used because the response speed can be improved.
It is preferable to use the ratio of % by weight, and the general formula (
I) The liquid crystalline lactic acid derivative of the present invention represented by
It is preferably used in a proportion of 99% by weight, particularly preferably from 1 to 90% by weight.

(1) cl(.

Phenyl ester 42 43.5 58.5
82CrysL-1→Sac”->SmA--SaCh, -Ch, Iso.

phenyl ester Cr1sL-1→SaA--→Iso.

+8', Stc' /43.5 Cryst, -14S+aC" -1→ SmA-1 and Igo.

Phenyl ester Sf" 148 Phenyl ester CrysL -1→S+wC" -1 groan Sm -1→
Iso.

CH.

■ -COOCH,CHC,H.

4.4'-7Zoxycinnamic acid bis(2-
methylbutyl) ester octyloxybiphenyl-4
-Carpoxylates, such as those shown by the following formulas 1) to 5), can be blended with smectic liquid crystals that are not chiral per se to obtain compositions that can be used as 5-ferroelectric liquid crystals.

In such a case, the optically active substance which is the lactic acid derivative of the present invention represented by the general formula (I) should be added in an amount of 0.1 to 90 weight (
It can be used at a rate of 4%. Also, general formula CI)
The liquid crystalline lactic acid derivative of the present invention represented by O81-99
It can be used in a ratio of fi amount%.

1'C, H,, O 擾
3. Lecture-5. - 剋18o.

Cr1st, 5IIB 74℃") C, H,, O Romasha OCmHtx 4,4',-decyloxyazoxybenzene Cr1
st-J Kaoru 4 Minoh 5-r Shi N-1 Re 1so-Cm H12
0eOCs Htz 2-(4'-hexyloxyphenyl)-5-(4-hexyloxyphenyl)pyrimidine Cryst-su< 4h^a [SO-'IH
I? +kic, Hll 2-(4'-octyloxyphenyl)-5-nonylpyrimidine CrvsL, 33"CSac 80'C
5IIA 75'0 1so.

4'-Pentyloxyphenyl-4-octyloxybenzoate Cryst, 58℃ 5sc84℃
SaA 88°C N 85°C rso.

−111−ri −−−−−◆ −−11−
H-1--) Here, the symbols indicate the following phases, respectively.

Crystal: crystalline phase, SaA: smectic A phase.

S-: Smectic B phase, )C: Smectic-2C phase.

N: Nematic phase, Iso,: Isolunar phase.

In addition, a nematic liquid crystal containing at least one lactic acid derivative of wood AIJI as a compounding ingredient is preferable because it can prevent the generation of reverse domains when used in a rice tea two-dney chic (TN) type cell.

When constructing an element using these liquid crystal materials, in order to maintain the liquid crystal material at a temperature such that it becomes, for example, an Smc" phase or an SmH" phase, it is necessary to use a copper block with a heater embedded in the barley. It can be supported by etc.

The first factor is a schematic drawing of an example cell to explain the operation of the ferroelectric liquid crystal. lla and llb are I n202.3n02 or I T O (I
A substrate (glass plate) coated with a transparent electrode made of a thin film such as ndium-Tin Oxide), between which liquid crystal of SmC" phase or SmH" phase, in which liquid crystal molecules ff112 are oriented perpendicular to the glass surface, is sealed. has been done. The bold line 1913 represents a liquid crystal molecule, and this liquid crystal molecule 3 has a dipole moment (P) 14 in a direction perpendicular to the molecule. When a voltage higher than a certain value is applied between the electrodes on the substrate 21 and llb, the helical structure of the liquid crystal molecules 13 is unraveled, and the liquid crystal molecules 13 are oriented so that all the dipole moments (P) 14 are directed in the direction of the electric field. You can change direction. The liquid crystal molecules 13 have an elongated shape and exhibit 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, the voltage application polarity can be changed. It is easily understood that the liquid crystal optical modulation element has optical characteristics that change depending on the amount of the liquid crystal.

The thickness of the liquid crystal cell preferably used in the optical modulation element of undeveloped IN'l can be made sufficiently thin (for example, 10= or less).As the liquid crystal layer becomes thinner in this way, As shown, the helical structure of the liquid crystal molecules unwinds even when no electric field is applied, and its dipole moment Pa or Pb points upward! ! (24a) or downward (24
Either state b) is taken. In such a cell, the second
As shown in the figure, when an electric field Ea or Eb of different polarity that is greater than a certain value is applied by the voltage applying means 21a and 21b,
The dipole moment changes its direction upward 24a or downward 24b in response to the electric field vector of the electric field Ea or Eb, and the liquid crystal molecules change direction accordingly.

