JPH01198683A - Ferroelectric liquid crystal composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent self shape-retaining properties, enabling high-speed response, by adding hydrogen bond group to a low-molecular liquid crystal compound having chiral smectic C phase and a noncrystalline polymer compound and combining the compounds. CONSTITUTION:The aimed composition consisting of (A) a low-molecular liquid crystal compound having a proton donor and/or proton acceptor and a chiral smectic C phase and (B) a noncrystalline polymer having a proton donor and/or proton acceptor preferably at both a main chain and a side chain. A compound shown by formula I {R<1> is OH or group shown by formula II; P is 1-20; R<2> is group shown by formula III-VI [Z is group shown by formula VII or VIII; R<3> is group shown by formula IX or X (n is 0-5; m is 1-6; R<4> is CH3 or halogen; X is halogen; C* is asymmetric carbon)]} may be cited as the component A.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a liquid crystal composition, and more specifically, a low molecular liquid crystal compound having a chiral smectic C phase and a non-liquid crystal polymer compound each having hydrogen bonding groups. This invention relates to a liquid crystal composition in which layer separation does not occur by using these in combination.

[Prior art and problems to be solved by the invention] Conventionally, various types of liquid crystals made of low-molecular compounds have been known. A general term for properties such as the ability to mold liquid crystal compounds.) It has the disadvantage of being poor.

Therefore, in order to improve this self-shape retention property, we have developed a composition that simply mixes a high molecular compound and a low molecular compound liquid crystal, or a low molecular liquid crystal that is formed by covalent bonding to the main chain or side chain of a high molecular compound. Products made by combining compounds have been proposed.

However, in general, the terminal groups of low-molecular liquid crystal compounds are alkyl groups, so even if a high-molecular and low-molecular liquid crystal compound is mixed, in the microscopic state, it has a sea-island structure and the mixture is uniform. It's not a state. The fact that the liquid crystal compound is not uniformly mixed exposes various drawbacks when this composition is utilized as a liquid crystal. For example, because low-molecular liquid crystal compounds are unevenly distributed in a polymer matrix, the response of polymer compositions used as liquid crystals becomes uneven, and when applied to display elements, the clarity deteriorates. There are things to do.

In addition, when trying to bond a low-molecular liquid crystal compound to a high-molecular compound through a covalent bond, corresponding reaction conditions are required, and it is possible to easily bond a low-molecular-weight liquid crystal compound to a high-molecular compound. It's not a thing.

The present inventors have already developed a liquid crystal compound that has excellent self-shape retention and is suitable for electro-optical devices, etc. by mixing a non-liquid crystal polymer capable of hydrogen bonding with a low-molecular liquid crystal compound (PCT/JP87100521 issue).

However, the high-speed response of this product was not yet fully satisfactory.

Currently, liquid crystals are widely used as display materials, but most liquid crystal display elements are T N (TwistedNe+n
atic) type display system, and uses liquid crystal belonging to the nematic phase as the liquid crystal material. This TN
The type display system is light-receiving, so it has the advantage of not tiring the eyes and consumes extremely little power, but has the disadvantages of slow response and the display not being visible depending on the viewing angle.

Recently, particularly high-speed response has been required for display devices, and attempts have been made to improve liquid crystal materials in order to meet this demand. However, when compared with other light-emitting displays (EL (electroluminescent) displays, plasma displays, etc.), there is still a large difference in response time. In order to take advantage of the characteristics of liquid crystals, such as light-receiving type and low power consumption, and to ensure responsiveness comparable to light-emitting displays, it is essential to develop a new liquid crystal display system to replace the TN display system. As one such attempt, a display method using the optical switching phenomenon of ferroelectric liquid crystals was proposed by N. A. Clark, S. T. Lagerwall, and others (Applied Physics Letters).
L, Phys, Lett,) Volume 36, Page 899 (
(1980)). Ferroelectric liquid crystal was developed in 1975 by R,B
, whose existence was first announced by Mayer et al.
e) Vol. 36, page L-69 (1975)); from the liquid crystal structure, chiral smectic C phase, chiral smectic I phase, chiral smectic F phase, chiral smectic C phase, and chiral smectic H phase (hereinafter referred to as Sc S) phase, Sr phase, sa' phase, and S)I phase).

When applying the optical switching effect of the ScI+ phase to a display element, there are three superior features compared to the TN display system. The first feature is that it responds very quickly, and its response time is 17,100 times or less compared to a normal TN display type element. The second feature is that there is a memory effect,
Coupled with the above-mentioned high-speed response, time-division driving is easy. What is the third characteristic? A-light gradation can be easily obtained. In contrast to the TN display method, which adjusts the applied voltage to obtain gradation, there are difficult issues such as the temperature dependence of the threshold voltage and the voltage dependence of the response speed. When applying the optical switching effect, gradations can be easily obtained by adjusting the polarity reversal time.
Very suitable for graphic display, etc.

[Means for Solving the Problems] The present invention imparts ferroelectricity to the above-mentioned liquid crystal compound that has excellent self-shape retention, so that it has excellent self-shape retention, and
The present invention provides a liquid crystal composition that enables high-speed response.

