JP2012167214A - Liquid crystalline polymer having diacetylene structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystalline polymer exhibiting large refractive index anisotropy, and a liquid crystal element and an optical element having excellent performance.SOLUTION: The liquid crystalline polymer having a diacetylene structure is obtained by reacting a compound represented by the following general formula: R1-Sp1-(Ar1)-(Ar3)-(Phe)-C≡C-C≡C-(Phe)-(Ar4)-(Ar2)-Sp2-R2 (wherein R1 and R2 are each a hydrogen atom, a halogen atom, a cyano group, an isothiocyanate group, an alkyl group, an alkenyl group, an alkynyl group, or a reactive group and at least one of R1 and R2 has a reactive group; SP1 and SP2 are each a spacer group; Ar1 and Ar2 are each an unsubstituted or substituted aromatic carbocyclic or heterocyclic group; Ar3 and Ar4 are each an unsubstituted or substituted heterocyclic group; Phe is an unsubstituted or substituted 1,4-phenylene group; p, q and r are each 0 or 1).

Description

  The present invention relates to a liquid crystal polymer having a diacetylene structure having a large refractive index anisotropy. The present invention also relates to applications of optical and electro-optical devices using a large refractive index anisotropy, such as a polarizing plate, a compensation plate, and a beam splitter.

In recent years, high performance of liquid crystal display elements has become indispensable with the progress of the information society. Among the physical properties of the liquid crystal composition, a material having a large refractive index anisotropy is required for higher speed or higher performance.
As a low molecular weight liquid crystal material having a large refractive index anisotropy, a compound having a Schiff base or pyrimidine structure (Non-patent Document 1), a tolan compound (Patent Documents 1 and 2) or a diacetylene compound (Non-patent Document 2) Patent Documents 3, 4, 5, and 6) are known. However, all of the above patent documents are compounds in which a phenylene group or a naphthylene group having an alkyl group or an alkoxy group bonded to both ends of the (di) acetylene skeleton, and a liquid crystal display utilizing a large refractive index anisotropy. It is described that it is used as a member of a liquid crystal material for improving the driving performance of the element.
On the other hand, liquid crystalline polymers (polymers) that can easily fix the alignment state of liquid crystals are used for optical elements such as compensators and polarizing plates of the liquid crystal display elements after fixing the alignment. Along with the thinning and high functionality of the element, the structural member is also required to have high functionality, and a liquid crystal polymer having higher functionality is required.
As a liquid crystalline polymer having a large refractive index anisotropy, a (meth) acrylate polymer having a tolan (acetylene) skeleton (Patent Document 7) is known. A polysiloxane having a diacetylene skeleton in the side chain and exhibiting liquid crystallinity (Non-patent Document 3) is also known, but it is difficult to say that the moldability is sufficient due to its high melting point.

Japanese Translation of National Publication No. 01-502831 Japanese Patent Laid-Open No. 06-239786 JP-A-11-001445 Japanese Patent Laid-Open No. 06-211704 US Pat. No. 5,338,481 Special table 2004-518608 gazette JP 2002-308832 A

Shoichi Matsumoto, Ryo Tsunoda, “Fundamentals and Applications of Liquid Crystals”, first edition, third edition, published by Industrial Research Co., Ltd., November 15, 1996, p. 123 B. Grant, Mol. Cryst. Liq. Cryst., 1978, vol. 48, 175-182 Yong-Hong Lu, Chain-Shu Hsu, Shin-Tson Wu, Mol. Cryst. Liq. Cryst., 1993, vol. 225, 1-14

  An object of the present invention is to provide a liquid crystal polymer exhibiting a large refractive index anisotropy, and to provide a liquid crystal element and an optical element having further excellent performance.

In order to solve the above-mentioned problems, the present inventors have made extensive studies and found that a liquid crystalline polymer having a diacetylene (1,3-butadiyne) structure has a large refractive index anisotropy. The invention has been completed.
That is, the means for solving the above problems are as follows.

[1] A liquid crystalline polymer having a diacetylene structure obtained by reacting a compound represented by the following general formula (A).
R1-Sp1- (Ar1) _p- (Ar3) _q- (Phe) _r- C≡CC≡C- (Phe) _r- (Ar4) _q- (Ar2) _p- Sp2-R2 (A)
Wherein R 1 and R 2 are independently of each other a hydrogen atom, a halogen atom, a cyano group, an isothiocyanate group, or an unsubstituted or halogen atom, a cyano group, trifluoromethyl having 1 to 15 carbon atoms. An alkyl group mono- or polysubstituted by a group or reactive group, having 2 to 15 carbon atoms and unsubstituted or mono- or polysubstituted by halogen atom, cyano group, trifluoromethyl group or reactive group Represents an alkenyl or alkynyl group or a reactive group, wherein one or more non-adjacent —CH ₂ — groups are substituted by —O—, —CO—, —COO— and / or —OCO—. Provided that at least one of R 1 and R 2 has a reactive group, and Sp 1 and Sp 2 are independently of each other —O—, S -, - CO -, - COO -, - OCO -, - OCO-O -, - CO-NR3 -, - NR3-CO -, - O (CH 2) n -, - (CH 2) n O- , -CH = CH-COO -, - OCO-CH = CH -, - (CH 2) m -, - (SiR4R5-O) n - or a single bond, 1 where m and n are independently Represents an integer of 10, R 3, R 4 and R 5 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Ar 1 and Ar 2 are independently of each other an unsubstituted or halogen atom, a cyano group, a trifluoromethyl group, An aromatic carbocyclic or heterocyclic group having up to 16 carbon atoms which is mono- or poly-substituted by a methyl group, an ethyl group, a methoxy group or an ethoxy group, and may contain a condensed ring, Ar 3 and Ar 4 Are independent of each other A heterocyclic group having up to 16 carbon atoms which is substituted or monosubstituted or polysubstituted by a halogen atom, cyano group, trifluoromethyl group, methyl group, ethyl group, methoxy group or ethoxy group, and contains a condensed ring It may be a plurality of heterocyclic groups linked by a single bond, and Phe is unsubstituted or monosubstituted by a halogen atom, a cyano group, a trifluoromethyl group, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. Represents a polysubstituted 1,4-phenylene group, and p, q and r are each 0 or 1)

