JP2015232122A - Thermosetting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured film having particularly excellent light fastness and surface smoothness, and also having excellent heat resistance; chemical resistance such as solvent resistance, acid resistance, and alkali resistance; water resistance; adhesion to a ground substrate such as glass; transparency; scratch resistance; and coatability, and to provide a composition which provides the cured film.SOLUTION: A thermosetting composition comprises a polyester amide acid, an epoxy group-containing polymer, an epoxy compound, and an epoxy curing agent. The polyester amide acid is obtained by reacting a tetracarboxylic acid dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components, and the epoxy group-containing polymer is obtained by reacting glycidyl (meth)acrylate and a difunctional (meth)acrylate as essential raw material components.

Description

  The present invention relates to thermosetting used for forming an insulating material in an electronic component, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a planarizing film, an interlayer insulating film in a liquid crystal display element, or a protective film for a color filter. The present invention relates to a conductive composition, a transparent film thereby, and an electronic component having the film.

  During the manufacturing process of elements such as liquid crystal display elements, various chemical treatments such as organic solvents, acids, and alkali solutions are performed, and when the wiring electrode is formed by sputtering, the surface is locally heated to a high temperature. Sometimes. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and alteration of the surface of various elements. These protective films are required to have various characteristics that can withstand various treatments during the manufacturing process as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to underlying substrates such as glass, transparency, scratch resistance, applicability, flatness, light resistance Etc. are required. In addition, liquid crystal display elements are required to have improved planarization characteristics when used as a color filter protective film as the performance of liquid crystal display elements increases, such as higher viewing angle, faster response, and higher definition. .

  With respect to light resistance, UV ozone treatment has been carried out for cleaning the surface of the protective film so far. However, in particular, in recent years, the color filter protective film for the transverse electric field mode requires higher energy UV ozone treatment to improve the coating property of the photo spacer. Ultraviolet exposure processes such as a photo-alignment process of an alignment film are increasing, and light resistance is a very important characteristic.

  Examples of the protective film material having these excellent properties include a silicon-containing polyamic acid composition (see Patent Document 1) and a polyester amic acid composition (see Patent Document 2 and Patent Document 3). The silicon-containing polyamic acid composition is a material that is very excellent in terms of flatness, but has a drawback of insufficient heat resistance and inferior alkali resistance. The polyester amide acid composition of Patent Document 2 has a drawback of insufficient flatness and heat resistance. The polyester amide acid composition of Patent Document 3 is a material with excellent flatness, heat resistance, and chemical resistance, but has insufficient light resistance, and transparency is lowered in UV ozone treatment and ultraviolet exposure process. There was a drawback of doing. Accordingly, none of the materials satisfy the light resistance, flatness, heat resistance, chemical resistance, and other characteristics as protective film materials.

JP-A-9-291150 JP 2005-105264 A JP 2008-156546 A

  The object of the present invention is excellent in heat resistance, chemical resistance such as solvent resistance / acid resistance / alkali resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, scratch resistance, and coatability. An object of the present invention is to provide an electronic component having a cured film excellent in flatness and light resistance and a composition that provides the cured film.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polyester amide acid, glycidyl (meth) acrylate and bifunctional compound obtained from the reaction of a compound containing tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound. The above object can be achieved by a composition containing an epoxy group-containing polymer obtained by reacting (meth) acrylate as an essential raw material component, an epoxy curing agent, and a cured film obtained by curing the composition. The inventors have found what can be done and have completed the present invention.
The present invention includes the following configurations.

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。 [1] A composition comprising a polyester amide acid, an epoxy group-containing polymer, an epoxy compound, and an epoxy curing agent, wherein the polyester amide acid is an essential raw material component comprising a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound Obtained by reacting as
The polyester amic acid is reacted with X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compounds in a ratio such that the relationship of the following formulas (1) and (2) is satisfied. And having a structural unit represented by the following formula (3) and a structural unit represented by the formula (4);
The epoxy group-containing polymer is obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw material components, and has a weight average molecular weight of 1,000 to 50,000;
The epoxy compound contains 2 to 10 epoxy groups per molecule and the weight average molecular weight is less than 3,000;
The total amount of the epoxy group-containing polymer and the epoxy compound is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amide acid, and the epoxy curing agent is 0.1 to 100 parts by weight with respect to the total amount of the epoxy group-containing polymer and the epoxy compound. 60 parts by weight thermosetting composition:

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)

In Formula (3) and Formula (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 diamine. R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound.

[2] The thermosetting composition according to item [1], wherein the raw material component of the polyester amide acid further contains a monohydroxy compound.

[3] The monohydroxy compound is one or more selected from isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane, [2] The thermosetting composition according to item.

[4] The thermosetting composition according to the item [1] or [2], wherein the raw material component of the polyester amide acid further contains a styrene-maleic anhydride copolymer.

[5] The thermosetting composition according to the item [1] or [2], wherein the weight average molecular weight of the polyester amide acid is 1,000 to 200,000.

[6] The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2, Selected from 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate) The thermosetting composition according to the item [1] or [2], which is one or more of the above.

[7] The item according to item [1] or [2], wherein the diamine is at least one selected from 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone. Thermosetting composition.

[8] The polyvalent hydroxy compound is ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, And the thermosetting composition according to item [1] or [2], which is at least one selected from tris (2-hydroxyethyl) isocyanurate.

[9] Bifunctional (meth) acrylate is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, The thermosetting composition according to item [1] or [2], which is at least one selected from neopentyl glycol di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate.

[10] The epoxy group-containing polymer can be obtained by further reacting a raw material component containing a radical polymerizable monomer other than a compound selected from the group consisting of glycidyl (meth) acrylate and bifunctional (meth) acrylate, [1 ] Or the thermosetting composition according to item [2].

[11] A radical polymerizable monomer other than a compound selected from the group consisting of glycidyl (meth) acrylate and bifunctional (meth) acrylate is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth ) Acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, (meth) acryloyloxypropyl-tris-trimethylsiloxysilane, (meth) acryloxyorganopolysiloxane, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate Tetrahydrofurfuryl (meth) acrylate, γ-butyrolactone (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, 2,2,2-trifluoroethyl (meth) acrylate, (meth) acrylic acid, and 4-hydroxy The thermosetting composition according to item [10], which is one or more selected from phenyl vinyl ketone.

[12] The epoxy compound is 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1, 1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1 -[4- [1- [4- (2,3-epoxypropoxyphenyl) -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol and 2- [4- (2,3- One or more selected from epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane , [1] or [2] The thermosetting composition according to item.

[13] The thermosetting according to the item [1] or [2], wherein the epoxy curing agent is at least one selected from trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole. Sex composition.

