JPH03237128A - Polymer liquid crystal compound, liquid crystal composition containing same compound and liquid crystal element - Google Patents

Abstract

PURPOSE:To obtain the title compound showing a chiral smectic phase in a wide temperature range, being readily formed into a thin film and film, easily made into large area, comprising a specific site in a repeating unit. CONSTITUTION:The objective compound containing a site shown by the formula X1-A-X2-B [A is bicyclic mesogen; B is group shown by formula I (X is H or methyl; Y is H or methyl; Xnot equal to Y; k is 0 or 1 ; m is 1-18) or group shown by formula II (m2 is 2-10; m3 is 2-5; k is 0 or 1]; X1 and X2 contains one of ester bond, ether bond and carbonate bond] in a repeating unit.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a novel liquid crystalline polymeric compound having an optically active group in the polymer main chain, a liquid crystalline composition containing the liquid crystalline polymeric compound, and a liquid crystalline composition containing the liquid crystalline polymeric compound. This invention relates to a liquid crystal element using.

[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.

■ 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 using low-molecular liquid crystals.

[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 spontaneous polarization 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 chain).

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; 63-99204, 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 has an optically active group in the main chain has been reported.

(“Proceedings of the 14th LCD Symposium” pp. 56-57, 1
However, what is shown in this example is a monotropic polymeric liquid crystal that assumes a chiral smectic phase only when the temperature drops, making it difficult to develop a stable liquid crystal phase. Ta. In addition, in order to use specific optically active groups, temperature characteristics, optical characteristics,
The range of choices was narrow in terms of control of electrical properties, etc., and the electrical properties were not fully satisfactory.

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 object of the present invention is to provide a novel liquid crystalline polymer compound, a copolymerized liquid crystalline compound, and a copolymerized liquid crystalline compound that exhibits a chiral smectic phase (S m' phase) over a wide temperature range and that can be easily formed into a thin film. The present invention aims to provide a liquid crystal composition containing a liquid crystal compound and other low-molecular liquid crystals.

Further, another object of the present invention is to provide the polymeric liquid crystal compound,
A liquid crystal composition containing a copolymerized polymer liquid crystal compound and the polymer liquid crystal compound and other polymer compounds (including polymer liquid crystals) or low molecular compounds (including low molecular liquid crystals) is used as an element. By using this method, we aim to provide a liquid crystal element that can easily realize a large area, exhibits stable and good switching effects, and can be used as an element that applies various electro-optic effects. be.

[Means to solve the problem]

That is, the present invention provides a polymer liquid crystal compound characterized by having a moiety represented by the following general formula (M) in a repeating unit, a liquid crystal composition having the polymer liquid crystal compound,
The present invention also provides a liquid crystal element.

General formula (M) X, -A-X2-B [wherein A is a bicyclic mesogen group, B is (wherein,
-f-Yl is O or 1, and ml is 1-18. ) or (wherein, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, X+YSm2 is 2-101m3 is 2-5, k
is 0 or 1. ) represents a group represented by

X and x2 each represent a group containing one of an ester bond, an ether bond, and a carbonate bond, and may be the same or different. More specifically, a polymeric liquid crystalline compound whose main chain consists of a repeating unit represented by the following general formula (1), or a copolymerized polymeric liquid crystalline compound represented by the general formula (II), and a polymeric liquid crystalline compound containing them. This is a polymeric liquid crystal composition.

General formula (1) % formula %) () [wherein A is a bicyclic mesogen group, B is (wherein, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group,
≠Y, 0 or 1, ml is 1-18. ) or (wherein, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, X≠Y, m2 is 2 to 101 m3 is 2 to 5, k
is O or l. ) represents a group represented by

C is a mesogen group that may be the same as or different from A, D is the same general formula as B but has a different molecular structure or a different flexible group, and Xl and x2 are each one of an ester bond, an ether bond, or a carbonate bond. and may be the same or different. n represents 5 to 1000. x+y=1] The present invention also provides a liquid crystalline polymer compound whose main chain is composed of repeating units represented by the general formula (1) above, or a copolymer liquid crystalline compound represented by the general formula (n). A liquid crystal element characterized by having a film made of a compound and a liquid crystal composition containing the compound.

In addition, the present invention particularly provides a copolymerized liquid crystalline polymer compound represented by the general formula (If), in which the monopolymer has a repeating unit of a polymeric liquid crystal represented by the following general formula (■1) exhibiting a smectic C phase. A copolymerized polymer liquid crystal compound is provided.

General formula (■1) (:X, -C-X2-E). 1 (In the formula, C represents a mesogen group, E represents a flexible chain containing no optically active group, and Xl and X2 each represent a group containing one of an ester bond, an ether bond, and a carbonate bond.) In other words, this The invention relates to a copolymerized liquid crystal compound whose main chain is composed of a repeating unit represented by the following general formula (III), and a liquid crystal composition containing one or more thereof.

General formula (III) +Xs A Xz BVXs-cX2 E can [In the formula, A is a bicyclic mesogen group, B is YX
X Y (CHCH-0) (CH2 sho-〇-CH-CH (wherein, ) or YX Y (wherein, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, X≠YSm2 is 2 to 10, m3 is 2 to 5, k
is O or 1. ) represents a group represented by

C is a mesogenic group that may be the same as or different from A, E is a flexible chain that does not contain an optically active group, xl and
2 each represents a group containing one of an ester bond, an ether bond, and a carbonate bond, and may be the same or different. x+y=l, n is 5~
Shows 1000. Furthermore, mo x in the formula, -C-X2-E
A polymer consisting of repeating units of polymeric liquid crystal represented by ':+ exhibits a non-chiral smectic C phase. Furthermore, the present invention provides a liquid crystal, characterized in that it has a film on a substrate made of a chiral smectic copolymer liquid crystal compound represented by the general formula (III) and a liquid crystal composition containing one or more thereof. It is element.