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 optically variable Elil 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, for example with reference to FIG. 2, the electric field Ea
When the voltage is applied, the liquid crystal molecules are aligned in a first stable state 23a, and this state remains stable even when the electric field is turned off. Furthermore, when an electric field Eb in the opposite direction is applied, the nine liquid crystal molecules are oriented to the second stable state 23b and the orientation of the molecules is changed, but they remain in this state even after the electric field is turned off. Further, 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 that the cell be as thin as possible, and generally 0.
51L to 20, especially 1#L to 5L are suitable.

Next, a specific example of a method for driving a ferroelectric liquid crystal will be explained using FIGS. 3 to 5.

Is Figure 3 strong in the middle? A Cell 31 having a matrix structure in which a TrL liquid crystal compound (not shown) is sandwiched
FIG. 32 is a scanning electrode group, and 33 is a signal electrode group. First, the case where scanning electrode Sl 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 S1 and other scanning electrodes (unselected scanning electrodes) S2, respectively. It shows electrical signals applied to Sm, Sm... FIG. 4(C) and FIG. 4(d) are information signals of selected signal electrodes I,...! ,
,! , and unselected signal electrode I2. It shows the electrical signal applied to I4.

In FIGS. 4 and 5 [iN, 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, the dark value voltage for providing the first stable state of the liquid crystal cell having bistability for a predetermined voltage application time t1 or t2 is -v th, and 2
When the threshold voltage for providing a stable state is +vth2, the electrode signal applied to the selected scanning electrode 32 (S□) has a phase (time) of 1 as shown in FIG. 4(a).
At +, the voltage is 2V, and at phase (time) t2, it is -2V. When electrical signals having a plurality of phase intervals with mutually different voltages are applied to the scanning electrodes selected in this way, the first or second stable state 18 of the liquid crystal corresponding to the optical "dark" or "bright" state is applied. This has the essential effect of being able to quickly cause a change in the state.

On the other hand, the other scan electrodes S2 to Ss... are b14
As shown in Figure (b), it is in a grounded state and the electrical signal is O. Also, the selected signal electrode r1. Is, Is
The electrical signal given to is.

As shown in FIG. 4(C), the electric signal is v, and the electric signal applied to the unselected signal electrodes I, I4 is <-V as shown in FIG. 4(d).

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

V<Vth2<3V -3V<-Vth, <-V When such an electric signal is applied to each pixel, for example, it is applied to pixels A and B in FIG. 3, respectively. It
The pressure waveforms are shown in FIGS. 5(a) and (b), i.e.
As is clear from Figures (a) and (b), in the pixel A on one selected scanning line, at phase t2, the darkness value v th2
A voltage exceeding 3V is applied. Furthermore, in the phase t1, a voltage of -3V exceeding the dark value -vt,h is applied to the pixel B existing on the same scanning line. Therefore, on the selected scanning electrode line, depending on whether a signal electrode is selected or not, if one is selected, the liquid crystal molecules are aligned in the first stable state, and if one is not 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 line, the voltage applied to all pixels is V or -V, neither of which exceeds the threshold voltage.Therefore, the liquid crystal molecules in each pixel other than 4 on the selected scanning line are in an aligned state. The orientation corresponding to the signal state when scanned last time is maintained without changing the orientation. That is, when a scanning electrode is selected, one line of signals is extracted, and the signal state can be maintained until the next selection after one frame is completed. 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 5l-S, . . . and the signal electrodes ~I5 . The pixels shall correspond to the "dark" state. Now, if we pay attention to the display above the signal electrode I in FIG. 3, we can see that the pixel (A
) is in the "bright" state, and all other pixels (B) are in the "dark" 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 pixel A.

For example, when driving as shown in Fig. 6, the scanning signal S
When 8 is scanned, a voltage of 3V exceeding the threshold value vth2 is applied to pixel A in 1 hour E2, so regardless of the previous history, 1 pixel A transitions to a stable state in one direction, that is, a "bright" state. After that, while 32~S,... are being scanned, a voltage of <-V continues to be applied as shown in Figure 6, but this does not exceed the dark value -vthl. Therefore, pixel A should be able to maintain a "bright" state, but in reality, one signal (corresponding to "dark" in this case) is continuously given on one signal electrode. In the case of display, when the number of scanning lines is extremely large and high-speed driving is required, an inversion phenomenon occurs. However, by using the above-mentioned specific liquid crystal compound or a liquid crystal composition containing it, it is possible to solve this problem. Reversal phenomena are completely prevented.

