TWI797295B - Thermosetting compositions, cured film and color filter - Google Patents

Abstract

在式（1）中，R¹ 為二價有機基。The present invention relates to a thermosetting composition comprising a polymer (A), a compound (B) having two or more epoxy groups, and a solvent (C). The polymer (A) is derived from A compound (a) having more than one acid anhydride group (-CO-O-CO-), and a compound (b) having an amino group and a hydroxyl group in the same molecule represented by the following formula (1). With the thermosetting composition of the present invention, it is possible to form a cured film in which the properties of heat resistance, transparency, flatness, and substrate adhesion are highly compatible. The cured film can be suitably used in electronic components.

In formula (1), R ¹ is a divalent organic group.

Description

Thermosetting composition, cured film and color filter

The present invention relates to a kind of insulating material that can be used to form the passivation film in semiconductor device, buffer coating film, interlayer insulating film, planarization film in electronic parts, interlayer insulating film in liquid crystal display element, color filter (color filter) A thermosetting composition such as a protective film for filter), a transparent film formed of the thermosetting composition, and an electronic component having the film.

In the manufacturing steps of elements such as liquid crystal display elements, a step of forming an organic thin film having various functions is included. For example, film formation/patterning/heat treatment steps of black matrix resists, film formation/patterning/heat treatment steps of color filter resists, film formation/patterning/heat treatment steps of color filter protective films, Indium tin oxide (Indium Tin Oxide, ITO) film formation process, photoresist for ITO patterning film formation / patterning / wet etching / resist stripping process, ITO annealing process, alignment film Film formation/heat treatment/rubbing (polarized light exposure) steps, etc. In these various steps, the element may come into contact with various chemicals such as organic solvents, acids, and alkali solutions, and when electrodes are formed by sputtering, the surface may be partially exposed to high temperature. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and deterioration of the surface of various elements. These protective films are required to have various properties that can withstand various treatments in the manufacturing steps as described above. Specifically, chemical resistance such as heat resistance, solvent resistance/acid resistance/alkali resistance, water resistance, adhesion to base substrates such as glass, transparency, scratch resistance, coatability, flatness, Light fastness etc. In particular, heat resistance required for display element components, specifically, reduction of outgassing during heat treatment, is being emphasized as the required characteristics of reliability required for display elements increase. The reason for this is that when forming various organic thin films as described above, the cross-linking reaction/densification of the thin film by heat treatment always proceeds, and therefore heat is applied to the element many times in the penetrating step. Therefore, if a protective film that generates a large amount of outgassing is used, the outgassing from the lower layer will affect the thin film formation of the upper layer, resulting in a decrease in display quality and a decrease in reliability.

Hitherto, in order to provide a protective film having high heat resistance, it has been proposed to use a polyimide material as the protective film (Patent Document 1). In addition, a protective film using a silicone material characterized by high heat resistance and transparency has also been proposed (Patent Document 2, Patent Document 3). Alternatively, protective films using epoxy resins and melamine resins, or protective films using acrylic resins or polyester resins have been proposed (Patent Document 4, Patent Document 5, and Patent Document 6).

However, in the protective film using polyimide material, in order to prepare polyimide or polyimide precursor (polyamic acid) solution, it is necessary to use N-methylpyrrolidone or γ-butyrolactone, etc. A so-called polyimide solvent with strong solvency has a problem of dissolving the organic thin film of the substrate. Especially when using it as a protective film for color filters, the said problem becomes a big problem. In addition, in polyimide, since the edge of the light absorption band extends to the visible light region due to charge transfer interaction (charge transfer (CT) interaction), there is also a problem of coloring. On the other hand, in the case of using a silicone material (sol-gel material), heat resistance and transparency are sufficient, but since the temperature required for the completion of the reaction of the silanol group is also 300°C or higher, it may cause the substrate The deterioration of the organic thin film or the problem of cracks (cracks) in the thin film due to curing shrinkage during thermal curing. In addition, there is also the difficulty that the -Si-O-Si- bond of the siloxane material is easily hydrolyzed by an alkaline solution. In addition, when materials such as epoxy resin and melamine resin are used, although there is no problem in the use of a solvent or heat treatment temperature, heat resistance is not sufficient, and problems of yellowing also occur. In the case of using an acrylic material or a polyester resin, the heat resistance of the acrylic part/polyester part as the basic skeleton is not sufficient, and a problem of outgassing occurs. In particular, polyester materials also have the problem that some raw materials remain in an unreacted state. Although they can be removed in a purification step, the cost increases. Therefore, it is required to reduce outgassing without a purification step.

On the other hand, a protective film using polyester amide having both polyester and amide structures is also disclosed (Patent Document 7). In such a case, the effect of reducing outgassing is limited due to the non-uniform presence of ester moieties and amide moieties in the polymer and the remaining raw material alcohol components.

