JP2014084355A - Thermosetting composition having a photo-aligning characteristic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material which yields, after the formation of a cured film therefrom, surface smoothness, a high solvent resistance, an excellent photo-aligning characteristic in relation to a polymerizable liquid crystal, a sufficient heat resistance, and a high transparency and which can be dissolved, at the time of the formation of the cured film therefrom, into a glycol-based solvent, ketone-based solvent, or lactic acid ester-based solvent applicable to the preparation of an overcoat for a color filter.SOLUTION: The thermosetting composition of the present invention having a photo-aligning characteristic comprises (A) a polymer having a photo-aligning characteristic and (B) polyesteramic acid; applications of the same are also provided.

Description

  The present invention relates to a thermosetting composition having photo-alignment and a cured film formed therefrom. More specifically, the present invention relates to a thermosetting composition excellent in transparency, liquid crystal alignment ability, solvent resistance and heat resistance in a thermosetting film, and application of the thermosetting film.

  During the manufacturing process of elements such as liquid crystal display elements, various chemical treatments such as organic solvents, acids, and alkali solutions are performed, and when the wiring electrode is formed by sputtering, the surface is locally heated to a high temperature. Sometimes. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and alteration of the surface of various elements. These protective films are required to have various characteristics that can withstand various treatments during the manufacturing process as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, alkali resistance, water resistance, adhesion to underlying substrates such as glass, transparency, scratch resistance, applicability, flatness, long-term There is a need for light resistance and the like that do not cause color change and the like.

  In particular, in recent years, liquid crystal display elements have been improved in performance such as high viewing angle, high speed response, and high definition, and when used as a color filter protective film, the transmittance of light transmitted through the color filter. In order to maintain the above, it is necessary that the film has high transparency.

  On the other hand, in recent years, by introducing a phase difference material into a cell of a liquid crystal display, cost reduction and weight reduction have been studied, and after coating and aligning a polymerizable liquid crystal solution as such a phase difference material, Photocured materials are generally used. In order to orient the retardation material, the lower layer film needs to be treated with a material having orientation after being rubbed or irradiated with polarized UV light. Therefore, after forming a liquid crystal alignment layer on the overcoat of the color filter, a retardation material is formed.

  If a film that doubles as a liquid crystal alignment layer and a color filter overcoat can be formed, it is expected to reduce costs and the number of processes. Therefore, in recent years, materials that serve both as a liquid crystal alignment layer and an overcoat of a color filter have been actively studied.

  In general, an acrylic resin having high transparency is used for the overcoat of the color filter, and a method of increasing heat resistance and solvent resistance by thermosetting or photocuring the acrylic resin (Patent Document 1 and 2).

  On the other hand, a material made of solvent-soluble polyimide or polyamic acid is usually used for the liquid crystal alignment layer. It has been reported that these materials are completely imidized by post-baking, imparted solvent resistance, and exhibit sufficient orientation by rubbing treatment (Patent Document 3).

  However, although the thermosetting or photocurable acrylic resins described in Patent Documents 1 and 2 have appropriate transparency and solvent resistance, an overcoat made of this type of acrylic resin is rubbed or irradiated with polarized UV light. However, sufficient orientation could not be shown.

  The liquid crystal alignment layer described in Patent Document 3 has a problem of low transparency when used as an overcoat material for a color filter. In addition, polyimide and polyamic acid have low solubility in glycol solvents, ester solvents, and ketone solvents, and are difficult to apply to overcoat production lines in which such solvents are used.

JP 2000-103937 A JP 2001-194797 A JP 2005-037920 A

  The present invention has been made on the basis of the above circumstances, and the problems to be solved are flatness, high solvent resistance, excellent photo-alignment with respect to polymerizable liquid crystals, sufficient heat resistance after forming a cured film. Another object of the present invention is to provide a material that exhibits high transparency as well as high transparency and can be dissolved in a glycol solvent, ketone solvent, or lactic acid ester solvent that can be applied in the production of a color filter overcoat.

  As a result of various studies to overcome the above problems, the present inventors have solved the above problems with a photo-orientable thermosetting composition containing a photo-orientable polymer and polyester amide acid. It has been found that it can be done, and the present invention has been completed.

The present invention has the following configuration.
[1] A thermosetting composition having photo-orientation, comprising a polymer (A) having photo-orientation and polyester amic acid (B).

  [2] The polymer (A) having photoalignment according to [1] is a copolymer of a polymerizable monomer (a1) having a cyclic ether and a polymerizable monomer (a2) having photoalignment. The thermosetting composition having a photo-alignment property according to [1].

  [3] The polymerizable monomer (a1) having the cyclic ether according to [2] is glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyl-3-oxetanyl). One or more selected from the group consisting of methyl acrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, (2-ethyl-2-oxetanyl) methyl acrylate and (2-ethyl-2-oxetanyl) methyl methacrylate The thermosetting composition having a photo-alignment property according to [2].

  [4] The above-mentioned [2] or [3], wherein the photo-alignment site of the photo-alignable polymerizable monomer (a2) according to [2] is a functional group having a structure that undergoes photodimerization or photoisomerization. A thermosetting composition having a photo-alignment property described in 1.

  [5] The photo-alignment site according to any one of [2] to [4], wherein the photo-alignment site of the polymerizable monomer (a2) having photo-alignment property according to [2] is cinnamoyl. Thermosetting composition.

  [6] The polyester amide acid (B) according to [1] is a polyester amide acid obtained by reacting tetracarboxylic dianhydride, diamine and a polyvalent hydroxy compound as essential components. ] The thermosetting composition which has the photo-alignment property in any one of [5].

  [7] The polyester amide acid (B) according to [1] is a polyester amide acid obtained by reacting tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound and monohydric alcohol as essential components. [1] A thermosetting composition having photo-alignment property according to any one of [5].

  [8] The heat having photoalignment property according to [7], wherein the monohydric alcohol is isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane. Curable composition.

[9] The polyester amide acid (B) according to the above [1] is obtained by converting X mol of tetracarboxylic dianhydride, Y mol of diamine and Z mol of polyvalent hydroxy compound into the following formulas (1) and ( The thermosetting composition having a photo-alignment property according to any one of [1] to [8], obtained by reacting at a ratio such that the relationship 2) is established.
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦1.5 (2)

  [10] The polyester amide acid (B) according to [1] is a compound having a structural unit represented by the following formulas (3) and (4), according to any one of [1] to [9] A thermosetting composition having photo-alignment properties.

（式中、Ｒ¹はテトラカルボン酸二無水物残基であり、Ｒ²はジアミン残基であり、Ｒ³は多価ヒドロキシ化合物残基である。）

(Wherein R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue.)

  [11] Tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2 [6] to [10], which is one or more compounds selected from-(bis (3,4-dicarboxyphenyl)) hexafluoropropanoic dianhydride and ethylene glycol bis (anhydrotrimellitate) A thermosetting composition having a photo-alignment property according to any one of the above.

  [12] One or more compounds wherein the diamine is selected from 3,3′-diaminodiphenylsulfone, bis (4- (3-aminophenoxy) phenyl) sulfone and bis (4- (4-aminophenoxy) phenyl) sulfone The thermosetting composition having photo-alignment property according to any one of [6] to [11].

  [13] The polyvalent hydroxy compound is selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol. The thermosetting composition having a photo-alignment property according to any one of [6] to [12], which is one or more kinds of compounds.

