KR101777880B1 - Photosensitive compound and its photosensitive polymer - Google Patents

Abstract

식 (1) 에 있어서, Y¹ 은 식 (2-1) 또는 (2-2) 로 나타내는 2 가의 기이고, A¹ 은 1,4-페닐렌 또는 1,4-시클로헥실렌이며, Z¹ 은 단결합, -COO-, -OCO- 이고, R¹ 및 R² 는 독립적으로 수소, 불소, 탄소수 1 ∼ 5 의 알킬이며, Q¹ 은 독립적으로 단결합 또는 탄소수 1 ∼ 12 의 알킬렌이고, n 은 0 또는 1 이다. 식 (2-1) 및 (2-2) 에 있어서, W¹ 및 W² 는 독립적으로 수소, 탄소수 1 ∼ 3 의 알킬 또는 탄소수 1 ∼ 3 의 알콕시이다.Disclosed is a photosensitive compound and a photosensitive polymer comprising the compound. A photo-alignment agent using the compound, and a liquid crystal alignment film using the photo-alignment agent.
(Solution) A photosensitive compound represented by formula (1).

In formula (1), Y ¹ is a divalent group represented by formula (2-1) or (2-2), A ¹ is 1,4-phenylene or 1,4-cyclohexylene, Z ¹ R ¹ and R ² are independently hydrogen, fluorine, or alkyl of 1 to 5 carbon atoms; Q ¹ is independently a single bond or alkylene of 1 to 12 carbon atoms; n is 0 or 1; In the formulas (2-1) and (2-2), W ¹ and W ² are independently hydrogen, alkyl having 1 to 3 carbon atoms, or alkoxy having 1 to 3 carbon atoms.

Description

PHOTOSENSITIVE COMPOUND AND ITS PHOTOSENSITIVE POLYMER [0002]

The present invention relates to a photosensitive polymer and a photosensitive polymer comprising the compound. Further, 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 or liquid crystal display device using the liquid crystal alignment film.

Liquid crystal display devices are used in various types of liquid crystal display devices such as a monitor of a notebook computer or a desktop computer, a viewfinder of a video camera, a projection display, and a television. It is also used as an optoelectronics-related element such as an optical printer head, an optical Fourier transform element, and a light valve. A conventional liquid crystal display device is a liquid crystal display device using a nematic liquid crystal. The liquid crystal display device has TN (twisted) liquid crystal display devices in which liquid crystal alignment directions in the vicinity of one substrate and the liquid crystal alignment direction in the other substrate are twisted by 90 degrees Nematic mode, STN (super twisted nematic) mode in which the alignment direction is warped at an angle of 180 DEG or more, and so-called TFT (Thin-Film-Transistor) mode liquid crystal display devices using thin film transistors are put to practical use.

However, in these liquid crystal display devices, there is a case where a viewing angle capable of appropriately recognizing an image is narrow and a luminance and a contrast are lowered when viewed in an oblique direction, and there is a case where a luminance inversion occurs in a halftone. In recent years, the problem of this viewing angle has arisen from a TN type liquid crystal display device using an optical compensation film, an MVA (Multi-domain Vertical Alignment) mode (see Patent Document 1) using a combination of a vertical orientation and a projection structure, (In-Plane Switching) mode (see Patent Document 2).

The development of the liquid crystal display device technology is achieved not only by improving the driving method and device structure thereof but also by improving the members used in the display device. Among the members used in the display element, the liquid crystal alignment film is one of the important factors related to the display quality of the liquid crystal display element, and the role of the liquid crystal alignment film becomes more important every year with the improvement of the quality of the display element.

The liquid crystal alignment film needs to uniformly control the molecular arrangement of the liquid crystal for uniform display characteristics of the liquid crystal display device. For this reason, it is required to uniformly orient liquid crystal molecules on a substrate in one direction and to express a constant tilt angle (a pretilt angle) from the substrate surface.

Further, in order to improve the contrast of the image display apparatus and to enlarge the viewing angle range, it is possible to use, for example, a stretched film having refractive index anisotropy as the optical compensation film or the retardation film, or a film obtained by orienting a polymerizable liquid crystal compound Film is being 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 a process of manufacturing a liquid crystal display device, and the technique is important and is indispensable.

The liquid crystal alignment film is prepared using a liquid crystal aligning agent. The liquid crystal aligning agent which is currently mainly used is a solution in which polyamic acid or soluble polyimide is dissolved in an organic solvent. After such a solution is applied to a substrate, a film is formed by means such as heating to form a polyimide-based liquid crystal alignment film. Although various liquid crystal alignment systems other than polyamic acid have been studied, most of them have not been practically used in terms of heat resistance, chemical resistance (liquid-phase stability), coating property, liquid crystal alignment property, electrical characteristics, optical characteristics and display characteristics.

Industrially, a rubbing method which is simple and capable of high-speed processing at a large area is widely used as an orientation treatment method. The rubbing process is a process of rubbing the surface of the liquid crystal alignment film in one direction by using cloth woven with fibers such as nylon, rayon, polyester, etc., thereby making it possible to obtain a uniform orientation of the liquid crystal molecules. However, in the rubbing method, generation of oscillation or static electricity is frequent, and therefore, there is concern about alignment defects and influences on liquid crystal devices.

Recently, a liquid crystal alignment control method replacing the rubbing method has been developed. As to the photo-alignment method in which light is irradiated and the alignment treatment is performed, many alignment methods such as a photo-decomposition method, a photo-isomerization method, a photo-dimerization method, and a photo-crosslinking method have been proposed (see Non-Patent Document 1, Patent Document 3 and Patent Document 4 Reference). Unlike the rubbing method, the photo alignment method is a non-contact alignment method. In principle, generation of oscillation or static electricity is less than rubbing treatment.

The molecular alignment state of the liquid crystal monocrystalline layer in contact with the liquid crystal alignment film can be controlled by using the liquid crystal alignment film having the excellent alignment property and subjected to the alignment treatment by the photo alignment method. Thus, it is expected that the performance as a liquid crystal display element is improved.

Japanese Patent Publication No. 2947350 Japanese Patent Publication No. 2940354 Japanese Patent Application Laid-Open No. 2005-275364 Japanese Patent Application Laid-Open No. 11-15001

 Liquid Crystal 3, No. 4, Edited by the Japan Liquid Crystal Society, published by Japan Liquid Crystal Society, 1999, page 262

An object of the present invention is to provide a photosensitive compound suitable for the photo alignment method and a photosensitive polymer comprising the compound. The present invention also provides an optical alignment agent comprising the polymer. Further, it is an object of the present invention to provide a liquid crystal alignment film which is excellent in alignment property and is suitable for the photo alignment method even if the alignment treatment by the conventional rubbing method using the photo-alignment agent is not performed.

As a result of intensive research and development, the inventors of the present invention have found that the use of a photo-alignment agent using a photosensitive polymer as a liquid crystal aligning agent makes it possible to provide a liquid crystal alignment film which is suitable for photo- . That is, the present invention is as follows.

[1] A photosensitive compound represented by the formula (1):

In the formula (1), Y ¹ is a divalent group represented by the formula (2-1) or (2-2);

A ¹ is 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 this 1,4-phenylene, any hydrogen may be substituted with one or more substituents selected from fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, 5 alkyl or alkoxy of 1 to 5 carbon atoms;

Z ¹ is 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-;

R ¹ and R ² are independently hydrogen, fluorine, chlorine, -OH, -C≡N, -NO ₂ , trifluoromethyl, alkyl of 1 to 10 carbon atoms or alkoxy of 1 to 10 carbon atoms;

Q ¹ is independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be substituted with fluorine, and arbitrary -CH ₂ - may be replaced by -O-, -COO-, -OCO-, -CH = CH- or -C? C-;

n is 0 to 3;

In formulas (2-1) and (2-2), W ¹ and W ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms.

