TW202012476A - Thermosetting compositions, cured film, and color filter - Google Patents

Abstract

The present invention relates to a thermosetting composition, a cured film and a color filter. The thermosetting composition comprises a polyester amic acid (A), an epoxy compound (B) and a polyfunctional acrylamide compound (C). The polyester amic acid (A) is a reaction product of a raw material comprising X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyhydric hydroxy compound in a ratio such that the following formulas (1) and (2) are satisfied. The polyfunctional acrylamide compound (C) is a compound having three or more (meth)acrylamide groups (CH2=CR-CO-NH-; R is hydrogen or methyl) per molecule. With the thermosetting composition of the present invention, it is able to form a cured film excellent in flatness that can be used for various electronic components. The formulas (1) and (2) are: 0.2 ≤ Z/Y ≤ 8.0, and 0.2 ≤ (Y+Z)/X ≤ 5.0.

Description

Thermosetting composition, cured film and color filter

The present invention relates to an insulating material that can be used to form an electronic component, a passivation film in a semiconductor device, a buffer coating film, 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 from the thermosetting composition, 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 using an organic solvent or the like, or may be subjected to heat treatment when forming a wiring electrode film by sputtering or the like. Therefore, a surface protection film is sometimes provided for the purpose of preventing surface deterioration, damage, and deterioration of various elements. These protective films are required to withstand the processing in the manufacturing steps 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.

With the improvement of the required characteristics of the reliability required for display elements and the improvement of the heat resistance required for display element members, a thermosetting composition containing polyester amidic acid and epoxy compounds with good heat resistance is advocated Thing (Patent Literature 1). Furthermore, due to the recent enlargement of production lines, 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, and therefore the scratch resistance of the protective film is required to be improved. On the other hand, it is proposed to adjust the molecular weight of the epoxy compound of the invention and further include a thermosetting composition containing an acrylic compound, which has improved heat resistance and improved scratch resistance (Patent Document 2).

With the recent demand for higher definition and thinner thickness in liquid crystal display elements, the protective film is required to have more excellent flatness than before. The flatness means the surface level difference when a film-forming protective film is applied to a color filter including pixels of red (R), green (G), and blue (B) used in a liquid crystal display element, If the surface level difference is large, the display quality is degraded. Compared with thermosetting materials, further improvement in flatness becomes a problem. [Prior Art Literature]

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

[Problems to be solved by the invention] The problem 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 further to provide an electronic component having the cured film.

[Technical Means for Solving the Problem] The inventors of the present invention conducted intensive studies to solve the problems, and found that the object can be achieved by using the following cured film, and the present invention was completed. Polyester amide acid, epoxy compound as a reaction product of tetracarboxylic dianhydride, diamine and polyhydroxy compound, and three or more (meth)acryl amide groups per molecule (CH ₂ =CR -CO-NH-; R is hydrogen or methyl) obtained by hardening the composition of the compound. 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), and the thermosetting composition is characterized by, The polyester amide acid (A) is a multicomponent including X molar tetracarboxylic dianhydride, Y molar diamine, and Z molar in a ratio established by the relationship of the following formula (1) and formula (2) A reaction product of a raw material of a hydroxy compound, the multifunctional acrylamide compound (C) has more than three (meth)acrylamide groups per molecule (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)

式（3）及式（4）中，R¹ 為自四羧酸二酐除去兩個-CO-O-CO-而成的殘基，R² 為自二胺除去兩個-NH₂ 而成的殘基，R³ 為自多元羥基化合物除去兩個-OH而成的殘基。[2] The thermosetting composition according to item [1], wherein the polyester amide acid (A) includes a structural unit represented by the following formula (3) and a formula represented by the following formula (4) Structural units.

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 a diamine R ³ is a residue obtained by removing two -OH groups from a polyhydroxy compound.

[3] The thermosetting composition according to item [1] or [2], wherein the content of the epoxy compound (B) is 100 parts by weight with respect to the polyester amide (A) 20 parts by weight to 400 parts by weight, and the content of the multifunctional acrylamide compound (C) is 1 part by weight to 100 parts by weight with respect to 100 parts by weight of the polyester amide acid (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 [4] as a transparent protective film.

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

In the present specification, the smaller the step difference of the cured film of the present invention, the cured film and the thermosetting composition for forming the cured film show "the more excellent the flatness".