  [14] The heat having photoalignment property according to any one of [1] to [13], wherein the polyester amic acid (B) according to [1] has a weight average molecular weight of 1,000 to 500,000. Curable composition.

  [15] The photo-alignment according to any one of [1] to [14], wherein the polymer (A) having the photo-alignment property according to [1] has a weight average molecular weight of 2,000 to 200,000. Thermosetting composition.

[16] A cured film obtained by heating the thermosetting composition having a photo-alignment property according to any one of [1] to [15].
[17] A color filter using the cured film according to [16] as a protective film.

[18] A liquid crystal display device using the color filter according to [17].
[19] A solid-state imaging device using the color filter according to [17].
[20] An optical device comprising a retardation layer obtained using the thermosetting composition having a photo-alignment property according to any one of [1] to [15].
[21] A patterned retardation plate formed from the thermosetting composition having photo-alignment property according to any one of [1] to [15].

  The thermosetting composition having photo-alignment property of the present invention is a cured film having liquid crystal alignment ability (photo-alignment property) by light irradiation in addition to high transparency, high solvent resistance and high heat resistance, and flatness. Since it can be formed, it can be used as a material for forming a photo-alignment liquid crystal alignment film and an overcoat. In particular, it is possible to form a film having both the characteristics of the liquid crystal alignment layer and the overcoat layer of the color filter at the same time, and it is possible to reduce the cost by simplifying the manufacturing process and reducing the number of processes.

  The photo-curable thermosetting composition of the present invention is particularly suitable for a patterned retardation plate used for 3D displays, a built-in retardation plate for liquid crystal displays, an overcoat of a color filter having a photo-alignment function, and the like. is there.

1. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting composition having photo-orientation, which contains a polymer (A) having photo-orientation and polyester amic acid (B).

  The preferred mixing ratio of the polymer (A) having photo-alignment and the polyester amic acid (B) is, from the viewpoint of photo-orientation, the polymer (A) having photo-orientation and the polyester amic acid (B). The content of the polymer (A) having photo-alignment is generally 50 to 95% by weight, more preferably 50 to 90% by weight, and still more preferably 50 to 85% by weight with respect to the total amount of is there. The content of the polyester amic acid (B) is usually 5 to 50% by weight, more preferably 10%, based on the total amount of the polymer (A) having photo-alignment properties and the polyester amic acid (B). -50% by weight, more preferably 15-50% by weight.

1-1. Polymer having photo-alignment (A)
The polymer (A) having photo-alignment property is a copolymer of a polymerizable monomer (a1) having a cyclic ether and a polymerizable monomer (a2) having photo-alignment property. The preferred mixing ratio (molar ratio) of the polymerizable monomer (a1) having a cyclic ether and the polymerizable monomer (a2) having a photoalignment property is a polymerizable monomer (a1) having a cyclic ether from the viewpoint of photoalignment property. The polymerizable monomer (a2) having photo-alignment property is 1 to 20 mol, more preferably 1 to 10 mol, and further preferably 1 to 5 mol with respect to 1 mol.

1-2. Polymerizable monomer (a1) having cyclic ether
Examples of the polymerizable monomer (a1) having a cyclic ether include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-ethyl- Examples include 3-oxetanyl) methyl methacrylate, (2-ethyl-2-oxetanyl) methyl acrylate, and (2-ethyl-2-oxetanyl) methyl methacrylate. Among them, glycidyl methacrylate is preferable. A polymerizable monomer having these cyclic ethers is desirable from the viewpoint of heat resistance and chemical resistance of the resulting thermosetting composition.

1-3. Polymerizable monomer (a2) having photo-alignment properties
The photo-alignment part of the polymerizable monomer (a2) having photo-alignment is a function having a structure in which anisotropy is caused by a reaction such as photodimerization, photoisomerization, photolysis, or photocrosslinking when irradiated with light. Among them, a structure that causes photodimerization and photoisomerization is preferable.

  Examples of functional groups that cause photodimerization include substances having a cinnamic acid skeleton (K. Ichimura et al., Macromolecules, 30, 903 (1997)) and substances having an azobenzene skeleton (K. Ichimura et al., Mol. Cryst). Liq. Cryst., 298, 221 (1997)), substances having a hydrazono-β-ketoester skeleton (S. Yamamura et al., Liquid Crystals, vol. 13, No. 2, page 189 (1993)), stilbene Substances having a skeleton (JG Victor and JM Torkelson, Macromolecules, 20, 2241 (1987)) and substances having a spiropyran skeleton (K. Ichimura et al., Chemistry Letters, page 1063 (1992); K. Ichimura et al. , Thin Solid Films, vol. 235, page 101 (1993)), and specific examples thereof include cinnamoyl, chalcone, coumarin, anthracene and the like. Among these, cinnamoyl having high transparency in the visible light region and photodimerization reactivity is preferable.

  Examples of the cinnamoyl include groups having at least one of the structures represented by the following general formulas (I-1) to (I-3).

上記式中、Ｒ⁴は水素、任意の水素がフッ素で置き換えられてもよい炭素数１〜２０のアルキルを示し、好ましくは任意の水素がフッ素で置き換えられてもよい炭素数１〜５のアルキルを示し、より好ましくはメチルを示す。ｍは０〜６の整数を表し、好ましくは２、４または６を表す。また、上記式中に含まれるフェニレン中の任意の水素１〜４個はフッ素、メチル、又はメトキシで置き換えられてもよい。

In the above formula, R ⁴ represents hydrogen, alkyl having 1 to 20 carbon atoms in which arbitrary hydrogen may be replaced with fluorine, and preferably alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be replaced with fluorine. More preferably methyl. m represents an integer of 0 to 6, preferably 2, 4 or 6. In addition, any one to four hydrogen atoms in the phenylene contained in the above formula may be replaced with fluorine, methyl, or methoxy.

Of the groups represented by the above (I-1) to (I-3), the group represented by (I-3) is preferable.
The structural part that causes photoisomerization, which is exemplified as the photo-alignment part of the polymerizable monomer (a2) having photo-orientation, refers to a structural part that changes into a cis isomer and a trans isomer by light irradiation, and specific examples thereof. Examples thereof include an azobenzene structure and a stilbene structure. Of these, an azobenzene structure is preferred because of its high reactivity.

  As the polymerizable monomer (a2) having photo-alignment property, a monomer serving as a structural unit represented by the following formula (I-1-1), (I-2-1), or (I-3-1) is used. It can be illustrated.

上記式中、添え字ｘが付された括弧部分がポリマー主鎖中に含まれる部分であり、ｘは光配向性を有する重合体中に含まれる上記構成単位のモル分率（ｘ＜１）を表す。

In the above formula, the parenthesis part to which the subscript x is attached is the part contained in the polymer main chain, and x is the molar fraction (x <1) of the constituent unit contained in the polymer having photo-orientation property. Represents.

In the above formula, R ⁴ represents hydrogen, alkyl having 1 to 20 carbon atoms in which arbitrary hydrogen may be replaced with fluorine, and preferably alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be replaced with fluorine. More preferably methyl.

In the above formula, R ⁵ represents hydrogen, alkyl having 1 to 20 carbon atoms in which arbitrary hydrogen may be replaced with fluorine, or alkoxy having 1 to 20 carbon atoms in which arbitrary hydrogen may be replaced with fluorine, Preferably, it represents alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be replaced with fluorine, or alkoxy having 1 to 5 carbon atoms in which arbitrary hydrogen may be replaced with fluorine, more preferably methyl or methoxy. Show.

