JP2012107198A - Compound suitable for optical orientation method and photosensitive polymer comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound suitable for optical orientation method, a photosensitive polymer obtained by performing polymerization of the compound, a photo-orientation agent comprising the polymer, and a liquid crystal orientation membrane using the photo-orientation agent.SOLUTION: The compound is represented by formula (1-1) or (1-2), and the polymer is obtained by performing polymerization of these compounds. In formula (1-1) or (1-2), W1 and W2 are independently hydrogen, fluorine, chlorine, trifluoromethyl, 1-5C alkyl or 1-5C alkoxy, Ais independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, or the like, Zis independently a single bond, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, or the like, Rand Rare independently hydrogen, fluorine, chlorine, trifluoromethyl, or 1-5C alkyl, Qand Qare independently a single bond or 1-12C alkylene, and arbitrary hydrogen of the alkylene can be substituted by fluorine, also arbitrary -CH2- can be substituted by -O-, -COO-, -OCO-, -CH=CH-, or -C≡C-, n is an integer of 0-4, and m is 0 or 1.

Description

  The present invention relates to a compound suitable for a photo-alignment method and a photosensitive polymer comprising the compound. Furthermore, the present invention relates to a photo-alignment agent comprising the polymer, a liquid crystal alignment film using the photo-alignment agent, and an optical film and a liquid crystal display element using the liquid crystal alignment film.

  Liquid crystal display elements are used in various liquid crystal display devices such as monitors for notebook computers and desktop computers, video camera viewfinders, projection displays, and televisions. Furthermore, it is also used as an optoelectronic-related element such as an optical printer head, an optical Fourier transform element, or a light valve. As a conventional liquid crystal display element, a display element using nematic liquid crystal is mainly used, and the alignment direction of the liquid crystal in the vicinity of one substrate and the alignment direction of the liquid crystal in the vicinity of the other substrate are twisted at an angle of 90 °. There are TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode in which the alignment direction is twisted at an angle of 180 ° or more, and so-called TFT (Thin-Film-Transistor) mode liquid crystal display elements using thin film transistors. It has been put into practical use.

  However, these liquid crystal display elements have a narrow viewing angle for properly recognizing an image, and when viewed from an oblique direction, luminance and contrast may be reduced, and luminance inversion may occur in a halftone. In recent years, this viewing angle problem has been caused by a TN liquid crystal display element using an optical compensation film, an MVA (Multi-domain Vertical Alignment) mode (see Patent Document 1) or a horizontal alignment and a technology of a protruding structure. This is improved by an electric field type IPS (In-Plane Switching) mode (see Patent Document 2).

  The development of the technology of the liquid crystal display element has been achieved not only by improving the drive system and the element structure, but also by improving the components used for the display element. Among the constituent members used in display elements, the liquid crystal alignment film is one of the important elements related to the display quality of the liquid crystal display element, and the role of the liquid crystal alignment film is increasing as the quality of the display element increases. It has become important year after year.

  The liquid crystal alignment film needs to uniformly control the molecular arrangement of the liquid crystal for the uniform display characteristics of the liquid crystal display element. Therefore, it is required to uniformly align the liquid crystal molecules on the substrate in one direction and to develop a certain tilt angle (pretilt angle) from the substrate surface.

  Further, in order to realize an improvement in contrast of an image display device and an expansion of a viewing angle range, for example, a stretched film having refractive index anisotropy or a polymerizable liquid crystalline compound is aligned as an optical compensation film or a retardation film. Thereafter, a film obtained by polymerizing a compound is used. A liquid crystal alignment film is also used for aligning the polymerizable liquid crystal compound. A liquid crystal alignment film that uniformly aligns the directions of liquid crystal molecules on a substrate is used in various scenes in the manufacturing process of a liquid crystal display element, and the technology is important and indispensable.

  The liquid crystal alignment film is prepared using a liquid crystal alignment agent. Currently, the liquid crystal aligning agent mainly used is a solution obtained by dissolving polyamic acid or soluble polyimide in an organic solvent. After applying such a solution to a substrate, a polyimide-based liquid crystal alignment film is formed by film formation by means such as heating. Various liquid crystal aligning agents other than polyamic acid are also being studied, but they are almost practical in terms of heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment properties, electrical properties, optical properties, display properties, etc. It has not reached.

  Industrially, a rubbing method that is simple and capable of high-speed processing of a large area is widely used as an alignment processing method. The rubbing method is a process of rubbing the surface of the liquid crystal alignment film in one direction using a cloth in which fibers of nylon, rayon, polyester, or the like are planted, and this makes it possible to obtain uniform alignment of liquid crystal molecules. However, the rubbing method generates a lot of dust and static electricity, and there is a concern about the influence on alignment defects and liquid crystal elements.

  Therefore, in recent years, an alignment treatment method that replaces the rubbing method has been developed. As for the photo-alignment method in which alignment treatment is performed by irradiating light, many alignment methods such as a photolysis method, a photoisomerization method, a photodimerization method, and a photocrosslinking method have been proposed (Non-patent Documents 1 and 3). And Patent Document 4). Unlike the rubbing method, the photo-alignment method is a non-contact alignment method, and in principle, dust generation and static electricity are less generated than the rubbing treatment.

  By using a liquid crystal alignment film that has been aligned by the photo-alignment method and has good alignment properties, it is possible to control the molecular alignment state of the liquid crystal monolayer that is in contact with the liquid crystal alignment film. Can be expected to improve the performance.

  Cinnamic acid compounds are known to undergo photoisomerization and photodimerization when irradiated with ultraviolet light. From this feature, a method of obtaining a liquid crystal alignment film by irradiating a polymer having a cinnamic acid compound or a derivative of a cinnamic acid compound in a side chain to perform alignment treatment has been proposed (see Patent Document 5 and Patent Document 6). .) These polymers use photoreactive groups in the molecular structure of cinnamic acid compounds to obtain a liquid crystal alignment film, so that the complicated processing steps found in conventional rubbing treatment and subsequent dust generation and static electricity are not generated. . Therefore, a liquid crystal alignment film having high optical uniformity without alignment defects can be obtained. The liquid crystal display element manufactured using this liquid crystal aligning film has high orientation. However, since these polymers are side chain type polymers, their alignment regulation force may be impaired by heat. For this reason, it is difficult to expect stable orientation of a liquid crystal display device manufactured using the liquid crystal alignment film. In recent years, optical films using polymerizable liquid crystals have been devised. As the optical film, an alignment film that has been subjected to an alignment treatment by a photo-alignment method is used (Patent Document 7). Such an alignment film is required to have properties such as solvent resistance, adhesion, transparency, and light resistance in addition to high orientation.

Japanese Patent No. 2947350 Japanese Patent No. 2940354 JP 2005-275364 A Japanese Patent Laid-Open No. 11-15001 Japanese Patent No. 3611342 Japanese Patent No. 4011652 JP 2009-109831 A

Liquid Crystal Vol. 3 No. 4, edited by the Japanese Liquid Crystal Society Editorial Board, published by the Japanese Liquid Crystal Society, 1999, page 262

  The present invention aims to solve the above-described problems, and provides a compound suitable for a photo-alignment method, a photosensitive polymer obtained by polymerizing the compound, and a photo-alignment agent comprising the polymer. is there. Furthermore, the orientation is good without orientation treatment by the conventional rubbing method using the photo-alignment agent, the orientation uniformity is excellent, the solvent resistance is excellent, the adhesion to the substrate is excellent, and the transparency is high. An object of the present invention is to provide a liquid crystal alignment film suitable for a photo-alignment method that satisfies a plurality of characteristics such as high characteristics and excellent light resistance.

  As a result of diligent research and development, the present inventors have used a photo-alignment agent composed of a photosensitive polymer obtained by polymerizing a compound suitable for the photo-alignment method as a liquid crystal aligning agent. The liquid crystal alignment film having good alignment, excellent alignment uniformity, excellent solvent resistance, excellent adhesion to the substrate, high transparency and excellent light resistance has been realized.

  Using a photosensitive polymer whose structural unit is a compound having a cyclic ether group represented by the formula (1), the photo-alignment agent comprising the polymer was irradiated with light and the alignment treatment was applied and formed. The present invention relates to a liquid crystal alignment film. That is, the present invention is as follows.

式（１）において、Ｙは独立して、式（２−１）または式（２−２）で表される２価の基であり、Ｙのうち少なくとも一つは式（２−１−１）または式（２−２−１）で表される基であり；
Ｒ^１およびＲ^２は独立して水素、フッ素、塩素、トリフルオロメチルまたは炭素数１〜５のアルキルであり；
Ｑ^１およびＱ^２は独立して単結合または炭素数１〜１２のアルキレンであり、このアルキレン中の任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；
ａは１〜５の整数であり；
ｍは０または１であり；

式（２−１）および式（２−２）において、Ａ^１は独立して、１，４−フェニレン、１，４−シクロヘキシレン、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、または１，３−ジオキサン−２，５−ジイルであり、この１，４−フェニレンにおいて、任意の水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシで置き換えられてもよく；
式（２−１）および式（２−２）において、Ｚ^１は独立して単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−であり；
式（２−１−１）および式（２−２−１）において、Ｗ^１およびＷ^２は独立して水素、フッ素、塩素、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシである。 [1] Compound represented by formula (1):

In Formula (1), Y is independently a divalent group represented by Formula (2-1) or Formula (2-2), and at least one of Y is represented by Formula (2-1-1). Or a group represented by formula (2-2-1);
R ¹ and R ² are independently hydrogen, fluorine, chlorine, trifluoromethyl or alkyl having 1 to 5 carbons;
Q ¹ and Q ² are each independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — is —O—, — May be replaced by COO-, -OCO-, -CH = CH- or -C≡C-;
a is an integer from 1 to 5;
m is 0 or 1;

In Formula (2-1) and Formula (2-2), A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl. , Naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, or 1,3-dioxane-2,5-diyl, in which 1,4-phenylene is optionally hydrogen, fluorine, chlorine, cyano , Hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
In Formula (2-1) and Formula (2-2), Z ¹ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO. _{, - - -CH 2 CH 2 CH} 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - _{OCF 2 -, - CONH -,} - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or -C≡C -Is;
In Formula (2-1-1) and Formula (2-2-1), W ¹ and W ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbons, or 1 to C carbons. 5 alkoxy.

