JP2020033558A - Low-temperature curing composition with high gas barrier property - Google Patents

Abstract

To provide a thermosetting composition that gives a cured film excellent in barrier property, to provide a cured film formed from the thermosetting composition and to provide an electronic component having the cured film.SOLUTION: The thermosetting composition includes (A) a polyester amide acid, (B) a cycloalkene oxide group-containing polymer and (C) a curing agent. The polyester amide acid (A) is a reaction product produced from a raw material including X mol of a tetracarboxylic dianhydride, Y mol of diamine and Z mol of a polyvalent hydroxy compound in such respective ratios as to satisfy the relationships of formula (1) as given below and formula (2) as given below and the cycloalkene oxide group-containing copolymer (B) is a polymer comprising (b1) a cycloalkene oxide compound having a polymerizable double bond. Formula (1): 0.2≤Z/Y≤8.0 and formula (2): 0.2≤(Y+Z)/X≤5.0.SELECTED DRAWING: None

Description

  The present invention is applicable to the formation of an insulating material in an electronic component, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a flattening film, an interlayer insulating film in a liquid crystal display element, and a heat treatment that can be used for forming a protective film for a color filter. As a curable composition, a composition for a protective film having a low-temperature curability and a high barrier property against elution of a base component, comprising a polyesteramic acid, a polymer containing a cycloalkene oxide group, and a curing agent, and a film thereof. And an electronic component having the same.

  In a process of manufacturing an element such as a liquid crystal display element, various chemical treatments such as an organic solvent, an acid, and an alkali solution are performed, and a surface is locally heated to a high temperature when a wiring electrode is formed by sputtering. Sometimes. For this reason, 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 the various kinds of processing during the manufacturing process as described above. Specifically, heat resistance, chemical resistance such as solvent resistance, acid resistance, alkali resistance, etc., water resistance, adhesion to underlying substrates such as glass, transparency, scratch resistance, flatness, light resistance, etc. are required. Is done.

  In recent years, the definition of images has been improved, and in the field of color filters, a response to a wider color gamut is required. For this reason, each color filter manufacturer has taken measures such as the use of dyes that have good color but are easily eluted and decomposed, and minimize the photo-curing of the color resist in the process of forming color filters to prevent fading. . As a result, when the conventional protective film is used, the dye is eluted by the penetration of the solvent used in the alignment film solution during the formation of the alignment film in a later step, and finally, the display quality of the display deteriorates. However, there is a problem that the yield is reduced. Accordingly, in addition to the above-mentioned conventional required characteristics, there is an increasing demand for characteristics (hereinafter, also referred to as barrier properties) for reducing the elution of base components.

  In recent years, flexible displays have been developed, and organic film substrates such as PET films and PEN films have been used as flexible substrates. Since the heat-resistant temperature of these organic film substrates is 180 ° C. or less, it is an essential condition that the baking temperature of the protective film is not more than the heat-resistant temperature of the organic film substrate. Further, from the viewpoint of energy saving, a lower heating temperature is required in the manufacturing process.

  Until now, as an excellent protective film, a thermosetting composition containing a polyesteramide acid and an epoxy compound having good heat resistance has been proposed (for example, see Patent Document 1, Patent Document 2, and Patent Document 3). There is room for improvement in barrier properties. Further, in these inventions, a heat treatment at 200 ° C. to 250 ° C. is required for curing the coating film, which greatly exceeds the heat resistance temperature of the organic film substrate, and thus cannot be applied to a flexible product using the organic film substrate. In these inventions, a glycidyl ether type epoxy compound is mentioned as a preferred embodiment of the epoxy compound which is a component of the composition. However, in a system using polyester amide acid, a glycidyl ether type epoxy compound requires a temperature of about 200 ° C. for reaction with polyester amide and trimellitic anhydride as a curing agent. Therefore, if the conventional coating film is fired at a temperature as low as 150 ° C., the required barrier properties cannot be satisfied.

JP 2005-105264A JP 2008-156546 JP 2006-282995 A

  An object of the present invention is to provide a thermosetting composition that prevents a base component from being eluted and provides a cured film obtained at a low firing temperature, and a cured film formed by the thermosetting composition. Another object of the present invention is to provide an electronic component having the cured film.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a polyesteramic acid, a cycloalkene oxide group-containing polymer, which is a reaction product of tetracarboxylic dianhydride, diamine and polyhydroxy compound, and curing It has been found that the above object can be achieved by a cured film obtained by curing a composition containing an agent, and the present invention has been completed.
The present invention includes the following configurations.

[1] A thermosetting composition comprising a polyester amic acid (A), a cycloalkene oxide group-containing polymer (B), and a curing agent (C),
The polyester amic acid (A) is obtained by combining X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyhydric hydroxy compound such that the following formulas (1) and (2) are satisfied. Reaction products from the raw materials contained in the proportions,
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
The cycloalkene oxide group-containing polymer (B) may be a homopolymer of a cycloalkene oxide compound (b1) having a polymerizable double bond or a copolymer of cycloalkene oxide compounds (b1) having a polymerizable double bond. Heat, which is at least one selected from a copolymer of a cycloalkene oxide compound (b1) having a polymerizable double bond and a compound (b2) having a polymerizable double bond containing no cycloalkene oxide group. Curable composition.

式（３）及び式（４）において、Ｒ^１はテトラカルボン酸二無水物から２つの−ＣＯ−Ｏ−ＣＯ−を除いた残基であり、Ｒ^２はジアミンから２つの−ＮＨ_２を除いた残基であり、Ｒ^３は多価ヒドロキシ化合物から２つの−ＯＨを除いた残基である。 [2] The thermosetting composition according to [1], wherein the polyester amic acid (A) includes a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4);

In the formulas (3) and (4), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two —NH ₂ from a diamine. And R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound.

[3] The heat according to [1] or [2], wherein the polyester amic acid (A) includes at least one selected from a terminal-blocked polyester amide acid and a non-terminal-blocked polyester amide acid. Curable composition.

[4] At least the cycloalkene oxide compound (b1) having a polymerizable double bond is selected from 3,4-epoxycyclohexylmethyl (meth) acrylate and 1,2-epoxy-4-vinyl-1-cyclohexane. The thermosetting composition according to [1] or [2], which is one.

[5] Any one of [1] to [4], wherein the content of the cycloalkene oxide group-containing polymer (B) is 20 to 1,000 parts by weight based on 100 parts by weight of the polyester amic acid (A). 3. The thermosetting composition according to item 1.

  [6] A cured film obtained by curing the thermosetting composition according to any one of [1] to [5].

  [7] A color filter having the cured film according to [6] as a transparent protective film.

  The thermosetting composition according to a preferred embodiment of the present invention is a material that prevents elution of a base component and is curable at a low temperature, and improves display quality when used as a color filter protective film of a color liquid crystal display device. Can be done. In particular, it is useful as a protective film of a color filter manufactured by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. Further, it can be used as a protective film and a transparent insulating film of various optical materials.

1. Thermosetting composition of the present invention The thermosetting composition of the present invention is a polyesteramic acid (A) which is a reaction product from a raw material containing a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound, a cycloalkene. A composition containing an oxide group-containing polymer (B) and a curing agent (C), wherein the cycloalkene oxide group-containing polymer (B) is a cycloalkene oxide compound (b1) having a polymerizable double bond. , A copolymer of cycloalkene oxide compounds (b1) having a polymerizable double bond, and a cycloalkene oxide compound (b1) having a polymerizable double bond and a polymerizable polymer containing no cycloalkene oxide group The thermosetting composition is at least one selected from a copolymer of the compound (b2) having a double bond.

1-1. Polyester amic acid (A)
The polyester amic acid (A) is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components. Specifically, the polyester amide acid (A) is obtained by mixing X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of the polyhydric hydroxy compound such that the relationship of the formulas (1) and (2) is satisfied. It is obtained by reacting at a suitable ratio.
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)

The polyester amide acid (A) preferably has a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

In the formulas (3) and (4), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and is preferably an organic group having 2 to 30 carbon atoms. . R ² is a residue obtained by removing two —NH ₂ from a diamine, and is preferably an organic group having 2 to 30 carbon atoms. R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound, and is preferably an organic group having 2 to 20 carbon atoms.

  At least a solvent is required for the synthesis of the polyesteramic acid (A), and the solvent may be left as it is to obtain a liquid or gel-like thermosetting composition in consideration of handling properties or the like. The composition may be a solid composition in consideration of transportability.

  In the synthesis of the polyester amide acid (A), one or more compounds selected from a styrene-maleic anhydride copolymer may be contained as a raw material, if necessary. If necessary, other compounds other than those described above may be contained as long as the purpose is not impaired. Examples of other raw materials include monohydroxy compounds and silicon-containing monoamines.

1-1-1. Tetracarboxylic dianhydride In the present invention, tetracarboxylic dianhydride is used as a material for obtaining the polyester amic acid (A). Specific examples of preferred tetracarboxylic dianhydrides include 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfonetetracarboxylic acid 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)] hexafluoropropane dianhydride 1,2,3,4-butanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate) (trade name: TMEG-100, Shin Nippon Rika Co., Ltd.), cyclobutanetetracarboxylic dianhydride, methyl Examples include cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride, and butanetetracarboxylic dianhydride. One or more of these can be used.

  Among these, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 2,3 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride and ethylene glycol bis (anhydrotrimellitate) are more Preferably, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic acid Acid dianhydrides are more preferred.

