JPH0463829A - Liquid crystalline copolymer, and liquid crystal composition and polymer liquid crystal element prepared therefrom - Google Patents

Abstract

PURPOSE:To prepare the title copolymer which exhibits a chiral smectic phase over a wide temp. range and a high spontaneous polarization and is easily formed into a thin film by incorporating two specific repeating units into the copolymer. CONSTITUTION:For instance, a dicarboxylic acid having a mesogen and an optically active diol are copolymerized to give the title copolymer which has a degree of polymn. of 5-1000, a wt.-average mol.wt. of 2000-100000, the repeating units of formula I or II (wherein X and Y are each H or CH3 provided that Xnot equal to Y; k is 0-1; m1 is 1-18; m2 is 2-10; m3 is 2-5; and a carbon atom to which CH3 is bound is an asymmetric carbon atom) in the main chain as the first flexible spacer, and the repeating units of formula III (wherein x and y are each 0-18 provided that xnot equal to y and x+y<=18; R is 1-5C alkyl; and * shows an asymmetric carbon atom) in the main chain as the second flexible spacer.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel copolymerized liquid crystal compound having an optically active group in the main chain of the polymer, and a polymer containing the copolymerized liquid crystal compound. The present invention relates to liquid crystal compositions and polymer liquid crystal devices using them.

[Conventional technology]

Recently, polymer liquid crystal materials have attracted attention as highly functional materials. The reason for this is said to be that polymer liquid crystals have the following excellent properties.

■ It is easy to make thin films, making it possible to enlarge the area of liquid crystal elements, which is difficult to achieve with low-molecular liquid crystals.

(2) A good alignment state can be obtained by applying an alignment treatment such as stretching.

■ Since the liquid crystal state of polymers can be maintained even below the glass transition point, memory storage stability is significantly improved compared to when low-molecular liquid crystals are used.

[Problem that the invention is trying to solve]

However, it has been said that a problem in putting polymer liquid crystals into practical use is that their response speed to electric fields is slow. However, the response speed to the electric field is thought to be significantly improved by using a ferroelectric polymer liquid crystal that has a chiral smectic phase, similar to that of low-molecular liquid crystals.

In order to make a polymeric liquid crystal exhibit ferroelectricity, it is necessary to introduce an optically active group into its flexible spacer (bent path).

Ferroelectric polymer liquid crystals having various molecular structures have already been reported in so-called side-chain type polymer liquid crystals having an acrylic or methacrylic main chain (for example, JP-A-63-72784; Publication No. 6399204,
63-161005, etc.).

On the other hand, main chain type polymer liquid crystals have superior strength when formed into a film, compared to side chain type polymer liquid crystals, and are also easier to orient molecular chains by stretching, etc., resulting in low molecular liquid crystals. It is also advantageous in that it is easy to increase the area of the film when it is contained.

As such a ferroelectric polymer liquid crystal, a main chain type polymer liquid crystal that uses a bicyclic biphenyl group as a mesogen and exhibits a chiral smectic C phase with an optically active group in the main chain has been reported ("14th Liquid Crystal Discussion Conference Lecture Proceedings J56-57
Page, September 1988, Japanese Patent Application Publication No. 64-65124,
(Japanese Unexamined Patent Publication No. 2-88630) Also, examples of main chain polymer liquid crystals exhibiting chiral smectic C phase due to tricyclic or other bicyclic mesogens (Japanese Unexamined Patent Publication No. 1-269926)
has been reported.

However, in order to obtain the chiral smectic C phase, the liquid crystal phase shown in these examples tends to become narrower when the temperature is raised, so it is necessary to utilize the liquid crystal phase when the temperature is lowered. It was difficult to develop a stable liquid crystal phase. In addition, since the flexible spacer is an alkyl chain,
Since it is necessary to apply a relatively high voltage to the electric field response of the obtained ferroelectric polymer liquid crystal, it was not fully satisfactory when used as a polymer liquid crystal element.

The inventors of the present invention discovered a novel ferroelectric liquid crystalline polymer compound and completed the present invention by conducting intensive research based on such conventional techniques.

The purpose of the present invention is to exhibit a chiral smectic phase (S m' phase) over a wide temperature range and have a thick spontaneous polarization (
The present invention also aims to provide a novel copolymerized liquid crystalline polymer compound that can be easily formed into a thin film and a polymeric liquid crystal composition containing the copolymerized liquid crystalline compound and a low molecular weight liquid crystal.