[2] The compound according to [1], wherein Y ¹ is a divalent group represented by formula (2-1) or (2-2) described in [1];

A ¹ is 1,4-phenylene or 1,4-cyclohexylene; In this 1,4-phenylene, any hydrogen may be substituted by fluorine, trifluoromethyl, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms;

Z ¹ is a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH ₂ - or -CH ₂ CH ₂ -COO-;

R ¹ and R ² are independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms;

Q ¹ is independently a single bond or alkylene having 1 to 12 carbon atoms, and arbitrary -CH ₂ - may be substituted with -O-;

n is 0 or 1;

In formulas (2-1) and (2-2), W ¹ and W ² are independently hydrogen, alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms;

The photosensitive compound according to [1].

[3] The photosensitive compound represented by the formula (1-1):

In the formula (1-1), W ¹ and W ² are independently hydrogen, alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms;

A ¹ is 1,4-phenylene or 1,4-cyclohexylene; In this 1,4-phenylene, any hydrogen may be substituted by fluorine, trifluoromethyl, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms;

Z ¹ is a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH ₂ - or -CH ₂ CH ₂ -COO-;

R ¹ is hydrogen or alkyl of 1 to 5 carbon atoms;

R ² is hydrogen, fluorine, alkyl having 1 to 5 carbon atoms or alkoxy having 1 to 5 carbon atoms;

Q ¹ is independently a single bond or an alkylene of 1 to 12 carbon atoms, and any -CH ₂ - may be substituted with -O-;

n is 0 or 1;

[4] A composition containing the photosensitive compound according to any one of [1] to [3].

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

[6] A photosensitive polymer having a constituent unit represented by the formula (3)

In the formula (3), Y ¹ is a divalent group represented by the formula (2-1) or (2-2);

A ¹ is 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 this 1,4-phenylene, any hydrogen may be substituted with one or more substituents selected from fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, 5 alkyl or alkoxy of 1 to 5 carbon atoms;

Z ¹ is 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-;

R ¹ and R ² are independently hydrogen, fluorine, chlorine, -OH, -C≡N, -NO ₂ , trifluoromethyl, alkyl of 1 to 10 carbon atoms or alkoxy of 1 to 10 carbon atoms;

Q ¹ is independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be substituted with fluorine, and arbitrary -CH ₂ - may be replaced by -O-, -COO-, -OCO-, -CH = CH- or -C? C-;

n is 0 to 3;

In formulas (2-1) and (2-2), W ¹ and W ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms.

[7] The compound according to [6], wherein Y ¹ is a divalent group represented by formula (2-1) or (2-2) described in [6];

A ¹ is 1,4-phenylene or 1,4-cyclohexylene; In this 1,4-phenylene, any hydrogen may be substituted by fluorine, trifluoromethyl, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms;

Z ¹ is a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH ₂ - or -CH ₂ CH ₂ -COO-;

R ¹ and R ² are independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms;

Q ¹ is independently a single bond or alkylene having 1 to 12 carbon atoms, and arbitrary -CH ₂ - may be substituted with -O-;

n is 0 or 1;

The photosensitive polymer according to [6], wherein in the formulas (2-1) and (2-2), W ¹ and W ² are independently hydrogen, alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms.

[8] A photosensitive polymer represented by the formula (3-1):

In formula (3-1), W ¹ and W ² are independently hydrogen, alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms;

A ¹ is 1,4-phenylene or 1,4-cyclohexylene; In this 1,4-phenylene, any hydrogen may be substituted by fluorine, trifluoromethyl, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms;

Z ¹ is a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH ₂ - or -CH ₂ CH ₂ -COO-;

R ¹ is hydrogen or alkyl of 1 to 5 carbon atoms;

R ² is hydrogen, fluorine, alkyl having 1 to 5 carbon atoms or alkoxy having 1 to 5 carbon atoms;

Q ¹ is independently a single bond or an alkylene of 1 to 12 carbon atoms, and any -CH ₂ - may be substituted with -O-;

n is 0 or 1;

[9] The photosensitive polymer according to any one of [5] to [8], wherein the weight average molecular weight is 1000 to 500000.

[10] A homopolymer having the constituent unit according to any one of [5] to [8].

[11] A copolymer comprising at least one of the constituent unit represented by the formula (3) and the constituent unit other than the constituent unit represented by the formula (3) described in [6].

[12] A photosensitive material using the polymer according to any one of [5] to [11].

[13] A photo-alignment agent for a liquid crystal alignment film using the polymer according to any one of [5] to [11].

[14] A liquid crystal alignment film produced by using the photo-alignment agent according to [13].

[15] A liquid crystal display element produced using the liquid crystal alignment film according to [14].

In the present invention, since a liquid crystal alignment film is formed using a compound having a photoreactive group, complicated processing steps as shown in the conventional rubbing treatment and subsequent oscillation and static electricity do not occur. Therefore, it is possible to produce a liquid crystal alignment film having high optical uniformity without alignment defects. In addition, the optical film and the liquid crystal display element manufactured using the liquid crystal alignment film can maintain high orientation stability.

The present invention will be described in detail.

In the present invention, at least one kind of polymer having a photoreactive group (hereinafter, " photosensitive polymer ") is used as the liquid crystal alignment film. The photosensitive polymer is a compound which causes at least one of a photo-isomerization reaction, a photo-dimerization reaction, and a photo-decomposition reaction by irradiation of plane polarized light, for example. The photosensitive polymer is preferably a compound that causes a photo-isomerization reaction or photo-dimerization reaction by light irradiation, and particularly preferably a compound that causes a photo-dimerization reaction. The photosensitive polymer preferably has a weight average molecular weight of about 1,000 to 500,000. May be a polymer of a single monomer, or may be 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.

In the photosensitive polymer, a compound causing a photo-isomerization reaction refers to a compound that causes stereoisomerization or structural isomerization by the action of light. As optical isomerization compounds, for example, cinnamic acid compounds (K. Ichimura et al., Macromolecules, 30, 903 (1997)), azobenzene compounds (K. Ichimura et al., Mol. Cryst. Liq. Cryst., 298, (Yamamura et al., Liquid Crystals, vol.13, No. 2, page 189 (1993)), stilbene compounds (JG Victor and JM Torkelson, (K. Ichimura et al., Chemistry Letters, page 1063 (1992); K. Ichimura et al., Thin Solid Films, vol. 235, page 101 (1993)) and spiropyran compounds (Macromolecules, 20, 2241 . Also included are compounds having these skeletons in the polymer main chain or polymer side chain. Of these, photo-isomerizing compounds containing a double bond structure composed of -CH = CH- or -N = N- are preferable.

Among the photosensitive polymer, a compound causing a photodimerization reaction refers to a compound that undergoes an addition reaction between two groups by irradiation with light to be cyclized. Examples of photodimerizing compounds include cinnamic acid derivatives (M. Schadt et al., J. Appl. Phys., Vol. 31, No. 7, page 2155 (1992)), coumarin derivatives (M. Schadt et al. (YK Jang et al., SID Int. Symposium Digest, P (2002), Nature, vol.381, page 212 (1996)), chalcone derivatives (Takahiro Ogawa et al. -53 (1997)). Also included are compounds having derivatives of these skeletons in the polymer main chain or side chains. Among them, a polymer having a cinnamic acid derivative and a coumarin derivative skeleton as a side chain is preferable, and a polymer (side chain polymer) having a skeletal derivative skeleton as a side chain is more preferable.

Such a material containing a photosensitive polymer is called a photosensitive material.

The photosensitive material can be used for a photoresist, a holography, an optical driving material, a retardation film, a polarized light emitting film, etc. in addition to a liquid crystal alignment film.

As photoreactive groups used in liquid crystal alignment layers, cinnamic acid derivatives are preferred for their high photoreaction sensitivity, transparency, ease of manufacture, and the like (JP-A-2007-224273). However, the photosensitive polymer in which the main chain of such a polymer is a polyimide is required to be dissolved in a solvent such as N-methyl-2-pyrrolidone for application to a substrate. In addition, at the time of film formation, Needs to be. Therefore, it is difficult to use it for a substrate (film such as TAC) that is eroded into a solvent such as N-methyl-2-pyrrolidone or has no heat resistance of 150 degrees or more.

