JPH03220160A - Polymer liquid crystal compound and intermediate epoxy compound therefor - Google Patents

Abstract

PURPOSE:To obtain a new polymer liquid crystal compound, capable of exhibiting ferroelectricity within a wide temperature range and excellent in film-forming, orienting properties and high speed responsiveness to external factors by using a new specific epoxy compound as an intermediate and polymerizing the aforementioned epoxy compound. CONSTITUTION:A new polymer liquid crystal compound having recurring units expressed by formula I [(p) is 6-12; R is Z(CH2)qH (Z is single bond, O or COO; (q) is 4-8)] with a smectic C phase. The aforementioned compound expressed by formula I is obtained by carrying out cationic polymerization of a new epoxy compound expressed by formula II in a solvent such as dichloromethane using a catalyst such as stannic chloride.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polymeric liquid crystal compound and its intermediate epoxy compound, and more specifically, the present invention relates to a polymeric liquid crystal compound and its intermediate epoxy compound. A polymer liquid crystal compound from which a strongly g-electric polymer liquid crystal composition exhibiting dielectric properties and excellent film formability, orientation, and high-speed response to external factors can be obtained, and an intermediate epoxy compound used in its production. It is related to. Ferroelectric polymer liquid crystal compositions obtained using such polymer liquid crystal compounds are used in the fields of electronics and electronics, particularly display elements such as calculators and watches, electro-optical shutters, electro-optical apertures, optical modulators,
It can be advantageously used as various electro-optical devices such as optical communication optical path changeover switches, memories, liquid crystal printer heads, and non-point distance variable lenses.

[Prior Art] Conventionally, display elements using low-molecular liquid crystals have been widely used for digital displays such as calculators and watches.

In these fields of application, conventional low-molecular liquid crystals are usually used by sandwiching them between two glass substrates whose spacing is controlled on the order of microns. However, such adjustment of the gap has not been possible with large screens and curved screens. As a means to solve this difficulty, attempts have been made to polymerize liquid crystals and make them moldable (J, Polym, Sci, Polym,
Lett, + Ed, Joshu, 243 (1975),
P.

lym, Bull, 6, 309 (1982)
, JP-A-55-21479, JP-A-61-137
1, Publication No. 33, etc.).

However, in these conventional polymer liquid crystals, the response speed of changes in the amount of transmitted light to changes in external factors such as electric fields is generally slow, and a satisfactory result has not yet been obtained.

In addition, the polymer liquid crystal disclosed in the above-mentioned publication does not exhibit liquid crystal properties at room temperature; it must be heated in a temperature range above the glass transition temperature and below the transparentization temperature to become a liquid crystal. It has the following drawbacks.

Furthermore, as a polymer liquid crystal composition, a liquid crystal composition consisting of a thermoplastic amorphous polymer compound and a low molecular weight liquid crystal compound (Japanese Patent Application Laid-Open No. 61-47427), a polymer liquid crystal compound and a low molecular weight liquid crystal composition as an information recording medium, Liquid crystal composition comprising a molecular liquid crystal compound and a polymer compound (Japanese Unexamined Patent Publication No. 10930/1983)
However, these polymer liquid crystal compositions have extremely narrow chiral smectic C phase temperature ranges, even if they are high or low, and moreover, the chiral smectic C phase only appears during the temperature cooling process, which is not practical. It was difficult to use.

The present applicant has previously proposed a ferroelectric polymer liquid crystal composition as a means of solving the drawbacks of the above-mentioned polymer liquid crystal compositions and obtaining a ferroelectric polymer liquid crystal composition excellent in film formability, orientation, and high-speed response. In addition to devising a mixture of a low-molecular liquid crystal compound and a side-chain type polymer liquid crystal compound having a smectic C phase,
(No. 287), and examples of polymeric liquid crystals used for this mixing are also disclosed in the Detailed Description of the Invention section of JP-A-64-66287. However, even in ferroelectric polymer liquid crystal compositions prepared by mixing these polymer liquid crystals with ferroelectric low-molecular liquid crystal compounds, the response speed to an external electric field near room temperature is often on the order of milliseconds. However, the speed of response was not fully satisfactory.

[Problem to be solved by the invention]

The present invention solves the above problems and exhibits ferroelectricity in a wide temperature range including room temperature by mixing an optically active compound such as a ferroelectric low-molecular liquid crystal compound or a non-liquid crystal optically active compound. A polymeric liquid crystal compound from which a ferroelectric polymeric liquid crystal composition not only excellent in film properties and orientation but also particularly excellent in high-speed response to an external electric field can be obtained, and an intermediate epoxy compound used in the production thereof. The purpose is to provide the following.

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the present inventors found that among the side chain type polymeric liquid crystal compounds having a smectic C phase disclosed in JP-A No. 64-66287,
When a polyether polymer liquid crystal compound with a specific structure is mixed with an optically active compound, it exhibits particularly excellent performance not only in high-speed response but also in the temperature range where it exhibits ferroelectricity, film formability, and orientation. It has been discovered that a ferroelectric polymer liquid crystal composition exhibiting the following can be obtained, and the present invention has been completed.

