TW201416387A - Thermosetting composition with photo-aligning characteristic, cured film, color filter, liquid crystal display element, solid imaging element and optical device - Google Patents

Abstract

The invention provides a material after a cured film is formed showing planarity, high solvent resistance, excellent photo-aligning characteristic with respect to polymerizable liquid crystal, sufficient heat resistance and high transparency, and being solvable by glycol-based solvent, ketone-based solvent or lactate-based solvent applicable for fabricating an overcoat of a color filter when the cured film is formed. The invention relates to a thermosetting composition with photo-aligning characteristic including a polymer (A) with photo-aligning characteristic and a polyesteramide acid (B) and application of the thermosetting compositions.

Description

Thermosetting composition having light alignment, cured film, color filter, liquid crystal display element, solid-state imaging element, patterned phase difference plate, and optical device

The present invention relates to a thermosetting composition having photoalignment properties and a cured film formed from the composition. More specifically, the present invention relates to a thermosetting composition which is excellent in transparency, liquid crystal alignment ability, solvent resistance, and heat resistance in a thermosetting film, and an application of the thermosetting film.

In the manufacturing steps of an element such as a liquid crystal display element, various chemicals such as an organic solvent, an acid, and an alkali solution may be treated, or the surface may be locally heated to a high temperature when a wiring electrode is formed by sputtering. Therefore, there is a case where a surface protective film is provided for the purpose of preventing deterioration, damage, and deterioration of the surface of various elements. These protective films are required to have various characteristics that are resistant to various treatments in the manufacturing steps as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, and adhesion to a base substrate such as glass are required. The light resistance, the transparency, the scratch resistance, the coating property, the flatness, and the light resistance which does not cause deterioration such as coloring after a long period of time.

In addition, in recent years, with the advancement of high performance such as high viewing angle, high-speed response, and high definition of liquid crystal display elements, in order to maintain color transmission color, it is used as a color filter protective film. The transmittance of light of the filter is required to be a film having high transparency.

On the other hand, in recent years, the industry is investigating the cost reduction and weight reduction by introducing a phase difference material into a cell of a liquid crystal display. Such a phase difference material generally uses coating polymerizability. A material obtained by aligning a liquid crystal solution and then photohardening it. In order to align the phase difference material, it is necessary to perform treatment by rubbing treatment or ultra violet (UV) irradiation on the underlayer film, and then using an anisotropic material. Therefore, a phase difference material is formed after the liquid crystal alignment layer is formed on the overcoat of the color filter.

When a film which also serves as a protective layer for the liquid crystal alignment layer and the color filter can be formed, reduction in cost, reduction in the number of processes, and the like can be expected. Therefore, in recent years, the industry is actively researching materials that serve as protective layers for liquid crystal alignment layers and color filters.

In the protective layer of the color filter, a method of improving heat resistance and solvent resistance by using an acrylic resin having high transparency and thermosetting or photohardening the acrylic resin (Patent Document 1 and Patent Document 2).

On the other hand, solvent-soluble polyfluorene is usually used in the liquid crystal alignment layer. A material of an imine or polyamic acid. The report indicates that these materials are completely imidized by post-bake, thereby imparting solvent resistance, and exhibiting sufficient orientation by rubbing treatment (Patent Document 3).

However, the thermosetting or photocurable acrylic resin described in Patent Document 1 to Patent Document 2 has appropriate transparency and solvent resistance, but the protective layer containing such an acrylic resin is subjected to rubbing treatment. Or polarized UV irradiation also does not show sufficient alignment.

When the liquid crystal alignment layer described in Patent Document 3 is used as a protective layer material of a color filter, there is a problem that transparency is low. Further, polyimine and polylysine have low solubility in a glycol solvent, an ester solvent, and a ketone solvent, and it is difficult to apply to a protective layer production line using such a solvent.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-103937

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-194797

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-037920

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a flatness, high solvent resistance, excellent optical alignment property to a polymerizable liquid crystal, and sufficient heat resistance and high after forming a cured film. A material of a glycol solvent, a ketone solvent or a lactic acid ester solvent which can be used for the production of a protective layer which can be dissolved in a color filter when a cured film is formed.

In order to overcome the above problems, the present inventors have conducted various studies, and as a result, it has been found that a thermosetting composition having photo-alignment properties of a polymer having a photo-alignment property and a polyester phthalic acid can solve the above problems, thereby completing the present invention. .

The present invention has the following constitution.

[1] A thermosetting composition having photo-alignment properties, comprising a polymer (A) having photo-alignment properties and a polyester proline (B).

[2] The thermosetting composition having photo-alignment property according to the above [1], wherein the polymer (A) having photo-alignment property as described in [1] above is a polymerizable single having a cyclic ether. a copolymer of the body (a1) and the photopolymerizable polymerizable monomer (a2).

[3] The thermosetting composition having photo-alignment property according to the above [2], wherein the polymerizable monomer (a1) having a cyclic ether as described in [2] above is selected from the group consisting of glycidyl acrylate. , glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyl-3-oxetanyl)methyl acrylate, A (3-ethyl-3-oxetanyl)methyl acrylate, (2-ethyl-2-oxetanyl)methyl acrylate and methacrylic acid (2-ethyl-2-oxa) More than one of the group consisting of cyclobutyl)methyl esters.

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

[5] The thermosetting composition having photo-alignment property according to the above [2], wherein the photo-alignment site of the photo-alignable polymerizable monomer (a2) according to the above [2] is cinnamon.醯基.

[6] The thermosetting composition having photo-alignment property according to the above [1], wherein the polyester proline (B) as described in [1] above is obtained by using tetracarboxylic dianhydride, A polyester proline which is obtained by reacting an amine and a polyvalent hydroxy compound as an essential component.

[7] The thermosetting composition having photo-alignment property according to the above [1], wherein the polyester phthalic acid (B) according to the above [1] is obtained by using tetracarboxylic dianhydride, A polyester proline which is obtained by reacting an amine, a polyvalent hydroxy compound and a monohydric alcohol as an essential component.

[8] The thermosetting composition having photo-alignment property according to the above [7], wherein the monohydric alcohol is isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3- Ethyl-3-hydroxymethyloxetane.

[9] The thermosetting composition having photo-alignment property according to any one of [1] to [8] wherein the polyester proline (B) as described in [1] above is X. Mohr tetracarboxylic dianhydride, Y-mole diamine, and Z-mole polyvalent hydroxy compound are obtained by reacting a ratio of the following formula (1) and formula (2), 0.2 ≦ Z / Y ≦8.0...(1)

0.2≦(Y+Z)/X≦1.5...(2).

[10] The thermosetting composition having photo-alignment property according to any one of the above [1], wherein the polyester proline (B) as described in [1] above has a compound of the structural unit represented by the formula (3) and the formula (4),

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

[11] The photohardenable thermosetting composition according to any one of [6] to [8] wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3', 4, 4'- Phenylhydrazine tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-(bis(3,4-dicarboxyphenyl))hexafluoropropanoic acid One or more compounds of anhydride and ethylene glycol bis(trimellitic anhydride).

[12] The thermosetting composition having photo-alignment property according to any one of [6] to [8] wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium and bis One or more compounds of (4-(3-aminophenoxy)phenyl)anthracene and bis(4-(4-aminophenoxy)phenyl)anthracene.

[13] The photohardenable thermosetting composition according to any one of [6] to [8] wherein the polyvalent hydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, and 1,4-butanediol. And one or more compounds selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol.