[2] The liquid crystalline polymer as described in [1] above, wherein the compound represented by the general formula (A) is a compound represented by the following general formula (1).
R1-Sp1-Ar1-Phe-C≡C-C≡C-Phe-Ar2-Sp2-R2 (1)

[3] The liquid crystalline polymer as described in [1] above, wherein the compound represented by the general formula (A) is a compound represented by the following general formula (2).
R1-Sp1-Ar3-C≡C-C≡C-Ar4-Sp2-R2 (2)

[4] The liquid crystalline polymer as described in [1] above, wherein the compound represented by the general formula (A) is a compound represented by the following general formula (3).
R1-Sp1-Phe-C≡C-C≡C-Phe-Sp2-R2 (3)

[5] The reactive group is a hydroxyl group, a carboxyl group, an acid anhydride group, a maleimide group, a vinyloxy group, an oxiranyl group, an oxetanyl group, a vinyl group, a (meth) acrylate group, or a silyl group. A liquid crystalline polymer having a diacetylene structure according to any one of [1] to [4].
[6] The liquid crystalline polymer having a diacetylene structure according to [5], wherein the reactive group is a vinyl group, a (meth) acrylate group, an oxiranyl group, or an oxetanyl group.

[7] Ar1 and Ar2 are thiophene-2,5-diyl group, 1,4-phenylene group, naphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5- The liquid crystalline polymer having a diacetylene structure according to the above [1] or [2], which is a diyl group.
[8] The above [1] or [3], wherein Ar3 and Ar4 are a thiophene-2,5-diyl group, a pyridine-2,5-diyl group, and a pyrimidine-2,5-diyl group. ] The liquid crystalline polymer which has a diacetylene structure as described in above.

[9] A liquid crystalline polymer composition comprising a liquid crystalline polymer having a diacetylene structure according to any one of [1] to [8].
[10] The liquid crystalline polymer as described in any one of [1] to [8], which is used for optical or electro-optical purposes.

  The liquid crystalline polymer having a diacetylene structure of the present invention has a large refractive index anisotropy and can be easily formed into a film or the like, and can be easily formed into an optical or electro-optical device such as a polarizing plate, a compensation plate, a beam splitter, etc. It can be used for

1 is a diagram showing a ¹ H-NMR spectrum of an acrylate monomer synthesized in Example 1. FIG. 1 is a diagram showing a DSC chart of an acrylate monomer synthesized in Example 1. FIG. The a line represents the behavior when the temperature is raised, and the b line represents the behavior when the temperature is lowered. 1 is a diagram showing a ¹ H-NMR spectrum of a polymer obtained in Example 1. FIG. 1 is a diagram showing a DSC chart of the polymer obtained in Example 1. FIG. The line c indicates the behavior when the temperature is increased, and the line d indicates the behavior when the temperature is decreased. It is a figure which shows the wavelength dependence of the birefringence of the polymer obtained in Example 1. The lines e and f respectively represent 137. of 1,4-bis (4-hexyloxyphenyl) buta-1,3-diyne having a structure similar to that of the polymer (at room temperature) and the side chain of the polymer. The results at 5 ° C are shown.

Hereinafter, the present invention will be described in detail.
The present invention is a liquid crystalline polymer having a diacetylene structure obtained by reacting a compound represented by the following general formula (A).
R1-Sp1- (Ar1) _p- (Ar3) _q- (Phe) _r- C≡CC≡C- (Phe) _r- (Ar4) _q- (Ar2) _p- Sp2-R2 (A)
In the compound represented by the general formula (A) of the present invention, the substituents R1 and R2 are bonded to the 1,3-butadiyne skeleton via a carbocyclic group such as a phenylene group or a heterocyclic group and spacer groups Sp1 and Sp2. It is a bonded compound, and at least one of R1 and R2 is a group having a reactive group, and compounds represented by the following general formulas (1) to (3) are preferable.
R1-Sp1-Ar1-Phe-C≡C-C≡C-Phe-Ar2-Sp2-R2 (1)
R1-Sp1-Ar3-C≡C-C≡C-Ar4-Sp2-R2 (2)
R1-Sp1-Phe-C≡C-C≡C-Phe-Sp2-R2 (3)

  The 1,3-butadiyne skeleton is a feature of the compounds of the general formulas (A) and (1) to (3) of the present invention. These compounds have surprisingly high chemical and thermal stability, except for the stability of reactive groups. In general, they have high anisotropy and exhibit nematic liquid crystallinity and / or smectic liquid crystallinity according to the structure.

In the formulas (A) and (1) to (3), R1 and R2 each independently represents a hydrogen atom, a halogen atom, a cyano group, an isothiocyanate group, or an unsubstituted or substituted group having 1 to 15 carbon atoms. A halogen atom, a cyano group, a trifluoromethyl group or an alkyl group mono- or polysubstituted by a reactive group, having 2 to 15 carbon atoms, unsubstituted or halogen, cyano group, trifluoromethyl group or reaction Represents an alkenyl group or alkynyl group which is mono- or poly-substituted by a functional group, or a reactive group, wherein one or more non-adjacent —CH ₂ — groups are —O—, —CO—, —COO— and / or Alternatively, it may be substituted by -OCO-. However, at least one of R1 and R2 needs to have a reactive group.

  Specifically, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl , Dodecenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl, ethynyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, 2-decenyl, 2-decyl Methylbutyl, 3-methylbutyl, 3-methylpentyl, 2-methylhexyl, 2-methyldecyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 6- Fluorohexyl, 4,4-difluorobutyl, 6,6-difluorohexyl, 2-chloroethyl, 3-chloropropyl, 4-chlorobutyl, 6-chlorohexyl, perfluoroethyl, perfluorobutyl, 1-cyanoethyl, 1-cyanobutyl, 2- Cyanobutyl, 1-trifluoromethylethyl, 1-trifluoromethylbutyl, methoxy, ethoxy, butyloxy, pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, trifluoromethoxy, 2-fluorobutyloxy, 2-fluorohexyl Examples include oxy, 2-fluorobutyloxycarbonyl, a group in which a reactive group described below is bonded to these groups, a hydrogen atom, a fluorine atom, a trifluoromethyl group, a cyano group, an isothiocyanate group, and a reactive group.