In this specification, in order to show one or both of "acrylate" and "methacrylate", it may be expressed as "(meth)acrylate". Similarly, in order to express either or both of "acryloyloxy" and "methacryloyloxy", it may sometimes be expressed as "(meth)acryloyloxy".

1. The thermosetting composition of the present invention The thermosetting composition of the present invention is a composition containing a polyester amide acid, an epoxy compound, and a polyfunctional acrylamide compound. The polyester amide acid contains a tetracarboxylic dianhydride, a diamine, and a polyhydroxy group The reaction product of the raw material of the compound, and the thermosetting composition is characterized in that the epoxy compound is 20 parts by weight to 400 parts by weight with respect to 100 parts by weight of the polyester amide acid, and the polyfunctional acrylamide compound is 1. Parts by weight to 100 parts by weight.

1-1. Polyester amide acid (A) Polyesteramide acid is a reaction product of raw materials containing tetracarboxylic dianhydride, diamine, and polyhydroxy compound. More specifically, the polyester amide acid is a tetracarboxylic dianhydride containing X moles, a diamine with Y moles, and a Z mole with a ratio established by the relationship of the following formula (1) and formula (2) The reaction product of the raw materials of the polyhydroxy compound. 0.2≦Z/Y≦8.0······(1) 0.2≦（Y+Z）/X≦5.0··（2）

The polyester amide acid (A) preferably has a structural unit represented by the following formula (3) and a structural unit represented by the 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 a diamine, and is preferably an organic group having 2 to 30 carbon atoms. R ³ is a residue obtained by removing two -OH groups from a polyhydroxy compound, and is preferably an organic group having 2 to 20 carbon atoms.

In the synthesis of the polyester amide acid (A), at least a solvent is required, and the solvent can be left directly to form a liquid or gel-like thermosetting composition in consideration of operability and the like. The solvent is removed to produce a solid composition in consideration of transportability and the like. In addition, in the synthesis of polyester amide acid (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, particularly preferably a monohydroxy compound . In addition, in the synthesis of the polyester amide acid (A), other compounds than the above may be included as a raw material as necessary within a range that does not impair the object of the present invention.

1-1-1. Tetracarboxylic dianhydride In the present invention, as a material for obtaining polyester amide acid (A), tetracarboxylic dianhydride is used. Specific examples of preferred 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 ash tetracarboxylic dianhydride, 2,2',3, 3'-diphenyl sulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfide 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-butane tetracarboxylic dianhydride, ethylene glycol bis (dehydrated trimellitate) (trade name; TMEG- 100, New Japan Physical and Chemical Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, ethane Tetracarboxylic dianhydride and butane tetracarboxylic dianhydride. One or more of these tetracarboxylic dianhydrides can be used.

Among these tetracarboxylic dianhydrides, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride and 3,3',4,4'-diphenyl ether which impart good transparency are more preferable. Tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride and ethylene glycol bis( Dehydrated trimellitate), further preferably 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid di Anhydride and 1,2,3,4-butane tetracarboxylic dianhydride.

1-1-2. Diamine In the present invention, as a material for obtaining polyester amide acid (A), diamine is used. Specific examples of preferred diamines are: 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl ash, 3,4'-diaminodiphenyl ash, bis [4-(4-Aminophenoxy)phenyl] phenanthrene, bis[4-(3-aminophenoxy)phenyl] phenanthrene, bis[3-(4-aminophenoxy)phenyl ] 碸, [4-(4-aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl] 碸, [4-(3-aminophenoxy)phenyl] [3-(4-Aminophenoxy)phenyl] benzene and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. One or more of these diamines can be used.

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

1-1-3. Polyhydroxy compounds In the present invention, as a material for obtaining the polyester amide acid (A), a polyhydroxy compound is used.