[14] The thermosetting composition having photo-alignment property according to any one of the above [1], wherein the weight average of the polyester proline (B) as described in [1] above is The molecular weight is 1,000 to 500,000.

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

[16] A cured film obtained by heating the thermosetting composition having photo-alignment property according to any one of the above [1] to [15].

[17] A color filter using the cured film according to [16] above as a protective film.

[18] A liquid crystal display element using the color filter according to [17] above.

[19] A solid-state image sensor which uses the color filter as described in [17] above.

[20] A patterned phase difference plate which is formed of the thermosetting composition having photo-alignment property according to any one of the above [1] to [15].

[21] An optical device comprising a phase difference plate obtained by using the photohardenable thermosetting composition according to any one of the above [1] to [15].

The thermosetting composition having photo-alignment property of the present invention can be formed to have high transparency, high solvent resistance, high heat resistance, further flatness, and light irradiation. The cured film of the liquid crystal alignment ability (photoalignment) can be used as a material for forming a photoalignment liquid crystal alignment film and a protective layer. In particular, a film having the characteristics of both the liquid crystal alignment layer and the protective layer of the color filter can be formed together, and the cost reduction by the simplification of the manufacturing process and the reduction in the number of processes can be achieved.

The thermosetting composition having photo-alignment property of the present invention is particularly useful for a patterned phase difference plate used in a 3D display, a built-in phase difference plate in a liquid crystal display, a protective layer of a color filter having a photo-alignment function, and the like. Better words.

1. The thermosetting composition having photo-alignment property of the present invention

The present invention relates to a thermosetting composition having photo-alignment properties, comprising a polymer (A) having photo-alignment properties and a polyester phthalic acid (B).

With respect to a preferred mixing ratio of the photo-alignment polymer (A) and the polyester glutamic acid (B), from the viewpoint of photo-alignment, the polymer (A) and the poly-alignment with respect to photo-alignment The total amount of the ester glutamic acid (B), the content of the photo-alignment polymer (A) is usually from 50% by weight to 95% by weight, more preferably from 50% by weight to 90% by weight, still more preferably 50% by weight. %~85% by weight. Further, the content of the polyester glutamic acid (B) is usually from 5% by weight to 50% by weight based on the total amount of the photo-alignment polymer (A) and the polyester glutamic acid (B), more preferably 10% by weight to 50% by weight, and more preferably 15% by weight to 50% by weight.

1-1. Polymer with photo-alignment (A)

The above photo-aligned polymer (A) is a copolymer of a polymerizable monomer (a1) having a cyclic ether and a polymerizable monomer (a2) having photo-alignment properties. The preferred mixing ratio (mohr ratio) of the polymerizable monomer (a1) having a cyclic ether and the polymerizable monomer (a2) having photo-alignment properties is relative to the viewpoint of optical alignment. The polymerizable monomer (a1) of the cyclic ether is 1 mol, and the photopolymerizable polymerizable monomer (a2) is 1 mol to 20 mol, more preferably 1 mol to 10 mol, and further preferably It is 1 mole to 5 moles.

1-2. Polymerizable monomer having a cyclic ether (a1)

Examples of the polymerizable monomer (a1) having a cyclic ether include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate. , (3-ethyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, acrylic acid (2-ethyl-2-oxa) Cyclobutyl)methyl ester and (2-ethyl-2-oxetanyl)methyl methacrylate, of which glycidyl methacrylate is preferred. These polymerizable monomers having a cyclic ether are preferred from the viewpoint of heat resistance and chemical resistance of the thermosetting composition obtained.

1-3. Polymerizable monomer having photoalignment property (a2)

The photo-alignment site of the photopolymerizable polymerizable monomer (a2) has a structure in which anisotropy is generated by a reaction such as photodimerization, photoisomerization, photolysis, or photocrosslinking by irradiation of light. A functional group, preferably a functional group having a structure which produces photodimerization and photoisomerization.

The functional group which produces photodimerization may, for example, be derived from a substance having a cinnamic acid skeleton (K. Ichimura et al., Macromolecules, 30, 903 (1997)), a substance having an azobenzene skeleton (K. Ichimura et al., Mol. Cryst. Liq. Cryst., 298, 221 (1997)), having an indenyl-β-ketone The substance of the ester skeleton (S. Yamamura et al., Liquid Crystals, vol. 13, No. 2, page 189 (1993)), having a stilbene skeleton Substance (JGVictor and JMTorkelson, Polymer (Macromolecules), 20, 2241 (1987)), and substances with a spiropyran skeleton (K. Ichimura et al., Chemistry Letters, page 1063 (page) (1992); K. Ichimura et al., Thin Solid Films, vol. 235, page 101 (1993)), and the like, specific examples thereof include: cinnamyl, chalcone, Coumarin, cockroach, etc. Among these, a cinnamyl group having high transparency and photodimerization reactivity in a visible light region is preferred.

The cinnamoyl group may, for example, be a group having at least one of the structures represented by the following formula (I-1) to formula (I-3).

In the above formula, R ⁴ represents hydrogen, an arbitrary alkyl group having 1 to 20 carbon atoms which may be substituted by fluorine, and preferably an alkyl group having 1 to 5 carbon atoms which may be substituted with fluorine, and more preferably Indicates a methyl group. m represents an integer of 0 to 6, preferably 2, 4 or 6. Further, any one to four hydrogens in the phenylene group contained in the above formula may be substituted with fluorine, a methyl group or a methoxy group.

Among the groups represented by the above (I-1) to (I-3), a group represented by (I-3) is preferred.

The photoisomerization-generating structure exemplified as the photo-alignment site of the photo-alignable polymerizable monomer (a2) means conversion to cis and trans by light irradiation. Specific examples of the structural part of the body include an azobenzene structure and a stilbene structure. Among these, in terms of high reactivity, an azobenzene structure is preferred.

The polymerizable monomer (a2) having a photo-alignment property is exemplified by a structural unit represented by the following formula (I-1-1), formula (I-2-1), or formula (I-3-1). monomer.

In the above formula, the parenthetical portion with the subscript x is a portion contained in the polymer main chain, and x represents the molar fraction (x < 1) of the above structural unit contained in the polymer having photoalignment.

In the above formula, R ⁴ represents hydrogen, an arbitrary alkyl group having 1 to 20 carbon atoms which may be substituted by fluorine, and preferably an alkyl group having 1 to 5 carbon atoms which may be substituted with fluorine, and more preferably Indicates a methyl group.

In the above formula, R ⁵ represents hydrogen, any alkyl group having 1 to 20 carbon atoms which may be substituted by fluorine, or an alkoxy group having 1 to 20 carbon atoms which may be optionally substituted by fluorine, and preferably represents any The hydrogen atom may be a fluorine-substituted alkyl group having 1 to 5 carbon atoms, or an arbitrary alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, and more preferably a methyl group or a methoxy group.

In the above formula, R ⁶ represents hydrogen or a methyl group, and preferably represents a methyl group.

In the above formula, Z ¹ represents a single bond, -COO- or -OCO-, and preferably represents -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 one to four hydrogens of the phenylene group contained in the above formula may be substituted by fluorine, methyl or methoxy, but are preferably unsubstituted or substituted with a methoxy group.

Examples of the photopolymerizable polymerizable monomer which is a structural unit of the above formula (I-1-1) include the following formula (I-1-1-a) to formula (I-1-1-1). The monomer to be represented (in the following formula, R ⁷ represents hydrogen or a methyl group, R ⁸ represents an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms).