  Ar1 and Ar2 in formulas (A) and (1) are each independently unsubstituted or monosubstituted or polysubstituted by a halogen atom, cyano group, trifluoromethyl group, methyl group, ethyl group, methoxy group or ethoxy group Is an aromatic carbocyclic or heterocyclic group having up to 16 carbon atoms and may contain a condensed ring. Preferably, it is an aromatic group or a 5- or 6-membered heterocyclic group, or a group containing 2 or 3 fused aromatic rings or 5- or 6-membered heterocyclic rings. It may contain more than one heteroatom, in particular a heteroatom selected from N, O and S.

Examples of preferred groups for Ar1 and Ar2 include furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, pyridine, pyrimidine, pyrazine, indane, naphthalene, tetrahydronaphthalene, anthracene, and phenanthrene.
Particularly preferred Ar1 and Ar2 are furan-2,5-diyl, thiophene-2,5-diyl, pyrrole-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5. -Diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl.
All groups of the unsubstituted these, _{or, F, Cl, CN, OH} , NO 2, CH 3, C 2 H 5, OCH 3, OC 2 H 5, COCH 3, COC 2 H 5, COOCH 3, COOC It can also be mono- or polysubstituted by ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ or OC ₂ F ₅ .

  Phe in the formulas (A), (1) and (3) is unsubstituted or monosubstituted or polysubstituted 1 by a halogen atom, cyano group, trifluoromethyl group, methyl group, ethyl group, methoxy group or ethoxy group Represents a 4-phenylene group. For example, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-chloro-1,4-phenylene, Examples include groups such as 2-cyano-1,4-phenylene, 2-methyl-1,4-phenylene, and 3-methyl-1,4-phenylene.

  Ar3 and Ar4 in formulas (A) and (2) are each independently unsubstituted or monosubstituted by a halogen atom, cyano group, trifluoromethyl group, methyl group, ethyl group, methoxy group or ethoxy group, or It is a polysubstituted heterocyclic group having up to 16 carbon atoms, may contain a condensed ring, or may be a plurality of heterocyclic groups connected by a single bond. Preferably, it is a 5- or 6-membered heterocyclic group, or a group containing 2 or 3 fused rings containing a heterocyclic group, and the number of atoms constituting the heterocyclic group is 1 or 2 or more Heteroatoms are preferred, particularly heteroatoms selected from N, O and S.

Examples of preferable groups for Ar3 and Ar4 include groups derived from furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, pyridine, pyrimidine, pyrazine and the like.
Particularly preferred Ar3 and Ar4 are furan-2,5-diyl, thiophene-2,5-diyl, pyrrole-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl.
All these groups are unsubstituted or monosubstituted by F, Cl, CN, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ or OC ₂ F ₅ It can also be polysubstituted.

Sp1 and Sp2 are groups also called spacer groups, and any group known for this purpose to those skilled in the art can be used.
Sp1 and Sp2 are independently of each other —O—, —S—, —CO—, —COO—, —OCO—, —OCO—O—, —CO—NR 3 —, —NR 3 —CO—, —O ( _{CH 2) n -, - (} CH 2) n O -, - CH = CH-COO -, - OCO-CH = CH -, - (CH 2) m -, - (SiR4R5-O) n - or a single bond Wherein m and n independently represent an integer of 1 to 10, and R3, R4 and R5 each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Preferred spacer groups include, for example, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene-N-methyl-iminoethylene, ethenylene, Examples include propenylene and butenylene.

ＣＨ_２＝ＣＷ^２−（Ｏ）ｋ１−、ＣＨ_３−ＣＨ＝ＣＨ−Ｏ−、（ＣＨ_２＝ＣＨ）_２ＣＨ−ＯＣＯ−、（ＣＨ_２＝ＣＨ−ＣＨ_２）_２ＣＨ−ＯＣＯ−、（ＣＨ_２＝ＣＨ）_２ＣＨ−Ｏ−、（ＣＨ_２＝ＣＨ−ＣＨ_２）_２Ｎ−、ＨＯ−ＣＷ^２Ｗ^３−、ＨＳ−ＣＷ^２Ｗ^３−、ＨＷ^２Ｎ−、ＨＯ−ＣＷ^２Ｗ^３−ＮＨ−、ＣＨ_２＝ＣＷ^１−ＣＯ−ＮＨ−、ＣＨ_２＝ＣＨ−（ＣＯＯ）ｋ^１−Ｐｈｅ−（Ｏ）ｋ^２−、Ｐｈ−ＣＨ＝ＣＨ−、ＨＯＯＣ−、ＯＣＮ−およびＷ^４Ｗ^５Ｗ^６Ｓｉから選択される。 The reactive group is a group capable of reacting to form a polymer by selecting appropriate conditions, and includes a hydroxyl group, a carboxyl group, an acid anhydride group, a maleimide group, a vinyl group, and a vinyloxy group. , An oxiranyl group, an oxetanyl group, a (meth) acrylate group, a silyl group, and the like. Among these, a group that is easily polymerized or condensed is preferable, and for example, preferably CH ₂ ═CW ¹ —COO—,

^{_{CH 2 = CW 2 - (O}} ) k1-, CH 3 -CH = CH-O -, (CH 2 = CH) 2 CH-OCO -, (CH 2 = CH-CH 2) 2 CH-OCO -, ( _{CH 2 = CH) 2 CH-} O -, (CH 2 = CH-CH 2) 2 N-, HO-CW 2 W 3 -, HS-CW 2 W 3 -, HW 2 N-, HO-CW 2 W ^{_{3 -NH-, CH 2 = CW 1}} -CO-NH-, CH 2 = CH- (COO) k 1 -Phe- (O) k 2 -, Ph-CH = CH-, HOOC-, OCN- and W Selected from ⁴ W ⁵ W ⁶ Si.