A polymer having a cinnamic acid derivative skeleton as a side chain is used as a liquid crystal alignment film (Japanese Patent Publication No. 4011652). As the polymerizable group constituting the repeating unit of the photosensitive polymer, for example, a vinyl ester group, an acryloyl group and a methacryloyl group are used. 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, and mechanical strength. In order to solve such a problem, it is conceivable to improve the heat resistance and the mechanical strength by a chemical technique such as copolymerization with a polyfunctional acrylate or a physical technique such as adding a filler. However, There are cases where new problems such as a decrease in the photoreaction sensitivity or a decrease in the transparency are caused.

Since the compound of the present invention represented by the formula (1) uses itaconic acid as a polymerizable group, unlike a derivative having an acryloyl group, it has a substituent in addition to a polymerizable group and a photosensitizer. These substituents are useful for improving properties such as solvent resistance, heat resistance, adhesion, and mechanical strength. Thus, the inventors synthesized a photosensitive polymer containing the constituent unit represented by the formula (3) and evaluated it as a liquid crystal alignment film. As a result, it was found that the liquid crystal compound can be aligned with a smaller irradiation dose than the known materials, and the alignment property is excellent. Further, the present inventors have found the properties such as excellent adhesion to a substrate and solvent resistance, high transmittance in a visible region, and high film hardness, and have reached the present invention.

In the present specification, the photosensitive compound represented by the formula (1) may be referred to as the compound (1). The same applies to compounds represented by other formulas. The term " arbitrary " used in describing the symbol of the formula means not only the position of the element (or the functional group) but also the number thereof can be freely selected. For example, the expression "arbitrary A may be substituted by B, C, D, or E" may be substituted by one of A, B, C, and D, and any two of A may be substituted by B , C, or D, and may be substituted with B and C, B and D, or C and D. When arbitrary -CH ₂ - may be substituted with -O-, the substitution resulting in the linking group -OO- is not included.

In addition, one having a polymerizable group may be referred to as a monofunctional. In addition, those having two or more polymerizable groups may be referred to as polyfunctional, or a designation depending on the number of polymerizable groups (for example, when two polymerizable groups are present, bifunctional).

A compound in which an arbitrary functional group is introduced into a certain compound or a compound in which an atom or the like is substituted is sometimes referred to as a derivative or an A derivative.

The photosensitive polymer is simply referred to as a polymer. In some cases, the liquid crystal display element is abbreviated as a display element and the liquid crystal alignment film is referred to as an alignment film.

The photosensitive compound of the present invention is represented by formulas (1-1) and (1-2). Is preferably a photosensitive compound represented by the formula (1-1).

Formula (1-1) ^{of, W 1, W 2, A} 1, Z 1, Q 1, R 1, R 2 and n have the formula (1-1) of the ^{W 1, W 2, A 1} , Z 1 , Q ¹ , R ¹ , R ² and n. The definitions of the symbols in the formula (1-2) are also the same as those in the formula (1-1).

Specific examples of the photosensitive compounds represented by the formulas (1-1) and (1-2) are shown below, but the present invention is not limited to these specific examples.

By using the photosensitive compound of the present invention, a photosensitive polymer is obtained. This photosensitive polymer contains at least one cinnamic acid derivative.

Preferably, it is a photosensitive polymer having a constituent unit represented by the formula (3).

More preferably, it is a photosensitive polymer having a constituent unit represented by the formula (3-1).

The definitions of the symbols in the formulas (3) and (3-1) are the same as those in the formulas (3) and (3-1).

Specific examples of the photosensitive polymer having the structural unit represented by the formula (3-1) are shown below, but the present invention is not limited to these specific examples.

The photosensitive polymer may be a mixture of polymers containing one or more structural units represented by formula (3). The photosensitive polymer may be a copolymer containing one or more structural units other than the structural unit represented by the formula (3). The structure of the structural unit other than the structural unit of the formula (3) in the copolymer is not particularly limited. The copolymer containing two or more constituent units may be a random copolymer or a block copolymer.

The constituent unit other than the constituent unit of the formula (3) is not particularly limited. For example, a constituent unit derived from a compound containing a cinnamic acid derivative represented by the formula (M-1) and (M-2) have.

Wherein (M-1) and (M-2) ^{of, W 1, W 2, A} 1, Z 1 and Q ¹ are each of the formula (3) of the ^{W 1, W 2, A 1} , Z 1 , and Q ^One N is 0 to 4, and R < ³ > Is a methyl group consisting of hydrogen, methyl, fluoro, trifluoromethyl, R ^M is an alkyl or hydrogen, fluoroalkyl of 1 to 10 carbon atoms in an alkyl, having 1 to 10, R ^N is C 1 -C 10 alkyl, having 1 to 10 carbon atoms in the Alkoxy, hydrogen, chlorine, fluorine, -OH, -C? N, -NO ₂ , -CF ₃ or -OCF ₃ .

Specific examples are shown below. But the present invention is not limited to these specific examples.

In the following description, the compound (M-1) and the compound (M-2) may be collectively referred to as the compound (M). When the photosensitive polymer of the present invention is a homopolymer of the compound (1), it shows a high degree of orientation, but the degree of polymerization tends to be lowered so that the solvent resistance tends to be lowered. The copolymer of the compound (1) and the compound (M) is more preferable from the viewpoint of expressing the desired properties. The proportion of the compound (1) is preferably 1 to 60% by weight, more preferably 1 to 50% by weight, based on the total weight of the compound (1) and the compound (M). The photosensitive polymer may contain a constituent unit derived from the compound (1), a constituent unit derived from the compound (M), and other constituent units.

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 can be used.

Hereinafter, concrete examples of monomers for deriving other constituent units are given. But the present invention is not limited to these specific examples.

Examples of the monomers for imparting a constituent unit derived from an industrially available monomer capable of radical polymerization include (meth) acrylic acid, methyl (meth) acrylate, ethyl (Meth) acrylic acid or its derivatives such as (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) Ryu;

(meth) acrylate compounds such as? -carboxypolycaprolactone mono (meth) acrylate, phthalic acid monohydroxyethyl (meth) acrylate, and 2-hydroxy- ;

(Meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di Acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethyl (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dicyclopentanyl di (meth) acrylate, ethoxylated hydrogenated bisphenol A (Meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol S di Polyfunctional (meth) acrylate compounds such as ethylene glycol bishydroxypropyl (meth) acrylate, and monohydroxypentaerythritol tri (meth) acrylate;

Cyclic ethers such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate and (3-ethyl-3-oxetanyl) methyl (Meth) acrylate compound.

As these compounds, monofunctional or polyfunctional (meth) acrylate compounds of commercially available products can be used as they are. Concretely, Aronix M-5400 (phthalic acid monohydroxyethyl acrylate), Dong M-5700 (2-hydroxy-3-phenoxypropyl acrylate), Dong M-5400 215 (polyethylene glycol (n? 9) diacrylate), M-305 (pentaerythritol diacrylate), M- M-315 (isocyanuric acid ethylene oxide-modified triacrylate), M-400 (dipentaerythritol pentaacrylate and dipentaerythritol triacrylate), M-309 (trimethylolpropane triacrylate) (Mixture of main component)}, M-450 (pentaerythritol tetraacrylate), M-8060, and M-8560;

(Trimethylolpropane triacrylate), # 300 (pentaerythritol triacrylate), # 360 (trimethylolpropane ethylene oxide-modified triacrylate), manufactured by Osaka Organic Chemical Industry Co., # 400 (pentaerythritol tetraacrylate);

KAYARAD TMPTA (trimethylol propane triacrylate) manufactured by Nippon Kayaku Co., Ltd., copper PET-30 (pentaerythritol triacrylate), copper DPHA {dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Main component)}, D-310 (dipentaerythritol pentaacrylate), D-330 and DPCA-60.

