JP4569233B2 - Thermosetting resin composition and cured film - Google Patents

Description

  The present invention relates to a thermosetting resin composition and a cured film obtained by heating and curing the composition.

  During the manufacturing process of devices such as liquid crystal display devices, various chemical treatments such as organic solvents, acids, and alkali solutions are performed, and when the wiring electrode is formed by sputtering, the surface is locally heated to a high temperature. Sometimes. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and alteration of the surface of various elements. These protective films are required to have various characteristics that can withstand various treatments during the manufacturing process as described above. Specifically, chemical resistance such as solvent resistance, acid resistance, and alkali resistance, water resistance, heat resistance, adhesion to underlying substrates such as glass, transparency, scratch resistance, coatability, flatness, long-term Light resistance or the like is required so as not to change coloration or the like. In particular, foreign matter characteristics have come to be regarded as important as characteristics when used as a color filter protective film. The term “foreign matter characteristics” means that when the resin composition is applied to a substrate on which foreign matter is present and dried, the film thickness around the foreign matter is disturbed, and as a result, the reflected light around the foreign matter is disturbed. A phenomenon in which a foreign object is easily noticeable when viewed in a shape enlarged from the size of the foreign object. “Excellent foreign material properties” means that such a phenomenon is unlikely to occur and foreign materials are not conspicuous. The foreign matter characteristics greatly affect the yield at the time of manufacturing the color filter.

As a protective film material excellent in these characteristics, there is a silicon-containing polyamic acid composition (see Patent Document 1). This composition is resistant to chemicals such as solvent resistance, acid resistance, alkali resistance, water resistance, heat resistance, adhesion to underlying substrates such as glass, transparency, scratch resistance, applicability, flatness, and light resistance. Although it was an excellent and excellent composition, there was a drawback that it had poor foreign material properties.
JP-A-9-291150

  The object of the present invention is to solve the drawbacks of the above-mentioned composition, such as chemical resistance such as solvent resistance, acid resistance and alkali resistance, water resistance, heat resistance, adhesion to an underlying substrate such as glass, and transparency. Another object of the present invention is to provide a cured film having excellent properties, scratch resistance, coating properties, flatness, and light resistance, and also having excellent foreign material properties, and a resin composition that provides this cured film.

As a result of various studies to solve the above problems, the inventors of the present invention comprise a polyester amide acid obtained from the reaction of a compound containing tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound, an epoxy resin, and a solvent. It has been found that the above object can be achieved by a cured film obtained by heat curing a resin composition, and the present invention has been completed.
The present invention has the following configuration.

(1) A resin composition comprising a polyester amide acid, an epoxy resin, an epoxy curing agent and a solvent obtained by reacting tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound as essential components, the polyester amide acid The thermosetting resin composition, wherein the epoxy resin is 20 to 400 parts by weight with respect to 100 parts by weight, and the epoxy curing agent is 15 to 60 parts by weight with respect to 100 parts by weight of the epoxy resin.

(2) The thermosetting resin composition according to item 1, wherein the polyesteramide acid is a reaction product obtained by reacting tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound and monohydric alcohol as essential components. .

(3) The thermosetting according to item 1, wherein the polyesteramic acid is a reaction product obtained by reacting tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound, monohydric alcohol and silicon-containing monoamine as essential components. Resin composition.

(4) The thermosetting resin composition according to item 2 or 3, wherein the monohydric alcohol is isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3-ethyl-3-hydroxymethyloxetane. .

(5) The thermosetting resin composition according to any one of Items 1 to 4, wherein the polyester amic acid is a polyester amic acid obtained by further reacting with a styrene-maleic anhydride copolymer.

(6) Polyester amide acid is a ratio such that X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyhydric hydroxy compound satisfy the relationship of the following formulas (1) and (2). Item 6. The thermosetting resin composition according to any one of Items 1 to 5, which is obtained by reacting with a thermosetting resin.
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦1.5 (2)

ここで、Ｒ_１はテトラカルボン酸二無水物残基であり、Ｒ_２はジアミン残基であり、Ｒ_３は多価ヒドロキシ化合物残基である。 (7) The thermosetting resin composition according to any one of Items 1 to 6, wherein the polyester amide acid is a compound having structural units represented by the following formulas (3) and (4).

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

(8) Tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2 Item 8 is one or more compounds selected from-(bis (3,4-dicarboxyphenyl)) hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate). The thermosetting resin composition described in 1.

(9) The item according to any one of items 1 to 8, wherein the diamine is one or more compounds selected from 3,3′-diaminodiphenylsulfone and bis (4- (3-aminophenoxy) phenyl) sulfone. Thermosetting resin composition.

(10) The polyvalent hydroxy compound is selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol. Item 10. The thermosetting resin composition according to any one of Items 1 to 9, which is one or more kinds of compounds.

(11) The epoxy resin is polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer. Item 11. The thermosetting resin composition according to any one of Items 1 to 10, which is one or more compounds selected from an epoxy group-containing polymer of a styrene-glycidyl methacrylate copolymer.