Where W ¹ is H, Cl, CN, phenyl or alkyl having 1 to 5 carbon atoms, in particular H, Cl or CH ₃ , W ² and W ³ are independently of each other H or Alkyl having 1 to 5 carbon atoms, in particular methyl, ethyl or n-propyl, wherein W ⁴ , W ⁵ and W ⁶ are independently of each other Cl, oxaalkyl having 1 to 5 carbon atoms Or oxacarbonylalkyl, Ph is phenyl, Phe is 1,4-phenylene, and k is 0, 1 or 2, and k ¹ and k ² are 0 or 1 independently of each other. Particularly preferred groups are vinyl groups, (meth) acrylate groups, oxiranyl groups or oxetanyl groups, most preferably (meth) acrylate groups.

Next, a method for synthesizing the compounds represented by formulas (1) to (3) will be described.
The compounds represented by the formulas (1) to (3) can be produced by a very simple method known per se. For example, it can be synthesized by the method described in Houben-Weyl, “Methoden der Organischen Chemie”, Thime-Verlag, Stuttgart, etc., which are standard academic books on organic chemistry, or similar methods. More specifically, for example, L. Brandsma, “Preparative Acetylenic Chemistry” 2nd Ed. Elsevier, Amsterdam NL, (1988) and Cadiot-Chodkiewicz (G. Eglinton, W. Mc Grae in Raphael, Taylor and Wynberg (eds) “ As described in Advances in Organic Chemistry ", Vol. 4, Interscience publishers, NY (1963), it can be prepared by coupling a terminal alkyne with a haloalkyne derivative in the presence of a copper complex.

The terminal alkynes and haloalkynes required as coupling partners are known or similar to known compounds and can be produced by methods known per se. For example, the aldehyde can be converted to the required alkyne by a Wittig reaction using CBr ₄ / PPh ₃ followed by an elimination reaction. If necessary, these alkynes can be converted from the corresponding haloalkenes by methods known per se, metallisation followed by halogenation. When R1 or R2 is chiral, the derivatives of the invention can be used as chiral dopants.
Introduction of a reactive group can be achieved by reacting a compound having a reactive group with a compound having a diacetylene group or by coupling a acetylene compound having a reactive group bonded with another acetylene compound. What is necessary is just to carry out so that the synthesis | combination of the compound which has this may be satisfactory.

  The liquid crystalline polymer having a diacetylene structure of the present invention can be obtained by reacting under conditions suitable for the reaction of the reactive groups of the above formulas (1) to (3). The reaction conditions are not particularly limited. For example, in the case of having a polymerizable group, other reactive groups such as a hydroxyl group and a carboxyl group are used for anionic polymerization, cationic polymerization, and radical polymerization according to the reactivity of the polymerizable group. In the case where it has, a liquid crystalline polymer can be easily obtained by conducting a condensation reaction such as esterification, or adding a carbon-carbon double bond to a hydrogen-silicon bond (hydrosilylation).

  The compounds represented by the formulas (1) to (3) having a reactive group may be added with various antioxidants, ultraviolet absorbers and light stabilizers in order to improve storage stability. . Furthermore, other additives such as a chain transfer agent, a copolymerizable compound (reactive diluent, etc.), a surfactant, a fluidity improver, an antifoaming agent as long as they do not interfere with the liquid crystal properties of the resulting polymer. Agents, colorants, pigments and the like may be added.

  The polymerization is preferably carried out in a solvent that can dissolve the compounds represented by the formulas (1) to (3) and the polymer to be produced. Examples of the solvent include hexane, heptane, octane, decane, and cyclohexane. , Decahydronaphthalene, benzene, toluene, xylene, mesitylene, methyl isobutyl ketone, tetrahydrofuran, cyclohexanone, N-methyl-2-pyrrolidinone, γ-butyrolactone, ethyl acetate, ethyl lactate, ethyl benzoate, dimethylformamide, dimethylacetamide, ethylene Examples thereof include glycol dimethyl ether, diethylene glycol dimethyl ether, ethanol, propanol, butoxyethanol, hexyloxyethanol, chloroform, chlorobenzene and the like, and mixtures thereof. The produced polymer (polymer) can be recovered by, for example, vacuum distillation of the solvent or reprecipitation in a poor solvent such as methanol.

  The polymerization can also be performed by photopolymerization. The photopolymerization may be appropriately selected from known methods and conditions. Examples of the light used include ultraviolet rays, infrared rays, visible light, and X-rays. For example, when ultraviolet rays are used, it is preferable that the photopolymerization initiator suitable for the wavelength of the ultraviolet rays to be irradiated in the absence of oxygen or moisture and the compounds of the formulas (1) to (3) to be polymerized is 0.05. UV light from an appropriate light source in a state where the composition added to 20% by mass, preferably 0.2 to 10% by mass, is applied onto a substrate having orientation ability described later, or is sandwiched between two substrates. Irradiation is sufficient. When the addition amount of the photopolymerization initiator is outside the above range, the polymerization becomes insufficient, and it is not preferable because it remains after the photopolymerization and tends to be colored.

Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, trihalomethyltriazines, aromatic iodonium salts, aromatic sulfonium salts, aromatic phosphonium salts, Examples include diazodisulfone compounds.
Although the irradiation amount of ultraviolet rays cannot be generally determined by the composition or irradiation temperature of the composition, it is 10 mJ / cm ^{2 to 2} J / cm ² , preferably 50 mJ / cm ^{2 to 1} J / cm ² . Outside this range, polymerization is insufficient, and it is not preferable because it tends to deteriorate due to overexposure.
The ultraviolet light source is not particularly limited as long as it is a light source that generates a large amount of ultraviolet light, and examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and an electrodeless discharge lamp.

  The liquid crystalline polymer of the present invention thus obtained has different liquid crystal phase behavior (phase transition temperature) and optical anisotropy (birefringence) depending on the compounds represented by formulas (1) to (3) and the molecular weight. However, the birefringence Δn (measured at 550 nm) measured in the liquid crystal phase is preferably 0.20 or more, particularly preferably 0.25 or more.