In the present invention, among the above-mentioned compounds, preferred are trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 300, Dong # 400, Nippon Kogyo Co., Ltd. (trade name) manufactured by Aronix M-305, Dong M-309, Dong M-400, Dong M-450 manufactured by Osaka Organic Chemical Industry Co., A polyfunctional acrylate having three or more functionalities such as KAYARA DTMPTA, copper DPHA, copper D-310 and copper PET-30 manufactured by Kayaku Co., Ltd. can be preferably used. These compounds may be used alone or in admixture of two or more.

Since the photosensitive polymer of the present invention is used not on a stand-alone basis but on a substrate, it can be used as an optical material for optical alignment, such as good alignment property as a material for a liquid crystal alignment film, adhesion to a substrate, uniformity of coating, chemical resistance, heat resistance, A property required for a film or an optical display device is required. Additives can be used to impart such properties.

The amount of the various additives to be added is determined depending on the required properties, and is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the polymer.

Examples of the additive include adhesiveness improvers such as acrylic, styrene, polyethyleneimine or urethane based polymer dispersing agents, anionic, cationic, nonionic or fluorine surfactants, coating improvers such as silicone resins, silane coupling agents and the like, Ultraviolet absorbers such as phenol, phenol and the like, anti-aggregation agents such as sodium polyacrylate, thermal crosslinking agents such as oxirane compounds, melamine compounds or bisazide compounds, and alkali solubility promoters such as organic carboxylic acids.

A photosensitizer may also be used as an additive. Colorless sensitizer and triplet sensitizer are preferable.

Examples of the photosensitizer include an aromatic nitro compound, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscumarin, aromatic 2- (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, (2-benzoylmethylene-3-methyl- beta -naphthothiazoline, 2- (beta -naphthoylmethylene) -3-methylbenzothiazoline, 2- (alpha -naphthoylmethylene) -3 -Methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methylbenzothiazoline, 2- Methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene- Oxazoline, 2- (? -Naphthoylmethyl (4-biphenoylmethylene) -3-methylbenzooxazoline, 2- (? -Naphthoylmethylene) -3-methylbenzooxazoline, 2- Methyl-β-naphthoxazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthoxazoline, 2- (p- (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroascenaphthene (5-nitroanaphthalene), (2 - [(m- Alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalene methanol, 2-naphthalenecarboxylic acid, 9-anthracene methanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolizine, merocoumarin and the like.

Preferred are aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonylbiscumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

A photosensitizer having a polymerizable group may be contained as a constitutional unit. Examples of the polymerizable group include an acryloyl group, a methacryloyl group, a vinyl group, a maleimide group and itaconic acid.

Specific examples are shown below, but the present invention is not limited to these specific examples.

In these compounds, Q ¹ and R ³ are as defined and Q ¹ and R ³ in the formula (M-1) and (M-2).

As an additive, a coupling agent may be used in order to improve adhesion with a substrate. As the coupling agent, silane-based, aluminum-based, and titanate-based compounds are used. Specific examples of the silane coupling agent include silane coupling agents such as 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltrimethoxysilane, and acetoalkoxy aluminum diisopropylate Aluminum titanate, and tetraisopropyl bis (dioctylphosphite) titanate.

As an additive, a surfactant may be used to improve the wettability, leveling property, and coating property of the base substrate. As the surfactant, a silicone surfactant, an acrylic surfactant, a fluorine surfactant, or the like is used. Specific examples thereof include silicone surfactants such as Byk-300, 306, 335, 310, 341, 344, and 370 manufactured by Big Chemical Co., Ltd., acrylic type surfactants such as 354, 358, Surfactant, SC-101 manufactured by Asahi Glass Co., Ltd., EF-351 and 352 manufactured by TOKEM PRODUCTS CO., LTD., And the like.

The weight average molecular weight of the photosensitive polymer having the constituent unit represented by the formula (3) is preferably from 1,000 to 500,000, more preferably from 1,000 to 100,000. The weight average molecular weight can be measured as a value in terms of polystyrene (PS) using gel permeation chromatography (GPC).

The production method of the photosensitive polymer having the constituent unit represented by the formula (3) is not particularly limited, and a widely used method which is industrially handled can be used. Specifically, it can be produced by cation polymerization, radical polymerization or anionic polymerization using a vinyl group of a monomer giving a compound represented by the formula (1). Of these, radical polymerization is particularly preferable from the viewpoints of ease of reaction control and the like.

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

The radical thermal polymerization initiator is a compound which generates radicals by heating at a decomposition temperature or higher. Examples of such a radical thermal polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, diacyl peroxides such as acetyl peroxide and benzoyl peroxide, hydroperoxides such as (Di-tert-butyl peroxide, dicumyl peroxide, di-lauroyl peroxide, etc.), peroxyketal (dibutyl peroxide, (Peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfate Azo compounds such as azobisisobutylonitrile and 2,2'-di (2-hydroxyethyl) azobisisobutyronitrile, and the like can be used in combination with an organic peroxide such as potassium persulfate, potassium persulfate, sodium persulfate, ammonium persulfate, . These radical thermal polymerization initiators may 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 a radical photopolymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone , 2-ethyl anthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, iso Benzoinone, 2-methyl-1- [4- ((2-methyl-1-benzyloxycarbonylamino) Methyl 4-methylthio) phenyl] -2-morpholinopropane-1-one, ethyl 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Dimethylaminobenzoic acid isoamyl, 4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) - (Trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis Bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)] - Bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) (P-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- Mercapto benzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2, 2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' bis (2,4-dibromophenyl) -4,4 ' -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl- Imidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, Di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di Peroxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3-methyl- 2-ylidene) -1-naphthalen-2-yl-ethanone, or 2- (3- -1,3-benzothiazol -2 (3H) - ylidene) -1- (2-benzoyl and the like) ethanone. 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, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a bulk polymerization method, a solution polymerization method and the like can be used. The same applies to other polymerization methods, and the details thereof are described in " Synthesis of Polymers (Phase) " (published by Endoshi Koshi Co., Ltd. in 2010). The outline of solution polymerization, which is a general radical polymerization method, will be described below.

The solution polymerization method is a reaction in which polymerization is carried out in a solvent using a usable 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 within the range of 50 to 200 占 폚 under atmospheric pressure, and are preferably organic compounds that uniformly dissolve monomers, polymerization process components and the like.

The organic solvent may have no inhibitory effect on the radical polymerization, 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;

And esters such as ethyl acetate, butyl acetate, amyl acetate and? -Butyrolactone. These organic solvents may be used singly or in combination of two or more.

The solution polymerization conditions are not particularly limited. For example, it is preferable to heat the solution within a temperature range of 50 to 200 占 폚 for 10 minutes to 20 hours. It is also preferable to carry out inactive gas grasping such as nitrogen during the solution polymerization as well as the solution polymerization to prevent the generated radical from being inactivated.

A radical polymerization method using a chain transfer agent is particularly effective in order to control the molecular weight of the photosensitive polymer having the structural unit represented by the formula (3), to homogenize the molecular weight distribution, or to promote polymerization. This makes it possible to obtain a polymer having a more uniform molecular weight distribution in a preferable molecular weight range.

Examples of the chain transfer agent include, but are not limited to,? -Mercaptopropionic acid,? -Mercaptopropionic acid methyl ester, isopropylmercaptan, octylmercaptan, decylmercaptan, dodecylmercaptan, tert-dodecylmercaptan, octadecylmercaptan, Mercaptans such as phenol and p-nonylthiophenol, thiosalicylic acid, mercaptoacetic acid, and mercapto;

Polyhalogenated alkyls such as carbon tetrachloride, chloroform, butyl chloride, 1,1,1-trichloroethane and 1,1,1-tribromooctane;

alpha -methylstyrene, alpha -methylstyrene dimer, and the like can be used. The amount of these chain transfer agents to be used depends on the activity of the chain transfer agent, the combination of monomers, the solvent, the temperature, and other polymerization conditions. But is usually about 0.01 mol% to 50 mol% based on the total number of moles of the monomers to be used.