Further, the present invention provides a polymeric liquid crystalline compound characterized in that when the above A is represented by +Y+←69←, the main chain consists of a repeating unit represented by the following general formula (Ia). .

General formula (Ia) Children X 1+Y 1+X 2 B% is 1-18. ) or yx xy壬CHC
H-0 Chimomo CH2←O←CHCHY1 is a single bond, −
CH=CH-, -CmiC-, -N=N-.

-N=N-, -(:H=N-, -CHzCH2-, -C
Shows one of H20-Noy. ] B is (wherein, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, X≠Y, is O or 1, ml (wherein, or methyl group, X+
YSm2 is 2-10, m3 is 2-5, and k is 0 or 1. ) represents a group represented by

X and X2 each represent a group containing any one of an ester bond, an ether bond, and a carbonate bond, and may be the same or different. n is 5
~1000 is shown. Similarly, a liquid crystal composition having the general formula (Ia) and a liquid crystal element having the liquid crystal composition are also provided.

Furthermore, the present invention provides a copolymerized polymeric liquid crystal compound characterized in that the main chain is composed of a repeating unit represented by the following general formula (IIa), a liquid crystal composition having the compound, and a liquid crystal having the liquid crystal composition. Provide an element.

General formula (I[a) B is (wherein, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group,
It is. ) or both indicate bet.

Y, single bond, -CH=CH-, -c=c-, -
N=N+.

Show one. (wherein, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, X≠Y, m2 is 2 to IO, m3 is 2 to 5, k
is 0 or 1. ) represents a group represented by

C is a mesogen group which may be the same as or different from -(TS←y,=(9←), D is the same general formula as B but has a different molecular structure or a different flexible chain, xI and x2 are each an ester bond, Represents a group containing either an ether bond or a carbonate bond, and each may be the same or different. n represents 5 to 1000. x+y=
11 Furthermore, the present invention provides a copolymerized liquid crystal compound characterized in that the main chain is composed of a repeating unit represented by the following general formula (I [[a)], a liquid crystal composition having the compound, and a liquid crystal composition A liquid crystal element having an object is provided.

General formula (lea) +X 10 Y JA X 2 B ¥X HKX 2
E Can [In the formula, -(), =(9→ is -(tsu-, -(nu'Y, single bond, -CH=CH-, -(: MiC-, -
N=N-.

-N=N-, -(:H=N-, -CH2CH2-, -(
: H2O-41 difference ↓ or one. ] B is (wherein, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, and X+Y is O or lSm1 is 1 to 18.) or

However, = (less than 9-2+) Tomo one is Beth shows.

(In the formula, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, X≠YSm2 is 2 to 10, m3 is 2 to 5, k
is O or 1. ) represents a group represented by

C is a mesogen group that may be the same as or different from 169←Y1+, E is a flexible chain that does not contain an optically active group,
l and X2 are respectively an ester bond, an ether bond,
Indicates a group containing any one carbonate bond, and each may be the same or different. x+y=l
, n represents 5 to 1000. Furthermore, 16X in the formula, -
A polymer consisting of repeating units of polymeric liquid crystal represented by C-X2-E) exhibits a non-chiral smectic C phase. ] Hereinafter, the present invention will be explained in detail.

In the polymeric liquid crystal compound of the present invention, the general formula (I
), (II), and (III), A represents a bicyclic mesogen group, and specific examples thereof include the following.

The bicyclic mesogen group used in the present invention has a lower liquid crystal temperature range than tricyclic or higher polycyclic systems in terms of liquid crystal phase formation, and is therefore easier to use in practice. In addition, bicyclic systems are preferable because the polycyclic systems tend to have a complicated transition pattern of the liquid crystal phase, and the control of the molecular structure for developing the desired chiral smectic phase is relatively difficult. X, , X2 are respectively ester bond, ether bond,
Indicates a group containing any one carbonate bond, and each may be the same or different. Among these, a polyester having an ester bond and represented by the following general formula (IV) is particularly preferable because a high molecular weight product can be easily obtained and it tends to have a chiral smectic phase.

B is (in the formula, Hydrogen atom or methyl group, Y is hydrogen atom or methyl group, X≠Y, m2 is 2-10, m3 is 2-5, k
is 0 or l. ) is a flexible group having a molecular structure derived from optically active lactic acid.

To give a specific example, CH3 (CH2F2-CH-CH2- ml * CH3
-L; 11-ti 2-sit-υshini 12-tJ-si Ml, 112*-l
*CH3 CH3 These groups are derived from diols, and their synthesis method is described in Japanese Patent Application No. 62-250567.

1′--＼＼ The optically active flexible group used in the present invention is
Since the polar oxygen atom is directly bonded to the asymmetric carbon atom, the spontaneous polarization is large, which is also preferable in terms of response speed. Furthermore, due to its ether bond, it has high flexibility and therefore has high liquid crystallinity, and the temperature range in which it forms a liquid crystal phase is wide.

C represents a mesogen group which may be the same as or different from A. A mesogen group has a skeletal structure that includes two or more cyclic groups and has a cyclic group arranged at the end. Among them, it is preferable to select from the above-mentioned bicyclic mesogen groups, and it is preferable to select the same group as A from the viewpoint of reactivity upon introduction of the mesogen group.

D has the same general formula as B but represents a different molecular structure or a different flexible group. A flexible group is a linear or branched chain group that does not contain a ring in the skeleton excluding the bonding group bonded to the mesogen group between the mesogen groups.

E represents a flexible group containing no optically active group.

Specific examples other than B mentioned above include Child CH2. , Child CH2> s, Child CH2) s, Mo CH2''+7, Child CH2 Chi 8, Thousand CH2) 9, -ec
Straight chain alkyl groups such as H2*+o, +CH2)o, (CH2)t2, etc., alkyl groups having branches such as CH3 -CH CH2CH2 3H7 -CHMOCH2CH m=3-18 m=3-18 The basics are given.

Specific examples of the branched alkyl group mentioned above also correspond to E above.