  Although there is no restriction | limiting in particular in the molecular weight of the liquid crystalline polymer of this invention, Usually, it is 2000-500000 in a number average molecular weight, Preferably it is 3000-50000. Outside this range, the molded product is brittle, and it is not preferable because it is difficult to develop a sufficient liquid crystal phase.

  The liquid crystalline polymer of the present invention can usually be used as an optical element such as a retardation film in the form of a film utilizing optical anisotropy. Molding is preferably performed by heating and melting on a substrate having orientation ability, or an appropriate solvent capable of dissolving the polymer, such as hexane, heptane, octane, decane, benzene, toluene, xylene, mesitylene, methyl isobutyl ketone, tetrahydrofuran. , Cyclohexanone, N-methyl-2-pyrrolidinone, γ-butyrolactone, ethyl acetate, ethyl lactate, ethyl benzoate, dimethylformamide, dimethylacetamide, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethanol, propanol, butoxyethanol, hexyloxyethanol, chloroform , Formed using a solution dissolved in chlorobenzene or the like or a mixture thereof. The solvent used is preferably removed by drying, and examples of the method include natural drying, heat drying, reduced pressure drying, and reduced pressure heating.

Further, in the above-described photopolymerization method, when the compounds of the formulas (1) to (3) which are monomers exhibit liquid crystallinity, polymerization is performed in a state where the alignment of the liquid crystal is maintained, and the alignment state is fixed. You can also
When using a solution, it can be performed using an appropriate apparatus such as a spin coater, a bar coater, a roll coater, or a die coater. Examples of the substrate having the alignment ability include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, norbornene-based resin subjected to alignment treatment such as alignment film coating, rubbing treatment, oblique vapor deposition, stretching, and photo-alignment. , Polyimide, polycarbonate, polysulfone, polyethersulfone, polyetheretherketone, polyarylate, polyvinyl alcohol, polyphenylene sulfide and other plastic films and glass plates, microgroove-attached iron, copper, aluminum and other metal plates and foils, etc. These may be a sheet or a long film.

  The obtained film is preferably heat-treated and sufficiently oriented. The heating temperature may be appropriately set according to the liquid crystal phase temperature range of the liquid crystalline polymer used and the heat resistance of the substrate, and the alignment is generally a temperature range in which a liquid crystal phase is formed, for example, a nematic phase transition temperature or higher. Although it is performed at a temperature lower than the phase transition temperature, the liquid crystal polymer can be heated to a temperature equal to or higher than the isotropic phase to obtain an isotropic phase, and then the desired orientation can be formed by adjusting the cooling rate. . The alignment treatment time can also be appropriately determined, but is usually 10 seconds to 30 minutes. It should be noted that various additives such as antioxidants, UV absorbers and light stabilizers for the purpose of improving the stability and uniformity of films in melt formation and solution coating, surfactants and antifoams for improving wettability. You may add an agent etc. in the range which does not deviate from the objective of this invention. These addition amounts can also be appropriately determined from a generally used range. Various compounds having an optically active group that can be mixed with or without liquid crystallinity can also be added to form cholesteric alignment.

  Since the thickness of the film varies depending on the application, it cannot be determined unconditionally, but is usually 0.05 μm to 50 μm, preferably 0.1 to 20 μm. Outside this range, the uniformity of the film thickness deteriorates and the orientation becomes insufficient, which is not preferable.

In the case where the substrate having the alignment ability is not optically preferable such as coloring or opaqueness, the heat-aligned film can be transferred to another substrate suitable for the purpose of use via an adhesive or an adhesive. .
The pressure-sensitive adhesive and adhesive used for transfer (hereinafter referred to as “sticky / adhesive”) are not particularly limited as long as they are optical grades having appropriate adhesive strength at both interfaces to be bonded. Examples of polymer systems, epoxy resin systems, ethylene-vinyl acetate copolymer systems, rubber systems, urethane systems, and mixtures thereof, and various reactive types such as thermosetting and / or photo-curing and electron beam curing However, the photo-curing type is preferable from the viewpoint of easy processing.

As the photo-curing acrylic tacky / adhesive, those which are appropriately modified according to the adhesiveness of a commercially available ultraviolet (UV) curable tacky / adhesive or a liquid crystalline composition can be used.
Acrylic viscosity / adhesives include various (meth) acrylic monofunctional and polyfunctional monomers, oligomers such as polyester (meth) acrylate and polyurethane (meth) acrylate, photopolymerization initiators, viscosity adjustment An agent (thickening agent), an additive such as a surfactant or a dispersant, and the like may be added as appropriate.
In addition, surface treatment such as corona discharge treatment, ultraviolet irradiation treatment, or flame treatment may be performed on the surface to be adhered in order to improve adhesion during transfer.

  Furthermore, for the purpose of light diffusion and scattering, (fine) particles having a refractive index different from that of the acrylic adhesive / adhesive may be added. Examples of the material of the (fine) particles include silica, alumina, ITO, silver, and various (crosslinked) plastics. In addition, the adhesive / adhesive layer includes, for example, natural and synthetic resins, in particular, tackifier resins, fillers made of glass fiber, glass beads, metal powder, other inorganic powders, pigments, coloring It may contain an additive that may be added to an adhesive or an adhesive such as an antioxidant or an antioxidant. The amount of these additives cannot be determined unconditionally depending on the type, components, functions, etc., but is usually preferably 0.01% by mass to 20% by mass with respect to the acrylic adhesive / adhesive.

As the other substrate, those hitherto known can be used without particular limitation, for example, a film of polycarbonate, norbornene resin, triacetyl cellulose, acrylic, maleimide, styrene resin or the like is stretched. And a reflective polarizing element made of a laminate of a plurality of resin thin films having different refractive indexes.
The obtained film can be used for an optical film, a polarizing plate, a compensation plate, a reflective film, and the like. For example, as a liquid crystal display element used for a compensation plate of a liquid crystal display element, a TN (twisted nematic) type, an STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical alignment) type , ECB (electrically controlled birefringence) type, ASM (axisymmetric microcell) type liquid crystal display elements, and the like.