Examples of the photopolymerizable polymerizable monomer which is a structural unit of the above formula (I-2-1) include the following formula (I-2-1-a) to formula (I-2-1-1). The polymerizable monomer (in the following formula, R ⁷ represents hydrogen or a methyl group, R ⁸ represents an alkyl group having 1 to 20 carbon atoms), and the like, and among them, the formula (I-2-1-a) is preferred.

Examples of the photopolymerizable polymerizable monomer which is a structural unit of the above formula (I-3-1) include the following formula (I-3-1-a) to formula (I-3-1-i). The polymerizable monomer (in the following formula, R ⁷ represents hydrogen or a methyl group, and R ⁸ represents an alkyl group having 1 to 20 carbon atoms).

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

1-4. Other polymerizable monomers

The polymer (A) having photo-alignability may further contain another polymerizable monomer from the viewpoint of improving the optical alignment and adhesion of the thermosetting composition having photo-alignment properties of the present invention. Specific examples of the other polymerizable monomer include, for example, (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, methyl maleic acid, methyl fumaric acid. a free-radical polymerizable monomer of a carboxylic acid or a carboxylic anhydride such as itaconic acid, maleic anhydride or itaconic anhydride, such as styrene, methylstyrene, ethylstyrene, methoxystyrene, ethoxylated Styrene-based radical polymerizable monomers such as styrene, ethoxylated styrene, vinyl toluene, chloromethylstyrene, hydroxystyrene, such as hydroxymethyl (meth)acrylate, (meth)acrylic acid 2-hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylamide, (methyl) Dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, isodecyl (meth)acrylate, methyl (meth)acrylate, (methyl) Ethyl acrylate, cyclohexyl (meth)acrylate, butyl (meth)acrylate, phenyl (meth)acrylate, glyceryl mono(meth)acrylate, etc. (meth)acrylic acid Based radical polymerizable monomer, for example, a radical polymerizable monomer having a condensed ring, (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decyl and the like, such as N- phenyl maleic imide XI N-substituted maleimide-based radical polymerizable monomers such as N-cyclohexylmethyleneimine, such as polystyrene macromonomers, polymethyl methacrylate macromolecules A macromonomer such as a monomer, a radically polymerizable monomer having a heterocyclic ring containing one or both of nitrogen and oxygen, such as N-propenylmorpholine, or a condensed ring radical polymerization such as hydrazine A monomer such as 3-methacryloxypropyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3 - decyl free radicals such as propylene methoxy propyl triethoxy decane, p-styryl trimethoxy decane, p-styryl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane The base polymerizable monomer, 4-hydroxyphenyl vinyl ketone or 3-ethyl decyl-4-hydroxyphenyl vinyl ketone, is not limited thereto.

The composition containing other polymerizable monomers constitutes the above-mentioned photoalignment The mixing ratio (mol ratio) of each monomer of the polymer (A) is 1 mol with respect to the polymerizable monomer (a1) having a cyclic ether, and the polymerizable monomer (a2) having photo-alignability is 5 Moer ~ 50 moles, preferably 10 moles ~ 45 moles, more preferably 15 moles ~ 40 moles, other polymerizable monomers are 5 moles ~ 40 moles, preferably 10 moles ~ 35 moles, more preferably 15 moles to 30 moles.

The above photoalignment-producing polymer (A) can be obtained, for example, by a cyclic ether polymerizable monomer (a1), a photo-alignable polymerizable monomer (a2), and optionally other monomers in a reaction solvent (for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene) An aliphatic hydrocarbon such as pentane, hexane, heptane, octane, cyclohexane or cycloheptane, for example, an alcohol such as methanol, ethanol, 1-propanol or 2-propanol, such as dibutyl ether. Ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone and the like For example, acetate such as ethyl acetate, butyl acetate or amyl acetate, γ-butyrolactone such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol monomethyl ether, three Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, 1-methoxy-2-propanol, 3-methoxy-3-methyl It is obtained by a reaction in a polyol such as 1-butanol or the like. Further, these reaction solvents may be used singly or in combination of two or more.

The photopolymerizable polymer (A) is produced by reacting the above-mentioned polymerizable monomer (a1) having a cyclic ether and a polymerizable monomer (a2) having photo-alignment properties in the above solvent, if necessary The polymerizable monomer (a1) having a cyclic ether, the polymerizable monomer (a2) having photo-alignment properties, and other monomers are reacted in the above solvent.

The weight average molecular weight of the obtained photo-alignment polymer (A) is usually 2,000 to 200,000, preferably 5,000 to 100,000. In the above range, the flatness of the thermosetting composition having photo-alignment properties of the present invention is good.

1-5. Polyester proline (B)

The polyester phthalic acid (B) can be obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential components. At least a solvent is required for the synthesis of the polyester phthalic acid (B), and the solvent can be directly left to form a liquid or gel-like thermosetting resin composition in consideration of handling, and the like. The solvent may be removed to form a solid shape composition in consideration of handling properties and the like. Further, in the synthesis of the polyester phthalic acid, a monohydric alcohol, a styrene-maleic anhydride copolymer, and a fluorene-containing monoamine may be contained as a raw material, and from the viewpoint of molecular weight control, it is preferably contained. Monohydric alcohol.

Further, from the viewpoint of improving the optical alignment, the polyester proline (B) may further contain a compound having a photoalignment site and a hydroxyl group.

The polyester phthalic acid (B) is, for example, a compound having a structural unit represented by the following formula (3) and formula (4).

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

1-6. Tetracarboxylic dianhydride

The tetracarboxylic dianhydride used in the present invention may, for example, be an organic acid having 2 to 30 carbon atoms, and specific examples thereof include, for example, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 2 , 2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-di Phenylhydrazine tetracarboxylic dianhydride, 2,2',3,3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium 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)]hexafluoropropane dianhydride, and ethylene glycol bis(trimellitic anhydride) (trade name: TMEG-100, New Japan Physical and Chemical Co., Ltd.) An aromatic tetracarboxylic dianhydride such as cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, and the like An alicyclic tetracarboxylic dianhydride such as cyclohexane tetracarboxylic dianhydride, such as ethane tetracarboxylic dianhydride and 1,2,3,4-butane tetracarboxylic dianhydride (trade name: RIKACID BT-100 , manufactured by Nippon Chemical and Chemical Co., Ltd.), etc., such as aliphatic tetracarboxylic dianhydride.

Among these, an aromatic tetracarboxylic dianhydride which provides a resin having good transparency, and more preferably 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3, 3 is preferable. ',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene glycol bis(trimellitic anhydride) (trade name: TMEG-100, manufactured by Nippon Chemical and Chemical Co., Ltd.), especially for 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and 3,3',4,4'-diphenylfluorene Carboxylic dianhydride.

1-7. Diamine

The diamine used in the present invention may, for example, be a diamine having 2 to 30 carbon atoms, and specific examples thereof include, for example, 4,4'-diaminodiphenylphosphonium and 3,3'-diaminodiphenyl. Anthracene, 3,4'-diaminodiphenylanthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene , bis[3-(4-aminophenoxy)phenyl]indole, [4-(4-aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl]indole , [4-(3-Aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl]indole, etc. Diaminodiphenylguanidines, 2,2-bis[4- (4-Aminophenoxy)phenyl]hexafluoropropane or the like.

Among these, diaminodiphenylguanidines which provide a resin having good transparency, and more preferably 3,3'-diaminodiphenylphosphonium, and bis[4-(3-amine) are preferable. Phenyloxy)phenyl]indole, especially preferably 3,3'-diaminodiphenylphosphonium.