Furthermore, 1 unreleased! For +1, it is preferable to provide an insulating film made of an insulating material on at least one of the opposing electrodes constituting the liquid crystal cell with L to prevent the above-mentioned inversion phenomenon.

The insulating materials used in this case are not particularly limited, but include silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide, boron nitride, and hydrogen. Inorganic insulating materials such as boron nitride, cerium oxide, aluminum oxide, zirconium oxide, titanium oxide and magnesium fluoride, or polyvinyl alcohol, polyimide, polyamideimide, polyesterimide, polyparaxylene, polyester, Organic insulating materials such as polycarbonate, 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 100 Å or less.
~1000 people, especially SOOλ~3000 people is suitable.

The unreleased optically active lactic acid derivative of 1 can be combined with a functional material intermediate having appropriate intermolecular force and shape without impairing optical activity, allowing for free molecular design. can. In particular, by selecting the length of the alkyl group, it is possible to control the type and temperature range of the liquid crystal phase developed in liquid crystal jf1. Furthermore, the liquid crystal composition of the present invention containing at least one type of optically active lactic acid derivative and optically active liquid crystalline lactic acid derivative as a compounding component can be used as a chiral nematic liquid crystal or a chiral smectic liquid crystal to achieve spontaneous polarization. Improve response speed by increasing viscosity and adjusting viscosity.

It is possible to improve performance by preventing the occurrence of reverse domains.

EXAMPLES Hereinafter, the optically active substance which is a lactic acid derivative, the liquid crystal lactic acid derivative, and the liquid crystal composition of the present invention will be explained in detail with reference to Examples.

P-7 cetyloxybenzoic acid 950 to 165g of p-hydroxybenzoic acid (2-ethoxy)propyl ester 5OC1□
g was added and heated at 60°C for 40 minutes. After cooling, the solvent was distilled off to obtain 164.5 g of CH*COO-@-COC.

2-Ethoxypropanol (c, Hs QC” H(C
10 g of Hs )CH20H) and 11.6 g of N,N-dimethylaniline were dissolved in 20 ml of ether and stirred to obtain the above-obtained C Hs c o -@-c.

22.3 g of Cl was added dropwise over 45 minutes. Thereafter, the mixture was heated to reflux and stirred for 1 hour and 30 minutes.

Water was added and the ether layer was separated and purified to obtain P-7 cetyloxybenzoic M(2-ethoxy)propyl ester. After adding methanol to it, a mixed solution of methanol:28% aqueous ammonia = 1:1 was added and stirred for hydrolysis.

Extract with 400 ml of ether, wash with water, dry (Na2
SO+)L and the solvent were distilled off to obtain 11.5 g of a crude product. Catem purification using 1 kg of silica gel (mobile phase: isopropyl ether: n-hexane = 1 + l), p-hydroxybenzoic acid (2-ethoxy) propyl ester 6
, 4 g < 1 J.

The following IR data was obtained for the product.

IR (cm""): P-7 Cetyloxybenzoic acid (2-ethoxy)propyl ester 2980.2880.1770.1720.1610.
1505.1375.1275゜1200.1160.
1120.1100゜p-hydroxybenzoic acid (2-
ethoxy)propyl ester 3310.2990.2900.1720°1700.
1620.1600.1520.1450.1390,
1280.1170, ttoo.

1 garden■ P-hydroxybenzoic acid (2-propoxy) propyl ester By the same operation as in Example 1, 14,'6 g of p-hydroxybenzoic acid (2-propoxy) ) Propyl ester was obtained.

The following IR and NMR data were obtained for the product.

■R: 3370.3000.2900.1720.1700.
1625, 1610.1525.1460.1395.
1280.1250°1180.1120°'H-NMR: 0.9-1.8ppm (8H), 2.3ppm (IH)
, 3.4-4.3 ppm (5H).

6.7-8.0 ppm (4H).

Tip "L carp"! The lactic acid derivative of the present invention was obtained by the same operation as in Example 1. The products, along with their specific optical rotations, are as listed in Table 1 above.