Specific examples of polyhydroxy compounds 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-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-decane Glycol, 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) ash), bisphenol F (bis( 4-hydroxyphenyl) methane), 4,4'-isopropylidenebis(2-phenoxyethanol), 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxydi 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 Ester, dipentaerythritol tetra(meth)acrylate, sorbitol mono(meth)acrylate, sorbitol di(meth)acrylate, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate Methacrylic acid ester, (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 modified product of glycerol diglycidyl ether, (meth)acrylic acid modified product of bisphenol A diglycidyl ether, (meth)acrylic acid modified of propylene oxide modified bisphenol A diglycidyl ether Substance, (meth)acrylic modified substance of bisphenol S diglycidyl ether, (meth)acrylic modified substance of propylene oxide modified bisphenol S diglycidyl ether, (meth)acrylic acid modified substance of bisphenol F diglycidyl ether ) Modification of acrylic acid and propylene oxide (Meth)acrylic acid modification of bisphenol F diglycidyl ether, (meth)acrylic acid modification of bixylenol diglycidyl ether, (meth)acrylic acid modification of biphenol diglycidyl ether, stilbene (Meth)acrylic acid modified product of phenol diglycidyl ether, (meth)acrylic acid modified product of cyclohexane-1,4-dimethanol diglycidyl ether, (methyl) of hydrogenated bisphenol A diglycidyl ether Modified acrylic acid, modified (meth)acrylic acid of tricyclodecane dimethanol diglycidyl ether, and modified (meth)acrylic acid of other compounds containing two or more epoxy groups per molecule.

Among these polyhydric hydroxy 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'-isopropylidenebis(2-phenoxy (Ethyl alcohol), (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 (Meth)acrylic acid modified product of 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 modified product of 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 Modified (meth)acrylic acid. Furthermore, particularly preferred are diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol (Meth)acrylic acid modified product of alcohol, 4,4'-isopropylidenebis(2-phenoxyethanol), 2-(4-hydroxyphenyl)ethanol, 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 glycerol diglycidyl ether, and bisphenol A diglycidyl ether ( (Meth)acrylic acid modified product and propylene oxide modified bisphenol A diglycidyl ether (meth)acrylic acid modified product.

Modified methacrylic acid as ethylene glycol diglycidyl ether, modified acrylic acid as propylene glycol diglycidyl ether, modified acrylic acid as tripropylene glycol diglycidyl ether, modified acrylic acid as glycerol diglycidyl ether, bisphenol A Modified methacrylic acid of glycidyl ether, modified acrylic acid of bisphenol A diglycidyl ether, modified methacrylic acid of propylene oxide modified bisphenol A diglycidyl ether, and modified bisphenol A dipropylene oxide As the acrylic acid-modified product of glycidyl 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 glycerol 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 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 compound In the present invention, as a material for obtaining the polyester amide acid (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, isopropanol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltol, linalool , Terpineol (terpineol), dimethyl benzyl methanol (dimethyl benzyl carbinol) and 3-ethyl-3-hydroxymethyl oxetane. One or more of these monohydroxy compounds can be used.

Among these monohydroxy compounds, isopropyl alcohol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane are more preferred. Considering the compatibility or thermosetting composition when the polyester amide acid (A) formed using these monohydroxy compounds is mixed with the epoxy compound (B) and the polyfunctional acrylamide compound (C) For the coating property of the object on the color filter, benzyl alcohol is preferably used for the monohydroxy compound.

The reaction is preferably carried out with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine and polyhydroxy compound, preferably containing 0 to 300 parts by weight of monohydroxy compound. More preferably, it is 5 to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer In addition, the polyester amide acid (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 transparency of the polyester amidic acid (A) synthesized by adding a compound having three or more acid anhydride groups is expected to be improved, so it is preferable. 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 mole 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 further preferably 1.

Specific examples of styrene-maleic anhydride copolymers are SMA3000P, SMA2000P, and SMA1000P (all are trade names; Sichuan Crude Oil Chemical Co., Ltd.). Among these styrene-maleic anhydride copolymers, SMA1000P having 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 polyhydroxy compound. More preferably, it is 10 parts by weight to 300 parts by weight.

1-1-6. Aminosilane compounds with one amine group In the synthesis of polyester amide acid (A), other raw materials other than those mentioned above may be included as raw materials as needed within a range that does not impair the object of the present invention. Examples of such other raw materials are having an amine group Of amino silane 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. If the thermosetting composition of the present invention containing polyester amide acid (A) is used, the acid resistance of the obtained cured film can be improved. The polyester amide acid (A) has one amine group by adding Obtained by reacting the aminosilane compound. Furthermore, when the reaction is carried out with the above-mentioned monomer structure, both a monohydroxy compound and an aminosilane compound having one amine group may be added and reacted.

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

Among these compounds, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane with improved acid resistance of the cured film are more preferred. From the viewpoint of acid resistance and compatibility, Furthermore, 3-aminopropyltriethoxysilane is preferable.