That is, the present invention provides a strongly readable liquid crystal comprising a non-liquid crystal polymer having a proton donor and/or a proton acceptor and a low molecular weight liquid crystal compound having a proton donor and/or a proton acceptor and having a chiral smectic C phase. A composition is provided.

The basis of this invention is to bond a functional group capable of hydrogen bonding to a low-molecular liquid crystal compound having a chiral smectic C phase, and to bond this liquid crystal compound to a non-liquid crystal polymer having a functional group capable of hydrogen bonding. The object is to form a liquid crystal composition by mixing.

Therefore, the non-liquid crystalline polymer in this invention needs to have a functional group capable of hydrogen bonding with a functional group in the low-molecular liquid crystal compound to be mixed.

Hydrogen bonds are generally formed by a proton donor and a proton acceptor and have a bond energy of 2 to 8, as shown schematically by the following formula.
It has a weak kcap/moc.

Therefore, the functional group capable of hydrogen bonding is not particularly limited as long as it has a proton donor and/or a proton acceptor; for example, c-o, -DH, -
COOH, -CONH-, -NO3, -CO-0-Co
- etc. In this case, for example, >C-0 is a proton acceptor, -OH is a proton donor,
-Coo)l is a functional group having a proton donor and a proton acceptor.

Examples of such non-liquid crystalline polymers having functional groups capable of hydrogen bonding include polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, polyacrylamide, polyvinyl alcohol, polyvinyl acetate, polycarbonate, dicarboxylic acid derivatives, and diol derivatives. Examples include polyester obtained by a condensation reaction with a dicarboxylic acid derivative, a polyamide obtained by a condensation reaction between a dicarboxylic acid derivative and a diamine derivative, and a polyamide obtained by a condensation reaction between a dicarboxylic acid derivative and a monoalcohol or monoamine derivative.

Functional groups capable of hydrogen bonding may be bonded to the main chain or to the side chains of the polymer, but those that have functional groups in both the main chain and side chains is more preferable.

These non-liquid crystalline polymers may be used alone or in combination of two or more.

Among the above-mentioned non-liquid crystalline polymers, polyester, polycarbonate, and the like are preferred.

Furthermore, the degree of polymerization of this non-liquid crystalline polymer is 10 to 10.
000, preferably 100 to 2,000. If the degree of polymerization of the non-liquid crystal polymer is less than 10, the liquid crystal composition tends to lack self-retention properties. On the other hand, if the degree of polymerization exceeds 10,000, the processability of the liquid crystal composition tends to be difficult.

Next, the low-molecular liquid crystal compound used in the present invention will be explained. This low-molecular liquid crystal compound is characterized by having a ferroelectric chiral smectic C phase (SC" phase).

The low molecular weight liquid crystal compound used in the present invention can be obtained by reacting an optically active alcohol with an optically active carboxylic acid. The optically active alcohol used here includes (R)-2-fluoro-1-hexanol, (S)-
2-Fluoro-1-hexanol, (R)-2-fluoro-1-heptatool, (S)-2-fluoro-1-heptatool.

(R)-2-fluoro-1-octatool, (S)
-2-fluoro-1-decanol, (R)-2-fluoro-1-decanol, (S)-2-fluoro-1-
decanol, (R)-2-fluoro-1-nonanol,
(S)-2-Fluoro-1-nonanol.

(R)-2-methylbutanol, (S)-2-methylbutanol, (R)-2-chlorobutanol.

(S)-2-chlorobutanol, (R)-2-methylpentanol, (S)-2-methylpentanol.

(R)-3-methylpentanol, (S)-3-methylpentanol, (R)-4-methylhexanol, (S)
)-4-methylhexanol, (R)-2-chlorpropatol, (S)-2-chlorpropatol,
(R) -1-methylheptatool, (S) -1
-Methylheptatool, (R)-6-methyloctatool, (S)-6-methyloctatool.

(2S,3S)-2-chloro-3-methyl-1-pentanol, (2S,3S)-2-fluoro-3-
Methyl-1-pentanol, (2S,3S)-2
-bromo-3-methyl-1-pentanol, (3S
, 4S) -3-chloro-4-methyl-1-hexanol, (4S, 55) -4-chloro-5-methyl-1
-Heptatool.

(5S, 6S) -5-chloro-6-methyl-1-octatool, (6S, 7S) -6-chloro-7-methyl-1-nonanol, and the like.

In addition, examples of optically active carboxylic acids include (2S,
3S) -2-ri-4-3-methyl-1-pentanoic acid,
(2S,3S)-2-fluoro-3-methyl-1-
Pentanoic acid, (2S,3S)-2-bromo-3-
Examples include methyl-1-pentanoic acid, (R)-1-methylbutanoic acid, (S)-t-methylbutanoic acid, and the like.