1-1-2. Diamine In the present invention, a diamine is used as a material for obtaining the polyester amic acid (A). Specific examples of preferred diamines include 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, and 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, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3 '-Dihydroxybiphenyl, 2,2-bis (3-amino-4-hydroxyphenyl) propane, and 2,2- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane can be mentioned. One or more of these can be used.

  Among these, 3,3'-diaminodiphenylsulfone, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, and 4,4'-diamino-3,3'-dihydroxybiphenyl which give good transparency. , 2,2-bis (3-amino-4-hydroxyphenyl) propane and bis [4- (3-aminophenoxy) phenyl] sulfone are more preferred, and 3,3'-diaminodiphenylsulfone is still more preferred.

  Although the above compounds include compounds containing a plurality of hydroxyl groups (-OH), in the present invention, they are treated as diamines instead of polyvalent hydroxy compounds.

1-1-3. Polyvalent hydroxy compound In the present invention, a polyvalent hydroxy compound is used as a material for obtaining the polyesteramic acid (A).

  Specific examples of the polyhydroxy compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and weight average. 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 -F Tandiol, 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-dodecanediol Glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxyphenyl) ) Sulfone), bisphenol F (bis (4-hydroxy Enyl) methane), 4,4'-isopropylidenebis (2-phenoxyethanol) 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol , 2- (4-hydroxyphenyl) ethanol, diethanolamine, and triethanolamine.

  In addition to the above, glycerin monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, dipentaerythritol monoallyl ether, dipentaerythritol diallyl ether, dipentaerythritol triallyl ether, dipentalyl Erythritol tetraallyl ether, sorbitol monoallyl ether, sorbitol diallyl ether, sorbitol triallyl ether, sorbitol tetraallyl ether, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol Di (meth) acrylate, dipentaerythritol mono (meth A) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate Sorbitol tetra (meth) acrylate, ethylene glycol diglycidyl ether-modified (meth) acrylic acid, propylene glycol diglycidyl ether-modified (meth) acrylic acid, tripropylene glycol diglycidyl ether-modified (meth) acrylic acid , Glycerin diglycidyl ether modified with (meth) acrylic acid, bisphenol A diglycidyl ether modified with (meth) acrylic acid, propylene oxide modified Phenol A diglycidyl ether modified (meth) acrylic acid, bisphenol S diglycidyl ether modified (meth) acrylic acid, propylene oxide modified bisphenol S diglycidyl ether modified (meth) acrylic acid, bisphenol F diglycidyl ether (Meth) acrylic acid modified product, propylene oxide modified bisphenol F diglycidyl ether (meth) acrylic acid modified product, bixylenol diglycidyl ether modified (meth) acrylic acid, biphenol diglycidyl ether (meth) acrylic acid Modified product, modified (meth) acrylic acid of full orange phenol diglycidyl ether, modified (meth) acrylic acid of cyclohexane-1,4-dimethanol diglycidyl ether, hydrogenated bisphenol A diglycidyl (Meth) acrylic acid-modified products of tricyclodecane dimethanol diglycidyl ether and (meth) acrylic acid-modified products of other compounds containing two or more epoxy groups per molecule. Can be mentioned.

  Among these, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 7-heptanediol, 1,8-octanediol, glycerin, tris (2-hydroxyethyl) isocyanurate, 2,2-bis (4-hydroxycyclohexyl) propane, 4,4′-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol , 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethanol, 4,4'-isopropylidenebis (2-phenoxyethanol), (meth) acrylic acid-modified ethylene glycol diglycidyl ether, propylene glycol Modified (meth) acrylic acid of glycidyl ether, modified (meth) acrylic acid of tripropylene glycol diglycidyl ether, modified (meth) acrylic acid of glycerin diglycidyl ether, (meth) acrylic acid of bisphenol A diglycidyl ether Modified products, propylene oxide-modified bisphenol A diglycidyl ether modified with (meth) acrylic acid, bisphenol S diglycidyl ether modified with (meth) acrylic acid, propylene oxide modified bisphenol S diglycidyl ether modified with (meth) acrylic acid And (meth) acrylic acid-modified bisphenol F diglycidyl ether, and (meth) acrylic acid-modified propylene oxide-modified bisphenol F diglycidyl ether. Furthermore, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 4,4′-isopropylidene Bis (2-phenoxyethanol), 2- (4-hydroxyphenyl) ethanol, ethylene glycol diglycidyl ether-modified (meth) acrylic acid, propylene glycol diglycidyl ether-modified (meth) acrylic acid, tripropylene glycol diglycidyl Modified (meth) acrylic acid of ether, modified (meth) acrylic acid of glycerin diglycidyl ether, modified (meth) acrylic acid of bisphenol A diglycidyl ether, and modified with propylene oxide The scan phenol A diglycidyl ether (meth) acrylic acid modified product are more preferable.

  Modified methacrylic acid of ethylene glycol diglycidyl ether, modified acrylic acid of propylene glycol diglycidyl ether, modified acrylic acid of tripropylene glycol diglycidyl ether, modified acrylic acid of glycerin diglycidyl ether, bisphenol A diglycidyl ether The following commercially available products are used as methacrylic acid-modified products, bisphenol A diglycidyl ether-modified acrylic acid products, propylene oxide-modified bisphenol A diglycidyl ether-methacrylic acid-modified products, and propylene oxide-modified bisphenol A diglycidyl ether-acrylate-modified products. Can be used.

  A specific example of the methacrylic acid-modified product of ethylene glycol diglycidyl ether is epoxy ester 40EM (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified propylene glycol diglycidyl ether is epoxy ester 70PA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of tripropylene glycol diglycidyl ether is epoxy ester 200PA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified glycerin diglycidyl ether is epoxy ester 80MFA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of methacrylic acid-modified bisphenol A diglycidyl ether is epoxy ester 3000MK (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of acrylic acid-modified bisphenol A diglycidyl ether is epoxy ester 3000A (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of methacrylic acid-modified propylene oxide-modified bisphenol A diglycidyl ether is epoxy ester 3002M (N) (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of propylene oxide-modified bisphenol A diglycidyl ether is epoxy ester 3002A (N) (trade name; Kyoeisha Chemical Co., Ltd.).

1-1-4. Monohydroxy compound In the present invention, a monohydroxy compound may be used as a material for obtaining the polyester amic acid (A).

In the synthesis of the polyester amic acid (A), under the condition of using X in excess of Y + Z within the range of the above formula (2), an acid anhydride group derived from tetracarboxylic dianhydride (—CO—O Since -CO-) is present in excess of an amino group derived from a diamine or a hydroxyl group derived from a polyhydric hydroxy compound, it is considered that many molecules having an acid anhydride group at a terminal are generated. On the other hand, when reacting with such a monomer configuration, when a monohydroxy compound is added, the hydroxyl group of the monohydroxy compound reacts with the acid anhydride group, and the molecular terminal can be esterified. The polyesteramic acid (A) obtained by adding and reacting the monohydroxy compound has improved compatibility with the epoxy compound (B), and has improved storage stability of the thermosetting composition. The coatability of the curable composition is improved.

  Specific examples of the monohydroxy compound include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and ethylene. Glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltol, linalool, terpineol, dimethylbenzylcarbinol, 4-hydroxybenzyl alcohol, and 3-ethyl-3-hydroxymethyloxetane Can be mentioned. One or more of these can be used.

  Among them, isopropyl alcohol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, 4-hydroxybenzyl alcohol or 3-ethyl-3-hydroxymethyloxetane is more preferable. Compatibility when polyesteramidic acid (A) formed using these, cycloalkene oxide group-containing polymer (B), and curing agent (C) are mixed, and onto the color filter of thermosetting composition Considering the applicability of the compound, it is more preferable to use benzyl alcohol as the monohydroxy compound.

  It is preferable that the monohydroxy compound is reacted while containing 0 to 300 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. More preferably, it is 0 to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer The polyester amide acid (A) used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups to the above-mentioned raw materials. Polyester amic acid (A) synthesized by adding a compound having three or more acid anhydride groups is preferable because transparency is expected to be improved. An example of a compound having three or more acid anhydride groups is a styrene-maleic anhydride copolymer. As for the ratio of each component constituting the styrene-maleic anhydride copolymer, the molar ratio of styrene / maleic anhydride is 0.5 to 4, preferably 1 to 3. The molar ratio of styrene / maleic anhydride is preferably 1 or 2, and more preferably 1.

  Specific examples of the styrene-maleic anhydride copolymer are SMA3000P, SMA2000P, and SMA1000P (all trade names; Kawahara Yuka Co., Ltd.). Among these, SMA1000P, which has good heat resistance and alkali resistance, is particularly preferred.

  The styrene-maleic anhydride copolymer is preferably contained in an amount of 0 to 500 parts by weight based on 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine and polyhydroxy compound. More preferably, it is 10 to 300 parts by weight.

1-1-6. In the synthesis of the aminosilane compound polyester amic acid (A) having one amino group, other raw materials other than those described above may be contained as necessary, as long as the purpose of the present invention is not impaired. Examples of such other raw materials are aminosilane compounds having one amino group. The aminosilane compound having one amino group is used to react with an acid anhydride group at the terminal of the polyester amide acid (A) to introduce a silyl group at the terminal. When the thermosetting composition of the present invention containing the polyesteramic acid (A) obtained by adding and reacting an aminosilane compound having one amino group is used, the acid resistance of the obtained cured film is improved. Is done. Further, when the reaction is carried out with the above-mentioned monomer configuration, the reaction can be carried out by adding both a monohydroxy compound and an aminosilane compound having one amino group.

