KR20200035337A - Thermosetting compositions, cured film and color filter - Google Patents

Abstract

The present invention relates to a thermosetting composition including: (A) polyester amide acid; (B) an epoxy compound; and (C) a multifunctional acrylamide compound. The present invention also relates to a cured film and a color filter. Particularly, the polyester amide acid (A) is a reaction product of raw materials including X moles of a tetracarboxylic acid dianhydride, Y moles of a diamine and Z moles of a multifunctional hydroxyl compound at such a ratio that the formula (1) of 0.2 <= Z / Y <= 8.0 and formula (2) of 0.2 <= (Y + Z) / X <= 5.0 may be satisfied. In addition, the multifunctional acrylamide compound (C) is a compound having at least three (meth)acrylamide groups (CH_2=CR-CO-NH-, wherein R represents H or methyl) in one molecule. It is possible to form a cured film having excellent surface smoothness and applicable to various electronic parts by using the thermosetting composition.

Description

Thermosetting composition, cured film and color filter {THERMOSETTING COMPOSITIONS, CURED FILM AND COLOR FILTER}

The present invention can be used for the formation of insulating materials in electronic components, passivation films in semiconductor devices, buffer coating films, interlayer insulating films, planarizing films, interlayer insulating films in liquid crystal display elements, protective films for color filters, and the like. It relates to a composition, a transparent film according to it, and an electronic component having the film.

In the manufacturing process of an element such as a liquid crystal display element, the element may be subjected to chemical treatment with an organic solvent or the like, or may be subjected to heat treatment during deposition of a wiring electrode by sputtering or the like. Therefore, a surface protective film may be provided for the purpose of preventing surface deterioration, damage and deterioration of various elements. These protective films are required to withstand the treatment in the above manufacturing process. Specifically, chemical resistance such as heat resistance and solvent resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, scratch resistance, coatability, flatness, light resistance, and the like are required.

As the required characteristics of reliability required for a display element have improved, while the heat resistance required for the display element member has been improved, a thermosetting composition comprising a polyesteramic acid and an epoxy compound having good heat resistance has been proposed (Patent Document 1). ). In addition, due to the enlargement of the production line 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 in the prior art, and for this reason, it is required to improve the scratch resistance of the protective film. On the other hand, the molecular weight of the epoxy compound of the present invention was adjusted, and a thermosetting composition containing an acrylic compound was proposed, and in addition to good heat resistance, scratch resistance was improved (Patent Document 2).

In accordance with the demands for high precision and thinness in the liquid crystal display elements of recent years, the protective film is required to have superior flatness than before. Flatness refers to the surface level difference when a protective film is applied and deposited on a color filter composed of pixels such as R (red), G (green), and B (blue) used in a liquid crystal display element. The display quality decreases. For a thermosetting material, improvement of the flatness of the temporary layer has been a problem.

Japanese Patent Publication 2005-105264 Japanese Patent Publication 2018-028062

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 of the thermosetting composition, and also to provide an electronic component having the cured film.

The present inventors, as a result of diligent investigation to solve the above problems, the tetracarboxylic acid dianhydride, a diamine and a polyhydric hydroxy compound reaction product of polyesteramic acid, epoxy compound, and (meth) acrylamide group (CH ₂ = CR-CO-NH-; R is hydrogen or methyl) by finding a curable film obtained by curing a composition comprising three or more compounds per molecule, the above object can be achieved, and the present invention is completed. I came to Hagi.

The present invention includes the following configurations.

[1] A thermosetting composition comprising a polyester amide acid (A), an epoxy compound (B) and a polyfunctional acrylamide compound (C),

The polyester amide acid (A) is a ratio in which the relationship between the following formulas (1) and (2) holds the X mole of tetracarboxylic dianhydride, the Y mole of the diamine and the Z mole of the polyhydric hydroxy compound. It is the reaction product of the containing raw material,

The polyfunctional acrylamide compound (C) is a compound having three or more (meth) acrylamide groups (CH ₂ = CR-CO-NH-; R is hydrogen or methyl) per molecule, thermosetting composition .

0.2≤Z / Y≤8.0 (One)

0.2≤ (Y + Z) /X≤5.0 (2)

[2] The thermosetting composition according to [1], wherein the polyesteramic acid (A) comprises a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

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

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

[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 [4] as a transparent protective film.

The thermosetting composition according to a preferred embodiment of the present invention is a material particularly excellent in flatness, and when used as a color filter protective film of a color liquid crystal display device, the display quality can be improved. In particular, it is useful as a protective film for color filters produced by dyeing, pigment dispersion, electrodeposition and printing methods. Moreover, it can also be used as a protective film and a transparent insulating film of various optical materials.

In this specification, the smaller the level difference of the cured film according to the present invention, the cured film and the thermosetting composition for forming the cured film are expressed as "excellent flatness".

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

1. Thermosetting composition of the present invention

The thermosetting composition of the present invention is a composition comprising a polyesteramide acid, an epoxy compound, and a polyfunctional acrylamide compound which is a reaction product of a raw material containing a tetracarboxylic dianhydride, a diamine and a polyhydric hydroxy compound, and a polyesteramide It is a thermosetting composition characterized in that the epoxy compound is 20 to 400 parts by weight, and the polyfunctional acrylamide compound is 1 to 100 parts by weight based on 100 parts by weight of the acid.

1-1. Polyester amide acid (A)

Polyesteramic acid is a reaction product of a raw material containing tetracarboxylic dianhydride, diamine and polyhydric hydroxy compound. More specifically, the reaction product of a raw material containing X mole of tetracarboxylic dianhydride, Y mole of diamine and Z mole of polyhydric hydroxy compound at a ratio in which the relationship of the following formulas (1) and (2) holds to be.

0.2≤Z / Y≤8.0 (One)

0.2≤ (Y + Z) /X≤5.0 (2)

It is preferable that polyesteramic acid (A) has a structural unit represented by following formula (3) and a structural unit represented by formula (4).

In Formulas (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from tetracarboxylic dianhydride, and is preferably an organic group having 2 to 30 carbon atoms. R ² is a residue obtained by removing two -NH ₂ from 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.

For the synthesis of the polyester amide acid (A), at least a solvent is required, and the solvent can be left as it is and used as a liquid or gel thermosetting composition in consideration of handling properties and the like. You may make it a composition. Further, the synthesis of the polyester amide acid (A) may include, as necessary, one or more compounds selected from a monohydroxy compound and a styrene-maleic anhydride copolymer, as a raw material, in particular a monohydroxy compound It is preferable to include. Moreover, in the synthesis | combination of polyesteramic acid (A), as a raw material, you may contain the compound other than the above as needed in the range which does not spoil the objective of this invention.