[14] One or more tetracarboxylic dianhydrides selected from 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride Is;
The diamine is 3,3′-diaminodiphenyl sulfone;
The polyvalent hydroxy compound is 1,4-butanediol;
An epoxy group-containing polymer is a copolymer having a weight average molecular weight of 1,000 to 50,000 obtained by reacting glycidyl methacrylate, diethylene glycol dimethacrylate and tetrahydrofurfuryl methacrylate as raw material components;
The epoxy compound is 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate;
The epoxy curing agent is one or more selected from trimellitic anhydride and 2-undecylimidazole;
The thermosetting composition according to item [1], further comprising at least one selected from methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent.

[15] A cured film obtained from the thermosetting composition according to any one of [1] to [14].

[16] A color filter using the cured film according to the item [15] as a protective film.

[17] A liquid crystal display device using the color filter according to the item [16].

[18] A solid-state imaging device using the color filter according to the item [16].

[19] A liquid crystal display element using the cured film according to the item [15] as a transparent insulating film formed between the TFT and the transparent electrode.

[20] A liquid crystal display element using the cured film according to the item [15] as a transparent insulating film formed between the transparent electrode and the alignment film.

[21] An LED illuminator using the cured film according to the item [15] as a protective film.

  The thermosetting composition according to a preferred embodiment of the present invention is a material particularly excellent in flatness and light resistance, and improves the display quality and reliability when used as a color filter protective film of a color liquid crystal display element. Can do. Further, the cured film obtained by heating the thermosetting composition according to a preferred embodiment of the present invention is well balanced in transparency, chemical resistance, adhesion and sputtering resistance, and is very It is highly practical. In particular, it is useful as a protective film for a color filter produced by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. It can also be used as a protective film and a transparent insulating film for various optical materials.

1. Thermosetting composition The thermosetting composition of the present invention comprises a polyester amide acid obtained by reacting tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound as essential raw material components, glycidyl (meth) acrylate, and An epoxy group-containing polymer obtained by reacting bifunctional (meth) acrylate as an essential raw material component, an epoxy compound, and an epoxy curing agent, wherein the epoxy compound is contained in 100 parts by weight of polyester amic acid. 20 to 400 parts by weight, and the epoxy curing agent is 0.1 to 60 parts by weight with respect to 100 parts by weight of the epoxy group-containing polymer. Moreover, the thermosetting composition of this invention may further contain other components other than the above in the range in which the effect of this invention is acquired.

1-1. Polyester amide acid Polyester amide acid is obtained by reacting tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound as essential raw material components. More specifically, X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compound are reacted at a ratio such that the relationship of the following formulas (1) and (2) is established. Is obtained.

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)

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、好ましくは炭素数２〜３０の有機基である。Ｒ^２はジアミンから２つの−ＮＨ_２を除いた残基であり、好ましくは炭素数２〜３０の有機基である。Ｒ^３は多価ヒドロキシ化合物から２つの−ＯＨを除いた残基であり、好ましくは炭素数２〜２０の有機基である。 The polyester amide acid has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4).

In Formula (3) and Formula (4), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, 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 polyester amide acid, and this solvent may be left as it is, and it may be a liquid or gel thermosetting composition in consideration of handling properties. It is good also as a solid composition which considered etc. In addition, the synthesis of the polyester amide acid may contain, as necessary, one or more compounds selected from a monohydroxy compound and a styrene-maleic anhydride copolymer as a raw material. It preferably contains a hydroxy compound. In addition, the synthesis of the polyester amic acid may contain other compounds than the above as a raw material as necessary, as long as the object of the present invention is not impaired. Examples of such other raw materials include silicon-containing monoamines.

1-1-1. Tetracarboxylic dianhydride In the present invention, tetracarboxylic dianhydride is used as a material for obtaining the polyester amide acid. Specific examples of preferred tetracarboxylic dianhydrides include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2, 3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfonetetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Diphenyl ether tetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1 2,3,4-butanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, Shin Nippon Rika Co., Ltd.), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetra Mention may be made of carboxylic dianhydrides, cyclopentanetetracarboxylic dianhydrides, cyclohexanetetracarboxylic dianhydrides, ethanetetracarboxylic dianhydrides, and butanetetracarboxylic dianhydrides. One or more of these can be used.

  Among these, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, which gives good transparency, 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and TMEG-100 are more preferred, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride are particularly preferred. .

1-1-2. Diamine In the present invention, a diamine is used as a material for obtaining a polyester amide acid. Specific examples of preferred diamines include 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [ 4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, Mention may be made of [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane. One or more of these can be used.

  Among these, 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone that give good transparency are more preferable, and 3,3′-diaminodiphenylsulfone is particularly preferable.

1-1-3. Polyvalent hydroxy compound In the present invention, a polyvalent hydroxy compound is used as a material for obtaining polyester amide acid. Specific examples of preferable polyvalent hydroxy compounds 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, weight Polypropylene glycol having an average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentane Diol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1, 7 Heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 1,2-nonanediol, 1 , 9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecane Diol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, isocyanuric acid tris (2-hydroxyethyl), bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxy Phenyl) sulfone), bisphenol F (bis (4-hydro) Shifeniru) methane) can be exemplified diethanolamine, and triethanolamine. One or more of these can be used.

  Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 have good solubility in solvents. -Octanediol and tris (2-hydroxyethyl) isocyanurate are more preferred, and 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol are particularly preferred.

1-1-4. Monohydroxy Compound In the present invention, a monohydroxy compound may be used as a material for obtaining polyester amide acid. By using a monohydroxy compound, the storage stability of the thermosetting composition is improved. Specific examples of preferable monohydroxy compounds include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene. Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, phenol, borneol, maltol, linalool, terpineol, dimethylbenzyl carbinol, and 3-ethyl-3-hydroxymethyloxetane Can be mentioned. One or more of these can be used.

  Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane is more preferable. In consideration of the compatibility when a polyester amide acid formed using these, an epoxy group-containing polymer, an epoxy compound and an epoxy curing agent are mixed, and the applicability of a thermosetting composition on a color filter, monohydroxy The use of benzyl alcohol is particularly preferred for the compound.

  The monohydroxy compound is preferably reacted in an amount of 0 to 300 parts by weight with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound. More preferably, it is 5-200 weight part.

1-1-5. Styrene-maleic anhydride copolymer The polyesteramic acid used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups to the above raw material. Doing so is preferred because it improves transparency. Examples of the compound having 3 or more acid anhydride groups include a styrene-maleic anhydride copolymer. About the ratio of each component which comprises a styrene-maleic anhydride copolymer, the molar ratio of styrene / maleic anhydride is 0.5-4, Preferably it is 1-3. Furthermore, 1 or 2 is more preferable, and 1 is particularly preferable.

  Specific examples of the styrene-maleic anhydride copolymer include SMA3000P, SMA2000P, and SMA1000P (all trade names: Kawa Crude Chemical Co., Ltd.). Among these, SMA1000P having good heat resistance and alkali resistance is particularly preferable.