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 polyhydroxy compound. More preferably, it is 5 to 200 parts by weight.

1-1-7. Solvent used in the synthesis reaction of polyester amide acid (A) Specific examples of the solvent used in the synthesis reaction to obtain polyester amide acid (A) (hereinafter sometimes referred to as "reaction solvent") 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, methyl 3-methoxypropionate, 3-ethyl Ethyloxypropionate, 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 acid (A) The polyester amide acid (A) used in the present invention is preferably synthesized by reacting tetracarboxylic dianhydride X mole, diamine Y mole and polyhydroxy compound Z mole in the solvent. At the time, X, Y, and Z are determined as the ratios in which the relationship of the following formula (1) and formula (2) is established. Within the above range, the solubility of the polyester amidic acid (A) in the solvent is high, so 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······(1) 0.2≦（Y+Z）/X≦5.0··（2） In formula (1), preferably 0.7≦Z/Y≦7.0, more preferably 1.0≦Z/Y≦5.0. In addition, in formula (2), 0.5≦(Y+Z)/X≦4.0 is preferable, and 0.6≦(Y+Z)/X≦2.0 is more preferable.

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

If 100 parts by weight or more of a reaction solvent is used with respect to a total of 100 parts by weight of tetracarboxylic dianhydride, diamine, and polyhydroxy compound, the reaction proceeds smoothly, which is preferable. The reaction is preferably carried out at 40°C to 200°C for 0.2 hours to 20 hours.

The order of adding the reaction raw materials to the reaction system is not particularly limited. That is, any of the following methods may also be used: a method of adding tetracarboxylic dianhydride, diamine, and polyhydroxy compound to the reaction solvent at the same time; after dissolving the diamine and polyhydroxy compound in the reaction solvent, adding tetracarboxylic acid The method of dianhydride; the method of adding the diamine to the reaction product after reacting the tetracarboxylic dianhydride with the polyhydroxy compound in advance; or the method of adding the diamine to the reaction product after reacting the tetracarboxylic dianhydride and the diamine in advance Methods of polyhydric hydroxy compounds, etc.

In the case of reacting the amine silane compound having one amine group, after the reaction of the tetracarboxylic dianhydride, diamine and polyhydric hydroxy compound is completed, the solution after the reaction is cooled to 40°C or less, 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. In addition, the monohydroxy compound can be added at any point in the reaction.

The polyester amide acid (A) synthesized in the above manner includes the structural unit represented by the formula (3) and the structural unit represented by the formula (4), and its terminal is derived from the tetracarboxylic dianhydride as a raw material, The anhydride group, amine group or hydroxyl group of the diamine or polyhydroxy compound, or additives other than these compounds constitute the terminal. By including such a structure, curability becomes good.

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

The weight average molecular weight of the polyester amide acid (A) is polyphenylene obtained by gel permeation chromatography (Gel Permeation Chromatography, GPC) method (column temperature: 35°C, flow rate: 1 ml/min) Value converted from ethylene. As the standard polystyrene, polystyrene with a weight average molecular weight of 645, 2590, 10290, 37600, and 124500 of Agilent Technologies Co., Ltd. polystyrene calibration kit (PL2010-0102) was used. PL gel mixing (PLgel MIXED)-D (Agilent Technologies Co., Ltd.) was used for the column, and tetrahydrofuran (THF) was used as the mobile phase. In addition, the weight average molecular weight of the polymer of the commercial item 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 epoxy compound (B) may be one kind, or two or more kinds 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 Novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, aliphatic polyglycidyl ether compounds, cyclic aliphatic epoxy compounds, monomers with epoxy groups and Copolymers of other monomers and epoxy compounds with silicone bonding sites.