In addition, another object of the present invention is to provide the copolymerized polymeric liquid crystalline compound and the copolymerized polymeric liquid crystalline compound and other polymers,
By using a polymer liquid crystal composition containing a polymer liquid crystal, a low molecule, and a low molecular liquid crystal in an element, it is possible to easily realize a large area, exhibit a stable and good switching effect, and The present invention aims to provide a polymer liquid crystal element that can be used as an element that applies electro-optic effects.

[Means for Solving the Problems (and Effects)] That is, the present invention has a repeating unit represented by the following general formula (I) or (n) in the main chain as a first flexible spacer, The present invention provides a copolymerized liquid crystalline polymer compound having a repeating unit represented by <m> as a second flexible spacer, and a liquid crystalline polymer composition containing the compound.

General formula (I)
In the formula, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, X≠Y is 0 or 1, and ml is 1 to 18. A carbon with a methyl group indicates an asymmetric carbon. ) General formula (n) X Y (wherein, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group,
3 is 2-5. A carbon with a methyl group indicates an asymmetric carbon. ) General formula (III) (where x and y each represent an integer from 0 to 18, Xf-Y, or x+y≦18, R is an alkyl group having 1 to 5 carbon atoms, * is an asymmetric carbon ) Furthermore, the present invention provides a substrate with a repeating unit represented by the following general formula (1) or (Ir) as a flexible spacer on the main chain, and a repeating unit represented by the general formula (m). The present invention is a polymer liquid crystal element having a film made of a copolymerized polymer liquid crystal compound having a unit as a second flexible spacer and a polymer liquid crystal composition containing the compound.

General formula (I) yx x y child CH
CH-OMCH2←0-CH-CH (wherein, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, XfYX
k is 0 or 1, and ml is 1 to I8. A carbon with a methyl group indicates an asymmetric carbon. ) General formula (n)
3 is 2-5. A carbon with a methyl group indicates an asymmetric carbon. ) General formula (m) (In the formula, x and y each represent an integer from O to 18, Xfy1 or x+y≦18, and R has a carbon number of 1 to 5.)
The alkyl groups up to * represent an asymmetric carbon. ) Hereinafter, the present invention will be explained in detail.

In the copolymerized liquid crystal compound of the present invention, the flexible spacer represented by the general formulas (I) and (II) has a molecular structure derived from optically active lactic acid. , CH3 CH3 HO (-CH2ho-CH2-CH-OH* The oxypule spacer has a polar oxygen atom directly bonded to the asymmetric carbon atom, so it has a thick spontaneous polarization (and is also slow in terms of response speed). This is preferable.Furthermore, due to its ether bond, it has high flexibility and thus has high liquid crystallinity, and has characteristics such as a wide temperature range in which it forms a liquid crystal phase.

Further, the second flexible spacer used in the present invention has a molecular structure that can further enhance the effect of the above-mentioned lactic acid-based flexible spacer, and has the following general formula (III) general formula ( The synthesis method thereof is described in Japanese Patent Application No. 62-250567.

The first optically active film used in the present invention (in the formula,
X+Y each represents an integer from O to 18, and X≠
y1 or x10y≦18, R is an alkyl group having 1 to 5 carbon atoms), and specific examples include: CH3 CH2CH2:J-□ * m=2 to I7 2H5 CH2)- □ 3～18 2H5 CH2CH(CH2'+□ * 2～17 3H7 -CH-("CH2arrow□ Thurs 3～18 3H7 CH2CH child CH2ヂ□ Thu 2～17 4H9 CH2CH child CH2n.

* 2-17 C5HI+ CH child CH2 □ 3-18 15HII -CH2CHmoCH2di□ Nei 2-17 CH3 CH3 CHmoCH2arrow □ Tree 3-18 2H5 3-16 3-16 3-16, etc. are mentioned. (* represents an asymmetric carbon.) Further, specific examples of the meso-kene group that can be used in the copolymerized liquid crystal compound of the present invention include the following.