That is, the present invention provides a polymeric liquid crystal compound having a repeating unit of the following format and having a smectic C phase.

(In the formula, p represents an integer of 6 to 12, R represents -Z(C)1.)9) 1, provided that Z represents a single bond, -〇- or -COO-, and q
represents an integer from 4 to 8. ) Furthermore, the present invention provides an intermediate uboxy compound having a structure of the following format, which is used in the production of the above-mentioned polymeric liquid crystal compound.

However, Z represents a single bond, -〇- or -COO-, and q
represents an integer from 4 to 8. ) The polymeric liquid crystal compound of the present invention can be obtained by polymerizing this intermediate epoxy compound by a known method.

In the column of detailed description of the invention of JP-A No. 64-66287, it is stated that a polyether-based polymeric liquid crystal compound represented by the following -Shipin can be used, (wherein k is is an integer from 1 to 30, X is 10-(oxygen) or -COO-, (in the formula, p
represents an integer from 6 to 12, R represents -Z C)12),)l, Y is -A(CH2)lIIH or -ACN, where A is a single bond, -〇~ or - COO-, m is O
~10 integer. ) There is no description of specific examples in which the polymeric liquid crystal compound of the present invention was actually used. It has been found that by using the compound of the present invention, excellent effects as shown below can be obtained.

In the polymeric liquid crystal compound of the present invention, the number (p) corresponding to the length (k) of the polymethylene group of the spacer of the above formula (■)
) is an integer from 6 to 12. When ρ is shorter than 6, the temperature range of the nematic phase of the polymeric liquid crystal compound becomes wide, and the smectic C phase is often not expressed. On the other hand, when p is longer than 12, the temperature range of the smectic phase becomes wide, and also It was found that smectic C phase was not expressed in many cases. Therefore, by limiting P to 6 to 12, a polymeric liquid crystal compound that stably exhibits a smectic C phase can be obtained.

The X that connects the spacer and the rigid portion R1 in the above formula (I) is 10- or -000-, but X is -COO
When the value is -, the spontaneous polarization of the resulting ferroelectric polymer liquid crystal composition is greater than when the composition is -0-, but the viscosity is also increased and the response speed is not very fast. When the polymeric liquid crystal compound of the present invention in which the number of groups corresponding to X is limited to 10 or more is used, the resulting ferroelectric liquid crystal composition has excellent high-speed response.

In the polymer liquid crystal compound of the present invention, the side chain meson liquid crystal compound has a slightly narrower temperature range of the smectic C phase, and the spontaneous polarization of the ferroelectric polymer liquid crystal composition obtained using it is also smaller. is found, and the rigid part is @CH
A polymeric liquid crystal compound in which =N@ lacks chemical stability. Although it stably expresses the smectic C phase,
The temperature range in which it exhibits a liquid crystal state is high, and it often becomes a glass state near room temperature. In the polymeric liquid crystal compound of the present invention, the rigid part of the side chain mesogenic group is @COO
Since it is limited to @-, the smectic C phase is stably expressed over a wide temperature range including room temperature.

In the polymeric liquid crystal compound of the present invention, the terminal groups of the side chain mesogenic groups are limited to -z(cL) and H. −Z(
CHz) -H is more likely to stably express the smectic C phase than -ACN. - In the case of ACN, the nematic temperature range is wide and the smectic C phase is not often expressed, and the dielectric constant in the long axis direction of the molecule is large, so when an electric field is applied, the molecule is perpendicular to the electrode. It's easy to stand up.

Z is a single bond, -0- or -000-. These three types of bonding groups are arranged in the order of -coo->-o->single bond to stably develop a smectic C phase in a polymeric liquid crystal compound, or to form a ferroelectric polymeric liquid crystal composition obtained using the same. This results in large spontaneous polarization. However, the viscosity may increase in this order, so its superiority cannot be determined unconditionally, and the length of the terminal alkyl chain (
q) must also be considered. The length (q) of the terminal alkyl chain in the present invention is 4-8. q
Polymer liquid crystal compounds with a value shorter than 4 have a wide nematic phase temperature range and often do not develop a smectic C phase, while those with a value longer than 8 have a wide smectic A phase temperature range and often do not develop a smectic C phase. Many things were discovered. Therefore, the polymeric liquid crystal compound of the present invention in which q is limited to 4 to 8 can stably exhibit a smectic C phase.

The number average molecular weight of the polymeric liquid crystal compound of the present invention is preferably 1,000 to 20,000. If it is less than 1000, the film forming properties of the strong dielectric polymer liquid crystal composition prepared using it may deteriorate;
If it is larger than 0, the response speed may become slow.

A general method for synthesizing the polymeric liquid crystal compound of the present invention is shown below.