The photo-alignment agent of the present invention is used as a coating liquid in which a photosensitive polymer is dissolved in an organic solvent. The liquid crystal alignment film of the present invention can be produced by a known method using a known method (for example, spin coating, gravure coater, reverse gravure, Meyer bar coater, die coater, reverse roll coater, panthene reverse coater, Coating on a substrate by a coater, knife coater, lip coater, resist coater method), removing the organic solvent, and orienting the resulting coating film by polarized irradiation.

Further, the liquid crystal alignment film of the present invention irradiates the film in a single direction in order to impart an alignment function. The photosensitive polymer in the film is oriented by light irradiation, and an alignment function is thereby developed in the liquid crystal alignment film. At this time, X-rays, electron beams, ultraviolet rays, visible rays or infrared rays (heat rays) are used as irradiation light, and ultraviolet rays are particularly preferably used. The wavelength of ultraviolet rays is preferably 400 nm or less, more preferably 180 to 360 nm. As the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, a high-pressure mercury lamp, a high-pressure discharge lamp, or a short arc discharge lamp are preferably used. In general, linearly polarized light is irradiated, but an orientation function may be imparted by non-polarized light irradiation. It is particularly preferable to use linearly polarized light. The dose is preferably from 10 mJ / cm 2 to 20000 mJ / cm 2, and most preferably from 20 mJ / cm 2 to 5000 mJ / cm 2.

The liquid crystal alignment film of the present invention can be obtained by applying a photo-alignment agent containing a photosensitive polymer and various compounds to be added as needed, on a transparent substrate, and irradiating light to orient the photosensitive polymer. The liquid crystal alignment film of the present invention exhibits the optical anisotropy expressed by the orientation of the photosensitive polymer.

By using the liquid crystal alignment film of the present invention, an optical film can be obtained. The optical film of the present invention means an optical compensation film or a retardation film for realizing the enhancement of the contrast of the liquid crystal display element or the expansion of the viewing angle range. Generally, it has a substrate, an orientation film, and an optically anisotropic layer. The optically anisotropic layer is obtained by applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and various compounds added as needed in addition to the alignment layer to align molecules of the liquid crystal compound and then polymerizing. The optically anisotropic layer exhibits optical anisotropy expressed by the orientation of molecules of the liquid crystalline compound.

Example

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to 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 crystals, and I represents an isotropic liquid phase. The measurement method of the property value is shown below.

≪ Weight average molecular weight (Mw) and polydispersity (Mw / Mn) >

Shimazu LC-9A type gel permeation chromatograph (GPC) manufactured by Shimadzu Seisakusho, and Shodex (registered trademark) GF-7M HQ (manufactured by Showa Denko KK) (DMF or THF as a developing solvent and polystyrene whose molecular weight is already known) Were used.

<Orientation of Liquid Crystal Molecules>

Was confirmed by the following method.

(1) Visual observation method

The substrate on which the anisotropic polymer was formed on the liquid crystal alignment film was sandwiched and observed on two polarizers arranged by Cross-Nicol, and the substrate was rotated in a horizontal plane to check the light and dark state. The substrate on which the anisotropic polymer was formed on the liquid crystal alignment film was observed under a polarizing microscope to confirm the presence of alignment defects.

(2) Measurement by a polarization analyzer

Light having a wavelength of 550 nm was irradiated to a substrate on which an anisotropic polymer was formed on a liquid crystal alignment film, using an OPTIPRO polarization analyzer manufactured by Shin-Tek. The retardation was measured while reducing the angle of incidence of this light from 90 DEG with respect to the film surface. The retardation (retardation) is expressed as? N x d. The symbol? N is the optical anisotropy value, and the symbol d is the thickness of the polymer film.

&Lt; Measurement of film thickness &

Two layers of a liquid crystal alignment film and an anisotropic polymer were cut out from the substrate on which an anisotropic polymer was formed on the liquid crystal alignment film, and the step was measured using a fine shape measuring device (Alpha Step IQ manufactured by KLA TENCOR Co., Ltd.).

<Evaluation of optical anisotropy value? N>

The retardation and the film thickness value were calculated for the liquid crystal alignment film causing the homogeneous alignment and the composite layer composed of two layers of the anisotropic polymer to calculate Δn = retardation / film thickness.

<Evaluation of Adhesion to Substrate>

The adhesive tape peeling test was evaluated by the test method of JIS standard "JIS-5400 8.5 Adhesiveness (8.5.2 checkerboard tape method)", that is, the remaining squares in 100 chambers. On the substrate, a TAC film (hereinafter referred to as a saponified TAC) manufactured by FUJIFILM Corporation subjected to a saponification treatment was used.

<Photopolymerization Conditions of Polymerizable Liquid Crystal Composition>

Light of 90 mW / cm 2 (365 nm) intensity was irradiated for 30 seconds under an atmosphere of nitrogen or in the air using an ultrahigh pressure mercury lamp (manufactured by Ushio Co., Ltd.) of 500 W at room temperature.

[Example 1]

Compound (1-1-4) was synthesized as follows.

(First step)

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 under reflux for 5 hours. After cooling to room temperature, methanol was distilled off under reduced pressure. The resulting 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 hydrogencarbonate and water, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the obtained residue was recrystallized from ethanol to obtain 280 g of a compound (ex-1).

(Second step)

250 g of anhydrous itaconic acid was added to 150 ml of isopropyl alcohol, and the mixture was stirred under heating in a nitrogen atmosphere at 100 占 폚 for 6 hours. After cooling to room temperature, 200 g of compound (ex-2) was obtained by distillation.

(Final stage)

20 g of the compound (ex-1), 19 g of the compound (ex-2) and 2.7 g of 4-dimethylaminopyridine (DMAP) were added to 200 ml of dichloromethane and the mixture was stirred under cooling in a nitrogen atmosphere. Then, 50 ml of a dichloromethane solution of 24 g of 1,3-dicyclohexylcarbodiimide (DCC) was added dropwise thereto. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated 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, eluant: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized from methanol to obtain 1- 1-4) was obtained.

The phase transition temperature and NMR analysis values of the obtained compound (1-1-4) are as follows.

Phase transition temperature: C 64 I

[Example 2]

Compound (1-1-1) was synthesized as follows.

31 g of the compound (ex-1), 25 g of monomethyl itaconic acid and 4.2 g of DMAP were added to 200 ml of dichloromethane, and the mixture was stirred under cooling in a nitrogen atmosphere. To the solution, 80 ml of a dichloromethane solution of 37.6 g of DCC was added dropwise. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated 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, eluant: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized from methanol to obtain 1- 1-1).

The phase transition temperature and NMR analysis values of the obtained compound (1-1-1) are as follows.

Phase transition temperature: C 80 I

[Example 3]

Compound (1-1-7) was synthesized as follows.

27.4 g of the compound (ex-1), 10 g of itaconic acid and 3.8 g of DMAP were added to 200 ml of dichloromethane, and the mixture was stirred under cooling in a nitrogen atmosphere. To this was added dropwise 70 ml of a dichloromethane solution of 33.3 g of DCC. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated 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, eluant: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) and recrystallized with toluene to obtain compound 1- 1-7).

The phase transition temperature and NMR analysis value of the obtained compound (1-1-7) are as follows.

Phase transition temperature: C 131 I

[Example 4]

Compound (1-1-11) was synthesized as follows.