式（１−１）または（１−２）において、Ｗ^１およびＷ^２は独立して水素、フッ素、塩素、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシであり；
Ａ^１は独立して、１，４−フェニレン、１，４−シクロヘキシレン、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、または１，３−ジオキサン−２，５−ジイルであり、この１，４−フェニレンにおいて、任意の水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシで置き換えられてもよく；
Ｚ^１は独立して単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−であり；
Ｒ^１およびＲ^２は独立して水素、フッ素、塩素、トリフルオロメチルまたは炭素数１〜５のアルキルであり；
Ｑ^１およびＱ^２は独立して単結合または炭素数１〜１２のアルキレンであり、このアルキレン中の任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；
ｎは０〜４の整数であり；
ｍは０または１である。 [2] Compound represented by formula (1-1) or (1-2):

In formula (1-1) or (1-2), W ¹ and W ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons. ;
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6. -Diyl or 1,3-dioxane-2,5-diyl, in which 1,4-phenylene is optionally hydrogen, fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl , Trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
Z ¹ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—. , —C≡C—COO—, —OCO—C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CONH—, —NHCO—, — (CH _{2) 4 -, - CH 2} CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or a -C≡C-;
R ¹ and R ² are independently hydrogen, fluorine, chlorine, trifluoromethyl or alkyl having 1 to 5 carbons;
Q ¹ and Q ² are each independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — is —O—, — May be replaced by COO-, -OCO-, -CH = CH- or -C≡C-;
n is an integer from 0 to 4;
m is 0 or 1.

[3] In the formula (1-1) or (1-2) according to [2], W ¹ and W ² are independently hydrogen, fluorine, alkyl having 1 to 3 carbons, or having 1 to 3 carbons. Is alkoxy;
A ¹ is independently 1,4-phenylene or 1,4-cyclohexylene, and in this 1,4-phenylene, arbitrary hydrogen is fluorine, trifluoromethyl, alkyl having 1 to 3 carbons or carbon number. 1 to 3 alkoxy may be substituted;
Z ¹ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ — or —CH ₂ CH ₂ —COO—. Is;
Q ¹ and Q ² are each independently a single bond or alkylene having 1 to 12 carbons, and any —CH ₂ — in the alkylene may be replaced by —O—;
R ¹ is hydrogen or methyl;
R ² is hydrogen, methyl or ethyl;
n is an integer from 0 to 2;
The compound according to [2], wherein m is 0 or 1.

[4] A photosensitive polymer obtained by polymerizing the compound according to any one of [1] to [3].

式（３）において、Ｙは独立して、式（２−１）または式（２−２）で表される２価の基であり、Ｙのうち少なくとも一つは式（２−１−１）または式（２−２−１）で表される基であり；
Ｒ^１およびＲ^２は独立して水素、フッ素、塩素、トリフルオロメチルまたは炭素数１〜５のアルキルであり；
Ｑ^１およびＱ^２は独立して単結合または炭素数１〜１２のアルキレンであり、このアルキレン中の任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；
ａは１〜５の整数であり；
ｍは０または１であり；
式（２−１）および式（２−２）において、Ａ^１は独立して、１，４−フェニレン、１，４−シクロヘキシレン、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、または１，３−ジオキサン−２，５−ジイルであり、この１，４−フェニレンにおいて、任意の水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシで置き換えられてもよく；
式（２−１）および式（２−２）において、Ｚ^１は独立して単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−であり；
式（２−１−１）および式（２−２−１）において、Ｗ^１およびＷ^２は独立して水素、フッ素、塩素、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシである。 [5] Photosensitive polymer having a structural unit represented by formula (3)

In Formula (3), Y is independently a divalent group represented by Formula (2-1) or Formula (2-2), and at least one of Y is represented by Formula (2-1-1). Or a group represented by formula (2-2-1);
R ¹ and R ² are independently hydrogen, fluorine, chlorine, trifluoromethyl or alkyl having 1 to 5 carbons;
Q ¹ and Q ² are each independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — is —O—, — May be replaced by COO-, -OCO-, -CH = CH- or -C≡C-;
a is an integer from 1 to 5;
m is 0 or 1;
In Formula (2-1) and Formula (2-2), A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl. , Naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, or 1,3-dioxane-2,5-diyl, in which 1,4-phenylene is optionally hydrogen, fluorine, chlorine, cyano , Hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
In Formula (2-1) and Formula (2-2), Z ¹ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO. _{, - - -CH 2 CH 2 CH} 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - _{OCF 2 -, - CONH -,} - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or -C≡C -Is;
In Formula (2-1-1) and Formula (2-2-1), W ¹ and W ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbons, or 1 to C carbons. 5 alkoxy.

式（３−１）または（３−２）において、Ｗ^１およびＷ^２は独立して水素、フッ素、塩素、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシであり；
Ａ^１は独立して、１，４−フェニレン、１，４−シクロヘキシレン、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、または１，３−ジオキサン−２，５−ジイルであり、この１，４−フェニレンにおいて、任意の水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシで置き換えられてもよく；
Ｚ^１は独立して単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−であり；
Ｒ^１およびＲ^２は独立して水素、フッ素、塩素、トリフルオロメチルまたは炭素数１〜５のアルキルであり；
Ｑ^１およびＱ^２は独立して単結合または炭素数１〜１２のアルキレンであり、このアルキレン中の任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；
ｎは０〜４の整数であり；
ｍは０または１である。 [6] Photosensitive polymer having a structural unit represented by formula (3-1) or (3-2):

In formula (3-1) or (3-2), W ¹ and W ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons. ;
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6. -Diyl or 1,3-dioxane-2,5-diyl, in which 1,4-phenylene is optionally hydrogen, fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl , Trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
Z ¹ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—. , —C≡C—COO—, —OCO—C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CONH—, —NHCO—, — (CH _{2) 4 -, - CH 2} CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or a -C≡C-;
R ¹ and R ² are independently hydrogen, fluorine, chlorine, trifluoromethyl or alkyl having 1 to 5 carbons;
Q ¹ and Q ² are each independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — is —O—, — May be replaced by COO-, -OCO-, -CH = CH- or -C≡C-;
n is an integer from 0 to 4;
m is 0 or 1.

[7] In the formula (3-1) or (3-2) according to [6], W ¹ and W ² are independently hydrogen, fluorine, alkyl having 1 to 3 carbon atoms, or having 1 to 3 carbon atoms. Is alkoxy;
A ¹ is independently 1,4-phenylene or 1,4-cyclohexylene, and in this 1,4-phenylene, arbitrary hydrogen is fluorine, trifluoromethyl, alkyl having 1 to 3 carbons or carbon number. 1 to 3 alkoxy may be substituted;
Z ¹ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ — or —CH ₂ CH ₂ —COO—. Is;
Q ¹ and Q ² are each independently a single bond or alkylene having 1 to 12 carbons, and any —CH ₂ — in the alkylene may be replaced by —O—;
R ¹ is hydrogen or methyl;
R ² is hydrogen, methyl or ethyl;
n is an integer from 0 to 2;
The photosensitive polymer as described in [6] whose m is 0 or 1.

[8] The photosensitive polymer according to any one of [4] to [7], which has a weight average molecular weight of 1,000 to 500,000.

[9] A homopolymer having the structural unit according to any one of [5] to [7].

[10] A copolymer comprising at least one of the structural unit represented by the formula (3) according to [5] and a structural unit other than the structural unit represented by the formula (3).

[11] Photosensitive material using the polymer according to any one of [4] to [10]

[12] A photo-alignment agent for a liquid crystal alignment film using the polymer according to any one of [4] to [10].

[13] A liquid crystal alignment film produced using the photoalignment agent according to [12].

[14] A liquid crystal display device manufactured using the liquid crystal alignment film according to [13].

  In the present invention, since the liquid crystal alignment film is formed using a compound having a photoreactive group, the complicated processing steps found in the conventional rubbing treatment and subsequent dust generation and static electricity are not generated. Therefore, a liquid crystal alignment film having high optical uniformity without alignment defects can be produced. In addition, an optical film and a liquid crystal display element manufactured using the liquid crystal alignment film can maintain high alignment stability.

The present invention will be described in detail.
In the present invention, the liquid crystal alignment film uses at least one kind of polymer having a photoreactive group (hereinafter referred to as “photosensitive polymer”). The photosensitive polymer is, for example, a compound that causes at least one of a photoisomerization reaction, a photodimerization reaction, and a photolysis reaction by irradiation with plane polarized light. The photosensitive polymer is preferably a compound that causes a photoisomerization reaction or a photodimerization reaction by light irradiation, and particularly preferably a compound that causes a photodimerization reaction. The photosensitive polymer preferably has a weight average molecular weight of about 1,000 to 500,000. It may be a single monomer polymer or a polymer of two or more different monomers. In the case of a copolymer composed of two or more different monomers, a monomer having a plurality of polymerizable groups may be used.

