JPH04164920A - Copolymeric liquid crystal compound, liquid crystal composition containing same, and polymeric liquid crystal element - Google Patents

Abstract

PURPOSE:To obtain the title compound which can develop a chiral smectic phase over a wide temperature range and can be easily formed into a thin film or a film by constituting the main chain to have at least two kinds of specified flexible spacers. CONSTITUTION:For example, diethyl 4,4'-biphenyldicarboxylate is reacted with a diol of formula I or II in the presence of tetraisobutyl titanate to obtain the title compound wherein the main chain has at least two kinds of spacers selected from among flexible spacers of structures of formula III (wherein x and y are each 0-18; xnot equal to y; x+y<=18; R is 1-5C alkyl; and an asterished carbon atom is an asymmetric carbon atom) and desirably the main chain comprises repeating units of formulas IV-V (wherein A1 and A2 are each a mesogenic group; B1 is an optically active flexible spacer of formula III, B2 is an optically active flexible spacer of formula III other than B1; and X is an ester bond, an ether bond or a carbonate bond) or repeating units of formula VI (wherein 0<z<1).

Description

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

[Prior Art] 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-weight liquid crystals.

(2) A good orientation state can be obtained by performing an orientation 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.

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

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

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; Japanese Patent Publication No. 63-99204
(Japanese Patent Application Laid-Open No. 63-161005).

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 make a film with a large area when it is contained therein.

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 having an optically active group in the main chain has been reported. (“The 14th LCD Conference Lecture Proceedings” 5
pp. 6-57, September 1988, JP-A-64-65124
(Japanese Patent Application Laid-open No. 2-88630, etc.) Also, examples of main chain polymer liquid crystals exhibiting a chiral smectic C phase due to tricyclic or other two-system mesogens (Japanese Patent Application Laid-Open No.
-269926) has been reported.

However, in order to obtain the chiral smectic C phase, the polymer liquid crystals shown in these examples are monotropic, which means that when the temperature is raised, the temperature tends to become narrow, so it is necessary to utilize the liquid crystal phase when the temperature is lowered. It is a polymeric liquid crystal with a characteristic of In terms of control, the range of choices was narrow and the results were not completely satisfactory.

The inventors of the present invention have conducted extensive research based on such conventional techniques, and have discovered a novel ferroelectric copolymerized liquid crystal compound and completed the present invention.

The object of the present invention is to provide a novel copolymerized liquid crystalline polymer compound that exhibits a chiral smectic phase (Sm'' phase) over a wide temperature range and that can be easily formed into a thin film. It is an object of the present invention to provide a polymer liquid crystal composition containing.

Another object of the present invention is to combine the copolymerized liquid crystalline polymer compound and at least one compound of the copolymerized liquid crystalline compound and other polymeric compounds, polymeric liquid crystals, low molecular weight compounds, or low molecular liquid crystals. By using a polymer liquid crystal composition containing , it is possible to easily realize a large area, and it also shows stable and good switching effects, and can be used as a device that applies various electro-optic effects. The purpose of this invention is to provide a polymer liquid crystal device that is capable of

[Means for Solving the Problems] That is, the present invention is characterized in that the main chain has at least two types selected from the group of flexible spacers having a structure represented by the following general formula (I). It is a copolymerized polymer liquid crystal compound.

General formula (I) ■ HCHa h-CHCHzhy- (in the formula, x + y each represent an integer of 0N18,
x#y, xy≦18, R represents an alkyl group having 1 to 5 carbon atoms, and * represents an asymmetric carbon atom. ) The present invention also provides a copolymer liquid crystalline compound having a main chain having at least two types selected from the group of flexible spacers having a structure represented by the general formula (I), and another polymer. A polymer liquid crystal composition characterized by containing at least one compound selected from a compound, a polymer liquid crystal, a low-molecular compound, and a low-molecular liquid crystal.

Furthermore, the present invention provides a method for disposing on a substrate at least one of the copolymerized liquid crystalline compound or the copolymerized liquid crystalline compound, and at least one of other polymeric compounds, polymeric liquid crystals, low molecular weight compounds, and low molecular liquid crystals. This is a polymer liquid crystal element characterized by having a film made of a polymer liquid crystal composition containing one kind of compound.

The present invention will be explained in detail below.