(First step)

40 g of the compound (ex-1) and 9.9 g of sodium hydroxide were added to 400 ml of N, N-dimethylformamide (DMF), and the mixture was heated and stirred at 60 占 폚 in a nitrogen atmosphere. Thereto, 30.9 g of 2-bromoethanol was added dropwise. After dropwise addition, the mixture was stirred at 80 DEG C for 8 hours. The precipitated precipitate was separated by filtration, and 800 ml of ethyl acetate and 800 ml of water were added to extract an organic layer. The obtained organic layer was washed with saturated aqueous sodium hydrogencarbonate solution and then 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, eluant: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) and recrystallized with toluene to obtain compound (ex- 2).

(Final stage)

15 g of the compound (ex-2), 9.7 g of monomethyl itaconic acid and 1.7 g of DMAP were added to 100 ml of dichloromethane, and the mixture was stirred under cooling in a nitrogen atmosphere. Then, 50 ml of a dichloromethane solution containing 14.6 g of DCC was added dropwise thereto. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated 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, eluant: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 6/1)) and recrystallized from methanol to obtain 1- 1-11).

The phase transition temperature and NMR analysis values of the obtained compound (1-1-11) are as follows.

Phase transition temperature: C 50 I

[Example 5]

Compound (1-2-2) was synthesized as follows.

(First step)

40 g of monoethyl itaconic acid and 68.4 g of 1,4-butanediol were added to 160 ml of toluene. Three drops of concentrated sulfuric acid were added dropwise, and the mixture was stirred for 16 hours while being dehydrated under heat reflux using Dean-Stark. Water was added to the reaction solution, and the organic layer was extracted and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure. 29.7 g of the compound (ex-3) was obtained by distillation.

(Final stage)

10 g of the compound (ex-3), 9 g of 3,4-dimethoxy cinnamic acid and 1.1 g of DMAP were added to 100 ml of dichloromethane, and the mixture was stirred under cooling in a nitrogen atmosphere. Thereto was added 30 ml of a dichloromethane solution of 9.4 g of DCC dropwise. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated 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, eluant: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized from methanol to obtain 1- 2-2).

The phase transition temperature and NMR analysis values of the obtained compound (1-2-2) are as follows.

Phase transition temperature: C 39 I

[Example 6]

The compound (1-1-13) was synthesized as follows.

(First step)

100 g of anhydrous itaconic acid was added to 200 ml of t-butanol, and the mixture was stirred under heating at 100 占 폚 for 6 hours in a nitrogen atmosphere. After cooling to room temperature, 128 g of compound (ex-4) was obtained by distillation.

(Second step)

20 g of the compound (ex-1), 21 g of the compound (ex-4) and 2.3 g of DMAP were added to 200 ml of dichloromethane, and the mixture was stirred under cooling in a nitrogen atmosphere. Then, 50 ml of a dichloromethane solution of 14.4 g of DCC was added dropwise. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated 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 to obtain compound ex- 5).

(Final stage)

24.7 g of the compound (ex-5) was added to 500 ml of acetic acid, and the mixture was stirred at 100 ° C under a nitrogen atmosphere. Thereto was added 25 ml of 47% hydrobromic acid dropwise. After dropwise addition, the mixture was stirred under reflux for 4 hours. 1000 ml of ethyl acetate and 1000 ml of water were added, and the organic layer was extracted. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure and recrystallized from ethanol to obtain 11.8 g of a compound (1-1-13).

The phase transition temperature and NMR analysis values of the obtained compound (1-1-13) are as follows.

Phase transition temperature: C 127 I

[Example 7]

Compound (1-1-14) was synthesized as follows.

(First step)

100 g of trans-p-coumaric acid and 60 g of pyridine were added to 1000 ml of tetrahydrofuran (THF), and the mixture was stirred under cooling in a nitrogen atmosphere. Thereto was added 75 g of acetic anhydride dropwise. After dropwise addition, the mixture was stirred at room temperature for 4 hours. The precipitate was separated by filtration and washed with toluene to obtain 68 g of a compound (ex-6).

(Second step)

30 g of the compound (ex-6), 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 stirred at room temperature for 8 hours Respectively. The organic layer was extracted with saturated aqueous sodium bicarbonate. 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 to obtain 39 g of a colorless liquid compound (ex-7).

(Third step)

39 g of the compound (ex-7) was added to a mixed solution of 300 ml of THF and 300 ml of methanol, and the mixture was stirred under cooling in a nitrogen atmosphere. Thereto was added dropwise 18 ml of 28% aqueous ammonia solution. After dropwise addition, 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 with heptane to obtain 18.7 g of a compound (ex-8).

(Step 4)

18.7 g of the compound (ex-8) and 3.3 g of sodium hydroxide were added to 200 ml of DMF, and the mixture was heated and stirred at 60 占 폚 in a nitrogen atmosphere. Then, 11.3 g of 2-bromoethanol was added dropwise thereto. After dropwise addition, the mixture was stirred at 80 DEG C for 8 hours. The precipitated precipitate was separated by filtration, and 800 ml of ethyl acetate and 800 ml of water were added to extract an organic layer. The obtained organic layer was washed with saturated aqueous sodium hydrogencarbonate solution and then with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was recrystallized with heptane to obtain 15.6 g of a compound (ex-9).

(Step 5)

15.6 g of the compound (ex-9), 8.5 g of monomethyl itaconic acid and 0.7 g of DMAP were added to 160 ml of dichloromethane, and the mixture was stirred under cooling in a nitrogen atmosphere. 30 ml of a dichloromethane solution of 11.6 g of DCC was added dropwise thereto. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated 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 recrystallized from methanol to obtain 13.6 g of a compound (ex-9).

(Final stage)

13.6 g of the compound (ex-9) was added to a mixed solution of 150 ml of THF and 150 ml of methanol, and the mixture was stirred under cooling in a nitrogen atmosphere. Thereto was added 20 ml of 6N hydrochloric acid water dropwise. After dropwise addition, the mixture was stirred at room temperature for 4 hours. 500 ml of ethyl acetate and 500 ml of water were added to extract an 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 recrystallized from ethanol to obtain 8 g of a compound (1-1-14).

The phase transition temperature and NMR analysis values of the obtained compound (1-1-14) are as follows.

Phase transition temperature: C 138 I

[Example 8]

A copolymer polymer of the compound (1-1-4) and the compound (M-1-2) was synthesized as follows.

2.5 g of the compound (1-1-4), 2.5 g of the compound (M-1-2) and 0.3 g of azobisisobutyronitrile (AIBN) were added to 40 ml of THF and the mixture was stirred under reflux for 10 hours under nitrogen atmosphere Respectively. The reaction solution was poured into methanol and re-dialed. The crystals were separated by filtration and dried to obtain 4.3 g of polymer (P-1).

The polymer thus obtained had Mw of 6400 and Mw / Mn of 2.3.

Compound (M-1-2) was synthesized according to the method described in Japanese Patent Publication No. 4011652.

[Example 9]

A copolymer polymer of the compound (1-1-11) and the compound (M-1-2) was synthesized as follows.

0.5 g of the compound (1-1-11), 4.5 g of the compound (M-1-2) and 0.04 g of AIBN were added to 40 ml of THF and the mixture was stirred under reflux for 10 hours under a nitrogen atmosphere. The reaction solution was poured into methanol and re-dialed. The crystals were separated by filtration and dried to obtain 4.7 g of polymer (P-2).

The polymer thus obtained had Mw of 57200 and Mw / Mn of 2.9.

[Example 10]

The copolymer polymer of the compound (1-1-7), the compound (M-1-1) and the compound (S-5-1) was synthesized as follows.

2.5 g of the compound (1-1-7), 2.5 g of the compound (M-1-1), 0.2 g of the compound (S-5-1) and 0.1 g of AIBN were added to 40 ml of THF and heated under a nitrogen atmosphere for 10 hours And the mixture was stirred under reflux. The reaction solution was poured into methanol and re-dialed. The crystals were separated by filtration and dried to obtain 3.2 g of polymer (P-3).

The obtained polymer had Mw of 22800 and Mw / Mn of 2.5.

Compound (M-1-1) was synthesized according to the method described in Japanese Patent Publication No. 4011652.