  Among the photosensitive polymers, a compound that undergoes a photoisomerization reaction refers to a compound that undergoes stereoisomerization or structural isomerization by the action of light. Examples of photoisomerized compounds include cinnamic acid compounds (K. Ichimura et al., Macromolecules, 30, 903 (1997)) and azobenzene compounds (K. Ichimura et al., Mol. Cryst. Liq. Cryst., 298, 221 (1997). ), Hydrazono-β-ketoester compounds (S. Yamamura et al., Liquid Crystals, vol. 13, No. 2, page 189 (1993)), stilbene compounds (JGVictor and JMTorkelson, Macromolecules, 20, 2241 (1987) )), And spiropyran compounds (K. Ichimura et al., Chemistry Letters, page 1063 (1992); K. Ichimura et al., Thin Solid Films, vol. 235, page 101 (1993)). Moreover, the compound which has these frame | skeleton in a polymer principal chain or a polymer side chain is also contained. Among these, a photoisomerized compound containing a double bond structure consisting of —CH═CH— or —N═N— is preferable.

  Among the photosensitive polymers, a compound that causes a photodimerization reaction refers to a compound that undergoes an addition reaction between two groups upon irradiation with light to cyclize. Examples of photodimerization compounds include cinnamic acid derivatives (M. Schadt et al., J. Appl. Phys., Vol. 31, No. 7, page 2155 (1992)) and coumarin derivatives (M. Schadt et al., Nature., Vol. 381, page 212 (1996)), chalcone derivatives (Toshihiro Ogawa et al., Proceedings of Liquid Crystal Panel Discussion, 2AB03 (1997)), benzophenone derivatives (YK Jang et al., SID Int. Symposium Digest, P -53 (1997)). Moreover, the compound which has the derivative which has these frame | skeleton in a polymer principal chain or a side chain is also contained. Among them, a polymer having a cinnamic acid derivative or a coumarin derivative skeleton in the side chain is preferable, and a polymer having a cinnamic acid derivative skeleton in the side chain (side chain polymer) is more preferable.

A material having such a photosensitive polymer is called a photosensitive material.
In addition to the liquid crystal alignment film, the photosensitive material can be used for a photoresist, holography, a light driving material, a retardation film, a polarized light emitting film, and the like.

  As the photoreactive group used for the liquid crystal alignment film, cinnamic acid derivatives are preferred because of their high photoreaction sensitivity, transparency, ease of production, and the like (Japanese Patent Laid-Open No. 2007-224273). However, a photosensitive polymer whose main chain of such a polymer is polyimide needs to be dissolved in a solvent such as N-methyl-2-pyrrolidone in order to be applied to a substrate, and further, about 180 degrees during film formation. It is necessary to fire at a high temperature. Therefore, it is difficult to use for a substrate (film such as TAC) which is eroded by a solvent such as N-methyl-2-pyrrolidone or does not have heat resistance of 150 ° C. or more.

  A polymer having a cinnamic acid derivative skeleton in the side chain is also used for this purpose (Japanese Patent No. 4011652). Examples of the polymerizable group constituting the repeating unit of the photosensitive polymer include a vinyl ester group, an acryloyl group, and a methacryloyl group. This is due to the ease of polymerization. However, side chain polymers having these polymerizable groups tend to have low solvent resistance, heat resistance, adhesion, mechanical strength, and the like. In order to solve such problems, improvement of heat resistance and mechanical strength can be considered by chemical methods such as copolymerization with polyfunctional acrylates and physical methods such as adding fillers. However, such a method may cause new problems such as a decrease in photoreaction sensitivity and a decrease in transparency.

  In the field of polymerizable liquid crystals, a method of introducing an oxetanyl group into a terminal group is known for the purpose of fixing the orientation of a side chain polymer such as (meth) acrylate (Japanese Patent Application Laid-Open No. 2004-123882). By increasing the cross-linked structure in this way, it is possible to expect improvement in properties such as solvent resistance. However, such a compound is not known in a side chain type polymer having a photoreactive group in a side chain such as a cinnamic acid derivative skeleton.

In the present specification, the compound represented by the formula (1) may be referred to as the compound (1). Similarly, compounds represented by other formulas may be abbreviated. The term “arbitrary” used in describing chemical formula symbols means “not only the position of an element (or functional group) but also its number can be freely selected”. And for example, the expression “any A may be replaced by B, C, D or E” means that one A may be replaced by any one of B, C and D, and any A May be replaced with two of B, C or D, and any two of A may be replaced with B and C, B and D, or C and D. When any —CH ₂ — may be replaced by —O—, such a replacement that results in the linking group —O—O— is not included.
In addition, having one polymerizable group may be referred to as monofunctional. In addition, having two or more polymerizable groups may be referred to as polyfunctional or a designation according to the number of polymerizable groups (for example, a bifunctional group having two polymerizable groups).
Further, a compound in which an arbitrary functional group is introduced into a certain A compound, or a compound in which an atom or the like is replaced may be referred to as a derivative or an A derivative.
The photosensitive polymer may be simply abbreviated as a polymer. Further, a liquid crystal display element may be abbreviated as a display element, and a liquid crystal alignment film may be abbreviated as an alignment film or a film.

式（１）中の各記号の定義は、前記式（１）中の記号の定義と同義である。 The compound of the present invention is a compound having at least one cinnamic acid skeleton represented by the formula (1).

The definition of each symbol in Formula (1) is synonymous with the definition of the symbol in Formula (1).

式（１−１）および（１−２）中の各記号の定義は、前記式（１−１）および（１−２）中の記号の定義と同義である。
以下に、式（１−１）および（１−２）で表される構成単位を有する化合物の具体例を示すが、本発明はこれらの具体例によって限定されるものではない。 Preferred are compounds represented by formulas (1-1) and (1-2).

The definition of each symbol in Formula (1-1) and (1-2) is synonymous with the definition of the symbol in said Formula (1-1) and (1-2).
Specific examples of the compound having structural units represented by formulas (1-1) and (1-2) are shown below, but the present invention is not limited to these specific examples.

The photosensitive polymer used in the present invention contains at least one cinnamic acid derivative. Preferably, it is a polymer having a structural unit represented by the formula (3).

More preferred is a photosensitive polymer having a structural unit represented by the formula (3-1) or (3-2).

The definitions of the symbols in the formulas (3), (3-1), and (3-2) are the same as the symbols in the formulas (3), (3-1), and (3-2). .
Specific examples of the photosensitive polymer having the structural units represented by formulas (3-1) and (3-2) are shown below, but the present invention is not limited to these specific examples.

  The photosensitive polymer may be a polymer mixture containing one or more structural units represented by the formula (3). The photosensitive polymer may be a copolymer containing one or more types of structural units other than the structural unit of the formula (3). There are no particular restrictions on the structure of other structural units other than the structural unit of formula (3) in the copolymer. Further, the copolymer containing two or more kinds of structural units may be a random copolymer or a block copolymer.

The structural unit other than the structural unit of the formula (3) is not particularly limited, but is, for example, a structure derived from a compound containing a cinnamic acid derivative represented by the formulas (M-1) and (M-2). Units can be used.

In formula (M-1) and formula (M-2), W ¹ , W ² , A ¹ , Z ¹ , R ¹ and Q ¹ are the definitions of formulas (1-1) and (1-2), respectively. ^{W 1, W 2, a 1} , Z 1, has the same meaning as ^{R 1} and ^{Q 1,} n is an integer of 0 to 4, ^{R M} is alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms , hydrogen, chlorine, fluorine, -OH, _-CN, -NO 2, a -CF ₃ or -OCF _3, ^{R N} is a fluoroalkyl or hydrogen having 1 to 10 alkyl, carbon 1 to 10 carbon atoms .
A specific example is shown below. The present invention is not limited to these specific examples.

As other structural units other than those derived from the formulas (M-1) and (M-2), structural units derived from industrially available monomers capable of radical polymerization reaction can be used.
Specific examples of monomers for deriving other structural units are given below. The present invention is not limited to these specific examples.

As a monomer giving a structural unit derived from a commercially available monomer capable of radical polymerization reaction, as a compound having at least one ethylenically unsaturated double bond, (meth) acrylic acid, methyl (meth) acrylate, (Meth) acrylic acid or derivatives thereof such as ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate;
monofunctional (meth) acrylate compounds such as ω-carboxypolycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate;
1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane Tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dicyclopentanyl di (meth) acrylate, ethoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) Acrylate, ethoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol S di (meth) acrylate, hydroxypropyl di (meth) acrylate, diethylene glycol bishydroxypropyl (meth) acrylate, monohydroxypentaerythritol tri (meth) acrylate, etc. A polyfunctional (meth) acrylate compound of
There are (meth) acrylate compounds having cyclic ethers such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate.