 1-1-1. Tetracarboxylic acid dianhydride

In the present invention, tetracarboxylic dianhydride is used as a material for obtaining the polyesteramic acid (A). Specific examples of the preferred tetracarboxylic dianhydride include 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3, 3 ', 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylsulfonetetracarboxylic dianhydride Water, 2,3,3 ', 4'-diphenylsulfonetetracarboxylic 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-butane tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, Shin Nippon Ewha Corporation), cyclobutane tetracarboxylic dianhydride, methylcyclobutane Tetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid Dianhydrides, cyclohexanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride, and butanetetracarboxylic dianhydride. One or more of these can be used.

Among these, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, which gives good transparency, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2 -[Bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate) are more preferable. , 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride and 1,2,3,4-butanetetracar The native dianhydride is more preferred.

1-1-2. Diamine

In the present invention, diamine is used as a material for obtaining the polyesteramic acid (A). Specific examples of preferred diamines are 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, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, and 2,2-bis [4- (4-amino Phenoxy) phenyl] hexafluoropropane. One or more of these can be used.

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

1-1-3. Polyhydric hydroxy compounds

In the present invention, a polyhydric hydroxy compound is used as a material for obtaining the polyesteramic acid (A).

Specific examples of the polyhydric hydroxy compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and weight average Polypropylene glycol having a molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2 , 5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1,7-heptane Diol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1 , 12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, isocia Lesantris (2-hydroxyethyl), bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxyphenyl) sulfone), bisphenol F (bis (4-hydroxy Hydroxyphenyl) methane), 4,4'-isopropylidenebis (2-phenoxyethanol), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethanol, diethanolamine, triethanolamine, glycerin monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether , Pentaerythritol diallyl ether, dipentaerythritol monoallyl ether, dipentaerythritol diallyl ether, dipentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, sorbitol monoallyl ether, sorbitol diallyl ether, Sorbitol triallyl ether, sorbitol tetraallyl ether, glycerin (Meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythrate Litoldi (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) ) Acrylate, sorbitol tetra (meth) acrylate, (meth) acrylic acid modified product of ethylene glycol diglycidyl ether, (meth) acrylic acid modified product of propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether (Meth) acrylic acid modified product, (meth) acrylic acid modified product of glycerin diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, (Meth) acrylic acid modified product of propylene oxide-modified bisphenol A diglycidyl ether, (meth) acrylic acid modified product of bisphenol S diglycidyl ether, (meth) acrylic acid of propylene oxide modified bisphenol S diglycidyl ether Modified product, (meth) acrylic acid modification of bisphenol F diglycidyl ether, (meth) acrylic acid modification of propylene oxide modified bisphenol F diglycidyl ether, (meth) acrylic acid modification of bixylenol diglycidyl ether Water, (meth) acrylic acid modified product of biphenol diglycidyl ether, (meth) acrylic acid modified product of fluorenediphenol diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether ( Meta) acrylic acid modified product, (meth) acrylic acid modified product of hydrogenated bisphenol A diglycidyl ether, (meth) acrylic acid modified product of tricyclodecane dimethanol diglycidyl ether, and two or more epoxy groups per molecule doing Of the other compound (meth) acrylic acid modified products.

Among them, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptane, which have good solubility as a reaction solvent Diol, 1,8-octanediol, isocyanurate tris (2-hydroxyethyl), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, 2 -Of hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethanol, 4,4'-isopropylidenebis (2-phenoxyethanol), ethylene glycol diglycidyl ether ( Meta) acrylic acid modified product, (meth) acrylic acid modified product of propylene glycol diglycidyl ether, (meth) acrylic acid modified product of glycerin diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, Propylene oxide-modified bisphenol A diglycidyl ether (meth) acrylic acid modified product, bisphenol S diglycidyl ether (meth) (Meth) acrylic acid modified product of methacrylate modified product, propylene oxide modified bisphenol S diglycidyl ether, (meth) acrylic acid modified product of bisphenol F diglycidyl ether, and propylene oxide modified bisphenol F diglycidyl Ether (meth) acrylic acid modified products are preferred. In addition, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 4,4'-iso Propylidenebis (2-phenoxyethanol), 2- (4-hydroxyphenyl) ethanol, (meth) acrylic acid modification of ethylene glycol diglycidyl ether, (meth) acrylic acid modification of propylene glycol diglycidyl ether Water, (meth) acrylic acid modified product of tripropylene glycol diglycidyl ether, (meth) acrylic acid modified product of glycerin diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, and propylene oxide The (meth) acrylic acid modified product of the seed-modified bisphenol A diglycidyl ether is particularly preferred.

Methacrylic acid modified products of ethylene glycol diglycidyl ether, acrylic acid modified products of propylene glycol diglycidyl ether, acrylic acid modified products of tripropylene glycol diglycidyl ether, acrylic acid modified products of glycerin diglycidyl ether, Bisphenol A diglycidyl ether methacrylic acid modified product, bisphenol A diglycidyl ether acrylic acid modified product, propylene oxide modified bisphenol A diglycidyl ether methacrylic acid modified product, and propylene oxide modified bisphenol As the acrylic acid modified product of A diglycidyl ether, the following commercially available products can be used.

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

1-1-4. Monohydroxy compounds

In the present invention, a monohydroxy compound may be used as a material for obtaining the polyesteramic acid (A). By using a monohydroxy compound, the storage stability of the thermosetting composition is improved. Specific examples of preferred monohydroxy compounds include 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, bornol, maltol, linarol, terpineol, dimethylbenzylcarbinol, and 3-ethyl-3-hydroxymethyloxetane. One or more of these can be used.

Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane is more preferable. Compatibility when the polyester amide acid (A) obtained using these, the epoxy compound (B), and the polyfunctional acrylamide compound (C) are mixed, or the thermosetting composition is applied onto the color filter Considering the properties, it is more preferable to use benzyl alcohol for the monohydroxy compound.

It is preferable that the monohydroxy compound is reacted by containing 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 to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer

Moreover, the polyesteramic acid (A) used for this invention may be synthesize | combined by adding the compound which has three or more acid anhydride groups to the said raw material. The polyesteramic acid (A) synthesized by adding a compound having three or more acid anhydride groups is preferable because improvement in transparency is expected. An example of a compound having three or more acid anhydride groups is 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. The molar ratio of styrene / maleic anhydride is more preferably 1 or 2, and more preferably 1.

Specific examples of the styrene-maleic anhydride copolymer are SMA3000P, SMA2000P, and SMA1000P (all are trade names; Kawahara Oil Works Co., Ltd.). Among them, SMA1000P having good heat resistance and alkali resistance is particularly preferable.