1(ZC=CH(CI(2), 0@Cool) ■As shown in the above reaction formula, 4-alkenyloxybenzoic acid (■) in a suitable solvent such as chloroform in the presence of a catalytic amount of pyridine, Synthesize acid halide ■ by halogenating with a halogenating agent such as thionyl chloride.The obtained acid halide ■
is esterified by reacting with phenol derivative (1) in a solvent such as tetrahydrofuran (THF) to synthesize compound (2). The obtained compound (1) is epoxidized with a peracid such as m-chloroperbenzoic acid (acPBA) in a solvent such as dichloromethane to synthesize the intermediate epoxy compound (2) of the present invention.

Specifically, the 4-alkenyloxybenzoic acid ■ used in the above synthesis method is 4-(7-octenyloxy)benzoic acid, 4-(8-nonenyloxy)benzoic acid,
4-(9-decenyloxy)benzoic acid, 4-(10-undecenyloxy)benzoic acid, 4-(11-dodecenyloxy)benzoic acid, 4-(12-1lysocenyloxy)
These are benzoic acid and 4-(13-tetradecenyloxy)benzoic acid. In addition, the phenol derivatives (2) used in the above synthesis method are specifically 4-n-butylphenol, 4-n-pentylphenol, 4-n-hexylphenol, 4-n-hebutylphenol, 4-n-octylphenol. , 4-n-butyloxyphenol,
4-n-pentyloxyphenol, 4-n-hexyloxyphenol, 4-n-hebutyloxyphenol, 4-n-octyloxyphenol, 4-hydroxybenzoic acid n-butyl ester, 4-hydroxybenzoic acid n -pentyl ester, 4-hydroxybenzoic acid n-hexyl ester, 4-hydroquinebenzoic acid n-hebutyl ester and 4-hydroxybenzoic acid n-octyl ester.

Next, the epoxy compound thus obtained is cationically polymerized in a solvent such as dichloromethane using a catalyst such as stannic chloride to synthesize the liquid crystal polymer compound (2) of the present invention. Catalysts for the cationic polymerization of epoxy compounds (■) include, in addition to stannic chloride, Lewis acids such as boron trifluoride, aluminum chloride, and titanium tetrachloride; Boron etherate and the like can be used.

As the polymerization method, the above solution polymerization method is preferred, but
Various methods such as bulk polymerization, slurry polymerization, etc. The polymerization temperature depends on the type of catalyst and is generally suitable to be 0 to 30°C.

The polymerization time varies depending on other factors such as the polymerization temperature, but is usually several hours to 6 days.

The molecular weight can be adjusted by adding a known molecular weight regulator or adjusting the concentration of the catalyst relative to the hexamer.

In addition, in the polymerization reaction and the epoxidation reaction,
Although not essential, it is preferable to replace the system with an inert gas such as argon or nitrogen.

The polymer liquid crystal compound of the present invention can be used as a ferroelectric polymer liquid crystal composition by adding an optically active low molecular compound. In this case, the polymeric liquid crystal compound of the present invention may be used alone or in combination as appropriate.

As the optically active low molecular weight compound used for preparing the ferroelectric polymer liquid crystal composition, not only those having liquid crystal properties but also non-liquid crystal properties can be used.

When preparing a ferroelectric polymer liquid crystal composition by mixing a non-liquid crystal optically active low molecular compound and the polymer liquid crystal compound of the present invention, the optically active low molecular weight compound in the ferroelectric polymer liquid crystal composition is The content of the molecular compound is 30 mol% or less, preferably 10
It is desirable to set it to 20 mol%. If the amount of the non-liquid crystal optically active low molecular weight compound is more than 30 mol %, phase separation may occur in the composition.

In addition, when preparing a ferroelectric polymer liquid crystal composition by mixing a liquid crystal optically active low molecular compound and the polymer liquid crystal compound of the present invention, the optical activity in the ferroelectric polymer liquid crystal composition may be It is desirable that the content of low molecular weight compounds be 95 mol% or less, preferably 10 to 90 mol%. If the amount of the optically active low molecular weight compound is more than 95 mol %, the orientation and film forming properties of the composition may be significantly reduced.

Various known optically active low molecular compounds can be used as the liquid crystal optically active low molecular compound to be mixed with the polymeric liquid crystal compound of the present invention in preparing the ferroelectric liquid crystal composition. ferroelectric low-molecular liquid crystal compounds, Ab-based and azoxy-based ferroelectric low-molecular liquid crystal compounds,
Biphenyl-based and aromatics ester-based ferroelectric low-molecular liquid crystal compounds, biphenyl-based and aromatic ester-based ferroelectric low-molecular liquid crystal compounds with ring substituents such as halogens and cyano groups, and heterocyclic Examples include ferroelectric low-molecular liquid crystal compounds that have ferroelectric properties. Representative examples of these liquid crystal optically active low molecular weight compounds are shown below.

Schiff CH.