1 < i + 4 1 x i + k < 4 1 < i + ≦ 4 1 x i + k < 4 1 < i + lc': 4 n = 1 ~ 5 i, j, k = 1 ~ 3 i + j + k = 5 1 , 3. k=l~3 i+j+≦5 i, j,=1~3 i+j+≦5 j=1~2 r,=0~2 1≦i+≦4 2≦i+j+≦5 U 10・・Next, the copolymer liquid crystalline compound of the present invention has a main ring containing repeating units represented by the following general formulas (IV) and (V). It is a copolymer containing

-eX-A I-X-B I) (r
V)% X A 2 X B 2 E”
(V) (wherein, Alr A2 represents a men-ken group and may be the same or different; B1 is a flexible spacer containing an optically active group represented by the general formula (I) or (n); B2 is a This represents a flexible spacer containing the second optically active group, and X represents a bonding group.) X represents a bonding group such as an ester bond, ether bond, or carbonate bond, but it is preferable in that it tends to exhibit a chiral smectic phase. Ester bonds are preferred.

The general formula (V
) The liquid crystal phase exhibited by a single polymeric liquid crystalline compound represented by ) is a cholesteric phase, a smectic A phase, a chiral smectic C, G, H phase, etc., but when used as a copolymerized liquid crystalline polymeric compound of the present invention, Spontaneous polarization is large,
In terms of improving the response speed, those exhibiting a chiral smectic C phase are preferred.

Furthermore, polyesters obtained by conventional polycondensation such as melt polymerization or solution polymerization from dicarboxylic acids containing mesogenic groups represented by general (IV) below and optically active diols can be easily adjusted in molecular weight and copolymerization ratio. It is particularly preferable.

(In the formula, A, , A2.B, , B2 are the same as above.) In the copolymerized liquid crystalline polymer compound of the present invention, the proportion of the flexible spacer represented by B1 in the total spacers is , is used in an amount of 1 mol % or more, preferably 10 mol % or more, and if it is less than 1 mol %, it becomes difficult to develop a chiral smectic phase.

Further, in the copolymerized liquid crystal compound of the present invention, it is also preferable to use a flexible spacer that does not contain an optically active group in order to control the type of liquid crystal phase, temperature range, optical properties, electrical properties, etc.

Specific examples of these include +CH2arrow4, child CH2γ5, and 壬CH2ji. , child CH2
Arrow 7, Child CH2 8, Child CH2 Arrow 9, Child CH2 Arrow 1°,
Straight chain alkyl group such as CH2''+-11, 1,000CH2) 12, CH2CH2CH2E' m m =
2-17CH+CH2)-□ m=3-I8-(=CH2'+mCH-ecH2),.

m=2-8, n=3-16 Any R is CH3, C2H5, C3H7, C4H9, Cs H.

Examples include alkyl groups having branches such as these, and carbon atoms in these alkyl chains may be substituted with atoms such as sulfur and silicon.

The proportion of these spacers in the total spacer is 90 mol% or less, preferably 50 mol% or less.

A, A2. B., 132 can also be used as a copolymerized polymeric liquid crystalline compound in combination of two or more of each, in order to control temperature characteristics, optical characteristics, electrical characteristics, etc.

The copolymerized liquid crystalline polymer compound obtained in this reaction is purified by a conventional method such as reprecipitation or filtration, and used as it is or after chromatographic purification if necessary.

The degree of polymerization of the copolymerized liquid crystal compound of the present invention is preferably 5 to 1000, but the weight average molecular weight (M w
) is 2,000 to 1,000,000, preferably 5,000 to 400,000.

Specific examples of the copolymerized liquid crystal compound of the present invention are listed below, but the present invention is not limited thereto.

■ (n = 1 ~ 5. m1 = 1 ~ 18. m2 = 2 ~ 17) ■ m1 = 1-18 m2 = 3-16) m 1 = 1-18 m 2 = 3-18 ) 1
-18°3~18) (i.

J l~2゜1~18゜4~15) [F] (n 1~5゜m2=3~16゜2~17゜4~18) 1-18゜m2=3~16゜4~18) (i, j, k=1~3.i+j+≦5ml
= 1~I8, m2=3~18,
m 3 = 4 to l 8 ) 1 to 18° 3 to 18 2 to 17) Next, the polymer liquid crystal composition of the present invention is composed of the copolymerized polymer liquid crystal compound and a low molecular liquid crystal, A wide range of known low-molecular liquid crystals can be used without particular limitation as long as they have good compatibility with the copolymerized liquid crystal compound.

