JP6269952B2 - Composition for photo-alignment film - Google Patents

Description

The present invention relates to a composition for a photoalignment film, a photoalignment film formed using the composition, and an optical film or a liquid crystal display device using the composition.

Liquid crystal display elements are used in various liquid crystal display devices such as monitors for notebook computers and desktop computers, as well as 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 °. TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode in which the orientation direction is twisted at an angle of usually 180 ° or more, IPS (In Plane Switching) in which the orientation direction is oriented horizontally with respect to the substrate, Liquid crystal display elements such as FFS (Fringe Field Switching) mode have 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 type liquid crystal display element using an optical compensation film, an MVA (Multi-domain Vertical Alignment) mode using a technique of vertical alignment and a protruding structure (see Patent Document 1). Or a lateral electric field type IPS (In-Plane Switching) mode (see Patent Document 2).

The development of the technology of the liquid crystal display element is achieved not only by simply improving these driving methods and element structures but also by improving members used for the display element. Among the members used for the display element, 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 year by year as the quality of the display element is improved. It is becoming important.

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.

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 formed using a liquid crystal alignment agent. Currently, the liquid crystal aligning agent mainly used is a solution in which polyamic acid or soluble polyimide is dissolved 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.

A rubbing method that is industrially simple and capable of high-speed processing over 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 deterioration of the display performance of the liquid crystal element is regarded as a problem due to alignment defects caused by this.

Therefore, in recent years, a liquid crystal alignment control method has been developed in place of the rubbing method. Many photo-alignment methods such as photolysis, photo-isomerization, photo-dimerization, and photo-crosslinking methods have been proposed for photo-alignment methods in which alignment treatment is performed by irradiating light (Non-patent Document 1, Patent Document). 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.

The alignment state of the liquid crystal monolayer in contact with the liquid crystal alignment film can be controlled by using a liquid crystal alignment film that has been aligned by the photo-alignment method and has good alignment properties, and alignment division is easy It becomes possible. Thus, it can be expected to improve the performance as a liquid crystal display element.

As a compound that can be used in the photo-alignment method, a polymer in which a photoreactive cinnamate is bonded to a side chain of a copolymer has been proposed (see Patent Documents 5 and 6). However, in these systems, for the purpose of improving the long-term reliability of the liquid crystal display element, the liquid crystal alignment ability often deteriorates when baked at a high temperature in the element manufacturing process, and there is a problem with the base adhesion. There was also a case. On the other hand, since the polymerization is performed after synthesizing a monomer having a special structure, there is a problem that the cost becomes high.

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

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

An object of the present invention is to provide a composition for a photoalignment film suitable for a photoalignment method. Furthermore, a liquid crystal alignment film formed using the composition for photo-alignment film of the present invention, having good photo-alignment sensitivity after high-temperature baking, good adhesion to the substrate, and capable of being manufactured at low cost. Is to provide.

As a result of diligent research and development, the present inventor has realized a liquid crystal alignment film that can achieve the above object by using a specific composition for photo-alignment film.

The present invention includes the following items.
[1] For a photo-alignment film containing a polymer (A) obtained by polymerizing a compound (a1) having two or more azide groups and a compound (a2) having two or more (meth) acryl groups and an organic solvent (B) Composition.

式中、Ｒ^１〜Ｒ^８はそれぞれ独立に水素、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、または−ＳＯ_３Ｍであり；
Ｍは水素、アルカリ金属原子、炭素数１〜１０のアルキル、または−ＮＲ^ＡＲ^Ｂであり、
Ｒ^ＡおよびＲ^Ｂは独立して水素、炭素数１〜１０のアルキル、炭素数１〜１０のヒドロキシアルキル、炭素数１〜１０のアルコキシアルキル、または炭素数１〜１０のヒドロキシアルコキシアルキルあり；
Ｘは単結合、−ＣＯ−、−Ｓ−、炭素数１〜８のアルキレン、または下記式（２）〜（５）で表される２価の基から選ばれる１つであり；そして、
Ｒ^９は水素、炭素数１〜１０の直鎖アルキルまたは炭素数３〜１０の分岐鎖アルキルである。

[2] The composition for photoalignment film according to item [1], wherein the compound (a1) having two or more azide groups is a compound represented by the following formula (1):

In the formula, R ^{1 to} R ⁸ are each independently hydrogen, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or —SO ₃ M;
M is hydrogen, an alkali metal atom, alkyl having 1 to 10 carbon atoms, or -NR ^A R ^B ;
R ^A and R ^B are independently hydrogen, alkyl having 1 to 10 carbons, hydroxyalkyl having 1 to 10 carbons, alkoxyalkyl having 1 to 10 carbons, or hydroxyalkoxyalkyl having 1 to 10 carbons;
X is a single bond, —CO—, —S—, alkylene having 1 to 8 carbon atoms, or one selected from divalent groups represented by the following formulas (2) to (5);
R ⁹ is hydrogen, linear alkyl having 1 to 10 carbons or branched alkyl having 3 to 10 carbons.

[3] The composition for a photoalignment film according to the item [1] or [2], further comprising a polymer (C);
Polymer (C) excludes polymer (A).

[4] The composition for a photoalignment film according to the item [3], wherein the polymer (C) is at least one selected from a (meth) acrylic polymer, an ester polymer, an amic acid polymer, and a siloxane polymer. However,
The (meth) acrylic polymer excludes the polymer (A).

[5] The composition for a photoalignment film according to any one of [1] to [4], wherein the liquid crystalline compound is aligned by irradiating linearly polarized light having a wavelength of 200 to 500 nm.

[6] A photo-alignment film produced using the composition for photo-alignment film according to the item [5].

[7] An optical film produced using the photo-alignment film according to the item [6].

[8] A liquid crystal display device manufactured using the photo-alignment film according to the item [6].

Since the photo-alignment film of the present invention forms a liquid crystal alignment film using a compound having a photoreactive group, complicated processing steps in the conventional rubbing method and subsequent generation of dust and static electricity are not generated. Therefore, a liquid crystal alignment film having high optical uniformity without alignment defects can be produced. Moreover, the optical film and liquid crystal display element which were manufactured using this liquid crystal aligning film can maintain high alignment stability.

The photo-alignment film of the present invention contains a polymer (A) obtained by polymerizing a compound (a1) having two or more azide groups and a compound (a2) having two or more (meth) acryl groups, and an organic solvent (B). To do.