CH.

n=7.8, 14 n=4.8, 12 Azo 7, Biazoxy, Tef=脣CF3 n=4, 5 n=8 n=16 n=6, 8, 10 Kidnapping 1 Ma ■ Criminal ball As the non-liquid crystal optically active low molecular weight compound to be mixed with the polymeric liquid crystal compound of the present invention in the preparation of the ferroelectric liquid crystal composition, there are various known non-liquid crystal optically active low molecular weight compounds. The following optically active low molecular weight compounds can be used, and among them, the following compounds can be mentioned as suitable representative examples.

HO@C00CHzεHC6HI3 Note that when preparing a ferroelectric polymer liquid crystal composition by mixing these optically active low molecular compounds with the polymer liquid crystal compound of the present invention, these optically active low molecular compounds are
A ferroelectric polymer liquid crystal composition obtained by blending the polymer liquid crystal compound of the present invention and an optically active low molecular compound in this manner, which can be used alone or in combination as appropriate. The product can be used by being formed into a film by a known film forming method, such as a casting method, a T-die method, an inflation method, a calendar method, or a stretching method. A film-like polymeric liquid crystal composition can be placed between two ordinary glass substrates, as well as a flexible substrate such as a large glass substrate, a curved glass substrate, or a polyester film, with an ordinary conductive film interposed between them. It can be used in various optoelectronic fields such as liquid crystal displays, electro-optical shutters, and electro-optical apertures. Alternatively, by applying a solution of a polymeric liquid crystal composition dissolved in an appropriate solvent to the substrate surface and evaporating the solvent, it is possible to form a film in direct contact with the substrate surface.

As a method suitable for orienting the film of the ferroelectric polymer liquid crystal composition thus formed, a mechanical orientation method is preferred, and particularly preferred is a stretching orientation method, and bending deformation of the film using a roll. There is bending orientation in which the material is oriented by applying shear stress.

Examples of the stretching method include methods commonly used for stretching plastic films, such as -axial stretching method, biaxial stretching method, press stretching method, and inflation stretching method. Among these methods, the uniaxial stretching method is preferably used. The stretching ratio is usually 30-1000%, preferably 50-6
It is 00%.

If the stretching ratio is less than 30%, the degree of orientation of the liquid crystal will be low and a good contrast ratio will not be obtained. Moreover, if it exceeds 1000%, a continuous film cannot be obtained.

The alignment treatment of the polymeric liquid crystal composition may be performed on the polymeric liquid crystal composition alone, or may be performed by sandwiching the polymeric liquid crystal composition between two flexible plastic snack films. Orientation can also be achieved by pressing a polymer liquid crystal composition sandwiched between transparent substrates.

At least one of the two conductive films located on both sides of the film of the polymeric liquid crystal composition is a transparent conductive film. As the transparent conductive film, a NESA film coated with tin oxide, an ITO film made of tin oxide and indium oxide, or the like can be used. This transparent conductive film is preferably provided inside a transparent substrate made of glass or plastic (poly, methyl methacrylate, polycarbonate, polyether sulfone resin, etc.). When using the polymer liquid crystal composition as a display element, it is preferable to provide a polarizing plate or a reflecting plate on the outside of the transparent substrate.

Examples of the opaque conductive film used when a transparent conductive film is not used include aluminum, gold vapor deposited films, sputtering films, and the like.

In addition, in preparing the ferroelectric polymer liquid crystal composition, in addition to the polymer liquid crystal compound and optically active compound of the present invention, various inorganic, organic, and Improvements can be made by treatment methods well known in the art, such as the addition of additives such as metals.

[Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

The structure of the obtained epoxy compound was confirmed by 1H NMR and elemental analysis, and the structure of the obtained polymer liquid crystal compound was confirmed by 'H-NMR. Further, the measurement of phase transition temperature and confirmation of phase were performed using DSC and polarizing microscope, respectively.

Phase states are indicated using the following abbreviations: (glass state, Cry: crystalline state, 5IIX: unidentified higher-order smectic phase, SmC: smectic C phase, Sm
C'': chiral smectic C phase, 5LllA = smectic A phase, N: nematic phase, Iso: isokyoshi phase) Furthermore, in the formula expressing phase transition behavior, the number represents the phase change temperature in °C.

Example 1 A polymeric liquid crystal compound having a repeating unit represented by the following formula was synthesized.

1, (1) CH,・ell(CHz)a-00QCO
Synthesis of CLGCOOC mountain 4-(9-decenyloxy)benzoic acid 10 mmol (2
, 76 g) of chloroform (CFfCI3) 20 d
20 mmol (2.38 g) of thionyl chloride and a few drops of pyridine were added to the solution. After heating the resulting mixture under reflux for 2 hours, the solvent and excess thionyl chloride were distilled off. The remaining oily substance was dissolved in 10 Jd of tetrahydrofuran, and 10 mmol (1.94 g) of 4-hydroxybenzoic acid n-butyl ester and 10 mmol (10 mmol) of triethylamine were added.
Tetrahydrofuran 201 in which 1,01 g) is dissolved
d solution and stirred at room temperature for 6 hours. After distilling off the solvent from the obtained reaction solution, it was extracted with ether, and the extract was washed with a dilute aqueous hydrochloric acid solution. After drying the ether layer with magnesium sulfate, the ether was distilled off and the residue was recrystallized from methanol to obtain 3.85 g of the desired phenylbenzoate derivative.