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

1-1-6. Aminosilane compound having one amino group

In the synthesis of the polyester amide acid (A), raw materials other than the above may be included as necessary as long as the raw material does not impair the object of the present invention, and examples of such other raw materials include amino having one amino group. It is a silane compound. The aminosilane compound having one amino group is used to react with an acid anhydride group at the end of the polyesteramic acid (A) to introduce a silyl group at the end. When the thermosetting composition of the present invention containing the polyesteramic acid (A) obtained by adding and reacting an aminosilane compound having one amino group is reacted, the acid resistance of the obtained cured film is improved. Moreover, when reacting with the structure of the above-mentioned monomer, it is also possible to react by adding both a monohydroxy compound and an aminosilane compound having one amino group.

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

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

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

1-1-7. Solvent used for the synthesis reaction of polyesteramic acid (A)

Specific examples of the solvent used in the synthetic reaction for obtaining the polyesteramic acid (A) (hereinafter referred to as "reaction solvent") are diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol Diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl -2-pyrrolidone, and N, N-dimethylacetamide. Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ethyl ether are preferable.

1-1-8. Synthesis method of polyesteramic acid (A)

The polyesteramic acid (A) used in the present invention is synthesized by reacting X mole of tetracarboxylic dianhydride, Y mole of diamine, and Z mole of polyhydric hydroxy compound in the above solvent, wherein X, Y and Z are It is preferable to set it as the ratio which the relationship of following formula (1) and formula (2) holds between them. If it is within this range, the solubility of the polyesteramic acid (A) as a solvent is high, and thus the coating property of the composition is improved, and as a result, a cured film excellent in flatness can be obtained.

0.2≤Z / Y≤8.0 (One)

0.2≤ (Y + Z) /X≤5.0 (2)

In formula (1), it is preferably 0.7≤Z / Y≤7.0, and more preferably 1.0≤Z / Y≤5.0. Moreover, in Formula (2), it is preferably 0.5≤ (Y + Z) /X≤4.0, and more preferably 0.6≤ (Y + Z) /X≤2.0.

The polyesteramic acid (A) used in the present invention has an acid anhydride group (-CO-O-CO-) at the terminal under conditions in which X is excessively used for (Y + Z) in the above reaction conditions. It is thought that the molecule is produced more in excess than the molecule having an amino group or a hydroxyl group at the terminal. When reacting with the structure of such a monomer, the monohydroxy compound described above can be added, if necessary, in order to esterify the terminal by reacting with an acid anhydride group at the molecular terminal. The polyesteramic acid (A) obtained by reacting by adding a monohydroxy compound improves the compatibility with the epoxy compound and the epoxy curing agent, and improves the coating properties of the thermosetting composition of the present invention containing them.

The reaction solvent is preferably used when 100 parts by weight or more based on 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine and polyhydric hydroxy compound, so that the reaction proceeds smoothly. The reaction is preferably performed at 40 ° C to 200 ° C for 0.2 to 20 hours.

The order of addition of the reaction raw materials to the reaction system is not particularly limited. That is, a method of simultaneously adding a tetracarboxylic dianhydride, a diamine and a polyhydric hydroxy compound to a reaction solvent, a method of adding a diamine and a polyhydric hydroxy compound in a reaction solvent, and then adding a tetracarboxylic dianhydride, a tetracarboxylic dianhydride After reacting water and a polyhydric hydroxy compound in advance, any method such as a method of adding diamine to the product or a method of adding a polyhydric hydroxy compound to the product after reacting tetracarboxylic dianhydride and diamine in advance Can be used.

When the aminosilane compound having one amino group is reacted, after the reaction of the tetracarboxylic dianhydride and the diamine and the polyhydric hydroxy compound is finished, the solution after the reaction is cooled to 40 ° C. or less, and then the amino group 1 It is good to add the aminosilane compound which has dog, and to react at 10-40 degreeC for 0.1-6 hours. Moreover, you may add a monohydroxy compound at any time of reaction.

The polyesteramic acid (A) synthesized in this way contains the structural unit represented by formula (3) and the structural unit represented by formula (4), the terminal of which is tetracarboxylic dianhydride, diamine or polyvalent raw material. It is an acid anhydride group, an amino group or a hydroxy group derived from a hydroxy compound, or an additive other than these compounds constitutes the terminal. Curing property becomes favorable by including such a structure.

It is preferable that the weight average molecular weight of the obtained polyesteramic acid (A) is 1,000-200,000, and 2,000-50,000 are more preferable. When it is in these ranges, flatness and heat resistance will become favorable.

The weight average molecular weight of the said polyesteramic acid (A) is the value in polystyrene conversion calculated | required by GPC method (column temperature: 35 degreeC, flow rate: 1 ml / min). Polystyrene having a weight average molecular weight of 645, 2590, 10290, 37600, and 124500 of the polystyrene calibration kit PL2010-0102 of Agilent Technology Co., Ltd. was used as the standard polystyrene. As a column, PLgel MIXED-D (Agilent Technology Co., Ltd.) was used, and THF was used as a mobile phase. In addition, the weight average molecular weight of the commercially available polymer described in this specification is a catalog publication value.

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. One epoxy compound (B) may be used, or two or more may be used.

Examples of the epoxy compound (B) include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, biphenyl type epoxy compounds, and phenol novolak type epoxy compounds, It is a cresol novolak-type epoxy compound, a bisphenol A novolak-type epoxy compound, an aliphatic polyglycidyl ether compound, a cyclic aliphatic epoxy compound, a copolymer of a monomer having an epoxy group and other monomers, and an epoxy compound having a siloxane bonding site.

Specific examples of commercial products of the bisphenol A-type epoxy compound are jER 828, 1004, and 1009 (all trade names; Mitsubishi Chemical Co., Ltd.); specific examples of commercial products of the bisphenol F-type epoxy compound are jER 806, 4005P (all trade names; Mitsubishi Chemical) Ltd.); specific examples of commercial products of glycidyl ether-type epoxy compounds are Techmore VG3101L (trade name; Printec), EHPE3150 (trade name; Daicel Co., Ltd.), EPPN-501H, 502H (all trade names; Nippon Chemical Co., Ltd.) , And jER 1032H60 (trade name; Mitsubishi Chemical Co., Ltd.); specific examples of commercial products of glycidyl ester-type epoxy compounds include Denacol EX-721 (trade name; Nagase Chemtex Co., Ltd.), and 1,2-cyclohexanedicarbon Sandiglycidyl (trade name; manufactured by Tokyo Chemical Industry Co., Ltd.); specific examples of commercial products of biphenyl-type epoxy compounds include jER YX4000, YX4000H, and YL6121H (all trade names; Mitsubishi Chemical Corporation), and NC-3000, NC-30 00-L, NC-3000-H, NC-3100 (all are trade names; Nippon Chemical Co., Ltd.); specific examples of commercial products of phenol novolac-type epoxy compounds are EPPN-201 (brand name; Nippon Chemical Co., Ltd.), and jER 152 , 154 (all trade names; Mitsubishi Chemical Corporation), etc .; specific examples of commercial products of cresol novolac-type epoxy compounds are EOCN-102S, 103S, 104S, 1020 (all trade names; Nippon Chemical Co., Ltd.), and the like; bisphenol A novolac type Specific examples of commercial products of the epoxy compound are jER 157S65, 157S70 (all trade names; Mitsubishi Chemical Co., Ltd.); specific examples of commercial products of the cyclic aliphatic epoxy compound are Celloxide 2021P, 3000 (all trade names; Daicel Corporation); Specific examples of commercial products of epoxy compounds having a siloxane-bonding site include 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane (trade name: Jerest Inc.), TSL9906 ( Brand name: Momentive Performance Materials Materials Fan joint company), COATOSIL MP200 (brand name; Momentive Performance Materials Japan joint company), Composeran SQ506 (brand name; Arakawa Chemical Co., Ltd.), ES-1023 (brand name; Shin-Etsu Chemical Co., Ltd.).