[Rise-up] P-hyde 11-1-sibiphenylcarboxylic acid (2-pentyloxy)propyl ester KOH 9.42g (1.68X10-'mol) was added to the tree 3
15 g (7,02 Recrystallization yielded 5.9 g of P-7 cetyloxybiphenylcarboxylic acid. (Yield: 32.9
%) SOC1220g (1,68X10-'mol), p-7 cetyloxybiphenylcarboxylic acid 5.7g
(2,23XIO-201) was added, and the mixture was heated under reflux for 3° for 5 hours. After cooling, the solvent was distilled off to obtain 7.0 g of p-7 cetyloxybiphenylcarpon chloride.

2-pentyloxyheptatool 3.25g (2.23
X10-'a+ol), N,N-dimethylaniline 2
'． 69g (2.23X10-2a+ol) in ether 10. sl, and while stirring, 20 ml of toluene solution of P-7 cetyloxybiphenylcarboxylic acid chloride synthesized above was added dropwise at room temperature over 20 minutes. Dripping t
& Heated under reflux for 7 hours.

After the reaction is complete, add 501 ml of water to dissolve the crystals and dissolve 30 ml of ether.
1 was extracted three times. Wash the ether layer 4 times with 10% H2So, aqueous solution 501 and 3 times with water? After drying with anhydrous sodium sulfate, the solvent was distilled off to obtain 20.3 g of an oily substance. This was purified by silica gel column chromatography.

8, 6 which P-7 cetyloxybifutylcarpon M (
2-pentyloxy)propyl ester was obtained.

The p-7 cetyloxybifutechnylcarpon M obtained above (
2-pentyloxy)propyl ester in methanol 5
After diluting with 0 ml, methanol: NHa OH
(28%)==1:l was added under stirring and hydrolyzed.
Thereafter, the extract was extracted three times with anhydrous sodium VLate, and the ether layer was washed three times with 50 ml of water, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain an oil. This was purified by silica gel column chromatography and 2.6 g of P-
Hydroxybiphenylcarboxylic acid (2-pentyloxy)propyl ester was obtained.

The following IR data was obtained for the product.

IR: 3400, 2950.2875.1720.

1700, 1615.1600.1450.

1380, 1290.1260.1110.

1-5'P'-7' syloxybiphenylcarboxylic acid p#
ethoxyprobyloxycarponyl) phenyl esterdecyloxybiphenylcarboxylic acid 4g (1.

13X IO-2mol) to SOC122011
1 was added and heated under reflux for 3 to 5 hours. excessive SOCI,
was distilled off to obtain decyloxybiphenylcarboxylic acid chloride.

Dissolve the acid chloride () in 10ml of toluene,
2.35 g of optically active p-hydroxybenzoic acid 2-ethoxypropyl ester dissolved in pyridine 16-1 (
1.13XIO'mol), left at room temperature for 55 minutes, and then stirred for 3 hours and 50 minutes.

The reaction mixture was extracted into cold water, washed with 6N MCI solution, water, dried and the solvent was evaporated to yield 4.4 g of P'-7' siloxybifuenylcarbonylcarbonyl ) Phenyl ester was obtained. After further purification by silica gel column chromatography, the product was recrystallized to obtain 1.8 g of purified product.

The following IR and NMR data were obtained for the product.

IR: 2940.2870, 1740, 1610.1515.
1480.1395.1295.1135.1090°'H-NMR: 6.8-8.2ppm (12H), 3.3-4.3pp
m (7H), 0.8-1.8 ppm (25H).

-゛ 7.8 10-15 19 20 A liquid crystal compound was obtained in the same manner as in Example 9.

The product is as shown in Section 2 along with its phase transition temperature.

A TN cell (twisted nematic cell) using a liquid crystal mixture prepared by adding 2 parts by weight of the optically active substance of Example 5 to 4 parts of p,p'-pentylazoxybenzene 93% by weight
It was observed that the reverse number domain was significantly reduced in the TN cells produced without the addition of this compound compared to the TN cells produced without the addition of this compound.

Practical JL Example-17 Liquid crystal element using the liquid crystal compound produced in Example 9 Approximately 1000 ITO films were provided as electrodes on 1010 x 20 glass that had been polished with high precision, and approximately 1000 S
IO, was deposited by ion beam method. The liquid crystalline compound produced in Example 9 was dropped onto a glass substrate that had been processed in the same manner, and the glass substrates were stacked facing each other. 16
While holding the substrate at 0° C., parallel motion was performed by shifting the upper and lower substrates from each other while maintaining the distance between them under a polarizing microscope, and horizontally oriented monodomains were obtained. At that time, the liquid crystal thickness was 1.4 gm and 7) IJ was 80
When applying a pulse of ±lOv at ℃, approximately LOOILs
Switching was performed using ec.