Further, the low molecular liquid crystal may be used alone or in a mixture of two or more types.

Specific examples thereof include optically active low-molecular liquid crystals as shown in the following formulas (1) to (15), or formula (16).
Examples include non-optically active low-molecular liquid crystals as shown in (35), but the former is preferably used in terms of responsiveness.

m3-3 to 16) (All of the above are x + y = 1 or x + y + zgu-\ (below the margin), -/ CH3 CIOH210-◎-CH N-o-CH-CH COOCH2CHC2H5 * P-decyloxybencylidene-P' -Aminomethylbutylcinnamate (DOBAMBC) P-Desyloxybenzylidene-P'-Amino-2methylbutyl-α-soanocinnamate (DOBAMBCC) 92°C 104°C Crystal mA Tokichi phase C6H130-〇-CH=N- ◎-CHCH-COOC
H2CHCH3 * P-hexyloxybenzylidene=P'-aminochloropropyl lucinamate (HOBACPC) P-tetradecyloxybenzylidene-P'-amino-2methylbutyl-α-cyanocinname 1- (TDOBAMBCC)
78°C 104°C Crystal 47°C＼ mA 770°C Isokoshi phase SmC” 4.4′ Azoxycinnamic acid bismethylbutyl) ester 121°C 134°C 168°C H3 H3 C8H170ite CH=N÷CH =C-COOCH2C
HC2H5*4-.

Methyl) butyl resol cylidene methyl butyl-α-methyJ lennamate 4'-octylaniline (MBRA 8) 28°C 55°C 62°C Crystalline SmC” mA Tokichi phase H3 (2' methylbutyl) Phenyl 4' octyloxybiphenyl Carboquine rate 78°C 80°C 128,38C 76°C 88,68C 155,4°C Crystalline SmC Cholesteric phase Equilicious phase 171.0°C 174,2°C Cholesteric phase Equilicious phase Hexyloxyphenyl (2' monomethylbutyl) Biphenyl-4' carboxylate hexyl quinphenyl 4-(2' methylbutyl) Biphenyl 4' carboxylate 91, 5°C 93°C 112°C 131°C Crystalline SmC" mA Cholesteric phase Tokichitic phase 68, 8°C 80, 2°C 163, 5°C (2″ methylbutyl)phenyl(4′-methyl95.6°C 156C 187°C hexyl)hyphenyl-4′ carboxylate crystal SmC” h Tokichi phase 724°C 183°C 74, 3°C\ / 810°C SmC"←--- mA Ha Non-chiral smectic (I6) Denruphenyl (4'di(・lobenzoyloxy)benzo4' n-nonyl oxine 4-biphenylylcyanobenzoethoneh (DBIONO2 ) Tokichi phase nematic smectic C Tokichi phase nematic smectic A smectic C 4-n-hebutylphenyl (4' ditrohenzoyluoquine) benzotrans 4- (4'-octyloxybenzoyluoquine) 4' engineering) ( DB7NO2) Cyanostilbene (T8) Tokichi phase nematic smectic A Tokichi phase → Nematic → Smectic A1 → Nematic →
Smectic A2-n Octylphenyl 4-(4' nitrobenzoyloxy) Pentylphenyl-4 (4' cyanobenzoyluoquine) Benzoate (DB8NO2) Benzoate (DBsCN) Tokichi phase nematic smectic A Smectic C Tokichi phase nematic smectic A C4H9-◎ -N = CH-◎-CH=N-◎C4H
9n~nonyloxyphenyl 4- (4' nitrobenzoyloxy) N-terephthalylidenehis-4-〇-butylaniline (TBBA) Henshade (DB9ONO2) Tokichi phase nematic mectic A Smectic C Tokichi phase → nematic → smectic A → Smectic C
→Smectic G→Smectic HC C,, H++O-q→Ka-◎-Csl-12- (4' n-pentylphenyl)-5 (4'' n-pentyloxyC8H170-◎-◎-CN phenyl)pyrimidine cyano 4 ' Octyloxybiphenyl (80CB) isokitic phase → smetic A → smectic C → isotropic phase nematic smectic A smectic F → smectic G C5Hu-◎-N = CH-Q-CHN-o-05H
Telephthalylidene bispentylaniline (TBPA) Tokichi phase → Nematic → Smectic A - Smectic C
-Ethyl azobenzoate Smectic F → Smetic G → Smectic H Isotropic phase Smectic A (4' C4H90-G-CH= N-Q-csNI7-.