In addition, Techmore VG3101L (trade name; Printec Co., Ltd.) is 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypro) Foxy) phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2, 3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol; EHPE3150 (trade name; Daicel Co., Ltd.) is 2,2-bis (hydroxymethyl) -1 -1,2-epoxy-4- (2-oxyranyl) cyclohexane adduct of butanol; Celloxide 2021P (trade name; Daicel Co., Ltd.) is 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxy Cyclohexanecarboxylate; Celloxide 3000 (trade name; Daicel Co., Ltd.) is 1-methyl-4- (2-methyloxyranyl) -7-oxabicyclo [4.1.0] heptan; COATOSIL MP200 (trade name; Momentive Performance Materials Japan Joint Venture) is a polymer of 3-glycidoxy propyltrimethoxysilane.

The epoxy compound (B) may be used alone or in combination of two or more.

The ratio of the total amount of the epoxy compound (B) to 100 parts by weight of the polyesteramic acid (A) in the thermosetting composition of the present invention is 20 to 400 parts by weight. When the ratio of the total amount of the epoxy compound (B) is within this range, the balance between flatness, heat resistance, chemical resistance, and adhesion is good. It is preferable that the total amount of the epoxy compound (B) is in the range of 50 to 300 parts by weight.

1-3. Polyfunctional acrylamide compound (C)

The polyfunctional acrylamide compound (C) used in the present invention is particularly limited as long as it has three or more (meth) acrylamide groups (CH ₂ = CR-CO-NH-; R is hydrogen or methyl) per molecule. It is not.

Specific examples of the polyfunctional acrylamide compound (C) include N, N ', N' '-triacryloyldiethylenetriamine, N, N'-{[(2-acrylamide-2-[(3-acrylic Amidepropoxy) methyl] propane-1,3-diyl) bis (oxy)] bis (propane-1,3-diyl)} diacrylamide, N, N ', N' ', N' ''-tetraacrylic Loyltriethylenetetramine, 1,3,5-triacryloylhexahydro-1,3,5-triazine.

Moreover, the compound of the following structural formula is also mentioned as a specific example of a polyfunctional acrylamide compound (C).

As a polyfunctional acrylamide compound (C), the following commercial items can be used. Specific examples of N, N ', N' '-triacryloyldiethylenetriamine are FAM-301 (trade name; Fujifilm Co., Ltd.) or FFM-2 (trade name; Wako Junyaku Co., Ltd.), and N, N'-{[ The specific example of (2-acrylamide-2-[(3-acrylamide propoxy) methyl] propane-1,3-diyl) bis (oxy)] bis (propane-1,3-diyl)} diacrylamide FAM-401 (trade name; Fujifilm Co., Ltd.), and a specific example of N, N ', N' ', N' ''-tetraacryloyltriethylenetetramine is FAM-402 (trade name; Fujifilm Co., Ltd.).

The polyfunctional acrylamide compound (C) may be used alone or in combination of two or more.

The ratio of the total amount of the polyfunctional acrylamide compound (C) to 100 parts by weight of the polyesteramic acid (A) in the thermosetting composition of the present invention is preferably 1 to 100 parts by weight. When the ratio of the total amount of the polyfunctional acrylamide compound (C) is within this range, the balance between flatness, heat resistance, and scratch resistance is good.

1-4. Other ingredients

Various additives can be added to the thermosetting composition of the present invention in order to improve application uniformity and adhesion. Additives include adhesives such as curing agents, solvents, anionic, cationic, nonionic, fluorine or silicone leveling agents, surfactants, silane coupling agents, hindered phenolic, hindered amine, phosphorus, and sulfur compounds And antioxidants such as (meth) acrylate compounds.

1-4-1. Hardener

In order to further improve heat resistance and chemical resistance, a curing agent may be used in the thermosetting composition of the present invention. Examples of the curing agent include acid anhydride-based curing agents, amine-based curing agents, phenol-based curing agents, imidazole-based curing agents, pyrazole-based curing agents, triazole-based curing agents, catalytic curing agents, and sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts. There are thermosensitive acid generators and the like, and from the viewpoints of avoiding coloring of the cured film and heat resistance of the cured film, an acid anhydride-based curing agent or an imidazole-based curing agent and a pyrazole-based curing agent are preferable.

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

As specific examples of the carboxylic acid-containing polymer, ARUFON UC-3000, ARUFON UC-3090, ARUFON UC-3900 (all are trade names; Toa Synthetic Corporation), MARPROOF MA-0215Z, MARPROOF MA-0217Z, and MARPROOF MA-0221Z (all of them) Trade name; Nichiyu Co., Ltd.). Among these, ARUFON UC-3900, which has good heat resistance, solubility in a solvent, and good flatness, is preferable.

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

Specific examples of the pyrazole-based curing agent are pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, and 3-methyl-5-pyrazolone. 3,5-dimethylpyrazole, which has a good balance of curability and solubility in a solvent, is preferred.

Specific examples of the triazole-based curing agent are 4-amino-1,2,4-triazole, 1,2,4-triazole, 1,2,3-triazole, 1-hydroxybenzotriazole, 3-mercapto -1,2,4-triazole. 1-hydroxybenzotriazole with a good balance of curability and solubility in a solvent is preferred.

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

When using a hardening agent, it is preferable that it is 0.1 weight part or more and 60 weight part or less with respect to 100 weight part of epoxy compounds (B).

1-4-2. solvent

You may use a solvent in the thermosetting composition of this invention. The solvent optionally added to the thermosetting composition of the present invention is preferably a solvent capable of dissolving the polyesteramic acid (A), the epoxy compound (B), and the polyfunctional acrylamide compound (C). 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, and acetic acid Propyl, butyl propionate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid butyl, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3- Methyl oxypropionate, 3-hydroxypropionate ethyl, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, 2-hydroxypropionate methyl, 2-hydroxy Propyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2-meth Methyl propionate, 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 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, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tri Propylene glycol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclopentanone , Diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol 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, It is 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, or polypropylene glycol having a weight average molecular weight of 1,000 or less. One of these solvents may be used, or a mixture of two or more of these may be used.