The copolymerized liquid crystal compound of the present invention is characterized in that the main chain has at least two types selected from the group of flexible spacers having a structure represented by the following general formula (I).

General formula (I) ■ HCH*hr-CHCHx )-r- In the general formula (I), each of XT y is 0 to 1
It represents an integer of 8, preferably an integer of 0 to 12. However, X≠y and xyy≦18.

Further, R represents an alkyl group having 1 to 5 carbon atoms, and R represents an asymmetric carbon atom.

Next, specific examples of the flexible spacer represented by the general formula (I) used in the copolymerized liquid crystalline polymer compound of the present invention include the following.

Further, specific examples of mesogen groups that can be used in the copolymerized liquid crystalline polymer compound of the present invention include the following.

→◎廿 n=1-5 i+ j+ k=t-3 i+j+≦5 i, j,=1-3 i+j+≦5 i, j+ k=1-3 i+j+≦5 j=1-2 i , k=o~2 1 ≦ i+k ≦4 i, k=o~2 1 ≦i+ ≦4 j=1~2 i, k=o~2 1 ≦ i+k ≦4 i, k=o~2 1 ≦ i+k≦4 j=1-42 i, k=o~2 1≦i+k≦4 j=1~3 i, k=o~2 1≦i+k≦4 j=1~2 i, k=o~2 1 ≦i+k≦4 i, j=o~3 2≦i+j≦4 i+ j=0~3 2≦i +j≦4 i, j=l~2 11J= 1~2 11J= 1~2 i−+ J” 1 to 2 υ i, j=l to 3 i, k=1 to 2 j =0 to 2 i, k=o to 2 j=1 to 2 2≦i+j+≦5 i, j=1 to 2 i, k=o~2 j=1~2 2≦i + j + k=5 j, ni=1~2 ■ = O~2 i=1~3 i=1~3 υ i=1~2 i=1 ~2 Next, the copolymerized liquid crystal compound of the present invention is a copolymer whose main chain contains repeating units represented by the following general formula (n) and general formula (I[l). Preferably.

1←X-A, -X-8,← (U)-←X
Aa-X-Ba→-(I[[) (wherein, AIv Ax
represent mesogenic groups and may be the same or different. B1 is a flexible spacer containing an optically active group represented by the above general formula (I), B2 is the above general formula (1)
represents a flexible spacer containing an optically active group different from B1, and X represents a bonding group of an ester bond, an ether bond, or a carbonate bond. A bonding group such as a bond, an ether bond, or a carbonate bond is used, and an ester bond is preferred because it tends to exhibit a chiral smectic phase.

The liquid crystal phase exhibited by a single polymeric liquid crystal compound represented by the above general formula (n) or (m) is a cholesteric phase, a smectic A phase, a chiral smectic C, G, H phase, etc. When used as a polymerized polymeric liquid crystalline compound, those exhibiting a chiral smectic C phase are preferred because they have large spontaneous polarization and improve response speed.

The content ratio of the repeating units represented by the general formula (I[) and general formula (III) that constitute the main chain of the copolymerized liquid crystalline polymer compound of the present invention is 10% or more, particularly 50% of the total repeating units. The above is preferable.

Further, the copolymerized liquid crystalline polymer compound of the present invention is preferably a copolymer whose main chain contains a repeating unit represented by the following general formula (IV).

(In the formula, AI, A2.13., and L are the same as above. Z is a real number of O<Z<1.) In particular, the polyester represented by the general formula (rV) is is obtained from a mesogen group-containing dicarboxylic acid and an optically active diol by ordinary polycondensation such as melt polymerization or solution polymerization, and this polyester is particularly preferred because the molecular weight and copolymerization ratio can be easily adjusted.

In the copolymerized polymer liquid crystal compound of the present invention, B+.

The molar ratio of the flexible spacer denoted by B2 (B+
/Bt) is 1/99 to 99/1, preferably 10/9
By using it in the range of 0 to 90/10, the temperature of the liquid crystal phase is expanded even when the temperature is increased, and the thermal stability of the liquid crystal phase is improved.

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 are →CHz+r-, -+CHz÷", →CHz÷", →C
H2+y.

→CH=+T, -+CH2+v-, -+CHs+ry
, → Published by CHa.