(Yield: 85%) The 'H-NMR measurement results of the obtained phenylbenzoate derivative are shown below.

' H-N M R (cock3) 8.10 (d, 4H), 7.25 (d, 2H),
6.95 (d, 2H), 6.20~5.30 (m, IH), 5, 15~
4.80 (m, 2H), 4.30 (t, 2H
), 4.00 (t, 2H), 2.30~0.80 (
Synthesis 1 of phenylbenzoate derivative 1 obtained in (1)
In a solution of 0 mmol (4.53 g) in 20 ml of dichloromethane, 15 mmol (2.59 g) of m-chloroperbenzoic acid was added.
) was added and reacted at room temperature for 5 hours. After leaving the reaction mixture overnight, 30 mmol (4.15 g) of potassium carbonate
The dichloromethane layer was further dried with magnesium sulfate. The target epoxy compound 4.12 was obtained by distilling off the solvent from the dried dichloromethane layer and recrystallizing the residue from methanol.
I got g.

(Yield: 88%) The results of 'H-NMR measurement and elemental analysis of the obtained epoxy compound are shown below.

'H-NMR (CDCl2) 8.06 (d, 4H), 7.25 (d, 2H), 6
．． 92 (d, 2H), 4.30 (t, 2H), 4
．． 00 (t, 2H), 3.00-2.32 (m, 3H), 2, 10~
0.80 (m, 21 H) Elemental analysis results are shown below.

' H-N M R (CDCh) 8.07 (d, 4H), 7.21 (d, 2H),
6.87 (d, 2H), 4.28 (t, 2H),
3.92 (t, 2H), 3.25~3.80 (m, 3H), 2.05~
Synthesis 1 of 0.75 (m, 21 H), 5 mmol (2
0.25 mmol of stannic chloride (0,
029m) was added dropwise thereto, and the mixture was allowed to react at room temperature for 5 days. After the reaction was completed, the solvent was distilled off from the reaction solution, and the residue was purified by column chromatography (filled with silica gel, developed with ethyl acetate/n-hexane 20-50%) to obtain 1.62 g of the desired polymeric liquid crystal compound. Ta. (Conversion rate: 69%) The phase transition behavior and number average molecular weight of the obtained polymeric liquid crystal compound are shown in Table 1, and the results of H-NMR measurement are shown in Table 1. A polymeric liquid crystal compound having units was synthesized.

Synthesis Example 1. In (1), 4-hydroxybenzoic acid n-hexyl ester was used instead of 4-hydroxybenzoic acid n-butyl ester, and Example 1. (1) and (
By performing the same operation as 2), an epoxy compound represented by the following formula was obtained.

The results of 'H-NMR measurement and elemental analysis of the obtained epoxy compound are shown below.

' HN MR (CDCI 8.07 (d, 4H), 7.20 (d, 2H),
6.88 (d, 2H), 4.30 (t, 2H), 3
．． 95 (t, 2H), 3, 10~2.25 (m, 3H), 2.05~
0.70 (m, 25 H) Synthesis of elemental analysis values 2. By using the epoxy compound obtained in (1) and performing the same operation as in Example 1 and (3), the compound represented by the above formula A polymeric liquid crystal compound having repeating units was obtained.

The phase transition behavior and number average molecular weight of the obtained liquid crystal polymer compound are shown in Table 1, and the 'H-NMR measurement results are shown below.

'H-NMR (CDC13) 8.07 (d, 4H), 7.20 (d, 2H), 6
．． 88 (d, 2H), 4.30 (t, 2H), 3
．． 95 (t, 2H), 3.26-3.79 (m, 3H), 2, 10-0.80 (m, 25H) Example 3 Repetition expressed by the following formula A polymeric liquid crystal compound having units was synthesized.

Synthesis Example 1 of 2.05-0.70 (m, 25 H) elemental analysis values. In (1), 4-hexyloxyphenol was used instead of 4-hydroxybenzoic acid n-butyl ester, and Example 1. The same operations as (1) and (2) were performed to synthesize an epoxy compound represented by the above formula.

The results of 'H-NMR measurement and elemental analysis of the obtained epoxy compound are shown below.

'H-NMR (CDCI: l) 8.05 (d, 2H), 7, 20-6.70 (m, 6H), 3,',
5-4.15 (m, 4H), 3.05-2.3
Synthesis 3 of 0 (m, 3H), Using the epoxy compound obtained in (1), a polymer having a repeating unit represented by the above formula was prepared by performing the same operation as in Example 1, (3). A molecular liquid crystal compound was obtained.

The phase transition behavior and number average molecular weight of the obtained liquid crystal polymer compound are shown in Table 1, and the 'H-NMR measurement results are shown below.