  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 polyvalent hydroxy compound. More preferably, it is 10 to 300 parts by weight.

1-1-6. In the synthesis of silicon-containing monoamine polyester amic acid, as a raw material, other raw materials other than the above may be included as necessary, as long as the purpose of the present invention is not impaired. And silicon-containing monoamines.

  Specific examples of preferable silicon-containing monoamines used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 4-amino. Butyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenyl Mention may be made of methyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. One or more of these can be used.

  Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane that improve the acid resistance of the coating film are more preferable, and 3-aminopropyltriethoxysilane is particularly preferable from the viewpoint of acid resistance and compatibility. .

  The silicon-containing monoamine is preferably contained in an amount of 0 to 300 parts by weight based on 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound. More preferably, it is 5-200 weight part.

1-1-7. Solvents used in the synthesis reaction of polyester amide acid Specific examples of solvents used in the synthesis reaction to obtain polyester amide acid include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether. Mention may be made of acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetamide. Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ethyl ether is preferable.

1-1-8. Polyester amide acid synthesis method In the polyester amide acid synthesis method used in the present invention, tetracarboxylic dianhydride X mole, diamine Y mole, and polyhydric hydroxy compound Z mole are reacted in the solvent. At this time, it is preferable that X, Y, and Z are set to such a ratio that the relationship of the following formulas (1) and (2) is established between them. Within this range, the solubility of the polyester amide acid in the solvent is high, so that the coating property of the composition is improved, and as a result, a cured film having excellent flatness can be obtained.

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦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.

  In the polyester amic acid used in the present invention, the molecule having an acid anhydride group (—CO—O—CO—) at the terminal is formed at the terminal under the condition where X is excessively used relative to Y + Z in the above reaction conditions. It is thought that it is produced in excess of molecules having amino groups or hydroxyl groups. In the case of reacting in such a monomer structure, the monohydroxy compound described above can be added, if necessary, in order to react with the acid anhydride group at the molecular terminal to esterify the terminal. The polyester amic acid obtained by adding and reacting the monohydroxy compound has improved compatibility with the epoxy compound and the epoxy curing agent, and the applicability of the thermosetting composition of the present invention containing them is improved. Improved.

  Moreover, when making it react with the structure of the monomer mentioned above, in order to make it react with the acid anhydride group of a molecular terminal and introduce | transduce a silyl group at the terminal, a silicon-containing monoamine can be added. When the thermosetting composition of the present invention containing a polyester amide acid obtained by adding and reacting with a silicon-containing monoamine is used, the acid resistance of the obtained coating film is improved. Furthermore, when making it react by the structure of the monomer mentioned above, both a monohydroxy compound and a silicon-containing monoamine can also be added and made to react.

  The reaction solvent is preferably used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound, since the reaction proceeds smoothly. The reaction is preferably carried out at 40 to 200 ° C. for 0.2 to 20 hours.

  The order of adding the reaction raw materials to the reaction system is not particularly limited. That is, a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound are simultaneously added to the reaction solvent. After the diamine and the polyvalent hydroxy compound are dissolved in the reaction solvent, the tetracarboxylic dianhydride is added. After reacting acid dianhydride and polyvalent hydroxy compound in advance, diamine is added to the reaction product, or after reacting tetracarboxylic dianhydride and diamine in advance, polyhydric hydroxy is added to the reaction product. Any method such as adding a compound can be used.

  In the case of reacting the silicon-containing monoamine, after the reaction of the tetracarboxylic dianhydride, the diamine and the polyvalent hydroxy compound is completed, the reaction liquid is cooled to 40 ° C. or lower, and then the silicon-containing monoamine is added. It is good to make it react at 10-40 degreeC for 0.1 to 6 hours. The monohydroxy compound may be added at any point in the reaction.

  The polyester amide acid synthesized in this way contains the structural unit represented by the formula (3) and the structural unit represented by the formula (4), and the terminal thereof is a tetracarboxylic dianhydride or diamine as a raw material. Alternatively, it is an acid anhydride group, amino group or hydroxy group derived from a polyvalent hydroxy compound, or an additive other than these compounds constitutes the terminal. By including such a configuration, curability is improved.

  The resulting polyester amic acid preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 3,000 to 50,000. If it exists in these ranges, flatness and heat resistance will become favorable.

  The weight average molecular weight in this specification is a value in terms of polystyrene determined by the GPC method (column temperature: 35 ° C., flow rate: 1 ml / min). Standard polystyrene is polystyrene having a molecular weight of 645 to 132900 (for example, polystyrene calibration kit PL2010-0102 of Agilent Technologies, Inc.), and PLgel MIXED-D (Agilent Technology, Inc.) is used as the column, and as a mobile phase. It can be measured using THF. In addition, the weight average molecular weight of the commercial item in this specification is a catalog publication value.

1-2. Epoxy group-containing polymer The epoxy group-containing polymer used in the present invention is obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw material components. An epoxy group containing polymer will not be specifically limited if compatibility with the other component which forms the thermosetting composition of this invention is good. The bifunctional (meth) acrylate to be reacted with glycidyl (meth) acrylate may be one type or two or more types.

  The thermosetting composition of the present invention containing an epoxy group-containing polymer obtained by using glycidyl (meth) acrylate as one of the raw material monomers increases the transparency of the cured film obtained therefrom, There exists an advantage which can suppress the transparency fall in an ultraviolet-ray exposure process. It is preferable from a viewpoint of flatness, heat resistance, and chemical resistance that glycidyl (meth) acrylate is contained 40-99 weight part in all the monomers used as the raw material of an epoxy-group-containing polymer.

  Preferred examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,3-butanediol di (meth) acrylate. , Neopentyl glycol di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate. These are preferable because the compatibility of the epoxy group-containing polymer obtained by reacting with glycidyl (meth) acrylate with the polyester amide acid becomes good. It is preferable from a viewpoint of flatness, heat resistance, and chemical resistance that 1-30 weight part of bifunctional (meth) acrylate is contained in all the monomers used as the raw material of an epoxy group containing polymer.

  The monomer used as the raw material of the epoxy group-containing polymer may include a radical polymerizable monomer other than the compound selected from the group consisting of glycidyl (meth) acrylate and bifunctional (meth) acrylate as a raw material component. In the present specification, such a monomer is referred to as “another radical polymerizable monomer”. The other radical polymerizable monomer may contain 0 to 40 parts by weight in the total monomers used as the raw material of the epoxy group-containing polymer, without impairing the effects of the present invention. From the viewpoint of expressing

  Specific examples of other radical polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. , 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, (meth) acryloyloxypropyl-tris-trimethylsiloxysilane, ( (Meth) acryloxyorganopolysiloxane, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, γ-butyrolactone (meth) acrylate DOO, N- cyclohexyl maleimide, N- phenylmaleimide, 2,2,2-trifluoroethyl (meth) acrylate, (meth) acrylic acid, and 4-hydroxy-phenyl vinyl ketone and the like.