In the present invention, a liquid crystalline polymer compound into which an ester bond having a repeating unit represented by the general formula (II) is introduced is synthesized by melt polymerization or solution polymerization, which are common polycondensation reactions.

In the melt polymerization method, it is synthesized, for example, by a transesterification reaction between a dialkyl ester of a dicarboxylic acid and a diol containing an optically active group. In order to facilitate the reaction, for example, organic titanium compounds such as tetra-n-propyl ester, tetra-impropyl ester, and tetra-n-butyl ester of titanic acid, organic tin compounds, antimony trioxide, lead, zinc, manganese, etc. It is preferable to add a known esterification reaction catalyst such as an acetate of calcium or the like.

In the solution polymerization method, for example, a condensation reaction by dehydrohalogenation between an acid halogen compound containing a mesogen group and a diol containing an optically active group is used.

In the present invention, A or B in the general formula (I) is 2
It is also preferable to use a copolymerized polymeric liquid crystalline compound in combination of two or more species in order to control temperature characteristics, optical characteristics, electrical characteristics, etc.

The liquid crystalline polymer compound and liquid crystalline copolymer compound obtained in this reaction are purified by conventional methods such as reprecipitation and filtration, and used as they are or after chromatographic purification if necessary.

The degree of polymerization of the liquid crystalline polymer compound and copolymerized liquid crystalline compound of the present invention is from 5 to 1,000, and the weight average molecular weight (Mw) is from 2,000 to 500,000, preferably from 5,000 to 10,000. Ten thousand.

Specific examples of the polymeric liquid crystal compound and copolymerized polymeric liquid crystalline compound of the present invention having a repeating unit represented by the general formula (I) are listed below, but the invention is not limited thereto.

U SuU O ■D Among these, copolymerized polymeric liquid crystalline compounds (for example, ■, ■, ) Compounds exhibiting a chiral smectic phase are particularly good.

In the copolymerized polymeric liquid crystal compound of the present invention, the proportion of the flexible chains represented by B in the total flexible chains is as follows:
Used at 1 mol% or more, preferably 10 mol% or more,
If it is less than 1 mol%, it becomes difficult to develop a chiral smectic phase.

Next, the liquid crystal composition of the present invention is composed of the polymer liquid crystal compound, the copolymer liquid crystal compound, and, for example, 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 compound.

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

Specific examples of these include optically active low-molecular liquid crystals as shown in formulas (1) to (15) below, and non-optically active low-molecular liquid crystals as shown in formulas (16) and (34). However, the former is preferable in terms of responsiveness.

Desyloxybenzylidene P' Amino-methylbutylcinnamate (DOBAMBC) 76°C 95°C 117°C P-Hexyloxybenzylidene-P' Amino-2 Chlorbrovir cinnamate (HOBACPC) 60°C 64°C 78°C P -Desyloxybenzylidene-P' -Amino-octyloxybenzylidene P' Monoamino-methylbutyl-α-cyanocinnamate (DOBAMB
CC) Methyl butyl α-chlorocinnamate (OOBAMBCC) 92°C 104°C 41'C 66°C Crystal mA Equilibrium phase P-tetradecyloxybenzylidene-P'-amino-2
- P-octyloxybenzylidene-P'-amino-2-methylbutyl-α-cyanocinnamate (TDOBAM
BCC) Methylbutyl-α-methylcinnamate 78℃ 104℃ Crystal mA Tokichi phase 47'C\ 770℃ SmC" (7) (9) 4.4' Monoazoxycinnamic acid bis- (2' -methylbutyl) phenyl -4' Octyl (2-methylbutyl) esteroxybiphenyl-4-carboxylate 78°C 80°C 128.3°C Crystal m3 SmC” mA 171.0°C 174.2°C (8) (10) -o- (2- methyl) -butyl resol cylidene-4' octylaniline (MBRA 8) 4-hexyloxyphenyl-4 (2' methylbutyl) biphenyl-4' monocarboxylate 68.8°C 80.2°C 163.5°C ( 11) (13) 4-(2'-monomethylbutyl)phenyl-4-(4'-methylhexyl)biphenyl-4'-monocarboxylate 74.3℃\ / 81.0℃ SmC"←--- mA (12 ) (14) 4-hexyloxyphenyl-4-(2'-methylbutyl) biphenyl-4' monocarboxylate ml (15) Nonchiral smectic (16) C9HI90→◎-◎-oc-◎-CN4' nonyloxy -4 Biphenylylcyanobenzoate, etc. Nematic phase nematic mectic C /-\1, (below margin) / (17) n-hebutylphenyl-4-(4' nitrobenzoyloxy)benzoate (DB7NO2), etc. Auspicious phase nematics mectic A (18) n-octylphenyl 4-(4' nitrobenzoyloxy) benzony) (DB8NO2) Tomoyoshi phase nematics mectic A smectic C (19) (22) 4-n-decylphenyl-4-(4' -Nitrobenzoyloxy)benzo4-n-nonyloxyphenyl4- (4' nitrobenzoyloxy)ate (DBIONO2) Benzoate (DB9ONO2) Tobuyoshi phase nematics mectic A Smectic C Tobuyoshi phase nematics mectic A Smectic C (20) (23) CsHoOBere◇Pe←C5Hn 2-(4'-n-pentylphenyl)-5-(4'n-pentyloxytrans-4-(4'-octyloxybenzoyloxy)-4'phenyl)pyrimidinecyanostilbene ( T8) Tokichi phase → Smectic A → Smectic C → Tokichi phase → Nematic → Smectic A+ → Nematic → Smectic A2 Smectic F → Smectic G (21) (24) C5H11−◎−N=CH−◎−CH=N−◎− C5H
+ 14-n-pentylphenyl-4-(4'cyanobenzoyloxy) terephthalylidene-bis-4-n-pentylaniline (
TBPA) Benzoate (DBsCN) Tokichi phase → Nematic → Smectic A → Smectic C
→ Isotropic phase nematic Smectic A Smectic F → Smectic G → Smectic H (2
5) (28) C4H9-◎-N=CH-◎-CH=N-◎-C4H9
C4H90-◎-CH=N→◎-CaN+7, N-terephthalylidene-bis-4-n butylaniline (TBBA) N-(4'-n-butyloxybenzylidene)-4-n-octylaniline (408) Toyoshi phase → Nematic → Smectic A → Smectic C → Smectic G → Smectic H etc. Smectic A → Smectic B (29) (26) n-C6H130-〇-〇-CaH+3-nC3HI?
0←◎-◎-CN Hexyl-4' Hexyloxybiphenyl 4-cyano-4' -n-octyloxybiphenyl (80CB) Tomoyoshi phase smectic B→ Smectic E Tomoyoshi phase nematic smectic A (30) (27) n -C8H170 -C-Q-Co-◎-0CsH+3
-n1 4-n-hexyloxyphenyl-4'=4-carboxylate octyloxybiphenylethyl azobenzoate, etc., auspicious phase Smectic A, etc. Auspicious phase → Nematic → Smectic A → Smectic C → Smectic B (31) (34) C10H210-◎ -CO-◎-0C7HI51 4-n-hebutyloxyphenyl-4-n-decyloxybenzoniton octyl-4,4'-terphenyldicarboxylate etc. auspicious phase Smectic A Smectic C etc. auspicious phase → Smectic A → Smectic C ( 32) (35) ○ CgH+yO-◎-COH 1 4-n-octyloxybenzoic acid n-hexyl-4'-n-pentyloxybiphenyl-4 carboxylate (6508C) Togoyoshi phase nematic mectic C Togoyoshi phase → Smectic A → Smectic B → Smectic E (33) C10H210-◎-◎-Co-CsH+sn-hexyl-4'-n Decyloxybiphenyl 4-carboxylate etc. Auspicious phase Smectic A Smectic C In addition, the polymer liquid crystal composition of the present invention The material can be mixed with other low-molecular compounds, high-molecular compounds, high-molecular liquid crystals, etc. In other words, without causing the chiral smectic phase to disappear,
Those with good compatibility can be selected and used. For example, other polymeric compounds that can be combined include those shown below.