The low-molecular liquid crystal compound used in the present invention is a liquid crystal compound having a proton donor and/or proton acceptor and an SC phase, for example, the formula [wherein R1 is -OH or 10CCH, p is 1-2
o) Indicates an integer or or. (Here, n is an integer of O to 5, I is an integer of 1 to 6, R4 is C) 13- or a halogen atom, X is a halogen atom, and C is an asymmetric carbon. ))], S
It has a male phase.

Here, some methods for synthesizing the low-molecular liquid crystal compound represented by the above formula (I) will be described.

(1) When R' is -g)-gular ZR', acetyl chloride and 4'-hydroxybiphenylcarboxylic acid (compound (2)) are subjected to an esterification reaction to obtain the compound shown in (2) below.

Then, a compound having a group R3 is reacted with this ■ or the compound shown in ■ (the compound shown in ■ is as it is, the compound shown in ■ is converted into an acid chloride shown in ■-1, and then this) is reacted with a compound having a group R3. The following compound (1)-1, (2)-2 or (2)-1 having the following formula is obtained. In this case, when obtaining the compound shown in (1)-2, the compound shown in (2) can be used instead of the compound shown in (1)-1 to directly obtain a compound having a terminal hydroxyl group.

(Reaction when R3 is (a) and n-0 in formula (a)) ...■-1 U ...■-1 (When R3 is (a) and n-0 in formula (a)) (Reaction when n≧1 in formula (b)) υ (Reaction when R3 is (b) and n≧1 in formula (b)) Compound having a terminal acetyloxy group shown in ■-1 or ■-1 above By using benzylamine or the like, compound 1-3 or 2-2 having a terminal hydroxyl group can be obtained as follows.

In this way, the formula when Z is -CO-) 10 $ Z
A compound having an R2 group represented by R'...■ can be obtained.

υ Acetyl chloride and 4,4'-dihydroxybiphenyl are reacted to obtain the following compound (2).

CH3COC1+ + no$on --→ CH, C00$OH...■ This compound (2) is reacted with a compound having a group R3 to obtain the next compound (2) or (2) having a group R2.

The compound having a terminal acetyloxy group shown in (1) or (2) is converted into a compound (2) or [phase] having a terminal hydroxyl group by using benzylamine or the like as follows.

υ In this way, the formula when 2 is -DC- is HO$ Z R
A compound having an R2 group of 3...■ can be obtained.

Next, the compound (2) having an R2 group obtained in step (2) above is reacted with an alkylene civalide to obtain the following compound (◎).

Furthermore, this compound 0 is reacted with 2,2-dihydroxymethylpropionic acid to obtain the following compound @.

In this @ compound, 81 in formula (1) is -OH.

It can be obtained by reacting the above compound @ with acetic anhydride as follows.

[] When Z is -co- As shown in the following formula, 4-acetyloxybenzoic acid is converted into an acid chloride, and then a compound having a formula (a) group as the R group is reacted with this, The following compound shown in 0 is obtained.

In the same manner, the compound is reacted with a compound having a formula (b) group as the R3 group to obtain the compound shown in (2) below.

CI 3 C00+C00H←C) I 3C00+ G
OCIC1l, COOsha C0Cf + HO (CH2
) nCH (mountain), aCH3 This 0 or a compound having a terminal acetyloxy group shown in [phase] is reacted with benzylamine, etc., and the formula acetyl chloride and hydroquinone are reacted to obtain the compound shown in the next [phase]. .

C1hCOCIl+HO building OH → CH, Coo building OH・
...[Phase] Formula (a) or formula (b) is added to this as the R3 group.
) group is reacted to obtain the following O2 [phase].

This compound having a terminal acetyloxy group represented by O or [phase] is reacted with benzylamine, etc., and the formula (1) is obtained from the formula (1) obtained in (2) above. To obtain the compound, first, alkylene cybaride and benzyl 4-hydroxybenzoic acid ester are reacted as follows to obtain the compound.

Further, the compound shown in O is reduced to obtain the compound shown in O below.

After converting this O compound into an acid chloride, the above compound 0 is obtained.

Furthermore, F, 2,2-dihydroxymethylpropionic acid and [
phase] to obtain the following compound O.

This compound of O is a case where R1 in formula (I) is -OH, and when R1 is 10CCHa, acetic anhydride is added to the compound of O in the same manner as in obtaining the compound of 0 above. This can be obtained by

After converting the compound (2) above into an acid chloride, it is reacted with the compound (2) above to obtain the compound shown in the following (2).

X (CH,), 0 cocR + HO$ZR3 ■ ←X (CHx ) p O+ COO$ Z R3・
...■ Furthermore, 2,2-dihydroxymethylpropionic acid and the compound (■) are reacted to obtain the following compound shown in @.

! 1. This @ compound of ... is a case where nl is 10■ in formula (I), and when R1 is 10C0CR3, add acetic anhydride to the @ compound in the same manner as the above @. By doing this, you can obtain the desired object.

4'-Hydroxybiphenylcarboxylic acid and benzyl bromide are reacted to obtain the compound shown in the next [phase].

-1 → HO% co o movable...[Phase] This @ compound and alkylene cybaride are reacted to obtain the following compound represented by O.