  One type or two or more types of other radical polymerizable monomers may be used.

  The weight average molecular weight of the epoxy group-containing polymer is preferably 1,000 to 50,000, and more preferably 3,000 to 20,000. If the molecular weight is within these ranges, sufficient flatness, heat resistance, and chemical resistance can be obtained.

1-2-1. Solvent used for synthesis reaction of epoxy group-containing polymer At least a solvent is required for the synthesis of an epoxy group-containing polymer obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw material components.

  Specific examples of the solvent used in the polymerization reaction to obtain an epoxy group-containing polymer include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, Mention may be made of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetamide. Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate and diethylene glycol methyl ethyl ether are preferable.

  These solvents can be used alone or as a mixed solvent of two or more. Moreover, if it is a ratio of 30 weight% or less with respect to the whole quantity of a solvent, other solvents can also be mixed and used besides the said solvent.

1-2-2. Method for synthesizing epoxy group-containing polymer The method for synthesizing the epoxy group-containing polymer is not particularly limited, but radical polymerization in a solution using a solvent is preferred. When the reaction solvent is used in an amount of 100 parts by weight or more with respect to a total of 100 parts by weight of glycidyl (meth) acrylate, bifunctional (meth) acrylate, and other radical polymerizable monomers used as necessary, the reaction proceeds smoothly. Therefore, it is preferable. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator to be used. The polymerization time is not particularly limited, but is usually in the range of 1 to 24 hours. Further, the polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

  A known polymerization initiator can be used for the synthesis of the epoxy group-containing polymer. Examples of the polymerization initiator include compounds that generate radicals by heat, azo initiators such as azobisisobutyronitrile, and peroxide initiators such as benzoyl peroxide. In the radical polymerization reaction, an appropriate amount of a chain transfer agent such as thioglycolic acid may be added in order to adjust the molecular weight of the produced copolymer.

  The epoxy group-containing polymer may be an epoxy compound solution in which handling properties and the like are taken into consideration while leaving the solvent used in the synthesis as it is, or may be a solid epoxy compound in which the solvent is removed and in consideration of transportability.

1-3. Epoxy Compound The epoxy compound used in the present invention contains 2 to 10 epoxy groups per molecule and has a weight average molecular weight of less than 3,000. Flatness can be improved by adding an epoxy compound to the thermosetting composition of the present invention. When the epoxy compound is contained in an amount of 1 to 30 parts by weight with respect to 100 parts by weight of the epoxy group-containing polymer, the flatness is good, which is preferable.

  Preferable examples of the epoxy compound include a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, a glycidyl ether type epoxy compound, a bisphenol A novolac type epoxy compound, an aliphatic polyglycidyl ether compound, and a cyclic aliphatic epoxy compound. The following commercially available products can be used as these epoxy compounds.

  As glycidyl ether type epoxy compounds containing 2 to 10 epoxy groups per molecule and having a weight average molecular weight of less than 3,000, TECHMORE VG3101L (trade name; Printtech Co., Ltd.), EHPE-3150 (trade name; Daicel Corporation), EPPN-501H, 502H (all trade names; Nippon Kayaku Co., Ltd.), JER 1032H60 (trade names; Mitsubishi Chemical Corporation), and the like. Examples of the cycloaliphatic epoxy compound include Celoxide 2021P and 3000 (all trade names: Daicel Corporation). Examples of the bisphenol A novolak type epoxy compound include JER 157S65 and 157S70 (both trade names: Mitsubishi Chemical Corporation). As the phenol novolac type epoxy compound, EPPN-201 (trade name: Nippon Kayaku Co., Ltd.), JER 152, 154 (both trade names: Mitsubishi Chemical Corporation) and the like can be mentioned. Examples of the cresol novolac epoxy compound include EOCN-102S, 103S, 104S, and 1020 (all trade names: Nippon Kayaku Co., Ltd.).

1-4. Epoxy curing agent An epoxy curing agent is used in the thermosetting composition of the present invention in order to improve flatness and chemical resistance. Epoxy curing agents include acid anhydride curing agents, amine curing agents, phenol curing agents, imidazole curing agents, catalytic curing agents, and sulfonium salts, benzothiazolium salts, ammonium salts, phosphonium salts, etc. Although there exist a heat-sensitive acid generator etc., an acid anhydride type hardening | curing agent or an imidazole type hardening | curing agent is preferable from a viewpoint of avoiding coloring of a cured film and the heat resistance of a cured film.

  Specific examples of the acid anhydride curing agent include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrotrimellitic anhydride Aromatic carboxylic anhydrides such as phthalic anhydride and trimellitic anhydride, and styrene-maleic anhydride copolymers. Among these, trimellitic anhydride and hexahydrotrimellitic anhydride having a good balance between heat resistance and solubility in a solvent are particularly preferable.

  Specific examples of the imidazole 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. Among these, 2-undecylimidazole having a good balance between curability and solubility in a solvent is particularly preferable.

1-5. Ratio of Polyester Amic Acid, Epoxy Group-Containing Polymer, Epoxy Compound, and Epoxy Curing Agent In the thermosetting composition of the present invention, the ratio of the total amount of the epoxy group-containing polymer and the epoxy compound is 20 to 100 parts by weight of polyester amic acid. 400 parts by weight. When the ratio of the total amount of the epoxy group-containing polymer and the epoxy compound is within this range, the balance of flatness, heat resistance, chemical resistance, and adhesion is good. More preferably, the total amount of the epoxy group-containing polymer and the epoxy compound is in the range of 50 to 300 parts by weight.

  The ratio of the epoxy curing agent to the total amount of the epoxy group-containing polymer and the epoxy compound is 0.1 to 60 parts by weight of the epoxy curing agent with respect to 100 parts by weight of the total amount of the epoxy group-containing polymer and the epoxy compound. For example, with respect to the addition amount when the epoxy curing agent is an acid anhydride curing agent, more specifically, the carboxylic anhydride group or carboxyl group in the epoxy curing agent is 0.1 to 1.5 times the epoxy group. It is preferable to add so that it may become equivalent. At this time, the carboxylic acid anhydride group is calculated as divalent. It is more preferable to add the carboxylic acid anhydride group or the carboxyl group so that the equivalent amount of the carboxylic acid anhydride group or carboxyl group is 0.15 to 0.8 times, since the chemical resistance is further improved.

1-6. Other Components Various additives can be added to the thermosetting composition of the present invention in order to improve coating uniformity and adhesiveness. Additives include solvents, anionic, cationic, nonionic, fluorine or silicon leveling agents / surfactants, adhesion improvers such as silane coupling agents, hindered phenols, hindered amines, phosphorus And antioxidants such as sulfur compounds.