  Specific examples of preferred aminosilane compounds having one amino group used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxysilane. Silane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane , P-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. One or more of these can be used.

  Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane, which provide good acid resistance of the cured film, are more preferable, and 3-aminopropyltriethoxysilane is more preferable from the viewpoint of acid resistance and compatibility.

  The aminosilane compound having one amino group is preferably contained in an amount of 0 to 300 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. More preferably, it is 5 to 200 parts by weight.

1-1-7. Solvent used for the synthesis reaction of polyester amic acid (A) Specific examples of the solvent used for the synthesis reaction for obtaining the polyester amic acid (A) (hereinafter may be referred to as "reaction solvent") include diethylene glycol dimethyl ether and diethylene glycol. Methyl ethyl 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, cyclopentanone, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetamide. Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ethyl ether are preferred.

1-1-8. Synthetic method of polyester amic acid (A) The polyester amic acid (A) used in the present invention is obtained by reacting X mole of tetracarboxylic dianhydride, Y mole of diamine, and Z mole of polyvalent hydroxy compound in the above solvent. In this case, it is preferable that X, Y, and Z are determined at such a ratio that the relationship of the following formulas (1) and (2) is established therebetween. Within this range, the solubility of the polyesteramic acid (A) in the solvent is high, and therefore, the coatability of the composition is improved, and as a result, a cured film having excellent flatness can be obtained.
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)

  In the formula (1), preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.0 ≦ Z / Y ≦ 5.0. In the formula (2), preferably, 0.5 ≦ (Y + Z) /X≦4.0, and more preferably, 0.6 ≦ (Y + Z) /X≦2.0.

  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, because the reaction proceeds smoothly. The reaction is preferably carried out at 40 ° C to 200 ° C for 0.2 to 20 hours.

  The order of adding the reaction raw materials to the reaction system is not particularly limited. That is, a method of simultaneously adding a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound to a reaction solvent, a method of dissolving a diamine and a polyvalent hydroxy compound in a reaction solvent, and then adding a tetracarboxylic dianhydride, A method of reacting a tetracarboxylic dianhydride and a polyvalent hydroxy compound in advance and then adding a diamine to the product, or a method of reacting a tetracarboxylic dianhydride and a diamine in advance and then reacting the product with a polyvalent compound. Any method such as a method of adding a hydroxy compound can be used.

  When reacting the aminosilane compound having one amino group, after the reaction of the tetracarboxylic dianhydride and the diamine and the polyvalent hydroxy compound is completed, the solution after the reaction is cooled to 40 ° C. or lower. It is preferable to add an aminosilane compound having one amino group and react at 0.1 to 40 ° C. for 0.1 to 6 hours. Also, the monohydroxy compound may be added at any point in the reaction.

  The weight average molecular weight of the obtained polyester amic acid (A) is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000. Within these ranges, the flatness and heat resistance will be good.

  The weight average molecular weight of the polyester amic acid (A) is a value in terms of polystyrene obtained by a GPC method (column temperature: 35 ° C., flow rate: 1 ml / min). As the standard polystyrene, polystyrene having weight average molecular weights of 645, 2590, 10290, 37600, and 124500 of a polystyrene calibration kit PL2010-0102 manufactured by Agilent Technologies, Inc. was used. PLgel MIXED-D (Agilent Technology Co., Ltd.) was used as a column, and THF was used as a mobile phase. Further, the weight average molecular weight of the commercially available polymer described in this specification is a value published in a catalog.

1-2. Cycloalkene oxide group-containing polymer (B)
The cycloalkene oxide group-containing polymer (B) used in the present invention is a homopolymer of a cycloalkene oxide compound (b1) having a polymerizable double bond, or a cycloalkene oxide compound (b1) having a polymerizable double bond. And at least one selected from a copolymer of a cycloalkene oxide compound (b1) having a polymerizable double bond and a compound (b2) having a polymerizable double bond containing no cycloalkene oxide group. is there. The number of the cycloalkene oxide group-containing polymer (B) may be one or two or more.

  At least a solvent is required for the synthesis of the cycloalkene oxide group-containing polymer (B), and the solvent may be left as it is to obtain a liquid or gel-like thermosetting composition in consideration of handling properties and the like. The solvent may be removed to obtain a solid composition in consideration of transportability and the like.

1-2-1. Cycloalkene oxide compound having polymerizable double bond (b1)
Specific examples of the cycloalkene oxide compound (b1) having a polymerizable double bond include 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, trade name; CYM M100, Daicel Corporation) and 1,2-epoxy And 4-vinyl-1-cyclohexane (for example, trade name; CEL2000, Daicel Corporation).

1-2-2. Compound having a polymerizable double bond containing no cycloalkene oxide group (b2)
The compound (b2) having a polymerizable double bond that does not contain a cycloalkene oxide group is not particularly limited as long as it has at least one polymerizable double bond per molecule. Compounds having one double bond and compounds having two polymerizable double bonds per molecule are preferred.

Among the compounds (b2) having a polymerizable double bond not containing a cycloalkene oxide group, specific examples of the compound having one polymerizable double bond per molecule include glycidyl (meth) acrylate and 2-hydroxyethyl. (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N-hydroxyethyl (meth) acrylamide, 3-methyl-3 -(Meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxyethyloxetane, 3-ethyl-3- (meth) acryloxyethyloxetane , 2-phenyl-3- (meth) acryloxymethyl Xetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 4-trifluoromethyl-2- (meth) acryloxymethyloxetane, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tricyclo [5.2.1. 0 ^2,6 ] decanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acryl Rate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, ω-carboxypolycaprolactone mono (meth) acrylate, mono [2- (meth) acryloyloxy succinate Ethyl], mono [2- (meth) acryloyloxyethyl maleate], mono [2- (meth) acryloyloxyethyl] cyclohexene-3,4-dicarboxylate, (meth) acrylamide, N, N-dimethyl ( (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (meth) acryloylmorpholine, thioglycidyl (meth) acrylate, phenyl Thioethyl (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, dicyclopentanyl (meth) acrylate, γ-butyrolactone (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl ( (Meth) acrylate, methoxybutyl (meth) acrylate, and phenoxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N -Butylmaleimide, indene, crotonic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, styrene, methylstyrene, and vinyltoluene. Kill.

  Specific examples of the compound having two polymerizable double bonds per molecule among the compounds (b2) having a polymerizable double bond not containing a cycloalkene oxide group include ethylene glycol di (meth) acrylate, diethylene glycol di (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin-modified ethylene glycol di (meth) acrylate, epichlorohydrin-modified diethylene glycol di (meth) acrylate, Epichlorohydrin-modified triethylene glycol di (meth) acrylate, epichlorohydrin-modified tetraethylene glycol di (meth) acrylate, epichlorohydrin-modified polyethylene Recol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin Modified propylene glycol di (meth) acrylate, epichlorohydrin-modified dipropylene glycol di (meth) acrylate, epichlorohydrin-modified tripropylene glycol di (meth) acrylate, epichlorohydrin-modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin-modified polypropylene glycol di (meth) Acrylate, glycerol acrylate methacrylate, glycerol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin-modified 1,6-hexanediol di (meth) acrylate, methoxylated cyclohexyldi (meth) acrylate, neopentyl glycol di (meth) acrylate, Neopentylglycol hydroxypivalate di (meth) acrylate, caprolactone-modified neopentylglycol hydroxypivalate di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, allylated cyclohexyldi (meth) acrylate, bis [(meth ) Acryloxyneopentyl glycol] adipate, bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, bisphenol Di (meth) acrylate, ethylene oxide-modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, ethylene oxide-modified bisphenol S di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 3-butylene glycol di (meth) acrylate, dicyclopentanyl diacrylate, ethylene oxide modified di (meth) acrylate, caprolactone / ethylene oxide modified di (meth) acrylate, epichlorohydrin modified phthalic di (meth) acrylate, tetra Bromobisphenol A di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol-modified trimethylolpropane di (meth) acrylate, and isocyanu It can be exemplified acid-ethylene oxide-modified diacrylate.

Among these, glycidyl (meth) acrylate, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, Methyl-3- (meth) acryloxyethyloxetane, 3-ethyl-3- (meth) acryloxyethyloxetane, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meta ) Acryloxymethyloxetane, 4-trifluoromethyl-2- (meth) acryloxymethyloxetane, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) ) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, Sobornyl (meth) acrylate, phenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, γ-butyrolactone (meth) acrylate, Phenoxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and indene are preferred. Further, glycidyl (meth) acrylate, 3-methyl-3- (meth) acryloxymethyloxetane, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate Phenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and indene are more preferred.

1-2-3. Solvent used for polymerization reaction of cycloalkene oxide group-containing polymer (B) Solvent used for polymerization reaction for obtaining cycloalkene oxide group-containing polymer (B) (hereinafter may be referred to as “polymerization solvent”). Dissolve the cycloalkene oxide compound (b1) having a polymerizable double bond, the compound (b2) having a polymerizable double bond containing no cycloalkene oxide group, and the resulting polymer (B) having a cycloalkene oxide group to be used Preferably, it is a solvent that can be used. Specific examples of the polymerization solvent include methanol, ethanol, 1-propanol, 2-propanol, propylene glycol, acetone, methyl isobutyl ketone, 2-butanone, ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, and xylene. , Cyclohexanone, cyclopentanone, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate , N, N-dimethylformamide, acetic acid, and water. Kill. The solvent may be one of them or a mixture of two or more of them.

1-2-4. Polymerization Method of Cycloalkene Oxide Group-Containing Polymer (B) A cycloalkene oxide compound (b1) having a polymerizable double bond and a compound (b2) having a polymerizable double bond not containing a cycloalkene oxide group are copolymerized. In this case, the proportion of the cycloalkene oxide compound (b1) is preferably 10 to 90% by weight in the cycloalkene oxide group-containing polymer (B). When the proportion of the cycloalkene oxide compound (b1) is 50 to 90% by weight, the barrier properties are further improved.

  The polymerization method of the cycloalkene oxide group-containing polymer (B) used in the present invention is preferably radical polymerization in a solution. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator used, but is usually in the range of 50 ° C to 130 ° C, and preferably 110 ° C or less from the viewpoint of suppressing gelation. Although the polymerization time is not particularly limited, it is usually in the range of 1 to 24 hours, and preferably 8 hours or less from the viewpoint of workability. Further, the polymerization can be carried out under any of pressure, reduced pressure or atmospheric pressure.

  The polymerization initiator used for producing the polymer (B) may be a compound that generates a radical by heat, an azo initiator such as azobisisobutyronitrile, or a peroxide initiator such as benzoyl peroxide. Can be used.

  Examples of the polymerization initiator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70 (trade name; Fujifilm Wako Pure Chemical Industries, Ltd.), 2,2′-azobis) (2,4-dimethylvaleronitrile) (V-65) (trade name; Fujifilm Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (isobutyronitrile) (V-60) (trade name; FUJIFILM Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (2-methylbutyronitrile) (V-59) (trade name; FUJIFILM Wako Pure Chemical Industries, Ltd.), 2,2'- Azobis [N- (2-propenyl) -2-methylpropionamide] (VF-096) (trade name; FUJIFILM Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (N-butyl-2-methyl) Propionamide) (VAm-110) (trade name; Shimizu Wako Pure Chemical Industries, Ltd.), dimethyl 2,2'-azobis (isobutyrate) (V-601) (trade name; FUJIFILM Wako Pure Chemical Industries, Ltd.), VPE-0201, VPE-0401, VPE -0601 and VPS-1001 (both are trade names; Fujifilm Wako Pure Chemical Industries, Ltd.) and the like.

  The weight average molecular weight of the cycloalkene oxide group-containing polymer (B) is preferably from 2,000 to 200,000, and more preferably from 3,000 to 20,000 from the viewpoint of film formability.

  The weight average molecular weight of the cycloalkene oxide group-containing polymer (B) is determined by the GPC method (column temperature: 35 ° C., flow rate: 1 ml / min), similarly to the weight average molecular weight of the polyester amic acid (A). It is a value in terms of polystyrene. In the measurement of the weight average molecular weight of the cycloalkene oxide group-containing polymer (B), the weight average molecular weight of the standard polystyrene was 645, 2590, 10290, 37600 of the polystyrene calibration kit PL2010-0102 manufactured by Agilent Technologies, Inc. , And 285300 polystyrene. PLgel MIXED-D (Agilent Technology Co., Ltd.) was used as a column, and THF was used as a mobile phase.

  From the viewpoint of curability of the thermosetting composition, it is preferable to remove the unreacted product of the obtained cycloalkene oxide group-containing polymer (B) by a reprecipitation method. As a purification method by reprecipitation, a nonpolar solvent having a volume of 3 to 10 times the volume of the obtained polymer solution is stirred, and the polymer solution is added dropwise to precipitate the polymer. After removing the supernatant, it can be purified by redissolving it in a polymerization solvent.

  Hexane or heptane is preferred as the nonpolar solvent used in the reprecipitation method.

1-3. Ratio of cycloalkene oxide group-containing polymer (B) to polyesteramic acid (A) Total amount of cycloalkene oxide group-containing polymer (B) based on 100 parts by weight of polyesteramic acid (A) in the thermosetting composition of the present invention Is 20 to 1000 parts by weight. When the ratio of the total amount of the cycloalkene oxide group-containing polymer (B) is within this range, the balance between the barrier properties and the flatness is good.

1-4. Curing agent (C)
The curing agent (C) is used in the thermosetting composition of the present invention in order to improve flatness and chemical resistance. As the curing agent (C), acid anhydride-based curing agents, carboxylic acid-containing polymers, amine-based curing agents, phenol-based curing agents, imidazole-based curing agents, pyrazole-based curing agents, triazole-based curing agents, catalytic curing agents, And heat-sensitive acid generators such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts. However, from the viewpoint of avoiding discoloration of the cured film and the heat resistance of the cured film, an acid anhydride-based curing agent is used. Alternatively, an imidazole-based curing agent is preferable.

  Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride; An aromatic polycarboxylic anhydride such as phthalic anhydride and trimellitic anhydride, and a styrene-maleic anhydride copolymer. Among these, trimellitic anhydride and hexahydrotrimellitic anhydride having a good balance between heat resistance and solubility in a solvent are preferable.

  Specific examples of the carboxylic acid-containing polymer include ARUFON UC-3000, ARUFON UC-3090 (all trade names; Toagosei Co., Ltd.), Marproof MA-0215Z, Marproof MA-0217Z, and Marproof MA-0221Z. (Both are trade names; NOF CORPORATION). Among these, ARUFON UC-3000 having a good balance between heat resistance, solubility in a solvent, and flatness is preferable.

  Specific examples of the imidazole-based curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo [1,2- a] Benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-benzyl-2-methylimidazole and 1-benzyl-2-phenylimidazole. Among these, 2-undecylimidazole, 2-phenyl-4-methylimidazole and 1-benzyl-2-phenylimidazole, which have a good balance between curability and solubility in a solvent, are preferred.

  Specific examples of the phenolic curing agent include α, α, α′-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 9 , 9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 4,4 '-(3,3,5-trimethyl -1,1-cyclohexanediyl) bis (phenol), and 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane. Among them, α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and 1,1,1-tris (4-hydroxyphenyl) having a good balance between heat resistance and compatibility. ) Ethane and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene are preferred.

  The addition amount of the curing agent (C) is preferably 0.1 to 60 parts by weight based on 100 parts by weight of the cycloalkene oxide group-containing polymer (B). More specifically, when the curing agent (C) is an acid anhydride-based curing agent, the amount of the carboxylic acid anhydride group or carboxyl group in the curing agent is 0.1 to oxetanyl group and oxiranyl group. It is preferable to add so that the equivalent amount is 1.5 times or more. At this time, the carboxylic anhydride group is calculated divalently. It is more preferable to add the carboxylic acid anhydride group or the carboxyl group in an amount of 0.15 to 0.8 times equivalent, since the chemical resistance is further improved.

1-5. Other Components Various additives can be added to the thermosetting composition of the present invention in order to improve film properties such as flatness, scratch resistance, coating uniformity, and adhesiveness. The additives include epoxy compounds other than the cycloalkene oxide group-containing polymer, compounds having a polymerizable double bond, solvents, anionic, cationic, nonionic, fluorine-based or silicon-based leveling agents and surfactants, It mainly includes an adhesion improver such as a silane coupling agent, and an antioxidant such as a hindered phenol compound, a hindered amine compound, a phosphorus compound and a sulfur compound.

1-5-1. Epoxy compound other than cycloalkene oxide group-containing polymer The thermosetting composition of the present invention uses an epoxy compound other than the cycloalkene oxide group-containing polymer (B) to improve coating uniformity and flatness. Is also good. The epoxy compound optionally used in the thermosetting composition of the present invention is a compound having two or more epoxy groups per molecule. One epoxy compound may be used, or two or more epoxy compounds may be used.

  Examples of the above epoxy compounds include cycloalkene oxide compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, biphenyl type epoxy compounds, phenol novolak type epoxy compounds, and cresol novolak type. Examples thereof include an epoxy compound, a bisphenol A novolak type epoxy compound, an aliphatic polyglycidyl ether compound, a copolymer of a monomer having an epoxy group and another monomer, and an epoxy compound having a siloxane bonding site.

Specific examples of the cycloalkene oxide compound include the following compounds, but the present invention is not particularly limited thereto.

  Specific examples of commercially available bisphenol A type epoxy compounds are jER 828, 1004, 1009 (all trade names; Mitsubishi Chemical Corporation); specific examples of commercially available bisphenol F type epoxy compounds are jER 806, 4005P Specific examples of commercially available glycidyl ether type epoxy compounds include TECHMORE VG3101L (trade name; PRINTEC CORPORATION), EPPN-501H, and 502H (all trade names; Mitsubishi Chemical Corporation). Nippon Kayaku Co., Ltd.) and jER 1032H60 (trade name; Mitsubishi Chemical Corporation); specific examples of commercially available glycidyl ester type epoxy compounds are Denacol EX-721 (trade name; Nagase ChemteX Corporation); And 1,2-cyclohexanedicarboxylic Specific examples of commercially available biphenyl-type epoxy compounds include jER YX4000, YX4000H, YL6121H (all trade names; Mitsubishi Chemical Corporation), and NC-3000. , NC-3000-L, NC-3000-H, and NC-3100 (all trade names; Nippon Kayaku Co., Ltd.); Specific examples of commercially available phenol novolak epoxy compounds are EPPN-201 (trade name). Nippon Kayaku Co., Ltd.) and jER 152, 154 (all trade names; Mitsubishi Chemical Corporation); specific examples of commercially available cresol novolac epoxy compounds are EOCN-102S, 103S, 104S, and 1020. (Both are trade names; Nippon Kayaku Co., Ltd.); bisphenol A novolak A specific example of a commercially available type epoxy compound is jER157S65, 157S70 (both are trade names; Mitsubishi Chemical Corporation); a specific example of a commercially available epoxy compound having a siloxane binding site is 1,3-bis [ 2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane (trade name; Gerest Incorporated), TSL9906 (trade name; Momentive Performance Materials Japan GK), COATOSIL MP200 (trade name; momentative) -Performance Materials Japan GK), COMPOSELLAN SQ506 (trade name; Arakawa Chemical Co., Ltd.), and ES-1023 (trade name: Shin-Etsu Chemical Co., Ltd.).

  In addition, TECHMORE VG3101L (trade name; Printech Co., Ltd.) is 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxy) Propoxy) phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2, 3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol; COATOSIL MP200 (trade name; Momentive Performance Materials Japan G.K.) It is a polymer of sidoxypropyltrimethoxysilane.

  The above epoxy compounds may be used alone or in combination of two or more.

1-5-2. Ratio of epoxy compound other than cycloalkene oxide group-containing polymer (B) to polyesteramic acid (A) The above-mentioned cycloalkene oxide group-containing polymer relative to 100 parts by weight of polyesteramic acid (A) in the thermosetting composition of the present invention. The ratio of the total amount of the epoxy compound other than (B) is 0 to 500 parts by weight. When the ratio of the total amount of the epoxy compounds other than the cycloalkene oxide group-containing polymer (B) is within this range, the balance between flatness, heat resistance and barrier properties is good. When more emphasis is placed on barrier properties, the total amount of epoxy compounds other than the cycloalkene oxide group-containing polymer (B) is preferably in the range of 0 to 200 parts by weight.

1-5-3. Compound having a polymerizable double bond A compound having a polymerizable double bond may be used in the thermosetting composition of the present invention. The compound having a polymerizable double bond used in the thermosetting composition of the present invention is not particularly limited as long as it has two or more polymerizable double bonds per molecule.

  Among the compounds having a polymerizable double bond, specific examples of the compound having two polymerizable double bonds per molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di ( (Meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin-modified ethylene glycol di (meth) acrylate, epichlorohydrin-modified diethylene glycol di (meth) acrylate, epichlorohydrin-modified triethylene glycol di (meth) acrylate , Epichlorohydrin-modified tetraethylene glycol di (meth) acrylate, epichlorohydrin-modified polyethylene glycol di (meth) acrylate, propylene Glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin-modified propylene glycol di (meth) Acrylate, epichlorohydrin-modified dipropylene glycol di (meth) acrylate, epichlorohydrin-modified tripropylene glycol di (meth) acrylate, epichlorohydrin-modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin-modified polypropylene glycol di (meth) acrylate, glycerol acrylate methacrylate, glycerol Di (meth) acrylate, 1,6-hexane All di (meth) acrylate, epichlorohydrin-modified 1,6-hexanediol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, Caprolactone-modified neopentyl glycol hydroxypivalate di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, bis [(meth) acryloxy neopentyl glycol] adipate, bisphenol A di (Meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, ethyleneoxy Modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, ethylene oxide modified bisphenol S di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) Acrylate, dicyclopentanyl diacrylate, ethylene oxide modified di (meth) acrylate phosphate, caprolactone / ethylene oxide modified di (meth) acrylate, epichlorohydrin modified phthalic di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate , Triglycerol di (meth) acrylate, neopentyl glycol-modified trimethylolpropane di (meth) acrylate, and isocyanuric acid ethylene oxide-modified diacrylate. Rukoto can.

  Among the compounds having a polymerizable double bond, specific examples of the compound having three or more polymerizable double bonds per molecule include trimethylolpropane tri (meth) acrylate and ethylene oxide-modified trimethylolpropane tri (meth) acrylate. Propylene oxide-modified trimethylolpropane tri (meth) acrylate, epichlorohydrin-modified trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, alkyl-modified Dipentaerythritol tri (meth) acrylate, ethylene oxide-modified tri (meth) acrylate, caprolactone / ethylene oxide-modified tri (meth) acrylate Acrylate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, ditrimethylolpropanetetra (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and alkyl-modified dipentaerythritol tetra (meth) A) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and carboxyl group-containing polyfunctional ( (Meth) acrylates.

  As the compound having a polymerizable double bond, the above compound may be used alone, or two or more compounds may be used as a mixture.

  It is preferable from the viewpoint of scratch resistance that the compound having three or more polymerizable double bonds is contained in 50% by weight or more in 100% by weight of the compound having a polymerizable double bond.

  Among the compounds having a polymerizable double bond, among isocyanuric acid ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipenta It is preferable to use erythritol hexaacrylate and a carboxyl group-containing polyfunctional (meth) acrylate from the viewpoint of flatness and scratch resistance.

  As the compound having a polymerizable double bond, the following commercially available products can be used. A specific example of isocyanuric acid ethylene oxide-modified diacrylate is Aronix M-215 (trade name; Toagosei Co., Ltd.); a specific example of a mixture of isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate is Aronix M- 313 (30 to 40% by weight) and M-315 (3 to 13% by weight; hereinafter abbreviated as "M-315") (both are trade names; Toagosei Co., Ltd .; the content in parentheses is isocyanuric acid in the mixture) A specific example of trimethylolpropane triacrylate is Aronix M-309 (trade name; Toagosei Co., Ltd.); pentaerythritol triacrylate and pentaerythritol tetraa. Specific examples of the mixture of the relevants include Aronix M-306 (65 to 70% by weight), M-305 (55 to 63% by weight), M-303 (30 to 60% by weight), and M-452 (25 to 40% by weight). %) And M-450 (less than 10% by weight) (both trade names; Toagosei Co., Ltd., the content in parentheses is the value in the catalog of the content of pentaerythritol triacrylate in the mixture); Specific examples of the mixture of erythritol pentaacrylate and dipentaerythritol hexaacrylate include Aronix M-403 (50 to 60% by weight), M-400 (40 to 50% by weight), and M-402 (30 to 40% by weight, M-402), M-404 (30-40% by weight), M-406 (25-35% by weight), and M-405 (10-20% by weight). %) (Both trade names; Toagosei Co., Ltd., the content in parentheses is the value in the catalog of the content of dipentaerythritol pentaacrylate in the mixture); specific examples of the carboxyl group-containing polyfunctional acrylate are: Aronix M-510 and M-520 (hereinafter abbreviated as "M-520") (both trade names; Toagosei Co., Ltd.).

1-5-4. Ratio of the compound having a polymerizable double bond to the polyester amic acid (A) The ratio of the total amount of the compound having a polymerizable double bond to 100 parts by weight of the polyester amic acid (A) in the thermosetting composition of the present invention is as follows: 0 to 100 parts by weight. When the proportion of the total amount of the compound having a polymerizable double bond is within this range, the balance between flatness, heat resistance, scratch resistance and barrier properties is good. When more emphasis is placed on barrier properties, the total amount of the compound having a polymerizable double bond is preferably in the range of 0 to 50 parts by weight.

1-5-5. Solvent A solvent may be used in the thermosetting composition of the present invention. The solvent arbitrarily added to the thermosetting composition of the present invention is preferably a solvent capable of dissolving the polyesteramic acid (A), the cycloalkene oxide group-containing polymer (B), the curing agent (C) and the like. Specific examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, acetone, 2-butanone, ethyl acetate, butyl acetate, propyl acetate, Butyl propionate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-hydroxypropion Ethyl acid, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, 2-hydroxy Propyl lopionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, methyl acetoacetate Ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, Propylene glycol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, γ-butyrolactone, or N, N-dimethylacetamide, cyclopentanone, cyclohexanone, ethylene glycol, Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and polypropylene glycol having a weight average molecular weight of 1,000 or less are mentioned. Can The solvent may be one of them or a mixture of two or more of them.

  The content of the solvent is preferably 65 to 95% by weight based on the total amount of the thermosetting composition. More preferably, it is 70 to 90% by weight.

1-5-6. Surfactant A surfactant may be added to the thermosetting composition of the present invention in order to improve coating uniformity. As a specific example of the surfactant, Polyflow No. 75, polyflow no. 90, polyflow no. 95 (all trade names; Kyoeisha Chemical Co., Ltd.), Disperbyk-161, Disperbake-162, Disperbake-163, Disperbake-164, Disperbake-166, Disperbake-170, Disperbake- 180, Disperbake-181, Disperbake-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK- UV3570 (all trade names; Big Chemie Japan KK), KP-341, KP-368, KF-96-50CS, KF-50-100CS (all trade names; Shin-Etsu Chemical Co., Ltd.), Surflon S61 (Trade name: AGC Seimi Chemical Co., Ltd.), Futuregent 222F, Futuregent 208G, Futuregent 251, Futuregent 710FL, Futuregent 710FM, Futuregent 710FS, Futuregent 601AD, Futuregent 650A, FTX-218 (all above) Product name: Neos Co., Ltd., Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F-474, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac F-558, Megafac F-559, Megafac R-94, Megafac RS-75, Megafac KURS-72-K, Megafac RS-76-NS, Megafac DS-21 (all are trade names; DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (all of which are trade names; Evonik Japan KK), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfone Acid salt, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfur Fonate, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, poly Oxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, poly Oxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbita Stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, may be mentioned alkyl benzene sulfonates, and alkyl diphenyl ether disulfonates. It is preferable to use at least one selected from these.

  Among these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-358, KP-368, Surflon S611, Ptergent 710FL, Ptergent 710FM, Ptergent 710FS, and Ptergent 650A , Megafac F-577, Megafac F-556, Megafac RS-72-K, Megafac DS-21, TEGO Twin 4000, fluoroalkylbenzene sulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, When at least one selected from a fluoroalkyl sulfonate, a fluoroalkyltrimethylammonium salt, and a fluoroalkylaminosulfonate, the coating uniformity of the thermosetting composition is improved. It is preferred.

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

1-5-7. Adhesion improver The thermosetting composition of the present invention may further contain an adhesion improver from the viewpoint of further improving the adhesion between the formed cured film and the substrate. As an example of such an adhesion improver, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, Silaace S510; trade name; JNC Corporation), 2- (3 Silane-based couplings such as (4-silicone), 4-epoxycyclohexyl) ethyltrimethoxysilane (for example, SILAACE S530; trade name; JNC) and 3-mercaptopropyltrimethoxysilane (for example, SILAACE S810; trade name; JNC). Agents, aluminum coupling agents such as acetoalkoxyaluminum diisopropylate, and titanate coupling agents such as tetraisopropylbis (dioctylphosphite) titanate.

  Among these, 3-glycidyloxypropyltrimethoxysilane is preferable because of its great effect of improving the adhesion.

  The content of the adhesion improver is preferably 0.01% by weight or more and 10% by weight or less based on the total amount of the thermosetting composition.

1-5-8. Antioxidant The thermosetting composition of the present invention may further contain an antioxidant from the viewpoint of improving transparency and preventing yellowing when the cured film is exposed to a high temperature.

  An antioxidant such as a hindered phenol-based, hindered amine-based, phosphorus-based, or sulfur-based compound may be added to the thermosetting composition of the present invention. Among them, hindered phenols are preferred from the viewpoint of light resistance. As a specific example, Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425WL, Irganox1520L, Irganox245, Irganox245FF, Irganox259, Irganox3114, Irganox565, Irganox565DD (all trade name; BASF Japan Co., Ltd.) ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-80 (all trade names; Mention may be made of the formula company ADEKA). Among them, Irganox 1010 and ADK STAB AO-60 are more preferable.

  The antioxidant is used by adding 0.1 to 5 parts by weight to the total amount of the thermosetting composition.

1-6. Preparation of thermosetting composition The thermosetting composition of the present invention comprises a polyesteramic acid (A), a polymer having a cycloalkene oxide group (B), a curing agent (C), a solvent, and a cycloalkene oxide group. The compound, an epoxy compound other than the cycloalkene oxide group-containing polymer (B), a compound having a polymerizable double bond, a surfactant, an adhesion improver, an antioxidant, and other additives are selected as necessary. It can be obtained by adding and uniformly mixing and dissolving them.

1-7. Storage of thermosetting composition The thermosetting composition of the present invention is preferably stored at a temperature in the range of -30 ° C to 25 ° C because the composition has good temporal stability. If the storage temperature is -20 ° C to 10 ° C, it is more preferable that there is no precipitate.

2. Cured film obtained from thermosetting composition The thermosetting composition prepared as described above (after dissolving in a solvent in the case of a solid state without a solvent) is applied to the surface of a substrate, for example, When the solvent is removed by heating or the like, a coating film can be formed. The coating of the thermosetting composition on the surface of the substrate can be formed by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, and a slit coating method. Next, this coating film is pre-baked on a hot plate or an oven. The calcination conditions vary depending on the type and blending ratio of each component, but are usually 60 to 100 ° C, 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Thereafter, the main coating is performed to cure the coating. The firing conditions vary depending on the type and mixing ratio of each component, but are usually 120 to 250 ° C., preferably 120 to 180 ° C., 30 to 90 minutes for an oven, and 5 to 30 minutes for a hot plate, and heat treatment is performed. Thus, a cured film can be obtained.

  When heated, the cured film thus obtained has the following properties upon heating: 1) dehydration cyclization of the polyamic acid portion of the polyesteramic acid to form an imide bond; 2) reaction of the carboxylic acid of the polyesteramic acid with the cycloalkene oxide functional group. , And 3) high molecular weight by curing of the cycloalkene oxide group-containing copolymer, it is very tough and has excellent transparency, heat resistance, chemical resistance, flatness, and adhesion. ing. In addition, light resistance, spatter resistance, scratch resistance, and applicability are also expected to be excellent for the same reason. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display device or a solid-state imaging device can be manufactured using the color filter. Further, the cured film of the present invention can be effectively used as a transparent insulating film formed between a TFT and a transparent electrode or a transparent insulating film formed between a transparent electrode and an alignment film, in addition to a protective film for a color filter. It is. Furthermore, the cured film of the present invention is also effective when used as a protective film for an LED light emitter.

  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.

  First, polyester amide acids (A1) to (A8) were synthesized as shown in Synthesis Examples 1 to 8 below.

[Synthesis Example 1] Synthesis of polyester amide acid (A1) In a four-necked flask equipped with a stirrer, dehydrated and purified methyl 3-methoxypropionate (hereinafter, abbreviated as “MMP”), 3,3 ′, 4,4′- Diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as “ODPA”), 1,4-butanediol, and benzyl alcohol were charged at the following weights and stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis). .
MMP 49.00 g
ODPA 20.36g
3.54 g of 1,4-butanediol
2.84 g of benzyl alcohol

Thereafter, the solution after the reaction was cooled to 25 ° C., and 3,3′-diaminodiphenyl sulfone (hereinafter abbreviated as “DDS”) and MMP were charged at the following weights and stirred at 20 to 30 ° C. for 2 hours. At 125 ° C. for 1 hour (second stage of synthesis).
3.26 g of DDS
MMP 21.00g
[Z / Y = 3.0, (Y + Z) /X=0.8]

  The solution was cooled to 25 ° C. to obtain a 30% by weight solution of a pale yellow transparent polyesteramic acid (A1). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amic acid (A1) was 4,200.

[Synthesis Example 2] Synthesis of polyester amic acid (A2) Dehydrated and purified propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMEA”), 1,2,3,4-butanetetracarboxylic acid in a four-necked flask equipped with a stirrer. Dianhydride (hereinafter abbreviated as "BT-100"), SMA1000P (trade name; styrene / maleic anhydride copolymer, Kawahara Yuka Co., Ltd.), 1,4-butanediol, and benzyl alcohol in the following order: It was charged and stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis).
PGMEA 53.49 g
3.83 g of BT-100
SMA1000P 18.23g
1,4-butanediol 1.16 g
5.57 g of benzyl alcohol

Thereafter, the solution after the reaction was cooled to 25 ° C., DDS and PGMEA were added at the following weights, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then at 125 ° C. for 1 hour (second stage of synthesis).
DDS 1.20g
14.28 g of PGMEA
[Z / Y = 2.7, (Y + Z) /X=0.55]

  The solution was cooled to 25 ° C. to obtain a 30% by weight solution of a pale yellow transparent polyesteramic acid (A2). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amic acid (A2) was 10,000.

[Synthesis Example 3] Synthesis of polyester amic acid (A3) In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, and 1,4-butanediol were charged at the following weights, and dried at 125 ° C for 2 hours under a stream of nitrogen. The mixture was stirred (first stage of synthesis).
MMP 39.52 g
ODPA 17.33g
3.95 g of 1,4-butanediol

Thereafter, the solution after the reaction was cooled to 25 ° C., DDS and MMP were charged at the following weights, stirred at 20 to 30 ° C. for 2 hours, and then stirred at 125 ° C. for 1 hour (second stage of synthesis).
2.72 g of DDS
16.48 g of MMP
[Z / Y = 4.0, (Y + Z) /X=0.98]

  The solution was cooled to 25 ° C. to obtain a 30% by weight solution of a pale yellow transparent polyesteramic acid (A3). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amic acid (A3) was 6,900.

[Synthesis Example 4] Synthesis of polyesteramic acid (A4) Dehydrated and purified PGMEA, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (hereinafter abbreviated as "6FDA") in a four-necked flask equipped with a stirrer. And 1,4-butanediol were charged in the following weight and stirred at 125 ° C. for 2 hours in a dry nitrogen stream (first stage of synthesis).
40.69 g of PGMEA
18.87 g of 6FDA
1,4-butanediol 3.03 g

Thereafter, the solution after the reaction was cooled to 25 ° C., DDS and PGMEA were added at the following weights, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then at 125 ° C. for 1 hour (second stage of synthesis).
DDS 2.09g
15.30 g of PGMEA
[Z / Y = 4.0, (Y + Z) /X=0.99]

  The solution was cooled to 25 ° C. to obtain a 30% by weight solution of a pale yellow transparent polyesteramic acid (A4). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amic acid (A4) was 7,800.

[Synthesis Example 5] Synthesis of Polyester Amidic Acid (A5) In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, and epoxy ester 70PA (trade name; Kyoeisha Chemical Co., Ltd .; hereinafter, abbreviated as "70PA") were used as follows. The mixture was charged by weight and stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis).
MMP 41.07g
ODPA 12.02g
70PA 10.09g

Thereafter, the solution after the reaction was cooled to 25 ° C., DDS and MMP were charged at the following weights, stirred at 20 to 30 ° C. for 2 hours, and then stirred at 125 ° C. for 1 hour (second stage of synthesis).
DDS 1.89g
14.93 g of MMP
[Z / Y = 4.0, (Y + Z) /X=0.98]

  The solution was cooled to 25 ° C. to obtain a 30% by weight solution of a pale yellow transparent polyesteramic acid (A5). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amic acid (A5) was 7,600.

[Synthesis Example 6] Synthesis of polyester amic acid (A6) In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, and glycerin were charged at the following weights, and stirred at 125 ° C for 2 hours under a dry nitrogen stream (Synthesis 1). Stage).
MMP 41.84g
ODPA 18.72g
Glycerin 3.81 g

Thereafter, the solution after the reaction was cooled to 25 ° C., DDS and MMP were charged at the following weights, stirred at 20 to 30 ° C. for 2 hours, and then stirred at 125 ° C. for 1 hour (second stage of synthesis).
1.47 g of DDS
14.15 g of MMP
[Z / Y = 7.0, (Y + Z) /X=0.78]

  The solution was cooled to 25 ° C. to obtain a 30% by weight solution of a pale yellow transparent polyesteramic acid (A6). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amic acid (A6) was 4,200.

[Synthesis Example 7] Synthesis of polyester amic acid (A7) In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, diethylene glycol, and benzyl alcohol were charged at the following weights and stirred at 125 ° C for 2 hours under a dry nitrogen stream. (First stage of synthesis).
MMP 30.04g
ODPA 14.24g
0.96 g of diethylene glycol
0.97 g of benzyl alcohol

Thereafter, the solution after the reaction was cooled to 25 ° C., DDS and MMP were charged at the following weights, stirred at 20 to 30 ° C. for 2 hours, and then stirred at 125 ° C. for 1 hour (second stage of synthesis).
7.83 g of DDS
MMP 25.95g
[Z / Y = 0.29, (Y + Z) /X=0.88]

  The solution was cooled to 25 ° C. to obtain a 30% by weight solution of a pale yellow transparent polyesteramic acid (A7). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amic acid (A7) was 3,900.

[Synthesis Example 8] Synthesis of polyester amic acid (A8) In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, 6FDA, 1,4-butanediol were charged at the following weights, and dried at 125 ° C under a stream of dry nitrogen at 125 ° C. Stirred for 1 hour (first stage of synthesis).
MMP 32.85g
16.67 g of 6FDA
1,4-butanediol 1.01 g

Thereafter, the solution after the reaction was cooled to 25 ° C., and 3,3′-diamino-4,4′-dihydroxydiphenylsulfone (trade name, BPS-DA; Wakayama Seika Co., Ltd .; hereinafter, referred to as “BPS-DA”) Abbreviation), the following weight of MMP was added, and the mixture was stirred at 20 to 30 ° C for 2 hours, and then stirred at 125 ° C for 1 hour (second stage of synthesis).
6.31 g of BPS-DA
MMP 23.14 g
[Z / Y = 0.5, (Y + Z) /X=0.9]

  The solution was cooled to 25 ° C. to obtain a 30% by weight solution of a pale yellow transparent polyesteramic acid (A8). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amic acid (A8) was 3,800.

  The amounts of the raw materials charged, the reaction conditions, and the weight average molecular weight of the polyesteramic acid in Synthesis Examples 1 to 8 are shown in Table 1 below.

  Next, cycloalkene oxide group-containing polymers (B1) to (B8) were synthesized as shown in Synthesis Examples 9 to 16 below.

Synthesis Example 9 Synthesis of Cycloalkene Oxide Group-Containing Polymer (B1) In a four-necked flask equipped with a stirrer, PGMEA dehydrated and purified as a polymerization solvent, and cycloalkene oxide compound (b1) having a polymerizable double bond as 3 , 4-epoxycyclohexylmethyl (meth) acrylate (trade name, CYM M100; Daicel Corporation, hereinafter abbreviated as “CYM M100”) at the following weight, and dimethyl 2,2′-azobis (2 -Methylpropionate) (hereinafter abbreviated as "V-601") was charged at the following weight and stirred at 95 ° C for 2 hours in a dry nitrogen stream.
PGMEA 280.00g
CYM M100 120.00g
V-601 6.00 g

  The solution after the reaction was cooled to 25 ° C. to obtain a 30% by weight solution of the cycloalkene oxide group-containing polymer (B1). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained cycloalkene oxide group-containing polymer (B1) was 7,300.

[Synthesis Example 10] Synthesis of cycloalkene oxide group-containing polymer (B2) In a four-necked flask equipped with a stirrer, PGMEA, CYM M100, and N-cyclohexylmaleimide (hereinafter abbreviated as "CHMI") were charged at the following weights. Further, V-601 as a polymerization initiator was charged in the following weight and stirred at 95 ° C. for 2 hours in a dry nitrogen stream.
PGMEA 280.00g
CYM M100 96.00 g
CHMI 24.00 g
V-601 6.00 g

  The solution after the reaction was cooled to 25 ° C. to obtain a 30% by weight solution of the cycloalkene oxide group-containing polymer (B2). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained cycloalkene oxide group-containing polymer (B2) was 8,500.

Synthesis Example 11 Synthesis of Cycloalkene Oxide Group-Containing Polymer (B3) PGMEA, CYM M100, and n-butyl methacrylate (hereinafter abbreviated as “BMA”) were charged into a four-necked flask equipped with a stirrer at the following weight. Further, V-601 as a polymerization initiator was charged in the following weight and stirred at 95 ° C. for 2 hours under a dry nitrogen stream.
PGMEA 280.00g
CYM M100 72.00 g
BMA 48.00 g
7.20 g of V-601

  The solution after the reaction was cooled to 25 ° C. to obtain a 30% by weight solution of the cycloalkene oxide group-containing polymer (B3). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained cycloalkene oxide group-containing polymer (B3) was 6,800.

[Synthesis Example 12] Synthesis of cycloalkene oxide group-containing polymer (B4) PGMEA, CYM M100, and CHMI were charged into a four-necked flask equipped with a stirrer in the following weight, and V-601 was used as a polymerization initiator in the following weight ratio. The mixture was charged by weight and stirred at 95 ° C. for 2 hours under a stream of dry nitrogen.
PGMEA 280.00g
CYM M100 84.00 g
CHMI 36.00 g
V-601 14.40 g

  The solution after the reaction was cooled to 25 ° C. to obtain a 30% by weight solution of the cycloalkene oxide group-containing polymer (B4). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained cycloalkene oxide group-containing polymer (B4) was 4,300.

[Synthesis Example 13] Synthesis of cycloalkene oxide group-containing polymer (B5) In a four-necked flask equipped with a stirrer, PGMEA, CYM M100, CHMI, dicyclopentanyl methacrylate (trade name, FA-513M; Hitachi Chemical Co., Ltd.) ), Hereinafter referred to as “FA-513M”) at the following weight, and V-601 as the polymerization initiator at the following weight, and stirred at 95 ° C. for 2 hours under a dry nitrogen stream.
PGMEA 280.00g
CYM M100 60.00g
CHMI 36.00 g
FA-513M 24.00 g
V-601 6.00 g

  The solution after the reaction was cooled to 25 ° C. to obtain a 30% by weight solution of the cycloalkene oxide group-containing polymer (B5). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained cycloalkene oxide group-containing polymer (B5) was 9,600.

[Synthesis Example 14] Synthesis of cycloalkene oxide group-containing polymer (B6) PGMEA, CYM M100, and CHMI were charged to a four-necked flask equipped with a stirrer at the following weight, and V-601 was used as a polymerization initiator at the following weight. The mixture was charged by weight and stirred at 95 ° C. for 2 hours under a stream of dry nitrogen.
PGMEA 300.00g
CYM M100 50.00g
CHMI 50.00g
5.00 g of V-601

  The solution after the reaction was cooled to 25 ° C. to obtain a 30% by weight solution of the cycloalkene oxide group-containing polymer (B6). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained cycloalkene oxide group-containing polymer (B6) was 10,000.

[Synthesis Example 15] Synthesis of cycloalkene oxide group-containing polymer (B7) PGMEA, CYM M100, CHMI, and indene were charged into a four-necked flask equipped with a stirrer at the following weights, and V-601 was further used as a polymerization initiator. It was charged with the following weight and stirred at 95 ° C. for 2 hours under a dry nitrogen stream.
PGMEA 168.00 g
CYM M100 36.00 g
CHMI 22.00g
14.40 g of inden
3.60 g of V-601

  The solution after the reaction was cooled to 25 ° C. to obtain a 30% by weight solution of the cycloalkene oxide group-containing polymer (B7). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained cycloalkene oxide group-containing polymer (B7) was 8,900.

[Synthesis Example 16] Synthesis of cycloalkene oxide group-containing polymer (B8) In a four-necked flask equipped with a stirrer, PGMEA, CYM M100, CHMI, and indene were charged at the following weights, and V-601 was further used as a polymerization initiator. It was charged with the following weight and stirred at 95 ° C. for 2 hours under a dry nitrogen stream.
PGMEA 168.00 g
CYM M100 14.40g
CHMI 22.00g
36.00 g of indene
V-601 5.04 g

  The solution after the reaction was cooled to 25 ° C. to obtain a 30% by weight solution of the cycloalkene oxide group-containing polymer (B8). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained cycloalkene oxide group-containing polymer (B8) was 5,900.

  The amounts of raw materials charged, the reaction conditions, and the weight average molecular weight of the cycloalkene oxide group-containing polymer in Synthesis Examples 9 to 16 are shown in Table 2 below.