1-8. Polyols

The polyvalent hydroxy compound used in the present invention may be a plural having 2 to 20 carbon atoms. Specific examples of the hydroxy compound include polyethylene glycol having a molecular weight of 1,000 or less, such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, and examples thereof include propylene glycol, dipropylene glycol, tripropylene glycol, and 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-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octane Glycol, 1,8-octanediol, 3,6-octanediol, 1,2-decanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol a glycol such as 1,2-dodecanediol or 1,12-dodecanediol, such as 1,2,5-pentanetriol, 1,2,6-hexanetriol, 1,2, Triols such as 7-heptanetriol, 1,2,8-octanetriol, 1,2,9-nonanetriol, 1,2,10-nonanetriol, glycerin, trimethylolpropane, pentaerythritol, Dipentaerythritol, bisphenol A (trade name), bisphenol S (trade name), bisphenol F (trade name), diethanolamine, and triethanolamine.

Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- which are excellent in solubility in a solvent are preferred. Heptanediol and 1,8-octanediol are, in particular, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

1-9. Monohydric alcohol

Specific examples of the monohydric alcohol used in the present invention include monohydric alcohols having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and specific examples thereof include methanol, ethanol, 1-propanol, and isopropanol. , 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, diethyl Glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltol, linalool, terpineol, dimethylbenzyl methanol, 3-B 3-hydroxymethyloxetane Wait.

Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl oxetane are preferred. Considering the compatibility of the polyester phthalic acid to be mixed with the epoxy resin and the epoxy curing agent, or the coating property of the thermosetting composition of the final product on the color filter, The monohydric alcohol is more preferably benzyl alcohol.

1-10. Solvent used in the polymerization reaction

Specific examples of the solvent used in the polymerization reaction for obtaining the polyester phthalic acid (B) include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether. Diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, 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 may be used singly or in the form of a mixture of two or more. In addition, as long as the amount of the solvent used is 30% by weight or less based on the total amount of the added amount, other solvents may be used in addition to the above solvent.

1-11. Compounds having a photo-alignment site and a hydroxyl group

The polyester phthalic acid (B) may further contain a compound having a photo-alignment site and a hydroxyl group from the viewpoint of further improving the photo-alignment property of the thermosetting composition having photo-alignment properties of the present invention. Specific examples of the compound having a photo-alignment site and a hydroxyl group include, for example, methyl 4-(8-hydroxyoctyloxy)cinnamate and 4-(6-hydroxyhexyloxy). Methyl cinnamate, methyl 4-(4-hydroxybutoxy) cinnamate, methyl 4-(3-hydroxypropoxy) cinnamate, methyl 4-(2-hydroxyethoxy) cinnamate, Methyl 4-hydroxymethoxycinnamate, methyl 4-hydroxycinnamate, ethyl 4-(8-hydroxyoctyloxy)cinnamate, ethyl 4-(6-hydroxyhexyloxy)cinnamate, 4 Ethyl (4-hydroxybutoxy) cinnamate, ethyl 4-(3-hydroxypropoxy) cinnamate, ethyl 4-(2-hydroxyethoxy) cinnamate, 4-hydroxymethoxy Ethyl cinnamate, ethyl 4-hydroxyethoxycinnamate, ethyl 4-hydroxycinnamate, phenyl 4-(8-hydroxyoctyloxy) cinnamate, 4-(6-hydroxyhexyloxy) cinnamyl Phenyl phenyl ester, phenyl 4-(4-hydroxybutoxy) cinnamate, phenyl 4-(3-hydroxypropoxy) cinnamate, phenyl 4-(2-hydroxyethoxy) cinnamate, 4 - phenyl hydroxymethoxycinnamate, phenyl 4-hydroxycinnamate, biphenyl 4-(8-hydroxyoctyloxy) cinnamate, biphenyl 4-(6-hydroxyhexyloxy) cinnamate, 4-(4-hydroxybutoxy) cinnamic acid biphenyl ester, 4-(3-hydroxypropoxy) cinnamic acid biphenyl ester, 4-(2-hydroxyethoxy) cinnamic acid biphenyl ester, 4- Hydroxymethoxy cinnamic acid biphenyl ester, 4-hydroxyl Diphenyl cinnamate, 8-hydroxyoctyl cinnamate, 6-hydroxyhexyl cinnamate, 4-hydroxybutyl cinnamate, 3-hydroxypropyl cinnamate, 2-hydroxyethyl cinnamate, hydroxyl cinnamate a cinnamate such as an ester such as 4-(8-hydroxyoctyloxy)azobenzene, 4-(6-hydroxyhexyloxy)azobenzene, 4-(4-hydroxybutoxy)azobenzene, Azobenzenes such as 4-(3-hydroxypropoxy)azobenzene, 4-(2-hydroxyethoxy)azobenzene, 4-hydroxymethoxyazobenzene, 4-hydroxyazobenzene, For example 4-(8-hydroxyoctyloxy)chalcone, 4-(6-hydroxyhexyloxy)chalcone, 4-(4-hydroxybutoxy)chalcone, 4-(3-hydroxypropanol Oxygen) chalcone, 4-(2-hydroxyethoxy)chalcone, 4-hydroxymethoxychalcone, 4-hydroxychalcone, 4'-(8-hydroxyoctyloxy) Otoxone, 4'-(6-hydroxyhexyloxy)chalcone, 4'-(4-hydroxybutoxy)chalcone, 4'-(3-hydroxypropoxy)chalcone, 4' -(2-hydroxyethoxy)chalcone, 4'-hydroxyl Chalcone such as methoxychalcone or 4'-hydroxychalcone, such as 7-(8-hydroxyoctyloxy)coumarin, 7-(6-hydroxyhexyloxy)coumarin, 7 -(4-hydroxybutoxy)coumarin, 7-(3-hydroxypropoxy)coumarin, 7-(2-hydroxyethoxy)coumarin, 7-hydroxymethoxycoumarin , 7-hydroxycoumarin, 6-hydroxyoctyl coumarin, 6-hydroxyhexyl coumarin, 6-(4-hydroxybutoxy)coumarin, 6-(3-hydroxypropoxyl The coumarins such as coumarin, 6-(2-hydroxyethoxy)coumarin, 6-hydroxymethoxycoumarin, and 6-hydroxycoumarin are not limited thereto.

1-12. Method for producing polyester proline

The polyester phthalic acid used in the present invention is produced by reacting tetracarboxylic dianhydride X-mole, diamine Y-mole, and polyvalent hydroxy compound Z-mol in the above solvent. In this case, X, Y, and Z are preferably set to a ratio at which the relationship between the following formulas (1) and (2) is established. When it is in this range, since the solubility of the polyester valine acid in a solvent is high, the coating property of a composition improves, and it turns out that the cured film which is excellent in flatness is acquired.

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, more preferably 1.3 ≦ Z / Y ≦ 7.0. Further, the relationship of the formula (2) is preferably 0.5 ≦ (Y + Z) / X ≦ 0.9, and further preferably 0.7 ≦ (Y + Z) / X ≦ 0.8.

In the case where the polyester glutamic acid used in the present invention has an acid anhydride group at the molecular terminal, the above monohydric alcohol may be added as needed to carry out the reaction. By adding monohydric alcohol The compatibility of the polyester phthalic acid obtained by the reaction with the epoxy resin and the epoxy curing agent is improved, and the coatability of the thermosetting resin composition of the present invention containing the above is improved.

In addition, the above-mentioned monoamine-containing amine has an acid anhydride group at the molecular terminal. In the case of the ester proline reaction, the acid resistance of the obtained coating film is improved. Further, the monohydric alcohol and the fluorene-containing monoamine may be simultaneously reacted with the polyester proline.