Compound (S-5-1) was synthesized according to the method described in JP-A-2002-226429.

[Example 11]

The compound (1-2-2), the compound (M-2-1) and the copolymerized polymer of 4-hydroxybutyl methacrylate were synthesized as follows.

4.0 g of the compound (1-2-2), 1.0 g of the compound (M-2-1), 0.5 g of 4-hydroxybutyl methacrylate and 0.6 g of AIBN were added to 40 ml of THF and heated under a nitrogen atmosphere for 10 hours And the mixture was stirred under reflux. The reaction solution was poured into methanol and re-dialed. The crystals were separated by filtration and dried to obtain 2.8 g of polymer (P-4).

The obtained polymer had Mw of 4700 and Mw / Mn of 3.5.

[Example 12]

The following copolymerized polymers (P-5) to (P-10) were synthesized in the same manner as in Example 8 and Example 9.

Compound (M-1-11) was synthesized according to the method described in Japanese Published Patent Application No. 2005-528486.

Compound (M-1-12) was prepared according to the method described in Makromolekulare Chemie, 1989, 190 (6), 1369-77. . &Lt; / RTI &gt;

[Comparative Example 1]

5.0 g of the compound (M-1-2) and 0.1 g of azobisisobutyronitrile (AIBN) were added to 40 ml of THF and the mixture was stirred under reflux for 10 hours under a nitrogen atmosphere. The reaction solution was poured into methanol and re-dialed. The crystals were separated by filtration and dried to obtain 4.2 g of polymer (P-11). The polymer had Mw of 25000 and Mw / Mn of 2.8.

[Comparative Example 2]

5.0 g of the compound (M-1-11) and 0.1 g of azobisisobutyronitrile (AIBN) were added to 40 ml of THF and the mixture was stirred under reflux for 10 hours under a nitrogen atmosphere. The reaction solution was poured into methanol and re-dialed. The crystals were separated by filtration and dried to obtain 4.0 g of polymer (P-12). This polymer had Mw of 23,000 and Mw / Mn of 2.9.

[Example 13]

The polymer (P-1) was dissolved in a mixed solvent of cyclopentanone: propylene glycol monomethyl ether acetate (PGMEA) = 7: 3 (weight ratio) to prepare a solution having a solid concentration of 7% by weight. This solution was filtered with a filter having a pore size of 0.45 mu m to prepare a photo-alignment agent (H-1).

[Example 14]

A photo aligning agent (H-2) was prepared in the same manner as in Example 13 except that the polymer (P-1) was substituted with the polymer (P-2).

[Example 15]

A light director (H-3) was prepared in the same manner as in Example 13 except that the polymer (P-1) was substituted with the polymer (P-3).

[Example 16]

(H-4) to (H-10) were prepared by replacing the polymer (P-1) with the polymers (P-4) to (P-10) respectively by the same procedure as in Example 13.

[Comparative Example 3]

A light director (H-11) was prepared in the same manner as in Example 13 except that the polymer (P-1) was substituted with the polymer (P-11).

[Comparative Example 4]

A light director (H-12) was prepared in the same manner as in Example 13 except that the polymer (P-1) was substituted with the polymer (P-12).

[Example 17]

<Production of Liquid Crystal Alignment Film F-1>

The photo-alignment agent (H-1) was applied on a glass substrate by spin coating. At this time, the coatability was good. The substrate was heated at 80 DEG C for 3 minutes, and the mixed solvent was removed to form a coating film. A liquid crystal alignment film F-1 (manufactured by Wako Pure Chemical Industries, Ltd.) subjected to photo-alignment treatment was irradiated with linearly polarized ultraviolet rays having a wavelength of about 313 nm at a dose of 1.0 J / &Lt; / RTI &gt;

Next, a low-molecular liquid crystal JC-5100XX (manufactured by Chisso Corporation / JNC) was inserted between the two photo-alignment films F-1, heated for 30 seconds on a hot plate at 110 占 폚, and then stopped at room temperature. When it was sandwiched between two polarizers made of Cross-Nicols and rotated in a horizontal plane, it was confirmed that it was in the horizontal and horizontal state.

When the liquid crystal alignment film F-1 was superimposed, the coated surface was brought into contact with the liquid crystal so that the directions of the linearly polarized light were in the same direction (substantially parallel).

[Example 18]

A liquid crystal alignment film F-2 was obtained in the same manner as in Example 17 except that the photo-alignment agent (H-1) was replaced with the photo-alignment agent (H-2).

[Example 19]

A liquid crystal alignment film F-3 was obtained in the same manner as in Example 17 except that the photo-alignment agent (H-1) was replaced with the photo-alignment agent (H-3).

[Example 20]

(F-4) to (F-10) were prepared in the same manner as in Example 17, except that the photo-alignment agent (H-1) ).

[Example 21]

The photo-alignment agent (H-1) was applied on a glass substrate by spin coating. At this time, the coatability was good. The substrate was heated at 80 DEG C for 3 minutes, and the mixed solvent was removed to form a coating film. A liquid crystal alignment film F-1A obtained by photo-alignment treatment was irradiated from the ultra-high pressure mercury lamp to the surface of the coating film by 0.03 J / cm 2 of linearly polarized ultraviolet light having a wavelength of about 313 nm in the direction of 90 DEG to the coated surface.

[Example 22]

(F-2A) was prepared in the same manner as in Example 21 except that the photo-alignment agent (H-1) was replaced with photo-alignment agents (H-2) ), (F-5A) to (F-10A).

[Comparative Example 5]

A liquid crystal alignment film F-11 was obtained in the same manner as in Example 17 except that the photo-alignment agent (H-1) was replaced with the photo-alignment agent (H-11).

[Comparative Example 6]

A liquid crystal alignment film F-11A was obtained in the same manner as in Example 21 except that the photo-alignment agent (H-1) was replaced with the photo-alignment agent (H-11).

[Comparative Example 7]

A liquid crystal alignment film F-12 was obtained in the same manner as in Example 17 except that the photo-alignment agent (H-1) was replaced with the photo-alignment agent (H-12).

[Example 23]

&Lt; Preparation of polymerizable liquid crystal composition (1)

The two compounds were mixed at a compound (LC-1): compound (LC-2) = 50: 50 (weight ratio). This composition is referred to as MIX1. A nonionic ionic fluorine surfactant (trade name: Fotogen (registered trademark) FTX-218, manufactured by Neos Co., Ltd.) having a weight ratio of 0.002 and irgacure 907 having a weight ratio of 0.06 (manufactured by BASF) , Trademark registration) 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) having a mixed solvent ratio of 80% by weight.

A specific production method of the compound (LC-1) and the compound (LC-2) described above will be described. Compound (LC-1) was synthesized according to the method described in JP-A-2006-307150. Compound (LC-2) was synthesized according to the method described in JP-A-63-64029.

[Example 24]

&Lt; Formation of optical film &

The polymerizable liquid crystal composition (1) was applied to the liquid crystal alignment film F-1 obtained in Example 15 by spin coating. This substrate was heated at 80 占 폚 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 atmosphere by ultraviolet rays to obtain an optical film in which the alignment state of the liquid crystal was fixed. The optical film was observed with a polarizing microscope. As a result, it was confirmed that there was no alignment defect and that the film had a uniform orientation. As a result of measuring the retardation of the optical film, it was confirmed that the film was in homogeneous orientation.

[Example 25]

An optical film was obtained in the same manner as in Example 24 except that the liquid crystal alignment film F-1 was replaced with the liquid crystal alignment film F-2.

The optical film was observed with a polarizing microscope. As a result, it was confirmed that there was no alignment defect and that the film had a uniform orientation. As a result of measuring the retardation of the optical film, it was confirmed that the film was in homogeneous orientation.

[Example 26]

An optical film was obtained in the same manner as in Example 24 except that the liquid crystal alignment film F-1 was replaced with the liquid crystal alignment film F-3.