X (CH2) pX + HOHCOOCH, -@)
This O compound is reduced to a compound shown in [phase], and further to an acid chloride (compound shown at @).

−1→X (CH2) p OmCOOH”・@−−→
The compound of X (CH2) pOeCOCR-@[phase] is reacted with the compound of 0 to obtain the compound shown in the following Φ.

X (C)12) po$cocp + no+za3
■ ←X (CH2>p'o % c o O+Z R3
-s Furthermore, 2,2-dihydroxymethylpropionic acid and the compound Φ are reacted to obtain the compound shown in the following (2).

This compound (2) is obtained when R1 is -OH in formula (I), and when R1 is 10COCH3, the desired compound can be obtained by adding acetic anhydride to the compound (2) as described above.

In this way, a low molecular weight liquid crystal compound represented by formula [I] can be obtained.

The ferroelectric liquid crystal composition of the present invention is made by blending the above-mentioned non-liquid crystal polymer and a low molecular weight liquid crystal compound.
Assuming that the number of proton donors and/or proton acceptors in the non-liquid crystal polymer is A, and the number of terminal proton donors and/or proton acceptors in the low molecular weight liquid crystal compound is B, the blend ratio of A/B is 10/l. Possible in the range of ~1/2, preferably in the range of 8/1 to 1/1, and more preferably 3/1 to 1/2.
A range of /1 to 1/1 is optimal.

Then, the desired product can be obtained by dissolving the non-liquid crystal polymer and the low-molecular liquid crystal compound in a solvent, blending the mixture, stirring, concentrating, drying, or the like. Examples of the solvent used here include lower alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, chloroform, methylene chloride, and carbon tetrachloride.

There is no particular need for heating during mixing. Furthermore, by casting this concentrate into a suitable mold and then drying it, a sheet or film having a desired thickness and shape, or a block having a desired shape can be obtained.

Here, an example of manufacturing the non-liquid crystalline polymer used in the present invention will be shown.

Production Example 1 (Production of polyester) 2.2-dihydroxymethylpropionic acid 1 mmol,
Stir a THF 50 mA+ solution of 1 mmol of triethylamine, and add 1 mmol of sebacoyl chloride in THF.
Add 10 mA+ of the solution dropwise, raise the temperature to 80° C. and stir for 12 hours. The reaction solution was poured into a large amount of acetone to stop the polycondensation reaction, and then concentrated and reprecipitated with methanol to obtain a polyester having repeating units represented by the following formula. The conversion rate of this reaction was 83% and the MW
(Weight average molecular weight) was 9,000.

Production Example 2 (Production of polyester) A solution of 1 mmol of 1.6-hexanediol and 1 mmol of triethylamine in THF (50 mj) was stirred, 10 mg of a THF solution of 1 mmol of sebacoyl chloride was added dropwise, and the temperature was raised to 80°C. Stir for an hour. The reaction solution was poured into a large amount of acetone to stop the polycondensation reaction, and then concentrated and reprecipitated with methanol to obtain the following polyester. The conversion rate of this reaction was 75% and the MW was 10,000.

Next, a synthesis example of a low-molecular liquid crystal compound used in the present invention will be shown.

Synthesis Example 1 (1) Synthesis of 4'-hydroxybiphenyl-4-carboxylic acid-2-methylbutyl ester In 15 OiJ of benzene, 93 mmol (20 g') of 4'-hydroxybiphenyl-4-carboxylic acid, (S
) -(-)-2-methylbutanol 4 mmol (
41g) and 2ml of concentrated sulfuric acid, and
Esterification reaction was carried out by refluxing for 24 hours using 5 tark. After the reaction is completed, the reaction solution is concentrated, and the obtained product is recrystallized from a toluene-hexane mixed solvent (1).
The ester was obtained. (Yield 98%, [α]. = + 4
．． 25(CHCj'3)) (2) 30 mmol of ester obtained in synthesis (1) of 4'-(10-bromodecyloxy)biphenyl-4-carboxylic acid-2-methylbutyl ester, 60 mmol of dibromodecane, A solution of 120 mmol of potassium carbonate in 150 mA' of acetone was refluxed for 6 hours. After concentrating the reaction solution through a furnace, it was purified by column chromatography (2)
The ester was obtained. (Yield 88%.

[α]n= + 2.44 (CICI!, )) (3)
Synthesis of 4'-(10-(2,2-dihydroxymethylpropionyl)oxydecyloxy)biphenyl-4-carboxylic acid-2-methylbutyl ester 2.18 mmol of 2-dihydroxymethylpropionic acid and tetramethylammonium hydroxide ( 5) 20 mmol of D
Stirred in MF 10011R for 2 hours. next,
Add 18.0 mmol of the ester obtained in (2), and
Stir for hours. 100 mjl of water was added to the reaction solution, extracted with ether, dried, concentrated, and purified by column chromatography to obtain ester (3). (Yield 67
%, [α] Rho' + 2.11 (C) ICj! *)) (4) Obtained in synthesis (3) of 4'-(IQ-(2,2diacetoxy)propionyl° oxydecyloxy)biphenyl-4-carboxylic acid-2-methylbutyl ester (low molecular liquid crystal compound) 7.5 mmol of ester and 4 mmol of acetic anhydride
A 5mR solution of 5mmol pyridine was stirred at room temperature for 12 hours. The reaction solution was extracted with ether, washed with dilute hydrochloric acid, and dried.
After concentration, it was purified by column chromatography to obtain a low-molecular liquid crystal compound used in the present invention. (yield 85%,
[a]D=+2.31 (C)IC1'3))
The phase transition behavior of this low-molecular liquid crystal compound was as follows based on the results of DSC and polarizing microscope observation.