Straight chain alkyl group such as -+CFI 7, -CHxCH(CH2+f-m = 2~17■ -CH-+CH2+T-m=3-18 1+CH1+T-CH(CH3h-m=2-8n=3-
16 (In the above formula, each R is -CHs, -CJ'-,
-CsHt, -C4H-, (represents 5H31)
Examples include alkyl groups having branches such as the above, and carbon atoms in these alkyl group chains may be substituted with atoms such as sulfur and silicon.

The proportion of these flexible spacers not containing an optically active group in the total spacers is 90 mol% or less, preferably 50 mol% or less.

A8 above. Aa, B1. It is also possible to use a combination of two or more types of Bz as a copolymerized polymer liquid crystal compound in order to control the temperature characteristics, optical characteristics, and electrical characteristics.

The copolymerized liquid crystalline compound of the present invention can be obtained by a reaction such as condensation polymerization, but the obtained copolymerized liquid crystalline compound can be purified by a conventional method such as reprecipitation or filtration, and can be used as it is or It is used after chromatographic purification if necessary.

The degree of polymerization of the copolymerized liquid crystal compound of the present invention is preferably 5 to 1000, and the weight average molecular weight (!W
, ) is from 2,000 to 1,000,000, preferably from 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=2~1B, m2=3~1
4) (B) (i, to = o ~ 2. j: l ~ 2, 1≦i+≦4)
(ml=2~16. m2=3~16) (llJ=o
~3. 2≦i+j≦4) (ml=4-14.m
2 = 2-16) (D) (i, j = 1-2. ml ≦3-17. m2 =
3~Is) (i, j, = 1~3. i, j, ≦
5) (m2=3~16.m2=3~16.m3
= 4-18) CG) (i, = 0-2. j = 1-2.1≦i+≦4)
(m2=3~16. m2=3~14. m3=2
~17) Next, the polymer liquid crystal composition of the present invention comprises the copolymerized polymer liquid crystal compound and at least one compound selected from other polymer compounds, polymer liquid crystals, low molecular compounds, and low molecular liquid crystals. It consists of something containing. As the low-molecular liquid crystal, a wide range of known low-molecular liquid crystals can be used without particular limitation as long as it has good compatibility with the copolymerized polymeric 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 from the viewpoint of responsiveness.

P-decyloxybenzylidene-P'-amino-2-methylbutylcinnamate CDOBAMBG) P-hexyloxybenzylidene-P'-amino-2-chloropropylcinnamate (HOBACPC) P-decyloxybenzylidene-P'-amino -2-Methylbutyl-α-cyanocinnamate (DOBAMBCC) P-Tetradecyloxybenzylidene-P'-amino-2-methylbutyl-α-cyanocinnamate (TDOBAMBCC) P-
Octyloxybenzylidene-P'-amino-2-methylbutyl-α-chlorocinnamate (OOBAMBC
C) P-cutyloxybenzylidene-P'-amino-
2-Methylbutyl-a-methylcinnamate (2-methylbutyl) ester -4'-octylaniline (MBRA 8) Oxybiphenyl-4-carboxylate 4-hexyloxyphenyl-4-(2''-methylbutyl)biphenyl-4 ′
-carboxylate 4-cutyloxyphenyl-4-
(2″-Methylbutyl)biphenyl-4′-carboxylate 4-hexyloxyphenyl-4-(2″-methylbutyl)biphenyl-4′-carboxylate91.
5℃ 93℃ 112℃ 131℃−n → → → Crystal SmC” SmA Cholesteric phase Isotropic phase '-n-nonyloxy-4-biphenylyl-4-cyanobenzoate, etc., six phases → nematic → smectic C 4-n-hebutylphenyl-4-(4'-nitrobenzoyloxy)benzoate (DB, NO□), etc. six phases →
Nematic → Smectic A 4-n-year-old cutylphenyl-4-(4'-nitrobenzoyloxy)benzoate (DB, NO□), etc. →
Nematic glass metallic A + smectic C4-n-
Decylphenyl-4-(4'-nitrobenzoyloxy)benzoate (DB, oNO
4″-octyloxybenzoyloxy)-4′ to cyanostilbene (T8) etc. → Nematic clasmectic A1 → Nematic clasmectic A2 4-n-Pentylphenyl-4-(4′-cyanobenzoyloxy)benzoate (DB, CN) etc. 6 phases → Nematic → Smectic A 4-n-nonyloxyphenyl-4-(4'-nitrobenzoyloxy)benzoate (DB, ONO,) etc. etc. Phase → Nematic class Metic A + Smectic C2-
(4′-n-pentylphenyl)-5-(4″-〇-pentyloxyphenyl)pyrimidine, etc. Six phases → Smectic A → Smectic C → Smectic F → Smectic G CaH+ , +N=co+u=N+, n, □Terephthalylidene -bis-4-n-pentylaniline (TBPA)
) Tokichi phase → nematic → smectic A → smectic C
→ Smectic F + Smectic G → Smectic HC
4H, +N=CH+H=N+48゜N-terephthalylidene-bis-4-n-butyfuranione (TBBA) Six phases → nematic ÷ smectic A + smectic C → smectic G + smectic H c, H,, o (C Eaves@ToN 4-cyano-4'-〇-octyloxybiphenyl (8
0CB) Tomoyoshi phase → Nematic → Smectic A ethyl-4-azobenzoate Isotropic phase → Smectic A n-CJeO+cH:N+aH+t-nN-(4'-n
-butyloxybenzylidene) -4-n-octylaniline (408) Tokichi phase → smectic A → aH+ in smectic Bn-
J $J (+z-n 4-n-hexyl-4'-n-hexyloxybiphenyl etc. smectic B+smectic En-cgtb
to + constant BO + CaH + s-n4-n-hexyloxyphenyl-4'-n-octyloxybiphenyl-4
- Carboxylate, etc., six-phase lanematic class Metic A + Smectic C → Smectic B Di-n-octyl-4,4'-terphenyldicarboxylate, etc. Bi-phase → Smetic A → Smectic Cn-CsL
+O$0-CsH+ s-nn-hexyl-4'-〇-
Pentyloxybiphenyl-4-carboxylate (6
508G) etc. 6-phase → Smectic A → Smectic B →
Smectic E υ 4-n-hexyl-4'-n-decyloxybiphenyl-4-carboxylate etc. Auspicious phase → Smectic A → Smectic CC1゜H,,
0+CO+CJ+5 4-n-hebutyloxyphenyl-4-n-decyloxybenzoate, etc. six phases → Smectic A → Smectic CC8H17
0H Shazawa-ioH 4-n-octyloxybenzoic acid, etc., six phases → nematic → smectic Molecular compounds, polymer liquid crystals, etc. can be mixed.

That is, it is possible to appropriately select and use a material that does not eliminate the chiral smectic phase and has good compatibility. For example, other polymeric liquid crystalline compounds to be combined include those shown below.

(In the following formulas (36) to (48), 14≧p≧1.

) (14≧n≧1.nap) In the polymer liquid crystal composition containing the copolymerized liquid crystalline compound of the present invention, the content of the copolymerized polymeric liquid crystalline compound is 5% by weight or more, preferably 10% by weight or more. It is desirable that the amount is at least % by weight. 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.

Note that it is preferable to use a combination of the copolymerized polymeric liquid crystal compound and other polymeric compounds, polymeric liquid crystals, low-molecular compounds, or low-molecular liquid crystals from the standpoint of device design and temperature characteristics.・Optical properties, electrical properties, etc. can be controlled.

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 substrate having at least two or more types of fluxiple spacers whose main chain has a structure represented by the general formula (I) above. A thin film made of a polymer liquid crystal composition containing a polymer liquid crystal compound or a copolymer liquid crystal compound is provided.

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. Also, directly without a board,
Electrodes may be provided on a film of a copolymerized polymer liquid crystal compound or a polymer liquid crystal composition. In this case, a film-like flexible polymer liquid crystal element can be obtained.

In addition, the film of the copolymerized liquid crystalline polymer compound or the polymeric liquid crystal composition may be prepared by dissolving the copolymerized polymeric liquid crystalline compound or the polymeric liquid crystalline composition in a solvent such as dichloroethane, THF,
It can also be formed by dissolving it in cyclohexanone, chloroform, etc. to form a film in a molten state.

Specifically, as a method for producing a film-like membrane, a method for producing a usual 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 a liquid crystal molecule. 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 copolymerized polymeric liquid crystalline compounds or polymeric liquid crystalline compositions may be laminated and the entire laminate may be stretched, or a cell may be formed in which a liquid crystal film is sandwiched between two substrates, and then stretched. It may be oriented.

Furthermore, in the polymer liquid crystal element of the present invention, it is also possible to encapsulate a copolymer liquid crystal compound or a polymer liquid crystal composition in a molten state at a temperature equal to or higher than the six 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, SiO□, ZnS, M.
Applying uniaxial or biaxial alignment treatment to an inorganic thin film such as gO by a rubbing method, 5i02. MgO, MgF
A method using a surface obtained by oblique vapor deposition of an inorganic compound such as a is applicable.

Furthermore, as long as it is held between a pair of substrates, good alignment can be obtained by shearing by slightly shifting the upper and lower substrates.

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

Example 1 Diethyl-4,4'-biphenyl dilupochelate 3,
Og, 1 each of two types of diols represented by the following formulas
．． 5g% to 1.9g, ? H・HO−CH2−CH−CH2−CH2−0)1?1・H(HCH6+−CH−+CH2−←yOH Tetrain butyl titanate 0.0OL5g was added and heated to 150°C under nitrogen gas atmosphere. The reaction was carried out by heating for 1 hour with stirring, then the same reaction was carried out at 180°C for 2 hours, the temperature was raised to 230°C over 1 hour, the pressure inside the reaction system was reduced, and the reaction was continued for an additional 5 hours, and the pressure was reduced. degree 0.5 mmH
The polymerization reaction was completed at 1 g.

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 (gel permeation chromatography)
When the molecular weight distribution was measured in a chloroform solution,
The result was as follows.

M n = 9.3 x 10'Y? i, =2.5
' (c = 1.1, solvent: chloroform).

NMR data (δppm (TMSI) 1.1
(d, methyl) 1.7-2.2 (m, methine/methylene) 4.2-4.6 (m, methylene) 7.65 (d, phenylene) 8
．． 1 (d, phenylene) DSC measurement,
As a result of polarizing microscope observation, the liquid crystal phase transition point was as follows.

(cryst indicates a crystalline phase, Sac" indicates a chiral smectic phase, SmA indicates a smectic A phase, and Iso indicates six phases such as Example 1 except that 1.7g, 1.3g)
In the same manner as above, 1.8 g of copolymer (@) was obtained.

C,H.

HO-CH, -CH-CH, -CH, -OH? 1゛HO-CH-+-cH2-←rOH The measurement results of the molecular weight and specific optical rotation of Polymer ① were as follows.

Mn=g, s xlo" Rw = 2.3 Films were obtained using the polymerized liquid crystal compounds (1) and (2) in the following manner.

The above copolymerized polymeric liquid crystal compound was mixed with 20% of dichloroethane.
A wt% solution was cast on a glass plate and the dried film was uniaxially stretched to 200% at 100°C to a thickness of 10p.
A uniaxially oriented film of m was obtained.

This stretched film was used as a solid ITO transparent electrode (thickness: 130 mm)
A polyimide alignment film with a thickness of 600 people was formed on a polyimide alignment film with a thickness of 600 people. After cooling slowly to the chiral smectic C phase (SmC' phase), Sm
When a voltage of 2 V/pm is applied to the C” phase, 60 m5e
c (■) and 100m5ec (■).

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

Table 1 Example 5 The polymer liquid crystal composition shown in Example 4 (composition ratio of ■/(14) 1/4, 1/1) was prepared as shown in FIG.
A solid ITO transparent electrode (thickness: 1,300 mm) 2.2' is provided on the glass substrates 1 and 1', and a thick ITO electrode (Bo.

A liquid crystal cell was formed by adhering a pair of glass substrates on which human-rubbed polyimide alignment films 3 and 3' were formed with an adhesive layer 4 so that the thickness between the substrates was 101, and the six phases were sealed in the liquid crystal cell. When an electric field of ±20 V/pm was applied to the SmC'' phase while observing it under a polarizing microscope, inversion of the 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 plate 6°6'.

Table 2 Example 6 A copolymer represented by the following formula O was produced in the same manner as in Example 1 except that the diol in Example 1 was replaced with two compounds represented by the following formula (molar ratio 1:1). I got it.

? 1・ Ho-+CH--tr(H70=-hr OHC, H.

HO-CH-+-CHa+rOH A polymer liquid crystal element prepared in the same manner as in Example 3 was
The upper 20V/p speed in the C'' phase was 100m5ec.

Example 7 A copolymer represented by the following formula Obtained union.

? H・HO−+C H2 City 1H Bo H2 → 70H Sha HO − (”) I(−C)l , −h− OH?1・HO− CHffi−CH−(−C82day 70H...
■ A polymer liquid crystal element prepared in the same manner as in Example 3 was
The upper 20V/p speed in the C'' phase was 80m5ec.

Example 8 Diethyl-4.4″-terphenyl dicarboxylate)
3.0g, two types of diols represented by the following formulas, 3.1g and 1.8g respectively, and the initial temperature was 200℃
Example 1 except that the final temperature was changed to 250°C.
In the same manner as above, a copolymer represented by the following formula (2) was obtained.

? H・ HO-fCH aout (+CH a-←OHsH- 8 M C 1.→H) H2-←OH A polymer liquid crystal element prepared in the same manner as in Example 3 was coated with SmC'' phase.
The response speed when applying a voltage of V/gm is 100m5e
It was c.

[Effects of the Invention] As explained above, according to the present invention, a novel copolymer liquid crystalline polymer that exhibits a thermally stable chiral smectic phase (Sm'' phase) and is easy to form into a thin film and film. A polymer liquid crystal composition containing the compound and the copolymerized polymer liquid crystal compound 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 the copolymerized polymer liquid crystal compound and polymer liquid crystal composition to a liquid crystal element, it is possible to easily realize a large area, and by applying an electric field in the 5OIG'' phase, a stable and good It is possible to obtain a polymer liquid crystal element that exhibits a switching effect and can be used as an element applying various electro-optic effects.

In addition, by using a polymer liquid crystal composition containing the copolymer liquid crystal compound of the present invention, the responsiveness is improved compared to when the copolymer liquid crystal compound is used alone, so that film formation is possible. It is possible to make the device more capable in terms of functionality when used as a device with a built-in device.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing a liquid crystal cell used in Example 5, and FIG. 2 is a perspective view showing a liquid crystal cell with a polarizing plate used in Example 5. 1.1'...Substrate 2.2'...Transparent electrode 3.3'...Alignment film 4...Adhesive layer 5...Polymer liquid crystal layer 6.6'...Polarizing plate 7 .7'...Polarization direction 8...Liquid crystal cell

Claims (6)

[Claims] (1) A copolymeric liquid crystalline compound characterized in that the main chain has at least two types selected from the group of flexible spacers having a structure represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, x and y each represent an integer from 0 to 18,
≠y, x+y≦18, R represents an alkyl group having 1 to 5 carbon atoms, and * represents an asymmetric carbon atom. ) (2) The copolymer liquid crystal compound according to claim 1, wherein the copolymerized polymer liquid crystal compound is a copolymer whose main chain contains repeating units represented by the following general formulas (II) and (III). Polymerized polymer liquid crystal compound. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, A_1 and A_2 represent mesogen groups and may be the same or different. B_1 is The general formula ( I
), B_2 is a flexible spacer represented by the above general formula (I) and contains an optically active group different from B_1, and X is an ester bond, an ether bond, or a carbonate bond. Indicates the group. ) (3) The copolymer liquid crystal compound according to claim 2, wherein the copolymer liquid crystal compound is a copolymer whose main chain contains a repeating unit represented by the following general formula (IV). . ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, A_1 and A_2 represent mesogen groups and may be the same or different. B_1 is the general formula (I
B_2 is a flexible spacer containing an optically active group represented by the above general formula (I) and containing an optically active group different from B_1. Z represents a real number satisfying 0<Z<1. ) (4) A polymeric liquid crystal element comprising a film made of the copolymerized liquid crystalline compound according to claim 1, 2 or 3 on a substrate. (5) Containing the copolymerized liquid crystal compound according to claim 1, 2, or 3 and at least one compound selected from other polymer compounds, polymer liquid crystals, low molecular compounds, and low molecular liquid crystals. A polymer liquid crystal composition characterized by: (6) A polymer liquid crystal device comprising a film made of the polymer liquid crystal composition according to claim 5 on a substrate.