1-13. Monoterpenoids containing hydrazine

Specific examples of the monoamine-containing amine used in the present invention include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-aminopropylmethyldimethoxy. Baseline, 3-aminopropylmethyldiethoxydecane, 4-aminobutyltrimethoxydecane, 4-aminobutyltriethoxydecane, 4-aminobutylmethyldiethoxylate Decane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, p-aminophenylmethyldimethoxydecane, p-aminophenylmethyldiethoxydecane, Aminophenyltrimethoxydecane, m-aminophenylmethyldiethoxydecane, and the like.

Among these, 3-aminopropyltriethyl 3-B which is excellent in acid resistance of the coating film is preferred. Oxydecane, and p-aminophenyltrimethoxydecane, more preferably 3-aminopropyltriethoxydecane.

If the reaction solvent is relative to tetracarboxylic dianhydride, diamine and polyhydric hydroxy compound When 100 parts by weight or more of the total is used in an amount of 100 parts by weight or more, the reaction proceeds smoothly, which is preferable. The reaction is preferably carried out at 40 ° C to 200 ° C for 0.2 to 20 hours. In the case of reacting a ruthenium-containing monoamine, it is preferred that after the reaction of the tetracarboxylic dianhydride with the diamine and the polyvalent hydroxy compound is completed, the reaction liquid is cooled to 40 ° C or lower, and then added. The monoamine is added and reacted at 10 ° C to 40 ° C for 0.1 hour to 6 hours. Alternatively, the monohydric alcohol can be added at any point in the reaction.

The order of addition of the reaction raw materials to the reaction system is not particularly limited. That is, any of the following methods can be used: (1) adding a tetracarboxylic dianhydride to a diamine and a polyvalent hydroxy compound simultaneously to a reaction solvent; (2) dissolving the diamine and the polyvalent hydroxy compound in a reaction solvent, Adding tetracarboxylic dianhydride; (3) adding a diamine to the reaction product after pre-reacting the tetracarboxylic dianhydride with the polyvalent hydroxy compound; or (4) pre-reacting the tetracarboxylic dianhydride with the diamine, A polyvalent hydroxy compound or the like is added to the reaction product.

Further, the polyester phthalic acid used in the present invention may be subjected to a synthesis reaction by adding a compound having three or more acid anhydride groups. Specific examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. With respect to the ratio of the components constituting the styrene-maleic anhydride copolymer, the molar ratio of styrene/maleic anhydride is 0.5 to 4, preferably 1 to 3, and more preferably 0.8. ~1.2.

Specific examples of the styrene-maleic anhydride copolymer include commercially available products such as SMA3000P, SMA2000P, and SMA1000P manufactured by Kawasaki Crude Oil Co., Ltd. Among them, SMA1000P which is excellent in heat resistance and alkali resistance is particularly preferable.

The polyester phthalic acid synthesized in this manner contains a structural unit containing the above formula (3) and formula (4), and the terminal is preferably derived from a tetracarboxylic dianhydride, a diamine or a plural as a raw material. An acid anhydride group, an amine group or a hydroxyl group of a hydroxy compound, or an additive other than these compounds constitutes a terminal. In the general formula (3) and the general formula (4), R ¹ is a tetracarboxylic dianhydride residue, and preferably an organic group having 2 to 30 carbon atoms. R ² is a diamine residue, preferably an organic group having 2 to 30 carbon atoms. R ³ is a residue of a polyhydric hydroxy compound, preferably an organic group having a carbon number of 2 to 20.

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

1-14. Other ingredients

The thermosetting composition having photo-alignment properties of the present invention may contain other components than those described above as needed within the scope of the object of the present invention. Examples of such other components include an epoxy curing agent, a coupling agent, a surfactant, an antioxidant, a solvent, and the like.

1-14-1. Epoxy hardener

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. The epoxy curing agent is an acid anhydride-based curing agent, a polyamine-based curing agent, a polyphenol-based curing agent, and a catalyst-type curing agent, and is preferably an acid anhydride-based curing agent in terms of coloring and heat resistance.

Adding an epoxy hardener for the purpose of improving flatness and chemical resistance In the case, the ratio of the epoxy resin to the epoxy curing agent is from 1 part by weight to 13 parts by weight based on 100 parts by weight of the epoxy resin and the epoxy curing agent. It is preferably 5 parts by weight to 13 parts by weight, more preferably 8 parts by weight to 11 parts by weight. More specifically, the amount of the epoxy curing agent to be added is preferably such that the carboxylic anhydride group or the carboxyl group in the epoxy curing agent is 0.1 to 1.5 equivalents based on the epoxy group. At this time, the carboxylic anhydride group is calculated by generating two carboxyl groups. If the carboxylic anhydride group or carboxyl group is 0.15 times When it is added in an equivalent amount of -0.8 times equivalent, the flatness and chemical resistance are further improved, and thus it is further preferable.

Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic anhydride, aromatic polycarboxylic anhydride, and styrene-maleic anhydride copolymer.

Specific examples of the aliphatic dicarboxylic acid anhydride include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride. . Specific examples of the aromatic polycarboxylic acid anhydride include phthalic anhydride and trimellitic anhydride. Among these, in terms of balance of heat resistance and solubility in a solvent, trimellitic anhydride or hexahydrotrimellitic anhydride is particularly preferable.

1-14-2. Coupler

The thermosetting composition having photo-alignability of the present invention may contain a coupling agent from the viewpoint of improving the adhesion to the substrate. When the content of the coupling agent is 1% by weight or more based on the total amount of the thermosetting composition, it is preferable from the viewpoint of improving heat resistance and solvent resistance, and more preferably 1 weight in consideration of balance with other characteristics. %~20% by weight.

As the coupling agent, a decane-based, aluminum-based or titanate-based compound can be used. Specific examples thereof include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxy A decane type such as a decane (trade name: S510, manufactured by JNC Co., Ltd.), an aluminum system such as acetonitrile alkoxydiisopropyl aluminum or a bis(dioctylphosphite) tetraisopropyl titanate Titanate system. Among them, preferred is decane, 3-glycidoxypropyltrimethoxy Since decane has a large effect of improving the adhesion, it is particularly preferable.

1-14-3. Surfactant

The thermosetting composition having photo-alignability of the present invention may contain a surfactant in view of improving wettability, leveling, or coating property with the base substrate. From this point of view, the content of the surfactant is preferably from 0.005% by weight to 10% by weight, more preferably from 0.01% by weight to 8% by weight, still more preferably 0.01% by weight, based on the total amount of the thermosetting composition. ~5 wt%.

Such surfactants can be listed as: POLYFLOW No. 45, POLYFLOW KL-245, POLYFLOW No.75, POLYFLOW No.90, POLYFLOW No.95 (all of which are trade names, manufactured by Kyoei Chemical Industry Co., Ltd.), Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166 , Disperbyk 170, Disperbyk 180, Disperbyk 181, Disperbyk 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346 (all of which are trade names, manufactured by BYK-Chemie Japan Co., Ltd.), KP -341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all of which are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (above For the trade name, manufactured by SEIMI CHEMICAL Co., Ltd., Ftergent 222F, Ftergent 251, FTX-218 (all of which are trade names, manufactured by NEOS), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all of which are trade names, manufactured by Mitsubishi Materials Co., Ltd.), Megafac F-171, Megafac F-177, Megafac F-475, Megafac F-477 (all of which are trade names, manufactured by DIC Corporation), Denon 1826M, PC-6862, PC-7062C, and Elimina 208M (all of which are trade names, Maru Ling Oil Chemical Industry Co., Ltd.), fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonic acid Salt, diglycerol tetrakis(fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, poly Oxyethylene vinyl ether, polyoxyethylene lauryl ether, polyoxyethylene ether ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauric acid Ester, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbose Alcoholic anhydride oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, poly Ethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, or alkyl diphenyl ether disulfonate, among others, preferably For PC-7062C.