In the above formula, R ⁶ represents hydrogen or methyl, preferably methyl.
In the above formula, Z ¹ represents a single bond, —COO— or —OCO—, preferably —COO—.

In the above formula, o represents an integer of 2 to 6, preferably 2, 4 or 6, and p represents an integer of 0 to 2, preferably 0.
Any 1 to 4 hydrogen atoms of phenylene contained in the above formula may be replaced by fluorine, methyl, or methoxy, but are preferably unsubstituted or substituted by methoxy.

Examples of the polymerizable monomer having photo-alignment which is a constituent unit of the formula (I-1-1) are represented by the following formulas (I-1-1-a) to (I-1-1-l). And the like (in the following formula, R ⁷ is hydrogen or methyl, R ⁸ is alkyl having 1 to 20 carbon atoms, preferably alkyl having 1 to 10 carbon atoms), and the like.

上記式（Ｉ−２−１）の構成単位となる光配向性を有する重合性モノマーとしては、例えば、下記式（Ｉ−２−１−ａ）〜（Ｉ−２−１−ｌ）で表される重合性モノマー（下記式中、Ｒ⁷は水素又はメチルを示し、Ｒ⁸は炭素数１〜２０のアルキルを示す。）などが挙げられ、中でも式（Ｉ−２−１−ａ）が好ましい。

Examples of the polymerizable monomer having photo-alignment which is a constituent unit of the formula (I-2-1) are represented by the following formulas (I-2-1-a) to (I-2-1-l). Polymerizable monomers (wherein R ⁷ represents hydrogen or methyl, R ⁸ represents alkyl having 1 to 20 carbon atoms) and the like, among which formula (I-2-1-a) is preferable.

上記式（Ｉ−３−１）の構成単位となる光配向性を有する重合性モノマーとしては、例えば、下記式（Ｉ−３−１−ａ）〜（Ｉ−３−１−ｉ）で表される重合性モノマー（下記式中、Ｒ⁷は水素又はメチルを示し、Ｒ⁸は炭素数１〜２０のアルキルを示す。）などが挙げられる。

Examples of the polymerizable monomer having photo-alignment which is a constituent unit of the formula (I-3-1) are represented by the following formulas (I-3-1-a) to (I-3-1-i). Polymerizable monomers (in the following formula, R ⁷ represents hydrogen or methyl, and R ⁸ represents alkyl having 1 to 20 carbon atoms).

これら重合性モノマーの中でも、上記式（Ｉ−３−１）の構成単位となる光配向性を有する重合性モノマーが好ましく、上記式（Ｉ−３−１）で表され、Ｒ⁶がメチル、o＝２、ｐ＝０、Ｒ⁴がメチルの構成単位となる光配向性を有する重合性モノマーがより好ましい。

Among these polymerizable monomers, a polymerizable monomer having photo-alignment which is a constituent unit of the above formula (I-3-1) is preferable, represented by the above formula (I-3-1), R ⁶ is methyl, A polymerizable monomer having photoalignment in which o = 2, p = 0, and R ⁴ is a methyl structural unit is more preferable.

1-4. Other polymerizable monomer From the viewpoint of improving the photo-orientation property and adhesion of the thermosetting composition having the photo-orientation property of the present invention, the polymer (A) having the photo-orientation property is other polymerizable monomer. It may contain. Specific examples of other polymerizable monomers include, for example, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, maleic anhydride, itaconic anhydride, and other carboxylic acids or carboxylic acids. Radical polymerizable monomers containing anhydrides, for example, styrene radical polymerizable monomers such as styrene, methyl styrene, ethyl styrene, methoxy styrene, ethoxy styrene, acetoxy styrene, vinyl toluene, chloromethyl styrene, hydroxy styrene, such as hydroxymethyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic Imide, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylic acid ester radical polymerizable monomers such as butyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, for example, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) Radical polymerizable monomers having a condensed ring such as acrylate, for example, N-substituted maleimide radical polymerizable monomers such as N-phenylmaleimide and N-cyclohexylmaleimide, such as polystyrene macromonomer, polymethyl methacrylate A macromonomer of the above-mentioned monomer such as a relate macromonomer, a radically polymerizable monomer having a heterocyclic ring containing one or both of nitrogen and oxygen such as N-acryloylmorpholine, a condensed ring system radically polymerizable monomer such as indene, such as 3-methacrylate Roxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, vinyltrimethoxy Silane radical polymerizable monomers such as silane and vinyltriethoxysilane, 4-hydroxyphenyl vinyl ketone, and 3-acetyl-4-hydroxyphenyl vinyl ketone are exemplified, but not limited thereto.

  When other polymerizable monomer is contained, the mixing ratio (molar ratio) of each monomer constituting the polymer (A) having photoalignment is 1 mol of the polymerizable monomer (a1) having a cyclic ether. The polymerizable monomer (a2) having photo-alignment is 5 to 50 mol, preferably 10 to 45 mol, more preferably 15 to 40 mol, and the other polymerizable monomer is 5 to 40 mol, preferably 10 It is -35 mol, More preferably, it is 15-30 mol.

  For example, the polymer (A) having photo-alignment property may include a polymerizable monomer (a1) having the cyclic ether, a polymerizable monomer (a2) having photo-alignment property, and, if necessary, other monomers as a reaction solvent (for example, Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane and cycloheptane, such as methanol, ethanol, 1-propanol and 2-propanol Alcohols such as dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and other ethers such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone. Acetates such as ethyl acetate, butyl acetate, amyl acetate, γ-butyrolactone, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, Polyhydric alcohols such as 1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol). In addition, these reaction solvents can be used individually by 1 type, or can also be used in combination of 2 or more type.

  The production method of the polymer (A) having photo-alignment is carried out by reacting the polymerizable monomer (a1) having the cyclic ether and the polymerizable monomer (a2) having photo-alignment in the solvent, and as necessary. Then, the polymerizable monomer (a1) having the cyclic ether, the polymerizable monomer (a2) having photo-alignment properties, and other monomers are reacted in the solvent.

  The weight average molecular weight of the obtained polymer (A) having photo-alignment property is usually 2,000 to 200,000, preferably 5,000 to 100,000. If it exists in these ranges, the flatness of the thermosetting composition which has the photo-alignment property of this invention will become favorable.

1-5. Polyester amide acid (B)
The polyester amic acid (B) is obtained by reacting tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound as essential components. For the synthesis of the polyester amic acid (B), at least a solvent is required. The solvent may be left as it is, and a liquid or gel thermosetting resin composition considering handling properties may be used. It is good also as a solid composition which removed and considered conveyance property. In addition, the synthesis of polyester amic acid may contain, as necessary, a monohydric alcohol, a styrene-maleic anhydride copolymer, or a silicon-containing monoamine as a raw material, particularly from the viewpoint of molecular weight control. It is preferable to contain a monohydric alcohol.

Furthermore, the said polyester amide acid (B) may contain the compound which has a photo-alignment part and hydroxy from a viewpoint of a photo-alignment improvement.
Examples of the polyester amic acid (B) include compounds having structural units represented by the following formulas (3) and (4).

（式中、Ｒ¹はテトラカルボン酸二無水物残基であり、Ｒ²はジアミン残基であり、Ｒ³は多価ヒドロキシ化合物残基である。）

(Wherein R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue.)