In view of these circumstances, there is a demand for a material that combines high heat resistance (low outgassing) and other properties, particularly flatness, transparency, and adhesion to a substrate. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 62-163016 [Patent Document 2] Japanese Patent Laid-Open No. 62-242918 [Patent Document 3] Japanese Patent Laid-Open No. Hei 7-331178 [Patent Document 4] Japanese Patent Laid-Open No. 63-131103 [Patent Document 5] Japanese Patent Laid-Open No. 8-50289 [Patent Document 6] Japanese Patent Laid-Open No. 2013-253263 [Patent Document 7] Japanese Patent Laid-Open No. 2008-156546

[Problem to be Solved by the Invention]

The problem of the present invention is to provide a thermosetting composition that provides a cured film excellent in heat resistance (low outgassing), flatness, transparency, and adhesion, and a cured film formed of the thermosetting composition, and further provide An electronic component having the cured film. [Means to solve the problem]

The inventors of the present invention have made diligent research to solve the above problems, and as a result, have completed the present invention by using a thermosetting composition comprising a compound having two or more acid anhydride groups and a compound having two or more acid anhydride groups in the same molecule A copolymer formed by the thermal reaction of a compound having an amino group and a hydroxyl group, a compound having two or more epoxy groups, and a solvent that can dissolve these compounds. The present invention includes the following configurations.

在式（1）中，R¹ 為二價有機基。[1] A thermosetting composition comprising a polymer (A) derived from a compound (B) having two or more epoxy groups, and a solvent (C) The product of the compound (a) with an acid anhydride group and the compound (b) having an amino group and a hydroxyl group in the same molecule represented by the following formula (1):

In formula (1), R ¹ is a divalent organic group.

[2] The thermosetting composition according to [1], wherein the compound (a) having two or more acid anhydride groups is selected from the group consisting of aromatic acid dianhydrides and aliphatic acid dianhydrides in the copolymer composition. and at least one of polymers of maleic anhydride.

[3] The thermosetting composition according to item [1], wherein R ¹ of the compound (b) is a branchable alkylene group having 1 to 10 carbon atoms or represented by the following formula (2): Divalent group: -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _m - (2) In formula (2), m is an integer of 1-9.

[4] The thermosetting composition according to [1], wherein the compound (B) having two or more epoxy groups is a compound having an aromatic ring.

[5] A cured film formed of the thermosetting composition according to any one of [1] to [4].

[6] A color filter having the cured film according to item [5] as a transparent protective film. [Effect of the invention]

The thermosetting composition of a preferred embodiment of the present invention is a material that is particularly excellent in heat resistance, flatness, transparency, and adhesion, especially heat resistance, and is used as a color filter protective film for a color liquid crystal display element. In the case of , the display quality can be improved. In particular, it is effective as a protective film for color filters produced by dyeing, pigment dispersion, electrodeposition, and printing. In addition, it can also be used as a protective film and transparent insulating film for various optical materials.

1. The thermosetting composition of the present invention The thermosetting composition of the present invention includes a polymer (A), a compound (B) having two or more epoxy groups, and a solvent (C), the polymer (A) having two or more acid anhydride groups (-CO-O-CO-) compound (a) and compound (b) represented by formula (1) are thermally reacted, and the thermosetting composition is characterized in that: relative to the polymer ( A) 100 weight part, the compound (B) which has two or more epoxy groups is 10 weight part - 500 weight part.

1-1. Polymer (A) The polymer (A) is obtained by thermally reacting a compound (a) having two or more acid anhydride groups and a compound (b) represented by formula (1). In the scope of the selected compound (a), aromatic acid dianhydrides and aliphatic acid dianhydrides are included, and polymers obtained by copolymerizing maleic anhydride and other polymerizable monomers other than maleic anhydride (as long as there are two more than one acid anhydride group), at least one compound selected from these compounds can be used. Hereinafter, in this specification, "other polymerizable monomers other than maleic anhydride" are expressed as "other polymerizable monomers". Other polymerizable monomers to be copolymerized with maleic anhydride are not particularly limited, but N-substituted maleimides, indene, styrene, and the like are preferable from the viewpoint of heat resistance.

In the copolymerization of maleic anhydride and other polymerizable monomers, radical copolymerization can be utilized, and it is preferable to use a thermal radical initiator as an initiator.

In addition, at least a solvent is required in the synthesis of the polymer (A). The solvent may be left as it is to form a liquid or gel composition in consideration of handling properties, or the solvent may be removed to form a solid composition in consideration of transportability and the like.

Compounds other than those described above may also be contained within a range that does not impair the object of the present invention. As an example of other raw materials, a chain transfer agent may be contained.

1-1-1. Compound (a) having two or more acid anhydride groups In this invention, an acid dianhydride is used as a raw material for obtaining a polymer (A). Examples of the acid dianhydride include: 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'-diphenylsulfone tetracarboxylic dianhydride, 2,2',3,3'-diphenyl Diphenyl tetracarboxylic dianhydride, 2,3,3',4'-diphenyl 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-di Carboxyphenyl)]hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, ethylene glycol bis(dehydrated trimellitate) (trade name; TMEG-100, Shin Nippon Chemical Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, ethane tetracarboxylic dianhydride and butane tetracarboxylic dianhydride. One or more of these compounds may be used.

In addition, in the present invention, a copolymer of maleic anhydride and other polymerizable monomers can be used as a compound having two or more acid anhydride groups. In such a case, examples of usable other polymerizable monomers specifically include: N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide imine, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide. In addition, isobutylene, styrene, indene, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, glycidyl methacrylate, methacrylic acid -2-Hydroxyethyl methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, 2-phenylethyl methacrylate, isobornyl methacrylate, dicyclopentyl methacrylate ester, 2,2,2-trifluoroethyl methacrylate.