[Here, Cry indicates a crystalline state, S♂ indicates a chiral smectic C phase, and I8° indicates an isotropic phase. same as below. ] Synthesis Example 2 (1) Synthesis of 4-hydroxycarboxylic acid-2-methylbutyl ester 90 mmol of 4-hydroxybenzoic acid and 360 mmol of 2-methylbutanol were dehydrated in 150 mjl of toluene in the presence of 2 mN concentrated sulfuric acid for 25 hours. I did it.

After concentrating the reaction solution, it was purified by column chromatography to obtain ester (1).

(Yield 95%, [CE]o=+4.85(CHCj
s))(2) 4-(12-bromododecyloxy)
Synthesis of benzyl benzoate ester Dibromododecane 150 mmol, 4-hydroxybenzoic acid benzyl ester 50 mmol, potassium carbonate 0
, 3 mol of acetic acid, 500 mol. The reaction solution was filtered and concentrated, and then purified by column chromatography to obtain ester (2).

(Yield 82%) (3) Synthesis of 4-(12-bromododecyloxy)carboxylic acid 100 mmol of the ester obtained in (2), 2.0 g of palladium on carbon (5% catalyst), 150 m of ethyl acetate
The 1' solution was stirred in the presence of hydrogen gas for 5 hours.

The reaction solution was filtered, concentrated, and purified by column chromatography to obtain carboxylic acid (3). (Yield 98%) (4) Synthesis of 4-[4'-(12-bromododecyloxy)benzoquine]benzene-4-carboxylic acid-2-methylbutyl ester (3) 80 mmol of the carboxylic acid obtained in toluene 3
Add 10ml of thionyl chloride to the 0mj solution and stir at 80°C for 2 hours. After the reaction, excess thionyl chloride and toluene were distilled off under reduced pressure to obtain an acid chloride. A solution of 90 mmol of the ester obtained in (1) and 100 mmol of triethylamine in 200 ml of tetrahydrofuran was stirred, and the above THF solution of the acid chloride was added dropwise thereto, followed by stirring for 8 hours. After the reaction, extract with ether, wash with dilute NCR, and dry. After concentration, it was purified by column chromatography (4
) was obtained. (Yield 81%. [α]. = +
2.65 (CHCjs)) (5) 4- [4'-
(12-(2,2-dihydroxymethylpropionyloxy)dodecanyloxy)benzoquine]benzene-4-
Synthesis of carboxylic acid-2-methylbutyl ester (low-molecular-weight liquid crystal compound) 18.0 mmol of 2.2-dihydroxymethylpropionic acid and 20.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to D M F 1
The mixture was stirred at 50 mj for 2 hours. Next, 28 mmol of the ester obtained in (4) was added and stirred for 6 hours. 200 ml of water was added to the reaction solution and extracted with ether, dried, concentrated, and purified by column chromatography to obtain a low-molecular liquid crystal compound used in the present invention. (Yield 58%, [α]
o=+2.08 (C)lcR3)) The phase transition behavior of this low molecular weight liquid crystal compound was as follows.

F8 Z! + [However, SA indicates smectic A phase] Synthesis Example 3 4- [4'-(12-(2,2-diacetoxy)propionyloxy)dodecanyloxy)benzoquine]benzene-4-carboxylic acid-2-methylbutyl ester Synthesis of (Low-Molecular Liquid Crystal Compound) A solution of 7.5 mmol of the low-molecular liquid crystal compound obtained in Synthesis Example 2 (5) and 45 mmol of acetic anhydride in 5 mi' of pyridine was stirred at room temperature for 12 hours.

The reaction solution was extracted with ether, washed with dilute 1 (Cffi), dried, concentrated, and purified by column chromatography to obtain a low-molecular liquid crystal compound having a terminal acetyl group used in the present invention. (Yield 73%, [a]o=+2.
15((:HCf!3)) The phase transition behavior of this compound was as follows.