The liquid crystalline polymer of the present invention can be used as a composition for PDLC, polymer gel, polymer network display, or the like.
The liquid crystal polymer composition and the electro-optical device (liquid crystal cell) can be produced by a method known per se.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Various measurement methods and the like used in Examples and Comparative Examples will be described.

1. Measurement of birefringence The birefringence was measured using the following equipment.
Polarization microscope: ECLIPSE LV 100 POL (Nikon Corporation)
Optical fiber: BIF600-VIS-NIR, manufactured by Ocean optics, Inc. Spectrometer: USB4000, manufactured by Ocean optics, Inc. Evaluation liquid crystal cell: KSRP-03 / B311P1NSS05, manufactured by EACH Co., Ltd.)
The measurement temperature was a liquid crystal phase temperature that was 10 ° C. lower than the isotropic phase transition temperature, the spectrum was measured in the wavelength range of 400 to 1000 nm, and was determined according to the following.

(1) Measurement of cell gap Light is applied from below the cell without enclosing liquid crystal, and the transmitted interference light is measured to determine the thickness of the air layer (equation (1)). Is the cell gap.
2d = mλ (1)

(2) Microspectroscopy analysis A birefringent material prepared by enclosing liquid crystal in a cell with the cell gap d determined in (1) above and homogeneously aligning it is sandwiched between two polarizers whose polarization axes are orthogonal to each other. Cauchy's dispersion formula that expands the value of the wavelength (equation (2)) at which the spectral transmittance measured in this way is maximum or minimum and the retardation of the birefringent body (expression (3)) at each wavelength up to the fourth order. Fitting was performed according to (Expression (4)), and the birefringence Δn of the birefringent body and the wavelength dispersion of the retardation R were determined.

2. Measurement of DSC Using DSC7 manufactured by Perkin-Elmer, measurement was performed at a temperature increase / decrease rate of 10 ° C./min in a nitrogen atmosphere.

3. Polarized light microscope observation (judgment of liquid crystal phase behavior)
The phase behavior of the liquid crystals was examined together with the DSC measurement results using an Olympus polarizing microscope (model BX50) equipped with a Mettler FP82 hot stage equipped with a temperature controller Mettler FP90 central processor.
Cr represents a crystalline phase, S represents a smectic phase, N represents a nematic phase, and Iso represents an isotropic phase.

4). Measurement of NMR spectrum A sample was dissolved in deuterated Kurroform, deuterated dimethylformamide or deuterated dimethylsulfoxide solvent using tetramethylsilane (TMS) as an internal standard, and ¹ H and / or by an NMR apparatus (JEOL LNM-EX400). Alternatively, a ¹³ C-NMR spectrum was measured.

5. Measurement of molecular weight Set TOSOH TSKgel G3000HXL or G4000HXL as a separation column in a gel permeation chromatograph equipped with JASCO UV-2070 detector and JASCO RI-2031 detector as detectors, and THF solvent (flow rate: 1 ml / min at 25 ° C). ). Standard polystyrene was used for calibration of molecular weight.

6). In addition, the following equipment was used as needed.
FT-IR: JASCO FT-IR 460 plus spectrometer
UV-vis spectrum: Beckman Coutler DU800 UV-vis Spectrometer
High resolution mass spectrum: JEOL JMS700 mass spectrometer

[Example 1]
A. Synthesis of acrylate monomers

(Abbreviation)
n-BuLi n-Butyllithium
DIPEA Diisopropylethylamine
DMF Dimethylformamide
MeOH methanol,
MMACl Methacrylol chloride
Ph phenyl group
TBAF Tetrabutylammonium fluoride
TBDMSCl tert-butyldimethylsilyl chloride
TEA Triethylamine
THF tetrahydrofuran
TMS trimethylsilyl group

(1) Synthesis of Compound 1 4-iodophenol (5.5 g, 25.1 mmol), 6-bromo-1-hexanol (5.0 g, 27.6 mmol), potassium carbonate (4.2 g, 30.1 mmol) and A mixture of DMF (50 ml) was reacted at reflux for 18 h. The solvent was removed under reduced pressure, and the residue was extracted with diethyl ether, washed with water and dried over MgSO ₄ , and diethyl ether was distilled off. The residue was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain Compound 1 (8.1 g, yield: 99%).
<Spectral data>
¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 7.54 (d, J = 8.52 Hz, 2H), 6.67 (d, J = 8.56 Hz, 2H), 3.92 (t, J = 6.40 Hz, 2H), 3.67 (q, J = 6.01 Hz, 2H), 1.79 (quint, J = 6.95 Hz ,, 2H), 1.64-1.1.36 (m, 6H), 1.26 (s, 1H).

(2) Synthesis of Compound 2 A mixture of TEA (20 ml) degassed with argon and trimethylsilylacetylene (5.5 ml, 40 mmol) was converted into Compound 1 (8.0 g, 25 mmol), Pd (PPh ₃ ) ₄ obtained above. (0.58 g, 0.050 mmol), CuI (95 mg, 0.050 mmol) and PPh ₃ (0.13 g, 0.050 mmol) were added to the mixture, followed by stirring and reaction at 45 ° C. for 2 days.
Diethyl ether was added to the reaction mixture, insoluble salts were removed by filtration, washed with aqueous hydrochloric acid and water, dried over MgSO ₄ , diethyl ether was distilled off, and the residue was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/2) Treatment gave compound 2 (yield: 99%).
<Spectral data>
¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 7.34 (d, J = 8.32 Jz, 2H), 6.80 (d, J = 8.08 Hz, 2H), 4.12 (q, J = 7.41 Hz, 2H), 3.95 (t, J = 6.58 Hz, 2H), 1.82-1.75 (m, 2H), 1.64-1.1.39 (m, 6H), 1.26 (s, 1H).