As these compounds, commercially available monofunctional or polyfunctional (meth) acrylate compounds can be used as they are. Specifically, Aronix M-5400 (monohydroxyethyl acrylate phthalate), M-5700 (2-hydroxy-3-phenoxypropyl acrylate), M-215 (isocyanuric acid) manufactured by Toa Synthetic Chemical Industry Co., Ltd. Ethyleneoxycide-modified diacrylate), M-220 (tripropylene glycol diacrylate), M-245 {polyethylene glycol (n≈9) diacrylate}, M-305 (pentaerythritol triacrylate), M- 309 (trimethylolpropane triacrylate), M-315 (isocyanuric acid ethylene oxide modified triacrylate), M-400 {mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (main component) , The M-450 (pentaerythritol tetraacrylate), the M-8060, and the M-8560;
Biscoat # 295 (trimethylolpropane triacrylate), # 300 (pentaerythritol triacrylate), # 360 (trimethylolpropane ethylene oxide modified triacrylate), and # 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) Pentaerythritol tetraacrylate);
KAYARAD TMPTA (trimethylolpropane triacrylate), PET-30 (pentaerythritol triacrylate), DPHA {mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (main component)} manufactured by Nippon Kayaku Co., Ltd. D-310 (dipentaerythritol pentaacrylate), D-330, and DPCA-60.

  In the present invention, among the above-described compounds, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Aronix M-manufactured by Toa Gosei Chemical Co., Ltd. # 305, # 309, # M-400, # M-450, Biscoat # 295, # 300, # 400, manufactured by Osaka Organic Chemical Industry Co., Ltd., KAYAARDTMPTA, DPHA manufactured by Nippon Kayaku Co., Ltd., Trifunctional or higher polyfunctional acrylates such as D-310 and PET-30 can be preferably used. In addition, these compounds can be used individually or in mixture of 2 or more types.

  Since the photosensitive polymer of the present application is used by laminating it on a substrate instead of alone, the alignment ability as a material for a liquid crystal alignment film, adhesion to the substrate, coating uniformity, chemical resistance, heat resistance, permeability, gas barrier Properties required for optical films and optical display elements such as properties are required. Additives can be used to impart such properties.

The amount of each additive added is determined according to the required properties, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polymer of the present application.
Additives include acrylic, styrene, polyethyleneimine or urethane polymer dispersants, anionic, cationic, nonionic or fluorine surfactants, silicone resin and other coatability improvers, silane cups Adhesion improvers such as ring agents, ultraviolet absorbers such as alkoxybenzophenones, anti-aggregation agents such as sodium polyacrylate, thermal crosslinking agents such as oxirane compounds, melamine compounds or bisazide compounds, and alkali solubility such as organic carboxylic acids There are accelerators.

  A photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.

As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino substituted Aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) ) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Ftoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, melocoumarin and the like.
Aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.

A photosensitizer having a polymerizable group can also be contained as a structural unit. Examples of the polymerizable group include acryloyl group, methacryloyl group, vinyl group, maleimide group, and itaconic acid.
Specific examples are shown below, but the present invention is not limited to these specific examples.

これらの化合物において、Ｑ^１およびＲ^１は前記の式（Ｍ−１）および（Ｍ−２）中のＱ^１およびＲ^１と同義である。

In these compounds, ^{Q 1} and ^{R 1} has the same meaning as ^{Q 1} and ^{R 1} in the formulas (M-1) and (M-2).

  As other additives, a coupling agent, a surfactant and the like can also be used. The coupling agent is used to improve adhesion to the substrate, and is 10 per 100 parts by weight of the remaining component (hereinafter abbreviated as “solid content”) obtained by removing the solvent from the photosensitive polymer. Used in addition to parts by weight or less. As the coupling agent, silane, aluminum and titanate compounds are used. Specifically, silane systems such as 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and aluminum systems such as acetoalkoxyaluminum diisopropylate And titanate compounds such as tetraisopropyl bis (dioctyl phosphite) titanate.

  The surfactant is used to improve the wettability, leveling property, and coating property to the base substrate, and preferably 0.01 to 1 part by weight is added to 100 parts by weight of the photosensitive polymer. Used. As the surfactant, a silicon surfactant, an acrylic surfactant, a fluorine surfactant, or the like is used. Specifically, BYK-300, 306, 335, 310, 341, 344, 370, etc. manufactured by Big Chemie Co., Ltd., 354, 358, 361 Examples thereof include acrylic surfactants such as SC-101 manufactured by Asahi Glass Co., Ltd., EF-351 manufactured by Tochem Products Co., Ltd., and 352.

  The weight average molecular weight of the photosensitive polymer having the structural unit represented by the formula (3) is preferably 1000 or more and 500,000 or less, and more preferably 1000 or more and 100,000 or less. The weight average molecular weight can be measured as a value in terms of polystyrene (PS) using gel permeation chromatography (GPC).

  About the manufacturing method of the photosensitive polymer which has a structural unit represented by Formula (3), it is not specifically limited, It can manufacture by the general purpose method currently treated industrially. It can be produced by a polymerization method such as cationic polymerization, radical polymerization, or anionic polymerization using the vinyl group of the compound represented by formula (1). Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.

  As the polymerization initiator for radical polymerization, known compounds such as radical thermal polymerization initiators and radical photopolymerization initiators can be used.

  The radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation). Hydrogen, tert-butylhydroxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-amyl ester) Etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2′-di (2-hydroxyethyl) azobisisobutyronitrile) Etc.). Such radical thermal polymerization initiators can be used singly or in combination of two or more.

  The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy 2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- N-di-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (2′-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2, 6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4 ′ -Methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylamino) Coumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bi (2-Chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2'- Biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 3- (2-methyl-2- Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η5-2,4-cyclopentadi) En-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4 '-Di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2, -(3-methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone or 2- (3-methyl-1 3- benzothiazol -2 (3H) - ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more.

  The radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization, precipitation polymerization, bulk polymerization method, solution polymerization method and the like can be used. The same applies to other polymerization methods, and details thereof are described in “Synthesis of Polymers (above)” (Kou Endo, published by Kodansha 2010). An outline of solution polymerization, which is a general radical polymerization method, will be described below.

  Solution polymerization is a reaction in which polymerization is performed in a solvent using an oil-soluble polymerization catalyst. These organic solvents can be arbitrarily selected within a range suitable for the purpose and effect of the invention. These organic solvents are usually organic compounds having a boiling point in the range of 50 to 200 ° C. under atmospheric pressure, and organic compounds that uniformly dissolve monomers, polymerization process components, and the like are preferable.

The organic solvent should have no inhibitory action on radical polymerization, and preferably an aromatic compound such as benzene, toluene, xylene, and ethylbenzene;
Aliphatic compounds such as pentane, hexane, heptane, octane, cyclohexane, and cycloheptane;
Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and ethylene glycol;
Ethers such as dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone;
Esters such as ethyl acetate, butyl acetate, amyl acetate and γ-butyrolactone;
Etc. These organic solvents can be used alone or in combination of two or more.

  Also, the solution polymerization conditions are not particularly limited, but for example, it is preferable to heat within a temperature range of 50 to 200 ° C. for 10 minutes to 20 hours. Furthermore, in order not to deactivate the generated radicals, it is preferable to purge with an inert gas such as nitrogen not only during solution polymerization but also before the start of solution polymerization.

  In order to control the molecular weight of the polymer having the structural unit represented by the formula (3), to make the molecular weight distribution uniform or to promote the polymerization, a radical polymerization method using a chain transfer agent is particularly effective. As a result, a polymer having a more uniform molecular weight distribution in a preferable molecular weight range can be obtained.

As chain transfer agents, β-mercaptopropionic acid, β-mercaptopropionic acid methyl ester, isopropyl mercaptan, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, octadecyl mercaptan, thiophenol and p-nonylthiophenol, thiosalicil Mercaptans such as acid, mercaptoacetic acid, and mercapto;
Polyhalogenated alkyls such as carbon tetrachloride, chloroform, butyl chloride, 1,1,1-trichloroethane and 1,1,1-tribromooctane;
Low active monomers such as α-methylstyrene and α-methylstyrene dimer;
Can be used. The amount of these chain transfer agents used is determined by the activity of the chain transfer agent, the combination of monomers, the solvent, temperature, and other polymerization conditions. Usually, it is about 0.01 mol% to 50 mol% with respect to the total number of moles of monomers used.

  The photo-alignment agent of the present invention is used as a coating solution in which a photosensitive polymer is dissolved in an organic solvent. Then, the liquid crystal alignment film of the present invention is prepared by using a known method (for example, spin coating, gravure coater, reverse gravure, Mayer bar coater, die coater, reverse roll coater, phanten reverse roll coater, kiss roll coater, The coating film obtained after applying to the substrate by removing the organic solvent by a bar coater, knife coater, lip coater, resist coater method) can be subjected to orientation treatment by irradiation with polarized light.

The liquid crystal alignment film of the present invention irradiates light from a single direction to the film in order to provide an alignment function. The photosensitive polymer molecules in the film are aligned by the light irradiation, whereby the alignment function is developed in the liquid crystal alignment film. In this case, X-rays, electron beams, ultraviolet rays, visible rays or infrared rays (heat rays) are used as the irradiation light, and it is particularly preferable to use ultraviolet rays. The wavelength of the ultraviolet light is preferably 400 nm or less, and more preferably 180 to 360 nm. As the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a high-pressure discharge lamp, or a short arc discharge lamp is preferably used. It is preferable to irradiate the film from a single direction. In general, linearly polarized light is irradiated, but there are cases where an alignment function can be imparted by non-polarized light irradiation. It is particularly preferable to use linearly polarized light. Irradiation dose is preferably ^{10mJ / cm 2 ~20000mJ / cm 2} , and most preferably ^{20mJ / cm 2 ~5000mJ / cm 2} .