It is preferable that content of a solvent is 65-95 weight% with respect to the thermosetting composition whole quantity. More preferably, it is 70 to 90% by weight.

1-4-3. Surfactants

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.75, polyflow No.90, and polyflow No.95 (all are trade names; Kyoeisha Chemical Co., Ltd.), Disperbyk-161, and Disperbake- 162, DisperBake-163, DisperBake-164, DisperBake-166, DisperBake-170, DisperBake-180, DisperBake-181, DisperBake-182, BYK-300, BYK- 306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (all brand names; BIC Chem Japan Co., Ltd.), KP-341, KP -368, KF-96-50CS, KF-50-100CS (all are trade names; Shin-Etsu Chemical Co., Ltd.), Surflon S611 (trade name; AGC Semi-Chemical Co., Ltd.), Gift 222F, Gift 208G, Print GENT 251, PENTENT 710FL, PENTENT 710FM, PENTENT 710FS, PENTENT 601AD, PENTENT 602A, PENTENT 650A, FTX-218 (above, all trade names; Neos Inc.), Megapack F-410, Megapack F- 430, Megapack F-444, Mega Pack F-472SF, Megapack F-475, Megapack F-477, Megapack F-552, Megapack F-553, Megapack F-554, Megapack F-555, Megapack F-556, Megapack F -558, Megapack F-559, Megapack R-94, Megapack RS-75, Megapack RS-72-K, Megapack RS-76-NS, Megapack DS-21 (above, all trade names; DIC Corporation ), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (above, all trade names; Evonik Japan Co., Ltd.), fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate , Fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylsulfonic acid salt, diglycerintetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoro To alkylamino sulfonate, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl Ter, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene Laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan Stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these.

Among these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-368, Sufflon S611, Pleasant 710FL, Pleasant 710FM, Pleasant 710FS, Pleasant 650A, Megapack F-477 , Megapack F-556, Megapack RS-72-K, Megapack DS-21, TEGO Twin 4000, fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkyl If it is at least one selected from sulfonate salts, fluoroalkyl trimethylammonium salts, and fluoroalkyl amino sulfonate salts, it is preferable because the uniformity of application of the thermosetting composition is high.

It is preferable that content of surfactant in the thermosetting composition of this invention is 0.01-10 weight% with respect to the whole thermosetting composition.

1-4-4. Adhesion improver

The thermosetting composition of the present invention may further contain an adhesion improving agent from the viewpoint of further improving the adhesion between the cured film to be formed and the substrate. Examples of the adhesion improving agent include a silane-based, aluminum-based or titanate-based coupling agent. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, Cyraiace S510; ; JNC Corporation), 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane (e.g., Cyrace S530; trade name; JNC Corporation), 3-mercaptopropyl trimethoxysilane (e.g. , Cyraiace S810; trade name; JNC Corporation), a copolymer of 3-glycidyloxypropyl trimethoxysilane (e.g., trade name: COATOSIL MP200, Momentive Performance Materials, Japan Joint Venture), etc. Silane-based coupling agents, aluminum-based coupling agents such as acetoalkoxy aluminum diisopropylate, and titanate-based coupling agents such as tetraisopropylbis (dioctylphosphite) titanate.

Among these, 3-glycidyloxypropyl trimethoxysilane is preferable because the effect of improving adhesion is large.

It is preferable that content of an adhesive improver is 0.01 weight% or more and 10 weight% or less with respect to the thermosetting composition whole quantity.

1-4-5. 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 high temperatures.

An antioxidant such as hindered phenol, hindered amine, phosphorus, and sulfur compounds may be added to the thermosetting composition of the present invention. Among these, the hindered phenol system is preferred from the viewpoint of light resistance. Specific examples include Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425WL, Irganox1520L, Irganox245, Irganox, Irganox AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, and ADK STAB AO-80 (all are trade names; ADEKA Corporation). Among these, Irganox1010 and ADK STAB AO-60 are more preferable.

The antioxidant is used in an amount of 0.1 to 5 parts by weight based on the total amount of the thermosetting composition.

1-4-6. Molecular weight modifier

The thermosetting composition of the present invention may further contain a molecular weight modifier in order to suppress an increase in molecular weight by polymerization and to express excellent storage stability. As a molecular weight modifier, mercaptans, xanthogens, quinones, hydroquinones, 2,4-diphenyl-4-methyl-1-pentene, etc. are mentioned.

As specific examples of the molecular weight modifier, 1,4-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, methyl-p-benzoquinone, anthraquinone, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 1,4-dihydroxynaphthalene, 3,6-dihydroxybenzonorbornane, 4-methoxyphenol, 2 , 2 ', 6,6'-tetra-t-butyl-4,4'-dihydroxybiphenyl, 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl, 2 , 2'-methylenebis (6-t-butyl-4-ethylphenol), 2,4,6-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) methylene, pentaerythrate Litoltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4-t-butylpyrocatechol, n-hexylmercaptan, n-octylmercaptan, n -Dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, dimethyl xanthogen sulfide, diisopropyl xanthogen disulfide, 2,6-di-t-butyl-p-cresol, 4,4 ' -Butylidenebis (6-t-butyl-m-x Sol), 4,4'-thiobis (6-t-butyl-m-cresol), 2,4-diphenyl-4-methyl-1-pentene, phenothiazine, 2-hydroxy-1,4- And naphthoquinone.

The molecular weight modifier may be used alone or in combination of two or more. Among the molecular weight modifiers, a naphthoquinone-based molecular weight modifier is preferable in that it exhibits excellent storage stability.

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

1-4-7. UV absorber

The thermosetting composition of the present invention may contain an ultraviolet absorber from the viewpoint of further improving the deterioration preventing ability of the formed transparent film.

Specific examples of the ultraviolet absorber are TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571, and TINUVIN 765 (all trade names; BASF Japan Corporation).

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

1-4-8. Anticoagulant

The thermosetting composition of the present invention may contain an anti-aggregation agent from the viewpoint of preventing the aggregation by fusing polyesteramic acid (A) or an epoxy compound (B) with a solvent.

Specific examples of the anti-agglomeration agent are Disperbyk-145, Disperbake-161, Disperbake-162, Disperbake-163, Disperbake-164, Disperbake-182, Disperbake- 184, Disper Bake-185, Disper Bake-2163, Disper Bake-2164, BYK-220S, Disper Bake-191, Disper Bake-199, Disper Bake-2015 (all are trade names; BIC Chemie Japan Co., Ltd.) ), FTX-218, Prentent 710FM, Prentent 710FS (all brand names; Neos Co., Ltd.), Plenren G-600, and Plenren G-700 (all brand names; Kyoeisha Chemical Co., Ltd.).