(12) The thermosetting resin composition according to any one of Items 1 to 10, wherein the epoxy resin is an alicyclic epoxy resin.

(13) The thermosetting resin composition according to any one of Items 1 to 12, wherein the epoxy curing agent is trimellitic anhydride.

(14) The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the diamine is 3,3′-diaminodiphenyl sulfone, the polyvalent hydroxy compound is 1, Item 1 is 4-butanediol, the epoxy resin is an n-butyl methacrylate-glycidyl methacrylate copolymer, the epoxy curing agent is trimellitic anhydride, and the solvent is a solvent containing methyl 3-methoxypropionate. Or the thermosetting resin composition of 2.

(15) The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the diamine is 3,3′-diaminodiphenyl sulfone, the polyvalent hydroxy compound is 1, 4-butanediol, monohydric alcohol is benzyl alcohol, epoxy resin is n-butyl methacrylate-glycidyl methacrylate copolymer, epoxy curing agent is trimellitic anhydride, and solvent is 3-methoxypropionic acid Item 4. The thermosetting resin composition according to Item 2 or 3, which is a solvent containing methyl.

(16) The thermosetting resin composition according to any one of Items 1 to 15, wherein the polyesteramidic acid has a weight average molecular weight of 2,000 to 200,000.

(17) The thermosetting resin composition according to any one of items 1 to 15, wherein the epoxy resin has a weight average molecular weight of 10,000 to 1,000,000.

(18) A cured film obtained by heating the thermosetting resin composition according to any one of items 1 to 17.

(19) A color filter using the cured film according to item 18 as a protective film.

(20) A liquid crystal display device using the color filter according to item 19.

(21) A solid-state imaging device using the color filter according to Item 19.

(22) A liquid crystal display device using the cured film according to item 18 as a transparent insulating film formed between the TFT and the transparent electrode.

(23) A liquid crystal display device using the cured film according to item 18 as a transparent insulating film formed between the transparent electrode and the alignment film.

(24) An LED light emitter using the cured film according to item 18 as a protective film.

  The thermosetting resin composition of the present invention is excellent in foreign matter characteristics, and the yield is improved when used as a color filter protective film. Further, the cured film obtained by heating the thermosetting resin composition of the present invention is well balanced in transparency, heat resistance, chemical resistance, flatness, adhesion, and sputtering resistance. It is highly practical. In particular, it is useful as a protective film for a color filter produced by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. It can also be used as a protective film and a transparent insulating film for various optical materials.

  Specific examples of the tetracarboxylic dianhydride used in the present invention include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride and 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride. Anhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 2,2 ′ , 3,3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoro Professional Dianhydrides and aromatic tetracarboxylic dianhydrides such as ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.), cyclobutane tetracarboxylic dianhydride , Cycloaliphatic tetracarboxylic dianhydrides such as methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride, and ethanetetracarboxylic dianhydride and butane Mention may be made of aliphatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydrides.

  Among these, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride give resins having good transparency Product, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.) 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride are particularly preferable.

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

  Specific examples of the polyvalent hydroxy compound used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene. Glycol, polypropylene glycol having a molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4- Pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1 , 7 Heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 1,2-nonanediol, 1 , 9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecane Examples thereof include diol, 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-heptanediol, and 1,8-octanediol are preferable, and 1,4 -Butanediol, 1,5-pentanediol, and 1,6-hexanediol are particularly preferable because of their good solubility in solvents.

  Specific examples of the monohydric alcohol used in the present invention include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol. Monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, phenol, borneol, maltol, linalool, terpineol, dimethylbenzyl carbinol, 3-ethyl- And 3-hydroxymethyl oxetane .

  Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl oxetane are preferable. In consideration of the compatibility when the polyester amide acid formed by using these, an epoxy resin and an epoxy curing agent are mixed, and the applicability on the color filter of the thermosetting resin composition as the final product, As the alcohol, benzyl alcohol is more preferably used.

  Specific examples of the silicon-containing monoamine used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 4-amino. Butyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenyl Examples thereof include methyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane are preferable, and 3-aminopropyltriethoxysilane is particularly preferable because of good acid resistance of the coating film.

Specific examples of the solvent used in the polymerization reaction to obtain polyester amic acid include diethylene glycol dimethyl ether, 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 N-methyl-2-pyrrolidone are preferable.
These solvents can be used alone or as a mixed solvent of two or more. Moreover, if it is a ratio of 30 weight% or less, another solvent can also be mixed and used besides the said solvent.

In the method for producing the polyester amide acid used in the present invention, X mol of tetracarboxylic dianhydride, Y mol of diamine, and Z mol of polyvalent hydroxy compound are reacted in the above solvent. At this time, it is preferable that X, Y, and Z are set to such a ratio that the relationship of the following formulas (1) and (2) is established between them. If it is this range, the solubility to the solvent of a polyester amide acid is high, therefore the applicability | paintability of a composition improves, As a result, the cured film excellent in flatness can be obtained.
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦1.5 (2)
The relationship of the formula (1) is preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.3 ≦ Z / Y ≦ 7.0. In addition, the relationship of the formula (2) is preferably 0.5 ≦ (Y + Z) /X≦0.9, more preferably 0.7 ≦ (Y + Z) /X≦0.8.