式中、Ｒ^１〜Ｒ^８はそれぞれ独立に水素、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、または−ＳＯ_３Ｍであり、Ｍは水素、アルカリ金属原子、炭素数１〜１０のアルキル、または−ＮＲ^ＡＲ^Ｂであり、Ｒ^ＡおよびＲ^Ｂは独立して水素、炭素数１〜１０のアルキル、炭素数１〜１０のヒドロキシアルキル、炭素数１〜１０のアルコキシアルキル、または炭素数１〜１０のヒドロキシアルコキシアルキルある。Ｘは単結合、−ＣＯ−、−Ｓ−、炭素数１〜８のアルキレン、または下記式（２）〜（５）で表される２価の基から選ばれる１つであり、Ｒ^９は水素、炭素数１〜１０の直鎖アルキルまたは炭素数３〜１０の分岐鎖アルキルである。

1. Compound (a1) having two or more azide groups
As the compound (a1) having two or more azide groups, a compound having a structure represented by the following formula (1) is preferably used.

In the formula, each of R ^{1 to} R ⁸ is independently hydrogen, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or —SO ₃ M, and M is hydrogen, an alkali metal atom, or 1 to carbon atoms. 10 alkyl, or —NR ^A R ^B , wherein R ^A and R ^B are independently hydrogen, alkyl having 1 to 10 carbons, hydroxyalkyl having 1 to 10 carbons, alkoxyalkyl having 1 to 10 carbons, Or it is a C1-C10 hydroxy alkoxy alkyl. X is a single bond, —CO—, —S—, alkylene having 1 to 8 carbon atoms, or one selected from divalent groups represented by the following formulas (2) to (5), and R ⁹ is Hydrogen, straight-chain alkyl having 1 to 10 carbon atoms, or branched alkyl having 3 to 10 carbon atoms.

Specific examples of the compound (a1) having two or more azide groups include 4,4′-diazidochalcone, 4,4′-diazidodibenzalacetone, 2,6-bis (4′-azidobenzal) cyclohexanone, 2,6-bis (4′-azidobenzal) -4-methylcyclohexanone, 2,6-bis (4′-azidobenzal) -4-ethylcyclohexanone, 4,4′-diazidostilbene-2,2′-disulfonic acid Sodium, 4,4′-diazidodiphenyl sulfide, 4,4′-diazidobenzophenone, 4,4′-diazidobiphenyl, 2,7-diazidofluorene, 4,4′-diazidophenylmethane. Commercially available bisazide compounds are trade names BAC-H, BAC-M, BAC-E, BAC-TA, DAzST (Na), DAzST (4), DAzST (51), DAzBA (Na) and the like manufactured by Toyo Gosei Co., Ltd. Can be illustrated. Each of the bisazide compounds may be used alone or in combination of two or more.

2. Compound (a2) having two or more (meth) acryl groups
In this specification, an acrylic group and a methacryl group are collectively referred to as a (meth) acryl group. The compound (a2) having two or more (meth) acryl groups is a compound having an unsaturated double bond that reacts with the azide group of the compound (a1). When the number of (meth) acrylic groups is 2, a linear polymer is obtained, which is preferably used. These compounds may be used as a mixture of two or more. On the other hand, for the purpose of introducing a branched structure into the polymer to be produced, a compound having three or more (meth) acrylic groups can be used in combination. On the other hand, in order to control the molecular weight, a compound having only one (meth) acryl group may be used in combination with a compound having two or more (meth) acryl groups. If a polymerizable liquid crystal having a (meth) acryl group is used as the compound (a2), it is possible to easily impart liquid crystal properties to the polymer.

Examples of compounds having two (meth) acrylic groups used in the present invention are polyethylene glycol # 200 diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, polyethylene glycol # 1000 diacrylate, propoxylated ethoxy Bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, propoxylated bisphenol A diacrylate, tricyclodecane dimethanol diacrylate, 1,10 -Decanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dipropylene glycol diacrylate, tri Lopylene glycol diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 650 diacrylate (made by Shin-Nakamura Chemical Co., Ltd.), 1,4-butanediol diacrylate, diethylene glycol diacrylate (above, Hitachi Chemical Co., Ltd.) Co., Ltd.), 1,3-butylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, and alkoxylated neopentyl glycol diacrylate (manufactured by SARTOMER).

Examples of compounds having three or more (meth) acrylic groups used in the present invention include ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, ethoxylated glycerin triacrylate, penta Erythritol triacrylate, trimethylolpropane triacrylate, dimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.).

Examples of compounds having one (meth) acrylic group used in the present invention are ethoxylated o-phenylphenol acrylate, methoxypolyethylene glycol # 400 acrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, isostearyl acrylate 2-hydroxy-3-acryloyloxypropyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, benzyl acrylate, phenoxyethyl acrylate, Nonylphenoxypolyethylene glycol acrylate and tetrahydrofurfuryl acrylate (manufactured by Hitachi Chemical Co., Ltd.).

3. Method for Producing Polymer (A) Polymer (A) is produced by heating and stirring a compound (a1) having two or more azide groups and a compound (a2) having two or more (meth) acrylic groups in a solvent. can do. Although there is no restriction | limiting in particular about reaction conditions, It is preferable that the preparation amount of (a1) and (a2) shall be 1.0 / 0.5-1.0 / 1.5 by molar ratio, and is 1.0 / 0.0. It is more preferable to set it as 9-1.0 / 1.1. The reaction temperature is preferably in the range of 50 to 130 ° C, more preferably in the range of 70 to 100 ° C.

Examples of the solvent used for the production of the polymer (A) are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, acetone, 2-butanone, ethyl acetate. , Propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclopentanone, cyclohexanone, diacetone alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether , Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, 3-methoxypro Methyl propionic acid, ethyl 3-ethoxypropionate, N- methylpyrrolidone, and γ- butyrolactone. In particular, cyclopentanone and cyclohexanone can dissolve many types of polymers (A) and are preferably used.

Although a catalyst may be used for production of the polymer (A), it is not usually necessary to use a catalyst because it has sufficient reactivity even without a catalyst.

4). Organic solvent (B)
The organic solvent (B) in the present invention is an organic solvent that can dissolve the polymer (A). When the photo-alignment film is formed by spin coating, slit coating, or other printing methods, the coating is uniform. Organic solvents with high properties are preferred.

Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile. , Dioxane, toluene, xylene, cyclopentanone, cyclohexanone, diacetone alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl Ether, methyl 3-methoxypropionate, 3 Ethyl ethoxypropionate, N- methylpyrrolidone, and γ- butyrolactone.

5. Polymer (C)
The polymer (C) used in the composition for photo-alignment film in the present invention is not particularly limited except that it is not the same as the polymer (A), but acrylic and methacrylic polymers that can be easily used industrially. (Hereinafter, both may be collectively referred to as (meth) acrylic polymers.), Ester polymers (polyesters), amic acid polymers (polyamide acids), and siloxane polymers are preferably used. The weight average molecular weight of these polymers (C) is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 10,000 to 500,000, and still more preferably in the range of 30,000 to 500,000. The polymer (C) may be a single monomer polymer or a copolymer of two or more different monomers. Two or more kinds of polymers (C) may be mixed and used. In addition, although the case of molecular weight smaller than the molecular weight generally called a polymer is included in the above molecular weight range, here, a polymer obtained through a conventional polymerization reaction is called a polymer. .