1-1-2. Compound (b) having amino group and hydroxyl group in the same molecule In the present invention, a compound having an amino group and a hydroxyl group in the same molecule is used as a material for obtaining the polymer (A). Examples of such compounds include: 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 8-amino-1-octanol, 10 -Amino-1-decanol, 12-amino-1-dodecanol, 2-(2-aminoethoxy)ethanol, 2-(4-aminophenyl)ethanol, 2-(4-aminocyclohexyl) Ethanol, 4-aminocyclohexanol. From the viewpoint of ease of acquisition and heat resistance, 2-aminoethanol and 2-(2-aminoethoxy)ethanol are suitable. The compounds listed here may be used in combination of plural kinds.

1-1-3. Solvents used in the synthesis of polymer (A) Specific examples of the solvent used in the synthesis to obtain the polymer (A) include: ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate , ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propionate 2-hydroxypropionate ester, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate ester, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2 -Ethyl methylpropionate, methylpyruvate, ethylpyruvate, propylpyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, 2-oxobutanoic acid Ethyl ester, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether ethyl Ester, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol Alcohol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether . The solvent may be one of these solvents, or a mixture of two or more of these solvents.

1-1-4. Molecular weight modifier used in synthesis of copolymer containing maleic anhydride When synthesizing a copolymer containing maleic anhydride, a molecular weight modifier may be further contained in order to suppress an increase in the molecular weight and to develop excellent storage stability. Examples of the molecular weight modifier include mercaptans, xanthic acids, quinones, hydroquinones, 2,4-diphenyl-4-methyl-1-pentene, and the like.

Specific examples of molecular weight modifiers include: 2-hydroxy-1,4-naphthoquinone, benzoquinone, 1,4-naphthoquinone, 1,4-dihydroxynaphthalene, 2,5-di-tert-butylhydrogen Quinone, hydroquinone, methylhydroquinone, tert-butylhydroquinone, methoquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, anthraquinone, n-hexylmercaptan, n- Octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid, dimethyl xanthate sulfide, diisopropyl xanthate disulfide, 2,4-diphenyl Base-4-methyl-1-pentene, etc.

The molecular weight modifiers may be used alone or in combination of two or more.

1-1-5. Synthesis method of polymer (A) The polymer (A) used in the present invention is obtained by thermally reacting a compound (a) having two or more acid anhydride groups and a compound (b) represented by formula (1). In this case, the number of moles per functional group of the acid anhydride and the number of moles per functional group of the compound (b) represented by formula (1) need to be within the following ranges. Here, the term "functional group" refers to an acid anhydride group, an amino group, or a hydroxyl group. 0.5≦X≦5.0 X=the number of moles of acid anhydride groups/(the number of moles of amino groups+the number of moles of hydroxyl groups) Within this range, the solubility of the polymer in the solvent is high, and the heat resistance, flatness, and adhesiveness of the composition are good, more preferably 0.7≦X≦4.0, and still more preferably 1.0≦X≦3.0.

When using 80 weight part or more of reaction solvents with respect to 100 weight part of solutes, since reaction will progress smoothly, it is preferable. The reaction is carried out at 40°C to 200°C for 0.2 hours to 20 hours.

On the other hand, among compounds having an acid anhydride group, polymers obtained by copolymerizing maleic anhydride and other polymerizable monomers as described above can also be used. In the radical polymerization, the reaction temperature is preferably 40°C to 120°C, more preferably 60°C to 80°C. After completion of radical polymerization, it cools to room temperature, adds the compound represented by formula (1), and reacts at 40 degreeC - 200 degreeC for 0.1 hour - 6 hours.

In the polymer (A) synthesized in the above manner, even when the solubility of the compound (b) represented by the formula (1) in the copolymer or the solvent used is low, after thermal reaction, it can become uniform clear liquid to form a defect-free and uniform film. On the contrary, when the compound having two or more hydroxyl groups is simply added to the system without thermally reacting the compound having two or more hydroxyl groups after the polymerization of the radical copolymer, the compound having two or more hydroxyl groups may precipitate. In this case, a uniform film cannot be formed. Therefore, by derivatizing the polymer (A), a defect-free thin film can be formed.

The weight average molecular weight of the obtained polymer (A) is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000. Coatability and flatness are favorable in these ranges.

The weight average molecular weight in this specification is a polystyrene equivalent value calculated|required by gel permeation chromatography (Gel Permeation Chromatography, GPC) (column temperature: 35 degreeC, flow rate: 1 ml/min). The standard polystyrene uses polystyrene with a molecular weight of 645-132,900 (for example, the polystyrene calibration kit (calibration kit) PL2010-0102 from Agilent Technologies Inc.), and the column uses PL gel mixed (PLgel MIXED)-D (Agilent Technologies Inc.), can be measured using tetrahydrofuran (Tetrahydrofuran, THF) as the mobile phase. The weight average molecular weight of the commercially available item in this specification is a value described in a catalog (catalogue).

1-2. Compound (B) having two or more epoxy groups The epoxy compound used in the present invention is a compound having two or more epoxy groups per molecule. The compound (B) which has two or more epoxy groups may be one type, or may be two or more types.

1-2-1. Examples of compounds (B) having two or more epoxy groups Examples of the compound (B) having two or more epoxy groups are bisphenol A type epoxy compound, bisphenol F type epoxy compound, glycidyl ether type epoxy compound, glycidyl ester type epoxy compound, biphenyl Type epoxy compound, phenol novolak type epoxy compound, cresol novolak type epoxy compound, bisphenol A novolac type epoxy compound, aliphatic polyglycidyl ether compound, cycloaliphatic epoxy compound, with ring Polymers of monomers with oxygen groups, copolymers of monomers with epoxy groups and other monomers, and epoxy compounds with siloxane bonding sites.