The aggregation inhibitor is used in an amount of 0.01 to 10 parts by weight based on the total amount of the thermosetting composition.

1-4-9. Thermocrosslinking

The thermosetting composition of the present invention may contain a heat crosslinking agent from the viewpoint of further improving heat resistance, chemical resistance, uniformity in film surface, flexibility, flexibility, and elasticity.

Specific examples of the thermal crosslinking agent, Nikarac MW-30HM, Nikarac MW-100LM, Nikarac MX-270, Nikarac MX-280, Nikarac MX-290, Nikarac MW-390, Nikarac MW-750LM (all Trade name; Sanwa Chemical Co., Ltd.).

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

1-4-10. (Meth) acrylate compound

The (meth) acrylate compound may be used for the thermosetting composition of the present invention. The (meth) acrylate compound used in the present invention is not particularly limited as long as it has two or more (meth) acryloyl groups per molecule.

Among the (meth) acrylate compounds, specific examples of the compound having two (meth) acryloyl groups per molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di. (Meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate, epichlorohydrin modified diethylene glycol di (meth) ) Acrylate, epichlorohydrin-modified triethylene glycol di (meth) acrylate, epichlorohydrin-modified tetraethylene glycol di (meth) acrylate, epichlorohydrin-modified polyethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapro Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified propylene glycol di (meth) acrylate, epichlorohydrin modified dipropylene glycol di (meth) acrylate, epichloro Hydrin modified tripropylene glycol di (meth) acrylate, epichlorohydrin modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin modified polypropylene glycol di (meth) acrylate, glycerol acrylate methacrylate, Glycerol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin modified 1,6-hexanedioldi (meth) acrylate, methoxylated cyclohexyldi (meth) acrylate, Neopentyl glycol di (meth) acrylate, hydroxypivalic acid Neopentyl glycol di (meth) acrylate, caprolactone modified hydroxypivalic acid Offentyl glycol di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, allylated cyclohexyldi (meth) acrylate, bis [(meth) acryloxyneopentyl glycol] adipate, bisphenol A Di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate , Ethylene oxide modified bisphenol S di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, dicyclopentanyl diacrylate, ethylene oxide Modified diphosphate (meth) acrylate, caprolactone ethylene oxide modified diphosphate (meth) acrylate, epichlorohydrin modified phthalate di (meth) acrylate, tetrabromobisphenol Adi (meth) arc Rate, and triglycerol di (meth) acrylate, neopentyl glycol-modified trimethylolpropane di (meth) acrylate, and isocyanuric acid ethylene oxide modified diacrylate.

Among the (meth) acrylate compounds, specific examples of the compound having three or more (meth) acryloyl groups per molecule include trimethylolpropane tri (meth) acrylate and ethylene oxide-modified trimethylolpropane tri (meth) acrylic. Rate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylic Rate, pentaerythritol tri (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, ethylene oxide modified phosphate tri (meth) acrylate, caprolactone ethylene oxide modified phosphate tri (meth) acrylic Rate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, ditrimethylolpropanetetra (meth) acrylate , Diglycerintetra (meth) acrylate, pentaerythritoltetra (meth) acrylate, alkyl modified dipentaerythritoltetra (meth) acrylate, dipentaerythritolpenta (meth) acrylate, alkyl modified dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and carboxyl group-containing polyfunctional (meth) acrylate.

The (meth) acrylate compound may be used alone or in combination of two or more.

It is preferable from the viewpoint of scratch resistance to include at least 50% by weight of a compound having at least three (meth) acryloyl groups per molecule in 100% by weight of the (meth) acrylate compound.

Among the (meth) acrylate compounds, ethylene oxide-modified isocyanurate diacrylate, ethylene oxide-modified isocyanurate triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetra It is preferable from the viewpoint of flatness and scratch resistance to use acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and carboxyl group-containing polyfunctional (meth) acrylate.

The (meth) acrylate compound can use the following commercial items. Specific examples of the ethylene oxide-modified isocyanurate are Aronix M-215 (trade name: Toa Synthetic Co., Ltd.); ethylene oxide-modified isocyanurate diacrylate and ethylene oxide-modified isocyanurate. Specific examples of the mixture of triacrylates are Aronix M-313 (30-40% by weight) and M-315 (3-13% by weight, hereinafter simply referred to as "M-315") (all brand names; Toa Synthesis Co., Ltd., the content rate in parentheses is a catalog published value of the content rate of isocyanurate ethylene oxide-modified diacrylate in the mixture; a specific example of trimethylolpropane triacrylate is Aaronix M-309 (trade name; Toa Synthesis Co., Ltd.); specific examples of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate include: Aaronix M-306 (65-70 wt%), M-305 (55-63 wt%), M- 303 (30-60% by weight), M-452 (25-40% by weight), and M-450 (10 weights) (% By weight) (all brand names; Toa Synthetic Co., Ltd., the content in parentheses is the catalog value of the content of pentaerythritol triacrylate in the mixture); a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate Specific examples of Aronix M-403 (50-60% by weight), M-400 (40-50% by weight), M-402 (30-40% by weight, hereinafter simply referred to as "M-402") , M-404 (30-40% by weight), M-406 (25-35% by weight), and M-405 (10-20% by weight) (all trade names; Toa Synthetic Co., Ltd., content in parentheses is dipenta in the mixture) The erythritol pentaacrylate content is listed in the catalog); specific examples of the carboxyl group-containing polyfunctional (meth) acrylate are Aaronix M-510 and M-520 (hereinafter simply referred to as "M-520") ( All are trade names; Toa Synthetic Co., Ltd.).

The ratio of the total amount of the (meth) acrylate compound to 100 parts by weight of the polyesteramic acid (A) in the thermosetting composition of the present invention is 0 to 400 parts by weight. When the ratio of the total amount of the (meth) acrylate compound is within this range, the balance between flatness, heat resistance, and scratch resistance is good. It is preferable that the total amount of the (meth) acrylate compound is in the range of 0 to 100 parts by weight.

1-4-11. Other additives

As another component, a styrene-maleic anhydride copolymer may be added.

1-5. Preservation of thermosetting composition

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

2. Cured film obtained from thermosetting composition

The thermosetting composition of the present invention is a mixture of polyester amide acid (A), epoxy compound (B) and polyfunctional acrylamide compound (C), and depending on the desired properties, it is also an epoxy curing agent, solvent, surfactant, Adhesion improvers, antioxidants, (meth) acrylate compounds and other additives are selected and added as necessary, and can be obtained by uniformly mixing and dissolving them.