1-6. Tetracarboxylic dianhydride Examples of the tetracarboxylic dianhydride used in the present invention include organic acids having 2 to 30 carbon atoms. Specific examples thereof include, for example, 3,3 ′, 4,4′-benzophenone. Tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4 4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic acid Dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, and ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, Shin Nippon Chemical Co., Ltd.) Aromatic tetracarboxylic dianhydrides such as cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, and cyclohexane tetracarboxylic dianhydride Alicyclic tetracarboxylic dianhydrides such as ethanetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride (trade name; Ricacid BT-100, manufactured by Shin Nippon Rika Co., Ltd.) And the like, and the like.

  Among these, anhydrides are preferable for aromatic tetracarboxylic acids that give resins having good transparency, and in particular, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4, 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG- 100, manufactured by Shin Nippon Rika Co., Ltd.), 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride are more preferable. Particularly preferred.

1-7. Diamines Examples of diamines used in the present invention include those having 2 to 30 carbon atoms. Specific examples thereof include 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, and 3,4 ′. -Diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- Diaminodiphenyl sulfones such as (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone and [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, etc. Can be mentioned.

  Of these, diaminodiphenyl sulfones that give resins having good transparency are preferred, and 3,3′-diaminodiphenyl sulfone and bis [4- (3-aminophenoxy) phenyl] sulfone are more preferred, and 3,3 '-Diaminodiphenyl sulfone is particularly preferred.

1-8. Polyhydric hydroxy compound Examples of the polyhydric hydroxy compound used in the present invention include those having 2 to 20 carbon atoms, and specific examples thereof include molecular weights of 1 such as ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol. Polyethylene glycol having a molecular weight of 1,000 or less, for example, polypropylene glycol having a molecular weight of 1,000 or less, such as propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4 -Butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2- Heptane Diol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2-nonanediol, 1,9-nonanediol, 1,2-decanediol 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol and other diols such as 1,2,5-pentanetriol, 1,2,6-hexanetriol, 1,2,7 -Triols such as heptanetriol, 1,2,8-octanetriol, 1,2,9-nonanetriol, 1,2,10-decanetriol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A (Product name), Bisphenol S (Product name), Bisphenol F (Product name), Diethanol Min and triethanolamine can be mentioned.

  Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8 have good solubility in solvents. -Octanediol is preferred, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol are particularly preferred.

1-9.1 Monohydric alcohol Specific examples of the monohydric alcohol used in the present invention include those having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples thereof include methanol and ethanol. 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, phenol, borneol, maltol, linalool, terpineo And dimethylbenzyl carbinol, 3-ethyl-3-hydroxymethyloxetane, and the like.

  Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl oxetane are preferable. Considering the compatibility when mixing polyester amide acid and epoxy resin and epoxy curing agent, and the applicability on the color filter of the thermosetting composition as the final product, It is more preferable to use benzyl alcohol as the alcohol.

1-10. Solvents used in the polymerization reaction Specific examples of the solvent used in the polymerization reaction to obtain the polyester amic acid (B) include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, and ethylene glycol monoethyl ether acetate. And propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide.

Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ethyl ether are preferable.
These solvents can be used alone or as a mixed solvent of two or more. In addition, if the amount of solvent used is 30% by weight or less based on the total amount charged, other solvents can be mixed and used.

1-11. Compound having photo-alignment site and hydroxy From the viewpoint of further improving the photo-alignment property of the thermosetting composition having photo-alignment property of the present invention, the polyester amic acid (B) comprises a photo-alignment site and hydroxy. You may contain the compound which has. Specific examples of the compound having a photo-alignment site and hydroxy include, for example, 4- (8-hydroxyoctyloxy) cinnamic acid methyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid methyl ester, 4- (4 -Hydroxybutyloxy) cinnamic acid methyl ester, 4- (3-hydroxypropyloxy) cinnamic acid methyl ester, 4- (2-hydroxyethyloxy) cinnamic acid methyl ester, methyl 4-hydroxymethyloxycinnamic acid Ester, 4-hydroxycinnamic acid methyl ester, 4- (8-hydroxyoctyloxy) cinnamic acid ethyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid ethyl ester, 4- (4-hydroxybutyloxy) Cinnamic acid ethyl ester, 4- (3-hydroxypropyloxy) silicate Acid ethyl ester, 4- (2-hydroxyethyloxy) cinnamic acid ethyl ester, 4-hydroxymethyloxy cinnamic acid ethyl ester, 4-hydroxyethyloxy cinnamic acid ethyl ester, 4-hydroxycinnamic acid ethyl ester, 4- (8-hydroxyoctyloxy) cinnamic acid phenyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid phenyl ester, 4- (4-hydroxybutyloxy) cinnamic acid phenyl ester, 4- (3- Hydroxypropyloxy) cinnamic acid phenyl ester, 4- (2-hydroxyethyloxy) cinnamic acid phenyl ester, 4-hydroxymethyloxy cinnamic acid phenyl ester, 4-hydroxycinnamic acid phenyl ester, 4- (8- Hydroxyoctyloxy) Bifeni cinnamate Ester, 4- (6-hydroxyhexyloxy) cinnamic acid biphenyl ester, 4- (4-hydroxybutyloxy) cinnamic acid biphenyl ester, 4- (3-hydroxypropyloxy) cinnamic acid biphenyl ester, 4- ( 2-hydroxyethyloxy) cinnamic acid biphenyl ester, 4-hydroxymethyloxycinnamic acid biphenyl ester, 4-hydroxycinnamic acid biphenyl ester, cinnamic acid 8-hydroxyoctyl ester, cinnamic acid 6-hydroxyhexyl ester, Cinnamic acid esters such as cinnamic acid 4-hydroxybutyl ester, cinnamic acid 3-hydroxypropyl ester, cinnamic acid 2-hydroxyethyl ester, cinnamic acid hydroxymethyl ester, such as 4- (8-hydroxyoctyloxy) Azobenzene, 4 -(6-hydroxyhexyloxy) azobenzene, 4- (4-hydroxybutyloxy) azobenzene, 4- (3-hydroxypropyloxy) azobenzene, 4- (2-hydroxyethyloxy) azobenzene, 4-hydroxymethyloxyazobenzene, Azobenzenes such as 4-hydroxyazobenzene, such as 4- (8-hydroxyoctyloxy) chalcone, 4- (6-hydroxyhexyloxy) chalcone, 4- (4-hydroxybutyloxy) chalcone, 4- (3-hydroxypropyl) Oxy) chalcone, 4- (2-hydroxyethyloxy) chalcone, 4-hydroxymethyloxychalcone, 4-hydroxychalcone, 4 ′-(8-hydroxyoctyloxy) chalcone, 4 ′-(6-hydroxyhexyloxy) chalcone , '-(4-hydroxybutyloxy) chalcone, 4'-(3-hydroxypropyloxy) chalcone, 4 '-(2-hydroxyethyloxy) chalcone, 4'-hydroxymethyloxychalcone, 4'-hydroxychalcone, etc. Chalcones such as 7- (8-hydroxyoctyloxy) coumarin, 7- (6-hydroxyhexyloxy) coumarin, 7- (4-hydroxybutyloxy) coumarin, 7- (3-hydroxypropyloxy) coumarin, 7- (2-hydroxyethyloxy) coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxycoumarin, 6-hydroxyhexyloxycoumarin, 6- (4-hydroxybutyloxy) coumarin, 6- (3 -Hydroxypropyloxy) coumarin 6- (2-hydroxyethyl-oxy) coumarin, 6-hydroxy methyloxy coumarin, 6-hydroxy-but coumarins coumarin like, but is not limited thereto.