1-6-1. Solvent A solvent may be added to the thermosetting composition of the present invention. The solvent that is optionally added to the thermosetting composition of the present invention is preferably a solvent that can dissolve polyester amic acid, an epoxy group-containing polymer, an epoxy compound, an epoxy curing agent, 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, hydroxyethyl acetate, hydroxybutyl acetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-hydroxypropionate Ethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, 2-hydroxypropionate Propyl onate, 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, aceto Ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol , Tripropylene 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, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate , Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, acetonitrile, toluene, xylene, γ-butyrolactone, and N, N-dimethylacetamide. One of these may be sufficient as a solvent, and these 2 or more types of mixtures may be sufficient as it.

1-6-2. Surfactant A surfactant may be added to the thermosetting composition of the present invention in order to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (all are trade names: Kyoeisha Chemical Co., Ltd.), Disperbak 161, Dispersake 162, Dispersake 163, Dispersake 164, Dispersake 166, Dispersake 170, Dispersake 180, Dispersake 181 and Dispers Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (all of these are trade names; BIC Chemie Japan KK), KP-341, KP-358, KP- 368, KF-96-50CS, KF-50-100CS (all are trade names; Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon K -40, Surflon S611 (all are trade names; AGC Seimi Chemical Co., Ltd.), Aftergent 222F, Aftergent 208G, Aftergent 251, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, Aftergent 602A , TF 650A, FTX-218 (all are trade names; Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 Name: Mitsubishi Materials Corporation), Megafuck F-171, Megafuck F-177, Megafuck F-410, Megafuck F-430, Megafuck F-444, Megafuck F-4 72SF, Megafuck F-475, Megafuck F-477, Megafuck F-552, Megafuck F-553, Megafuck F-554, Megafuck F-555, Megafuck F-556, Megafuck F-558, Megafuck R-30, Megafuck R-94, Megafuck RS-75, Megafuck RS-72-K, Megafuck RS-76-NS (all are trade names; DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (all are trade names, Evonik Degussa Japan Co., Ltd.), fluoroalkylbenzenes Honates, fluoroalkylcarboxylates, fluoroalkylpolyoxyethylene ethers, fluoroalkylammonium iodides, fluoroalkylbetaines, fluoroalkylsulfonates, diglycerin tetrakis (fluoroalkylpolyoxyethylene ethers), fluoroalkyltrimethylammonium salts , Fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene Cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, poly Xylethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate , Polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these.

  Among these surfactants, BYK306, BYK342, BYK346, KP-341, KP-358, KP-368, Surflon S611, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 650A, Megafuck F-477 , Megafuck F-556, Megafuck RS-72-k, TEGO Twin 4000, Fluoroalkylbenzenesulfonate, Fluoroalkylcarboxylate, Fluoroalkylpolyoxyethylene ether, Fluoroalkylsulfonate, Fluoroalkyltrimethylammonium salt, And at least one selected from fluoroalkylaminosulfonates are preferred because the coating uniformity of the thermosetting composition is increased.

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

1-6-3. 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 such an adhesion improver, for example, 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 , 4-epoxycyclohexyl) ethyltrimethoxysilane (eg, Silaace S530; trade name; JNC Corporation), 3-mercaptopropyltrimethoxysilane (eg, Silaace S810; trade name; JNC Corporation) Agents, aluminum coupling agents such as acetoalkoxyaluminum diisopropylate, and titanate coupling agents such as tetraisopropylbis (dioctyl phosphite) titanate.

  Among these, 3-glycidyloxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.

  The content of the adhesion improver is preferably 10% by weight or less based on the total amount of the thermosetting composition. On the other hand, it is preferable that it is 0.01 weight% or more.

1-6-4. 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.

  You may add antioxidants, such as a hindered phenol type | system | group, a hindered amine type | system | group, a phosphorus type | system | group, and a sulfur type compound, to the thermosetting composition of this invention. Of these, hindered phenols are preferred from the viewpoint of weather resistance. Specific examples, Irganox1010, IrganoxFF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox295 (none Product name: BASF Japan Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50 ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80 (trade names; Ltd ADEKA) and the like. Among these, Irganox 1010 and ADK STAB AO-60 are more preferable.

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

1-6-7. Other Additives When the above-mentioned polyester amide acid does not contain a styrene-maleic anhydride copolymer as a raw material, a styrene-maleic anhydride copolymer may be added as another component.
1-7. Storage of Thermosetting Composition When the thermosetting composition of the present invention is stored in the range of −30 ° C. to 25 ° C., the stability with time of the composition is good, which is preferable. If the storage temperature is −20 ° C. to 10 ° C., there is no precipitate and it is more preferable.

2. Cured film obtained from thermosetting composition The thermosetting composition of the present invention is a mixture of a polyester amide acid, an epoxy group-containing polymer, an epoxy compound, and an epoxy curing agent. A coupling agent, a surfactant, and other additives may be selected and added as necessary, and they may be mixed and dissolved uniformly.

  When the thermosetting composition prepared as described above (after being dissolved in a solvent in the case of a solid state without a solvent) is applied to the surface of the substrate and the solvent is removed by heating, for example, the coating film Can be formed. Conventionally known methods such as spin coating, roll coating, dipping, and slit coating can be used to apply the thermosetting composition to the substrate surface. Next, this coating film is heated (prebaked) with a hot plate or an oven. The heating conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 150 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Then, in order to cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 250 ° C., for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.

  When heated, the cured film thus obtained has 1) the polyamic acid portion of the polyester amic acid dehydrated to form an imide bond, and 2) the carboxylic acid of the polyester amic acid reacts with the epoxy group-containing polymer. 3) Epoxy group-containing polymer is cured and has a high molecular weight, so it is very tough and has transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and spatter resistance. Is excellent. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state image sensor can be produced using this color filter. The cured film of the present invention is effective when used as a transparent insulating film formed between the TFT and the transparent electrode or a transparent insulating film formed between the transparent electrode and the alignment film, in addition to the protective film for the color filter. It is. Furthermore, the cured film of the present invention is effective even when used as a protective film for LED light emitters.

  Next, although a synthesis example, a reference example, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples. First, a polyester amic acid solution composed of a reaction product of tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound was synthesized as shown below (Synthesis Examples 1, 2, 3, and 4).

Synthesis Example 1 Synthesis of Polyesteramide Acid Solution (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 in the following weights, and stirred at 130 ° C for 3 hours in a dry nitrogen stream.
MMP 446.96g
ODPA 183.20g
31.93 g of 1,4-butanediol
Benzyl alcohol 25.54g
Thereafter, the reaction solution was cooled to 25 ° C., 3,3′-diaminodiphenylsulfone (hereinafter abbreviated as “DDS”) and MMP were added in the following weights, and stirred at 20 to 30 ° C. for 2 hours. Stir at 1 ° C. for 1 hour.
DDS 29.33g
MMP 183.04g
[Z / Y = 3.0, (Y + Z) /X=0.8]

  The solution was cooled to room temperature to obtain a 30% by weight solution (A1) of a pale yellow transparent polyester amide acid. 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 polymer (A1) was 4,200.