1-14-4. Antioxidants

From the viewpoint of weather resistance, the thermosetting composition having photo-alignment properties of the present invention may contain an antioxidant. From this point of view, the content of the antioxidant is preferably from 0.01% by weight to 10% by weight, more preferably from 0.05% by weight to 8% by weight, even more preferably 0.1% by weight, based on the total amount of the thermosetting composition. 5 wt%. Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds. More preferably, the antioxidant is a hindered phenol system.

Specific examples of the antioxidant include, for example, Irganox FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox295 (trade names, Japanese BASF (BASF Japan )), Adekastab AO-20, Adekastab AO-30, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80 (all of which are trade names, ADEKA shares) Co., Ltd. manufactures) and other hindered phenolic systems. Among them, Adekastab AO-60 is more preferable in terms of transparency, heat resistance, and crack resistance.

1-14-5. Solvent

The thermosetting composition having photo-alignment properties of the present invention is mainly used in the form of a solution dissolved in a solvent. The solvent to be used in this case is not particularly limited as long as it can dissolve the component (A) and the component (B), and other additives as necessary.

Specific examples of the solvent include, for example, methanol, ethanol, isopropanol, and 1-propanol. Butanol, 2-methyl-1-butanol, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl acesulfame acetate, ethyl acetate acesulfame, diethylene Alcohol, 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, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, 2-hydroxyl Ethyl 2-methylpropionate, ethyl ethoxyacetate, Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3- Methyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-di Methyl acetamide, and N-methyl-2-pyrrolidone.

These solvents may 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, 3-methyl Methyl oxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate can be applied to the production line of protective layer of color filter. The film forming property is good and the safety is high, so that it is more preferable.

1-15. Preservation of thermosetting composition having photoalignment

When the thermosetting composition having photo-alignment properties of the present invention is stored in a temperature range of -30 ° C to 25 ° C, the composition has a good stability over time, which is preferable. If the storage temperature is -20 ° C to 10 ° C, there is no precipitate, so it is more preferable.

1-16. Adjustment of coating liquid

The thermosetting composition having photo-alignability of the present invention can be further diluted with the above solvent to adjust the coating liquid depending on the film thickness of the cured film to be formed.

2. The cured film of the present invention

The thermosetting composition having photo-alignment property of the present invention can be obtained by mixing a polymer having photo-alignment property and a polyester valine acid, and optionally adding a solvent or epoxy hardening according to a target characteristic. The agent, the coupling agent and the surfactant are uniformly mixed and dissolved.

A thermosetting composition having photo-alignability prepared in the above manner (after being dissolved in a solvent in a solvent-free solid state) is applied to glass or polyethylene terephthalate (polyethylene). A surface of a substrate such as terephthalate (PET) or triacetyl cellulose (TAC) can be removed by, for example, heating to form a coating film. The coating of the thermosetting resin composition on the surface of the substrate can be carried out by a spin coating method, a roll coating method, a dipping method, and a slit coating method. A coating film is formed by a previously known method such as a slit coat method. Next, the coating film is heated (pre-bake) by a hot plate, an oven, or the like. The heating conditions vary depending on the type of each component and the blending ratio, and are usually 70 ° C to 120 ° C, 5 minutes to 15 minutes for the oven, and 1 minute to 5 minutes for the heating plate. Thereafter, in order to cure the coating film, at 180 ° C to 250 ° C, preferably 200 ° C to 250 ° C, if it is an oven, heat treatment is performed for 30 minutes to 90 minutes, and if it is a heating plate, it is performed for 5 minutes to 30 minutes. The heat treatment is performed, whereby a cured film can be obtained.

When the cured film obtained in this way is heated, 1) the polymerization of polyester proline The proline is partially dehydrated and cyclized to form a quinone bond, 2) the carboxylic acid of the polyester phthalic acid is reacted with a cyclic ether of a photo-alignment polymer to be polymerized, and 3) is photo-aligned. Since the polymer is hardened and highly polymerized, it is very strong, and is excellent in transparency, heat resistance, solvent resistance, flatness, adhesion, and sputtering resistance. Therefore, the cured film of the present invention is effective as a protective film for a color filter, and a color filter can be used to manufacture a liquid crystal display element or a solid-state image sensor.

Further, the cured film of the present invention is effective 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. Further, the cured film of the present invention is also effective as a protective film for a light-emitting diode (LED) light-emitting body.

Further, an optical film obtained by the liquid crystal alignment film obtained from the photohardenable thermosetting composition of the present invention can be used. The optical film is preferably an optical compensation film for realizing an improvement in contrast of a liquid crystal display element or an increase in a viewing angle range, a retardation film such as a patterned retardation film, or the like.

The above optical film generally includes a substrate, a liquid crystal alignment film, and an optically anisotropic layer. The optically anisotropic layer can be applied to the liquid crystal alignment film formed on the substrate by applying a polymerizable liquid crystal compound and other polymerizable liquid crystal composition of various components added as needed to form a liquid crystal compound. The molecules are obtained by polymerizing them after alignment. The optically anisotropic layer exhibits optical anisotropy exhibited by molecular alignment of a liquid crystalline compound. Therefore, the optical film can be preferably used as, for example, a patterned phase difference plate. Such an optical film can be preferably used for various optical devices such as liquid crystal display elements.

[Examples]

Hereinafter, the present invention will be further illustrated by the examples, but the present invention is not limited to the examples.

[Synthesis Example 1] Synthesis of photo-alignment polymer (A1)

2-{4-[(1E)-3-methoxy-3-oxo-l-propene-acrylic acid was added to a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet. 1,3-yl]phenoxy}ethyl=2-methyl ester 135.00 g, glycidyl methacrylate 15.00 g, 2,2'-azobis(2,4-dimethyl group as a polymerization initiator 15.00 g of valeronitrile and 50.00 g of cyclopentanone as a reaction solvent were heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization. The reaction liquid was cooled to 30 ° C or lower, whereby a 25 wt% solution of the photo-alignment polymer (A1) was obtained. The solution had a weight average molecular weight of 6,400 (in terms of polystyrene) as measured by gel permeation chromatography (GPC).

Further, in the present invention, the weight average molecular weight is a column oven CTD-20A, a detector RID-10A, a system controller CBM-20A, a solution sending pump LC-20AD. The automatic sampler (autosampler) SIL-10AF (all of which are trade names, manufactured by Shimadzu Corporation) was measured. In addition, the standard polystyrene is a polystyrene having a weight average molecular weight of 645 to 132,900 (for example, VARIAN Polystyrene Calibration Kit PL2010-0102), and the column is used. PLgel MIXED-D (VARIAN) was measured using tetrahydrofuran (THF) as a mobile phase at a column temperature of 35 ° C and a flow rate of 1 mL/min.

[Synthesis Example 2] Synthesis of photo-alignment polymer (A2)

2-{4-[(1E)-3-methoxy-3-oxo-l-propene-acrylic acid was added to a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet. 120.00 g of 1-yl]phenoxy}ethyl=2-methyl ester, 30.00 g of glycidyl methacrylate, 2,2'-azobis(2,4-dimethylpentene) as a polymerization initiator Nitrile) 15.00g, as 50.00 g of cyclopentanone in a reaction solvent was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization. The reaction liquid was cooled to 30 ° C or lower, whereby a 25 wt% solution of the photo-alignment polymer (A2) was obtained. The weight average molecular weight of this solution measured by GPC was 7,300 (in terms of polystyrene).