1-12. Production method of polyester amide acid In the production method of polyester amide acid used in the present invention, X mol of tetracarboxylic dianhydride, Y mol of diamine and Z mol of polyvalent hydroxy compound are reacted in the above solvent. At this time, it is preferable that X, Y, and Z are set to such a ratio that the relationship of the following formulas (1) and (2) is established between them. Within this range, the solubility of the polyester amide acid in the solvent is high, so that the coating property of the composition is improved, and as a result, a cured film having excellent flatness can be obtained.

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦1.5 (2)
The relationship of the formula (1) is preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.3 ≦ Z / Y ≦ 7.0. In addition, the relationship of the formula (2) is preferably 0.5 ≦ (Y + Z) /X≦0.9, more preferably 0.7 ≦ (Y + Z) /X≦0.8.

  When the polyester amide acid used in the present invention has an acid anhydride group at the molecular end, the above-described monohydric alcohol can be added and reacted as necessary. The polyester amic acid obtained by adding and reacting with a monohydric alcohol has improved compatibility with the epoxy resin and the epoxy curing agent, and the applicability of the thermosetting resin composition of the present invention containing them. Is improved.

  In addition, when the above-described silicon-containing monoamine is reacted with a polyester amide acid having an acid anhydride group at the molecular end, the acid resistance of the obtained coating film is improved. Furthermore, the monohydric alcohol and the silicon-containing monoamine can be reacted with the polyester amic acid at the same time.

1-13. Silicon-containing monoamine Specific examples of the silicon-containing monoamine used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p -Aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylmethyldiethoxysilane, etc. can be mentioned.

  Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane having good acid resistance of the coating film are preferable, and 3-aminopropyltriethoxysilane is particularly preferable.

  The reaction solvent is preferably used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound, since the reaction proceeds smoothly. The reaction is preferably carried out at 40 to 200 ° C. for 0.2 to 20 hours. When the silicon-containing monoamine is reacted, after the reaction of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound is completed, the reaction solution is cooled to 40 ° C. or lower, and then the silicon-containing monoamine is added. It is good to make it react at -40 degreeC for 0.1 to 6 hours. The monohydric alcohol may be added at any point in the reaction.

  The order of adding the reaction raw materials to the reaction system is not particularly limited. (1) Tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound are simultaneously added to the reaction solvent. (2) Tetracarboxylic dianhydride is dissolved after the diamine and polyvalent hydroxy compound are dissolved in the reaction solvent. (3) After reacting tetracarboxylic dianhydride and polyvalent hydroxy compound in advance, add diamine to the reaction product, or (4) reacting tetracarboxylic dianhydride and diamine in advance Then, any method can be used such as adding a polyvalent hydroxy compound to the reaction product.

  The polyester amide acid used in the present invention may be subjected to a synthesis reaction by adding a compound having 3 or more acid anhydride groups. Specific examples of the compound having 3 or more acid anhydride groups include a styrene-maleic anhydride copolymer. About the ratio of each component which comprises a styrene-maleic anhydride copolymer, the molar ratio of styrene / maleic anhydride is 0.5-4, Preferably it is 1-3, Specifically, 0.8- 1.2 is preferred.

  Specific examples of the styrene-maleic anhydride copolymer include commercially available products such as SMA3000P, SMA2000P, and SMA1000P manufactured by Kawa Crude Oil Co., Ltd. Among these, SMA1000P having good heat resistance and alkali resistance is particularly preferable.

The polyester amide acid synthesized in this way contains the structural unit consisting of the above general formulas (3) and (4), and its terminal is derived from the raw material tetracarboxylic dianhydride, diamine or polyvalent hydroxy compound. It is preferable that it is an acid anhydride group, an amino group, or hydroxy, or an additive other than these compounds constitutes the terminal. In general formula (3) and (4), R < ¹ > is a tetracarboxylic dianhydride residue, Preferably it is a C2-C30 organic group. R ² is a diamine residue, preferably an organic group having 2 to 30 carbon atoms. R ³ is a polyvalent hydroxy compound residue, preferably an organic group having 2 to 20 carbon atoms.

  The obtained polyester amide acid preferably has a weight average molecular weight of 1,000 to 500,000, more preferably 2,000 to 200,000. If it exists in these ranges, the flatness and heat resistance of the cured film obtained will become favorable.

1-14. Other Components The thermosetting composition having photo-alignment property of the present invention may contain other components other than those described above as necessary within the range not impairing the object of the present invention. Examples of such other components include an epoxy curing agent, a coupling agent, a surfactant, an antioxidant, and a solvent.

1-14-1. Epoxy Curing Agent The thermosetting composition having photo-alignment properties of the present invention may contain an epoxy curing agent from the viewpoint of improving flatness and chemical resistance. Examples of the epoxy curing agent include an acid anhydride curing agent, a polyamine curing agent, a polyphenol curing agent, and a catalyst curing agent, and an acid anhydride curing agent is preferable from the viewpoint of coloring and heat resistance.

  When an epoxy curing agent is added for the purpose of improving flatness and chemical resistance, the ratio of the epoxy resin to the epoxy curing agent is 1 to 13 parts by weight of the epoxy curing agent with respect to 100 parts by weight of the epoxy resin. Preferably, it is 5 to 13 parts by weight, and more preferably 8 to 11 parts by weight. More specifically, the addition amount of the epoxy curing agent is preferably added so that the carboxylic acid anhydride group or carboxyl in the epoxy curing agent is 0.1 to 1.5 times equivalent to the epoxy group. At this time, it is calculated that the carboxylic anhydride group generates two carboxyls. When the carboxylic acid anhydride group or carboxyl is added so as to have an equivalent amount of 0.15 to 0.8 times, the flatness and chemical resistance are further improved.

Specific examples of the acid anhydride curing agent include an aliphatic dicarboxylic acid anhydride, an aromatic polyvalent carboxylic acid anhydride, and a styrene-maleic anhydride copolymer.
Specific examples of the aliphatic dicarboxylic acid anhydride include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride, and the like. Specific examples of the aromatic polyvalent carboxylic acid anhydride include phthalic anhydride and trimellitic anhydride. Among these, trimellitic anhydride and hexahydrotrimellitic anhydride are particularly preferable from the viewpoint of the balance between heat resistance and solubility in solvents.

1-14-2. Coupling agent The thermosetting composition having photo-alignment property of the present invention may contain a coupling agent from the viewpoint of improving the adhesion to the substrate. The content of the coupling agent is preferably 1% by weight or more with respect to the total amount of the thermosetting composition, from the viewpoint of improving heat resistance and solvent resistance. More preferably, it is% by weight.

  As the coupling agent, silane-based, aluminum-based and titanate-based compounds can be used. Specifically, silanes such as 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane (trade name S510, manufactured by JNC Corporation) And aluminum systems such as acetoalkoxyaluminum diisopropylate and titanate systems such as tetraisopropylbis (dioctyl phosphite) titanate. Of these, silanes are preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable because it has a large effect of improving adhesion.