The coating film can be formed by applying the thermosetting composition prepared in the above manner (after dissolving in a solvent in a solid state without a solvent) to the surface of the base and removing the solvent by heating or the like. Application of the thermosetting composition to the substrate surface can form a coating film by a conventionally known method such as spin coating, roll coating, dipping, and slit coating. Then, this coating film is plasticized with a hot plate or an oven. The plasticity conditions vary depending on the type and blending ratio of each component, but usually at 70 to 150 ° C., for 5 to 15 minutes in an oven, and for 1 to 5 minutes in a hot plate. Subsequently, it is fired in order to cure the coating film. The firing conditions differ depending on the type and blending ratio of each component, but are usually 180 to 250 ° C, preferably 200 to 250 ° C, for 30 to 90 minutes in an oven and 5 to 30 minutes in a hot plate, and heat treatment By doing so, a cured film can be obtained.

In the cured film thus obtained, upon heating, 1) the polyamic acid portion of the polyesteramic acid dehydrates to form an imide bond, 2) the carboxylic acid of the polyesteramic acid reacts with the epoxy compound, and Molecular weight, and, 3) Since the epoxy compound is cured and has a high molecular weight, it is very strong and excellent in transparency, heat resistance, chemical resistance, flatness and adhesion. Moreover, regarding light resistance, sputter resistance, scratch resistance, and coatability, the same thing is expected to be excellent. Therefore, the cured film of this invention is effective when used as a protective film for color filters, and a liquid crystal display element or a solid-state imaging element can be manufactured using this color filter. In addition, the cured film of the present invention is effective when used as a transparent insulating film formed between a TFT and a transparent electrode or a transparent insulating film formed between a transparent electrode and an alignment film, in addition to the protective film for a color filter. Further, the cured film of the present invention is effective even when used as a protective film for an LED light emitter.

[Example]

Next, the present invention will be specifically described by Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by these Examples at all.

The following abbreviations respectively denote the following monomers, polymerization initiators, chain transfer agents, solvents, and the like.

ODPA: 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride

BT-100: 1,2,3,4-butanetetracarboxylic dianhydride, carboxylic acid BT-100 (brand name; Shin Nippon Ewha Corporation)

DDS: 3,3'-diaminodiphenylsulfone

Bis-A-2EOH: 4,4'-isopropylidenebis (2-phenoxyethanol)

70PA: Epoxy ester 70PA (brand name: Kyoeisha Chemical Co., Ltd.)

SMA1000P: Styrene-maleic anhydride copolymer SMA1000P (trade name; Kawahara Petrochemical Co., Ltd.)

PGMEA: Solvent propylene glycol monomethyl ether acetate

PGME: Solvent propylene glycol monomethyl ether

MMP: solvent 3-methoxypropionate methyl

VG3101L: Epoxy compound Techmore VG3101L (brand name; printec)

FAM-402: a polyfunctional acrylamide compound FAM-402 (trade name; Fujifilm Co., Ltd.)

FAM-301: East FAM-301 (trade name; Fujifilm Co., Ltd.)

FAM-201: bifunctional acrylamide compound N, N'-diacryloyl-4,7,10-trioxa-1,13-tridecanediamine, FAM-201 (trade name; Fujifilm Corporation)

DEAA: 1 functional acrylamide compound diethyl acrylamide

TMA: Curing agent trimellitic anhydride

C11Z: Curing agent Curesol C11Z (brand name: Shikoku Chemical Co., Ltd.)

MP200: Cohesiveness enhancer COATOSIL MP200 (brand name; Momentive, Performance, Materials, Japan joint company)

AO-60: Antioxidant ADK STAB AO-60 (brand name; ADEKA Co., Ltd.)

DS-21: Surfactant Mega Pack DS-21 (brand name; DIC Corporation)

M-402: (meth) acrylate compound Aronics M-402 (trade name; Toa Synthetic Co., Ltd.)

First, polyesteramic acid solutions, which are reaction products such as tetracarboxylic dianhydride, diamine, monohydroxy compound, and polyhydric hydroxy compound, were synthesized as shown below (Synthesis Examples 1 to 7).

[Synthesis Example 1] Synthesis of polyester amide acid (A1)

To a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, 1,4-butanediol and benzyl alcohol were added under the following weight, and stirred at 125 ° C for 2 hours under a stream of dry nitrogen (synthesis step 1).

MMP 49.00 g

ODPA 20.36 g

1,4-butanediol 3.55 g

Benzyl alcohol 2.84 g

Thereafter, the solution after the reaction was cooled to room temperature, DDS and MMP were added to the following weight, stirred at 20 to 30 ° C for 2 hours, and then stirred at 125 ° C for 1 hour (synthesis step 2).

DDS 3.26 g

MMP 21.00 g

(Z / Y = 3.0, (Y + Z) /X=0.8)

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

[Synthesis Example 2] Synthesis of polyester amide acid (A2)

In a four-necked flask equipped with a stirrer, dehydrated PGMEA, BT-100, SMA1000P, 1,4-butanediol, and benzyl alcohol were added in the following weight, followed by stirring at 125 ° C for 2 hours under a stream of dry nitrogen (Synthesis 1). Step).

PGMEA 53.49 g

BT-100 3.83 g

SMA1000P 18.23 g

1,4-butanediol 1.16 g

Benzyl alcohol 5.57 g

Thereafter, the solution after the reaction was cooled to room temperature, DDS and PGMEA were added to the following weight, stirred at 20 to 30 ° C for 2 hours, and then stirred at 125 ° C for 1 hour (synthesis step 2).

DDS 1.20 g

PGMEA 16.51 g

(Z / Y = 2.7, (Y + Z) /X=0.9)

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

[Synthesis Examples 3 to 7] Synthesis of polyester amide acids (A3) to (A7)

According to the method of Synthesis Examples 1 and 2, each component was reacted at the temperature, time, and ratio (unit: g) described in Table 1 to obtain polyesteramic acid (A3) to (A7) solutions.

[Table 1]

Next, a thermosetting composition was prepared as shown below using a 30% by weight solution of the polyesteramic acids (A1) to (A7) obtained in Synthesis Examples 1 to 7, and a cured film was obtained from the thermosetting composition to obtain this curing. The membrane was evaluated.

[Example 1]

30% by weight solution of the polyesteramic acid (A1) obtained in Synthesis Example 1, VG3101L, FAM-402, TMA, MP200, AO-60, DS-21, MMP, and PGMEA, PGME are listed in Table 2-1 (Unit: g) was mixed and dissolved, and filtered through a membrane filter (0.2 μm) to obtain a thermosetting composition.

[Examples 2 to 14 and Comparative Examples 1 to 4]

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

In addition, the total amount of the solvent contained in this thermosetting composition is the total amount of MMP or PGMEA and MMP, PGMEA and PGME contained in the polyesteramic acid (A) solution, and the solid content concentration in this process is approximately 17% by weight. Was adjusted to be.