Synthesis Example 4 (1) Synthesis of 4'-(4''-12-promotodecyloxybenzoyloxy)biphenyl-4-carboxylic acid-2-methylbutyl ester 50 mmol of the carboxylic acid obtained in (3) of Synthesis Example 2 8 in toluene 30fflI4, thionyl chloride 10 mA'
The mixture was stirred at 0°C for 2 hours. Next, excess thionyl chloride and toluene were distilled off under reduced pressure to obtain an acid chloride. A solution of 55 mmol of the ester obtained in (1) of Synthesis Example 1 and 60 mmol of triethylamine in 100 raR of THF was stirred, and the THF solution of the above acid chloride was added dropwise thereto, followed by stirring for 8 hours. After the reaction, extract with ether and dilute HC
After washing with 1', drying, and concentration, the product was purified by column chromatography to obtain ester (1). (yield 73%,
[αlo = + 2, 33 (CHCjs)) (2
) Synthesis of 4-(4''-12-(2,2-dihydroxymethylpropionyloxy)dodecanyloxy)biphenyl-4-levonic acid-2-methylbutyl ester (low-molecular liquid crystal compound) 2.2-dihydroxy 18.0 mmol of methylpropionic acid and 20.0 mmol of tetramethylammonium hydroxide (pentahydrate) were stirred in 150 ml of DMF for 2 hours. Next, the ester 1 obtained in (1)
8.0 mmol was added and stirred for 6 hours. After the reaction, the mixture was extracted with ether, dried, concentrated, and purified by column chromatography to obtain a low-molecular liquid crystal compound used in the present invention. (Yield, 78%, [α]o= + 2.10(C)ICf3)
) The phase transition behavior of this compound was as follows.

Synthesis Example 5 4'-(4''-(12-(2,2-diacetoxy)propionyloxy)dodecanyloxy]biphenyl-4-
Synthesis of carboxylic acid-2-methylbutyl ester (low-molecular liquid crystal compound) A solution of 7.5 mmol of the low-molecular liquid crystal compound obtained in Synthesis Example 4 (2) and 45 mmol of acetic anhydride in 5 mA of pyridine was stirred at room temperature for 12 hours. did. The reaction solution was extracted with ether and diluted with dilute HC! ! The mixture was washed with water, dried, and purified by column chromatography to obtain a low-molecular-weight liquid crystal compound having a terminal acetyl group used in the present invention. (yield 83%, [αlo
= + 2.48 (CHCj'a)) The phase transition behavior of this compound was as follows.

Synthesis Example 6 (1) Synthesis of 4'-hydroxybiphenyl-4-carboxylic acid benzyl ester 0.1 mol of 4'-hydroxybiphenyl-4-carboxylic acid and tetramethylammonium hydroxide (pentahydrate)
The mixture was stirred for 2 hours in a 0.11 mol DMF200mj+ solution. Next, 0.1 mol of benzyl bromide was added and stirred for 6 hours. After the reaction, the mixture was extracted with ether, dried, concentrated, and purified by column chromatography to obtain ester (1). (Yield 76%) (2) Synthesis of 4'-(12-bromododecanyloxy)biphenyl-4-carboxylic acid benzyl ester 0 mmol of Estesif obtained in (1), 0.21 mol of dibromododecane, potassium carbonate A 0.4M acetone 11 solution was refluxed for 6 hours. Filter the reaction solution.

After concentration, purify by column chromatography (2)
ester was obtained. (yield 89%) (3) 4'-(12
60 mmol of the ester obtained in synthesis (2) of -bromododecanyloxy)biphenyl-4-carboxylic acid, 2.0 g of palladium on carbon (5% catalyst), 500 mR of ethyl acetate
The solution was stirred under hydrogen gas atmosphere for 24 hours. After the reaction, the reaction mixture was filtered, reduced by ':a, and purified by reduced diameter ram chromatography to obtain carboxylic acid (3). (Yield 98%) (4) 4-(4'-12-bromododecanyloxybiphenyl-4'-carbonyloxy)carboxylic acid-
50 mmol of the carboxylic acid obtained in synthesis (3) of 2-methylbutyl ester, toluene 2
0mF, chloroform 1Onl, thionyl chloride 10mR
The solution is stirred at 80° C. for 2 hours. excess thionyl chloride,
Toluene and chloroform were distilled off under reduced pressure to obtain an acid chloride. Next, 55 mmol of the ester obtained in (1) of Synthesis Example 2 and 60 mmol of triethylamine were added to T.
A 200 mR HF solution was stirred, and the THF solution of the acid chloride was added dropwise thereto, and the mixture was reacted for 8 hours. After the reaction, extract with ether and dilute HCI! After washing, drying, and concentration, the residue was purified by column chromatography to obtain ester (4). (Yield 82%.

[α] o = + 2.09 (CHCRs)) (5) 4-
[4″-(12-(2,2-dihydroxymethylpropionyloxy)dodecanyloxy)biphenyl-4′-
Synthesis of 2-methylbutyl carbonyloxy]carboxylic acid ester (low-molecular liquid crystal compound) 18.0 mmol of 2,2-dihydroxymethylpropionic acid and 20.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF. Stirred in 100 ml for 2 hours. Next, the ester 1 obtained in (4)
8.0 mmol was added and stirred for 6 hours. After the reaction, the mixture was extracted with ether, dried, concentrated, and purified by column chromatography to obtain a low-molecular liquid crystal compound used in the present invention. (
Yield 63%, [α]o= + 2.10 (CHC4'3
)) This phase transition behavior was as follows.