1-14-3. Surfactant The thermosetting composition having photo-alignment property of the present invention may contain a surfactant from the viewpoint of improving wettability to the base substrate, leveling property, or coating property. From such a viewpoint, the content of the surfactant is preferably 0.005 to 10% by weight, more preferably 0.01 to 8% by weight, based on the total amount of the thermosetting composition. More preferably, the content is 0.01 to 5% by weight.

  As such a surfactant, Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (all are trade names, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181 , Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346 (all are trade names, manufactured by BYK Japan KK), KP-341, KP-358, KP-368, KF-96-50CS KF-50-100CS (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (all trade names, Seimi Chemical Co., Ltd.) Manufactured), aftergent 222F, aftergent 251, FTX-218 (all are trade names, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF- 802 (all are trade names, manufactured by Mitsubishi Materials Corporation), Megafuck F-171, Megafuck F-177, Megafuck F-475, Megafuck F-477 (all are trade names, manufactured by DIC Corporation) , Denon 1826M, PC-6862, PC-7062C, Elimina 208M (all are trade names, manufactured by Maruhishi Oil Chemical Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether , Fluoroalkylan Nium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amino sulfonate, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether , Polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, Polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laure Sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene Examples thereof include naphthyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonate, and among them, PC-7062C is preferable.

1-14-4. Antioxidant The thermosetting composition having photo-alignment property of the present invention may contain an antioxidant from the viewpoint of weather resistance. From such a viewpoint, the content of the antioxidant is preferably 0.01 to 10% by weight, more preferably 0.05 to 8% by weight, based on the total amount of the thermosetting composition. More preferably, the content is 0.1 to 5% by weight. Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds, and sulfur compounds. Among them, the hindered phenol type is more preferable as the antioxidant.

  Specific examples of the antioxidant, for example IrganoxFF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox295 (All are trade names, manufactured by BASF Japan Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK Bed AO-60, ADK STAB AO-70, ADK STAB AO-80 (both being trade names, ADEKA Co., Ltd.) are exemplified hindered phenol such. Among these, ADK STAB AO-60 is more preferable in terms of transparency, heat resistance, and crack resistance.

1-14-5. Solvent The thermosetting composition having photo-alignment property of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used in that case should just dissolve (A) component and (B) component and another additive as needed, and the kind and structure are not specifically limited.

  Specific examples of the solvent include, for example, methanol, ethanol, isopropanol, 1-propanol, butanol, 2-methyl-1-butanol, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve. Acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3 -Methyl-2-pentanone, -Pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethyl Examples include formamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone.

  These solvents can be used alone or in combination of two or more. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, 3-methoxypropion Ethyl acid, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate are more preferable because they can be applied in a color filter overcoat production line, have good film formability and high safety.

1-15. Preservation of thermosetting composition having photo-alignment property When the thermosetting composition having photo-alignment property of the present invention is stored in a temperature range of -30 ° C to 25 ° C, the composition is preferably stable over time. . If the storage temperature is −20 ° C. to 10 ° C., there is no precipitate and it is more preferable.

1-16. Adjustment of coating solution Depending on the thickness of the cured film to be formed, the coating solution may be adjusted by further diluting the thermosetting composition having photo-alignment property of the present invention with the above-mentioned solvent.

2. Cured film of the present invention The thermosetting composition having a photo-alignment property of the present invention is a mixture of a polymer having a photo-alignment property and a polyester amic acid. A ring agent and a surfactant can be selected and added as necessary, and they can be obtained by uniformly mixing and dissolving them.

  The photo-orientable thermosetting composition (after dissolving in a solvent in the case of a solid state without a solvent) prepared as described above, glass, PET (polyethylene terephthalate), TAC (triacetyl) A coating film can be formed by applying to a substrate surface such as cellulose) and removing the solvent by heating, for example. Application of the thermosetting resin composition to the substrate surface can form a coating film by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, or a slit coating method. Next, this coating film is heated (prebaked) with a hot plate or an oven. The heating conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 120 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Then, in order to cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 250 ° C., for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.

  The cured film obtained in this way is, when heated, 1) the polyamic acid portion of the polyester amic acid forms a dehydration cyclization to form an imide bond, and 2) the carboxylic acid of the polyester amic acid has a photo-alignment property. High molecular weight by reacting with cyclic ether, and 3) Since the polymer having photo-orientation is cured and high molecular weight, it is very tough and has transparency, heat resistance, solvent resistance, flatness, Excellent adhesion and sputtering resistance. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state imaging element can be produced using this color filter.

  The cured film of the present invention is effective when used as a transparent insulating film formed between the TFT and the transparent electrode or a transparent insulating film formed between the transparent electrode and the alignment film, in addition to the protective film for the color filter. It is. Furthermore, the cured film of the present invention is effective even when used as a protective film for LED light emitters.

  Furthermore, an optical film can be obtained by using a liquid crystal alignment film obtained from the thermosetting composition having photo-alignment property of the present invention. The optical film is suitable for an optical compensation film for realizing an improvement in contrast of a liquid crystal display element and an expansion of a viewing angle range, a retardation plate such as a patterned retardation plate, and the like.

  The optical film generally has a substrate, a liquid crystal alignment film, and an optically anisotropic layer. The optically anisotropic layer is formed by applying a polymerizable liquid crystal composition containing a polymerizable liquid crystalline compound and other components to be added as necessary onto the liquid crystal alignment film formed on the substrate. It can be obtained by aligning the molecules of the functional compound and polymerizing them. The optically anisotropic layer exhibits optical anisotropy expressed by molecular orientation of the liquid crystalline compound. Therefore, this optical film can be suitably used, for example, as a patterned retardation plate. Such an optical film can be suitably used for various optical devices such as liquid crystal display elements.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these.
[Synthesis Example 1] Synthesis of polymer (A1) having photo-alignment property In a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 2- {4-[(1E) -3-methoxy-3-oxoprop-1-en-1-yl] phenoxy} ethyl = 2methylprop-2-enoate 135.00 g, glycidyl methacrylate 15.00 g, 2,2′-azobis ( 2,4-dimethylvaleronitrile) (15.00 g) and 50.00 g of cyclopentanone as a reaction solvent were charged, and polymerization was carried out by heating at a polymerization temperature of 90 ° C. for 2 hours. By cooling the reaction solution to 30 ° C. or lower, a 25 wt% solution of the polymer (A1) having photo-alignment property was obtained. The weight average molecular weight measured by GPC of this solution was 6,400 (polystyrene conversion).

  In the present invention, the weight average molecular weight is as follows: column oven CTD-20A, detector RID-10A, system controller CBM-20A, liquid feed pump LC-20AD, autosampler SIL-10AF It was measured using a GPC system manufactured by Shimadzu Corporation. In addition, polystyrene having a weight average molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 from VARIAN) is used as standard polystyrene, and PLgel MIXED-D (VARIAN) is used as a column as a mobile phase. Measurement was performed using THF at a column temperature of 35 ° C. and a flow rate of 1 mL / min.

[Synthesis Example 2] Synthesis of polymer (A2) having photo-alignment property In a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 2- {4-[(1E) -3-Methoxy-3-oxoprop-1-en-1-yl] phenoxy} ethyl = 2methylprop-2-enoate 120.00 g, glycidyl methacrylate 30.00 g, 2,2′-azobis ( 2,4-dimethylvaleronitrile) (15.00 g) and 50.00 g of cyclopentanone as a reaction solvent were charged, and polymerization was carried out by heating at a polymerization temperature of 90 ° C. for 2 hours. The reaction solution was cooled to 30 ° C. or less to obtain a 25% by weight solution of the polymer (A2) having photoalignment. The weight average molecular weight measured by GPC of this solution was 7,300 (polystyrene conversion).