(Following formula (35) (47) % formula %) (37) (38) (39) (40) (46) (47) (42) (43) (44) Polymeric liquid crystal compound of the present invention, Or, in a liquid crystal composition containing a copolymerized polymeric liquid crystal compound, the content of the polymeric liquid crystalline compound or copolymerized polymeric liquid crystalline compound is 5
It is desirable that the amount is at least 10% by weight, preferably at least 10% 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 polymeric liquid crystal compound is 30% by weight or more, preferably 5% by weight or more.
It is desirable to contain 0% by weight or more from the viewpoint of shape retention.

Note that it is preferable to use a combination of multiple types of the above-mentioned polymeric liquid crystal compound, copolymerized polymeric liquid crystalline compound, and other polymers, polymeric liquid crystals, low molecules, or low-molecular liquid crystals from the viewpoint of device design. , temperature characteristics, optical characteristics, electrical characteristics, etc. can be controlled.

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

Next, in the liquid crystal element of the present invention, on a substrate, a polymer liquid crystal compound X, -A-X2-B, whose main chain is composed of a repeating unit having the following general formula (I), a copolymer liquid crystal It is provided with a film made of a liquid crystal composition containing a liquid crystal compound or a polymeric liquid crystal compound.

As a specific structure of the liquid crystal element of the present invention, the polymeric liquid crystal compound, copolymerized polymeric liquid crystalline compound, or polymeric liquid crystal composition is formed into a film-like thin film from a molten state, and electrodes are formed. It can be sandwiched and bonded between two substrates provided with the same. When adhering, an appropriate gap agent may be provided between the film of polymer liquid crystal compound, copolymer liquid crystal compound, or polymer liquid crystal composition and the electrode to maintain insulation between the electrodes. good. Further, electrodes may be provided directly on a film of a polymer liquid crystal compound, a copolymer polymer liquid crystal compound, or a polymer liquid crystal composition without a substrate. In this case, a film-like flexible liquid crystal element can be obtained.

In addition, the film of a polymeric liquid crystal compound, a copolymerized polymeric liquid crystalline compound, or a polymeric liquid crystal composition may be formed of a polymeric liquid crystalline compound,
A copolymerized polymer liquid crystal compound or a polymer liquid crystal composition is mixed with a solvent (dichloroethane, THF, etc.).

It can also be formed by dissolving it in a molten state (cyclohexanone, chloroform, etc.) and forming a film.

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 liquid crystal element,
By forming the polymeric liquid crystal compound, copolymerized polymeric liquid crystalline compound, or polymeric liquid crystal composition into a film-like film and then subjecting it to a stretching and alignment treatment, high alignment properties can be imparted to liquid crystal molecules.

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 polymeric liquid crystal compound, a copolymerized polymeric liquid crystalline compound, or a polymeric liquid crystal composition may be laminated and the entire laminate may be stretched, or a cell in which a liquid crystal film is sandwiched between two substrates may be used. After forming, the film may be stretched and oriented.

Furthermore, in the liquid crystal element of the present invention, a polymeric liquid crystal compound, a copolymerized polymeric liquid crystalline compound, or a polymeric liquid crystal composition may be sealed in a molten state at a temperature equal to or higher than the isotonic phase transition temperature between a pair of aligned substrates. It is possible.

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, 5i02゜Z n S,
Uniaxial or biaxial alignment treatment can be performed on an inorganic thin film such as M g O by a rubbing method, or S io 2 +S
A method using a surface obtained by oblique vapor deposition of an inorganic compound such as in, MgO, MgF 2 or the like can be applied.

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

Further, although the structure of the liquid crystal element of the present invention differs depending on the application, a commonly applied structure will be specifically shown below.