[Evaluation method of flatness]

A thermosetting composition on a color filter substrate without a cured film having pixels containing R, G, and B, whose surface level difference was measured using a step, surface roughness, and fine shape measuring device (trade name; P-17, KLA TENCOR Co., Ltd.) in advance. Was spin-coated at 300 rpm for 10 seconds, and prebaked on a hot plate at 90 ° C for 2 minutes. Subsequently, it was post-baked at 230 ° C for 30 minutes in an oven to obtain a color filter substrate having a cured film having an average film thickness of 1.5 µm. Then, the surface level difference was measured about the color filter substrate which has the obtained cured film. From the maximum value of the surface step difference of the color filter substrate without the cured film and the color filter substrate having the cured film (hereinafter simply referred to as "maximum step"), the following formula is used to calculate the flattening rate (DOP (%)), and the result Table 1 shows. When the flattening rate was 85.0% or more, the flatness (circle) and the case where it was less than 85.0% were evaluated as flatness ×. In addition, as for the color filter substrate without a cured film, a maximum step difference of 1.0 μm was used.

Planarization rate (DOP (%)) = (Maximum step difference of color filter substrate without cured film-maximum step of color filter substrate without cured film) / (Maximum step difference of color filter substrate without cured film) × 100%

[Evaluation method of scratch resistance]

The thermosetting composition was spin coated on a glass substrate at 300 rpm for 10 seconds, and prebaked on a hot plate at 90 ° C for 2 minutes. It was post-baked at 230 ° C for 30 minutes in an oven to obtain a glass substrate having a cured film having a film thickness of 1.5 µm. The pencil hardness of the cured film was measured by performing the 8.4.1 pencil scratch test of JIS K-5400-1990 on the obtained glass substrate having the cured film, and the results are shown in Table 1. When the pencil hardness was 3H or more, the scratch resistance was evaluated as ○, and when 2H or less, the scratch resistance was evaluated.

[How to evaluate transparency]

The thermosetting composition was spin coated on a glass substrate at 300 rpm for 10 seconds, and prebaked on a hot plate at 90 ° C for 2 minutes. It was post-baked at 230 ° C for 30 minutes in an oven to obtain a glass substrate having a cured film having a film thickness of 1.5 µm. The transmittance of the cured film was measured with an ultraviolet visible spectrophotometer for the obtained glass substrate having a cured film, and the results are shown in Table 1. Transparency when the transmittance at a wavelength of 400 nm was 95.0% or more was evaluated as transparency (circle) and when it was less than 95.0% as transparency x.

[Evaluation method of adhesion]

The thermosetting composition was spin coated on a glass substrate at 300 rpm for 10 seconds, and prebaked on a hot plate at 90 ° C for 2 minutes. It was post-baked at 230 ° C for 30 minutes in an oven to obtain a glass substrate having a cured film having a film thickness of 1.5 µm. The glass substrate with the obtained cured film was tested according to ISO2409. The case where the test result showed the adhesion of classification 0-classification 1 was made into (circle), and the case where the adhesion of classification 2-classification 5 was shown was made into x.

[Method for evaluating hygroscopicity]

The thermosetting composition was spin coated on a glass substrate at 300 rpm for 10 seconds, and prebaked on a hot plate at 90 ° C for 2 minutes. It was post-baked at 230 ° C for 30 minutes in an oven to obtain a glass substrate having a cured film having a film thickness of 1.5 µm. The obtained cured film was cut into a powder, and the weight reduction amount before and after heating by a thermogravimetric differential thermal analysis device was measured. At this time, in the thermogravimetric differential thermal analysis apparatus 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 amount showed 2.0% or less was designated as ○, and the case where the weight loss amount showed a value exceeding 2.0% was set as ×.

[Evaluation method of heat resistance]

The thermosetting composition was spin coated on a glass substrate at 300 rpm for 10 seconds, and prebaked on a hot plate at 90 ° C for 2 minutes. It was post-baked at 230 ° C for 30 minutes in an oven to obtain a glass substrate having a cured film having a film thickness of 1.5 µm. The obtained cured film was cut into a powder, and the weight reduction amount before and after heating by a thermogravimetric differential thermal analysis device was measured. 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, heated at 150 ° C for 20 minutes, and then heated from 150 ° C to 250 ° C at 10 ° C / min, at 250 ° C Heated for 30 minutes. Here, the difference from the weight after heating at 250 ° C for 30 minutes was taken as the weight reduction amount, based on the weight at the time when the temperature was raised from 150 ° C to 250 ° C. The case where the weight loss amount was 3.0% or less was designated as ○, and the case where the weight loss amount was more than 3.0% was set as ×.

[Table 2-1]

[Table 2-2]

[Table 3]

As can be seen from the results shown in Tables 2-1 to 2-2, it was found that the thermosetting compositions of Examples 1 to 14 were excellent in flatness. On the other hand, it can be seen that Comparative Examples 1 to 4, which are thermosetting compositions not containing the polyfunctional acrylamide compound (C), had poor flatness.

The cured film obtained from the thermosetting composition of the present invention has a high flatness and high scratch resistance, and thus a protective film such as a color filter, an LED light-emitting element and a light-receiving element, and other protective materials such as TFTs, transparent electrodes, and transparent electrodes. It can be used as an insulating film formed between alignment films.

Claims (5)

A thermosetting composition comprising a polyester amide acid (A), an epoxy compound (B) and a polyfunctional acrylamide compound (C),
The polyester amide acid (A) is a ratio in which the relationship between the following formulas (1) and (2) holds the X mole of tetracarboxylic dianhydride, the Y mole of the diamine and the Z mole of the polyhydric hydroxy compound. It is the reaction product of the containing raw material,
A thermosetting composition, wherein the polyfunctional acrylamide compound (C) is a compound having three or more (meth) acrylamide groups per molecule.
0.2≤Z / Y≤8.0 (1)
0.2≤ (Y + Z) /X≤5.0 (2) The method according to claim 1,
The said thermosetting composition which said polyester amide acid (A) contains the structural unit represented by following formula (3) and the structural unit represented by following formula (4).

In formulas (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two -NH ₂ from diamine, R ³ is a residue obtained by removing two -OH from a polyvalent hydroxy compound. The method according to claim 1 or claim 2,
The content of the epoxy compound (B) is 20 to 400 parts by weight based on 100 parts by weight of the polyester amide acid (A), and the content of the polyfunctional acrylamide compound (C) is polyester amide acid (A). 1 to 100 parts by weight based on 100 parts by weight, a thermosetting composition. A cured film obtained by curing the thermosetting composition according to claim 1. A color filter having the cured film according to claim 4 as a transparent protective film.