  The liquid crystal alignment film of the present invention is obtained by applying a photo-alignment agent containing a photosensitive polymer and other various compounds added as necessary onto a transparent support, and irradiating with light to align the molecules of the photosensitive polymer. Thus, optical anisotropy can be expressed. The liquid crystal alignment film of the present invention exhibits optical anisotropy expressed by the alignment of the photosensitive polymer molecules.

  An optical film can be obtained using the liquid crystal alignment film of the present invention. The optical film of the present invention means an optical compensation film or a retardation film for realizing an improvement in contrast of a liquid crystal display element and an expansion of a viewing angle range. Generally, it has a support, an alignment film, and an optically anisotropic layer. By applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and other various compounds added as necessary onto the alignment film, aligning the molecules of the polymerizable liquid crystal compound, and then polymerizing. It can be produced by a method including a step of forming an optically anisotropic layer. The optically anisotropic layer exhibits optical anisotropy expressed by molecular orientation of the polymerizable liquid crystalline compound.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not restrict | limited by these Examples. The structure of the compound was confirmed by nuclear magnetic resonance spectrum, infrared absorption spectrum, and mass spectrum. The unit of the phase transition temperature is ° C., C represents a crystal, and I represents an isotropic liquid phase. Below, the measuring method of a physical-property value is shown.

<Weight average molecular weight (Mw) and polydispersity (Mw / Mn)>
Shimadzu LC-9A type gel permeation chromatograph (GPC) manufactured by Shimadzu Corporation and column Shodex (registered trademark) GF-7M HQ (developing solvent: DMF or THF, standard material: polystyrene having a known molecular weight) manufactured by Showa Denko It was.

<Alignment of liquid crystal molecules>
It confirmed by the method shown below.
(1) Observation method by visual observation A substrate on which an anisotropic polymer is formed on a liquid crystal alignment film is sandwiched between two polarizing plates arranged in crossed Nicols, and the substrate is rotated in a horizontal plane, so that the state of light and darkness is observed. confirmed. The substrate on which the anisotropic polymer was formed on the liquid crystal alignment film was observed with a polarizing microscope to confirm the presence of alignment defects.
(2) Measurement by ellipsometer Using an OPTIPRO ellipsometer manufactured by Shintech Co., Ltd., a substrate having an anisotropic polymer formed on a liquid crystal alignment film was irradiated with light having a wavelength of 550 nm. Retardation was measured while decreasing the incident angle of this light from 90 ° with respect to the film surface. Retardation (phase lag) is represented by Δn × d. The symbol Δn is the optical anisotropy value, and the symbol d is the thickness of the polymer film.

<Film thickness measurement>
The two layers of the liquid crystal alignment film and the anisotropic polymer are cut out from the substrate on which the anisotropic polymer is formed on the liquid crystal alignment film, and the step is measured with a fine shape measuring device (alpha step IQ manufactured by KLA TENCOR Co., Ltd.). And measured.

<Evaluation of optical anisotropy value (Δn)>
From the retardation and film thickness value obtained for the liquid crystal alignment film for inducing homogeneous alignment and the composite layer composed of two layers of anisotropic polymer, it was calculated as Δn = retardation / film thickness.

<Photopolymerization conditions for polymerizable liquid crystal composition>
In a nitrogen atmosphere or in the air, light having an intensity of 90 mW / cm ² (365 nm) was irradiated for 30 seconds using a 500 W ultrahigh pressure mercury lamp at room temperature.

[Example 1]
Compound (1-1-1) was synthesized according to the following scheme.

(First stage)
100 g of 3-ethyloxetanylmethanol and 100 g of pyridine were added to 400 ml of toluene and stirred while cooling under a nitrogen atmosphere. Thereto, 197 g of p-toluenesulfonic acid chloride (TsCl) was added. After the addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the filtrate was washed with saturated aqueous sodium hydrogen carbonate and water. To the obtained organic layer, 400 ml of water was added and stirred at 40 ° C. for 2 hours. The organic layer was separated, and the obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure. The obtained residue was dried under reduced pressure to obtain 186 g of a colorless liquid (ex-1).

(Second stage)
400 g of trans-p-coumaric acid was added to 1200 ml of methanol, 10 g of concentrated sulfuric acid was added dropwise, and the mixture was stirred for 5 hours with heating under reflux. After cooling to room temperature, methanol was distilled off under reduced pressure. The obtained residue was poured into 2000 ml of ice water, 2000 ml of ethyl acetate was added, and the organic layer was separated. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the resulting residue was recrystallized from ethanol to obtain 280 g of compound (ex-2).

(3rd stage)
30 g of the compound (ex-2) and 7 g of sodium hydroxide were added to 230 ml of N, N-dimethylformamide (DMF) and stirred at 50 ° C. under a nitrogen atmosphere. Thereto, 100 ml of a DMF solution of 45 g of compound (ex-1) was added dropwise. After dropping, the mixture was stirred at 80 ° C. for 8 hours. The deposited precipitate was separated by filtration, and 300 ml of water and 300 ml of toluene were added to the filtrate to separate the organic layer. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and water. Toluene was distilled off under reduced pressure. To the obtained residue, 7 g of sodium hydroxide, 300 ml of methanol and 300 ml of water were added and stirred for 3 hours while heating under reflux. After cooling to room temperature, methanol was distilled off under reduced pressure. To the resulting residue, 300 ml of 3N hydrochloric acid aqueous solution and 300 ml of ethyl acetate were added to separate the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and 29 g of compound (ex-3) was obtained by recrystallization from toluene.

(Final stage)
14 g of 2-hydroxyethyl methacrylate, 29 g of the compound (ex-3) and 3 g of 4-dimethylaminopyridine (DMAP) were added to 300 ml of dichloromethane and stirred while cooling under a nitrogen atmosphere. Thereto was added dropwise 60 ml of a dichloromethane solution of 24 g of 1,3-dicyclohexylcarbodiimide (DCC). After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and dried under reduced pressure to give a compound. (1-1-1) 27 g was obtained as a colorless liquid.
NMR of the obtained compound (1-1-1) is as follows.
¹ H-NMR (CDCl ₃ ; δ ppm): 7.68 (d, 1H), 7.50 (d, 2H), 6.95 (d, 2H), 6.35 (d, 1H), 6.16 (S, 1H), 5.60 (s, 1H), 4.57 (d, 2H), 4.49 (d, 2H), 4.48-4.40 (m, 4H), 4.11 ( s, 2H), 1.96 (s, 3H), 1.92-1.85 (m, 2H), 0.94 (t, 3H).

[Example 2]
Compound (1-1-10) was synthesized according to the following scheme.

(First stage)
3-ethyloxetanyl methanol 50g and sodium hydroxide 172g were added to DMF500ml, and it stirred at 50 degreeC by nitrogen atmosphere. There, 158 g of 1,6-dibromohexane was added dropwise. After the addition, the mixture was stirred at 80 ° C. for 6 hours. After cooling to room temperature, 500 ml of water and 500 ml of toluene were added to separate the organic layer. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure. Purification by vacuum distillation gave 60 g of colorless liquid (ex-4).

(Second stage)
30 g of the compound (ex-2) and 7 g of sodium hydroxide were added to 230 ml of N, N-dimethylformamide (DMF) and stirred at 50 ° C. under a nitrogen atmosphere. Thereto, 47 g of the compound (ex-4) was added dropwise. After dropping, the mixture was stirred at 80 ° C. for 8 hours. After cooling to room temperature, 300 ml of water and 300 ml of toluene were added to separate the organic layer. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and water. Toluene was distilled off under reduced pressure. To the obtained residue, 7 g of sodium hydroxide, 300 ml of methanol and 300 ml of water were added and stirred for 3 hours while heating under reflux. After cooling to room temperature, methanol was distilled off under reduced pressure. To the resulting residue, 300 ml of 3N hydrochloric acid aqueous solution and 300 ml of ethyl acetate were added to separate the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and recrystallization with heptane gave 39 g of compound (ex-5).

(Final stage)
14 g of 2-hydroxyethyl methacrylate, 39 g of the compound (ex-5) and 3 g of DMAP were added to 400 ml of dichloromethane and stirred while cooling under a nitrogen atmosphere. Thereto, 60 ml of a dichloromethane solution of 24 g of DCC was dropped. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and dried under reduced pressure to give a compound. 32 g of (1-1-10) was obtained as a colorless liquid.
NMR of the obtained compound (1-1-10) is as follows.
¹ H-NMR (CDCl ₃ ; δ ppm): 7.68 (d, 1H), 7.50 (d, 2H), 6.93 (d, 2H), 6.35 (d, 1H), 6.16 (S, 1H), 5.60 (s, 1H), 4.51 (d, 2H), 4.22 (d, 2H), 3.98-3.91 (m, 4H), 3.81 ( s, 2H), 1.96 (s, 3H), 1.87-1.79 (m, 6H) 1.69-1.60 (m, 4H), 0.92 (t, 3H).

[Example 3]
Compound (1-1-11) was synthesized according to the following scheme.