Petyl oquinhenonoride/) -n Octylaniline (408) C8HI70COOOC0-C8H17 etc. Smectic A → Smectic B scene n octyl 4.4' Terphenyldicarboxylate Tokichi phase→ Smectic A.

Smectic C C6H+30-〇-〇-CsH+3-n4-n-hexyl4' n~hexyloquinobiphenyln-C3H1IO-◎-◎-Co-C61 (13-n etc. auspicious phase Smectic B→ Smectic E n- to quinol-4 ' -n-pentyloquinobiphenyl-4 carboxylate (650BC) Tomoyoshi phase → Smectic A → Smectic B → Smectic E Hexyloxymphenyl 4' Octyloxybiphenyl ClOH2+04◎ -Co-C6H13-4-Carbokylate Tomoyoshi phase Nematic smectic A n ~Hexyl~4' Denruoquinobiphenyl 4~Carbodoroot Smectic C Smectic B Iso-yoshi phase Smectic A Smectic C In addition, the polymer liquid crystal composition of the present invention may contain other low molecular compounds, polymer compounds, polymer liquid crystals. It can be mixed with etc.

In other words, a suitable smectic A smectic C which does not eliminate the benzoic/ethic phase and has good compatibility can be selected and used.

For example, in combination with other As the polymeric liquid crystalline compound, as shown below can be mentioned.

(Hereinafter in the margin) 4-n-octyloquine benzoic acid isotropic phase nematic mectic C (the following formula % formula %) (hereinafter in the margin) Polymer liquid crystal composition containing the copolymerized polymeric liquid crystal compound of the present invention In this case, the content of the copolymerized liquid crystal compound is desirably 5% by weight or more, preferably 10% by weight or more. If it is less than 5% by weight, the alignment stability caused by the anisotropy of the polymeric liquid crystalline compound against pressure, thermal stimulation, etc. will decrease. In addition, when used in the form of a film, the content of the copolymerized liquid crystal compound is 30% by weight or more,
Preferably, the content is preferably 50% by weight or more from the viewpoint of shape retention.

In addition, the above-mentioned copolymerized polymer liquid crystal compound and other polymers,
It is preferable to use a combination of multiple types of polymeric liquid crystals, low molecules, or low molecular liquid crystals from the viewpoint of device design, and it is possible to control temperature characteristics, optical characteristics, electrical characteristics, etc.

In addition, a dye, a light stabilizer, a light absorber, an antioxidant, a plasticizer, etc. can be added to the polymeric liquid crystal composition according to the present invention.

Next, the polymer liquid crystal device of the present invention has a structure represented by the general formula (I) or (II) as a first flexible spacer in the front main chain on the substrate, and the structure represented by the general formula (II)
It is provided with a film made of a copolymer liquid crystal compound having the structure represented by I) as a second flexible spacer or a polymer liquid crystal composition containing the copolymer liquid crystal compound.

A specific structure of the polymer liquid crystal element of the present invention is that the copolymer liquid crystal compound or polymer liquid crystal composition is formed from a molten state into a film-like thin film, and a substrate is provided with electrodes. It can be sandwiched and glued in between. At the time of adhesion, a suitable gap agent may be provided between the film of the copolymerized liquid crystalline polymer compound or the polymeric liquid crystalline composition and the electrodes to maintain insulation between the electrodes. Further, electrodes may be provided directly on a film of a copolymerized liquid crystalline polymer compound or a liquid crystalline polymer composition without a substrate. In this case, a film-like flexible polymer liquid crystal element can be obtained.

In addition, a film of a copolymerized polymer liquid crystal compound or a polymer liquid crystal composition can be formed by dissolving the compound or composition in a solvent (chloroethane, THF, nchlorohexanone, chloroform, etc.) in a molten state. It can also be formed by

Specifically, as a method for producing a film-like membrane, a method for producing a normal plastic film, such as a melt extrusion method, a melt casting method, a calender method, or a spin cord method, can be applied.