The optical film was observed with a polarizing microscope. As a result, it was confirmed that there was no alignment defect and that the film had a uniform orientation. As a result of measuring the retardation of the optical film, it was confirmed that the film was in homogeneous orientation.

[Example 27]

(F-3) to (F-10) and (F-1A), (F-2A) and (F-5A) to (F-10A) were obtained in the same manner as in Example 24 . These optical films were observed with a polarizing microscope. The results are shown in Table 1 below.

[Comparative Example 8]

Optical films were obtained using the liquid crystal alignment films (F-11), (F-11A) and (F-12) with the same scheme as in Example 24. These optical films were observed with a polarizing microscope. The results are shown in Table 1 below.

It can be seen from the comparison between Example 27 and Comparative Example 5 that the photo alignment film of the present invention has high sensitivity and high liquid crystal alignability.

[Example 28]

&Lt; Production of liquid crystal alignment film FA-1 &

The photo-alignment agent (H-6) was applied onto the saponified TAC film by spin coating. At this time, the coatability was good. The film was heated at 80 DEG C for 1 minute and the mixed solvent was removed to form a coating film. A liquid crystal alignment film FA-1 subjected to photo-alignment treatment was obtained from the ultra-high pressure mercury lamp by irradiating the surface of the coating film with linearly polarized ultraviolet rays having a wavelength in the vicinity of 313 nm in a direction of 90 DEG to the coated surface at 0.3 J / cm2.

[Example 29]

(FA-2) to (FA-4) were prepared in the same manner as in Example 28 except that the photo-alignment agent (H-6) ).

[Comparative Example 9]

A liquid crystal alignment film (FA-5) was obtained in the same manner as in Example 28 except that the photo-alignment agent (H-6) was replaced with the photo-alignment agent (H-11).

Table 2 shows the evaluation results of the adhesive tape peeling test of the obtained photo-alignment agents (FA-1) to (FA-5).

Comparing Example 28 and Example 29 with Comparative Example 9, it can be seen that the photo alignment layer of the present invention has excellent adhesion to the saponified TAC film.

The photo-alignment agent of the present invention comprises a photosensitive polymer and is an alignment agent suitable for the photo-alignment method. The liquid crystal alignment film obtained by using the photo alignment agent of the present invention is a liquid crystal alignment film in which alignment of liquid crystal molecules without orientation defects is uniform since there is no need of rubbing treatment. Therefore, it is suitable for use in optical films and liquid crystal display device applications.

Claims (15)

The photosensitive compound represented by the formula (1):

In the formula (1), Y ¹ is a divalent group represented by the formula (2-1) or (2-2);
A ¹ is 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 this 1,4-phenylene, any hydrogen may be substituted with one or more substituents selected from fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, 5 alkyl or alkoxy of 1 to 5 carbon atoms;
Z ¹ is a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH ₂ - or -CH ₂ CH ₂ -COO-;
R ¹ and R ² are independently hydrogen, fluorine, chlorine, -OH, -C≡N, -NO ₂ , trifluoromethyl, alkyl of 1 to 10 carbon atoms or alkoxy of 1 to 10 carbon atoms;
Q ¹ is independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be substituted with fluorine, and arbitrary -CH ₂ - may be replaced by -O-, -COO-, -OCO-, -CH = CH- or -C? C-;
n is 0 to 3;
In formulas (2-1) and (2-2), W ¹ and W ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms. The method according to claim 1,
The compound according to claim 1, wherein Y ¹ is a divalent group represented by formula (2-1) or (2-2) described in claim 1;
A ¹ is 1,4-phenylene or 1,4-cyclohexylene; In this 1,4-phenylene, any hydrogen may be substituted by fluorine, trifluoromethyl, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms;
Z ¹ is a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH ₂ - or -CH ₂ CH ₂ -COO-;
R ¹ and R ² are independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms;
Q ¹ is independently a single bond or alkylene having 1 to 12 carbon atoms, and arbitrary -CH ₂ - may be substituted with -O-;
n is 0 or 1;
In formulas (2-1) and (2-2), W ¹ and W ² are independently hydrogen, alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms;
Photosensitive compound. The photosensitive compound represented by the formula (1-1):

In the formula (1-1), W ¹ and W ² are independently hydrogen, alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms;
A ¹ is 1,4-phenylene or 1,4-cyclohexylene; In this 1,4-phenylene, any hydrogen may be substituted by fluorine, trifluoromethyl, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms;
Z ¹ is a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH ₂ - or -CH ₂ CH ₂ -COO-;
R ¹ is hydrogen or alkyl of 1 to 5 carbon atoms;
R ² is hydrogen, fluorine, alkyl having 1 to 5 carbon atoms or alkoxy having 1 to 5 carbon atoms;
Q ¹ is independently a single bond or an alkylene of 1 to 12 carbon atoms, and any -CH ₂ - may be substituted with -O-;
n is 0 or 1; A composition containing the photosensitive compound according to claim 1. A photosensitive polymer obtained by polymerizing the photosensitive compound according to claim 1. The photosensitive polymer having the constituent unit represented by the formula (3)

In the formula (3), Y ¹ is a divalent group represented by the formula (2-1) or (2-2);
A ¹ is 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 this 1,4-phenylene, any hydrogen may be substituted with one or more substituents selected from fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, 5 alkyl or alkoxy of 1 to 5 carbon atoms;
Z ¹ is a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH ₂ - or -CH ₂ CH ₂ -COO-;
R ¹ and R ² are independently hydrogen, fluorine, chlorine, -OH, -C≡N, -NO ₂ , trifluoromethyl, alkyl of 1 to 10 carbon atoms or alkoxy of 1 to 10 carbon atoms;
Q ¹ is independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be substituted with fluorine, and arbitrary -CH ₂ - may be replaced by -O-, -COO-, -OCO-, -CH = CH- or -C? C-;
n is 0 to 3;
In formulas (2-1) and (2-2), W ¹ and W ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms. The method according to claim 6,
The compound of the formula (3) according to claim 6, wherein Y ¹ is a bivalent group represented by formula (2-1) or (2-2) described in claim 6;
A ¹ is 1,4-phenylene or 1,4-cyclohexylene; In this 1,4-phenylene, any hydrogen may be substituted by fluorine, trifluoromethyl, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms;
Z ¹ is a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH ₂ - or -CH ₂ CH ₂ -COO-;
R ¹ and R ² are independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms;
Q ¹ is independently a single bond or alkylene having 1 to 12 carbon atoms, and arbitrary -CH ₂ - may be substituted with -O-;
n is 0 or 1;
In formulas (2-1) and (2-2), W ¹ and W ² are independently hydrogen, alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms;
Photosensitive polymer. The photosensitive polymer represented by the formula (3-1):

In formula (3-1), W ¹ and W ² are independently hydrogen, alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms;
A ¹ is 1,4-phenylene or 1,4-cyclohexylene; In this 1,4-phenylene, any hydrogen may be substituted by fluorine, trifluoromethyl, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms;
Z ¹ is a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH ₂ - or -CH ₂ CH ₂ -COO-;
R ¹ is hydrogen or alkyl of 1 to 5 carbon atoms;
R ² is hydrogen, fluorine, alkyl having 1 to 5 carbon atoms or alkoxy having 1 to 5 carbon atoms;
Q ¹ is independently a single bond or an alkylene of 1 to 12 carbon atoms, and any -CH ₂ - may be substituted with -O-;
n is 0 or 1; 6. The method of claim 5,
A photosensitive polymer having a weight average molecular weight of 1,000 to 500,000. A homopolymer having the constituent unit according to claim 6. A copolymer comprising at least one of the structural unit represented by the formula (3) and the structural unit other than the structural unit represented by the formula (3). A photosensitive material using the polymer according to claim 5. An optical alignment agent for a liquid crystal alignment film using the polymer according to claim 5. A liquid crystal alignment film produced by using the photo-alignment agent according to claim 13. A liquid crystal display device produced using the liquid crystal alignment film according to claim 14.