[Synthesis Example 3] Synthesis of photo-alignment polymer (A3)

2-{4-[(1E)-3-methoxy-3-oxo-l-propene-acrylic acid was added to a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet. 1-0.00]phenoxy}ethyl=2-methyl ester 100.00 g, glycidyl methacrylate 20.00 g, 2-hydroxyethyl methacrylate 40.00 g, 3-methylpropenyloxypropyltrimethoxy 40.00 g of decane, 20.00 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator, and 66.60 g of cyclopentanone as a reaction solvent, at a polymerization temperature of 90 ° C The polymerization was carried out by heating for 2 hours. The reaction liquid was cooled to 30 ° C or lower, whereby a 25 wt% solution of the photo-alignment polymer (A2) was obtained. The weight average molecular weight of this solution measured by GPC was 8,100 (in terms of polystyrene).

[Synthesis Example 4] Synthesis of photo-alignment polymer (A4)

2-{4-[(1E)-3-methoxy-3-oxo-l-propene-acrylic acid was added to a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet. 100.00 g of 1-yl]phenoxy}ethyl=2-methyl ester, 20.00 g of glycidyl methacrylate, 80.00 g of 2-hydroxyethyl methacrylate, 2,2'-couple as a polymerization initiator 20.00 g of nitrogen bis(2,4-dimethylvaleronitrile) and 66.60 g of cyclopentanone as a reaction solvent were heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization. The reaction liquid was cooled to 30 ° C or lower, whereby a 25 wt% solution of the photo-alignment polymer (A2) was obtained. The weight average molecular weight of this solution measured by GPC was 7,100 (in terms of polystyrene).

[Synthesis Example 5] Synthesis of photo-alignment polymer (A5)

2-{4-[(1E)-3-methoxy-3-oxo-l-propene-acrylic acid was added to a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet. 100.00 g of 1-yl]phenoxy}ethyl=2-methyl ester, 20.00 g of glycidyl methacrylate, 80.00 g of 3-methylpropenyloxypropyltrimethoxydecane, 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 heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization. The reaction liquid was cooled to 30 ° C or lower, whereby a 25 wt% solution of the photo-alignment polymer (A2) was obtained. The weight average molecular weight of this solution measured by GPC was 6,800 (in terms of polystyrene).

[Synthesis Example 6] Synthesis of polyester proline (B1)

The dehydrated purified methyl 3-methoxypropionate (hereinafter abbreviated as "MMP") was added to a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen inlet, and 446.96 g, 1,4- 31.93 g of butanediol, 25.54 g of benzyl alcohol, 183.20 g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA"), and stirred at 130 ° C under a stream of dry nitrogen gas. 3 hours. Thereafter, the reaction liquid was cooled to 25 ° C, and 29.33 g of 3,3'-diaminodiphenyl hydrazine (hereinafter abbreviated as "DDS") and 183.04 g of MMP were charged, and the mixture was stirred at 20 ° C to 30 ° C for 2 hours. The mixture was stirred at 115 ° C for 1 hour and cooled to 30 ° C or lower, whereby a 30 wt% solution of pale yellow transparent polyester glutamic acid (B1) was obtained. The weight average molecular weight of this solution measured by GPC was 4,200 (in terms of polystyrene).

[Synthesis Example 7] Synthesis of polyester proline (B2)

The dehydrated and purified propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA") 504.00 g and ODPA 47.68 g were sequentially added to a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen gas inlet. SMA1000P (trade name; styrene-maleic anhydride copolymer, manufactured by Sichuan Crude Oil Co., Ltd.) 144.97 g, benzyl alcohol 55.40 g, 1,4-butanediol 9.23 g, dehydrated purified diethylene glycol 96.32 g of methyl ethyl ether (hereinafter abbreviated as "EDM") was stirred at 130 ° C for 3 hours under a stream of a dry nitrogen gas. Thereafter, the reaction liquid was cooled to 25 ° C, and 12.72 g of DDS and 29.68 g of EDM were charged, and the mixture was stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 115 ° C for 1 hour, and cooled to 30 ° C or lower. A 30% by weight solution of yellow transparent polyester glutamic acid (B2). The weight average molecular weight of this solution measured by GPC was 21,000 (in terms of polystyrene).

[Synthesis Example 8] Synthesis of polyester proline (B3)

446.96 g of MMP, 31.93 g of methyl 4-(hydroxyethoxy)cinnamate, and 25.54 g of 1,4-butanediol were added to a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen inlet. ODPA 183.20 g was stirred at 130 ° C for 3 hours under a stream of dry nitrogen. Thereafter, the reaction liquid was cooled to 25° C., and 29.33 g of DDS and 18.04 g of MMP were charged, and the mixture was stirred at 20° C. to 30° C. for 2 hours, and then stirred at 115° C. for 1 hour, and cooled to 30° C. or lower. A 30% by weight solution of yellow transparent polyester glutamic acid (B3). The weight average molecular weight of this solution measured by GPC was 3,200 (in terms of polystyrene).

[Example 1] Production of thermosetting composition

A 25% by weight solution of the photo-alignment-producing polymer (A1) obtained in Synthesis Example 1 (hereinafter referred to as polymer (A1)), and a polyester proline (B1) obtained in Synthesis Example 3 were used. 30% by weight solution (hereinafter referred to as polymer (B1)), trimellitic anhydride (hereinafter referred to as TMA) as an epoxy curing agent, S510 (trade name, manufactured by JNC Co., Ltd.) as a coupling agent, as an interface PC-7062C (trade name, manufactured by Maruishi Oil Chemical Co., Ltd.) of the active agent, and cyclopentanone as a solvent were mixed and dissolved in the weight of the following Table 1, and filtered by a membrane filter (0.2 μm). A thermosetting composition is obtained. The composition of the obtained thermosetting composition is shown in Table 2.

[Example 2 to Example 11 and Reference Example 1] Production of thermosetting composition

The mixture of the compositions shown in Table 2 was mixed and dissolved in the same manner, and the thermosetting compositions of Examples 2 to 11 and Reference Example 1 were obtained. In addition, the numbers in parentheses in Table 2 indicate the parts by weight, and A1 to A5 are respectively a 25 wt% solution of the photo-alignment polymer (A1) to the polymer (A5), and B1 to B3 are respectively polyester decylamine. 30% by weight solution of acid (B1) ~ polyester glutamic acid (B3).

[Comparative Example 1 to Comparative Example 2] Production of Thermosetting Composition

The composition shown in Table 3 was mixed and dissolved in the same manner as in Example 1 to Example 11, and the thermosetting compositions of Comparative Examples 1 to 2 were obtained.

[Evaluation method]

1) Formation of hardened film

The thermosetting composition was spin-coated on a glass substrate and a color filter substrate at an arbitrary number of revolutions of 400 rpm to 1,200 rpm for 10 seconds, and then prebaked on a hot plate at 80 ° C for 3 minutes to form a coating film. Thereafter, the film was heated at 230 ° C for 30 minutes in an oven to cure the coating film to obtain a cured film having a film thickness of 0.5 μm. After returning the substrate taken out from the oven to room temperature, the film thickness of the obtained cured film was measured. The measurement of the film thickness was carried out using a stylus type film thickness meter P-15 manufactured by KLA-Tencor Japan Co., Ltd., and the average value of the measurement at three sites was defined as the film thickness of the cured film.