(3) Synthesis of Compound 3 The obtained compound 2 (3.07 g, 14.1 mmol), TBAF (16 ml, 16 mmol) and THF (50 ml) were stirred for 15 minutes, and then the solvent was removed under reduced pressure. The residue was extracted with diethyl ether, washed with water, MgSO4. Then, the diethyl ether was removed.
The residue was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 1/3) to obtain compound 3 (yield based on compound 2: 68%).
<Spectral data>
¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 7.41, (d, J = 8.76 Hz, 2H), 6.82 (d, J = 8.80 Hz, 2H), 3.96 (t, J = 6.52 Hz, 2H), 3.66 (t, J = 6.48 Hz, 2H), 2.99 (s, 1H), 1.80 (quint, J = 6.89 Hz, 2H), 1.64-1.35 (m, 6H), 1.29 (s, 1H)

(4) Synthesis of compound 4
To a solution of compound 3 (1.10 g, 5.00 mmol) and imidazole (0.45 g, 6.50 mmol) in CH ₂ Cl ₂ (30 mL) was added tert-butyl-dimethyl-silyl chloride (0.98 g, 6. 50 mmol) was added and stirred at room temperature for 3 h. The reaction mixture was extracted with CH ₂ Cl ₂ , washed with water, dried over MgSO ₄ and concentrated.
The crude product was treated with flash column chromatography using silica gel (eluent: ethyl acetate / hexane = 1/10) to obtain compound 4 (yield: 99%).
<Spectral data>
¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 7.41, (d, J = 8.56 Hz, 2H), 6.82 (d, J = 8.76 Hz, 2H), 3.95 (t, J = 6.46 Hz, 2H), 3.61 (t, J = 6.48 Hz, 2H), 2.99 (s, 1H), 1.79 (quin, J = 6.90 Hz, 2H), 1.56-1.34 (m, 6H), 0.89 (s, 9H), 0.04 (s , 6H).

(5) Synthesis of compound 5
At 0 ° C., carbon tetrabromide (6.6 g, 20 mmol) was added to a CH ₂ Cl ₂ solution in which PPh ₃ (10.5 g, 40 mmol) was dissolved. After stirring for 15 minutes, 4-hexyloxybenzaldehyde (2.10 g) was added. , 10 mmol). After 3 h, methanol was added to stop the reaction, extraction was performed with chloroform, and the organic layer was washed with an aqueous sodium thiosulfate solution and an aqueous sodium chloride solution and dried over MgSO ₄ .
After evaporating the solvent under reduced pressure, the residue was treated with silica gel column chromatography (eluent: ethyl acetate / hexane = 1/10) to obtain Compound 5 (1.79 g, yield: 49%).
<Spectral data>
¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 7.50, (d, J = 8.80 Hz, 2H), 7.40 (s, 1H), 6.88 (d, J = 7.68 Hz, 2H), 3.96 (t, J = 6.58 Hz, 2H), 1.78 (quin, J = 7.02 Hz, 2H), 1.49-1.29 (m, 6H), 0.91 (t, 3H).

(6) Synthesis of compound 6
The compound 4 (1.9 g, 5.7 mmol) / THF (30 mL) solution was cooled to −78 ° C., n-BuLi (2.2 mL, 2.6 M, 5.8 mmol) was added, and after 30 minutes of reaction, anhydrous ZnCl ₂ (0.79 g, 5.8 mmol) / THF (15 mL) solution was added at −78 ° C. After maintaining the same temperature for 15 minutes, the temperature was returned to 0 ° C. over 30 minutes.
A solution obtained by adding Compound 5 (2.0 g, 5.7 mmol) to the zinc-containing solution was added to Pd (PPh ₃ ) ₄ (0.33 g, 0.28 mmol) / THF (5 mL), and the solution was added at 0 ° C. for 2 days. The reaction was stirred. The reaction was stopped by adding NH ₄ Cl aqueous solution, extracted with diethyl ether, and the organic layer was washed with NaHCO ₃ aqueous solution and saturated aqueous sodium chloride solution. And dried over MgSO _4. Concentration under reduced pressure and silica gel column chromatography (eluent: ethyl acetate / hexane = 1/10) gave compound 6.
<Spectral data>
¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 7.69 (d, J = 9.04, 2H), 7.41 (d, J = 8.56 Hz, 2H), 7.21 (s, 1H), 6.89 (d, J = 8.80 , 2H), 6.85 (d, J = 8.76 Hz, 2H), 3.97 (q, J = 6.35 Hz, 4H), 3.62 (t, J = 6.46 Hz, 2H), 1.86-1.73 (m, 4H).

(7) Synthesis of compound 7
A 1.0 M / L TBAF / THF solution (4.80 mL, 4.80 mmol) was added to a solution of Compound 6 (1.60 g, 2.60 mmol) / THF (20 ml) under an argon atmosphere, and the mixture was reacted at room temperature for 1 day. It was.
The organic layer was extracted with chloroform, washed with water and dried over MgSO ₄ . The solvent was removed, and the residue was treated with silica gel column chromatography (eluent: chloroform / ethyl acetate / hexane = 1/1/1) to obtain Compound 7 (1.05 g).
<Spectral data>
¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 7.44 (d, J = 8.80 Hz, 4H), 6.83 (d, J = 8.56 Hz, 4H), 3.98-3.94 (m, 4H), 3.70-3.62 ( m, 2H), 1.83-1.74 (m, 4H), 1.64-1.33 (m, 12H), 0.90 (t, J = 6.84 Hz, 3H).

(8) Synthesis of Compound 8
To a solution of Compound 7 (0.97 g, 2.30 mmol) and TEA (3.00 ml, 3.00 mmol) / CH ₂ Cl ₂ (35 ml) was added methacryloyl chloride (0.29 ml, 3.00 mmol) and reacted at room temperature for 7 h. I let you.
The reaction mixture was extracted with chloroform, the organic layer was dried over MgSO ₄ , the solvent was distilled off, and the crude product was treated with flash column chromatography using silica gel (eluent: ethyl acetate / hexane = 1/2) to give a compound. 8 was obtained. The ¹ H-NMR spectrum of Compound 8 is shown in FIG. 1, and the DSC chart is shown in FIG.
<Spectral data>
¹ H NMR (400 MHz, CDCl ₃ , ppm) δ 7.47-7.40 (m, 4H), 6.83 (dd, J = 9.04 and 2.44 Hz, 4H), 6.10 (s, 1H), 5.55 (s, 1H), 4.16 (t, J = 6.58 Hz, 2H), 3.98-3.94 (m, 4H), 1.94 (s, 3H), 1.82-1.67 (m, 6H), 1.53-1.31 (m, 10H), 0.91 (t, J = 6.72 Hz, 3H).