[Synthesis Example 3] Synthesis of polymer (A3) having photo-alignment property In a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 2- {4-[(1E) -3-methoxy-3-oxoprop-1-en-1-yl] phenoxy} ethyl = 2-methylprop-2-enoate 100.00 g, glycidyl methacrylate 20.00 g, 2-hydroxyethyl methacrylate 40.00 g, 3- 40.00 g of methacryloxypropyltrimethoxysilane, 20.00 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and 66.60 g of cyclopentanone as a reaction solvent were charged at 90 ° C. Polymerization was carried out by heating at the polymerization temperature for 2 hours. The reaction solution was cooled to 30 ° C. or less to obtain a 25% by weight solution of the polymer (A2) having photoalignment. The weight average molecular weight measured by GPC of this solution was 8,100 (polystyrene conversion).

[Synthesis Example 4] Synthesis of polymer (A4) having photo-alignment property Into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, 2- {4-[(1E) -3-methoxy-3-oxoprop-1-en-1-yl] phenoxy} ethyl = 2-methylprop-2-enoate 100.00 g, glycidyl methacrylate 20.00 g, 2-hydroxyethyl methacrylate 80.00 g, polymerization started As the agent, 20.00 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 66.60 g of cyclopentanone as the reaction solvent were charged, and polymerization was carried out by heating at a polymerization temperature of 90 ° C. for 2 hours. . The reaction solution was cooled to 30 ° C. or less to obtain a 25% by weight solution of the polymer (A2) having photoalignment. The weight average molecular weight measured by GPC of this solution was 7,100 (polystyrene conversion).

[Synthesis Example 5] Synthesis of polymer (A5) having photo-alignment property In a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 2- {4-[(1E) -3-methoxy-3-oxoprop-1-en-1-yl] phenoxy} ethyl = 2-methylprop-2-enoate 100.00 g, glycidyl methacrylate 20.00 g, 3-methacryloxypropyltrimethoxysilane 80.00 g, As a polymerization initiator, 20.00 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 66.60 g of cyclopentanone as a reaction solvent were charged and heated at a polymerization temperature of 90 ° C. for 2 hours for polymerization. went. The reaction solution was cooled to 30 ° C. or less to obtain a 25% by weight solution of the polymer (A2) having photoalignment. The weight average molecular weight measured by GPC of this solution was 6,800 (polystyrene conversion).

[Synthesis Example 6] Synthesis of polyester amic acid (B1) In a 1000 ml four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet, dehydrated and purified methyl 3-methoxypropionate (hereinafter “ MMP ") 446.96 g, 1,4-butanediol 31.93 g, benzyl alcohol 25.54 g, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as" ODPA ") 183.20 g was charged and stirred at 130 ° C. for 3 hours under a dry nitrogen stream. Thereafter, the reaction solution was cooled to 25 ° C., 29.33 g of 3,3′-diaminodiphenylsulfone (hereinafter abbreviated as “DDS”) and 183.04 g of MMP were added, and the mixture was stirred at 20 to 30 ° C. for 2 hours. The mixture was stirred at 0 ° C. for 1 hour and cooled to 30 ° C. or less to obtain a 30% by weight solution of light yellow transparent polyester amic acid (B1).
The weight average molecular weight measured by GPC of this solution was 4,200 (in terms of polystyrene).

[Synthesis Example 7] Synthesis of polyester amic acid (B2) A 1000 ml four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet was dehydrated and purified propylene glycol monomethyl ether acetate (hereinafter "PGMEA"). "Abbreviated") 504.00 g, ODPA 47.68 g, SMA1000P (trade name; styrene / maleic anhydride copolymer, manufactured by Kawa Crude Chemical Co., Ltd.) 144.97 g, benzyl alcohol 55.40 g, 1,4-butanediol 9 .23 g and 96.32 g of dehydrated and purified diethylene glycol methyl ethyl ether (hereinafter abbreviated as “EDM”) were charged in this order, and the mixture was stirred at 130 ° C. for 3 hours under a dry nitrogen stream. Thereafter, the reaction solution was cooled to 25 ° C., charged with 12.72 g of DDS and 29.68 g of EDM, stirred at 20-30 ° C. for 2 hours, stirred at 115 ° C. for 1 hour, and cooled to 30 ° C. or lower to give a pale yellow color. A clear 30% by weight solution of polyester amic acid (B2) was obtained.
The weight average molecular weight measured by GPC of this solution was 21,000 (polystyrene conversion).

[Synthesis Example 8] Synthesis of polyester amic acid (B3) MMP446.96 g, 4- (hydroxyethyloxy) silicic acid was added to a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet. Methyl cinnamate 31.93 g, 1,4-butanediol 25.54 g, and ODPA 183.20 g were charged and stirred at 130 ° C. for 3 hours in a dry nitrogen stream. Thereafter, the reaction solution was cooled to 25 ° C., 29.33 g of DDS and 183.04 g of MMP were added, stirred at 20-30 ° C. for 2 hours, then stirred at 115 ° C. for 1 hour and cooled to 30 ° C. or less to obtain a pale yellow color. A clear 30% by weight solution of polyester amic acid (B3) was obtained.
The weight average molecular weight measured by GPC of this solution was 3,200 (in terms of polystyrene).

[Example 1] Production of thermosetting composition 25% by weight solution (hereinafter referred to as polymer (A1)) of polymer (A1) having photo-alignment property obtained in Synthesis Example 1 30% by weight solution of polyester amide acid (B1) obtained (hereinafter referred to as polymer (B1)), trimellitic anhydride (hereinafter referred to as TMA) which is an epoxy curing agent, and coupling agent S510 (trade name, manufactured by JNC Co., Ltd.), PC-7062C (trade name, manufactured by Maruhishi Oil Chemical Co., Ltd.) which is a surfactant, cyclopentanone as a solvent is mixed and dissolved at the weight shown in Table 1 below, and membrane The mixture was filtered through a filter (0.2 μm) to obtain a thermosetting composition. Table 2 shows the composition of the obtained thermosetting composition.

[Examples 2 to 11] Production of thermosetting composition In the same manner, the compositions shown in Table 2 were mixed and dissolved to obtain thermosetting compositions of Examples 2 to 11. The numbers in parentheses in Table 2 represent parts by weight, A1 to A5 are 25% by weight solutions of polymers (A1) to (A5) having photo-alignment properties, and B1 to B3 are respectively It is a 30% by weight solution of polyester amic acid (B1) to (B3).

[Comparative Examples 1 to 3] Production of Thermosetting Composition In the same manner as in Examples 1 to 11, the thermosetting compositions of Comparative Examples 1 to 3 were obtained by mixing and dissolving the compositions shown in Table 3.

[Evaluation method]
1) Formation of cured film The thermosetting composition was spin-coated on a glass substrate and a color filter substrate at an arbitrary rotation speed of 400 to 1,200 rpm for 10 seconds, and then pre-baked on a hot plate at 80 ° C. for 3 minutes. A coating film was formed. Then, the coating film was hardened by heating at 230 degreeC for 30 minutes in oven, and the cured film with a film thickness of 0.5 micrometer was obtained. After returning the substrate taken out of the oven to room temperature, the thickness of the obtained cured film was measured. For measurement of the film thickness, a stylus-type film thickness meter P-15 manufactured by KLA-Tencor Japan Co., Ltd. was used, and the average value of three measurements was taken as the film thickness of the cured film.

2) Flatness The level | step difference of the cured film surface of the color filter substrate with a cured film obtained by said 1) was measured using the stylus type film thickness meter P-15 by KLA-Tencor Japan Co., Ltd. The maximum value of the step between the R, G, and B pixels including the black matrix (hereinafter, abbreviated as the maximum step) was defined as the flatness value. The used color filter substrate is a pigment-dispersed color filter (hereinafter abbreviated as CF) using a resin black matrix having a maximum step of about 1.1 μm.

3) Transparency TC-1800 manufactured by Tokyo Denshoku Co., Ltd. is used as a reference, and the substrate on which the cured film obtained in 1) above is formed at a wavelength of 400 nm with the glass substrate not forming the cured film as a reference. The light transmittance was measured. When the transmittance was 95 T% or more, it was judged as good (G: Good), and when it was less than 95 T%, it was judged as bad (NG: No Good).

4) Heat resistance The substrate on which the cured film obtained in 1) above is formed is heated in an oven at 230 ° C. for 1 hour, the light transmittance is measured in the same manner as in 3) above, and the above 1 before and after heating. ), The film thickness was measured and calculated from the following equation.
(Film thickness after heating / film thickness before heating) x 100 (%)
When the rate of change in film thickness was less than −5%, it was judged good (G: Good), and when the rate of change in film thickness after heating was −5% or more, it was judged as bad (NG: No Good).

5) Solvent resistance The substrate on which the cured film obtained in the above 1) is formed is immersed in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) at 25 ° C. for 30 minutes to change the film thickness. It was measured. The film thickness was measured in the same manner as 1) before and after the immersion, and calculated from the following formula.
(Film thickness after immersion / film thickness before immersion) × 100 (%)
When the rate of change in film thickness was -5 to 5%, it was judged good (G: Good), and when it exceeded 5% due to swelling or decreased from -5% due to dissolution, it was judged as bad (NG: No Good).

6) Photoalignment The cured film surface obtained in 1) above was irradiated with 500 mJ / cm ² of linearly polarized ultraviolet light having a wavelength of about 313 nm from a direction of 90 ° with respect to the coated surface. A retardation material solution composed of a liquid crystal monomer was applied onto this substrate using a spin coater, and then prebaked on a hot plate at 80 ° C. for 1 minute to form a film having a thickness of 0.5 μm. This substrate was exposed at an exposure amount of 1000 mJ / cm ² in terms of 365 nm. Those that were aligned at an exposure amount of 500 mJ / cm ² at 313 nm of polarized UV were judged good (G: Good), and those that were not oriented were judged as bad (NG: No Good).
Table 4 shows the results obtained by the above evaluation methods for the thermosetting compositions of Examples 1 to 11.

  About the thermosetting polymer fat composition of Comparative Examples 1-3, the result obtained by said evaluation method is shown in Table 4.

  The thermosetting composition having photo-alignment property according to the present invention is very useful as a material for a liquid crystal alignment layer of an optically anisotropic film or a liquid crystal display device. Further, the thin film transistor (TFT) type liquid crystal display device, organic EL Materials for forming cured films such as protective films and insulating films in various displays such as devices, especially retardation films, patterned retardation plates for 3D displays, interlayer insulation films for TFT-type liquid crystal elements, and overcoats for color filters It is also suitable as a material for forming an insulating film of an organic EL element.

Claims (21)

  A thermosetting composition having photo-alignment property, comprising a polymer (A) having photo-alignment property and polyester amic acid (B).   The polymer (A) having a photo-alignment property according to claim 1 is a copolymer of a polymerizable monomer (a1) having a cyclic ether and a polymerizable monomer (a2) having a photo-alignment property. 2. A thermosetting composition having a photo-alignment property according to 1.   The polymerizable monomer (a1) having a cyclic ether according to claim 2 is glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyl-3-oxetanyl) methyl acrylate, ( 3 or more selected from the group consisting of (3-ethyl-3-oxetanyl) methyl methacrylate, (2-ethyl-2-oxetanyl) methyl acrylate and (2-ethyl-2-oxetanyl) methyl methacrylate. A thermosetting composition having a photo-alignment property described in 1.   The photo-alignment part according to claim 2 or 3, wherein the photo-alignment part of the photo-alignment polymerizable monomer (a2) according to claim 2 is a functional group having a structure that undergoes photodimerization or photoisomerization. A thermosetting composition.   The thermosetting composition having a photo-alignment property according to any one of claims 2 to 4, wherein the photo-alignment site of the polymerizable monomer (a2) having a photo-alignment property according to claim 2 is cinnamoyl.   The polyester amide acid (B) according to claim 1 is a polyester amide acid obtained by reacting tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound as essential components. A thermosetting composition having a photo-alignment property according to claim 1.   The polyester amide acid (B) according to claim 1 is a polyester amide acid obtained by reacting tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound and monohydric alcohol as essential components. A thermosetting composition having a photo-alignment property according to any one of the above.   The thermosetting composition having photo-alignment property according to claim 7, wherein the monohydric alcohol is isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3-ethyl-3-hydroxymethyloxetane. . The polyester amic acid (B) according to claim 1, wherein X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compound are represented by the following formulas (1) and (2): The thermosetting composition having a photo-alignment property according to any one of claims 1 to 8, obtained by reacting at a ratio such that
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦1.5 (2) The polyester amic acid (B) according to claim 1 is a compound having a structural unit represented by the following formulas (3) and (4): Thermosetting having photo-alignment property according to any one of claims 1 to 9 Sex composition.

(Wherein R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue.)   Tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- (bis The compound according to any one of claims 6 to 10, which is one or more compounds selected from (3,4-dicarboxyphenyl)) hexafluoropropanoic dianhydride and ethylene glycol bis (anhydrotrimellitate). A thermosetting composition having photo-alignment properties.   The diamine is one or more compounds selected from 3,3′-diaminodiphenylsulfone, bis (4- (3-aminophenoxy) phenyl) sulfone and bis (4- (4-aminophenoxy) phenyl) sulfone Item 12. A thermosetting composition having a photo-alignment property according to any one of Items 6 to 11.   1 wherein the polyhydroxy compound is selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol It is a compound more than a seed | species, The thermosetting composition which has the photo-alignment property in any one of Claims 6-12.   The thermosetting composition having a photo-alignment property according to any one of claims 1 to 13, wherein the polyester amic acid (B) according to claim 1 has a weight average molecular weight of 1,000 to 500,000.   The weight average molecular weight of the polymer (A) having photoalignment according to claim 1 is 2,000 to 200,000, and the thermosetting composition having photoalignment according to any one of claims 1 to 14. object.   The cured film obtained by heating the thermosetting composition which has the photo-alignment property in any one of Claims 1-15.   A color filter using the cured film according to claim 16 as a protective film.   A liquid crystal display element using the color filter according to claim 17.   A solid-state imaging device using the color filter according to claim 17.   The patterned phase difference plate formed from the thermosetting composition which has the photo-alignment property in any one of Claims 1-15.   The optical device provided with the phase difference plate obtained using the thermosetting composition which has the photo-alignment property in any one of Claims 1-15.