Synthesis Example 7 4-[4″-(12-(2,2-diacetoxy)propionyloxy)dodecanyloxy]bipheny Synthesis Example 6-
A solution of 7.5 mmol of the low-molecular liquid crystal compound obtained in step (5) and 45 mmol of acetic anhydride in pyridine was added at room temperature.
Stirred for 2 hours. The reaction solution was extracted with ether, washed with dilute NCR, dried, concentrated, and purified by column chromatography to obtain a low molecular weight liquid crystal compound having a terminal acetyl group for use in the present invention. (Yield 69%, [α]o= + 2.1
0(CHCi13)) The phase transition behavior of this compound was as follows.

Synthesis Example 8 (1) Synthesis of 4-acetoxybenzoic acid 2-chloro-3-methylpentyl ester 4-acetoxybenzoic acid 0.12 mol and thionyl chloride 15 mA+ toluene 70+nj! After stirring the solution at 80° C., excess thionyl chloride and toluene as a solvent were distilled under reduced pressure and concentrated to obtain an acid chloride. Next, (2S, 3
S) -2-chloro-3-methyl-1-pentanol 0
．． 1 mole, triethylamine 0.12 mole THF
300ml+ solution was stirred. The above THF solution of acid chloride was added dropwise to this, and the mixture was stirred for 8 hours. The reaction solution was extracted with ether, washed with dilute NCR, dried, concentrated, and purified by column chromatography to obtain ester (1).

(Yield 55%, [α]D= + 17.4 (CHCR3
)) (2) Synthesis of 4-hydroxybenzoic acid 2-chloro-3-methylpentyl ester 50 mmol of ester obtained in (1) ether 30
The 0 mA' solution was stirred, and 20 mjJ of benzylamine was added thereto, followed by stirring for 2 hours. The reaction solution was extracted with ether and dried.

After concentration, purify by column chromatography (2)
The ester was obtained. (Yield 95%, [αlo”+ 12
．． 8(CHCj!3)) (3) 4-(4″-12-bromododecanyloxybiphenyl-4′-carbonyloxy)carboxylic acid 2-
Synthesis of chloro-3-methylpentyl ester Synthesis example 6-
50 mmol of carboxylic acid obtained in (3), 2 toluene
0mg, chloroform 10mρ, thionyl chloride 10r#
Stir the j+ solution at 80°C for 2 hours. Excess thionyl chloride and the solvents toluene and chloroform were distilled off under reduced pressure to obtain an acid chloride. Next, the ester 5 obtained in (2)
5 mmol, triethylamine 60 mmol THF
A 200 ml solution was stirred, and the THF solution of the acid chloride was added dropwise thereto, followed by stirring for 8 hours. After the reaction, extract with ether and perform ICI! After washing, drying, and concentration, the residue was purified by column chromatography to obtain ester (3). (Yield 82%.

[α]o= + 10.8 ((:H(:i'3))(
4) Synthesis of 4-[4”-(12-(2,2-dihydroxymethyl)propionyloxy)dodecanyloxy]biphenyl-4′-carbonyloxycarboxylic acid 2-chloro-3-methylpentyl ester 2.2 - A solution of 18.0 mmol of dihydroxymethylpropionic acid and 20.0 mmol of tetramethylammonium hydroxide (pentahydrate) in 150 ml of DMF was stirred for 2 hours.

Next, 18.0 mmol of the ester obtained in (3) was added and stirred for 8 hours. After the reaction, the mixture was extracted with ether, dried, concentrated, and purified by column chromatography to obtain ester (4). (Yield 80%, [αlo−+ 10.
3 (CH(:l13)) (5) 4-[4″-(12-
Ester obtained in synthesis (4) of (2,2-diacetoxy)propionyloxy)dodecanyloxy]biphenyl-4'-carbonyloxycarboxylic acid 2-chloro-3-methylpentyl ester (low molecular M crystal compound) 7.5 mmol and acetic anhydride 4
5 mmol of Torizin 5mj+ solution was stirred at room temperature for 2 hours. The reaction solution was extracted with ether, washed with dilute HCJ), dried, concentrated, and purified by column chromatography to obtain a low-molecular liquid crystal compound used in the present invention. (yield 78%,
[α1°=+10.4 (COCl2)] The phase transition behavior of this compound was as follows.

[Example] Next, the present invention will be explained in detail with reference to examples.

Examples 1 to 8 As shown in Table 1, 0.42 mmol of each of the low-molecular liquid crystal compounds obtained in Synthesis Examples 1 to 8 and 0.50 g of the polyester of Production Example 1 were dissolved in methylene chloride, and After stirring, the mixture was concentrated and dried to obtain a liquid crystal polymer film. Table 1 shows these phase transition behaviors and electric field response speeds.

Note that the electric field response speed was measured as follows.

Measurement of electric field response speed 20X A polymer was sandwiched between two 10 mm ITO substrates, the thickness was adjusted to 25 μm with a spacer, and the electric field E
= 2 x 10' V/m, and the response time required for the amount of transmitted light to change (0-90%) was measured at a predetermined temperature.