Figure 1 is a cross-sectional view of a liquid crystal element, Figure 2 is a perspective view of a liquid crystal element with a polarizing plate, Figure 4 is a plan view of a liquid crystal element with transparent electrodes arranged in a matrix, and Figures 5 to 7. shows another cross-sectional view of the liquid crystal element.

In each figure, reference numeral 1. 1' is a substrate, 2 and 2' are transparent electrodes, 3 and 3' are alignment films, 4 is an adhesive layer, 5 is a polymeric liquid crystal layer, 6.6' is a polarizing plate, 7 and 7' are polarization directions, and 8 is a liquid crystal element, 9 is a polyester film, 10 is
11 represents an electrode/reflection layer, and 11 represents an A1 reflection layer.

In addition, when each of the liquid crystal elements mentioned above is particularly a film-like liquid crystal element, FIG. 8 shows a configuration diagram of a display device when the liquid crystal element is used as a display element. FIG. 9 shows a block diagram of the recording apparatus used.

In the figure, 12 and 12' are rollers, 13 is a display unit, 14 is a temperature sensor, 15 is a sheet heater, 16 is an erasing means, 17 is a light source, 18 is a Fresnel lens, and 19 is a thermal head (writing means) , 20 is a semiconductor laser 21
is a polarizer, 22 is a beam splitter, and 123 is an analyzer.
24 is a moving stage, and 25 is a light intensity detector.

〔Example〕

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

Example 1 Diethyl-4,4'-biphenyldicarboxylate 3
．． 0g, 2.6g of diol represented by the following formula, H
3 Add 0.0015 g of tetra-impropyl titanate, raise the temperature to 150°C under a nitrogen gas atmosphere, react by heating for 1 hour while stirring, then react in the same manner at 180°C for 2 hours, and then heat to 230°C. The temperature was raised over 1 hour, the pressure inside the reaction system was reduced, and the reaction was continued for another 5 hours until the degree of pressure reduction reached 0.
．． The polymerization reaction was terminated at 5 mmHg.

After the reaction, the 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 a milky white polymer (■).

As a result of DSC measurement and polarizing microscope observation, the liquid crystal phase transition point was as follows.

(Cryst is a crystalline phase, SmC tree is a chiral smectic C phase, SmA is a smectic A phase, Is.

indicates Tokichi phase. ) The molecular weight distribution of Polymer (1) was measured using GPC (gel permeation chromatography) in a chloroform solution, and the results were as follows.

shoulder. =1.2X10' Hw = 3, Ox l O' Also, the specific optical rotation is [α]F=+4.5° (C=1.0
5, solvent: chloroform).

NMR data (δppm (TMS)) 1.2
(d, 3H, methine) 3.7 -3.85
(III, 2H, methylene)4.5 (I
II, 6H, methylene) 7.65 (d,
4H, phenylene) 8.1 (d, 4H,
Phenylene) Example 2 The diol of Example 1 was converted into a compound (3
2.8 g of a milky-white polymer (■) was obtained in the same manner as in Example 1, except that 2.8 g of a milky white polymer (■) was used.

As a result of observation using a DSC111 constant and a polarizing microscope, the liquid crystal phase transition point was as follows.

(gl indicates the glass transition point.) The results of measuring the molecular weight and specific rotation of Polymer (2) were as follows.

Bu. =1.3X10'Mw=4.0xlO' [αcoV=+4. O° (C=1.02, solvent: chloroform) NMR data (δppm (TMS)) 1.2 (d
, H, methine) 4.5 (III, IH, methylene) 7.7
(d, 4H, phenylene) 8.1 (d, 4
H, Phenylene) Example 3 Using the liquid crystalline polymer compounds (1) and (2) obtained in Examples 1 and 2, films were obtained using the following methods.

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

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 top of a polyimide alignment film with a thickness of 600 people. After being slowly cooled to the chiral smectic C phase (SmC* phase), the SmC
*Approximately 80 m if a voltage of 20 μm/μm is applied on the phase
The response was sec(■) and 90m5ec(■).

Example 4 When a compatibility test was conducted between the polymeric liquid crystal compound ■ obtained in Example 1 and the aforementioned 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 polymer liquid crystal compositions of (1) and (14).

Table 1 Table 2 shows the speed of electric field response.

Furthermore, as shown in Fig. 2, when the liquid crystal element 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
．． The arrow 7' indicates the polarization direction of the polarizing plate 6.6'.

Table 2 Example 5 The polymer liquid crystal composition shown in Example 4 (composition ratio of ■/(14) 1/4.l/1) was prepared as shown in FIG.
Glass substrate 1. A solid ITO transparent electrode (thickness 1300A) 2.2' is provided on 1', and a 600A thick
A liquid crystal cell was formed by adhering a pair of glass substrates on which the rubbed polyimide alignment films 3 and 3' of A were bonded with NI4 adhesive so that the thickness between the substrates was 10 .mu.m, and the liquid crystal cell was sealed in the Tokichi phase. SmC while observing under a polarizing microscope.
When an electric field of ±20 v/μm was applied to the * phase, inversion of molecules in response to the electric field was observed. Example 6 A copolymer represented by the following formula Obtained union.

Comparative example 1 X in Example 6 show.

The results using 0 are shown in Table 3. CH3 HOmo CH260-CH2--H-OHHO+CH2C
H2O No.H
Table 3 shows the response speed when a voltage of v/μm was applied.

Example 7 Copolymer ■-1 obtained in Example 6-1 and low molecular liquid crystal (
When a compatibility test for 14) was conducted, the same phase as the low molecular liquid crystal (14) was confirmed over a wide composition range. ■−
Table 4 shows the phase transition temperatures of the blended liquid crystal compositions of No. 1 and No. 1 and No. 1 (14).

The polymer liquid crystal composition shown in Example 7 in Table 4 was filled into a liquid crystal element similar to that in Example 5 starting from the Tokichi phase. SmC Kiso upper 20V
When an electric field of /μm was applied, inversion of molecules in response to the electric field was observed. Table 5 shows the speed of the electric field response.