[Synthesis Example 2] Synthesis of polyester amic acid solution (A2) In a four-necked flask equipped with a stirrer, dehydrated and purified propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMEA”), 1,2,3,4-butanetetra Carboxylic dianhydride (hereinafter abbreviated as “BT-100”), SMA1000P (trade name; styrene / maleic anhydride copolymer, Kawa Crude Oil Co., Ltd.), 1,4-butanediol, benzyl alcohol And stirred at 125 ° C. for 3 hours under a stream of dry nitrogen.
PGMEA 324.00g
BT-100 30.64g
SMA1000P 145.88g
1,4-butanediol 9.29g
Benzyl alcohol 44.59g
Thereafter, the reaction solution was cooled to 25 ° C., DDS and PGMEA were added at the following weights, stirred at 20-30 ° C. for 2 hours, and then stirred at 125 ° C. for 2 hours.
DDS 9.60g
PGMEA 36.00g
[Z / Y = 2.7, (Y + Z) /X=0.9]

  The solution was cooled to room temperature to obtain a 30% by weight solution (A2) of a pale yellow transparent polyester amide acid. 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 polymer (A2) was 10,000.

[Synthesis Example 3] Synthesis of polyester amic acid solution (A3) In a four-necked flask equipped with a stirrer, dehydrated and purified PGMEA, BT-100, SMA1000P, 1,4-butanediol, and benzyl alcohol were charged in the following weights in this order: The mixture was stirred at 125 ° C. for 3 hours under a dry nitrogen stream.
PGMEA 324.00g
BT-100 30.04g
SMA1000P 143.05g
9.11 g of 1,4-butanediol
Benzyl alcohol 54.66g
Thereafter, the reaction solution was cooled to 25 ° C., DDS and PGMEA were added at the following weights, stirred at 20-30 ° C. for 2 hours, and then stirred at 125 ° C. for 2 hours.
DDS 3.14g
PGMEA 36.00g
[Z / Y = 8.0, (Y + Z) /X=0.8]

  The solution was cooled to room temperature to obtain a 30% by weight solution (A3) of a pale yellow transparent polyester amide acid. 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 polymer (A3) was 9,000.

Synthesis Example 4 Synthesis of Polyesteramide Acid Solution (A4) In a four-necked flask equipped with a stirrer, dehydrated and purified PGMEA, diethylene glycol methyl ethyl ether (hereinafter abbreviated as “EDM”), ODPA, SMA1000P, 1,4-butane Diol and benzyl alcohol were charged in the order of the following weights and stirred at 120 ° C. for 3 hours under a dry nitrogen stream.
PGMEA 504.00g
EDM 96.32g
ODPA 47.7g
SMA1000P 144.97g
1,4-butanediol 9.23g
Benzyl alcohol 55.40 g
Thereafter, the reaction solution was cooled to 25 ° C., DDS and MMP were added at the following weights, stirred at 20 to 30 ° C. for 2 hours, and then stirred at 120 ° C. for 2 hours.
DDS 12.72g
EDM 29.68g
[Z / Y = 2.0, (Y + Z) /X=1.0]

  The solution was cooled to room temperature to obtain a 30% by weight solution (A4) of a pale yellow transparent polyester amide acid. 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 polymer (A4) was 21,000.

  Next, an epoxy group-containing polymer obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw material components was synthesized as shown below (Synthesis Examples 5, 6, 7, 8 and 9).

[Synthesis Example 5] Synthesis of epoxy group-containing polymer solution (B1) In a 1000 ml four-necked flask equipped with a thermometer, stirrer, raw material inlet and nitrogen gas inlet, 420.00 g of dehydrated and purified MMP (hereinafter referred to as glycidyl methacrylate) , Abbreviated as “GMA”) 162.00 g, diethylene glycol dimethacrylate 18.00 g, and 2,2′-azobis (2,4-dimethylvaleronitrile) 27.00 g as a polymerization initiator were charged at a polymerization temperature of 110 ° C. Polymerization was carried out by heating for 2 hours. The reaction solution was cooled to 30 ° C. or less to obtain a 30 wt% solution (B1) of an epoxy group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 3,600 (polystyrene conversion).

[Synthesis Example 6] Synthesis of epoxy group-containing polymer solution (B2) In a 1000 ml four-necked flask equipped with a thermometer, stirrer, raw material inlet and nitrogen gas inlet, 300.00 g of dehydrated and purified MMP, 180.00 g of GMA, 20.00 g of 1,4-butanediol dimethacrylate and 20.00 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator were charged and polymerized by heating at a polymerization temperature of 90 ° C. for 2 hours. Went. The reaction solution was cooled to 30 ° C. or less to obtain a 40 wt% solution (B2) of an epoxy group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 12,000 (polystyrene conversion).

[Synthesis Example 7] Synthesis of epoxy group-containing polymer solution (B3) In a 1000 ml four-necked flask equipped with a thermometer, stirrer, raw material inlet and nitrogen gas inlet, 420.00 g of dehydrated and purified MMP, 126.00 g of GMA, Charge 18.00 g of diethylene glycol dimethacrylate, 36.00 g of tetrahydrofurfuryl methacrylate and 27.00 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and heat at a polymerization temperature of 110 ° C. for 2 hours. Then, polymerization was performed. The reaction solution was cooled to 30 ° C. or lower to obtain a 30 wt% solution (B3) of an epoxy group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 3,500 (polystyrene conversion).

[Synthesis Example 8] Synthesis of epoxy group-containing polymer solution (B4) In a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 420.00 g of dehydrated and purified MMP, 144.00 g of GMA, 27.00 g of diethylene glycol dimethacrylate, 9.00 g of methacryloxyorganopolysiloxane (trade name; FM-0721, JNC Corporation), 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator 00 g was charged and polymerized by heating at a polymerization temperature of 110 ° C. for 2 hours. The reaction solution was cooled to 30 ° C. or lower to obtain a 30 wt% solution (B4) of an epoxy group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 3,900 (polystyrene conversion).

[Synthesis Example 9] Synthesis of epoxy group-containing polymer solution (B5) In a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, 420.00 g of dehydrated and purified MMP 126.00 g, 18.00 g of diethylene glycol dimethacrylate, 36.00 g of 2-hydroxyethyl acrylate, and 27.00 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were charged as a polymerization initiator, and the polymerization temperature was 110 ° C. for 2 hours. Polymerization was performed by heating. The reaction solution was cooled to 30 ° C. or lower to obtain a 30 wt% solution (B5) of an epoxy group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 4,500 (polystyrene conversion).