'H-NMR (CDC13) 8.05 (d, 2H), 7.20-6.70 (m, 6H), 3.75
~4.15 (m, 4H), 3.20-3.7
5 (m, 3H), 2.05-0.70
(m, 25 H) Example 4 A polymeric liquid crystal compound having a repeating unit represented by the following formula was synthesized.

AOCH2CH well synthesized things.

The results of 'H-NMR measurement and elemental analysis of the obtained epoxy compound are shown below.

'H-NMR (CDCI+) 8.10 (d, 2H), 7.10 (d, 4) 1),
6.90 (d, 2H), 4.00 (t, 2H),
3.00-2.25 (m 5 H), 2, 10-0
．． Synthesis Example 1 of 70 (m, 25 H) elemental analysis values. In (1), 4-hydroxybenzoic acid n
- Using 4-hexylphenol instead of butyl ester, Example 1. Synthesis 4 of the epoxy compound represented by the above formula by performing the same operations as in (1) and (2). Using the epoxy compound obtained in (1), the same procedure as in Example 1 and (3) was carried out. By performing the operation, a polymeric liquid crystal compound having a repeating unit represented by the above formula was obtained.

The phase transition behavior and number average molecular weight of the obtained liquid crystal polymer compound are shown in Table 1, and the IH-NMR measurement results are shown below.

HNMR (CDC13) 8.10 (d, 21(), 7.10 (d,
4H), 6.90 (d, 4H), 4.00 (t
, 2H), 3.70-3.30 (m, 3H), 2.60 (t, 2) (), 2, 10-0.70 (m, 25H) Example 5 A polymeric liquid crystal compound having a repeating unit represented by the following formula was synthesized.

Synthesis Example 1. In (1), 4-(7-octynyloxy) instead of 4-(9-decenyloxy)benzoic acid
Example 1 was prepared by using benzoic acid, 4-hydroxybenzoic acid n-octyl ester instead of 4-hydroxybenzoic acid n-butyl ester. By performing the same operations as (1) and (2), an epoxy compound represented by the above formula was synthesized.

The results of 'H-NMR measurement and elemental analysis of the obtained epoxy compound are shown below.

'H-NMR (CDC13) 8.05 (d, 4H), 7.20 (d, 2H),
6.88 (d, 2H), 4.25 (t, 2H),
3.90 (t, 2H), 3.05-2.30 (m, 3H), 2,10-0.80 (m, 21H) Elemental analysis value 3.80-3.25 (m, 3H) ), 2.
05-0.75 (m, 21 H) Example 6 A polymeric liquid crystal compound having a repeating unit represented by the following formula was synthesized.

By using the epoxy compound obtained in Synthesis 5, (1) and performing the same operation as in Example 1, (3), a polymeric liquid crystal compound having a repeating unit represented by the above formula was obtained.

The phase transition behavior and number average molecular weight of the obtained liquid crystal polymer compound are shown in Table 1, and the 'H-NMR measurement results are shown below.

HN M R (CDCh) 8.05 (d, 4H), 7.20 (d, 2H), 6
．． 88 (d, 2H), 4.25 (t, 2H), 3
．． 90 (t, 2H), in Synthesis Example 1.0), 4-(9-decenyloxy)
1-(10-undecenyloxy) instead of benzoic acid
In Example 1, benzoic acid was used, and 4-n-butylphenol was used in place of 4-hydroxybenzoic acid n-butyl ester. The same operations as (1) and (2) were performed to synthesize an epoxy compound represented by the above formula.

The results of IH-NMR measurement and elemental analysis of the obtained epoxy compound are shown below.

' H-N MR (CDCI: l > 8.10 (d, 2H), 7.10 (d,
4H), 6.95 (d, 2H), 4.05 (t,
2H), 3.05-2.30 (m, 5H), 2
, 10 to 0.70 (m, 23 H) A polymeric liquid crystal compound having a repeating unit determined by elemental analysis was obtained.

The phase transition behavior and number average molecular weight of the obtained liquid crystal polymer compound are shown in Table 1, and the 'H-NMR measurement results are shown below.

' HN MR (CDCI3) 8.10 (d, 2H), 7.10 (d,
4H), 6.95 (d, 2H,), 4.05
(t, 2H), 3,75-3.30 (m,
3H), 2.60 (t, 2H), 2゜10-0.75 (m, 23H) Synthesis 6, (Using the epoxy compound obtained in 11, Example), Same as (3) By performing the following operations, a homogeneous solution was obtained using the above formula in Table Example 7 A: Polymer liquid crystal compound (polymer liquid crystal compound obtained in Example 2).This solution was heated to 50°C at normal pressure. Then, the solvent was removed.Furthermore, the solvent was completely removed by drying under reduced pressure to obtain the desired ferroelectric polymer liquid crystal composition.

The phase transition behavior of this ferroelectric liquid crystal composition was determined by observation under a microscope and was as shown below.