Example 9 A copolymer represented by the following formula (■) 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, and the composition was as shown in Table 6. I got it.

CH3 ■ HO (-CH2 0-CH-CH2-OHCH3 HO-CH2CHmoCH2+1-OH From the copolymers of each composition, a polymer liquid crystal device prepared in the same manner as in Example 3 was coated with a chiral smectic C phase. 20
Table 6 shows the response speed when a voltage of V/μm was applied.

Comparative example 2 Table 6 shows the results using Example 9 where x=0.

Table 6 and Figure 3 show the phase diagram of iii) based on the results of DSC measurement and observation using a polarizing microscope. In the figure, ch indicates a cholesteric phase.

Comparative Example 3 A polymer liquid crystal compound represented by the following structural formula was formed into a film, uniaxially stretched, sandwiched between glass substrates with a polyimide alignment film provided on an ITO transparent electrode, and heat-pressed to a thickness of about 5 μm. When the mixture was then slowly cooled, a multidomain orientation was obtained.

Using a relatively large domain in it, the upper 20V/μ
When a voltage of m is applied, the response speed is approximately 500 m
It was sec.

Example 10 A copolymer was obtained in the same manner as in Example 9 except that the diol in Example 1 was replaced with two types of compounds represented by the following formulas.

CH3 HOmo CH2) 2CHmo CH2) aOH correction n=5.3X
1 and Viw = 8.5X, 10'' Figure 10 shows a phase diagram based on the results of DSC measurement and observation using a polarizing microscope. In the figure, Tg indicates the glass transition point.

Molecular weight of the copolymer shown in Figure 10 Comparative example 5 The diol of Example 1 is converted into a compound represented by the following formula: (1.5g) Except for replacing it with Example 1 Do the same thing as Polymer (■) 1.2g was obtained.

Comparative Example 4 CH3 The diol of Example 1 was converted into a compound represented by the following formula) 10
A polymeric liquid crystal compound CH3 HO-CH2CHCH2CH2-OH* having the structural formula shown below was obtained in the same manner except that -CH2-CH-OH* was used.

Phase transition temperature of ■: Mn=1.2xlO'Mn=7,8XlO" W 3.3X10'W=1.8X10' As a result of DSC measurement and polarizing microscope observation, the liquid crystal phase transition point was as in Examples 11 to 16. Example 8 was prepared in the same manner as in Example 1 except that the combination of the mesogen group precursor and diol shown in Table 7 below was used, and the SmC* phase was developed only when the temperature was lowered.

The polymers shown in the table were obtained.

As a result of observation under a polarizing microscope with DSC #I, the liquid crystal phase transition points were as shown in Table 9.

Table 9 Example 17 3.7 g of 4.4'-dihydroxybiphenyl 150 m of pyridine! ! The solution was kept at 5° C. or lower under a nitrogen gas atmosphere, and a dichloromethane solution H3 containing 5.1 g of a chlorocarbonate compound represented by the following formula was added dropwise while stirring, and after stirring for 1 hour, the mixture was further stirred at room temperature for 40 hours. After treating the reaction solution with diluted hydrochloric acid, the dichloromethane solution was washed with water. The precipitate produced by pouring the concentrated dichloromethane solution into methanol was purified several times in the same manner and dried under reduced pressure to obtain 1.8 g of polymer.

M n / M w = 8, 300 / 19,
It was 000.

[α] Otsu' = +4.8' (C = 0.95, solvent: chloroform) NMR data (δppm (TMS)) 1.4 (d; 3H, methyl) 2.1
(III; 2H, methylene) 3.6.4.5
(III, t; 6H, methylene) 5.3
(III; IH, methine) 7.6
(d; 4H, phenylene) 8.0 (d
; 4H, phenylene) The liquid crystal phase transition points were as follows.

Example 18 The following polymers were obtained in the same manner as in Example 1.

un=1.0X10' Mw=2.3xlO' As a result, the liquid crystal phase transition was as follows.

6 5 50 [Effects of the Invention] As explained above, according to the present invention, a chiral smectic phase (Sm wood phase) is exhibited over a wide temperature range, and the chiral smectic phase is stable both when the temperature rises and when the temperature falls. New polymeric liquid crystalline compounds, copolymerized polymeric liquid crystalline compounds, and polymeric liquid crystalline compositions containing the polymeric liquid crystalline compounds and low molecular weight liquid crystals that can be easily formed into thin films and formed into films. can be 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, when these polymeric liquid crystal compounds, copolymerized polymeric liquid crystalline compounds, and polymeric liquid crystal compositions are applied to liquid crystal elements, it is possible to easily realize a large area, and
By applying an electric field to the SmC* phase, it is possible to obtain a polymer liquid crystal device that exhibits a stable and good switching effect and can be used as a device applying various electro-optic effects.

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

Furthermore, in the present invention, even if the polymer has an optically active group, it is copolymerized with a polymer liquid crystal having a smectic phase in order to be more effective in stably expressing the chiral smectic phase and expanding the temperature range when the polymer is converted into liquid crystal. This expands the temperature range of the chiral smectic phase and stabilizes it. Therefore,
It is possible to provide a more useful copolymerized liquid crystalline polymer compound and a composition thereof, and as a result, there have been few examples of polymeric liquid crystals having an optically active group and a mesogenic group in the main chain sufficiently exhibiting a chiral smectic phase. , it can be said that it is more effective in solving the current situation where usage is restricted.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing a liquid crystal element used in Example 4, FIG. 2 is a perspective view showing a liquid crystal element with a polarizing plate used in Example 4, and FIG. 3 is a diagram illustrating Example 9. Figure 4 is a plan view of a liquid crystal element in which transparent electrodes are arranged in a matrix, Figures 5 to 7 are cross-sectional views of the liquid crystal element, Figure 8 is a configuration diagram of a display device, and Figure 9 is a configuration of a recording device. 10A and 10B are diagrams for explaining the 10th embodiment. 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 element 9...Polyester film lO...Electrode and reflective layer 11...At reflective layer 12, 12'...Roller 13...Display section 14 ... Temperature sensor 15 ... Planar heater 16 ... Extinguishing means 17 ... Light source 18 ... Fresnel lens 19 ... Thermal head (writing means) 20 ... Semiconductor laser 21 ... Polarizer 22...beam splitter 23...analyzer 24...movement stage 25...light intensity detector Z