(First stage)
Methyl 4-hydroxybenzoate (50 g) and sodium hydroxide (13 g) were added to DMF (250 ml), and the mixture was stirred at 50 ° C. in a nitrogen atmosphere. Thereto, 150 ml of a DMF solution of 81 g of compound (ex-1) was added dropwise. After dropping, the mixture was stirred at 80 ° C. for 8 hours. The deposited precipitate was separated by filtration, and 300 ml of water and 300 ml of toluene were added to the filtrate to separate the organic layer. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and water. Toluene was distilled off under reduced pressure. To the obtained residue, 13 g of sodium hydroxide, 300 ml of methanol and 300 ml of water were added and stirred for 3 hours while heating under reflux. After cooling to room temperature, methanol was distilled off under reduced pressure. To the resulting residue, 300 ml of 3N hydrochloric acid aqueous solution and 300 ml of ethyl acetate were added to separate the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and recrystallization with toluene gave 42 g of compound (ex-6).

(Second stage)
120 g of trans-p-coumaric acid was added to 1200 ml of acetic anhydride and stirred while cooling under a nitrogen atmosphere. The pyridine 64g was dripped there. After dropping, the mixture was stirred at room temperature for 4 hours. The deposited precipitate was separated by filtration, and the obtained crystal was recrystallized from ethanol to obtain 103 g of Compound (ex-7).

(3rd stage)
50 g of 2-hydroxyethyl methacrylate, 80 g of compound (ex-7) and 9 g of DMAP were added to 800 ml of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere. Thereto was added dropwise 160 ml of a DCC 84 g dichloromethane solution. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)). The obtained residue was added to 500 ml of methanol and stirred while cooling. Thereto, 47 ml of 28% aqueous ammonia solution was added dropwise. After dropping, the mixture was stirred at room temperature for 2 hours. Methanol was distilled off under reduced pressure, 500 ml of water and 500 ml of ethyl acetate were added to the residue, and the organic layer was separated. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)). Drying under reduced pressure gave 92 g of colorless liquid (ex-8).

(Final stage)
30 g of compound (ex-6), 35 g of compound (ex-8) and 3 g of DMAP were added to 300 ml of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere. Thereto was added dropwise 60 ml of a DCC 28 g dichloromethane solution. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 6/1)) and recrystallized from methanol. , 47 g of the compound (1-1-11) was obtained.
The phase transition point and NMR of the obtained compound (1-1-11) are as follows.
Phase transition temperature: C 81 I
¹ H-NMR (CDCl ₃ ; δ ppm): 8.17 (d, 2H), 7.73 (d, 1H), 7.60 (d, 2H), 7.27 (d, 2H), 7.04 (D, 2H), 6.46 (d, 1H), 6.17 (s, 1H), 5.62 (s, 1H), 4.59 (d, 2H), 4.53 (d, 2H) , 4.49-4.42 (m, 4H), 4.19 (s, 2H), 1.97 (s, 3H), 1.94-1.88 (m, 2H) 0.96 (t, 3H).

[Example 4]
Compound (1-1-12) was synthesized according to the following scheme.

(First stage)
50 g of 4-acetoxybenzoic acid, 28 g of 3,4-dihydro-2H-pyran and 6.7 g of pyridinium p-toluenesulfonic acid (PPTS) were added to 1000 ml of dichloromethane, followed by stirring at room temperature for 8 hours under a nitrogen atmosphere. Saturated aqueous sodium bicarbonate was added to extract the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure and dried under reduced pressure. The obtained residue was added to a mixed solution of 500 ml of THF and 500 ml of methanol, and stirred while cooling under a nitrogen atmosphere. Thereto, 30 ml of 28% aqueous ammonia solution was added dropwise. After dropping, the mixture was stirred at room temperature for 8 hours. THF and methanol were distilled off under reduced pressure, and 1000 ml of ethyl acetate and 1000 ml of water were added to extract the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was recrystallized from heptane to obtain 41 g of compound (ex-9).

(Second stage)
41 g of compound (ex-9) and 38 g of potassium carbonate were added to 500 ml of DMF and stirred while heating at 60 ° C. in a nitrogen atmosphere. There, 76 g of epibromohydrin was dropped. After dropping, the mixture was stirred at 60 ° C. for 6 hours. The precipitate was filtered off, and 1000 ml of ethyl acetate and 1000 ml of water were added to the filtrate to extract the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure and dried under reduced pressure. The obtained residue was added to a mixed solution of 300 ml of THF and 300 ml of methanol and stirred while cooling under a nitrogen atmosphere. Thereto, 30 ml of 6N hydrochloric acid water was added dropwise. After dropping, the mixture was stirred at room temperature for 4 hours. The organic layer was extracted by adding 1000 ml of ethyl acetate and 1000 ml of water. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and recrystallization with ethanol gave 23 g of compound (ex-10).

(Final stage)
5 g of the compound (ex-10), 7 g of the compound (ex-8) and 0.3 g of DMAP were added to 100 ml of dichloromethane and stirred while cooling under a nitrogen atmosphere. Thereto was added dropwise 20 ml of a DCC 6 g dichloromethane solution. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 6/1)) and recrystallized from methanol. , 6 g of the compound (1-1-12) was obtained.
The phase transition point and NMR of the obtained compound (1-1-12) are as follows.
Phase transition temperature: C 154 I
¹ H-NMR (CDCl ₃ ; δ ppm): 8.21 (d, 2H), 7.78 (d, 1H), 7.60 (d, 2H), 7.32 (d, 2H), 7.12 (D, 2H), 6.46 (d, 1H), 6.24 (s, 1H), 5.62 (s, 1H), 4.51-4.43 (m, 4H), 4.19- 4.08 (m, 2H), 3.08-3.01 (m, 1H), 2.64-2.58 (m, 1H), 2.51-2.44 (m, 1H), 1. 97 (s, 3H).

[Example 5]
Compound (1-2-2) was synthesized according to the following scheme.

(First stage)
100 g of trans-p-coumaric acid and 60 g of pyridine were added to 1000 ml of tetrahydrofuran (THF) and stirred while cooling under a nitrogen atmosphere. The acetic anhydride 75g was dripped there. After dropping, the mixture was stirred at room temperature for 4 hours. The precipitate was filtered off and washed with toluene to obtain 72 g of compound (ex-11).

(Second stage)
30 g of the compound (ex-11), 15 g of 3,4-dihydro-2H-pyran and 3.6 g of pyridinium p-toluenesulfonic acid (PPTS) were added to 600 ml of dichloromethane, and the mixture was stirred at room temperature for 8 hours in a nitrogen atmosphere. Saturated aqueous sodium bicarbonate was added to extract the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure and dried under reduced pressure. The obtained residue was added to a mixed solution of 300 ml of THF and 300 ml of methanol and stirred while cooling under a nitrogen atmosphere. Thereto, 18 ml of 28% aqueous ammonia solution was added dropwise. After dropping, the mixture was stirred at room temperature for 8 hours. THF and methanol were distilled off under reduced pressure, and 500 ml of ethyl acetate and 500 ml of water were added to extract the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was recrystallized from heptane to obtain 19 g of compound (ex-12).

(3rd stage)
19 g of compound (ex-12) and 12 g of triethylamine were added to 200 ml of dichloromethane, followed by stirring while cooling under a nitrogen atmosphere. 9.6 g of methacrylic acid chloride was dripped there. After dropping, the mixture was stirred at room temperature for 4 hours. Ice water was added to extract the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure and dried under reduced pressure. The obtained residue was added to a mixed solution of 200 ml of THF and 200 ml of methanol and stirred while cooling under a nitrogen atmosphere. Thereto, 20 ml of 6N aqueous hydrochloric acid was added dropwise. After dropping, the mixture was stirred at room temperature for 4 hours. Ethyl acetate 500 ml and water 500 ml were added to extract the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and recrystallization from ethanol gave 9.6 g of compound (ex-13).

(Final stage)
Glycidol (3.1 g), compound (ex-13) (9.6 g) and DMAP (0.5 g) were added to dichloromethane (100 ml), followed by stirring under cooling in a nitrogen atmosphere. Thereto, 20 ml of a DCC 8.9 g dichloromethane solution was dropped. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) and recrystallized from methanol. , 7.2 g of compound (1-2-2) was obtained.
The phase transition point and NMR of the obtained compound (1-2-2) are as follows.
Phase transition temperature: C 94 I
¹ H-NMR (CDCl ₃ ; δ ppm): 7.95 (d, 2H), 7.65 (d, 1H), 7.43 (d, 2H), 6.62 (d, 1H), 6.38 (S, 1H), 6.12 (s, 1H), 4.45-4.21 (m, 2H), 3.17-3.09 (m, 1H), 2.82-2.74 (m , 1H), 1.98 (s, 3H).

[Example 6]
Compound (1-2-10) was synthesized according to the following scheme.

(First stage)
50 g of 2-hydroxyethyl methacrylate and 50 ml of pyridine were added to 150 ml of toluene, 80 g of p-toluenesulfonic acid chloride was added under cooling, and the mixture was stirred at room temperature for 16 hours under a nitrogen atmosphere. The precipitated salt was removed by vacuum filtration. Water (100 ml) was added to the filtrate and stirred at 40 ° C. for 2 hours. The organic layer was separated, and the obtained organic layer was washed successively with 2N hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and water, and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure to obtain 98 g of a crude colorless liquid (ex-14).

(Second stage)
100 g of trans-ferulic acid and 45 g of pyridine were added to 1000 ml of tetrahydrofuran (THF) and stirred while cooling under a nitrogen atmosphere. Thereto, 63 g of acetic anhydride was added dropwise. After dropping, the mixture was stirred at room temperature for 4 hours. The precipitate was filtered off and washed with toluene to obtain 81 g of compound (ex-15).