In the present invention, when a polymer having a carbon-carbon double bond is used as the polymer (C), the photo-alignment sensitivity of the photo-alignment film becomes particularly good, so that it is preferably used. As the group containing a carbon-carbon double bond, a group such as acryl, methacryl, cyclopentenyl, cyclohexenyl is preferably used.

The polymer (C) may be copolymerized with a component having no carbon-carbon double bond. 30-100 mol% is preferable, as for the molar ratio of the component which has a carbon-carbon double bond, 50-100 mol% is more preferable, and 70-100 mol% is further more preferable.

In synthesizing a polymer (C) having a carbon-carbon double bond, after synthesizing a polymer having no carbon-carbon double bond, a compound containing a carbon-carbon double bond later in the side chain May be added to give a carbon-carbon double bond.

5-1. Method for synthesizing polymer (C) The method for synthesizing polymer (C) is not particularly limited. In order to obtain a (meth) acrylic polymer, a method of obtaining a polymer by radical polymerization of a (meth) acrylic monomer is common.

Examples of (meth) acrylic monomers used in the present invention include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, glycidyl ( (Meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate It is.

Methods for obtaining ester polymers include a method in which a compound having two carboxyls and a compound having two hydroxyl groups are polycondensed in the presence of an acid catalyst, and a compound having tetracarboxylic dianhydride and two hydroxyl groups. The method of polycondensation is common.

Examples of compounds having two carboxyls used in the present invention are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid 1,3-adamantanedicarboxylic acid, benzophenone-4,4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1, 2-dicarboxylic acid, decahydro-1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid.

Specific examples of the compound having two hydroxyl groups used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, Tetrapropylene glycol, polypropylene glycol having a molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2, 4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol , , 7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 1,2-nonane Diol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decantriol, 1,2-dodecanediol, 1, 12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A (trade name), bisphenol S (trade name), bisphenol F (trade name), diethanolamine, and triethanolamine.

Examples of tetracarboxylic dianhydrides used in the present invention are aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides. Specific examples of the aromatic tetracarboxylic dianhydride include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2 , 3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfonetetracarboxylic Acid dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2 ′, 3,3 '-Diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoro Propane dianhydride, and ethylene glycol bis (anhydrotrimellitate); a (trade name TMEG-100, New Japan Chemical Co., Ltd.). Specific examples of the alicyclic tetracarboxylic dianhydride are cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride. . Specific examples of the aliphatic tetracarboxylic dianhydride are ethanetetracarboxylic dianhydride and butanetetracarboxylic dianhydride.

In order to introduce a branched structure into the polymer, it is also possible to use a compound having three or more acid anhydride groups (—CO—O—CO—) and / or a compound having three or more hydroxyl groups. . Specific examples of compounds having three or more hydroxyl groups are glycerin, tris (2-hydroxyethyl) isocyanurate and erythritol.

In order to obtain an amic acid-based polymer, a method of polycondensing tetracarboxylic dianhydride and diamine is generally used. As the tetracarboxylic dianhydride, the above compounds can be used similarly.

Specific examples of the diamine used in the present invention include 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, and bis [4- (4-aminophenoxy) phenyl]. Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) Phenyl] sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane. . Among these, 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone that give a resin having good transparency are preferable, and 3,3'-diaminodiphenylsulfone is particularly preferable.

Also in this case, it is possible to use a compound having two or more acid anhydrides or a compound having two or more amino groups in order to introduce a branched structure into the polymer.

In order to obtain a siloxane-based polymer, a general method is to obtain a polymer by hydrolytic condensation of a bifunctional, trifunctional, tetrafunctional or pentafunctional or higher functional alkoxysilane in the presence of an acid catalyst or a base catalyst and water. Trifunctional, tetrafunctional and pentafunctional or higher functional alkoxysilanes are used to introduce more branched structures or to further increase the molecular weight.

Specific examples of the bifunctional alkoxysilane compound used in the present invention include diethoxydimethylsilane, dimethoxydimethylsilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3- Chloropropyldimethoxymethylsilane, 3-glycidyloxypropyldimethoxymethylsilane, 3-mercaptopropyldimethoxymethylsilane, cyclohexyldimethoxymethylsilane, diethoxy (3-glycidyloxypropyl) methylsilane, diethoxymethylphenylsilane, dimethoxymethylphenylsilane, di Ethoxydiphenylsilane, dimethoxydiphenylsilane, diethoxymethylsilane, dimethoxymethylsilane, diethoxymethylvinylsilane, dimethoxymethylvinyl Rushiran, and Jimetokishiji -p- tolylsilane.

Specific examples of the trifunctional alkoxysilane compound used in the present invention include (3-bromopropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, and chloromethyltriethoxy. Silane, 1- [3- (trimethoxysilyl) propyl] urea, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxy Silane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) methacrylate Propyl, 3-aminopropyltriethoxy Silane, 3-aminopropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-trimethoxysilylpropyl chloride, 3-ureidopropyltriethoxysilane, methacrylic acid-3- [Tris (Trimethylsilyloxy) silyl] propyl, allyltriethoxysilane, allyltrimethoxysilane, triethoxyvinylsilane, trimethoxyvinylsilane, benzyltriethoxysilane, cyclohexyltrimethoxysilane, dodecyltrimethoxysilane, ethyltrimethoxysilane, hexyltriethoxysilane , Hexyltrimethoxysilane, Octyltriethoxysilane, Octadecyltriethoxysilane, Octadecyltrimethoxysilane, Pentillier Xysilane, triethoxyphenylsilane, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, triethoxymethylsilane, [bicyclo [2.2.1] hept-5-en-2-yl] triethoxysilane, triethoxy- 1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane, triethoxyethylsilane, triethoxyfluorosilane, triethoxysilane, trimethoxysilane, and trimethoxy [3- (phenylamino) propyl] silane.

Specific examples of the tetrafunctional alkoxysilane compound used in the present invention are tetrabutyl orthosilicate, tetrapropyl orthosilicate, tetraisopropyl orthosilicate, tetraethyl orthosilicate, and tetramethyl orthosilicate.

A specific example of the pentafunctional or higher functional alkoxysilane compound used in the present invention is tris (3- (trimethoxysilyl) propyl) isocyanurate.

In order to obtain a polymer containing a carbon-carbon double bond, a method obtained by radical polymerization of a monomer having a (meth) acryl group and a carbon-carbon double bond in the same molecule, or a polymerization having an epoxy group After polymerization of the polymerizable monomer, addition reaction of (meth) acrylic acid etc. to the epoxy group of the polymer side chain and introducing (meth) acrylic group into the side chain, or conversely, a monomer having a carboxyl or a monomer having a hydroxyl group, etc. After polymerizing, the monomer having an epoxy group such as glycidyl (meth) acrylate and a carbon-carbon double bond in the same molecule is added to the carboxyl or phenol of the polymer side chain, and the (meth) acrylic group is added to the side chain. There is a method to introduce.