According to the present invention, when forming a liquid crystal phase in a polymer liquid crystal element, the copolymerized polymer liquid crystal compound or polymer liquid crystal composition is made into a film-like film, and further subjected to a stretching and alignment treatment to form liquid crystal molecules. can provide high orientation.

As a method of stretching and orientation treatment, -axis stretching method etc. can be applied, but by coating on a plastic substrate as a support,
Films of a copolymerized polymer liquid crystal compound or a copolymerized polymeric liquid crystal composition may be laminated and the laminate may be subjected to stretching treatment, or after forming a cell in which a liquid crystal film is sandwiched between two substrates. , may be stretched or oriented.

Further, in the polymer liquid crystal device of the present invention, it is also possible to seal a copolymer liquid crystal compound or a polymer liquid crystal composition in a molten state at a temperature equal to or higher than the isotonic phase transition temperature between a pair of aligned substrates.

As for orientation treatment of the substrate, organic thin films such as polyimide, polyamide, polyvinyl alcohol, polysiloxane, polyimide amide, etc. are subjected to uniaxial or biaxial orientation treatment by rubbing method, SiO2゜ZnS,
Uniaxial or biaxial alignment treatment can be performed on an inorganic thin film such as MgO by a rubbing method, or SiO□.

A method using a surface obtained by oblique vapor deposition of an inorganic compound such as Sin, MgO, MgF 2 or the like is applicable.

FIG. 1 is a sectional view showing a liquid crystal cell using the alignment film.

Symbols in the figure, ■, 1' are substrates, 2, 2' are transparent electrodes, 3.
3' is an alignment film, 4 is an adhesive layer, and 5 is a polymer liquid crystal layer.

It should be noted that the alignment film shown in FIG. 1 can be omitted during the above-mentioned stretching and alignment.

Furthermore, if the substrates are held between a pair of substrates, good alignment can be obtained by shearing by slightly shifting the upper and lower substrates.

(Margin below) 〔Example〕 Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example: Diethyl-4,4'-hyphenyl dicarboxylate 3
．． 5 g of CH3 CH3 HO-CH2-CH-CH2-CH2-OH*tetra-isopropyl titanate O, OO] was added to 2.6 g and 1.5 g of two diols represented by the following formulas, respectively, and nitrogen gas was added. The temperature was raised to 150°C in an atmosphere, and the mixture was reacted by heating for 1 hour with stirring. Then, the reaction was carried out in the same manner at 180°C for 2 hours, and then the temperature was raised to 230°C over 1 hour, and the pressure inside the reaction system was reduced. The reaction was continued for another 5 hours, and the degree of vacuum was reduced to 0.
．． The polymerization reaction was terminated at 5 mmHg.

The reacted polymer was dissolved in chloroform and poured into 20 times the volume of methanol, and the resulting precipitate was filtered off and dried under reduced pressure to obtain 2.5 g of copolymer (■). Polymer ■
GPC (Körpermienoyon chromatography)
When the molecular weight distribution was measured in a chloroform solution,
The result was as follows.

Mn = 12 x 10' MW = 3. OX 10' Also, the specific optical rotation is [α] Otsu 5-+s, 2° (C=1.
05, solvent dichloroform).

NMR data (δppm (TMS)) 1.2 (d, 3H, methine) 3.7
-3.85 (m, 2H, methylene) 4.5
(m, 6H, methylene) 7.65 (
d, 4H, phenylene) 8.1 (d,
4H, phenylene) or-1, / Example 2 The same procedure as Example I was carried out, except that the diol in Example 1 was replaced with two compounds (2.5 g, 1.2 g) represented by the following formulas. , 2.8 g of copolymer (■) was obtained.

CH3 2H5 HO-CH2-CH-CH2-CH2-oH* The measurement results of the molecular weight and specific optical rotation of polymer (1) were as follows.

Mn=1.3X10''MW=4.0X10' [(1]F=+4.0° (C=1.02, solvent: chloroform) Example 3 Copolymer polymer obtained in Examples 1 and 2 Using liquid crystal compounds (1) and (2), respective films were obtained in the following manner.

The above compound was made into a 20wt% solution in dichloroethane, and the film was cast on a glass plate and dried at 100°C.
The film was uniaxially stretched to 200% to obtain a uniaxially oriented film having a thickness of 10 μm.