(3rd stage)
10 g of 3-ethyl-3-oxetanemethanol, 20 g of compound (ex-15) and 1.0 g of DMAP were added to 400 ml of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere. Thereto was added dropwise 40 ml of a dichloromethane solution of 19 g of DCC. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)). The obtained residue was added to a mixed solution of 300 ml of THF and 300 ml of methanol and stirred while cooling under a nitrogen atmosphere. Thereto, 25 ml of 28% aqueous ammonia solution was added dropwise. After dropping, the mixture was stirred at room temperature for 8 hours. THF and methanol were distilled off under reduced pressure, and 500 ml of ethyl acetate and 500 ml of water were added to extract the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was recrystallized from toluene to obtain 12 g of Compound (ex-16).

(Final stage)
14 g of compound (ex-14), 12 g of compound (ex-16) and 1.6 g of NaOH were added to 120 ml of DMF, and the mixture was stirred for 8 hours while heating at 80 ° C. in a nitrogen atmosphere. The deposited precipitate was separated by filtration, and 500 ml of ethyl acetate and 500 ml of water were added to the filtrate to extract the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) to give compound (1- 2-10) 8.4 g was obtained as a colorless liquid.
NMR of the obtained compound (1-2-10) is as follows.
¹ H-NMR (CDCl ₃ ; δ ppm): 7.54 (d, 1H), 7.38-7.26 (m, 2H), 6.69 (d, 1H), 6.32 (d, 1H) 6.14 (d, 1H), 5.60 (s, 1H), 4.59 (d, 2H), 4.53 (d, 2H), 4.51 (t, 2H), 4.25 ( t, 2H), 4.19 (s, 2H), 3.97 (s, 3H), 3.80 (s, 3H), 1.93-1.88 (m, 2H) 0.94 (t, 3H).

[Example 7]
Compound (1-2-4) was synthesized according to the following scheme.

(First stage)
80 g of pyridine was added to 100 g of 4-chlorobutanol and stirred while cooling in a nitrogen atmosphere. Thereto, 113 g of acetic anhydride was added dropwise. After dropping, the mixture was stirred at room temperature for 4 hours. 500 ml of water and 500 ml of toluene were added to the reaction solution, and the organic layer was separated. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue was distilled to obtain 116 g of compound (ex-17).

(Second stage)
Methyl 4-hydroxybenzoate (50 g) and sodium hydroxide (13 g) were added to DMF (150 ml), and the mixture was stirred at 60 ° C. in a nitrogen atmosphere. Thereto, 5 g of sodium iodide was added, and then 74 g of compound (ex-17) was added dropwise. After dropping, the mixture was stirred at 80 ° C. for 8 hours. After cooling to room temperature, 300 ml of ethyl acetate and 300 ml of water were added to separate the organic layer. The obtained organic layer was washed successively with 2N hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and water, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, 200 ml of methanol, 26 g of sodium hydroxide and 200 ml of water were added to the residue, and the mixture was stirred for 3 hours with heating under reflux. Methanol was distilled off under reduced pressure, and the residue was poured into 3N aqueous hydrochloric acid. The precipitate was separated by filtration, and the obtained crystal was recrystallized from ethanol to obtain 37 g of Compound (ex-18).

(3rd stage)
37 g of compound (ex-18) and 30 g of N, N-dimethylaminopyridine were added to 400 ml of THF and stirred while cooling under a nitrogen atmosphere. Thereto, 19 g of acrylic acid chloride was added dropwise. After dropping, the mixture was stirred at room temperature for 16 hours. The reaction solution was poured into ice water, and 500 ml of ethyl acetate was added to extract the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and recrystallization with ethanol gave 33 g of compound (ex-19).

(Fourth stage)
11 g of 3-ethyl-3-oxetanemethanol, 20 g of the compound (ex-11) and 1.2 g of DMAP were added to 400 ml of dichloromethane and stirred while cooling under a nitrogen atmosphere. Thereto, 40 ml of a dichloromethane solution of 21 g of DCC was dropped. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)). The obtained residue was added to a mixed solution of 300 ml of THF and 300 ml of methanol and stirred while cooling under a nitrogen atmosphere. Thereto, 25 ml of 28% aqueous ammonia solution was added dropwise. After dropping, the mixture was stirred at room temperature for 8 hours. THF and methanol were distilled off under reduced pressure, and 500 ml of ethyl acetate and 500 ml of water were added to extract the organic layer. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was recrystallized from toluene to obtain 11 g of compound (ex-20).

(Final stage)
11 g of compound (ex-19), 11 g of compound (ex-20) and 0.5 g of DMAP were added to 200 ml of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere. Thereto was added dropwise 20 ml of a DCC 9.0 g dichloromethane solution. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) and recrystallized from methanol. , 10 g of compound (1-2-4) was obtained.
The phase transition point and NMR of the obtained compound (1-2-4) are as follows.
Phase transition temperature: C 127 I
¹ H-NMR (CDCl ₃ ; δ ppm): 8.15 (d, 2H), 7.68 (d, 1H), 7.51 (d, 2H), 7.31 (d, 2H), 7.14 (D, 2H), 6.34-6.30 (m, 2H), 6.19-6.11 (m, 1H), 6.02-5.93 (m, 1H), 4.58 (d , 2H), 4.53 (d, 2H), 4.50-4.38 (m, 4H), 4.11 (t, 2H), 2.19-2.10 (m, 2H), 1. 86-1.77 (m, 4H) 0.96 (t, 3H).

[Example 8]
A homopolymer of the compound (1-1-1) was synthesized according to the following scheme.

  Compound (1-1-1) (5.0 g) and azobisisobutyronitrile (AIBN) (0.3 g) were added to THF (40 ml), and the mixture was stirred under reflux with heating in a nitrogen atmosphere for 10 hours. The reaction solution was poured into methanol and reprecipitated. The crystal was filtered off and dried to obtain 4.7 g of polymer (P-1).

  The obtained polymer had Mw of 7800 and Mw / Mn of 1.9.

[Example 9]
A homopolymer of compound (1-1-11) was synthesized according to the same scheme as in Example 4.

  Compound (1-1-11) (5.0 g) and azobisisobutyronitrile (AIBN) (0.02 g) were added to THF (40 ml), and the mixture was stirred for 10 hours with heating under reflux in a nitrogen atmosphere. The reaction solution was poured into methanol and reprecipitated. Crystals were separated by filtration and dried to obtain 4.5 g of polymer (P-2).

The obtained polymer had Mw of 64000 and Mw / Mn of 2.4.
[Example 10]
A copolymer of compound (1-1-1) and compound (M-1-1) was synthesized according to the following scheme.

  2.5 g of compound (1-1-1), 2.5 g of compound (M-1-1) and 0.1 g of azobisisobutyronitrile (AIBN) were added to 40 ml of THF, and the mixture was heated under reflux for 10 hours under a nitrogen atmosphere. Stir. The reaction solution was poured into methanol and reprecipitated. Crystals were separated by filtration and dried to obtain 4.3 g of polymer (P-3).

  The obtained polymer had Mw of 12000 and Mw / Mn of 2.3.

Here, the compound (M-1-1) was synthesized according to the method of International Publication No. 1994/00797 pamphlet.
[Example 11]
A copolymer of compound (1-1-1) and glycidyl methacrylate was synthesized according to the following scheme.

  4.0 g of compound (1-1-1), 1.0 g of glycidyl methacrylate and 0.05 g of azobisisobutyronitrile (AIBN) were added to 40 ml of THF, and the mixture was stirred under heating and reflux for 10 hours under a nitrogen atmosphere. The reaction solution was poured into methanol and reprecipitated. The crystals were filtered off and dried to obtain 4.6 g of polymer (P-3).

The obtained polymer had Mw of 45000 and Mw / Mn of 1.9.
[Example 12]
A copolymer of compound (1-2-10), methyl methacrylate and hydroxybutyl methacrylate was synthesized according to the following scheme.

  Compound (1-2-10) 3.5 g, methyl methacrylate 1.0 g, hydroxybutyl methacrylate 0.5 and azobisisobutyronitrile (AIBN) 0.07 g are added to THF 40 ml and heated for 10 hours under a nitrogen atmosphere. Stirred under reflux. The reaction solution was poured into methanol and reprecipitated. Crystals were separated by filtration and dried to obtain 4.2 g of polymer (P-4).

The obtained polymer had Mw of 38000 and Mw / Mn of 2.0. [Example 13]
A copolymer of compound (1-2-4), methyl methacrylate and hydroxybutyl methacrylate was synthesized according to the following scheme.

  Compound (1-2-10) 2.0 g, compound (M-2-10) 2.6 g, compound (S-5-1) 0.4 and azobisisobutyronitrile (AIBN) 0.03 g were added to THF 40 ml. In addition, the mixture was stirred with heating under reflux in a nitrogen atmosphere for 10 hours. The reaction solution was poured into methanol and reprecipitated. Crystals were separated by filtration and dried to obtain 4.4 g of polymer (P-4).

  The obtained polymer had Mw of 58000 and Mw / Mn of 2.2.

Here, the compound (M-1-2) was synthesized according to the method described in Japanese Patent No. 4011652. Compound (S-5-1) was synthesized according to the method described in JP-A-2002-226429.

[Example 14]
The polymer (P-1) was dissolved in a mixed solvent of cyclopentanone: propylene glycol monomethyl ether acetate (PGMEA) = 7: 3 (weight ratio) to obtain a solution having a solid content concentration of 7% by weight. The solution was filtered with a filter having a pore size of 0.45 μm to prepare a photoalignment agent (H-1).