Claims (52)

[Claims] (1) A liquid crystalline polymer compound characterized by having a moiety represented by the following general formula (M) in a repeating unit. General formula (M) is a hydrogen atom or a methyl group; X≠Y; k is 0 or 1; Y is a hydrogen atom or a methyl group, X≠Y) m2 is 2 to 10, m3 is 2 to 5, k
is 0 or 1. ) represents a group represented by X_1 and X_2 each represent a group containing any one of an ester bond, an ether bond, and a carbonate bond, and may be the same or different. ] (2) A liquid crystal element comprising a film made of the polymer liquid crystal compound according to claim 1 on a substrate. (3) The liquid crystal element according to claim 2, wherein the film is subjected to an alignment treatment. (4) The liquid crystal element according to claim 3, wherein the alignment treatment is a stretching alignment treatment. (5) The liquid crystal element according to claim 3, further comprising an alignment film. (6) A liquid crystal composition comprising the polymeric liquid crystal compound according to claim 1 and at least one compound selected from other polymeric compounds and low molecular weight compounds. (7) The content of the polymeric liquid crystal compound is 10 in the liquid crystal composition.
7. The liquid crystal composition according to claim 6, wherein the amount is 5 parts by weight or more relative to 0 parts by weight. (8) The content of the polymeric liquid crystal compound is 10 in the liquid crystal composition.
7. The liquid crystal composition according to claim 6, wherein the amount is 10 parts by weight or more relative to 0 parts by weight. (9) A liquid crystal element comprising a film made of the liquid crystal composition according to claim 6 on a substrate. (10) The liquid crystal element according to claim 9, wherein the film is subjected to an alignment treatment. (11) The liquid crystal element according to claim 10, wherein the alignment treatment is a stretching alignment treatment. (12) The liquid crystal element according to claim 10, further comprising an alignment film. (13) The main chain has the following general formula (I), general formula (II),
2. The polymeric liquid crystalline compound according to claim 1, comprising a repeating unit represented by any one of the general formulas (III). General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is a bicyclic mesogen group, B is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X is a hydrogen atom or methyl (wherein, Methyl group, Y is a hydrogen atom or methyl group, X≠Y, m2 is 2-10, m3 is 2-5, k
is 0 or 1. ) represents a group represented by X_1 and X_2 each represent a group containing any one of an ester bond, an ether bond, and a carbonate bond, and may be the same or different. n represents 5 to 1000. ] General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is a bicyclic mesogen group, B is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X is a hydrogen atom or Methyl group, Y is a hydrogen atom or methyl group, X≠Y, k is 0 or 1, m1 is 1 to 18.) Or ▲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, m2 is 2 to 10, m3 is 2 to 5, k
is 0 or 1. ) represents a group represented by C is a mesogen group that may be the same as or different from A, D is the same general formula as B but has a different molecular structure or a different flexible chain, and X_1 and X_2 are each one of an ester bond, an ether bond, or a carbonate bond. and may be the same or different. n represents 5 to 1000. x + y = 1] General formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is a bicyclic mesogen group, B is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X is (Hydrogen atom or methyl group, Y is a hydrogen atom or methyl group, X≠Y, k is 0 or 1, m1 is 1 to 18.) Or, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, X≠Y, m2 is 2 to 10, m3 is 2 to 5, k
is 0 or 1. ) represents a group represented by C is a mesogen group that may be the same as or different from A, E is a flexible chain that does not contain an optically active group, X_1 and X_2 each represent a group containing any one of an ester bond, an ether bond, and a carbonate bond, and may be the same or different. x+y=1, n=
Indicates 5 to 1000. Furthermore, ▲mathematical formula, chemical formula,
A polymer composed of repeating units of a polymeric liquid crystal represented by ▼ exhibits a non-chiral smectic C phase. ] (14) A liquid crystal element comprising a film made of the polymeric liquid crystal compound according to claim 13 on a substrate. (15) The liquid crystal element according to claim 14, wherein the film is subjected to an alignment treatment. (16) The liquid crystal element according to claim 15, wherein the alignment treatment is a stretching alignment treatment. (17) The liquid crystal element according to claim 15, further comprising an alignment film. (18) A liquid crystal composition comprising the polymeric liquid crystal compound according to claim 13 and at least one compound selected from other polymeric compounds or low molecular weight compounds. (19) The content of the polymeric liquid crystal compound is liquid crystal composition 1
19. The liquid crystal composition according to claim 18, wherein the amount is 5 parts by weight or more based on 00 parts by weight. (20) The content of the polymeric liquid crystal compound is liquid crystal composition 1
19. The liquid crystal composition according to claim 18, wherein the amount is 10 parts by weight or more based on 00 parts by weight. (21) A liquid crystal element comprising a film made of the liquid crystal composition according to claim 18 on a substrate. (22) The liquid crystal element according to claim 21, wherein the film is subjected to an alignment treatment. (23) The liquid crystal element according to claim 22, wherein the alignment treatment is a stretching alignment treatment. (24) The liquid crystal element according to claim 22, further comprising an alignment film. (25) The liquid crystalline polymer compound according to claim 1, wherein the A is a bicyclic mesogen group represented by ▼, which has a numerical formula, a chemical formula, a table, etc. ▼. [In the formula, there are ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas,
There are chemical formulas, tables, etc. ▼ is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
selected from one of the following. However, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
At least one of these indicates ▲There is a mathematical formula, chemical formula, table, etc.▼. Y_1 is a single bond, -CH=CH-, -C≡C-, -N=
N-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH=N