Actual JL Example-L1 Characteristics of a liquid crystal composition containing the liquid crystal compound produced in Example 1O as a compounding component and a liquid crystal composition containing 79% by weight of the liquid crystal compound of Example 10. ℃ showed S mC''.

Disaster 1f2Lヱ'2 Polyimide film (polyamic acid consisting of a combination of pyromellitic anhydride and 4,4'-diaminodiphenylether 511 of resin
! Apply ffi% N-methylpyrrolidone solution and
(formed by a heating ring-closing reaction at a temperature of 0.degree. C.) was provided, and the surfaces of this polyimide film were rubbed so as to be parallel to each other to create a cell having a cell thickness of 1JL.

Next, the following composition A was injected into the above-mentioned cell by a vacuum injection method under the Tokichi phase, and the cell was sealed. After that, slow cooling (
1° C./hour) to create a liquid crystal cell of “S m C”.

A cross-niffle polarizer and analyzer are placed on both sides of this liquid crystal cell. ．． Signals having the waveforms shown in FIGS. 4 and 5 were applied between opposing matrix electrodes. At this time, the scanning signal is
The alternating waveforms of +8 volts and -8 volts shown in Figure (a) were used, and the written information was set to +4 volts and 14 volts, respectively. Further, the 1 frame period was set to 30 m@sec.

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 was prepared by omitting the liquid crystal compound represented by the above-mentioned general formula (I) in the liquid crystal composition A used in preparing the liquid crystal element of Example 21. , created a liquid crystal device. Although these liquid crystal elements were driven in the same manner as described above, normal moving images were not displayed due to an inversion phenomenon.

[Brief explanation of drawings]

1 and 2 are perspective views schematically showing a time-division driving liquid crystal element used in the present invention, FIG. 3 is a plan view of a matrix electrode structure used in the present invention, and FIGS. (d
) is an explanatory diagram showing the electric signal applied to the matrix electrodes, FIGS. 5(a) to 5(d) are explanatory diagrams showing the waveform of the voltage applied between the matrix electrodes, and FIG. FIG. 3 is an explanatory diagram of a time chart showing an electric signal applied to a liquid crystal element. 11a, Llb... one substrate, 12... liquid crystal molecule layer, 13... liquid crystal molecule, 14... dipole moment (PL). 23a...first stable state. 23b...Second stable state. 24a...Upward dipole moment, 24b...Downward dipole moment, 31...Cell. 32...(Sz, S2, Ss,...)...Scanning electrode group, 33...(It, It, Eng,, ・φ・)...
・Signal electrode group. Brown f Figure No. 2 Air 33 Telegraph a It I2 13 1-t 15 ----- Ditch 3
Figure (a) Product 4 Figure (4) Figure 5

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the above general formula, R is a linear, branched, or cyclic saturated group having 1 to 18 carbon atoms. or represents an unsaturated hydrocarbon group,
n is 1 or 2, and C^* represents an asymmetric carbon atom. X represents a removable substituent selected from an OH group, a halogen, a benzyloxy group, a phenoxy group, a toluenesulfonic acid group, an acetyloxy group, and a trifluoroacetyloxy group). 2. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the above general formula, R is a linear, branched or cyclic saturated or unsaturated hydrocarbon having 1 to 18 carbon atoms. represents a group. n is 1 or 2, and C^* represents an asymmetric carbon atom. 1. A liquid crystal composition comprising at least one optically active substance represented by the following (representing a removable substituent selected from the group). 3. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the above general formula, R represents an alkyl group having 1 to 18 carbon atoms. n is 1 or 2, and C^* is Indicates an asymmetric carbon atom. Liquid crystalline lactic acid derivative. 4. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the above general formula, R represents an alkyl group having 1 to 18 carbon atoms. n is 1 or 2, and C^* is Indicates an asymmetric carbon atom. A liquid crystal composition comprising at least one liquid crystal lactic acid derivative as a compounding component. 5. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the above general formula, R represents an alkyl group having 1 to 18 carbon atoms. n is 1 or 2, and C^* is Indicates an asymmetric carbon atom. A liquid crystal element using a liquid crystal composition containing at least one liquid crystal lactic acid derivative as a compounding component.