B: Ferroelectric low-molecular liquid crystal compound (H3-78P, manufactured by Teikoku Kagaku Co., Ltd., trade name) From polymer liquid crystal compound A and ferroelectric low-molecular liquid crystal compound B, the content of B was determined by the following method. A ferroelectric polymer liquid crystal composition containing 70 mol % of ferroelectric polymer was prepared.

That is, 1.41 g (3 mmol) of high molecular liquid crystal compound A and 82.68 g (7 mmol) of ferroelectric low molecular liquid crystal compound.
was dissolved in dichloromethane 20II11, and the response time of this ferroelectric liquid crystal composition to an electric field was measured and found to be 600IIs at 25°C. The response time to an electric field was measured as follows.

That is, a ferroelectric liquid crystal composition was sandwiched between two ITO glass substrates, and an alignment cell having a thickness of about 2 μm was produced by a shearing method. Furthermore, an electric field of ±20 MV/m was applied under crossed Nicol conditions, and the amount of change in light transmittance at that time was 0 to 90%.
The time required to reach this point was measured.

Example 8 A liquid crystal optical element was manufactured using the ferroelectric polymer liquid crystal composition prepared in Example 7 as the liquid crystal material, using two flexible continuous substrates with transparent electrodes as substrate materials. The manufacturing equipment used for the fabrication is schematically shown in FIG.

The manufacturing apparatus shown in FIG. 1 includes a coating step A in which a melt or solution of a ferroelectric polymer liquid crystal composition is applied onto one continuous substrate, and a liquid crystal layer made of a ferroelectric polymer liquid crystal composition is applied. The process consists of a stacking process B in which the continuous substrate and the opposing substrate are laminated together, and an alignment process C in which the ferroelectric polymer liquid crystal composition sandwiched between the obtained laminates is aligned. The production line is operated at a constant speed V.

At the same time as the flexible substrate 25 with transparent electrodes is fed out from the substrate feeding roll 1, the substrate protection films 21 and 22 attached to both sides of the substrate 250 are wound up by the protective film winding rolls 2 and 3, respectively, and the substrate 2
5 peeled off from 6 substrate 2 with protective film removed
5 is sent to the coating process A via the auxiliary roll 4.

The coating device used in the coating process A includes a metering discharger 7 that quantitatively discharges the melt or solution of the ferroelectric polymer liquid crystal composition, an impregnation coating head 5 equipped with an impregnation material at the tip, and a metering discharger. It consists of a silicone rubber tube 6 for conveying the melt or solution of the ferroelectric polymer liquid crystal composition discharged from the tube 7 to the impregnating coating head 5. The impregnating coating head 5 makes a constant periodic motion using the end of the silicone rubber tube 6 as a fixed point so that the impregnating material intermittently contacts the surface of the transparent electrode layer of the substrate 25. While the impregnating material is in contact with the transparent electrode layer of the substrate 25, the metering dispenser 7 quantitatively dispenses the melt or solution of the ferroelectric polymer liquid crystal composition in conjunction with the movement of the impregnation coating head 5. The discharged melt or solution of the ferroelectric polymer liquid crystal composition is sent through the silicone rubber tube 6 to the impregnating material of the impregnating coating head 5 that is in contact with the substrate 25, and is maintained at a constant line speed V. Board 5 moving with
The transparent electrode layer is coated on the transparent electrode layer.

The substrate 25 coated with the melt or solution of the ferroelectric polymer liquid crystal composition is sent to the lamination step B via auxiliary rolls 8 and 9. When a solution of a ferroelectric polymer liquid crystal composition is applied, the applied layer is dried in a hot air dryer 28 provided between auxiliary rolls 8 and 9, and the solvent used for preparing the solution is removed. Remove.

The substrate 25 coated with the ferroelectric polymer liquid crystal layer is sent to the lamination process B, and the opposing flexible substrate 26 with transparent electrodes is fed out from the opposing substrate feeding roll 18 and protected in the same way as the substrate 25. The substrate protection films 23 and 24 are removed by the film take-up rolls 19 and 20.
After being removed, it is fed at the same line speed V as the substrate 25. Next, by passing the group Fi 25 sent to the laminating process B and the counter substrate 26 between a pair of laminating rolls 1O111, the ferroelectric polymer liquid crystal composition coated on the transparent electrode of the substrate 25 is The transparent electrodes on the substrate 25 and the counter substrate 26 are stacked so as to be sandwiched between them. The laminating rolls 10 and 11 are heated in order to flatten small irregularities created during application of the liquid crystal composition and to prevent air bubbles from being trapped (surface temperature of the laminating roll: T
,).

The obtained laminate is sent to orientation treatment step C via auxiliary rolls 12 and 29.