-, -CH_2CH_2-, -CH_2O-. ] (26) The liquid crystalline polymer compound according to claim 25, wherein said ▲, which includes a mathematical formula, a chemical formula, a table, etc., is selected from the following structural formulas. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables etc.▼, (27) The liquid crystalline polymer compound according to claim 25, wherein the film B is selected from the following structural formulas. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, (28) A liquid crystal element comprising a film made of the polymeric liquid crystal compound according to claim 25 on a substrate. (29) The liquid crystal element according to claim 28, wherein the film is subjected to an alignment treatment. (30) The liquid crystal element according to claim 29, wherein the alignment treatment is a stretching alignment treatment. (31) The liquid crystal element according to claim 29, further comprising an alignment film. (32) A liquid crystal composition comprising the polymeric liquid crystal compound according to claim 25 and at least one compound selected from other polymeric compounds and low-molecular compounds. (33) The content of the polymeric liquid crystal compound is in liquid crystal composition 1.
33. The liquid crystal composition according to claim 32, wherein the amount is 5 parts by weight or more based on 00 parts by weight. (34) The content of the polymeric liquid crystal compound is liquid crystal composition 1
33. The liquid crystal composition according to claim 32, wherein the amount is 10 parts by weight or more based on 00 parts by weight. (35) A liquid crystal element comprising a film made of the liquid crystal composition according to claim 32 on a substrate. (36) The liquid crystal element according to claim 35, wherein the film is subjected to an alignment treatment. (37) The liquid crystal element according to claim 36, wherein the alignment treatment is a stretching alignment treatment. (38) The liquid crystal element according to claim 36, further comprising an alignment film. (39) The main chain has the following general formula (Ia), general formula (IIa)
), or a repeating unit represented by general formula (IIIa). General formula (I a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
selected from one of the following. However, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
At least one of these indicates ▲There is a mathematical formula, chemical formula, table, etc.▼. Y_1 is a single bond, -CH=CH-, -C≡C-, -N=
N-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH=N
-, -CH_2CH_2-, -CH_2O-. ] B has ▲ 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 to 18 ) or ▲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, m2 is 2 to 10, m3 is 2 to 5, k
is 0 or 1. ) represents a group represented by X_1 and X_2 each represent a group containing any one of an ester bond, an ether bond, and a carbonate bond, and may be the same or different. n represents 5 to 1000. ] General formula (IIa) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
selected from one of the following. However, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
At least one of these indicates ▲There is a mathematical formula, chemical formula, table, etc.▼. Y_1 is a single bond, -CH=CH-, -C≡C-, -N=
N-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH=N
-, -CH_2CH_2-, -CH_2O-. ] B has ▲ 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 to 18 ) or ▲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, m2 is 2 to 10, m3 is 2 to 5, k
is 0 or 1. ) represents a group represented by C is a mesogen group that may be the same as or different from ▼, which has a mathematical formula, chemical formula, table, etc., D is the same general formula as B but has a different molecular structure or a different flexible chain, and X_1 and X_2 are ester bonds and ethers, respectively. represents a group containing either a bond or a carbonate bond, and each may be the same or different. n represents 5 to 1000. x
+y=1] General formula (IIIa) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas,
There are chemical formulas, tables, etc. ▼ is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. Choose one from ▼. However, there are mathematical formulas, chemical formulas, tables, etc.
▲There are mathematical formulas, chemical formulas, tables, etc.▼ At least one
One shows ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Y_1 is a single bond, -CH=CH-, -C≡C-, -N=
N-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH=N
-, -CH_2CH_2-, -CH_2O-. ] B has ▲ 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 to 18 ) or ▲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, m2 is 2 to 10, m3 is 2 to 5, k
is 0 or 1. ) represents a group represented by C is a mesogen group that may be the same as or different from ▼, which has a mathematical formula, chemical formula, table, etc., E is a flexible chain that does not contain an optically active group, and X_1 and X_2 are each an ester bond, an ether bond, or a carbonate bond. and may be the same or different. x+y=1, n indicates 5 to 1000. Furthermore, a polymer consisting of repeating units of a polymeric liquid crystal represented by ▼ in the formula ▼ has a numerical formula, a chemical formula, a table, etc. shows a non-chiral smectic C phase. ] (40) The liquid crystalline polymer compound according to claim 39, wherein the ▲, which includes a mathematical formula, a chemical formula, a table, etc., is selected from the following structural formulas. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables etc.▼, (41) The liquid crystalline polymer compound according to claim 39, wherein the B is selected from the following structural formulas. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, (42) A liquid crystal element comprising a film made of the polymeric liquid crystal compound according to claim 39 on a substrate. (43) The liquid crystal element according to claim 42, wherein the film is subjected to an alignment treatment. (44) The liquid crystal element according to claim 43, wherein the alignment treatment is a stretching alignment treatment. (45) The liquid crystal element according to claim 43, further comprising an alignment film. (46) A liquid crystal composition comprising the polymeric liquid crystal compound according to claim 39 and at least one compound selected from other polymeric compounds or low molecular weight compounds. (47) The content of the polymeric liquid crystal compound is liquid crystal composition 1
47. The liquid crystal composition according to claim 46, wherein the amount is 5 parts by weight or more based on 00 parts by weight. (48) The content of the polymeric liquid crystal compound is liquid crystal composition 1
47. The liquid crystal composition according to claim 46, wherein the amount is 10 parts by weight or more based on 00 parts by weight. (49) A liquid crystal element comprising a film made of the liquid crystal composition according to claim 46 on a substrate. (50) The liquid crystal element according to claim 49, wherein the film is subjected to alignment treatment. (51) The liquid crystal element according to claim 50, wherein the alignment treatment is a stretching alignment treatment. (52) The liquid crystal element according to claim 50, further comprising an alignment film.