B. Synthesis of Polymer Under argon atmosphere, 5 mol% of n-BuLi solution is added to 0.5 mol / L THF solution of Compound 8 obtained in (8) above, and reacted at −10 ° C. for 24 hours. I let you.
The polymerization solution was dropped into an excess amount of MeOH to precipitate a polymer, and then purified by reprecipitation.
The polymer obtained had a number molecular weight (Mn) of 7990 (measured by GPC) and a molecular weight distribution (Mw / Mn) of 1.69. From the results of DSC measurement of the polymer (FIG. 4), the liquid crystal phase behavior was as follows.
C 70.3 ° C N 141.3 ° C I
In addition, a polymer heated to an isotropic phase temperature is poured into a cell having a gap adjusted to 3 μm, cooled to below the glass transition temperature at 10 ° C./min, and then optical properties (wavelength dependence of birefringence) at room temperature. It was measured. The results are shown in FIG.

  The liquid crystalline polymer having a diacetylene structure of the present invention has a large refractive index anisotropy, is useful as a constituent member of various liquid crystal display elements, and can be easily formed into a film or the like, and is optical or electro-optical. It can be used for such purposes.

Claims (10)

A liquid crystalline polymer having a diacetylene structure obtained by reacting a compound represented by the following general formula (A).
R1-Sp1- (Ar1) _p- (Ar3) _q- (Phe) _r- C≡CC≡C- (Phe) _r- (Ar4) _q- (Ar2) _p- Sp2-R2 (A)
Wherein R 1 and R 2 are independently of each other a hydrogen atom, a halogen atom, a cyano group, an isothiocyanate group, or an unsubstituted or halogen atom, a cyano group, trifluoromethyl having 1 to 15 carbon atoms. An alkyl group mono- or polysubstituted by a group or reactive group, having 2 to 15 carbon atoms and unsubstituted or mono- or polysubstituted by halogen atom, cyano group, trifluoromethyl group or reactive group Represents an alkenyl or alkynyl group or a reactive group, wherein one or more non-adjacent —CH ₂ — groups are substituted by —O—, —CO—, —COO— and / or —OCO—. Provided that at least one of R 1 and R 2 has a reactive group, and Sp 1 and Sp 2 are independently of each other —O—, S -, - CO -, - COO -, - OCO -, - OCO-O -, - CO-NR3 -, - NR3-CO -, - O (CH 2) n -, - (CH 2) n O- , -CH = CH-COO -, - OCO-CH = CH -, - (CH 2) m -, - (SiR4R5-O) n - or a single bond, 1 where m and n are independently Represents an integer of 10, R 3, R 4 and R 5 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Ar 1 and Ar 2 are independently of each other an unsubstituted or halogen atom, a cyano group, a trifluoromethyl group, An aromatic carbocyclic or heterocyclic group having up to 16 carbon atoms which is mono- or poly-substituted by a methyl group, an ethyl group, a methoxy group or an ethoxy group, and may contain a condensed ring, Ar 3 and Ar 4 Are independent of each other A heterocyclic group having up to 16 carbon atoms which is substituted or monosubstituted or polysubstituted by a halogen atom, cyano group, trifluoromethyl group, methyl group, ethyl group, methoxy group or ethoxy group, and contains a condensed ring It may be a plurality of heterocyclic groups linked by a single bond, and Phe is unsubstituted or monosubstituted by a halogen atom, a cyano group, a trifluoromethyl group, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. Represents a polysubstituted 1,4-phenylene group, and p, q and r are each 0 or 1) The liquid crystalline polymer according to claim 1, wherein the compound represented by the general formula (A) is a compound represented by the following general formula (1).
R1-Sp1-Ar1-Phe-C≡C-C≡C-Phe-Ar2-Sp2-R2 (1) The liquid crystalline polymer according to claim 1, wherein the compound represented by the general formula (A) is a compound represented by the following general formula (2).
R1-Sp1-Ar3-C≡C-C≡C-Ar4-Sp2-R2 (2) The liquid crystalline polymer according to claim 1, wherein the compound represented by the general formula (A) is a compound represented by the following general formula (3).
R1-Sp1-Phe-C≡C-C≡C-Phe-Sp2-R2 (3)   The reactive group is a hydroxyl group, a carboxyl group, an acid anhydride group, a maleimide group, a vinyloxy group, an oxiranyl group, an oxetanyl group, a vinyl group, a (meth) acrylate group, or a silyl group. Item 5. A liquid crystalline polymer having a diacetylene structure according to any one of Items 1 to 4.   6. The liquid crystalline polymer having a diacetylene structure according to claim 5, wherein the reactive group is a vinyl group, a (meth) acrylate group, an oxiranyl group, or an oxetanyl group.   Ar1 and Ar2 are thiophene-2,5-diyl group, 1,4-phenylene group, naphthalene-2,6-diyl group, pyridine-2,5-diyl group, or pyrimidine-2,5-diyl group. The liquid crystalline polymer having a diacetylene structure according to claim 1 or 2, wherein the liquid crystalline polymer has a diacetylene structure.   4. The di of claim 1, wherein Ar 3 and Ar 4 are a thiophene-2,5-diyl group, a pyridine-2,5-diyl group, or a pyrimidine-2,5-diyl group. A liquid crystalline polymer having an acetylene structure.   The liquid crystalline polymer composition containing the liquid crystalline polymer which has a diacetylene structure in any one of Claims 1-8.   The liquid crystalline polymer according to claim 1, wherein the liquid crystalline polymer is used for optical or electro-optical use.

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