[Comparative Synthesis Example 1] Synthesis of epoxy group-containing polymer (C1) In a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, 300.00 g of dehydrated and purified MMP, 180.00 g of GMA, Polymerization was carried out by charging 20.00 g of methyl methacrylate and 8.00 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and heating at a polymerization temperature of 90 ° C. for 2 hours. The reaction solution was cooled to 30 ° C. or less to obtain a 40 wt% solution (C1) of an epoxy group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 15,000 (polystyrene conversion).

[Comparative Synthesis Example 2] Synthesis of epoxy group-containing polymer (C2) In a 1000 ml four-necked flask equipped with a thermometer, stirrer, raw material inlet, and nitrogen gas inlet, 300.00 g of dehydrated and purified MMP, 180.00 g of GMA, Charged 20.00 g of 1,4-butanediol dimethacrylate and 13.00 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and heated at a polymerization temperature of 90 ° C. for 2 hours for polymerization. Went. The reaction solution was cooled to 30 ° C. or less to obtain a 40 wt% solution (C1) of an epoxy group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 58,000 (polystyrene conversion).

  Next, the polyester amide acids (A1, A2, A3, and A4) obtained in Synthesis Examples 1, 2, 3, and 4, and the epoxy group-containing products obtained in Synthesis Examples 5, 6, 7, 8, and 9 Polymer (B1, B2, B3, B4, and B5), epoxy group-containing polymer (C1 and C2) obtained in Comparative Synthesis Examples 1 and 2, commercially available polyfunctional epoxy compound having a weight average molecular weight of less than 3,000 , And an epoxy curing agent, a thermosetting composition was prepared as shown below. A cured film was obtained from the thermosetting composition, and the cured film was evaluated (Reference Examples 1 to 8, Examples 1 to 4, and Comparative Examples 1 to 5).

[Reference Example 1]
A 500 ml separable flask with a stirring blade was purged with nitrogen, and 100.0 g of the polyester amic acid solution (A1) obtained in Synthesis Example 1 and the epoxy group-containing polymer solution obtained in Synthesis Example 5 ( B1) 175.0 g, trimellitic anhydride (hereinafter abbreviated as “TMA”) 6.0 g as an epoxy curing agent, 4.4 g 3-glycidoxypropyltrimethoxysilane and ADK STAB AO-60 (as additives) Trade name: ADEKA Co., Ltd. 0.4 g, 230.8 g of MMP dehydrated and purified as a solvent, and 105.8 g of EDM were charged, and stirred at room temperature for 3 hours to be uniformly dissolved. Next, 0.2 g of Megafac F-477 (trade name; DIC Corporation) was added, stirred for 1 hour at room temperature, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a coating solution.

  Next, this coating solution was spin-coated on a glass substrate and a color filter substrate at 800 rpm for 10 seconds, and then pre-baked on a hot plate at 80 ° C. for 3 minutes to form a coating film. Thereafter, the coating film was cured by heating at 230 ° C. for 30 minutes in an oven to obtain a cured film having a thickness of 1.5 μm.

  The cured film thus obtained was evaluated for its transparency, light resistance, flatness, heat resistance, and chemical resistance.

[Transparency evaluation method]
The transmittance | permeability in wavelength 400nm of the light of only a cured film was measured with the ultraviolet visible near-infrared spectrophotometer (brand name; V-670, JASCO Corporation) in the obtained glass substrate with a cured film. The case where the transmittance was 97% or more was rated as ◯, and the case where the transmittance was less than 97% was rated as ×.

[Method for evaluating light resistance]
The glass substrate with a cured film after the transparency was evaluated in the above [Transparency Evaluation Method] was 1 J / cm ² with a UV ozone cleaning device (trade name: PL2003N-12, light source: low-pressure mercury lamp, Sen Special Light Source Co., Ltd.). (254 nm conversion) UV ozone treatment was performed, and after heating for 30 minutes at 230 ° C. in an oven, light of only the cured film was obtained with an ultraviolet-visible near-infrared spectrophotometer (trade name; V-670, JASCO Corporation). The transmittance at a wavelength of 400 nm was measured. The case where the transmittance was 96% or more was rated as ○, and the case where the transmittance was less than 96% was rated as ×.

[Evaluation method of flatness]
The step of the cured film surface of the obtained color filter substrate with a cured film was measured using a step / surface roughness / fine shape measuring device (trade name: P-15, KLA TENCOR Co., Ltd.). A case where the maximum value of the step between the R, G, and B pixels including the black matrix (hereinafter abbreviated as the maximum step) is less than 0.3 μm is indicated as “◯”, and a case where it is 0.3 μm or more is indicated as “X”. The color filter substrate used is a pigment dispersion color filter (hereinafter abbreviated as CF) using a resin black matrix having a maximum step of about 0.5 μm.

[Evaluation method of heat resistance]
After the obtained glass substrate with a cured film was reheated at 250 ° C. for 1 hour, the film thickness before heating and the film thickness after heating were measured, and the remaining film ratio was calculated by the following formula. For the measurement of the film thickness, the step, surface roughness, and fine shape measuring apparatus (trade name: P-15, KLA TENCOR Co., Ltd.) was used. The case where the remaining film ratio after heating was 95% or more was evaluated as ◯, and the case where the remaining film ratio after heating was less than 95% was evaluated as x.

Residual film ratio = (film thickness after heating / film thickness before heating) × 100

[Chemical resistance evaluation method]
The obtained glass substrate with a cured film was immersed in a 5 wt% aqueous sodium hydroxide solution at 60 ° C. for 10 minutes (hereinafter abbreviated as NaOH treatment), 36% hydrochloric acid / 60% nitric acid / water = 40/20/40 5 minutes immersion treatment (hereinafter abbreviated as acid treatment) at 50 ° C. and 30 minutes immersion treatment (hereinafter abbreviated as NMP treatment) in N-methyl-2-pyrrolidone at 50 ° C. for 30 minutes. And then reheated at 230 ° C. for 1 hour. The residual film rate after reheating and the transmittance after reheating were measured. A case where the remaining film ratio after reheating was 90% or more and the transmittance at 400 nm after reheating was 95% or more was evaluated as ◯. The case where the residual film rate after reheating was less than 90% or the transmittance after reheating was less than 95% was evaluated as x.

Remaining film ratio after reheating = (film thickness after reheating / film thickness before reheating) × 100

[Reference Examples 2 to 8]
According to the method of Reference Example 1, each component was mixed and dissolved at the ratio (unit: g) described in Table 1 to obtain a thermosetting composition. In addition, about the abbreviation of the additive in Tables 1-3, S510 is an adhesion improver Silaace S510 (trade name; JNC Corporation), and AO-60 is an antioxidant ADK STAB AO-60 (trade name; ADEKA Corporation). ), F-477, F-556, and RS-72-K are surfactants Megafac F-477, Megafac F-556, and Megafac RS-72-K (all trade names; DIC Corporation) Indicates.