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

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

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

  The order of adding the reaction raw materials to the reaction system is not particularly particular. That is, tetracarboxylic dianhydride and diamine and polyvalent hydroxy compound are simultaneously added to the reaction solvent, diamine and polyvalent hydroxy compound are dissolved in the reaction solvent, and then tetracarboxylic dianhydride is added, or tetra Any method can be used such as reacting carboxylic dianhydride and diamine in advance, and then adding a polyvalent hydroxy compound to the reaction product. The weight average molecular weight of the obtained polyester amide acid is preferably 2,000 to 200,000, and more preferably 3,000 to 150,000. This is because a higher molecular weight is preferable for the foreign matter characteristics, and a lower molecular weight is more preferable for the solubility in the solvent.

  In order to increase the weight average molecular weight of the polyester amide acid, a synthetic reaction may be performed by adding a compound having 3 or more acid anhydride groups. Specific examples of the compound having 3 or more acid anhydride groups include a styrene-maleic anhydride copolymer.

The polyester amide acid synthesized in this way contains the structural unit consisting of the above formulas (3) and (4), and the terminal thereof is an acid derived from tetracarboxylic dianhydride, diamine or polyvalent hydroxy compound as a raw material. It is an anhydride group, an amino group or a hydroxy group, or an additive other than these compounds constitutes the terminal. In Formulas 3 and 4, R ₁ is a tetracarboxylic dianhydride residue, 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 polyvalent hydroxy compound residue, preferably an organic group having 2 to 20 carbon atoms.

  The epoxy resin used in the present invention is not particularly limited as long as it has good compatibility with the other components forming the thermosetting resin composition of the present invention, but is preferably a bisphenol A type epoxy resin or a glycidyl ester type. Examples thereof include an epoxy resin, an alicyclic epoxy resin, a polymer of a monomer having an epoxy group, and a copolymer of a monomer having an epoxy group and another monomer. Among these, an alicyclic epoxy resin, a polymer of a monomer having an epoxy group, and a copolymer of a monomer having an epoxy group and another monomer are particularly preferable because of excellent transparency and foreign matter characteristics.

  As specific examples of the alicyclic epoxy resin, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (above trade name, manufactured by Japan Epoxy Resin Co., Ltd.), Araldite CY177, Araldite CY184 (above trade name, manufactured by Ciba Geigy Japan), Celoxide 2021, and EHPE-3150 (above trade name, Daicel Chemical Industries, Ltd.) ) Made). Two or more epoxy resins used in the present invention may be mixed and used. When a mixture of an epoxy resin having a molecular weight of less than 10,000 and an epoxy resin having a molecular weight of 10,000 or more is used, if the epoxy resin having a molecular weight of 10,000 or more is 5% by weight or more of the total epoxy resin, the foreign matter characteristics are good. preferable.

  Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate. Among these, glycidyl methacrylate is preferable because it can provide a cured film having good foreign matter characteristics.

  Specific examples of other monomers copolymerized with a monomer having an epoxy group include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methyl Examples include styrene, chloromethylstyrene, and N-phenylmaleimide. Among these, methyl (meth) acrylate, benzyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl whose copolymer is excellent in compatibility with the polyester amide acid used in the present invention. More preferred are (meth) acrylates and styrene.

  Preferable specific examples of a polymer of a monomer having an epoxy group and a copolymer of a monomer having an epoxy group and another monomer include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, and benzyl methacrylate-glycidyl methacrylate copolymer. Examples of the polymer include n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

The proportion of the copolymer of the monomer having an epoxy group and another monomer is preferably 30% by mole or more of the monomer having an epoxy group because the chemical resistance is excellent. More preferably, the monomer having an epoxy group is 50 mol% or more.
The molecular weight of the polymer of the monomer having an epoxy group or the copolymer of a monomer having an epoxy group and another monomer is preferably 10,000 to 1,000,000 in terms of weight average molecular weight, and preferably 50,000 to 500, 000 is more preferable. This is because the foreign matter characteristics are better as the molecular weight is higher, and the solubility in the solvent is better as the molecular weight is lower.

  In order to improve heat resistance and chemical resistance, it is effective to add an epoxy curing agent to the thermosetting resin composition of the present invention. Examples of the epoxy curing agent include an acid anhydride curing agent, a polyamine curing agent, a polyphenol curing agent, and a catalyst curing agent, and an acid anhydride curing agent is preferable from the viewpoint of coloring and heat resistance.

  Specific examples of the acid anhydride-based curing agent include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and aliphatic dicarboxylic anhydrides such as methylhexahydrophthalic anhydride, phthalic anhydride, and trimellitic anhydride. And aromatic polycarboxylic acid anhydrides such as styrene-maleic anhydride copolymer. Among these, trimellitic anhydride is particularly preferable from the viewpoint of the balance between heat resistance and solubility in a solvent.