This stretched film was then coated with an ITO transparent electrode (thickness: 130 mm).
A polyimide alignment film with a thickness of 600 people was formed on top of a polyimide alignment film with a thickness of 600 people. After being slowly cooled to the chiral smectic C phase (SmC* phase), S m
When a voltage of 20V/μm is applied to the C* phase, the distance is approximately 80m.
The response was 5ec (■) and 90m5ec (■).

Example 4 When a compatibility test was conducted between the polymeric liquid crystalline compound obtained in Example 1 and the low-molecular liquid crystal (Technique 4), the same phase as the low-molecular liquid crystal (14) was confirmed over a wide composition range. . Table 1 shows the phase transition temperatures of various blended polymer liquid crystal compositions of (1) and (14).

As shown in Table 1, when an electric field of 20 V/μm was applied to the SmC* phase, inversion of molecules in response to the electric field was observed. The speed of the electric field response is shown in Table 2.

Furthermore, as shown in Fig. 2, when the liquid crystal cell 8 is sandwiched between two orthogonal polarizing plates 6 and 6' and an electric field is applied in the same manner as above, the brightness and darkness of the transmitted light can be observed in response to the electric field. It was done. 7
, 7' indicate the polarization direction of the polarizing plates 6, 6'.

Table 2 Example 5 The polymer liquid crystal composition shown in Example 4 (composition ratio of ■/(14) 1/4.1/1) was applied to a glass substrate 1. A pair of glass substrates on which a solid ITO transparent electrode (1300 mm thick) 2.2' is provided on 1', and a rubbed polyimide alignment film 3, 3' with a thickness of 600 mm formed thereon. The Tokichi phase was sealed into a liquid crystal cell formed by adhering with adhesive layer 4 so that the thickness between them was 10 μm. Observation under a polarizing microscope Example 6 The diol in Example 1 was replaced with two compounds (molar ratio 1:1) represented by the following formula, and the same procedure as in Example 1 was carried out to obtain a compound represented by the following formula @. A copolymer was obtained.

CH3 HO-eCH2←0-CH2-CH-OH* CH3 Example 7 In the same manner as in Example 1, except that nool in Example 1 was replaced with two types of compounds represented by the following formulas (molar ratio 1-1). hand,
A copolymer represented by the following formula (2) was obtained.

CH3CH3 CH3 When a voltage of 20 v/μm was applied to a polymer liquid crystal device prepared in the same manner as in Example 3 in chiral smectic C phase, the response speed was 80 m5ec.

When a voltage of ±20 V/μm was applied to the polymer liquid crystal device prepared in the same manner as in Example 3 in the chiral smectic C phase, the response speed was 60 m5ec.

Example 8 3.0 g of diethyl-4,4"-terphenylnocarpoquinate was replaced with 3.1 g and 1.8 g of two types of diols represented by the following formulas, and the initial temperature was set to 2000 g.
C, CH except that the final temperature was changed to 250 °C.
3 When a voltage of ±20 V/μm was applied to a polymer liquid crystal device prepared in the same manner as in Example 3 in chiral smectic C phase, the response speed was 50 m5ec.

(The following is a blank space) CH3 HO+:CH2-)ycH-fEcH2i0H* In the same manner as in Example 1, a copolymer represented by the following formula [F] was obtained.

...[F] Example 9 In the same manner as in Example 1, the diol of Example 8 was replaced with two compounds represented by the following formula (molar ratio 1:1), and the diol represented by the following formula [F] was prepared. A copolymer was obtained.

CH3 HO (: CH2i 0-CH2-C,H-OHCH3 Example 1O The diol in Example 8 was replaced with two compounds represented by the following formula (molar ratio l 1), and the same procedure as in Example 1 was carried out. A copolymer represented by the following formula ◎ was obtained.

CH3CH3 HO-CH2C1-To÷CH2虻0CHCH2-OH
* * CH3 When a voltage of ±20 V/μm was applied to a polymer liquid crystal device prepared in the same manner as in Example 3 in chiral smectic C phase, the response speed was 50 m sec.

When a voltage of ±20 V and 7 μm was applied in the chiral smectic C phase to a polymer liquid crystal device prepared in the same manner as in Example 3, the response speed was 50 m sec.