[Example 1]
A 500 ml separable flask equipped with stirring blades was purged with nitrogen, and the flask was charged with 12.00 g of the polyesteramic acid (A1) solution obtained in Synthesis Example 1 and 72 mL of the cycloalkene oxide group-containing polymer (B2) solution. 0.000 g, 3.60 g of the cycloalkene oxide group-containing compound (E1), 7.20 g of trimellitic anhydride (hereinafter abbreviated as "TMA") as a curing agent, and SILAACE S510 (trade name; JNC stock) as an adhesion improver 1.80 g of a company, hereinafter abbreviated as "S510"), 0.038 g of ADK STAB AO-60 (trade name; ADEKA Corporation, hereinafter abbreviated as "AO-60") as an antioxidant, and dehydration and purification as a diluting solvent 82.46 g of the purified MMP and 10.17 g of dehydrated and purified PGMEA were charged, and the mixture was stirred at room temperature for 3 hours. It was dissolved.

  Next, 0.019 g of Megafac F-556 (trade name; DIC Corporation, hereinafter abbreviated as “F-556”) was added as a surfactant, and the mixture was stirred at room temperature for 1 hour, followed by a membrane filter (pore size: 0.2 μm). To prepare a thermosetting composition. The amount of the MMP and PGMEA charged is determined by considering the weight of the solvent contained in the polyesteramic acid (A1) solution and the weight of the solvent contained in the cycloalkene oxide group-containing polymer (B2) solution. The conversion was performed so that the total weight of components other than the solvent such as the polymer, the curing agent, the adhesion improver, and the antioxidant in the product was 20% by weight.

  Abbreviations of compounds used in Examples and Comparative Examples indicate the following raw materials.

Cycloalkene oxide group-containing compound (E)
E1: CEL2021P (trade name; Daicel Corporation)
E2: EPL GT401 (trade name; Daicel Corporation)
E3: GCI-100% NBE (trade name; Gunei Chemical Industry Co., Ltd.)

Epoxy compound (F) containing no cycloalkene oxide group
F1: Methyl methacrylate-glycidyl methacrylate copolymer (molar ratio 30:70, weight average molecular weight 250,000)
F2: butyl methacrylate-glycidyl methacrylate copolymer (molar ratio 20:80, weight average molecular weight 80,000)
F3: TECHMORE VG3101L (trade name; PRINTEC CORPORATION)
F4: EPPN-501H (trade name; Nippon Kayaku Co., Ltd.)
F5: N-phenylmaleimide-glycidyl methacrylate copolymer (molar ratio 30:70, weight average molecular weight 80,000)

[Examples 2 to 17]
According to the method of Example 1, each component was mixed and dissolved at a ratio (unit: g) shown in Tables 3-1 to 3-2 to obtain a thermosetting composition.

[Comparative Examples 1 to 5]
According to the method of Example 1, each component was mixed and dissolved at a ratio (unit: g) shown in Table 4 to obtain a thermosetting composition.

  The barrier properties, flatness and heat resistance of the thermosetting compositions obtained in Examples 1 to 18 and Comparative Examples 1 to 5 were evaluated according to the following methods.

[Evaluation method of barrier properties]
A substrate of a color filter without a cured film having pixels containing R, G, and B having an absorption around 560 nm when measured with an ultraviolet-visible-near-infrared spectrophotometer (trade name: V-670, JASCO Corporation) On top, the thermosetting composition was spin-coated at 350 rpm for 10 seconds and prebaked on a 90 ° C. hot plate for 2 minutes. Subsequently, post-baking was performed in an oven at 150 ° C. for 30 minutes to obtain a color filter substrate with a cured film having an average thickness of the protective film of 2.0 μm.

  Next, 0.5 mL of 1-methyl-2-pyrrolidone was dropped on a color filter substrate with a cured film cut into a 10 cm square, and a glass (hereinafter referred to as a cover glass) cut into a 9 cm square was used as a color filter substrate with a cured film. It was left still and heated at 180 ° C. for 5 minutes using a hot plate. After the heating was completed, the cover glass was removed, the cover glass and the color filter substrate with a cured film were washed with 5 mL of 1-methyl-2-pyrrolidone, and the washing solution was transferred to a 10 mL volumetric flask. 1-Methyl-2-pyrrolidone was added to the volumetric flask containing the washing solution to make up to 10 mL, and the mixed solution was used as an eluate for a color filter substrate with a cured film. Thereafter, the transmittance of the eluate was measured with the above-mentioned ultraviolet-visible-near-infrared spectrophotometer using 1-methyl-2-pyrrolidone as a reference sample. From the measurement results, the case where the transmittance at 560 nm was 90% or more was evaluated as ◎, the case where the transmittance was 89 to 80% was evaluated as ○, the case where the transmittance was 80 to 50% was evaluated as △, and the evaluation of less than 50% ×.

[Flatness evaluation method]
A thermosetting composition was formed on a color filter substrate without a cured film having pixels containing R, G, and B, whose surface steps were measured using a fine shape measuring device (trade name: P-17, KLA TENCOR CORPORATION) in advance. Was spin coated at 350 rpm for 10 seconds and prebaked on a hot plate at 90 ° C. for 2 minutes. Subsequently, post-baking was performed in an oven at 150 ° C. for 30 minutes to obtain a color filter substrate with a cured film having an average thickness of the protective film of 2.0 μm. Thereafter, a surface step was measured on the obtained color filter substrate with a cured film.

The flattening rate (DOP) was calculated from the maximum value of the surface steps of the color filter substrate without the cured film and the color filter substrate with the cured film (hereinafter abbreviated as “maximum step”) using the following formula. When the flattening ratio was 80% or more, flatness was evaluated as ◎, when 79 to 60%, flatness was evaluated as 、, and when less than 60%, flatness X was evaluated. The color filter substrate without a cured film used had a maximum step of 1.5 μm.
Flattening rate = [(maximum step of color filter substrate without cured film-maximum step of color filter substrate with cured film) / (maximum step of color filter substrate without cured film)] x 100%

[Evaluation method of heat resistance]
Next, the thermosetting composition was spin-coated on a glass substrate at 450 rpm for 10 seconds, and prebaked on a 90 ° C hot plate for 2 minutes. Subsequently, post-baking was performed in an oven at 150 ° C. for 30 minutes to obtain a glass substrate with a cured film having a protective film thickness of 1.5 μm. After reheating the obtained glass substrate with a cured film at 180 ° C. for 1 hour, the film thickness before heating and the film thickness after heating were measured, and the residual film ratio was calculated by the following formula. For the measurement of the film thickness, the aforementioned fine shape measuring device (trade name: P-17, KLA TENCOR CORPORATION) was used. The case where the residual film ratio after heating was 95% or more was evaluated as ○, and the case where the residual film ratio after heating was less than 95% was evaluated as ×.

  The evaluation results are shown in Tables 5-1, 5-2 and 6.

  As is clear from the results shown in Tables 5-1 and 5-2, curing obtained by baking the composition containing the cycloalkene oxide group-containing polymer (B) of Examples 1 to 18 at 150 ° C. The film was found to have high barrier properties while maintaining good flatness and good heat resistance.

  The cured film obtained by baking the composition containing only the epoxy compound (F) containing no cycloalkene oxide group of Comparative Examples 1 to 5 at 150 ° C. at 150 ° C. had poor heat resistance and poor barrier properties. became. This is considered to be due to the fact that the epoxy compound (F) containing no cycloalkene oxide group cannot be cured sufficiently at 150 ° C. On the other hand, Comparative Examples 1 to 5 all exhibited excellent flatness. This is also considered to be due to the insufficient fluidity of the coating film during the firing process due to insufficient curing.

  As described above, only when the cycloalkene oxide group-containing polymer (B) was used as an essential component, the cured film obtained by firing at 150 ° C. was able to satisfy all the characteristics.

  The cured film obtained from the thermosetting composition of the present invention has a high barrier property, and exhibits good flatness and high heat resistance, such as color filters, various optical materials such as LED light emitting elements and light receiving elements. It can be used as a protective film and an insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (7)

A thermosetting composition comprising a polyesteramic acid (A), a cycloalkene oxide group-containing polymer (B), and a curing agent (C),
The polyester amic acid (A) is obtained by combining X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyhydric hydroxy compound such that the following formulas (1) and (2) are satisfied. Reaction products from the raw materials contained in the proportions,
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
The cycloalkene oxide group-containing polymer (B) may be a homopolymer of a cycloalkene oxide compound (b1) having a polymerizable double bond or a copolymer of cycloalkene oxide compounds (b1) having a polymerizable double bond. Heat, which is at least one selected from a copolymer of a cycloalkene oxide compound (b1) having a polymerizable double bond and a compound (b2) having a polymerizable double bond containing no cycloalkene oxide group. Curable composition. The thermosetting composition according to claim 1, wherein the polyester amic acid (A) includes a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4);

In the formulas (3) and (4), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two —NH ₂ from a diamine. And R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound. The thermosetting composition according to claim 1, wherein the polyester amic acid (A) includes at least one selected from a polyester amide acid having a terminal end-capture and a polyester amide acid having no terminal end-capture.   The cycloalkene oxide compound (b1) having a polymerizable double bond is at least one selected from 3,4-epoxycyclohexylmethyl (meth) acrylate and 1,2-epoxy-4-vinyl-1-cyclohexane. The thermosetting composition according to claim 1 or 2, wherein   The thermosetting according to any one of claims 1 to 4, wherein the content of the cycloalkene oxide group-containing polymer (B) is 20 to 1,000 parts by weight based on 100 parts by weight of the polyesteramic acid (A). Composition.   A cured film obtained by curing the thermosetting composition according to claim 1.   A color filter comprising the cured film according to claim 6 as a transparent protective film.