[Examples 1 to 4]
According to the method of Reference Example 1, each component was mixed and dissolved at a ratio (unit: g) shown in Table 2 to obtain a thermosetting composition.

[Comparative Examples 1-5]
According to the method of Reference Example 1, each component was mixed and dissolved at the ratio (unit: g) shown in Table 3 to obtain a thermosetting composition.

Hereinafter, the evaluation results of the cured films of Reference Examples 1 to 8 are shown in Table 4, the evaluation results of the cured films of Examples 1 to 4 are shown in Table 5, and the evaluation results of the cured films of Comparative Examples 1 to 5 are shown in Table 6. Each is listed together.

  As is clear from the results shown in Tables 5 and 6, the cured films of Examples 1 to 4 are excellent in light resistance and flatness, and further have all points of transparency, heat resistance, and chemical resistance. It can be seen that there is a balance. On the other hand, the cured film using the epoxy group-containing polymer obtained by reacting the glycidyl methacrylate and the monofunctional methacrylate of Comparative Example 1 and Comparative Example 2 is excellent in light resistance, but the flatness is on the evaluation drop line. Yes, heat resistance and chemical resistance are poor. The cured film using the epoxy group-containing polymer obtained by reacting glycidyl methacrylate having a molecular weight of 50,000 or more and bifunctional methacrylate in Comparative Example 3 has poor flatness. Moreover, the cured film using the polyfunctional epoxy compound having a weight average molecular weight of less than 3,000 without using the epoxy group-containing polymer of Comparative Example 4 and Comparative Example 5 is inferior in light resistance in Comparative Example 4, and compared. In Example 5, heat resistance and chemical resistance were inferior. As described above, when an epoxy group-containing polymer (weight average molecular weight; 1,000 to 50,000) obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw material components is used. Only all the characteristics could be satisfied.

  Moreover, although the cured film of the reference examples 1-8 which do not use the epoxy compound shown in Table 4 is all evaluation items "(circle)", it shows a numerical value inferior to an Example in part about light resistance, and flatness Thus, it can be seen that all values are larger than those of the examples.

  The cured film obtained from the thermosetting composition of the present invention is excellent in properties as an optical material such as transparency, light resistance, and sputtering resistance, so that it can be used for color filters, LED light emitting elements, light receiving elements, etc. It can be used as a protective film such as various optical materials, and a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (21)

A composition comprising a polyester amide acid, an epoxy group-containing polymer, an epoxy compound, and an epoxy curing agent, wherein the polyester amide acid reacts with tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound as essential raw material components Obtained by:
The polyester amic acid is reacted with X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compounds in a ratio such that the relationship of the following formulas (1) and (2) is satisfied. And having a structural unit represented by the following formula (3) and a structural unit represented by the formula (4);
The epoxy group-containing polymer is obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw material components, and has a weight average molecular weight of 1,000 to 50,000;
The epoxy compound contains 2 to 10 epoxy groups per molecule and the weight average molecular weight is less than 3,000;
The total amount of the epoxy group-containing polymer and the epoxy compound is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amide acid, and the epoxy curing agent is 0.1 to 100 parts by weight with respect to the total amount of the epoxy group-containing polymer and the epoxy compound. 60 parts by weight thermosetting composition:

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)

In Formula (3) and Formula (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 diamine. R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound.   The thermosetting composition according to claim 1, wherein the raw material component of the polyester amide acid further contains a monohydroxy compound.   The monohydroxy compound is at least one selected from isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. Thermosetting composition.   The thermosetting composition according to claim 1 or 2, wherein the raw material component of the polyester amic acid further contains a styrene-maleic anhydride copolymer.   The thermosetting composition according to claim 1 or 2, wherein the polyester amic acid has a weight average molecular weight of 1,000 to 200,000.   Tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [ 1 selected from bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate) The thermosetting composition according to claim 1 or 2, which is a seed or more.   The thermosetting composition according to claim 1 or 2, wherein the diamine is at least one selected from 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone.   Polyhydric hydroxy compounds are ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and isocyanuric acid The thermosetting composition according to claim 1 or 2, wherein the thermosetting composition is at least one selected from tris (2-hydroxyethyl).   Bifunctional (meth) acrylate is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol The thermosetting composition according to claim 1 or 2, which is at least one selected from di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate.   The epoxy group-containing polymer is obtained by further containing a radical polymerizable monomer other than the compound selected from the group consisting of glycidyl (meth) acrylate and bifunctional (meth) acrylate as a raw material component and reacting them. The thermosetting composition described in 1.   Radical polymerizable monomers other than the compound selected from the group consisting of glycidyl (meth) acrylate and bifunctional (meth) acrylate are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, (Meth) acryloyloxypropyl-tris-trimethylsiloxysilane, (meth) acryloxyorganopolysiloxane, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetra Drofurfuryl (meth) acrylate, γ-butyrolactone (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, 2,2,2-trifluoroethyl (meth) acrylate, (meth) acrylic acid, and 4-hydroxyphenylvinyl The thermosetting composition according to claim 10, which is one or more selected from ketones.   The epoxy compound is 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4 -[1- [4- (2,3-epoxypropoxyphenyl) -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol and 2- [4- (2,3-epoxypropoxy) 1. One or more selected from phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane. Or thermosetting composition according to 2.   The thermosetting composition according to claim 1 or 2, wherein the epoxy curing agent is at least one selected from trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole. The tetracarboxylic dianhydride is one or more selected from 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride;
The diamine is 3,3′-diaminodiphenyl sulfone;
The polyvalent hydroxy compound is 1,4-butanediol;
An epoxy group-containing polymer is a copolymer having a weight average molecular weight of 1,000 to 50,000 obtained by reacting glycidyl methacrylate, diethylene glycol dimethacrylate and tetrahydrofurfuryl methacrylate as raw material components;
The epoxy compound is 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate;
The epoxy curing agent is one or more selected from trimellitic anhydride and 2-undecylimidazole;
The thermosetting composition according to claim 1, further comprising at least one selected from methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent.   The cured film obtained from the thermosetting composition of any one of Claims 1-14.   A color filter using the cured film according to claim 15 as a protective film.   A liquid crystal display element using the color filter according to claim 16.   A solid-state imaging device using the color filter according to claim 16.   The liquid crystal display element using the cured film of Claim 15 as a transparent insulating film formed between TFT and a transparent electrode.   The liquid crystal display element using the cured film of Claim 15 as a transparent insulating film formed between a transparent electrode and alignment film. The LED light-emitting body which used the cured film of Claim 15 as a protective film.