Specific examples of the monomer having a (meth) acryl group and a carbon-carbon double bond in the same molecule are dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl acrylate, and dicyclopentenyloxyethyl methacrylate. . Specific examples of the polymerizable monomer having an epoxy group are glycidyl acrylate, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether. Specific examples of the monomer having carboxyl include acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, and 2-acryloyl. Oxyethyl succinate, and 2-methacryloyloxyethyl succinate. Specific examples of the monomer having a hydroxyl group are hydroxystyrene and 4-vinyl ketone phenol.

Although there is no restriction | limiting in particular as a catalyst used for the said radical polymerization, An azo initiator is mentioned as what can be obtained easily. Specific examples of the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile). ), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropio) Nate).

The solvent used for radical polymerization is not particularly limited as long as the monomer used is soluble, but cyclopentanone, cyclohexanone, butyl acetate, butyl propionate, ethyl lactate, methyl hydroxyacetate, hydroxyethyl acetate, hydroxybutyl acetate , Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 -Methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl toxipropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 2-methoxy-2-methylpropionic acid Methyl, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether Ter, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol mono Ethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether , Toluene, xylene, γ-butyrolactone, and N, N-dimethylacetamide. These may be used alone or in combination of two or more.

As the acid catalyst used for the synthesis of the ester polymer, p-toluenesulfonic acid is preferably used.

As the solvent used for the synthesis of the ester-based polymer, a solvent obtained by removing a solvent having a hydroxyl group from the solvents mentioned as preferred solvents for radical polymerization is used.

Examples of the solvent used for the synthesis of the amic acid-based polymer include the solvents mentioned above as preferred solvents for radical polymerization.

Examples of the acid catalyst used for the synthesis of the siloxane polymer include formic acid, oxalic acid, hydrochloric acid, nitric acid, sulfuric acid, and p-toluenesulfonic acid. Base catalysts include ammonia, tetramethylammonium hydroxide, imidazole, diazabicycloundecene, and diazabicyclononene.

Examples of the solvent used for the synthesis of the siloxane-based polymer include the solvents mentioned above as preferred solvents for radical polymerization.

6). Other components The composition for photo-alignment films of the present invention may further contain components other than the components (A) to (C) described above within the range in which the effects of the present invention are obtained. For example, various additives can be added to the composition for photo-alignment films of the present invention in order to improve coating uniformity, film hardness, and adhesion. Examples of such additives include acrylic, styrene, polyethyleneimine, or urethane polymer dispersants, anionic, cationic, nonionic, or fluorine surfactants, and improved silicone coating properties. Agents, hindered phenols, hindered amines, phosphorus, sulfur compounds and other antioxidants, coupling agents and other adhesion improvers, epoxy compounds and other thermal crosslinking agents, photoradical initiators and thermal radical initiators, etc. These radical polymerization initiators.

6-1. In the polymer dispersant, the surfactant, the coatability improver, the polymer dispersant, the surfactant, and the coatability improver, components used for these applications in the composition can be used. These may be one type or two or more types. Examples of such a polymer dispersant, surfactant, and coatability improver include, for example, Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (all are trademarks, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disperse Bake 162, Disperse Bake 163, Disperse Bake 164, Disperse Bake 166, Disperse Bake 170, Disperse Bake 180, Disperse Bake 181 , Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346, BYK361N (all are trademarks, manufactured by BYK Japan KK), KP-341, KP-358, KP-368, KF -96-50CS, KF-50-100CS (all are trademarks, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (all are trademarks, Chemical Co., Ltd.), Aftergent 222F, Aftergent 251, FTX-218 (all are trademarks, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801 , EFTOP EF-802 (all of which are trademarks, manufactured by Mitsubishi Materials Corporation), Megafuck F-171, Megafuck F-177, Megafuck F-475, Megafuck R-08, Megafuck R-30 (and above) All are trademarks, manufactured by DIC Corporation), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (Fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxy Ethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate , Sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester Ter, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonate .

Among these, fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether) ), Fluorosurfactants such as fluoroalkyltrimethylammonium salts and fluoroalkylaminosulfonates, and silicon-based such as BYK306, BYK342, BYK344, BYK346, KP-341, KP-358, and KP-368 It is preferable that at least one selected from the group consisting of coatability improvers is included in the additive from the viewpoint of enhancing the coating uniformity of the composition for photo-alignment films of the present invention.

The content of the polymer dispersant, the surfactant, and the coatability improver in the composition for photo-alignment film of the present invention is 0.001 to 0 based on 100 parts by weight of the total solid content of the composition, respectively. .1 part by weight is preferred.

6-2. As the antioxidant, antioxidants of hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds can be suitably used. One type or two or more types of antioxidants may be used. The antioxidant is preferably an antioxidant of a hindered phenol compound from the viewpoint of weather resistance. The antioxidant, e.g. Irganox1010, IrganoxFF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD Irganox 295 (trade name; manufactured by BASF Japan Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO -50, ADK STAB AO-60, ADK STAB AO-70, and ADK STAB AO-80 (trade name; manufactured by ADEKA Corporation). Among these, ADK STAB AO-60 is more preferable.

The content of the antioxidant in the composition for photo-alignment films of the present invention is preferably 0.1 to 15 parts by weight and preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polymer (C). More preferred.

6-3. Adhesion improver The adhesion improver is used to improve the adhesion between the composition for photo-alignment film and the substrate. A coupling agent can be suitably used as the adhesion improver. The adhesion improver may be one type or two or more types. As the coupling agent, a silane-based, aluminum-based or titanate-based compound can be used. Examples of such coupling agents include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, acetoalkoxyaluminum diisopropylate, and tetra And isopropyl bis (dioctyl phosphite) titanate. Among these, 3-glycidoxypropyltrimethoxysilane is preferable because of its great effect of improving adhesion.

The content of the adhesion improver in the composition for photo-alignment films of the present invention is preferably 10 parts by weight or less with respect to 100 parts by weight of the polymer (C).

6-4. As the thermal crosslinking agent, a component that causes a crosslinking reaction under heating conditions in film formation using the composition for photo-alignment film as a material can be used. One or more thermal crosslinking agents may be used. A thermal crosslinking agent such as an epoxy compound can be used as the thermal crosslinking agent. Examples of such a thermal crosslinking agent include Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P, and Epicoat. 1004, Epicoat 1256, YX8000 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), Araldite CY177, Araldite CY184 (trade name; manufactured by BASF Japan), Celoxide 2021P, EHPE-3150 (trade name; Daicel Chemical Industries, Ltd.) And techmore VG3101L (trade name; manufactured by Printec Co., Ltd.)).

The content of the thermal crosslinking agent in the composition for photo-alignment films of the present invention is preferably 1 to 30 parts by weight and more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the solid content of the composition. preferable.

6-5. Radical polymerization initiators Photoradical generators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 1173), 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane -1-one (IRGACURE 651), 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184), IRGACURE 127, IRGACURE 500 (mixture of IRGACURE 184 and IRGACURE 184, IRGAC URE, IRGAC URE, IRGAC URE, IRGAC URE, IRGAC URE, IRGAC URE, IRGAC IRGACURE 850, IRGACURE1870, DAROCUR4265, DAROCUR MBF, DAROCUR TPO, IRGACURE784, IRGACURE754, IRGACURE OXE01, and IRGACURE OXE02 the like. Both DAROCUR and IRGACURE are product names of BASF Japan. Known sensitizers (isopropylthioxanthone, diethylthioxanthone, ethyl 4-dimethylaminobenzoate (DAROCUR EDB), 2-ethylhexyl 4-dimethylaminobenzoate (DAROCUR EHA), etc.) may be added thereto.

Examples of the thermal radical generator include 2,2′-Azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-Azobis (2,4-dimethylvaleronitile). ) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-Azobis (isobutyronitrile) (V-60 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-Azobis (2-methylbutyronitrile) ( V-59) manufactured by Wako Pure Chemical Industries, Ltd., 2,2′-Azobis [N- (2-propenyl) -2-methylpropionamide] (VF-096 manufactured by Wako Pure Chemical Industries, Ltd.), 2, 2 ′ -Azobis (N-butyl-2-methylpropiona ide) (manufactured by Wako Pure Chemical Industries, Ltd. VAm-110), include Dimethyl 2,2'-azobis (isobutyrate) (manufactured by Wako Pure Chemical Industries, Ltd. V-601).

The content of the radical polymerization initiator in the composition for photo-alignment films of the present invention is preferably 1 to 10 parts by weight and preferably 3 to 10 parts by weight with respect to 100 parts by weight of the solid content of the composition. More preferred.

The composition for photo-alignment film of the present invention is preferably stored while being shielded from light in the temperature range of −30 ° C. to 25 ° C. from the viewpoint of the temporal stability of the composition for photo-alignment film. A storage temperature of −20 ° C. to 10 ° C. is even more preferable from the viewpoint of preventing the generation of precipitates from the photosensitive composition.

7). Deposition of Photo Alignment Film and Evaluation of Alignment of Polymerizable Liquid Crystal Hereinafter, a method of forming a photo alignment film and an evaluation of alignment using a polymerizable liquid crystal as a material to be aligned on the photo alignment film will be described.
7-1. Film-forming method of photo-alignment film The composition for photo-alignment film of the present invention is applied on a substrate by a known method such as spin coating, roll coating, slit coating or the like. As the substrate, for example, transparent glass substrate such as white plate glass, blue plate glass, silica coated blue plate glass, synthetic resin sheet such as polycarbonate, polyethersulfone, polyester, acrylic, vinyl chloride, aromatic polyamide, polyamideimide, polyimide, Examples of the semiconductor substrate include a film or substrate, a metal substrate such as an aluminum plate, a copper plate, a nickel plate, and a stainless plate, other ceramic plates, and a photoelectric conversion element. These substrates may be subjected to a pretreatment such as a chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, a gas phase reaction method, or vacuum deposition.

Next, the coating film of the composition for photo-alignment films on a board | substrate is dried with a hotplate or oven. Usually, it is dried at 60 to 150 ° C. for 1 to 5 minutes. The film thickness of the photo-alignment film is not particularly limited, but is generally formed to a film thickness of about 1 nm to 300 nm. The photo-alignment film on the dried substrate is irradiated with light irradiated from a light irradiation device such as an ultra-high pressure mercury lamp converted into polarized light by a polarizing plate such as a wire grid. The irradiation amount is suitably about 1 to 3000 mJ / cm ² at a wavelength of 300 nm to 500 nm.

7-2. Method for evaluating orientation of polymerizable liquid crystal First, a polymerizable liquid crystal composition used for evaluation was prepared as follows. LC242 (BASF Japan Co., Ltd.) 5.0g, IRGACURE907 (BASF Japan Co., Ltd.) 0.25g, BYK361N (Bic Chemie Japan Co., Ltd.) 0.0050g, and toluene as an organic solvent was added. The organic solvent is prepared so as to be 85 wt% of the whole, and mixed and dissolved uniformly. This composition is referred to as “polymerizable liquid crystal composition (1)”.

A polymerizable liquid crystal composition (1) is formed on a substrate with a photo-alignment film irradiated with polarized light by a coating method such as spin coating, and dried at 80 ° C. for 1 minute on a hot plate. After the substrate is cooled to room temperature, the entire alignment line is irradiated by irradiating all lines such as an ultra-high pressure mercury lamp, and the alignment is fixed by photocuring the polymerizable liquid crystal composition. The prepared polymerizable liquid crystal photocured substrate was sandwiched between two polarizing plates in an orthogonal (crossed Nicols) state and observed by irradiating a backlight from below. If the polymerizable liquid crystal is horizontally aligned, the light and dark states are repeated when the substrate is rotated. The minimum exposure amount that can display bright and dark without alignment defects (light loss) is defined as photoalignment sensitivity.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not restrict | limited by these Examples.

[Synthesis Example 1] Synthesis of polymer (A1) Thermometer, stirrer, and cooling tube provided in a four-necked flask, cyclopentanone as a polymerization solvent, 4,4'-diazidochalcone as a compound (a1), compound As (a2), 1,6-hexanediol diacrylate was charged in the following weight and polymerized at 80 ° C. for 3 hours.

Cyclopentanone 8.90g
4,4'-diazide chalcone 5.00g
1,6-hexanediol diacrylate 3.90 g

After the reaction, the solution was cooled to room temperature, and n-hexane was added to precipitate and collect the polymer. The recovered polymer was vacuum-dried and then dissolved again in cyclopentanone. Cyclopentanone was added so that the solid content concentration of the polymer was 3 wt%.

A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). For GPC analysis, polystyrene having a molecular weight of 645 to 132,900 (polystyrene calibration kit PL2010-0102 manufactured by VARIAN) was used as standard polystyrene, and PLgel MIXED-D (manufactured by VARIAN) was used as the column, and the mobile phase was used. As THF, the column temperature was set to 35 ° C., and the measurement was performed using a differential refractive index detector. As a result, the weight average molecular weight of the polymer (A1) was 23,000.

[Synthesis Example 2] Synthesis of Polymer (A2) Thermometer, stirrer, and cooling tube provided in a four-necked flask, cyclopentanone as a polymerization solvent, 4,4'-diazidochalcone as a compound (a1), compound As (a2), 1,4-butanediol diacrylate was charged in the following weight and polymerized at 80 ° C. for 3 hours.

8.41 g of cyclopentanone
4,4'-diazide chalcone 5.00g
1,41-butanediol diacrylate 3.41 g

After the reaction, the solution was cooled to room temperature, and n-hexane was added to precipitate and collect the polymer. The recovered polymer was vacuum-dried and then dissolved again in cyclopentanone. Cyclopentanone was added so that the solid content concentration of the polymer was 3 wt%.

  As a result of GPC analysis performed in the same manner as in Synthesis Example 1, the weight average molecular weight of the polymer (A2) was 31,000.

[Synthesis Example 3] Synthesis of Polymer (A3) Thermometer, stirrer, and cooling tube provided in a four-necked flask, cyclopentanone as a polymerization solvent, 4,4'-diazidochalcone as a compound (a1), compound As (a2), tricyclodecane dimethanol diacrylate was charged in the following weight and polymerized at 80 ° C. for 3 hours.

Cyclopentanone 10.2g
4,4'-diazide chalcone 5.00g
Tricyclodecane dimethanol diacrylate 5.24g

After the reaction, the solution was cooled to room temperature, and n-hexane was added to precipitate and collect the polymer. The recovered polymer was vacuum-dried and then dissolved again in cyclopentanone. Cyclopentanone was added so that the solid content concentration of the polymer was 3 wt%.

As a result of performing GPC analysis in the same manner as in Synthesis Example 1, the weight average molecular weight of the polymer (A3) was 7,000.

[Synthesis Example 4] Synthesis of polymer (A4) In a four-necked flask equipped with a thermometer, a stirrer, and a condenser tube, cyclopentanone as a polymerization solvent and 4,4'-diazidostilbene-2 as a compound (a1) , 2′-bis (hydroxypropylsulfonamide), 1,6-hexanediol diacrylate as compound (a2) was charged in the following weight and polymerized at 80 ° C. for 3 hours.

Cyclopentanone 8.90g
4,4′-diazidostilbene-2,2′-bis (hydroxypropylsulfonamide)
5.00g
1,6-hexanediol diacrylate 3.90 g

After the reaction, the solution was cooled to room temperature, and n-hexane was added to precipitate and collect the polymer. The recovered polymer was vacuum-dried and then dissolved again in cyclopentanone. Cyclopentanone was added so that the solid content concentration of the polymer was 3 wt%.

As a result of GPC analysis performed in the same manner as in Synthesis Example 1, the weight average molecular weight of the polymer (A4) was 6,000.

[Synthesis Example 5] Synthesis of polymer (A5) In a four-necked flask equipped with a thermometer, stirrer, and condenser, cyclopentanone as a polymerization solvent and 2,6-bis (4-azidobenzylidene as a compound (a1) ) 1,6-hexanediol diacrylate as cyclohexanone and compound (a2) was charged in the following weight and polymerized at 80 ° C. for 3 hours.

Cyclopentanone 8.17g
2,6-bis (4-azidobenzylidene) cyclohexanone 5.00 g
1,17-hexanediol diacrylate 3.17g

After the reaction, the solution was cooled to room temperature, and n-hexane was added to precipitate and collect the polymer. The recovered polymer was vacuum-dried and then dissolved again in cyclopentanone. Cyclopentanone was added so that the solid content concentration of the polymer was 3 wt%.

As a result of performing GPC analysis by the same method as in Synthesis Example 1, the weight average molecular weight of the polymer (A5) was 4,000.

Synthesis Example 6 Synthesis of Polymer (A6) In a four-necked flask equipped with a thermometer, stirrer, and condenser, cyclopentanone as a polymerization solvent and 2,6-bis (4-azidobenzylidene as a compound (a1) ) -4-Methylcyclohexanone and 1,6-hexanediol diacrylate as compound (a2) were charged in the following weights and polymerized at 80 ° C. for 3 hours.

Cyclopentanone 8.05g
2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone
5.00g
1,5-hexanediol diacrylate 3.05g

After the reaction, the solution was cooled to room temperature, and n-hexane was added to precipitate and collect the polymer. The recovered polymer was vacuum-dried and then dissolved again in cyclopentanone. Cyclopentanone was added so that the solid content concentration of the polymer was 3 wt%.

As a result of performing GPC analysis by the same method as in Synthesis Example 1, the weight average molecular weight of the polymer (A6) was 4,100.

[Synthesis Example 7] Synthesis of polymer (A7) In a four-necked flask equipped with a thermometer, stirrer, and condenser, cyclopentanone as a polymerization solvent and 2,6-bis (4-azidobenzylidene as a compound (a1) ) -4-methylcyclohexanone, DA-F3EO (manufactured by Shin-Nakamura Chemical Co., Ltd., see formula below) as a compound (a2) was charged in the following weight, and polymerized at 80 ° C. for 3 hours.

Cyclopentanone 10.4g
2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone
5.00g
DA-F3EO 5.43g

After the reaction, the solution was cooled to room temperature, and n-hexane was added to precipitate and collect the polymer. The recovered polymer was vacuum-dried and then dissolved again in cyclopentanone. Cyclopentanone was added so that the solid content concentration of the polymer was 3 wt%.

As a result of conducting GPC analysis in the same manner as in Synthesis Example 1, the weight average molecular weight of the polymer (A7) was 9000.

Synthesis Example 8 Synthesis of Polymer (A8) In a four-necked flask equipped with a thermometer, stirrer, and condenser, cyclopentanone as a polymerization solvent and 2,6-bis (4-azidobenzylidene as a compound (a1) ) -4-ethylcyclohexanone and 1,6-hexanediol diacrylate as compound (a2) were charged in the following weights and polymerized at 80 ° C. for 3 hours.

Cyclopentanone 7.94g
2,6-bis (4-azidobenzylidene) -4-ethylcyclohexanone
5.00g
1,6-hexanediol diacrylate 2.94 g

After the reaction, the solution was cooled to room temperature, and n-hexane was added to precipitate and collect the polymer. The recovered polymer was vacuum-dried and then dissolved again in cyclopentanone. Cyclopentanone was added so that the solid content concentration of the polymer was 3 wt%.

As a result of performing GPC analysis in the same manner as in Synthesis Example 1, the weight average molecular weight of the polymer (A8) was 4,500.

Synthesis Example 9 Synthesis of Polymer (A9) In a four-necked flask equipped with a thermometer, stirrer, and condenser, cyclopentanone as a polymerization solvent and 2,6-bis- (4-azido as a compound (a1) Benzylidene) -4-tert-amylcyclohexanone and 1,6-hexanediol diacrylate as compound (a2) were charged in the following weights and polymerized at 80 ° C. for 3 hours.

Cyclopentanone 7.65g
2,6-bis- (4-azidobenzylidene) -4-tert-amylcyclohexanone
5.00g
1,6-hexanediol diacrylate 2.65 g

After the reaction, the solution was cooled to room temperature, and n-hexane was added to precipitate and collect the polymer. The recovered polymer was vacuum-dried and then dissolved again in cyclopentanone. Cyclopentanone was added so that the solid content concentration of the polymer was 3 wt%.

As a result of performing GPC analysis in the same manner as in Synthesis Example 1, the weight average molecular weight of the polymer (A9) was 4,000.

[Synthesis Example 10] Synthesis of Polymer (A10) Thermometer, stirrer, and cooling tube provided in a four-necked flask, cyclopentanone as a polymerization solvent, 4,4'-diazidodiphenylmethane as a compound (a1), compound As (a2), 1,6-hexanediol diacrylate was charged in the following weight and polymerized at 80 ° C. for 3 hours.

Cyclopentanone 9.52g
4,4'-diazidodiphenylmethane 5.00g
1,6-hexanediol diacrylate 4.52 g

After the reaction, the solution was cooled to room temperature, and n-hexane was added to precipitate and collect the polymer. The recovered polymer was vacuum-dried and then dissolved again in cyclopentanone. Cyclopentanone was added so that the solid content concentration of the polymer was 3 wt%.

As a result of performing GPC analysis by the same method as in Synthesis Example 1, the weight average molecular weight of the polymer (A10) was 4,300.

[Synthesis Example 11] Synthesis of polymer (A11) In a four-necked flask equipped with a thermometer, a stirrer, and a condenser, cyclopentanone as a polymerization solvent and 2,6-bis (4-azidobenzylidene as a compound (a1) ) -4-Methylcyclohexanone, 1,6-hexanediol diacrylate and trimethylolpropane triacrylate as the compound (a2) were charged in the following weights and polymerized at 80 ° C. for 2 hours.

Cyclopentanone 7.82g
2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone
5.00g
1,22-hexanediol diacrylate 1.22 g
1.60 g of trimethylolpropane triacrylate

After the reaction, the solution was cooled to room temperature, and n-hexane was added to precipitate and collect the polymer. The recovered polymer was vacuum-dried and then dissolved again in cyclopentanone. Cyclopentanone was added so that the solid content concentration of the polymer was 3 wt%.

As a result of GPC analysis performed in the same manner as in Synthesis Example 1, the weight average molecular weight of the polymer (A11) was 22,000.

[Synthesis Example 12] Synthesis of polymer (A12) In a four-necked flask equipped with a thermometer, a stirrer and a condenser, cyclopentanone as a polymerization solvent and 2,6-bis (4-azidobenzylidene as a compound (a1) ) -4-methylcyclohexanone and 1,6-hexanediol diacrylate, isocyanuric acid EO-modified diacrylate and triacrylate as the compound (a2) were charged in the following weights and polymerized at 80 ° C. for 2 hours.

8.51 g of cyclopentanone
2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone
5.00g
1,22-hexanediol diacrylate 1.22 g
Isocyanuric acid EO-modified di- and triacrylate 2.29 g

After the reaction, the solution was cooled to room temperature, and n-hexane was added to precipitate and collect the polymer. The recovered polymer was vacuum-dried and then dissolved again in cyclopentanone. Cyclopentanone was added so that the solid content concentration of the polymer was 3 wt%.

As a result of conducting GPC analysis by the same method as in Synthesis Example 1, the weight average molecular weight of the polymer (A12) was 6,800.

Synthesis Example 13 Synthesis of Polymer (C1) Cyclopentanone as a polymerization solvent, glycidyl methacrylate as a polymerizable monomer, and 2,2′-azobis (as a polymerization initiator) while bubbling nitrogen into a four-necked flask equipped with a stirrer 2,4-dimethylvaleronitrile) was charged at the following weight, polymerized at 80 ° C. for 1 hour, further heated to 100 ° C. and aged for 2 hours to obtain a polymer (C1) solution having a solid concentration of 40 wt%. .
Cyclopentanone 15.0g
Glycidyl methacrylate 10.0g
2,2'-azobis (2,4-dimethylvaleronitrile) 0.500 g

As a result of GPC analysis performed in the same manner as in Synthesis Example 1, the weight average molecular weight of the polymer (C1) was 11,000.

[Synthesis Example 14] Synthesis of polymer (C2) In a four-necked flask with a stirrer, diethylene glycol methyl ethyl ether as a polymerization solvent, 1,2,3,4-cyclobutanetetracarboxylic dianhydride as an acid dianhydride, dialcohol 1,6-hexanediol was charged at the following weight and polymerized at 140 ° C. for 3 hours to obtain a polymer (C8) solution having a solid concentration of 50 wt%.

Diethylene glycol methyl ethyl ether 16.0g
1,2,3,4-cyclobutanetetracarboxylic dianhydride 10.0 g
1,6-hexanediol 6.03 g

As a result of GPC analysis performed in the same manner as in Synthesis Example 1, the weight average molecular weight of the polymer (C2) was 186,000.

[Comparative Synthesis Example 1] Synthesis of Polymer (E1) Cyclopentanone as a polymerization solvent while bubbling nitrogen through a 4-neck flask with a stirrer, monomer e having the following structure as an example of a cinnamic acid monomer, and 2 as a polymerization initiator , 2′-azobis (2,4-dimethylvaleronitrile) is charged at the following weight, polymerized at 80 ° C. for 1 hour, further heated to 100 ° C. and aged for 2 hours, and a polymer having a solid content concentration of 40 wt% ( E1) A solution was obtained.

Cyclopentanone 15.0g
Monomer e 10.0g
2,2'-azobis (2,4-dimethylvaleronitrile) 0.500 g

As a result of GPC analysis performed in the same manner as in Synthesis Example 1, the weight average molecular weight of the polymer (E1) was 9,000.

[Examples 1 to 14] and [Comparative Example 1]
The compositions of Examples 1 to 14 and Comparative Example 1 were prepared and evaluated as shown in the following table. The numerical value in () of each component is the molar ratio. Moreover, the numerical value in [] of a polymer (C) column is the weight part added with respect to 100 weight part of polymers (A). All compositions were prepared to a solid content concentration of 3 wt%. Here, solid content refers to components other than an organic solvent. Cyclopentanone (CPN) was used as the organic solvent for dilution. When there are a plurality of organic solvents, the mixing ratio of the solvents is shown in []. Abbreviations in the table below are as follows.

Compound (a1)
BAC-H: 2,6-bis (4-azidobenzylidene) cyclohexanone BAC-M: 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone BAC-E: 2,6-bis (4-azidobenzylidene) ) -4-ethylcyclohexanone BAC-TA: 2,6-bis- (4-azidobenzylidene) -4-tert-amylcyclohexanone)
DAzST (4): 4,4′-diazidostilbene-2,2′-bis (hydroxypropylsulfonamide)
DAzC: 4,4′-diazidochalcone DAzDPM: 4,4′-diazidophenylmethane (all are trade names, manufactured by Toyo Gosei Co., Ltd.)

Compound (a2)
M309: Trimethylolpropane triacrylate M315: Isocyanuric acid EO-modified di- and triacrylate (all are trade names, manufactured by Toagosei Co., Ltd.)
IRR-214K: Tricyclodecane dimethanol diacrylate (trade name, manufactured by Daicel Cytec Co., Ltd.)
1,6-HDA: 1,6-hexanediol diacrylate 1,4-BDA: 1,4-butanediol diacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

Organic solvent (B)
CPN: Cyclopentanone EDM: Diethylene glycol methyl ethyl ether

[Evaluation of pre-bake post-polymerizable liquid crystal photoalignment sensitivity]
The composition for photo-alignment film of Example 1 was spin-coated at a rotation speed of 1500 rpm for 10 seconds, and a thin film was formed on a glass substrate (Corning Co., Ltd. EagleXG, 40 mm × 40 mm × 0.7 mm). Next, drying was performed at 100 ° C. for 3 minutes on a hot plate.

The thickness of the dried photo-alignment film was measured with a profiler P-16 (step, surface roughness, fine shape measuring device manufactured by KLA-Tencor Corporation). The film thickness was 85 nm.

The light irradiated from the ultra-high pressure mercury lamp was converted into linearly polarized light through a filter that cuts light of 300 nm or less and a wire grid polarizing plate, and irradiated onto the glass substrate coated with the photo-alignment film. In the table of Examples, the exposure amount in terms of 313 nm is shown in mJ / cm ² unit.

Next, the polymerizable liquid crystal composition (1) was spin-coated on the substrate at a rotation speed of 1300 rpm for 10 seconds, and dried on a hot plate at 80 ° C. for 1 minute. After cooling the substrate to room temperature, the entire line of the ultra-high pressure mercury lamp was irradiated with 300 mJ / cm ² (value at 313 nm) to photocur the polymerizable liquid crystal composition to fix the alignment.

The prepared polymerizable liquid crystal photocured substrate was sandwiched between two polarizing plates in an orthogonal (crossed Nicols) state and observed by irradiating a backlight from below. The minimum exposure amount (photoalignment sensitivity) at which bright and dark display was possible without alignment defects (light loss) was 200 mJ / cm ² .

[Evaluation of Post-bake Post-polymerizable Liquid Crystal Photoalignment Sensitivity]
The composition for photo-alignment film of Example 1 was spin-coated at a rotation speed of 1500 rpm for 10 seconds, and a thin film was formed on a glass substrate (Corning Co., Ltd. EagleXG, 40 mm × 40 mm × 0.7 mm). Next, drying was performed at 100 ° C. for 3 minutes on a hot plate. Thereafter, post-bake was performed in an oven at 230 ° C. for 30 minutes.

The film thickness of the photo-alignment film after the post-bake was measured with a profiler P-16 (step, surface roughness, fine shape measuring device manufactured by KLA-Tencor Corporation). The film thickness was 73 nm.

The light irradiated from the ultra-high pressure mercury lamp was converted into linearly polarized light through a filter that cuts light of 300 nm or less and a wire grid polarizing plate, and irradiated onto the glass substrate coated with the photo-alignment film. In the table of Examples, the exposure amount in terms of 313 nm is shown in mJ / cm ² unit.

Next, the polymerizable liquid crystal composition (1) was spin-coated on the substrate at a rotation speed of 1300 rpm for 10 seconds, and dried on a hot plate at 80 ° C. for 1 minute. After cooling the substrate to room temperature, the entire line of the ultra-high pressure mercury lamp was irradiated with 300 mJ / cm ² (converted to 313 nm), and the polymerizable liquid crystal composition was photocured to fix the alignment.

[Evaluation of photo-alignment sensitivity]
The substrate after photocuring the prepared polymerizable liquid crystal composition was sandwiched between two polarizing plates in an orthogonal (crossed Nicols) state, and the backlight was irradiated from below and observed. If the polymerizable liquid crystal is horizontally aligned, the light and dark states are repeated when the substrate is rotated. Sensitivity was defined as the minimum exposure amount at which bright and dark display could be achieved without alignment defects (light loss). In Example 1, it was 50 mJ / cm ² .

[Substrate adhesion test]
A cross-cut test was performed using the substrate prepared in the evaluation of the photo-alignment sensitivity. Using a cutter and a cross-cut guide, an incision of 1 square mm 100 squares was created, and an adhesive test was conducted by applying an adhesive tape from the cut and peeling it off. The case where peeling did not occur in all of the 100 squares after the tape was peeled was marked as ◯, and the case where peeling occurred was marked as x (the test was the substrate after the pre-bake photo-alignment sensitivity test, after the post-bake photo-alignment sensitivity test) ) Was performed on both of the substrates, and if any of them was peeled off, it was marked as x).

Hereinafter, also in Examples 2 to 14 and Comparative Example 1, the same evaluation as in Example 1 was performed. In Comparative Example 1, the photo-alignment sensitivity was remarkably lowered after Post-bake, and the substrate adhesion was not good.

With the photo-alignment film of the present invention, a liquid crystal alignment film having high optical uniformity without alignment defects can be produced. By using this liquid crystal alignment film, an optical film having high alignment stability and a liquid crystal display element excellent in display quality can be produced.

Claims (8)

A composition for a photoalignment film, comprising a polymer (A) obtained by polymerizing a compound (a1) having two or more azide groups and a compound (a2) having two or more (meth) acryl groups, and an organic solvent (B). The composition for photo-alignment films according to claim 1, wherein the compound (a1) having two or more azide groups is a compound represented by the following formula (1):

In the formula, R ^{1 to} R ⁸ are each independently hydrogen, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or —SO ₃ M;
M is hydrogen, an alkali metal atom, alkyl having 1 to 10 carbon atoms, or -NR ^A R ^B ;
R ^A and R ^B are independently hydrogen, alkyl having 1 to 10 carbons, hydroxyalkyl having 1 to 10 carbons, alkoxyalkyl having 1 to 10 carbons, or hydroxyalkoxyalkyl having 1 to 10 carbons;
X is a single bond, —CO—, —S—, alkylene having 1 to 8 carbon atoms, or one selected from divalent groups represented by the following formulas (2) to (5);
R ⁹ is hydrogen, linear alkyl having 1 to 10 carbons or branched alkyl having 3 to 10 carbons.

The composition for a photoalignment film according to claim 1 or 2, further comprising a polymer (C);
Polymer (C) excludes polymer (A). The composition for a photoalignment film according to claim 3, wherein the polymer (C) is at least one selected from a (meth) acrylic polymer, an ester polymer, an amic acid polymer, and a siloxane polymer;
The (meth) acrylic polymer excludes the polymer (A). The composition for photo-alignment films according to any one of claims 1 to 4, wherein the liquid crystalline compound is aligned by irradiating linearly polarized light having a wavelength of 200 to 500 nm. The photo-alignment film manufactured using the composition for photo-alignment films of Claim 5. An optical film produced using the photo-alignment film according to claim 6. The liquid crystal display element manufactured using the photo-alignment film of Claim 6.