2) Flatness

The step of the surface of the cured film of the cured film-attached color filter substrate obtained in the above 1) was measured using a stylus type film thickness meter P-15 manufactured by KLA-Tencor Japan Co., Ltd. The maximum value of the step (hereinafter simply referred to as the maximum step) between the R, G, and B pixels including the black matrix is set to a value of flatness. Further, the color filter substrate used was a pigment dispersion color filter (hereinafter abbreviated as CF) using a resin black matrix having a maximum step difference of about 1.1 μm.

3) Transparency

The transmittance of the substrate on which the cured film obtained in the above 1) was formed at a wavelength of 400 nm was measured using a TC-1800 manufactured by Tokyo Electro-Color Co., Ltd. as a reference using a glass substrate on which no cured film was formed. When the transmittance was 95 T% or more, it was judged to be good (G: Good), and when the transmittance was less than 95 T%, it was judged to be bad (NG: No Good).

4) Heat resistance

The substrate on which the cured film obtained in the above 1) was formed was heated in an oven at 230 ° C for 1 hour, and the light transmittance was measured in the same manner as in the above 3), and further measured in the same manner as in the above 1) before and after the heating. The film thickness was calculated according to the following formula.

(film thickness after heating/film thickness before heating) × 100 (%)

When the rate of change in film thickness was less than -5%, it was judged to be good (G: Good), and when the rate of change in film thickness after heating was -5% or more, it was judged to be bad (NG: No Good).

5) Solvent resistance

The substrate on which the cured film obtained in the above 1) was formed was immersed in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) at 25 ° C for 30 minutes, and the change in film thickness was measured. The film thickness was measured in the same manner as in the above 1) before and after the immersion, and was calculated according to 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 to be good (G: Good), and when it was more than 5% due to swelling or less than -5% due to dissolution, it was judged to be bad (NG: No Good).

6) Light alignment

The surface of the cured film obtained in the above 1) was irradiated with linearly polarized ultraviolet rays having a wavelength of around 313 nm at 500 mJ/cm ² from a direction of 90° with respect to the coated surface. A phase difference material solution containing a liquid crystal monomer was applied onto the substrate by a spin coater, and then prebaked on a hot plate at 80 ° C for 1 minute to form a film having a film thickness of 0.5 μm. The substrate was exposed to light at an exposure amount of 1000 mJ/cm ² in terms of 365 nm. When the polarizing UV was 313 nm and the exposure amount was 500 mJ/cm ² , the film which was aligned was judged to be good (G: Good), and the film which was not aligned was judged to be defective (NG: No Good).

The results obtained by the above evaluation methods for the thermosetting compositions of Examples 1 to 11 and Reference Example 1 are shown in Table 4.

The results obtained by the above evaluation methods for the thermosetting compositions of Comparative Examples 1 to 2 are shown in Table 4.

[Industrial availability]

The thermosetting composition having photo-alignment properties obtained by the present invention is very useful as a material of a liquid crystal alignment layer of an optically anisotropic film or a liquid crystal display element, and further, as a thin film transistor (TFT) type liquid crystal display element, organic EL A material of a cured film such as a protective film or an insulating film in various displays such as a device is preferable, and particularly used as a retardation film, a patterned phase difference plate for a 3D display, an interlayer insulating film of a TFT liquid crystal element, and a color filter. A material such as a protective layer or an insulating film of an organic EL element is also preferable.

Claims (21)

A thermosetting composition having photo-alignment properties, which comprises a photo-alignment polymer (A) and a polyester proline (B). The photohardenable thermosetting composition according to the first aspect of the invention, wherein the photo-alignable polymer (A) according to claim 1 is a polymerizable property having a cyclic ether. A copolymer of the monomer (a1) and the photopolymerizable polymerizable monomer (a2). The thermosetting composition having photo-alignment property according to claim 2, wherein the polymerizable monomer (a1) having a cyclic ether as described in claim 2 is selected from glycidol acrylate. Ester, glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, (2-ethyl-2-oxetanyl)methyl acrylate and methacrylic acid (2-ethyl-2-oxo) More than one of the groups consisting of heterocyclic butyl)methyl esters. The photohardenable thermosetting composition according to claim 2, wherein the photoalignment site of the photo-alignable polymerizable monomer (a2) according to claim 2 is A functional group of a structure in which photodimerization or photoisomerization occurs. The photohardenable thermosetting composition according to claim 2, wherein the photoalignment site of the photo-alignable polymerizable monomer (a2) according to claim 2 is Cinnamon base. A thermosetting group having photo-alignment as described in claim 1 The polyester phthalic acid (B) as described in claim 1 is a polyester guanamine obtained by reacting a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound as essential components. acid. The thermosetting composition having photo-alignment property according to claim 1, wherein the polyester phthalic acid (B) according to claim 1 is a tetracarboxylic dianhydride or a diamine. A polyester phthalic acid obtained by reacting a polyvalent hydroxy compound and a monohydric alcohol as an essential component. The photohardenable thermosetting composition according to claim 7, wherein the monohydric alcohol is isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3- Ethyl-3-hydroxymethyloxetane. The thermosetting composition having photo-alignment properties according to any one of claims 1 to 8, wherein the polyester proline (B) according to claim 1 is such that The X-molar tetracarboxylic dianhydride, the Y-mole diamine, and the Z-mole polyvalent hydroxy compound are obtained by reacting a ratio at which the relationship of the following formula (1) and formula (2) is established, 0.2 ≦ Z / Y≦8.0...(1) 0.2≦(Y+Z)/X≦1.5...(2). The thermosetting composition having photo-alignment property according to any one of claims 1 to 8, wherein the polyester proline (B) according to claim 1 has a compound of a structural unit represented by the following formula (3) and formula (4), (wherein R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a residue of a polyvalent hydroxy compound). The photohardenable thermosetting composition according to any one of claims 6 to 8, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3, 3', 4, 4'- Phenylhydrazine tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-(bis(3,4-dicarboxyphenyl))hexafluoropropanoic acid One or more compounds of anhydride and ethylene glycol bis(trimellitic anhydride). The photohardenable thermosetting composition according to any one of claims 6 to 8, wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenyl fluorene and double One or more compounds of (4-(3-aminophenoxy)phenyl)anthracene and bis(4-(4-aminophenoxy)phenyl)anthracene. The photohardenable thermosetting composition according to any one of claims 6 to 8, wherein the polyhydric hydroxy compound is selected from the group consisting of One or more compounds selected from the group consisting of alcohol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. The thermosetting composition having photo-alignment properties according to any one of claims 1 to 8, wherein the weight of the polyester proline (B) according to claim 1 is The average molecular weight is from 1,000 to 500,000. The photohardenable thermosetting composition according to any one of claims 1 to 8, wherein the photo-alignment polymer (A) according to claim 1 The weight average molecular weight is 2,000 to 200,000. A cured film obtained by heating a thermosetting composition having photo-alignment properties according to any one of claims 1 to 15. A color filter using the cured film as described in claim 16 of the patent application as a protective film. A liquid crystal display element using the color filter described in claim 17 of the patent application. A solid-state image pickup element using the color filter described in claim 17 of the patent application. A patterned phase difference plate which is formed of a thermosetting composition having photo-alignment properties according to any one of claims 1 to 15. An optical device comprising a phase difference plate obtained by using the photo-alignment thermosetting composition according to any one of claims 1 to 15.