Example 11 A copolymer represented by the following formula (■) was obtained in the same manner as in Example 1 except that 7-ol in Example 8 was replaced with two compounds represented by the following formula (molar ratio 1:1). Ta.

CH3 HO (CH2-Oj CH2-C, H-OH3H7 Example 12 The diol in Example 1 was replaced with two compounds represented by the following formulas (molar ratio 1:1), and the same procedure as in Example 1 was carried out. A copolymer represented by the following formula (2) was obtained.

CH3 HO C■ (2 loaves 0-CH2-CH-OH* CH3 Response speed when a voltage of ±20 V/μm was applied in the chiral smectic C phase to a polymer liquid crystal element prepared in the same manner as in Example 3. was 50m5ec.

...■ When a voltage of ±20 V/μm was applied to a polymer liquid crystal device prepared in the same manner as in Example 3 in chiral smectic C phase, the response speed was 40 m sec.

Example 13 A copolymer represented by the following formula was obtained in the same manner as in Example except that the polymer in Example 8 was replaced with two compounds (molar ratio 11) represented by the following formula.

CH.

HO-ecH2-0ga CH2-1-OHC3H'r HO+CH2→7 CH+ CH2 piece OH* A voltage of ±20 μm/μm was applied to the polymer liquid crystal element prepared in the same manner as in Example 3 in the chiral smectic C phase. The response speed was 50 m5ec.

〔Effect of the invention〕

As explained above, the present invention provides a novel copolymer liquid crystalline compound that exhibits a chiral smectic phase (Sm* phase) over a wide temperature range and is easy to form into a thin film. A polymer liquid crystal composition containing a molecular liquid crystal compound and a low molecular liquid crystal can be easily obtained.

Further, by using various copolymerized polymeric liquid crystal compounds, it becomes possible to diversify control of the liquid crystal temperature range, control of electrical characteristics, etc.

Furthermore, by applying these copolymerized polymer liquid crystal compounds and polymer liquid crystal compositions to liquid crystal elements, it is possible to easily realize a large area, and by applying an electric field in the SmC* phase, stable and good performance can be achieved. It is possible to obtain a polymer liquid crystal device that exhibits excellent switching effects and can be used as a device applying various electro-optic effects.

Furthermore, by obtaining a polymer liquid crystal composition containing the copolymer liquid crystal compound of the present invention, the responsiveness is improved compared to the copolymer liquid crystal compound used alone, so that it can be used as a film element. It can be made more useful in terms of functionality when used.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing a liquid crystal cell, and FIG. 2 is a perspective view showing a liquid crystal cell with a polarizing plate. 1, 1'...Substrate 2,2'...Transparent electrode 3.3'...Alignment film 4...Adhesive layer
・Polymer liquid crystal layer 6.6' ... Polarizing plate 77'
...Polarization direction 8...Liquid crystal cell No. 10 Figure 2 Teitomerine Hosho (self-proposal) Target of amendment October 29, 1990 Specification 6゜Contents of amendment 1, Description of incident Page 63, lines 7 and 8, 1990 patent application 7 Title of the invention: Copolymerized polymeric liquid crystal compound, and polymeric liquid crystal element.Relationship with the case concerning those who amend the liquid crystal composition.

Claims (4)

[Claims] (1) Copolymerization characterized by having a first repeating unit represented by the following general formula (I) or (II) and a second repeating unit represented by the general formula (III) in the main chain Polymer liquid crystal compound. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, X≠Y, k is 0 or 1, m1 is 1-18 (The carbon with a methyl group indicates an asymmetric carbon.) General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (In the formula, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, X≠Y, k is 0 or 1, m2 is 2 to 10, m
3 is 2-5. A carbon with a methyl group indicates an asymmetric carbon. ) General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, x and y each represent an integer from 0 to 18, x≠y, or x+y≦18, and R has 1 to 5 carbon atoms. (* represents an asymmetric carbon.) (2) A polymeric liquid crystal device comprising a film made of the copolymerized polymeric liquid crystal compound according to claim 1 on a substrate. (3) A polymer liquid crystal composition containing the copolymer liquid crystal compound according to claim 1 and at least one compound among other polymers, polymer liquid crystals, low molecules, and low molecular liquid crystals. thing. (4) A polymer liquid crystal device comprising a film made of the polymer liquid crystal composition according to claim 3 on a substrate.