  The thermosetting resin composition of this invention is 20-400 weight part of epoxy resins with respect to 100 weight part of polyester amic acid. When the epoxy resin is within this range, the balance of flatness, heat resistance, chemical resistance, adhesion, and foreign material characteristics is good. The epoxy resin is more preferably in the range of 50 to 200 parts by weight.

  When the epoxy curing agent is added for the purpose of improving heat resistance and chemical resistance, the ratio of the epoxy resin and the epoxy curing agent is 0 for the carboxylic anhydride group or carboxylic acid group as the epoxy curing agent with respect to the epoxy group. It is preferable to add in an amount equivalent to 2 to 2 times. At this time, the carboxylic acid anhydride group is calculated as divalent. Addition of the carboxylic acid anhydride group or the carboxylic acid group in an amount of 0.5 to 1.5 times equivalent is more preferable because the chemical resistance is further improved.

  As the solvent used in the resin composition of the present invention, the solvent used in the polymerization reaction when synthesizing the polyester amide acid can be used as it is. The solid content of the thermosetting resin composition is selected depending on the film thickness of the coating film, but is generally contained in the range of 5 to 40 parts by weight in 100 parts by weight of the resin composition. .

The thermosetting resin composition according to the present invention may contain other components other than the above, if necessary, as long as the object of the present invention is not impaired. Examples of such other components include a coupling agent and a surfactant.
The coupling agent is used to improve the adhesion to the substrate, and is 100 parts by weight of the solid content of the thermosetting resin composition (the remaining component excluding the solvent from the resin composition). It is used by adding 10 parts by weight or less.

As the coupling agent, silane-based, aluminum-based and titanate-based compounds can be used.
Specifically, silanes such as 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane, and aluminum such as acetoalkoxyaluminum diisopropylate And titanate systems such as tetraisopropyl bis (dioctyl phosphite) titanate. Among these, 3-glycidoxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.

  The surfactant is used to improve the wettability, leveling property, or coating property to the base substrate, and is added in an amount of 0.01 to 1 part by weight with respect to 100 parts by weight of the thermosetting resin composition. Used. As the surfactant, a silicon surfactant, an acrylic surfactant, a fluorine surfactant, or the like is used. Specifically, silicon systems such as Byk-300, Byk-306, Byk-335, Byk-310, Byk-341, Byk-344, and Byk-370 (above trade names, manufactured by BYK Chemie Co., Ltd.) , Byk-354, ByK-358, and Byk-361 (above trade names, manufactured by Big Chemie Co., Ltd.) and the like, DFX-18, Aftergent 250, and Aftergent 251 (above trade names, Neos ( Product)).

In the thermosetting resin composition of the present invention, a polyester amide acid, an epoxy resin and a solvent are mixed, and an epoxy curing agent, a coupling agent and a surfactant are further optionally selected and added depending on the intended characteristics. These can be obtained by uniformly mixing and dissolving them.
When the thermosetting resin composition prepared as described above is applied to the substrate surface and the solvent is removed by heating, a coating film can be formed. Application of the thermosetting resin composition to the substrate surface can form a coating film by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, or a slit coating method. Next, this coating film is heated (prebaked) with a hot plate or an oven. The heating conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 120 ° C, 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Then, in order to cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 250 ° C., for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.

The cured film thus obtained has a high molecular weight when heated, 1) the polyamic acid portion of the polyester amic acid is dehydrated to form an imide bond, and 2) the carboxylic acid of the polyester amic acid reacts with the epoxy resin. And 3) Since the epoxy resin is cured and has a high molecular weight, it is very tough and excellent in transparency, heat resistance, chemical resistance, flatness, adhesion, and sputtering resistance.
Next, although a synthesis example, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples.
A polyester amic acid solution comprising a reaction product of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound was synthesized as shown below.

Synthesis example 1
A 500 ml separable flask equipped with a thermometer and a stirring blade was purged with nitrogen, and then 9.93 g of 3,3′-diaminodiphenylsulfone (hereinafter abbreviated as “DDS”) and 14.42 g of 1,4-butanediol. Then, 202 g of dehydrated and purified methyl 3-methoxypropionate (hereinafter abbreviated as “MMP”) was added and stirred at room temperature to dissolve DDS and 1,4-butanediol. Thereafter, 62.04 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as “ODPA”) was added. The mixture was heated to 130 ° C. in an oil bath, stirred for 4 hours, and then cooled to obtain a 30% by weight solution of a pale yellow transparent polyester amic acid. The rotational viscosity of this solution was 36.5 mPa · s. Here, the rotational viscosity is a viscosity measured at 25 ° C. using an E-type viscometer (trade name; VISCONIC END, manufactured by Tokyo Keiki Co., Ltd.) (hereinafter the same). The weight average molecular weight measured by GPC was 7,600.

Synthesis example 2
A 500 ml flask equipped with a thermometer and stirring blades was purged with nitrogen, and then charged with 12.75 g of DDS and 16.20 g of 1,4-butanediol, and then with 280 g of dehydrated and purified MMP, stirred at room temperature, DDS, 1 , 4-butanediol was dissolved. Thereafter, 79.67 g of ODPA was added. The mixture was heated to 130 ° C. in an oil bath, stirred for 4 hours, and then cooled to 30 ° C. 11.37 g of 3-aminopropyltriethoxysilane was added and stirred for 4 hr to obtain a 30% by weight solution of a pale yellow transparent ester group-containing polyamic acid. The rotational viscosity of this solution was 18.2 mPa · s. The weight average molecular weight measured by GPC was 3,800.

Synthesis example 3
A 500 ml separable flask equipped with a thermometer and stirring blades was purged with nitrogen, then charged with 9.93 g of DDS and 14.42 g of 1,4-butanediol, and then charged with 206 g of dehydrated and purified MMP, stirred at room temperature, DDS and 1,4-butanediol were dissolved. Thereafter, 55.84 g of ODPA and 8.09 g of styrene-maleic anhydride copolymer SMA-1000 (trade name, manufactured by Kawa Crude Chemical Co., Ltd.) were added. The mixture was heated to 130 ° C. with an oil bath, stirred for 4 hours, and then cooled. A light yellow transparent 30% by weight solution of polyester amide acid was obtained. The rotational viscosity of this solution was 91.7 mPa · s. The weight average molecular weight measured by GPC was 24,000.

Synthesis example 4
A 500 ml separable flask equipped with a thermometer and stirring blades was purged with nitrogen, then charged with 9.93 g of DDS and 24.03 g of triethylene glycol, and then with 224 g of dehydrated and purified MMP, stirred at room temperature, and DDS, and Triethylene glycol was dissolved. Thereafter, 62.04 g of ODPA was added. The mixture was heated to 130 ° C. with an oil bath, stirred for 6 hours, and then cooled. A light yellow transparent 30% by weight solution of polyester amide acid was obtained. The rotational viscosity of this solution was 31.9 mPa · s. The weight average molecular weight measured by GPC was 7,200.

Synthesis example 5
A 500 ml flask equipped with a thermometer and stirring blades was purged with nitrogen, and then charged with 13.03 g of DDS and 14.19 g of 1,4-butanediol, and then with 280 g of dehydrated and purified MMP, stirred at room temperature, , 4-butanediol was dissolved. Thereafter, 81.42 g of ODPA and 11.35 g of benzyl alcohol were added. The mixture was heated to 130 ° C. with an oil bath, stirred for 4 hours, and then cooled. A 30% by weight solution of a pale yellow transparent ester group-containing polyamic acid was obtained. The rotational viscosity of this solution was 20.1 mPa · s. The weight average molecular weight measured by GPC was 4,400.

  A 1,000-ml separable flask equipped with a stirring blade was purged with nitrogen, and 100 g of the polyester amic acid solution obtained in Synthesis Example 1 and a methyl methacrylate-glycidyl methacrylate copolymer (molar ratio 30:70, weight) were added to the flask. An average molecular weight of 250,000) 30 g, trimellitic anhydride 6 g, 3-glycidoxypropyltrimethoxysilane 3 g, and dehydrated and purified MMP 558 g were charged, and stirred at room temperature for 5 hours to be uniformly dissolved. Next, 0.69 g of Byk-344 (trade name; manufactured by Big Chemie Co., Ltd.) was added, stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a coating solution. First, the foreign material characteristics of this coating solution were evaluated. Next, this coating solution was spin-coated on a glass substrate and a color filter substrate at 600 rpm for 10 seconds, and then pre-baked on a hot plate at 80 ° C. for 3 minutes to form a coating film. Thereafter, the coating film was cured by heating in an oven at 220 ° C. for 30 minutes to obtain a cured film having a thickness of 1.5 μm. The cured film thus obtained was evaluated for properties with respect to transparency, heat resistance, chemical resistance, flatness, adhesion, and sputtering resistance. These evaluation results are shown in Table 1.

[Evaluation methods]
Foreign material characteristics: A chromium substrate was set on a spreader of bead spacers, and bead spacers having a diameter of 20 μm were spread at a rate of 3 to 5 pieces / cm ² . The coating solution was spin-coated on this substrate at 600 rpm for 10 seconds, and then pre-baked on a hot plate at 80 ° C. for 3 minutes to form a coating film. Thereafter, the coating film was cured by heating in an oven at 220 ° C. for 30 minutes to obtain a cured film having a thickness of 1.5 μm. The surface of this cured film was observed at a magnification of 50 using a differential interference microscope (trade name; AFX-IIA, manufactured by Nikon Co., Ltd.), and the diameter of the portion where the film around the bead spacer was raised was measured.

Transparency: In the obtained glass substrate with a cured film, a spectrophotometer (trade name: MICRO COLOR ANALYZER TC-1800M, manufactured by Tokyo Denshoku Technical Center) transmits only the cured film at a wavelength of 400 nm. Was measured. The case where the transmittance was 99% or more was rated as ◯, and the case where the transmittance was less than 99% was rated as ×.

Heat resistance: After the obtained glass substrate with a cured film was reheated at 250 ° C. for 1 hour, the remaining film ratio after heating with respect to the film thickness before heating and the transmittance at 400 nm after heating were measured. A case where the remaining film ratio after heating was 95% or more and the transmittance at 400 nm after heating was 99% or more was evaluated as ◯. The case where the residual film rate after heating was less than 95% or the transmittance at 400 nm after heating was less than 99% was evaluated as x.

Chemical resistance: Immersion treatment (hereinafter abbreviated as “NaOH treatment”) in a 5 wt% aqueous sodium hydroxide solution at 30 ° C. for 30 minutes, 36% hydrochloric acid / 60% nitric acid / water = 40 / 20/40 in a mixed solution (weight ratio) at 50 ° C. for 15 minutes (hereinafter abbreviated as mixed acid treatment), and in N-methyl-2-pyrrolidone at 40 ° C. for 30 minutes (hereinafter, referred to as “mixed acid treatment”). NMP treatment was abbreviated separately, and then the remaining film rate after each treatment and the transmittance before and after each treatment with respect to the film thickness before each treatment were measured. A case where the remaining film rate after each treatment was 95% or more and the transmittance at 400 nm after each treatment was 99% or more was evaluated as ◯. The case where the residual film rate after each treatment was less than 95% or the transmittance after each treatment was less than 99% was evaluated as x.

Flatness: The level difference of the cured film surface of the obtained color filter substrate with a cured film was measured using a stylus type film thickness meter (trade name: alpha-step200, manufactured by TENCOR INSTRUMENTS). The case where the maximum value of the step between the R, G and B pixels including the black matrix (hereinafter abbreviated as the maximum roughness) is less than 0.05 μm is indicated as “◯”, and the case where it is 0.05 μm or more is indicated as “X”. The color filter substrate used was an electrodeposition color filter with a maximum roughness of about 0.8 μm (hereinafter abbreviated as electrodeposition CF) and a printing method color filter with a maximum roughness of about 0.2 μm (hereinafter referred to as print CF). Abbreviated).

Adhesion: The obtained glass substrate with a cured film was subjected to a pressure cooker test (hereinafter abbreviated as PCT treatment) for 24 hours under the conditions of 120 ° C., 100%, and 0.2 MPa, and then the tape was peeled off from the cured film. The Goban eye test (JIS-K-5400) was performed and the remaining number was counted. The case where the remaining number / 100 was 100/100 was evaluated as ◯, and the case where it was 99/100 or less was evaluated as ×.

Sputtering resistance: When the ITO film was formed on the cured film by sputtering at 240 ° C. so that a resistance value of 10 Ω / cm ² was obtained in the obtained glass substrate with a cured film, the presence or absence of wrinkling of the film I investigated. The case where there was no wrinkle was marked as ◯, and the case where wrinkles occurred was marked as x.

  In the same manner as in Example 1, only the polyesteramic acid solution was changed to the solution obtained in Synthesis Example 2 to prepare a coating solution. In the same manner as in Example 1, the characteristics were evaluated with respect to foreign matter characteristics, transparency, heat resistance, chemical resistance, flatness, adhesion, and sputtering resistance. These evaluation results are shown in Table 1.

  In the same manner as in Example 1, only the polyesteramic acid solution was changed to the solution obtained in Synthesis Example 3 to prepare a coating solution. In the same manner as in Example 1, the characteristics were evaluated with respect to foreign matter characteristics, transparency, heat resistance, chemical resistance, flatness, adhesion, and sputtering resistance. These evaluation results are shown in Table 1.

  In the same manner as in Example 1, only the polyesteramic acid solution was changed to the solution obtained in Synthesis Example 4 to prepare a coating solution. In the same manner as in Example 1, the characteristics were evaluated with respect to foreign matter characteristics, transparency, heat resistance, chemical resistance, flatness, adhesion, and sputtering resistance. These evaluation results are shown in Table 1.

  In the same manner as in Example 1, the polyester amic acid solution was changed to the solution obtained in Synthesis Example 5, and the methyl methacrylate / glycidyl methacrylate copolymer was changed to a butyl tacrylate / glycidyl methacrylate copolymer (molar ratio 20). : 80, weight average molecular weight 80,000) The coating solution was adjusted to 30 g. In the same manner as in Example 1, the characteristics were evaluated with respect to foreign matter characteristics, transparency, heat resistance, chemical resistance, flatness, adhesion, and sputtering resistance. These evaluation results are shown in Table 1.

  In a 500-ml separable flask purged with nitrogen with a stirring blade, 100 g of the polyester amic acid solution obtained in Synthesis Example 3, alicyclic epoxy resin Epicoat 191P (trade name; manufactured by Yuka Shell Epoxy Co., Ltd., weight average) 30 g of molecular weight 284), 15 g of trimellitic anhydride, 3 g of 3-glycidoxypropyltrimethoxysilane and 206 g of dehydrated and purified MMP were charged and stirred at room temperature for 5 hours to be dissolved uniformly. Next, 0.69 g of Byk-344 (trade name; manufactured by Big Chemie Co., Ltd.) was added, stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a coating solution. Evaluation similar to Example 1 was performed about this coating liquid. These evaluation results are shown in Table 1.

  In a 500 ml separable flask substituted with nitrogen with a stirring blade, 20 g of the ester group-containing polyamic acid solution obtained in Synthesis Example 1 and alicyclic epoxy resin Epicoat 191P (trade name: manufactured by Yuka Shell Epoxy Co., Ltd.) 24 g, trimellitic anhydride 13 g, 3-glycidoxypropyltrimethoxysilane 3 g and dehydrated and purified MMP 206 g were charged and stirred at room temperature for 5 hours to be dissolved uniformly. Next, 0.69 g of Byk-344 (trade name: manufactured by Big Chemie Co., Ltd.) was added, stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a coating solution. Evaluation similar to Example 1 was performed about this coating liquid. These evaluation results are shown in Table 1.

(Comparative Example 1)
A 500 ml separable flask equipped with a thermometer and stirring blades was purged with nitrogen, and then 4.85 g of DDS and 43.22 g of 3-aminopropyltriethoxysilane were added, and 197 g of dehydrated and purified MMP was added and stirred at room temperature. , DDS and 3-aminopropyltriethoxysilane were dissolved. Thereafter, the flask was cooled in an ice bath, and 36.36 g of ODPA was added when the temperature of the content liquid reached 10 ° C. When the temperature increase due to the exothermic reaction stopped, the ice bath was removed and the mixture was stirred at room temperature for 8 hours to obtain a pale yellow transparent silicon-containing polyamic acid solution. The rotational viscosity of this solution was 12 mPa · s.
In a 500-ml separable flask purged with nitrogen with a stirring blade, 100 g of the above silicon-containing polyamic acid solution, 30 g of Epicoat 191P (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), 16.95 g of trimellitic anhydride, 3- 3.85 g of glycidoxypropyltrimethoxysilane and 172.4 g of dehydrated and purified MMP were charged and stirred at room temperature to dissolve uniformly. Next, 0.17 g of Byk-344 (trade name; manufactured by Big Chemie Co., Ltd.) was added, stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a coating solution. Evaluation similar to Example 1 was performed about this coating liquid. These evaluation results are shown in Table 1.

(Comparative Example 2)
In a 500-ml separable flask purged with nitrogen with a stirring blade, 100 g of the silicon-containing polyamic acid solution synthesized in Comparative Example 1 and 30 g of methyl methacrylate-glycidyl methacrylate copolymer (molar ratio 30:70, weight average molecular weight 250,000) Then, 16.95 g of trimellitic anhydride, 3.85 g of 3-glycidoxypropyltrimethoxysilane and 172.4 g of dehydrated and purified MMP were charged and stirred at room temperature. As a result, the solution became cloudy and a uniform solution could not be obtained.

(Comparative Example 3)
A 500 ml separable flask equipped with a thermometer and stirring blades was purged with nitrogen, and after charging 29.10 g of DDS, 153 g of dehydrated and purified MMP was charged and stirred at room temperature to dissolve DDS. Thereafter, the flask was cooled in an ice bath, and 36.36 g of ODPA was added when the temperature of the content liquid reached 10 ° C. When the ice bath was removed and stirring was continued at room temperature, it became a slightly grayish slurry, and a polyamic acid solution could not be obtained.

(Comparative Example 4)
A 500 ml separable flask equipped with a thermometer and stirring blades was purged with nitrogen, charged with 10.56 g of 1,4-butanediol and 109 g of dehydrated and purified MMP, and charged with 36.36 g of ODPA while stirring at room temperature. The mixture was heated to 120 ° C. with an oil bath, stirred for 4 hours, and then cooled. A 30% by weight solution of a pale yellow transparent polyester was obtained. The rotational viscosity of this solution was 67.2 mPa · s. The weight average molecular weight measured by GPC was 15,000.
Next, in a nitrogen-substituted 500 ml separable flask equipped with a stirring blade, 100 g of the above polyester solution, 30 g of Epicoat 191P (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), 16.95 g of trimellitic anhydride, 3- 3.85 g of glycidoxypropyltrimethoxysilane and 172.4 g of dehydrated and purified MMP were charged and stirred at room temperature to dissolve uniformly. Next, 0.17 g of Byk-344 (trade name; manufactured by Big Chemie Co., Ltd.) was added, stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a coating solution. Evaluation similar to Example 1 was performed about this coating liquid. These evaluation results are shown in Table 1.

  As is clear from the results shown in Table 1, the cured films of Examples 1 to 7 have small foreign matters, and all points of transparency, heat resistance, chemical resistance, flatness, adhesion, and sputtering resistance. It can be seen that there is a balance. On the other hand, the coating solution using the polyamic acid solution containing no ester group of Comparative Example 1 is inferior in terms of foreign matter characteristics, and a decrease in yield is expected when used as a color filter protective film.

The cured film obtained from the thermosetting resin composition of the present invention is excellent in properties as an optical material such as sputtering resistance and transparency, and thus various optical materials such as a color filter, an LED light emitting element, and a light receiving element. And a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (23)

A resin composition comprising a polyester amide acid, an epoxy resin, an epoxy curing agent and a solvent obtained by reacting tetracarboxylic dianhydride, diamine and a polyvalent hydroxy compound as essential components, wherein the polyester amide acid is X Obtained by reacting mol tetracarboxylic dianhydride, Y mol diamine and Z mol polyhydric hydroxy compound at a ratio such that the relationship of the following formulas (1) and (2) is satisfied,
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦1.5 (2)
The thermosetting resin composition is characterized in that the epoxy resin is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amic acid, and the epoxy curing agent is 15 to 60 parts by weight with respect to 100 parts by weight of the epoxy resin. .   The thermosetting resin composition according to claim 1, wherein the polyester amic acid is a reaction product obtained by reacting tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound and monohydric alcohol as essential components.   Polyester amide acid is a reaction product obtained by reacting tetracarboxylic dianhydride, diamine, polyhydric hydroxy compound, monohydric alcohol and silicon-containing monoamine as essential components, and the silicon-containing monoamine is 3-aminopropyltriamine. Methoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldi Ethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxy Silane or thermosetting resin composition according to claim 1 is a m- aminophenyl methyl diethoxy silane.   The thermosetting resin composition according to claim 2 or 3, wherein the monohydric alcohol is isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3-ethyl-3-hydroxymethyloxetane.   The thermosetting resin composition according to any one of claims 1 to 4, wherein the polyester amic acid is a polyester amic acid obtained by further reacting with a styrene-maleic anhydride copolymer. The thermosetting resin composition according to any one of claims 1 to 5, wherein the polyester amide acid is a compound having structural units represented by the following formulas (3) and (4).

Here, R ₁ is a tetracarboxylic dianhydride residue, R ₂ is a diamine residue, and R ₃ is a polyvalent hydroxy compound residue.   Tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- (bis The compound according to any one of claims 1 to 6, which is one or more compounds selected from (3,4-dicarboxyphenyl)) hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate). Thermosetting resin composition.   The thermosetting according to any one of claims 1 to 7, wherein the diamine is one or more compounds selected from 3,3'-diaminodiphenylsulfone and bis (4- (3-aminophenoxy) phenyl) sulfone. Resin composition.   1 wherein the polyhydroxy compound is selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol It is a compound more than a seed | species, The thermosetting resin composition of any one of Claims 1-8.   The epoxy resin is polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer and styrene- The thermosetting resin composition according to any one of claims 1 to 9, which is one or more compounds selected from an epoxy group-containing polymer of a glycidyl methacrylate copolymer.   The thermosetting resin composition according to any one of claims 1 to 9, wherein the epoxy resin is an alicyclic epoxy resin.   The thermosetting resin composition according to claim 1, wherein the epoxy curing agent is trimellitic anhydride.   The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the diamine is 3,3′-diaminodiphenyl sulfone, and the polyvalent hydroxy compound is 1,4-butane. The diol, the epoxy resin is an n-butyl methacrylate-glycidyl methacrylate copolymer, the epoxy curing agent is trimellitic anhydride, and the solvent is a solvent containing methyl 3-methoxypropionate. The thermosetting resin composition described in 1.   The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the diamine is 3,3′-diaminodiphenyl sulfone, and the polyvalent hydroxy compound is 1,4-butane. Diol, monohydric alcohol is benzyl alcohol, epoxy resin is n-butyl methacrylate-glycidyl methacrylate copolymer, epoxy curing agent is trimellitic anhydride, and solvent contains methyl 3-methoxypropionate The thermosetting resin composition according to claim 2, which is a solvent to be used.   The thermosetting resin composition according to claim 1, wherein the polyester amic acid has a weight average molecular weight of 2,000 to 200,000.   The thermosetting resin composition according to any one of claims 1 to 14, wherein the epoxy resin has a weight average molecular weight of 10,000 to 1,000,000.   The cured film obtained by heating the thermosetting resin composition of any one of Claims 1-16.   A color filter using the cured film according to claim 17 as a protective film.   A liquid crystal display device using the color filter according to claim 18.   A solid-state imaging device using the color filter according to claim 18.   A liquid crystal display element using the cured film according to claim 17 as a transparent insulating film formed between a TFT and a transparent electrode.   A liquid crystal display device using the cured film according to claim 17 as a transparent insulating film formed between a transparent electrode and an alignment film.   The LED light-emitting body which used the cured film of Claim 17 as a protective film.