Specific examples of commercially available bisphenol A epoxy compounds are jER 828, jER 1004, and jER 1009 (all are brand names; Mitsubishi Chemical Corporation). Specific examples of commercially available bisphenol F-type epoxy compounds are jER 806 and jER 4005P (both are brand names; Mitsubishi Chemical Corporation). Specific examples of commercially available glycidyl ether-type epoxy compounds include TECHMORE VG3101L (trade name; Printec Co., Ltd.); EHPE3150 (trade name; Daicel Co., Ltd. Company); EPPN-501H, EPPN-502H (both trade names; Nippon Kayaku Corporation); and jER 1032H60 (trade name; Mitsubishi Chemical Corporation). Specific examples of commercially available glycidyl ester epoxy compounds include Denacol EX-721 (trade name; Nagase ChemteX Co., Ltd.) and 1,2-cyclohexanedicarboxylate Acid diglycidyl ester (trade name; Tokyo Chemical Industry Co., Ltd.). Specific examples of commercially available biphenyl-type epoxy compounds are jER YX4000, jER YX4000H, jER YL6121H (all trade names; Mitsubishi Chemical Corporation); and NC-3000, NC-3000-L, NC-3000- H, NC-3100 (both trade names; Nippon Kayaku Co., Ltd.). Specific examples of commercially available phenol novolac epoxy compounds include EPPN-201 (trade name; Nippon Kayaku Co., Ltd.); jER 152 and jER 154 (both trade names; Mitsubishi Chemical Corporation). Specific examples of commercially available products of cresol novolac-type epoxy compounds include EOCN-102S, EOCN-103S, EOCN-104S, and EOCN-1020 (all are brand names; Nippon Kayaku Co., Ltd.). Specific examples of commercially available bisphenol A novolak-type epoxy compounds are jER 157S65 and jER 157S70 (both trade names; Mitsubishi Chemical Corporation). Specific examples of commercially available cycloaliphatic epoxy compounds include Celloxide 2021P and Celloxide 3000 (both are brand names; Daicel Co., Ltd.). A specific example of a commercially available epoxy compound having a siloxane bonding site is 1,3-bis[2-(3,4-epoxycyclohexyl)ethyl]tetramethyldisiloxane (trade name ; Gelest Incorporated (Gelest Incorporated)), TSL9906 (trade name; Momentive Performance Materials Japan Co., Ltd.), Coat Oslo (COATOSIL) MP200 (trade name; Japan Momentive High-tech Materials (Momentive Performance Materials Japan Co., Ltd.), Conpoceran SQ506 (trade name; Arakawa Chemical Co., Ltd.), ES-1023 (trade name; Shin-Etsu Chemical Co., Ltd.).

Furthermore, TECHMORE VG3101L (trade name; Printec Co., Ltd.) is 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4 -[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane and 1,3-bis[4-[1-[4-(2,3 -Glycidyloxy)phenyl]-1-[4-[1-[4-(2,3-Glycidoxy)phenyl]-1-methylethyl]phenyl]ethyl] Mixtures of phenoxy]-2-propanol. EHPE3150 (trade name; Daicel Co., Ltd.) is 1,2-epoxy-4-(2-oxiranyl) of 2,2-bis(hydroxymethyl)-1-butanol Cyclohexane adducts. Celloxide 2021P (trade name; Daicel Co., Ltd.) is 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. Celloxide 3000 (trade name; Daicel Co., Ltd.) is 1-methyl-4-(2-methyloxirane)-7-oxabicyclo[4.1.0 ] Heptane. COATOSIL (COATOSIL) MP200 (trade name; Momentive Performance Materials Japan Co., Ltd.) is a polymer with 3-glycidyloxypropyltrimethoxysilane as its raw material.

The compound (B) which has two or more epoxy groups may be used individually or in mixture of 2 or more types.

1-2-2. Ratio of compound (B) having two or more epoxy groups to polymer (A) The ratio of the total amount of the compound (B) which has two or more epoxy groups in the thermosetting composition of this invention with respect to 100 weight part of polymers (A) is 10 weight part - 500 weight part. When the ratio of the total amount of the compound (B) which has two or more epoxy groups falls within the said range, the balance of flatness, heat resistance, chemical resistance, and substrate adhesion will be favorable. The total amount of the compound (B) having two or more epoxy groups is preferably in the range of 50 parts by weight to 300 parts by weight, but the total amount is determined by adjusting the molar ratio with the polymer (A) and the epoxy curing agent. quantity.

1-3. Solvent (C) A solvent (C) can be used in the thermosetting composition of the present invention. The solvent (C) used in the thermosetting composition of the present invention is preferably a solvent that can dissolve the polymer (A) and the compound (B) having two or more epoxy groups. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl Methyl oxyacetate, ethyl ethoxyacetate, 3-methoxybutyl acetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy- Methyl 2-Methylpropionate, Ethyl 2-Hydroxy-2-Methylpropionate, Methyl 2-Methoxy-2-Methylpropionate, Ethyl 2-Ethoxy-2-Methylpropionate ester, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 4-hydroxy -4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol Monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate , Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether. The solvent may be one of these solvents, or a mixture of two or more of these solvents.

1-4. Other ingredients In the thermosetting composition of the present invention, various additives can be added to improve coating uniformity, adhesiveness, transparency, flatness and chemical resistance. Additives mainly include: solvents; anionic, cationic, nonionic, fluorine or silicon-based leveling agents/surfactants; silane coupling agents and other adhesion enhancers; hindered phenols, hindered amines, phosphorus Antioxidants such as series and sulfur compounds; Molecular weight regulator; Epoxy hardener.

1-4-1. Surfactant In the thermosetting composition of the present invention, a surfactant may also be added to improve coating uniformity. Specific examples of surfactants include: Polyflow No.75, Polyflow No.90, Polyflow No.95 (both trade names, Kyoeisha Chemical Co., Ltd.), Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-170, Disperbyk-180, Disperbyk-181, Disperbyk ( Disperbyk)-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (all trade names, BYK Chemie Japan Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF-50-100CS (all trade names, Shin-Etsu Chemical Industry Co., Ltd.), Saffron (Surflon)-S611 (trade name, AGC Seimi Chemical Co., Ltd.), Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, FTX-218 (all trade names, Neos Co., Ltd.), Megafa (Megafac) F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F- 477. Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac ( Megafac) F-558, Megafac F-559, Megafac R-94, Megafac RS-75, Megafac RS-72-K, Megafac RS -76-NS, Megafac DS-21 (all trade names, DIC Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (all trade names, Evonik Japan ) Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, di Glycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl sulfamate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl 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 Laurate, Sorbitan Palmitate, Sorbitan Stearate, Sorbitan Oleic Acid Esters, sorbitan fatty acid esters, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, Polyoxyethylene naphthyl ether, alkylbenzene sulfonate and alkyl diphenyl ether disulfonate. It is preferable to use at least one kind selected from these surfactants.

Among these surfactants, if selected from BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surflon-S611, Ftergent 710FL, Ftergent ) 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac F-559 , Megafac RS-72-K, Megafac DS-21, Tego Twin 4000, Fluoroalkylbenzenesulfonate, Fluoroalkyl Carboxylate, Fluoroalkyl Polyoxygen At least one of vinyl ether, fluoroalkylsulfonate, fluoroalkyltrimethylammonium salt, and fluoroalkylsulfamate is preferable since the coating uniformity of the thermosetting composition becomes high.

The content of the surfactant in the thermosetting composition of the present invention is preferably 0.01% by weight to 10% by weight relative to the total amount of the thermosetting composition.

1-4-2. Coupling agent The thermosetting composition of this invention may further contain a coupling agent from a viewpoint of further improving the adhesiveness of the formed cured film and a board|substrate.

As such a coupling agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, examples include: 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxy Silane (for example, trade name, Sarah Ace (Sila-Ace) S510, JNC Co., Ltd.), 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane (for example, commercial name, Sarah Ace (Sila-Ace) S530, JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane (for example, trade name; Sarah Ace (Sila-Ace) S810, JNC Enzhi (JNC) Co., Ltd.), a copolymer of 3-glycidoxypropyltrimethoxysilane (for example, trade name, COATOSIL (COATOSIL) MP200, Momentive Performance Materials Japan Co., Ltd. Responsible company) and other silane-based coupling agents; aluminum-based coupling agents such as acetyl alkoxy diisopropoxide; and titanate-based coupling agents such as tetraisopropylbis(dioctyl phosphite) titanate joint agent.

Among these coupling agents, 3-glycidoxypropyltrimethoxysilane is preferable because of its large effect of improving the adhesion.

From the viewpoint of improving the adhesion between the formed cured film and the substrate, the content of the coupling agent is preferably 0.01% by weight or more and 10% by weight or less based on the total amount of the thermosetting composition.

1-4-3. Antioxidant The thermosetting composition of the present invention may further contain an antioxidant from the viewpoint of improving transparency and preventing yellowing of the cured film when exposed to high temperatures.

In the thermosetting composition of the present invention, antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added. Among them, hindered phenols are preferable from the viewpoint of weather resistance. Specific examples include: Irganox 1010, Irganox 1010FF, Irganox 1035, Irganox 1035FF, and Irganox Irganox 1076, Irganox 1076FD, Irganox 1098, Irganox 1135, Irganox 1330, Yilujia Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Irganox 245FF, Yilu Irganox 259, Irganox 3114, Irganox 565, Irganox 565DD (all trade names, shares of BASF Japan) Ltd.); ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB STAB) AO-60, ADK STAB AO-80 (both trade names, ADEKA Co., Ltd.). Among them, Irganox 1010 and ADK STAB AO-60 are more preferred.

The antioxidant is added in an amount of 0.1 to 10 parts by weight based on the total amount of the thermosetting composition.

1-4-4. Epoxy Hardener In order to improve flatness and chemical resistance, the thermosetting composition of the present invention may further contain an epoxy curing agent. As epoxy hardeners, there are acid anhydride hardeners, amine hardeners, phenolic hardeners, imidazole hardeners, pyrazole hardeners, triazole hardeners, catalyst hardeners, and sulfonium salts. ), benzothiazolium salts, ammonium salts, phosphonium salts and other thermosensitive acid generators, from the viewpoint of avoiding coloring of the cured film and the heat resistance of the cured film, acid anhydride-based hardeners or imidazole-based hardeners are preferred Alternatively, use an acid anhydride hardener and an imidazole hardener in combination.

Specific examples of the acid anhydride hardener are aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride; Aromatic polycarboxylic anhydrides such as phthalic anhydride and trimellitic anhydride; and styrene-maleic anhydride copolymers. Among these acid anhydride-based curing agents, trimellitic anhydride and hexahydrotrimellitic anhydride are preferable in terms of heat resistance and solubility in solvents.

Specific examples of the imidazole hardener are 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro- 1H-pyrrolo[1,2-a]benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate. Among these imidazole-based curing agents, 2-undecylimidazole having a good balance between curability and solubility in solvents is preferable.

When using an epoxy curing agent, the ratio of an epoxy curing agent with respect to 100 weight part of compounds (B) which have two or more epoxy groups is 0.1 weight part - 60 weight part. When the epoxy curing agent is an acid anhydride-based curing agent, more specifically, it is preferable that the amount of carboxylic acid anhydride groups or carboxyl groups in the epoxy curing agent is 0.1 times to 1.5 times the equivalent of epoxy groups. to add. At this time, the carboxylic acid anhydride group is calculated as divalent. When adding a carboxylic acid anhydride group or a carboxyl group so that it may become 0.15 times equivalent - 0.8 times equivalent, since chemical resistance will improve more, it is more preferable.

1-4-5. UV absorber The thermosetting composition of the present invention may contain an ultraviolet absorber from the viewpoint of further improving the degradation suppressing ability of the formed transparent film.

Specific examples of ultraviolet absorbers include TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN (TINUVIN) 326, TINUVIN (TINUVIN) 571, TINUVIN (TINUVIN) 765 (both trade names, BASF Japan Co., Ltd.).

The ultraviolet absorber is added and used in an amount of 0.01 to 10 parts by weight with respect to the total amount of the thermosetting composition.

1-4-6. Anti-agglomeration agent The thermosetting composition of the present invention may contain an anti-aggregation agent from the viewpoint of preventing aggregation by melting the solid content with the solvent.

Specific examples of the anti-coagulant are Disperbyk-145, Disperbyk-161, Disperbyk-162, and Disperbyk-163 , Disperbyk-164, Disperbyk-182, Disperbyk-184, Disperbyk-185, Disperbyk (Disperbyk)-2163, Disperbyk-2164, BYK-220S, Disperbyk-191, Disperbyk-199, Disperbyk )-2015 (all trade names; BYK Chemie Japan Co., Ltd.); FTX-218, Ftergent 710FM, Ftergent 710FS (all trade names, Neos ( Neos) Co., Ltd.); Floren (Flowlen) G-600, Floren (Flowlen) G-700 (both trade names, Kyorongsha Chemical Co., Ltd.).

0.01 to 10 parts by weight of an anti-aggregation agent is added to the total amount of the thermosetting composition and used.

1-4-7. Thermal crosslinking agent From the viewpoint of further improving heat resistance, chemical resistance, film in-plane uniformity, flexibility, softness, and elasticity, the thermosetting composition of the present invention may contain a thermal crosslinking agent.

Specific examples of thermal crosslinking agents are Nikalac (Nikalac) MW-30HM, Nikalac (Nikalac) MW-100LM, Nikalac (Nikalac) MX-270, Nikalac (Nikalac) MX-280, Nikalac Nikalac (Nikalac) MX-290, Nikalac (Nikalac) MW-390, Nikalac (Nikalac) MW-750LM (all trade names, Sanhe Chemical (stock)).

The thermal crosslinking agent is added and used in an amount of 0.1 to 10 parts by weight based on the total amount of the thermosetting composition.

1-5. Preservation of thermosetting composition When the thermosetting composition of the present invention is stored in the range of -30°C to 25°C, the stability of the composition over time becomes good. When the storage temperature is -20°C to 10°C, no precipitates are present, which is more preferable.

2. Cured film formed from a thermosetting composition Regarding the thermosetting composition of the present invention, the polymer (A), the compound (B) having two or more epoxy groups, and the solvent (C) are mixed, and epoxy can be optionally added according to the target characteristics. Hardeners, surfactants, coupling agents, antioxidants and other additives.

When the thermosetting composition prepared as described above (in the case of a solvent-free solid state, after being dissolved in a solvent) is applied on the surface of a substrate, and the solvent is removed by heating, for example, a coating film can be formed . Coating of the thermosetting composition on the substrate surface can be performed by conventionally known methods such as spin coating, roll coating, dipping, and slit coating to form a coating film. Next, the coating film is once calcined using a hot plate, an oven, or the like. Temporary calcination conditions vary depending on the type and blending ratio of each component, but usually at 70°C to 150°C, 5 minutes to 15 minutes if an oven is used, and 1 minute to 5 minutes if a hot plate is used. Thereafter, main firing is performed to harden the coating film. The main calcination conditions vary depending on the type and blending ratio of each component, usually at 180°C to 250°C, preferably at 200°C to 250°C, for 30 minutes to 90 minutes if an oven is used, and for 5 minutes if a heating plate is used ~ 30 minutes, a cured film can be obtained by performing heat treatment.

When the cured film obtained in the above manner is heated, the polymer (A) reacts with the compound (B) having two or more epoxy groups to form a three-dimensional network, so it is very tough, and has transparency, heat resistance, and Excellent chemical resistance, flatness, and adhesion. In addition, excellent light resistance, sputter resistance, scratch resistance, and applicability are also expected for the same reason. Therefore, if the cured film of this invention is used as the protective film for color filters, it is effective, and a liquid crystal display element or a solid-state imaging element can be manufactured using the said color filter. In addition, in addition to the protective film for color filters, if the cured film of the present invention is used as a transparent insulating film formed between a thin film transistor (Thin Film Transistor, TFT) and a transparent electrode or formed between a transparent electrode and an alignment film A transparent insulating film is also effective. Furthermore, even if the cured film of this invention is used as a protective film of a light emitting diode (Light Emitting Diode, LED) light-emitting body, it is effective. [Example]

Next, the present invention will be specifically described with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to these examples.

The compounds used in the synthesis examples, examples, and comparative examples are described for each component.

[Synthesis Example 1] Synthesis of polymer (A1) solution In a four-necked flask with a stirrer, put diethylene glycol methyl ethyl ether (EDM), 4,4'-oxydiphthalic anhydride (ODPA), 2-aminoethanol ( AE) were heated and stirred at 150° C. for 3 hours under a dry nitrogen stream to obtain a polymer solution. EDM 10.01g ODPA 8.360 g AE 1.646 g

Thereafter, the solution was cooled to room temperature to obtain a light yellow and transparent 50% by weight solution of the polymer (A1). A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standards). As a result, the weight average molecular weight of the obtained polymer (A1) was 3,000.

[Synthesis Example 2] Synthesis of Polymer (A2) As shown below, put methyl 3-methoxypropionate (MMP, use 70% of the total charge), N-cyclohexylmaleimide, and maleic anhydride into a mixer with a cooling In a four-neck flask in a vacuum cleaner, it was heated and stirred at 80° C. under nitrogen flow. Next, the MMP solution of the mixture of the radical initiator V-65 (manufactured by Wako Pure Chemical Industries) and α-methylstyrene dimer (using 30% of the total charge) was charged to the dropping funnel , dropwise polymerization was carried out over 1 hour. Then, it heated and stirred at 80 degreeC for 2 hours, and obtained the radical copolymer. MMP 25.90g N-cyclohexylmaleimide 6.464 g Maleic anhydride 3.537 g V-65 0.1000g α-Methylstyrene dimer 0.0500 g

After cooling to room temperature, 1.102 g of 2-aminoethanol (AE) was added, followed by heating and stirring at 150° C. for 3 hours to obtain a polymer (A2) solution. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standards). As a result, the weight average molecular weight of the obtained polymer (A2) was 16,100.

[Synthesis Example 3 to Synthesis Example 5] Synthesis of Polymer (A3) to Polymer (A5) Solution According to the methods of Synthesis Example 1 and Synthesis Example 2, each component was reacted at the temperature, time, and ratio (unit: g) described in Table 1 to obtain a polymer solution.

[Comparative synthesis example 1] Synthesis of polyester amide acid (R1) solution The polyester amide acid was reacted at the temperature, time, and ratio described in Table 1 to obtain a polyester amide acid (R1) solution. Among them, the first stage of the reaction is to react ODPA with 1,4-butanediol (BD) at 150°C for 3 hours, and then react with 3,3'-diaminodiphenylsulfone at 120°C A 1-hour reaction was carried out as a second-stage reaction.

裝入量的單位：克Table 1

The unit of loading amount: grams

The compounds described by abbreviations in Table 1 and used in the synthesis examples and comparative synthesis examples are as follows. ODPA: 4,4'-oxydiphthalic anhydride CHMI: N-Cyclohexylmaleimide IN: indene MAH: maleic anhydride AE: 2-aminoethanol AEE: 2-(2-Aminoethoxy)ethanol BD: 1,4-Butanediol mDDS: 3,3'-Diaminodiphenylsulfone V-65: 2,2'-azobis(2,4-dimethylvaleronitrile); manufactured by Wako Pure Chemical Industries, Ltd. α-MSD: α-methylstyrene dimer EDM: Diethylene glycol methyl ethyl ether MMP: methyl 3-methoxypropionate

[Example 1] A 50% by weight solution of the polymer (A1) obtained in Synthesis Example 1, VG3101L as a trifunctional epoxy compound, trimellitic anhydride (TMA) as a hardener, and silane S510 as a coupling agent, ADK STAB AO-60 as an antioxidant, F-556 as a surfactant, and methyl 3-methoxypropionate (MMP) as a diluting solvent are mixed and dissolved , and filtered through a membrane filter (pore size 0.2 μm) to obtain a thermosetting composition.

[Example 2 to Example 5 and Comparative Example 1] According to the method of Example 1, each component was mixed and dissolved in the ratio (parts by weight) described in Table 2, thereby obtaining a thermosetting composition.

單位：重量份（表面活性劑除外）Table 2

Unit: parts by weight (excluding surfactants)

Using each of the obtained thermosetting compositions, heat resistance, flatness, and substrate adhesion were evaluated by the methods described below. The evaluation results of the cured films of Examples 1 to 5 are collectively described in Table 3. In addition, regarding Comparative Example 1, the heat resistance, flattening property, and substrate adhesiveness of the thermosetting composition containing polyester amide acid were evaluated. The evaluation results are collectively described in Table 3.

[Evaluation method of heat resistance] The obtained thermosetting composition was spin-coated on a glass substrate at 650 rpm for 10 seconds, and prebaked on a hot plate at 80° C. for 2 minutes. Then, it heat-processed in oven at 230 degreeC for 30 minutes, and obtained the glass substrate with a cured film. For the obtained glass substrate with a cured film, the film thickness was measured using a step difference/surface roughness/micro shape measuring device (trade name; P-17, KLA TENCOR Co., Ltd.) Spin-coating conditions were adjusted so that the thickness became 1.5 μm. Thereafter, the cured film was scraped off from the glass substrate with the cured film, and the thermogravimetric/differential thermal analysis (Thermogravimetric-Differential Thermal Analysis, TG-DTA) was used to hold the measurement at 230°C for 60 minutes. The case where the weight loss at the time was 0.5% or less was marked as ◯, and the case of more than that was marked as ×, and shown together with the actual measurement value.

[Evaluation method of flatness] On a concave-convex substrate (line 100 μm, a space of 50 μm, and a film thickness of 1 μm), the obtained thermosetting composition was spin-coated at 650 rpm for 10 seconds, and prebaked on a hot plate at 80°C for 2 minutes. Then, heat treatment was carried out at 230° C. for 30 minutes in an oven to obtain a color filter substrate with a cured film having an average film thickness of the protective film of 1.5 μm. Then, the surface level difference was measured about the obtained color filter board|substrate with a cured film. Calculate the planarization rate from the maximum value of the surface level of the color filter substrate without a hardening film and the color filter substrate with a hardening film (hereinafter abbreviated as "maximum level difference"), using the following formula , and the results are shown in Table 3. Regarding the results of flatness, 100% to 80% was evaluated as ⊚, 79% to 60% was evaluated as ◯, and less than 60% was evaluated as x. Planarization rate (%) = ((maximum step difference of concave-convex substrate - maximum step difference of concave-convex substrate with hardened film)/maximum step difference of concave-convex substrate) × 100

[Evaluation method of adhesion] The obtained thermosetting composition was spin-coated on a concave-convex substrate (line: 100 μm, space: 50 μm, film thickness: 1.0 μm) at 650 rpm for 10 seconds, and prebaked on a heating plate at 80°C for 2 minute. Then, heat treatment was carried out at 230° C. for 30 minutes in an oven to obtain a cured film-attached uneven substrate. A cross-cut test (Japanese Industrial Standards (JIS) K 5400, peeling tape: Using 3M Manufacturing No. 361), evaluation was performed according to the following classification 0 to classification 5, classification 0 to classification 1 was made ○, classification 2 to classification 3 was made Δ, and classification 4 to classification 5 was made x. <Category 0> The edges of the ¼ cut are completely smooth and there is no flaking in the mesh of either grid. <Classification 1> Small peeling of the coating film at the intersection of ¼ cut. In the cross-cut section, the affected portion will not clearly exceed 5%. <Category 2> ¼ of the film peels off along cut edges and/or at intersections. In the cross-cut section, the affected portion is definitely more than 5% but not more than 15%. <Classification 3> ¼ of the coating film is partially or completely peeled off along the cut edge, and/or many parts of the grid are partially or completely peeled off. In the cross-cut section, the affected portion is definitely more than 15% but not more than 35%. <Classification 4> ¼ of the coating film is partially or completely peeled off along the edge of the cut, and/or many grids are partially or completely peeled off. In the cross-cut section, the affected portion will not clearly exceed 35%. <Classification 5> ¼ Any degree of peeling that cannot be classified even in Classification 4.

[Evaluation method of transparency] The obtained thermosetting composition was spin-coated on a glass substrate at 650 rpm for 10 seconds, and prebaked on a hot plate at 80° C. for 2 minutes. Then, it heat-processed at 230 degreeC for 30 minutes in an oven, and obtained the glass substrate with a cured film with a film thickness of 1.5 micrometers. The light transmittance at 400 nm of the cured film was measured with an ultraviolet-visible-near-infrared spectrophotometer (trade name: V-670, JASCO Corporation) for the obtained glass substrate with the cured film. In this case, only the glass substrate was used as a reference, and the light transmittance of the cured film alone was calculated (interference due to multiple reflections was not considered in this case). When the light transmittance was 98% or more, it was evaluated as transparency ◯, when the transmittance was less than 95%, it was evaluated as transparency ×, and between them was evaluated as △.

From the results shown in Table 3, it is clear that the thermosetting compositions of Examples 1 to 5 satisfy heat resistance, flatness, adhesiveness, and transparency. On the other hand, in Comparative Example 1, all the characteristics could not be satisfied.

table 3

[industrial availability] The cured film obtained from the thermosetting composition of the present invention has good heat resistance, flatness, and substrate adhesion, and can be used as a protective film for various optical materials such as color filters, LED light-emitting elements, and light-receiving elements. Insulation film between TFT and transparent electrode and between transparent electrode and alignment film.

none.

none.

Claims (4)

A thermosetting composition comprising a polymer (A), a compound (B) having two or more epoxy groups, and a solvent (C), wherein the polymer (A) is derived from an acid anhydride group having two or more The product of the compound (a) and the compound (b) having an amino group and a hydroxyl group in the same molecule, wherein the compound (a) derived from having two or more anhydride groups is a compound selected from N-cyclohexyl in the copolymerization composition A polymer of at least one of the group consisting of maleimide and indene and maleic anhydride, wherein the compound (b) having an amino group and a hydroxyl group in the same molecule is 2-aminoethanol. The thermosetting composition according to claim 1, wherein the compound (B) having two or more epoxy groups is a compound having an aromatic ring. A cured film formed of the thermosetting composition described in claim 1 or claim 2. A color filter having the hardened film as described in claim 3 as a transparent protective film.