In the alignment treatment step C, the laminate is first heated through a heating furnace 13 equipped with an infrared heater and a blower to a temperature at which the liquid crystal exhibits a togoyoshi phase or a mixed phase of a togoyoshi phase and a liquid crystal phase (heating furnace temperature 2T2). After that, the ferroelectric polymer liquid crystal composition in the laminate is brought into bending deformation and oriented by moving it in close contact with the roll surfaces of the alignment cooling rolls 14 and 15 one after another. In this alignment process, in order to orient the liquid crystal by shearing while cooling it, the surface temperatures of the alignment cooling rolls 14 and 150 are set to a temperature at which the liquid crystal exhibits a liquid crystal phase such as a smectic A phase or a chiral smectic C phase, respectively. Surface temperature of orientation cooling roll 14: T3,
The surface temperature of the orientation cooling roll 15 is adjusted to T4).

A liquid crystal optical element 27 obtained by aligning the laminate is wound up onto a winding roll 17 via an auxiliary roll 16.

The liquid crystal optical element 27 wound up on the winding roll 17 can then be cut into a suitable size.

In this manner, by manufacturing a liquid crystal optical element using a continuous substrate and the manufacturing apparatus shown in FIG. 1, coating, lamination, and alignment treatments of a polymeric liquid crystal composition can be performed continuously.

In this example, a PES (polyethersulfone) substrate with ITo (thickness: 10
A liquid crystal optical element was manufactured using a material (FST-135) (trade name, manufactured by Sumitomo Bakelite ■) under the following conditions.

Line speed: v = 2.2 m/min Temperature inside hot air dryer: Ts ``'' 40°C Surface temperature of laminating roll 10.11: T I = 40°C Temperature inside heating furnace 13: Tz = 85°C For orientation Surface temperature of cooling roll 14: T3 = 76°C Surface temperature of cooling roll 15 for orientation: T4 = 70°C As auxiliary rolls 4.8.9.12. ■, width 300 mm) was used. As the laminating roll 10, a rubber roll (
The laminating roll 11 is an iron tube (φ80+an, width 300III [ll) with a chrome-plated surface.
80 mm, width 300 mm) was used. As the orientation cooling rolls 14 and 15, iron tubes (φ80mlTl, width 300mm) whose surfaces were plated with chrome were used.

Using a 10% by weight solution of the ferroelectric polymer liquid crystal composition prepared in Example 7 in dichloromethane, 2.7 cc was sent from the metering dispenser 7 to the impregnation coating head 5 for each coating. The impregnating coating head 5 uses Bertalin (trade name) manufactured by Kanebo ■ cut into a width of 25 cm as an impregnating material, and for each coating, a length of about 40 cm is applied onto the transparent electrode layer of the substrate 25. Then, a solution of the above ferroelectric polymer liquid crystal composition was applied. Next, a lamination process under the above conditions,
and an alignment treatment step, and the obtained liquid crystal optical element was wound up with a winding roll 17. After about 30 minutes after winding, remove the 25cm x 40cm from the roll-shaped liquid crystal optical element.
An r++ liquid crystal optical element was cut out. The film thickness of the liquid crystal portion of the cut out liquid crystal optical element was approximately 2.3 μm. When the contrast of this liquid crystal optical element was measured under crossed nicol conditions, a good value of 46 was obtained when ±5 V was applied. In addition, no contrast unevenness or color unevenness due to uneven thickness of the liquid crystal part was observed throughout the device.
It was confirmed that a good oriented film was obtained.

〔Effect of the invention〕

By mixing the polymeric liquid crystal compound obtained by the present invention with an optically active compound, it not only shows ferroelectricity in a wide temperature range including room temperature, but also has excellent film formability and orientation.
A ferroelectric polymer liquid crystal composition particularly excellent in high-speed response to an external electric field can be obtained.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing a manufacturing apparatus for a liquid crystal optical element used in Examples. Explanation of symbols A: Coating process B: Laminating process C: Orientation treatment process Board line drawing roll 2.3.19.20: Protective film winding roll 4.8.9, ]2.16.29: Auxiliary Roll 5: Impregnation coating head 6: Silicone rubber tube 7: Metering dispenser 10.11
: Laminating roll 13: Heating furnace equipped with an infrared heater and blower 14.15
: Orientation cooling roll 17 : Winding roll 18 Two opposing substrate feeding rolls 21.22.23.24 : Substrate protection film 25.26
: Flexible continuous substrate with transparent electrode 27 : Liquid crystal optical element (before cutting) 28 : Warm air dryer V Ni line speed T, : Surface temperature of laminating roll 10.11 T2 : Temperature in heating furnace 13 T : l : Surface temperature T4 of the cooling roll for orientation 14 : Surface temperature T5 of the cooling roll for orientation 15 : Hot air dryer 28
temperature inside

Claims (1)

[Scope of Claims] 1. A polymeric liquid crystal compound having a repeating unit represented by the following general formula and having a smectic C phase. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, p represents an integer from 6 to 12, R represents -Z(CH_2)_qH, provided that Z is a single bond, -O- or - represents COO-, and q represents an integer of 4 to 8.) 2. An epoxy compound having a structure represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, p represents an integer from 6 to 12, R represents -ZCH_2)_qH, where Z is a single bond, -O- or -COO- q represents an integer from 4 to 8. )