Example 9 0.44 mmol of the low-molecular liquid crystal compound obtained in Synthesis Example 5 and 0.50 g of the polyester obtained in Production Example 2 were dissolved in methylene chloride, thoroughly stirred, concentrated, and dried to obtain a liquid crystal polymer. Got the film.

Table 1 shows the phase transition behavior and electric field response speed of this liquid crystal polymer film.

Example 10 0.49 mmol of the low molecular weight liquid crystal compound obtained in Synthesis Example 5 and commercially available polycarbonate (MW = 15.00
0) 0.50 g was dissolved in methylene chloride, thoroughly stirred, concentrated and dried to obtain a liquid crystal polymer film. Table 1 shows the phase change υ behavior and electric field response speed of this liquid crystal polymer film.

Examples 11 to 18 Two types of low-molecular liquid crystal compounds were blended in the proportions shown in Table 2, and 0.42 mmol of the obtained low-molecular liquid crystal compound and 0.50 g of the polyester of Production Example 1 were dissolved in methylene chloride, After sufficient stirring, the mixture was concentrated and dried to obtain a liquid crystal polymer film. Table 2 shows the phase transition behavior and electric field response speed of these liquid crystal polymer films.

Example 19 The low molecular liquid crystal compound obtained in Synthesis Example 4 was used as the low molecular liquid crystal compound, and PV was used as the non-liquid crystal polymer.
AC (polyvinyl acetate, MW=250.000
) is dissolved in methylene chloride in a ratio of the total number of proton donor and acceptor functional groups (non-liquid crystal polymer) to 1 (low-molecular liquid crystal compound), and this solution is dropped onto glass. , and dried to obtain a liquid crystal polymer film. This film was heated to an isotropic phase (137°C), annealed for 30 minutes, cooled at a rate of 3°C/min, turned into an SA phase (110°C), and examined with a polarizing microscope. It was found that the liquid crystalline polymer and the low molecular weight liquid crystal compound were well mixed.

Comparative Example 1 A liquid crystal polymer film was obtained in the same manner as in Example 19, except that a low molecular liquid crystal compound having no proton donor represented by the formula was used instead of the compound of Synthesis Example 4 as the low molecular liquid crystal compound. This film was heated to the isotropic phase (171 t) in the same manner as in Example 19, and then annealed for 30 minutes at 3°C.
/min to become the SA phase (150℃
) When examined using a polarizing microscope, it was found that the non-liquid crystal polymer and the low-molecular liquid crystal compound were poorly mixed and were partially separated.

Example 20 The liquid crystal polymer film obtained in Example 4 was heated to the isotropic phase (137°C) and then cooled at a cooling rate of 3°C.
Example 19 except that 10°C/min was used instead of /min.
After changing to the SA phase (110° C.) in the same manner as above, examination using a polarizing microscope revealed that the non-liquid crystal polymer and the low-molecular liquid crystal compound were well mixed.

Example 21 0.42 mmol of each of the low-molecular liquid crystal compounds and mixtures thereof used in Examples 1 to 8.11 to 18 and 0.42 mmol of polyacrylic acid (commercially available polyacrylic acid, M W = 250,000).
12g, polyvinyl acetate (commercially available polyvinyl acetate,
MW = 250,000) 0.14 g and polyvinyl alcohol (commercially available polyvinyl alcohol, MW = 2
Polarizing microscope observation of various liquid crystal polymer films prepared by adding 0.07 g of 50.000) also revealed that the non-liquid crystal polymer and the low-molecular liquid crystal compound were well mixed, as in Examples 19 and 20 above. I understand.

[Effects of the Invention] The liquid crystal composition of the present invention is not simply a mixture of a non-liquid crystal polymer and a low-molecular liquid crystal compound, but is uniformly dispersed through hydrogen bonding, and has excellent self-shape retention without causing layer separation. , and has a strong power phase. Therefore, this composition is stable evenly when subjected to electrical or optical manual force,
Moreover, it has high-speed response. Therefore, this liquid crystal composition is extremely useful in industry, particularly in optoelectronics such as switching elements, display elements, electro-optical shutters, optical modulation, optical communication optical path switching switches, memories, and variable focus lenses.

Claims (3)

[Claims] (1) Ferroelectric liquid crystal composition consisting of a non-liquid crystal polymer having a proton donor and/or proton acceptor and a low molecular weight liquid crystal compound having a proton donor and/or proton acceptor and having a chiral smectic C phase. . (2) The liquid crystal composition according to claim 1, wherein the non-liquid crystal polymer has a proton donor and/or a proton acceptor in its main chain and side chain. (3) Low-molecular liquid crystal compounds have the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 is -OH or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, p is an integer from 1 to 20, R ^2 has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas,
There are chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (However, Z is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R^3 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼.(In addition, n is an integer from 0 to 5, m is an integer from 1 to 6, R^4 is CH_3
- or a halogen atom, X represents a halogen atom, and C represents an asymmetric carbon. ))] The liquid crystal composition according to claim 1, which is represented by: