TWI813756B - Thermosetting compositions, cured film, and color filter - Google Patents

Abstract

The invention relates to a thermosetting composition, a cured film and a color filter, which include polyester amide (A), epoxy compound (B) and multifunctional acrylamide compound (C). The polyester amide (A) contains X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyhydric acid in a ratio such that the relationship between the following formulas (1) and (2) is established. The reaction product of the raw material of the hydroxy compound, the multifunctional acrylamide compound (C) has more than three (meth)acrylamide groups (CH ₂ =CR-CO-NH-) in each molecule; R is hydrogen or methyl) compounds. A cured film that can be used for various electronic parts and has excellent flatness can be formed from the thermosetting composition of the present invention. 0.2≦Z/Y≦8.0·······（1） 0.2≦（Y+Z）/X≦5.0···（2）

Description

Thermosetting compositions, cured films and color filters

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

In the manufacturing steps of elements such as liquid crystal display elements, the elements may be subjected to chemical treatment using organic solvents or the like, or may be subjected to heat treatment during formation of wiring electrode films by sputtering or the like. Therefore, surface protection films are sometimes provided for the purpose of preventing surface degradation, damage, and deterioration of various components. These protective films are required to withstand the treatment in the manufacturing steps as described above. Specifically, chemical resistance such as heat resistance and solvent resistance, water resistance, adhesion to base substrates such as glass, transparency, scratch resistance, coating properties, flatness, light resistance, etc. are required.

As the requirements for reliability of display elements increase and the heat resistance required for display element components increases, thermosetting compositions containing polyester amide and epoxy compounds with good heat resistance are advocated. thing (Patent Document 1). Furthermore, due to the enlargement of production lines in recent years, for example, in order to reduce in-plane unevenness during rubbing of the alignment film, it is necessary to press the rubbing roller more strongly than before, so the scratch resistance of the protective film is required to be improved. On the other hand, it is advocated that the molecular weight of the epoxy compound of the invention be adjusted, and the thermosetting composition containing an acrylic compound is recommended to have improved scratch resistance in addition to good heat resistance (Patent Document 2).

With the recent demands for high definition and thinning of liquid crystal display elements, protective films are required to have better flatness than before. Flatness refers to the surface level difference when a film-forming protective film is coated on a color filter containing pixels such as red (R), green (G), and blue (B) used in liquid crystal display elements. If the surface step difference is large, the display quality will be reduced. Compared with thermosetting materials, further improvement in flatness is a problem. [Prior art documents]

[Patent Document] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-105264 [Patent Document 2] Japanese Patent Publication No. 2018-028062

[Problem to be solved by the invention] An object of the present invention is to provide a thermosetting composition that provides a cured film excellent in flatness and a cured film formed from the thermosetting composition, and to further provide an electronic component having the cured film.

[Technical Means for Solving the Problem] The inventors of the present invention have diligently studied in order to solve the above-mentioned problem, and as a result found that the above-mentioned object can be achieved by using a cured film containing Polyester amide acid, epoxy compound, which is the reaction product of tetracarboxylic dianhydride, diamine and polyvalent hydroxyl compound, and polyester amide groups with more than three (meth)acrylamide groups (CH ₂ =CR) per molecule -CO-NH-; R is hydrogen or methyl) is obtained by hardening the composition of the compound. The present invention includes the following structures.

[1] A thermosetting composition containing polyester amide (A), an epoxy compound (B), and a multifunctional acrylamide compound (C), and the thermosetting composition is characterized by: The polyester amide (A) contains X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyhydric acid in a ratio such that the relationship between the following formulas (1) and (2) is established. The reaction product of the raw material of the hydroxyl compound, the multifunctional acrylamide compound (C) has more than three (meth)acrylamide groups (CH ₂ =CR-CO-NH-; R is hydrogen or methyl) compounds. 0.2≦Z/Y≦8.0·······（1） 0.2≦（Y+Z）/X≦5.0···（2）

[2] The thermosetting composition according to item [1], wherein the polyester amide (A) contains a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4) structural unit. 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 obtained by removing two -NH ₂ from diamine. The residue, R ³ is a residue obtained by removing two -OH from the polyvalent hydroxy compound.

[3] The thermosetting composition according to item [1] or [2], wherein the content of the epoxy compound (B) is 100 parts by weight of the polyester amide (A). 20 to 400 parts by weight, and the content of the multifunctional acrylamide compound (C) is 1 to 100 parts by weight relative to 100 parts by weight of polyester amide (A).

[4] A cured film obtained by curing the thermosetting composition according to any one of [1] to [3].

[5] A color filter having the cured film according to item [4] as a transparent protective film.

[Effects of the invention] The thermosetting composition according to the preferred embodiment of the present invention is a material particularly excellent in flatness, and can improve display quality when used as a color filter protective film for a color liquid crystal display element. In particular, it is effectively used as a protective film for color filters manufactured by dyeing, pigment dispersion, electrodeposition, and printing. In addition, it can also be used as a protective film and transparent insulating film for various optical materials.

In this specification, it is expressed that the smaller the step difference of the cured film of the present invention, the more excellent the flatness of the cured film and the thermosetting composition for forming the cured film.

In this specification, in order to express one or both of "acrylate" and "methacrylate", it may be expressed as "(meth)acrylate". Similarly, in order to represent one or both of "acryloxy" and "methacryloxy", it may be expressed as "(meth)acryloxy".

1. The thermosetting composition of the present invention The thermosetting composition of the present invention is a composition containing polyester amide, an epoxy compound and a multifunctional acrylamide compound. The polyester amide contains tetracarboxylic dianhydride, diamine and polyvalent hydroxyl group. The reaction product of the raw material of the compound, and the thermosetting composition is characterized in that: relative to 100 parts by weight of polyester amide, the epoxy compound is 20 to 400 parts by weight, and the multifunctional acrylamide compound is 1 Parts by weight ~ 100 parts by weight.

1-1. Polyester amide (A) Polyester amide is a reaction product of raw materials including tetracarboxylic dianhydride, diamine and polyvalent hydroxyl compound. More specifically, the polyester amide contains X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles in a ratio such that the relationship between the following formulas (1) and (2) is established. The reaction product of the raw material of the polyhydric hydroxyl compound. 0.2≦Z/Y≦8.0·······(1) 0.2≦（Y+Z）/X≦5.0···（2）

Polyester amide (A) preferably 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, and is preferably an organic group having 2 to 30 carbon atoms. R ² is a residue obtained by removing two -NH ₂ from 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.

In the synthesis of the polyester amide (A), at least a solvent is required, and the solvent may be left as it is to prepare a liquid or gel-like thermosetting composition in consideration of workability, etc., or the solvent may be The solvent is removed to prepare a solid composition in consideration of transportability and the like. In addition, in the synthesis of the polyester amide (A), if necessary, one or more compounds selected from a monohydroxy compound and a styrene-maleic anhydride copolymer may be included as a raw material, and a monohydroxy compound is particularly preferably included. . In addition, in the synthesis of the polyester amide (A), compounds other than those described above may be included as raw materials as necessary within a range that does not impair the object of the present invention.

1-1-1.Tetracarboxylic dianhydride In the present invention, tetracarboxylic dianhydride is used as a material for obtaining polyester amide (A). Preferred specific examples of tetracarboxylic dianhydride are: 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 2,2',3, 3'-diphenyl tetracarboxylic dianhydride, 2,3,3',4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid 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(dehydrated trimellitate) (trade name; TMEG- 100, New Nippon Rika Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, ethane Tetracarboxylic dianhydride and butane tetracarboxylic dianhydride. One or more types of these tetracarboxylic dianhydrides can be used.

Among these tetracarboxylic dianhydrides, 3,3',4,4'-diphenyltetracarboxylic dianhydride and 3,3',4,4'-diphenyl ether, which impart good transparency, are more preferred. Tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride and ethylene glycol bis( Dehydrated trimellitate), more preferably 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride anhydride and 1,2,3,4-butanetetracarboxylic dianhydride.

1-1-2.Diamine In the present invention, diamine is used as a material for obtaining polyester amide (A). Specific examples of preferred diamines are: 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, bis [4-(4-Aminophenoxy)phenyl]terine, bis[4-(3-aminophenoxy)phenyl]terine, bis[3-(4-aminophenoxy)phenyl ]碢, [4-(4-aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl]碢, [4-(3-aminophenoxy)phenyl] [3-(4-Aminophenoxy)phenyl]trines and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. More than one type of these diamines may be used.

Among these diamines, 3,3'-diaminodiphenyl terine and bis[4-(3-aminophenoxy)phenyl] terine, which impart good transparency, are more preferred, and 3, 3'-Diaminodiphenylsine.

1-1-3.Polyhydric hydroxyl compounds In the present invention, a polyvalent hydroxyl compound is used as a material for obtaining the polyester amide (A).

Specific examples of the polyhydric hydroxyl compound include: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, Polypropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2 ,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol , 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanediol, 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 Diol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, isocyanuric acid Tris(2-hydroxyethyl) ester, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol S (bis(4-hydroxyphenyl)propane), bisphenol F (bis( 4-Hydroxyphenyl)methane), 4,4'-isopropylidenebis(2-phenoxyethanol), 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxybis(2-phenoxyethanol) Cyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-(4-hydroxyphenyl)ethanol, diethanolamine, triethanolamine, glycerol monoallyl ether, trimethylolpropane monoallyl ether, Pentaerythritol monoallyl ether, pentaerythritol diallyl ether, dipentaerythritol monoallyl ether, dipentaerythritol diallyl ether, dipentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, sorbitol mono Allyl ether, sorbitol diallyl ether, sorbitol triallyl ether, sorbitol tetraallyl ether, glycerol mono(meth)acrylate, trimethylolpropane mono(methyl) ) Acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate Esters, dipentaerythritol tetra(meth)acrylate, sorbitol mono(meth)acrylate, sorbitol di(meth)acrylate, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate Meth)acrylate, (meth)acrylic acid modified product of ethylene glycol diglycidyl ether, (meth)acrylic acid modified product of propylene glycol diglycidyl ether, (meth)acrylic acid modified product of tripropylene glycol diglycidyl ether , (meth)acrylic acid modification of glycerol diglycidyl ether, (meth)acrylic acid modification of bisphenol A diglycidyl ether, (meth)acrylic acid modification of propylene oxide modified bisphenol A diglycidyl ether substance, (meth)acrylic modified product of bisphenol S diglycidyl ether, (meth)acrylic modified product of propylene oxide modified bisphenol S diglycidyl ether, (methyl)modified product of bisphenol F diglycidyl ether )Acrylic acid modified product, (meth)acrylic acid modified product of propylene oxide modified bisphenol F diglycidyl ether, (meth)acrylic acid modified product of dixylenol diglycidyl ether, biphenol diglycidyl ether (Meth)acrylic acid modified product, (meth)acrylic acid modified product of fendiphenol diglycidyl ether, (meth)acrylic acid modified product of cyclohexane-1,4-dimethylol diglycidyl ether, hydrogenated bisphenol A (meth)acrylic acid modified product of diglycidyl ether, (meth)acrylic acid modified product of tricyclodecane dimethanol diglycidyl ether and other compounds containing two or more epoxy groups per molecule ( Meth)acrylic acid modified product.

Among these polyvalent hydroxyl compounds, preferred are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1 which have good solubility in the reaction solvent. ,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 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'-isopropylidene bis(2-phenoxy ethanol), (meth)acrylic acid modified product of ethylene glycol diglycidyl ether, (meth)acrylic acid modified product of propylene glycol diglycidyl ether, (meth)acrylic acid modified product of glycerol diglycidyl ether, bisphenol The (meth)acrylic acid modified product of bisphenol A diglycidyl ether, the (meth)acrylic acid modified product of bisphenol A diglycidyl ether modified with propylene oxide, the (meth)acrylic acid modified product of bisphenol S diglycidyl ether , the (meth)acrylic acid modified product of propylene oxide modified bisphenol S diglycidyl ether, the (meth)acrylic acid modified product of bisphenol F diglycidyl ether and the propylene oxide modified bisphenol F diglycidyl ether Modified (meth)acrylic acid. Furthermore, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, and 4-hydroxybenzyl are particularly preferred. Alcohol, 4,4'-isopropylidenebis(2-phenoxyethanol), 2-(4-hydroxyphenyl)ethanol, (meth)acrylic acid modified product of ethylene glycol diglycidyl ether, propylene glycol di (Meth)acrylic acid modified product of glycidyl ether, (meth)acrylic acid modified product of tripropylene glycol diglycidyl ether, (meth)acrylic acid modified product of glyceryl diglycidyl ether, (meth)acrylic acid modified product of bisphenol A diglycidyl ether Meth)acrylic acid modified product and (meth)acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether.

As methacrylic modified product of ethylene glycol diglycidyl ether, acrylic modified product of propylene glycol diglycidyl ether, acrylic modified product of tripropylene glycol diglycidyl ether, acrylic modified product of glycerol diglycidyl ether, bisphenol A di Methacrylic modified product of glycidyl ether, acrylic modified product of bisphenol A diglycidyl ether, methacrylic modified product of bisphenol A diglycidyl ether modified with propylene oxide, and bisphenol A modified with propylene oxide. As an acrylic modified product of glycidyl ether, the following commercially available products can be used.

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

1-1-4.Monohydroxy compounds In the present invention, as a material for obtaining the polyester amide (A), a monohydroxy compound can be used. By using a monohydroxy compound, the storage stability of the thermosetting composition is improved. Specific examples of preferred monohydroxy compounds are: methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monomethyl ether. , Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltol, linalool , terpineol, dimethyl benzyl carbinol and 3-ethyl-3-hydroxymethyloxetane. More than one type of these monohydroxy compounds may be used.

Among these monohydroxy compounds, isopropyl alcohol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane is more preferred. When considering the compatibility or thermosetting composition when the polyesteramide (A) formed using these monohydroxy compounds is mixed with the epoxy compound (B) and the polyfunctional acrylamide compound (C) In view of the coating properties of the substance on the color filter, benzyl alcohol is more preferably used as the monohydroxy compound.

It is preferable to carry out the reaction containing 0 to 300 parts by weight of the monohydroxy compound relative to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound. More preferably, it is 5 parts by weight to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer In addition, the polyester amide (A) used in the present invention can also be synthesized by adding a compound having three or more acid anhydride groups to the raw material. The polyester amide (A) synthesized by adding a compound having three or more acid anhydride groups is preferred since improvement in transparency is expected. An example of a compound having three or more acid anhydride groups is a styrene-maleic anhydride copolymer. Regarding 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 more preferably 1 or 2, and still more preferably 1.

Specific examples of styrene-maleic anhydride copolymers are SMA3000P, SMA2000P, and SMA1000P (all are trade names; Sichuan Oil Chemical Co., Ltd.). Among these styrene-maleic anhydride copolymers, SMA1000P, which has excellent heat resistance and alkali resistance, is particularly preferred.

The styrene-maleic anhydride copolymer preferably contains 0 to 500 parts by weight relative to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound. More preferably, it is 10 parts by weight to 300 parts by weight.

1-1-6. Aminosilane compound having one amine group In the synthesis of polyester amide (A), raw materials other than those mentioned above may be included as raw materials as necessary within the scope that does not impair the object of the present invention. Examples of such other raw materials include those having one amine group. of aminosilane compounds. The aminosilane compound having one amine group is used to react with the acid anhydride group at the terminal of the polyester amide acid (A) to introduce a silane group at the terminal. The acid resistance of the cured film obtained can be improved by using the thermosetting composition of the present invention containing polyester amide (A) having one amine group. Obtained by reacting aminosilane compounds. Furthermore, when reacting with the above-mentioned monomer structure, both a monohydroxy compound and an aminosilane compound having one amino group may be added and reacted.

Specific examples of preferred aminosilane compounds having one amino group used in the present invention are: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Propylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-amine Butylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyl Diethoxysilane, m-aminophenyltrimethoxysilane and m-aminophenylmethyl diethoxysilane. More than one of these compounds may be used.

Among these compounds, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane, which improve the acid resistance of the cured film, are more preferred from the viewpoint of acid resistance and compatibility. More preferred is 3-aminopropyltriethoxysilane.

The aminosilane compound having one amine group preferably contains 0 to 300 parts by weight relative to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound. More preferably, it is 5 parts by weight to 200 parts by weight.

1-1-7. Solvent used in the synthesis reaction of polyester amide (A) Specific examples of the solvent (hereinafter sometimes referred to as "reaction solvent") used in the synthesis reaction to obtain polyester amide (A) are: 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, 3-methoxypropionic acid methyl ester, 3-ethyl ether Ethyl oxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N,N-dimethylacetamide. Among these solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate and diethylene glycol methyl ethyl ether are preferred.

1-1-8. Synthesis method of polyester amide (A) The polyester amide (A) used in the present invention is preferably synthesized by reacting tetracarboxylic dianhydride X mole, diamine Y mole and polyvalent hydroxy compound Z mole in the solvent. In this case, X, Y, and Z are determined as ratios at which the relationship between the following equations (1) and (2) is established. If it is the said range, the solubility of the polyester amide (A) in a solvent is high, so the coating property of a composition is improved, and as a result, a cured film excellent in flatness can be obtained. 0.2≦Z/Y≦8.0·······(1) 0.2≦（Y+Z）/X≦5.0···(2) In formula (1), 0.7≦Z/Y≦7.0 is preferred, and 1.0≦Z/Y≦5.0 is more preferred. In addition, in the formula (2), 0.5≦(Y+Z)/X≦4.0 is preferred, and 0.6≦(Y+Z)/X≦2.0 is more preferred.

It is considered that the polyester amide (A) used in the present invention is more stable than a molecule having an amine group or a hydroxyl group at the terminal under the reaction conditions described above and using an excess of X relative to (Y + Z). Molecules having an acid anhydride group (-CO-O-CO-) at the end are produced excessively. When reacting with such a monomer structure, the above-mentioned monohydroxy compound may be added as necessary in order to react with an acid anhydride group at the terminal of the molecule to esterify the terminal. The polyester amide (A) obtained by adding and reacting a monohydroxy compound can improve compatibility with epoxy compounds and epoxy hardeners, and can improve the properties of the thermosetting composition of the present invention containing these compounds. Coatability.

It is preferable to use 100 parts by weight or more of the reaction solvent 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°C to 200°C for 0.2 to 20 hours.

The order in which the reaction raw materials are added to the reaction system is not particularly limited. That is, any of the following methods may also be used: a method of simultaneously adding tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound to the reaction solvent; dissolving the diamine and polyvalent hydroxy compound in the reaction solvent and then adding tetracarboxylic acid The method of dianhydride; the method of preliminarily reacting tetracarboxylic dianhydride and a polyvalent hydroxy compound and then adding diamine to the reaction product; or the method of preliminarily reacting tetracarboxylic dianhydride and diamine and then adding diamine to the reaction product. Methods of polyhydroxyl compounds, etc.

When reacting the aminosilane compound having one amine group, after the reaction of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound is completed, the reacted solution is cooled to 40° C. or lower, and then added The aminosilane compound having one amine group is preferably reacted at 10°C to 40°C for 0.1 to 6 hours. Additionally, the monohydroxy compound can be added at any point in the reaction.

The polyester amide (A) synthesized in this manner contains a structural unit represented by formula (3) and a structural unit represented by formula (4), and its terminal is derived from tetracarboxylic dianhydride as a raw material, An acid anhydride group, an amino group, a hydroxyl group of a diamine or a polyvalent hydroxy compound, or an additive other than these compounds constitutes the terminal thereof. By including such a structure, hardenability becomes good.

The weight average molecular weight of the obtained polyester amide (A) is preferably 1,000 to 200,000, more preferably 2,000 to 50,000. If it is within these ranges, the flatness and heat resistance will be good.

The weight average molecular weight of the polyester amide (A) is the polyphenylene glycol obtained by gel permeation chromatography (GPC) (column temperature: 35°C, flow rate: 1 ml/min). Ethylene conversion value. The standard polystyrene uses the polystyrene calibration kit PL2010-0102 of Agilent Technologies Co., Ltd. with weight average molecular weights of 645, 2590, 10290, 37600, and 124500. The column used PLgel MIXED-D (Agilent Technologies Co., Ltd.), and tetrahydrofuran (THF) was used as the mobile phase. In addition, the weight average molecular weight of the commercially available polymer described in this specification is the value described in a catalog.

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

Examples of the epoxy compound (B) are: bisphenol A type epoxy compound, bisphenol F type epoxy compound, glycidyl ether type epoxy compound, glycidyl ester type epoxy compound, biphenyl type epoxy compound, phenol Novolak-type epoxy compounds, cresol novolak-type epoxy compounds, bisphenol A novolac-type epoxy compounds, aliphatic polyglycidyl ether compounds, cycloaliphatic epoxy compounds, monomers with epoxy groups and Copolymers of other monomers and epoxy compounds with siloxane bonding sites.

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

Furthermore, TECHMORE VG3101L (trade name; Printec Co., Ltd.) is 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4 -[1,1-bis[4-(2,3-glycidoxy)phenyl]ethyl]phenyl]propane and 1,3-bis[4-[1-[4-(2,3 -glycidoxy)phenyl]-1-[4-[1-[4-(2,3-glycidoxy)phenyl]-1-methylethyl]phenyl]ethyl] Mixture of phenoxy]-2-propanol; EHPE3150 (trade name; Daicel Co., Ltd.) is the 1,2-epoxy group of 2,2-bis(hydroxymethyl)-1-butanol -4-(2-oxiranyl) cyclohexane adduct; Celloxide 2021P (trade name; Daicel Co., Ltd.) is 3',4'- Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; Celloxide 3000 (trade name; Daicel Co., Ltd.) is 1-methyl-4-( 2-methyloxyethyl)-7-oxabicyclo[4.1.0]heptane; COATOSIL MP200 (trade name; Momentive Performance Materials Japan Co., Ltd.) It is a polymer of 3-glycidoxypropyltrimethoxysilane.

As the epoxy compound (B), these compounds may be used alone or two or more types thereof may be mixed and used.

The proportion of the total amount of the epoxy compound (B) is 20 to 400 parts by weight relative to 100 parts by weight of the polyester amide (A) in the thermosetting composition of the present invention. If the ratio of the total amount of the epoxy compound (B) is within the above range, the balance between flatness, heat resistance, chemical resistance and adhesion will be good. The total amount of the epoxy compound (B) is preferably in the range of 50 parts by weight to 300 parts by weight.

1-3. Multifunctional acrylamide compound (C) The multifunctional acrylamide compound (C) used in the present invention only needs to have three or more (meth)acrylamide groups (CH _{2 )} per molecule. =CR-CO-NH-; R is hydrogen or methyl), there is no particular limitation.

Specific examples of the polyfunctional acrylamide compound (C) are: N,N',N''-triacrylamide-diethylenetriamine, N,N'-{[(2-acrylamide-2-[( 3-Acrylamide propoxy)methyl]propane-1,3-diyl)bis(oxy)]bis(propane-1,3-diyl)}diacrylamide, N,N',N '',N'''-Tetraacrylyltriethylenetetramine, 1,3,5-triacrylylhexahydro-1,3,5-triazine.

In addition, specific examples of the polyfunctional acrylamide compound (C) include compounds of the following structural formula.

The following commercially available products can be used as the polyfunctional acrylamide compound (C). Specific examples of N,N',N''-triacrylyldiethylenetriamine are FAM-301 (trade name: Fuji Film Co., Ltd.) or FFM-2 (trade name: Wako Pure Chemical Industries, Ltd.), N,N'-{[(2-acrylamide-2-[(3-acrylamide propoxy)methyl]propane-1,3-diyl)bis(oxy)]bis(propane-1 ,3-diyl)} Specific examples of diacrylamide are FAM-401 (trade name: Fuji Film Co., Ltd.), N,N',N'',N'''-tetraacrylamide triethylenetetra A specific example of the amine is FAM-402 (trade name: Fuji Film Co., Ltd.).

The polyfunctional acrylamide compound (C) may be used alone, or two or more types thereof may be mixed and used.

The ratio of the total amount of the polyfunctional acrylamide compound (C) to 100 parts by weight of the polyester amide (A) in the thermosetting composition of the present invention is preferably 1 to 100 parts by weight. If the ratio of the total amount of the polyfunctional acrylamide compound (C) is within the above range, the balance between flatness, heat resistance, and scratch resistance will be good.

1-4.Other ingredients Various additives may be added to the thermosetting composition of the present invention to improve coating uniformity and adhesion. Main examples of additives include: hardeners, solvents, anionic, cationic, nonionic, fluorine-based or silicone-based leveling agents and surfactants, adhesion improvers such as silane coupling agents, hindered phenols, and hindered amines. Antioxidants such as antioxidants, phosphorus compounds, and sulfur compounds, and (meth)acrylate compounds.

1-4-1. Hardener In the thermosetting composition of the present invention, a curing agent may be used to further improve heat resistance and chemical resistance. As the hardener, there are acid anhydride-based hardeners, amine-based hardeners, phenol-based hardeners, carboxylic acid-containing polymers, imidazole-based hardeners, pyrazole-based hardeners, triazole-based hardeners, catalyst-type hardeners, and Heat-sensitive acid generators such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts are preferably acid anhydride-based hardeners or imidazole-based hardeners from the viewpoint of preventing coloration of the cured film and improving heat resistance of the cured film. agent, pyrazole hardener.

Specific examples of acid anhydride-based hardeners include aliphatic dicarboxylates such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride. Acid anhydrides; aromatic polycarboxylic anhydrides such as phthalic anhydride and trimellitic anhydride; and styrene-maleic anhydride copolymers. Among these acid anhydride-based hardeners, trimellitic anhydride and hexahydr trimellitic anhydride, which have a good balance between heat resistance and solubility in solvents, are preferred.

Specific examples of carboxylic acid-containing polymers include: ARUFON UC-3000, ARUFON UC-3090, and ARUFON UC-3900 (all are trade names; East Asia Hesheng Co., Ltd.), Marproof MA-0215Z, Marproof MA-0217Z and Marproof MA-0221Z (all are trade names; NOF Co., Ltd.) . Among these carboxylic acid-containing polymers, ARUFON UC-3900, which has excellent heat resistance, solubility in solvents, and flatness, is preferred.

Specific examples of imidazole-based hardeners include: 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 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 imidazole-based hardeners, 2-undecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenyl have a good balance between hardening properties and solubility in solvents. imidazole.

Specific examples of the pyrazole-based hardener include pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, and 3-methyl-5-pyrazolone. Preferred is 3,5-dimethylpyrazole with a good balance between hardening properties and solubility in solvents.

Specific examples of triazole-based hardeners include: 4-amino-1,2,4-triazole, 1,2,4-triazole, 1,2,3-triazole, 1-hydroxybenzotriazole, 3-Mercapto-1,2,4-triazole. Preferred is 1-hydroxybenzotriazole with a good balance between hardening properties and solubility in solvents.

Specific examples of the phenolic hardener 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)benzene, 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 these phenolic hardeners, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 1, 1,1-tris(4-hydroxyphenyl)ethane and 9,9-bis(4-hydroxy-3-methylphenyl)fluoride.

When a hardening agent is used, it is preferably 0.1 parts by weight or more and 60 parts by weight or less based on 100 parts by weight of the epoxy compound (B).

1-4-2. Solvent A solvent may also be used in the thermosetting composition of the present invention. The solvent optionally added to the thermosetting composition of the present invention is preferably a solvent that can dissolve polyesteramide (A), epoxy compound (B), and multifunctional acrylamide compound (C). Specific examples of the solvent are: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, acetone, 2-butanone, ethyl acetate Ester, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, methoxy Butyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate Ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2-methyl Methyl propionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyruvic acid Methyl ester, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxybutyrate, ethyl 2-oxybutyrate, 4-hydroxy-4-methyl Base-2-pentanone, 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 ethyl Acid ester, 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, dioxane, toluene, xylene, γ-butyrolactone, or N,N-dimethylacetamide and cyclohexanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a weight average molecular weight of less than 1,000 alcohol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and polypropylene glycol with a weight average molecular weight of less than 1,000. The solvent may be one type of these solvents or a mixture of two or more types of these solvents.

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

1-4-3. Surfactant In the thermosetting composition of the present invention, a surfactant may also be added to improve coating uniformity. Specific examples of surfactants are: Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (the above are all trade names; Kyoeisha Chemical Co., Ltd.), Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-170, Disperbyk-180, Disperbyk-181, Disperbyk ( Disperbyk)-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (the above are trade names ; BYK Chemie Japan Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF-50-100CS (the above are trade names; Shin-Etsu Chemical Industry Co., Ltd.), Sha Surflon S611 (trade name; AGC Seimi Chemical Co., Ltd.), Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL , Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 602A, Ftergent 650A, FTX-218 (the above are all trade names; Neos ( Neos Co., Ltd.), Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F- 475. Megafac F-477, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac ( Megafac F-556, Megafac F-558, Megafac F-559, Megafac R-94, Megafac RS-75, Megafac RS-72 -K, Megafac RS-76-NS, Megafac DS-21 (the above are trade names; DIC Co., Ltd.), TEGO Twin 4000, TEGO TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (above) All are trade names; Evonik Japan Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl Betaine, fluoroalkyl sulfonate, diglyceryl tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amino sulfonate, polyoxyethylene nonyl phenyl ether, Polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene Ethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan Alcoholic anhydride stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate ester, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate and alkyl diphenyl ether disulfonate. It is preferred to use at least one selected from these compounds.

Among these surfactants, if they are selected from BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surflon S611, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac RS-72-K, Megafac DS-21, TEGO Twin 4000, fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl trimethyl ammonium At least one kind of salt and fluoroalkylamine sulfonate is preferred because the coating uniformity of the thermosetting composition becomes high.

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

1-4-4. Adhesion improving agent From the viewpoint of further improving the adhesion between the formed cured film and the substrate, the thermosetting composition of the present invention may further contain an adhesion improving agent. Examples of the adhesion improving agent include silane-based, aluminum-based, or titanate-based coupling agents. Specifically: 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane ( For example, Sila-Ace S510; trade name; JNC Co., Ltd.), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (e.g., Sila-Ace Sila-Ace S530; trade name; JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane (e.g., Sila-Ace S810; trade name; JNC) JNC Co., Ltd.), copolymers of 3-glycidoxypropyltrimethoxysilane (e.g., trade name; COATOSIL MP200, Momentive Performance Materials Japan Co., Ltd. ) and other silane-based coupling agents, aluminum-based coupling agents such as acetyl alkoxy aluminum diisopropoxide, and titanate-based coupling agents such as tetraisopropylbis(dioctylphosphite) titanate.

Among these adhesion improving agents, 3-glycidoxypropyltrimethoxysilane has a large adhesion improving effect and is therefore preferable.

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

1-4-5. Antioxidants The thermosetting composition of the present invention may further contain an antioxidant from the viewpoint of improving transparency and preventing yellowing of the cured film when exposed to high temperatures.

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

An antioxidant is added in an amount of 0.1 to 5 parts by weight relative to the total amount of the thermosetting composition.

1-4-6.Molecular weight regulator The thermosetting composition of the present invention may further contain a molecular weight regulator to suppress an increase in molecular weight due to polymerization and to exhibit excellent storage stability. Examples of molecular weight regulators include thiols, xanthogens, quinones, hydroquinones, and 2,4-diphenyl-4-methyl-1-pentene.

Specific examples of the molecular weight regulator include: 1,4-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, methyl-p-benzoquinone, anthraquinone, hydroquinone, methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-pentylhydroquinone, 1,4-dihydroxynaphthalene, 3,6-dihydroxybenzoquinone Bornane, 4-methoxyphenol, 2,2',6,6'-tetra-tert-butyl-4,4'-dihydroxybiphenyl, 3-(3,5-di-tert-butyl -4-Hydroxyphenyl) stearyl propionate, 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,4,6-tris(3',5' -Di-tert-butyl-4'-hydroxybenzyl) mesitylene, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4-th Tributylcatechol, n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, tertiary-dodecylmercaptan, thioglycolic acid, dimethyl yellow Orthosulfide, diisopropylxanthate disulfide, 2,6-di-tert-butyl-p-cresol, 4,4'-butylene bis(6-tert-butyl-m-cresol ), 4,4'-thiobis(6-tert-butyl-m-cresol), 2,4-diphenyl-4-methyl-1-pentene, phenothiazine, and 2-hydroxy- 1,4-naphthoquinone, etc.

The molecular weight adjuster may be used alone or in combination of two or more types. Among molecular weight regulators, a naphthoquinone-based molecular weight regulator is preferred in terms of exhibiting excellent storage stability.

Among the molecular weight regulators, 2-hydroxy-1,4-naphthoquinone having a phenolic hydroxyl group is more preferred from the viewpoint of storage stability.

1-4-7.UV absorber From the viewpoint of further improving the deterioration-inhibiting ability of the formed transparent film, the thermosetting composition of the present invention may contain an ultraviolet absorber.

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

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

1-4-8. Anti-aggregation agent The thermosetting composition of the present invention may contain an anti-aggregation agent from the viewpoint of preventing aggregation by preventing the polyester amide (A) or the epoxy compound (B) from fusing with the solvent.

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

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

1-4-9. Thermal cross-linking agent From the viewpoint of further improving heat resistance, chemical resistance, film in-plane uniformity, flexibility, softness, and elasticity, the thermosetting composition of the present invention may contain a thermal crosslinking agent.

Specific examples of thermal crosslinking agents are: Nikalac MW-30HM, Nikalac MW-100LM, Nikalac MX-270, Nikalac MX-280, Nikalac Nikalac MX-290, Nikalac MW-390, and Nikalac MW-750LM (all trade names; Samhwa Chemical Co., Ltd.).

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

1-4-10.(Meth)acrylate compound In the thermosetting composition of the present invention, a (meth)acrylate compound can also be used. The (meth)acrylate compound used in the present invention is not particularly limited as long as it has two or more (meth)acrylyl groups per molecule.

Specific examples of compounds having two (meth)acrylyl groups per molecule among the (meth)acrylate compounds are: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate Acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, epichlorohydrin modified ethylene glycol di(meth)acrylate base) acrylate, epichlorohydrin-modified diethylene glycol di(meth)acrylate, epichlorohydrin-modified triethylene glycol di(meth)acrylate, epichlorohydrin-modified tetraethylene glycol di(meth)acrylate Meth)acrylate, epichlorohydrin modified polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate Ester, 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, glycerin acrylic acid Ester methacrylate, glycerin di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, epichlorohydrin modified 1,6-hexanediol di(meth)acrylic acid Ester, methoxylated cyclohexyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, caprolactone modification Hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, bis[(meth)acrylate ) Acryloxy neopentyl glycol] adipate, bisphenol A di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate ) 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, 1,3-butanediol di(meth)acrylate, dicyclopentyl diacrylate, ethylene oxide modified phosphoric acid di(meth)acrylate Ester, caprolactone·ethylene oxide modified phosphate di(meth)acrylate, epichlorohydrin modified phthalate 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.

Specific examples of compounds having three or more (meth)acrylyl groups per molecule in the (meth)acrylate compound include: trimethylolpropane tri(meth)acrylate, ethylene oxide modified Quality 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 phosphate, caprolactone·ethylene oxide-modified tri(meth)acrylate phosphate, caprolactone-modified tris[(meth)acryloxyethylene base] isocyanurate, di-trimethylolpropane tetra(meth)acrylate, diglyceryl tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkyl modified dipentaerythritol tetra(meth)acrylate Meth)acrylate, dipentaerythritol penta(meth)acrylate, alkyl modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate (meth)acrylate and carboxyl-containing polyfunctional (meth)acrylate.

The (meth)acrylate compound may be used alone, or two or more types thereof may be mixed and used.

In 100% by weight of the (meth)acrylate compound, from the viewpoint of scratch resistance, it is preferable to include at least 50% by weight of a compound having three or more (meth)acrylyl groups per molecule. .

Among the (meth)acrylate compounds, from the viewpoint of flatness and scratch resistance, it is preferable to use one selected from the group consisting of ethylene oxide isocyanurate modified diacrylate, ethylene oxide isocyanurate. Alkane modified triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and carboxyl-containing multifunctional (meth)acrylate of at least one.

The following commercially available products can be used as the (meth)acrylate compound. Specific examples of ethylene oxide isocyanurate-modified diacrylate are Aronix M-215 (trade name; Toa Gosei Co., Ltd.); ethylene oxide isocyanurate-modified diacrylate Specific examples of mixtures of isocyanuric acid ethylene oxide modified triacrylate are Aronix M-313 (30% to 40% by weight) and Aronix M-315 (3 Weight % to 13 weight %, hereafter abbreviated as "M-315") (all are trade names; Toa Gosei Co., Ltd., the content rate in parentheses isocyanuric acid ethylene oxide modified diacrylate in the mixture catalog value of the content rate); specific examples of trimethylolpropane triacrylate are Aronix M-309 (trade name; Toa Gosei Co., Ltd.); pentaerythritol triacrylate and pentaerythritol tetraacrylate Specific examples of the mixture are Aronix M-306 (65% to 70% by weight), Aronix M-305 (55% to 63% by weight), Aronix M-303 (30% to 60% by weight), Aronix M-452 (25% to 40% by weight) and Aronix M-450 (less than 10% by weight) (all is a trade name; Toa Gosei Co., Ltd., the content rate in parentheses is the catalog value of the content rate of pentaerythritol triacrylate in the mixture); a specific example of the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is Aronix M-403 (50% to 60% by weight), Aronix M-400 (40% to 50% by weight), Aronix M-402 (30% by weight) ~40% by weight (hereinafter referred to as "M-402"), Aronix M-404 (30% by weight ~ 40% by weight), Aronix M-406 (25% by weight ~ 35% by weight) %) and Aronix M-405 (10% to 20% by weight) (all are trade names; Toa Gosei Co., Ltd., the content in parentheses is the content of dipentaerythritol pentaacrylate in the mixture catalog value); specific examples of carboxyl group-containing polyfunctional (meth)acrylates are Aronix M-510 and Aronix M-520 (hereinafter abbreviated as "M-520") (Both are trade names; Dong-A Synthetic Co., Ltd.).

The proportion of the total amount of the (meth)acrylate compound is 0 to 400 parts by weight relative to 100 parts by weight of the polyester amide (A) in the thermosetting composition of the present invention. If the ratio of the total amount of the (meth)acrylate compound is within the above range, the balance between flatness, heat resistance, and scratch resistance will be good. The total amount of (meth)acrylate compounds is preferably in the range of 0 to 100 parts by weight.

1-4-11.Other additives As other components, styrene-maleic anhydride copolymer may be added.

1-5. Storage of thermosetting compositions When the thermosetting composition of the present invention is stored in the range of -30°C to 25°C, the stability of the composition over time becomes good, which is preferable. It is better if the storage temperature is -20°C to 10°C, since no precipitates will be produced.

2. Cured film obtained from thermosetting composition The thermosetting composition of the present invention can be obtained by mixing the polyester amide (A), the epoxy compound (B) and the multifunctional acrylamide compound (C), and then, as necessary, depending on the target properties. Select to add epoxy hardener, solvent, surfactant, adhesion improver, antioxidant, (meth)acrylate compound and other additives, and mix and dissolve these compounds evenly.

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

When the cured film obtained in the above manner is heated, 1) the polyamide acid part of the polyester amide acid is dehydrated and cyclized to form an amide imine bond, and 2) the carboxylic acid of the polyester amide acid reacts with the epoxy compound. The high molecular weight, and 3) the epoxy compound hardens and becomes high molecular weight, so it is very strong and has excellent transparency, heat resistance, chemical resistance, flatness, and adhesion. In addition, for the same reason, it is also expected to be excellent in light resistance, sputter resistance, scratch resistance, and coating properties. Therefore, the cured film of the present invention is effective when used as a protective film for color filters, and the color filters can be used to manufacture liquid crystal display elements or solid-state imaging elements. In addition, in addition to the protective film for color filters, if the cured film of the present invention is used as a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode or formed between a transparent electrode and an alignment film The transparent insulating film is effective. Furthermore, the cured film of the present invention is effective even when used as a protective film for a light emitting diode (Light Emitting Diode, LED) light body. [Example]

Next, the present invention will be specifically described through synthesis examples, working examples, and comparative examples, but the present invention is not limited to these examples at all.

The following abbreviations represent the following monomers, polymerization initiators, chain transfer agents, solvents, etc. respectively. ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride BT-100: 1,2,3,4-butanetetracarboxylic dianhydride, Rikacid BT-100 (trade name; New Nippon Rika Co., Ltd.) DDS: 3,3'-Diaminodiphenylsine Bis-A-2EOH: 4,4'-isopropylidene bis(2-phenoxyethanol) 70PA: Epoxy ester 70PA (trade name; Kyoreisha Chemical Co., Ltd.) SMA1000P: Styrene-maleic anhydride copolymer SMA1000P (trade name; Sichuan Yuanyuan Chemical Co., Ltd.) PGMEA: solvent propylene glycol monomethyl ether acetate PGME: solvent propylene glycol monomethyl ether MMP: solvent methyl 3-methoxypropionate VG3101L: Epoxy compound TECHMORE VG3101L (trade name; Printec Co., Ltd.) FAM-402: Multifunctional acrylamide compound FAM-402 (trade name; Fuji Film Co., Ltd.) FAM-301: Multifunctional acrylamide compound FAM-301 (trade name; Fuji Film Co., Ltd.) FAM-201: Difunctional acrylamide compound N,N'-diacryloyl-4,7,10-trioxa-1,13-tridecanediamine (N,N'-diacryloyl-4,7 ,10-troxa-1,13-tridecanediamine), FAM-201 (trade name; Fujifilm Co., Ltd.) DEAA: monofunctional acrylamide compound diethyl acrylamide TMA: hardener trimellitic anhydride C11Z: Hardener Curezole C11Z (trade name; Shikoku Chemical Co., Ltd.) MP200: Adhesion improving agent COATOSIL MP200 (trade name; Momentive Performance Materials Japan Co., Ltd.) AO-60: Antioxidant ADK STAB AO-60 (trade name; ADEKA Co., Ltd.) DS-21: Surfactant Megafac DS-21 (trade name; DIC Co., Ltd.) M-402: (meth)acrylate compound Aronix M-402 (trade name; Toa Gosei Co., Ltd.)

First, a polyester amide solution that is a reaction product of tetracarboxylic dianhydride, diamine, monohydroxy compound, polyvalent hydroxy compound, etc. is synthesized as shown below (Synthesis Examples 1 to 7).

[Synthesis Example 1] Synthesis of polyester amide (A1) In a four-necked flask equipped with a stirrer, the dehydrated and purified MMP, ODPA, 1,4-butanediol, and benzyl alcohol were put into the following weights, and stirred at 125°C for 2 hours under a dry nitrogen flow (synthesis first stage). MMP 49.00g ODPA 20.36 g 1,4-butanediol 3.55 g Benzyl alcohol 2.84 g

Thereafter, the reacted solution was cooled to room temperature, DDS and MMP were added in the following weights, stirred at 20°C to 30°C for 2 hours, and then stirred at 125°C for 1 hour (synthesis second stage). DDS 3.26g MMP 21.00g [Z/Y=3.0, (Y+Z)/X=0.8]

The solution was cooled to room temperature to obtain a 30% by weight solution of pale yellow and transparent polyester amide (A1). A portion of the solution was sampled and the weight average molecular weight was determined using GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amide (A1) was 4,200.

[Synthesis Example 2] Synthesis of polyester amide (A2) In a four-necked flask with a stirrer, put the dehydrated and purified PGMEA, BT-100, SMA1000P, 1,4-butanediol, and benzyl alcohol in order with the following weights, and place under a dry nitrogen flow at 125°C. Stir for 2 hours (first stage of synthesis). PGMEA 53.49 g BT-100 3.83 g SMA1000P 18.23g 1,4-butanediol 1.16 g Benzyl alcohol 5.57 g

Thereafter, the reacted solution was cooled to room temperature, DDS and PGMEA were added in the following weights, stirred at 20°C to 30°C for 2 hours, and then stirred at 125°C for 1 hour (synthesis second stage). DDS 1.20g PGMEA 16.51 g [Z/Y=2.7, (Y+Z)/X=0.9]

The solution was cooled to room temperature to obtain a 30% by weight solution of pale yellow and transparent polyester amide (A2). A portion of the solution was sampled and the weight average molecular weight was determined using GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amide (A2) was 10,000.

[Synthesis Example 3 to Synthesis Example 7] Synthesis of polyester amide acid (A3) to polyester amide acid (A7) According to the methods of Synthesis Example 1 and Synthesis Example 2, each component was reacted at the temperature, time, and ratio (unit: g) listed in Table 1 to obtain polyester amide (A3) to polyester amide (A7). solution.

Table 1 The unit of loading amount of each reagent and solvent is grams (g)

Next, a thermosetting composition was prepared as follows using a 30% by weight solution of polyester amide (A1) to polyester amide (A7) obtained in Synthesis Examples 1 to 7. A cured film was obtained from the thermosetting composition, and the cured film was evaluated.

[Example 1] The 30% by weight solution of polyester amide (A1) obtained in Synthesis Example 1, VG3101L, FAM-402, TMA, MP200, AO-60, DS-21, MMP, PGMEA, and PGME are mixed and dissolved, and filtered with a membrane filter (0.2 μm) to obtain a thermosetting composition. The weight of the polyester amide (A1) described in Table 2-1 is the weight of the polymer other than the solvent of the 30% by weight solution.

[Example 2 to Example 14 and Comparative Example 1 to Comparative Example 4] According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) described in Table 2-1 to Table 2-2 and Table 3 to obtain a thermosetting composition. The flattening rate and pencil hardness were measured according to the method of Example 1, and the evaluation results of flatness are shown in Tables 2-1 to 2-2 and Table 3.

Furthermore, the total amount of the solvent contained in the thermosetting composition is the total amount of MMP or PGMEA contained in the polyester amide (A) solution and the MMP, PGMEA, and PGME of the solvent, and is In the above step, the solid content concentration is adjusted so that it becomes approximately 17% by weight.

[Evaluation method of flatness] The thermosetting composition was spin-coated at 300 rpm for 10 seconds, and the surface level was measured using a step, surface roughness, and fine shape measuring device (trade name; P-17, KLA TENCOR Co., Ltd.) in advance. On a poor color filter substrate without a cured film having pixels of R, G, and B, pre-bake it on a hot plate at 90° C. for 2 minutes. Then, it was post-baked at 230°C for 30 minutes in an oven to obtain a color filter substrate with a cured film in which the average film thickness of the protective film was 1.5 μm. Thereafter, the surface level difference of the obtained color filter substrate with a cured film was measured. The flattening rate is calculated using the following calculation formula based on the maximum value of the surface step difference between the color filter substrate without a cured film and the color filter substrate with a cured film (hereinafter abbreviated as "maximum step difference"). (DOP (%)), the results are shown in Table 1. The case where the flattening rate was 85.0% or more was evaluated as flatness ○, and the case where the flattening rate was less than 85.0% was evaluated as flatness ×. In addition, use a color filter substrate without a cured film with a maximum step difference of 1.0 μm. Planarization rate (DOP (%)) = (maximum step difference of color filter substrate without cured film - maximum step difference of color filter substrate with cured film) / (color filter without cured film Maximum step difference of substrate)×100%

[Evaluation method of scratch resistance] The thermosetting composition was spin-coated on the glass substrate at 300 rpm for 10 seconds, and prebaked on a hot plate at 90° C. for 2 minutes. Post-bake at 230°C for 30 minutes in an oven to obtain a glass substrate with a cured film with a film thickness of 1.5 μm. The obtained glass substrate with a cured film was subjected to the pencil scratch test of 8.4.1 of JIS K-5400-1990 to measure the pencil hardness of the cured film. The results are shown in Table 1. The case where the pencil hardness was 3H or more was evaluated as scratch resistance ○, and the case where it was 2H or less was evaluated as scratch resistance ×.

[Evaluation method of transparency] The thermosetting composition was spin-coated on the glass substrate at 300 rpm for 10 seconds, and prebaked on a hot plate at 90° C. for 2 minutes. Post-bake at 230°C for 30 minutes in an oven to obtain a glass substrate with a cured film with a film thickness of 1.5 μm. The transmittance of the cured film on the obtained glass substrate with a cured film was measured using an ultraviolet-visible spectrophotometer, and the results are shown in Table 1. Transparency ○ was evaluated when the transmittance at a wavelength of 400 nm was 95.0% or more, and transparency × was evaluated when it was less than 95.0%.

[Evaluation method of adhesion] The thermosetting composition was spin-coated on the glass substrate at 300 rpm for 10 seconds, and prebaked on a hot plate at 90° C. for 2 minutes. Post-bake at 230°C for 30 minutes in an oven to obtain a glass substrate with a cured film with a film thickness of 1.5 μm. The obtained glass substrate with a cured film was tested in accordance with ISO2409. The case where the test result showed adhesion between categories 0 and 1 was marked as ○, and the case where the test results showed adhesion between categories 2 and 5 was marked as ×.

[Evaluation method of hygroscopicity] The thermosetting composition was spin-coated on the glass substrate at 300 rpm for 10 seconds, and prebaked on a hot plate at 90° C. for 2 minutes. Post-bake at 230°C for 30 minutes in an oven to obtain a glass substrate with a cured film with a film thickness of 1.5 μm. The obtained cured film was scraped off and made into powder, and the weight loss before and after heating was measured using a thermogravimetric differential thermal analysis device. At this time, in the thermogravimetric differential thermal analysis device test, the temperature was raised from room temperature to 150°C at 10°C/min, and heated at 150°C for 20 minutes. The case where the weight loss shows a value of 2.0% or less is marked as ○, and the case where the weight loss shows a value exceeding 2.0% is marked as ×.

[Evaluation method of heat resistance] The thermosetting composition was spin-coated on the glass substrate at 300 rpm for 10 seconds, and prebaked on a hot plate at 90° C. for 2 minutes. Post-bake at 230°C for 30 minutes in an oven to obtain a glass substrate with a cured film with a film thickness of 1.5 μm. The obtained cured film was scraped off and made into powder, and the weight loss before and after heating was measured using a thermogravimetric differential thermal analysis device. At this time, in the thermogravimetric differential thermal analysis device test, the temperature was raised from room temperature to 150°C at 10°C/min, and heated at 150°C for 20 minutes. Then, the temperature was raised from 150°C to 250°C at 10°C/min, and heated at 10°C/min. Heat at 250°C for 30 minutes. Here, the weight at the time when the temperature rise from 150° C. to 250° C. is started is used as a reference, and the difference from the weight after heating at 250° C. for 30 minutes is used as the weight loss amount. The case where the weight loss shows a value of 3.0% or less is marked as ○, and the case where the weight loss shows a value exceeding 3.0% is marked as ×.

table 2-1 The unit of loading amount is grams (g)

Table 2-2 The unit of loading amount is grams (g)

table 3 The unit of loading amount is grams (g)

From the results shown in Table 2-1 to Table 2-2, it is clear that the thermosetting compositions of Examples 1 to 14 are excellent in flatness. On the other hand, it was found that Comparative Examples 1 to 4, which are thermosetting compositions not containing the polyfunctional acrylamide compound (C), have poor flatness. [Industrial availability]

The cured film obtained from the thermosetting composition of the present invention has high flatness and high scratch resistance. In terms of these aspects, it can be used as various optical materials such as color filters, LED light-emitting elements, and light-receiving elements. protective film, and an insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

without

without

Claims (4)

A thermosetting composition comprising polyester amide (A), an epoxy compound (B) and a multifunctional acrylamide compound (C), and the thermosetting composition is characterized in that the polyester amide Esteramide (A) contains X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of a polyvalent hydroxy compound in a ratio such that the relationship between the following formulas (1) and (2) is established. The reaction product of raw materials, the multifunctional acrylamide compound (C) is a compound with more than three (meth)acrylamide groups in each molecule, 0.2≦Z/Y≦8.0. ． ． ． ． ． ． (1) 0.6≦(Y+Z)/X≦2.0． ． ． (2) The content of the epoxy compound (B) is 20 to 400 parts by weight relative to 100 parts by weight of the polyester amide (A), and the polyfunctional acrylamide compound (C) is The content is 1 to 100 parts by weight relative to 100 parts by weight of the polyester amide (A). The thermosetting composition according to claim 1, wherein the polyester amide (A) includes a structural unit represented by the following formula (3) and a structure represented by the following formula (4) Unit:

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 obtained by removing two -NH ₂ from diamine. The residue, R ³ is a residue obtained by removing two -OH from the polyvalent hydroxy compound. A cured film obtained by curing the thermosetting composition described in claim 1 or claim 2. A color filter having the cured film described in Item 3 of the patent application as a transparent protective film.