[Example 15]
A photoalignment agent (H-2) was prepared by the same scheme as in Example 8 except that the polymer (P-1) was replaced with the polymer (P-2).

[Example 16]
<Preparation of liquid crystal alignment film F-1>
The photo-alignment agent (H-1) was applied onto a glass substrate by spin coating. At this time, the coating property was good. The substrate was heated at 80 ° C. for 3 minutes to remove the mixed solvent, thereby forming a coating film. By applying 1.0 J / cm ² of linearly polarized ultraviolet light having a wavelength of about 313 nm from the direction of 90 ° to the coating surface on the coating surface from an ultrahigh pressure mercury lamp, the liquid crystal alignment film F- 1 was obtained.

Next, the low molecular liquid crystal JC-5100XX (manufactured by Chisso Corporation) was sandwiched between the two photo-alignment films F-1, heated on a 110 ° C. hot plate for 30 seconds, and allowed to stand at room temperature. When it was sandwiched between two polarizing plates made of crossed Nicols and rotated in a horizontal plane, it became bright and dark. From this, it was confirmed that the photo-alignment film F-1 was horizontally aligned.
In addition, when the liquid crystal alignment film F-1 was overlapped, the coating surface was in contact with the liquid crystal so that the direction of linearly polarized light was the same (substantially parallel).

[Example 17]
<Preparation of polymerizable liquid crystal composition (1)>
Two compounds were mixed with compound (LC-1): compound (LC-2) = 50: 50 (weight ratio). This composition is designated as MIX1. Based on the total weight of this MIX1, a nonionic fluorosurfactant (trade name FTX-218 (registered trademark), manufactured by Neos Co., Ltd.) having a weight ratio of 0.002, and a weight ratio of 0.06 Polymerization initiator irgacure907 (manufactured by BASF) was added. A mixed solvent of cyclopentanone: PGMEA = 1: 1 (weight ratio) was added to this composition to obtain a polymerizable liquid crystal composition (1) in which the ratio of the mixed solvent was 80% by weight.

  The specific manufacturing method of the said compound (LC-1) and compound (LC-2) is demonstrated. Compound (LC-1) was synthesized according to the method described in JP 2006-307150 A. Compound (LC-2) was synthesized according to the method described in JP-A-63-64029.

[Example 18]
<Formation of optical film>
The polymerizable liquid crystal composition (1) was applied to the liquid crystal alignment film F-1 obtained in Example 10 by spin coating. The substrate was heated at 80 ° C. for 3 minutes, then cooled at room temperature for 3 minutes, and the coating film from which the solvent had been removed was polymerized in the air with ultraviolet rays to obtain an optical film in which the alignment state of the liquid crystal was fixed. . When this optical film was observed with a polarizing microscope, it was confirmed that there was no alignment defect and the film had a uniform alignment. When the retardation of this optical film was measured, it was confirmed that the orientation was homogeneous.

Since the photo-alignment agent of the present invention comprises a photosensitive polymer, it is an alignment agent suitable for the photo-alignment method. In addition, the liquid crystal alignment film obtained using the photoalignment agent of the present invention is a liquid crystal alignment film having no alignment defects and uniform alignment of liquid crystal molecules because there is no need for rubbing treatment. Therefore, it is suitable for use in optical film and liquid crystal display element applications.

Claims (14)

Compound represented by formula (1):

In Formula (1), Y is independently a divalent group represented by Formula (2-1) or Formula (2-2), and at least one of Y is represented by Formula (2-1-1). Or a group represented by formula (2-2-1);
R ¹ and R ² are independently hydrogen, fluorine, chlorine, trifluoromethyl or alkyl having 1 to 5 carbons;
Q ¹ and Q ² are each independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — is —O—, — May be replaced by COO-, -OCO-, -CH = CH- or -C≡C-;
a is an integer from 1 to 5;
m is 0 or 1;
In Formula (2-1) and Formula (2-2), A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl. , Naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, or 1,3-dioxane-2,5-diyl, in which 1,4-phenylene is optionally hydrogen, fluorine, chlorine, cyano , Hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
In Formula (2-1) and Formula (2-2), Z ¹ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO. _{, - - -CH 2 CH 2 CH} 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - _{OCF 2 -, - CONH -,} - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or -C≡C -Is;
In Formula (2-1-1) and Formula (2-2-1), W ¹ and W ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbons, or 1 to C carbons. 5 alkoxy. Compound represented by formula (1-1) or (1-2):

In formula (1-1) or (1-2), W ¹ and W ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons. ;
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6. -Diyl or 1,3-dioxane-2,5-diyl, in which 1,4-phenylene is optionally hydrogen, fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl , Trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
Z ¹ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—. , —C≡C—COO—, —OCO—C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CONH—, —NHCO—, — (CH _{2) 4 -, - CH 2} CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or a -C≡C-;
R ¹ and R ² are independently hydrogen, fluorine, chlorine, trifluoromethyl or alkyl having 1 to 5 carbons;
Q ¹ and Q ² are each independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — is —O—, — May be replaced by COO-, -OCO-, -CH = CH- or -C≡C-;
n is an integer from 0 to 4;
m is 0 or 1. In formula (1-1) or (1-2) according to claim 2, ^{W 1} and ^{W 2} are independently hydrogen, fluorine, an alkyl or a C 1-3 alkoxy having 1-3 carbon atoms ;
A ¹ is independently 1,4-phenylene or 1,4-cyclohexylene, and in this 1,4-phenylene, arbitrary hydrogen is fluorine, trifluoromethyl, alkyl having 1 to 3 carbons or carbon number. 1 to 3 alkoxy may be substituted;
Z ¹ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ — or —CH ₂ CH ₂ —COO—. Is;
Q ¹ and Q ² are each independently a single bond or alkylene having 1 to 12 carbons, and any —CH ₂ — in the alkylene may be replaced by —O—;
R ¹ is hydrogen or methyl;
R ² is hydrogen, methyl or ethyl;
n is an integer from 0 to 2;
The compound according to claim 2, wherein m is 0 or 1.   The photosensitive polymer obtained by superposing | polymerizing the compound of any one of Claims 1-3. Photosensitive polymer having structural unit represented by formula (3)

In Formula (3), Y is independently a divalent group represented by Formula (2-1) or Formula (2-2), and at least one of Y is represented by Formula (2-1-1). Or a group represented by formula (2-2-1);
R ¹ and R ² are independently hydrogen, fluorine, chlorine, trifluoromethyl or alkyl having 1 to 5 carbons;
Q ¹ and Q ² are each independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — is —O—, — May be replaced by COO-, -OCO-, -CH = CH- or -C≡C-;
a is an integer from 1 to 5;
m is 0 or 1;
In Formula (2-1) and Formula (2-2), A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl. , Naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, or 1,3-dioxane-2,5-diyl, in which 1,4-phenylene is optionally hydrogen, fluorine, chlorine, cyano , Hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
In Formula (2-1) and Formula (2-2), Z ¹ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO. _{, - - -CH 2 CH 2 CH} 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - _{OCF 2 -, - CONH -,} - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or -C≡C -Is;
In Formula (2-1-1) and Formula (2-2-1), W ¹ and W ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbons, or 1 to C carbons. 5 alkoxy. Photosensitive polymer having a structural unit represented by formula (3-1) or (3-2):

In formula (3-1) or (3-2), W ¹ and W ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons. ;
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6. -Diyl or 1,3-dioxane-2,5-diyl, in which 1,4-phenylene is optionally hydrogen, fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl , Trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
Z ¹ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—. , —C≡C—COO—, —OCO—C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CONH—, —NHCO—, — (CH _{2) 4 -, - CH 2} CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or a -C≡C-;
R ¹ and R ² are independently hydrogen, fluorine, chlorine, trifluoromethyl or alkyl having 1 to 5 carbons;
Q ¹ and Q ² are each independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — is —O—, — May be replaced by COO-, -OCO-, -CH = CH- or -C≡C-;
n is an integer from 0 to 4;
m is 0 or 1. In formula (3-1) or (3-2) according to claim 6, W ¹ and W ² are independently hydrogen, fluorine, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons. ;
A ¹ is independently 1,4-phenylene or 1,4-cyclohexylene, and in this 1,4-phenylene, arbitrary hydrogen is fluorine, trifluoromethyl, alkyl having 1 to 3 carbons or carbon number. 1 to 3 alkoxy may be substituted;
Z ¹ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ — or —CH ₂ CH ₂ —COO—. Is;
Q ¹ and Q ² are each independently a single bond or alkylene having 1 to 12 carbons, and any —CH ₂ — in the alkylene may be replaced by —O—;
R ¹ is hydrogen or methyl;
R ² is hydrogen, methyl or ethyl;
n is an integer from 0 to 2;
The photosensitive polymer of Claim 6 whose m is 0 or 1.   The weight average molecular weight is 1000-500000, The photosensitive polymer of any one of Claims 4-7.   The homopolymer which has a structural unit of any one of Claims 5-7.   A copolymer comprising at least one of a structural unit represented by formula (3) according to claim 5 and a structural unit other than represented by formula (3).   The photosensitive material using the polymer of any one of Claims 4-10.   The photo-alignment agent for liquid crystal aligning films using the polymer of any one of Claims 4-10.   The liquid crystal aligning film manufactured using the photoalignment agent of Claim 12.   A liquid crystal display device manufactured using the liquid crystal alignment film according to claim 13.