Specific examples of commercially available products of bisphenol A type epoxy compounds are jER 828, jER 1004, and jER 1009 (all trade names; Mitsubishi Chemical Corporation); specific examples of commercially available products of bisphenol F type epoxy compounds JER 806, jER 4005P (both trade names; Mitsubishi Chemical Co., Ltd.); a specific example of a commercially available product of a glycidyl ether epoxy compound is TECHMORE VG3101L (trade name; Plintech ( Printec) Co., Ltd.), EHPE3150 (trade name; Daicel) Co., Ltd., EPPN-501H, EPPN-502H (both trade names; Nippon Kayaku Co., Ltd.), and jER 1032H60 (trade name; Mitsubishi Chemical Corporation); specific examples of commercially available products of glycidyl ester 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 products of 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 trade names; Nippon Kayaku Co., Ltd.); phenol novolak type ring Specific examples of commercially available products of oxygen compounds are EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), and jER 152, jER 154 (both trade names; Mitsubishi Chemical Co., Ltd.), etc.; cresol novolac type Specific examples of commercially available products of epoxy compounds are EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all are trade names; Nippon Kayaku Co., Ltd.), etc.; bisphenol A novolac epoxy compound Specific examples of commercially available products are jER 157S65, jER 157S70 (both trade names; Mitsubishi Chemical Co., Ltd.); specific examples of commercially available products of cycloaliphatic epoxy compounds are Celloxide 2021P, Celloxide 3000 (both trade names; Daicel) Co., Ltd.; a specific example of a commercial product of an epoxy compound having a siloxane bond site is 1,3-bis[2 -(3,4-epoxycyclohexyl)ethyl]tetramethyldisilaxane (trade name; Gelest Incorporated), TSL9906 (trade name; Momentive, Japan) Performance Materials Japan) Co., Ltd., COATOSIL MP 200 (trade name; Momentive Performance Materials Japan), 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-epoxypropoxy)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] Phenoxy]-2-propanol mixture; EHPE3150 (trade name; Daicel Corporation) is 1,2-epoxy of 2,2-bis(hydroxymethyl)-1-butanol -4-(2-oxiranyl) cyclohexane adduct; Celloxide 2021P (trade name; Daicel Corporation) is 3', 4'- Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate; Celloxide 3000 (trade name; Daicel Corporation) is 1-methyl-4-( 2-methyloxirane)-7-oxabicyclo[4.1.0]heptane; COATOSIL MP200 (trade name; Momentive Performance Materials Japan Co., Ltd.) It is a polymer of 3-glycidoxypropyltrimethoxysilane.

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 polyester amide acid (A) in the thermosetting composition of the present invention is 20 to 400 parts by weight. If the ratio of the total amount of epoxy compounds (B) is within the above range, the balance of flatness, heat resistance, chemical resistance, and adhesion is 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), it is not particularly limited.

Specific examples of the multifunctional acrylamide compound (C) are: N,N',N''-tripropenyl diethylenetriamine, N,N'-{[(2-propenamide-2-[( 3-Acrylamidopropoxy)methyl]propane-1,3-diyl)bis(oxy)]bis(propane-1,3-diyl))diacrylamide, N,N',N '',N'''-tetrapropenyltriethylenetetramine, 1,3,5-tripropenylhexahydro-1,3,5-triazine.

In addition, as specific examples of the polyfunctional acrylamide compound (C), compounds of the following structural formulas may also be mentioned.

As the polyfunctional acrylamide compound (C), commercially available products as described below can be used. Specific examples of N,N',N''-tripropylene diethylenetriamine 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-Acrylamidopropoxy)methyl]propane-1,3-diyl)bis(oxy)]bis(propane-1 ,3-diyl)}The specific example of diacrylamide is FAM-401 (trade name: Fuji Film Co., Ltd.), N,N',N'',N'''-tetrapropenyl triethylene tetra 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 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 polyester amide acid (A) in the thermosetting composition of the present invention is preferably 1 part by weight 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 of flatness, heat resistance, and scratch resistance is good.

1-4. Other ingredients In the thermosetting composition of the present invention, various additives may be added to improve coating uniformity and adhesion. Additives mainly include hardeners, solvents, anionic, cationic, nonionic, fluorine or silicon leveling agents and surfactants, adhesion enhancers such as silane coupling agents, hindered phenols, hindered amines (Meth)acrylate compounds such as antioxidants such as phosphorous-based, phosphorous-based, and sulfur-based 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 an anhydride hardener, an amine hardener, a phenol hardener, a carboxylic acid-containing polymer, an imidazole hardener, a pyrazole hardener, a triazole hardener, a catalyst hardener, and From the viewpoint of avoiding the coloring of the cured film and the heat resistance of the cured film, heat-sensitive acid generators such as samium salts, benzothiazolium salts, ammonium salts, phosphonium salts, etc. are preferably anhydride-based hardeners or imidazole-based hardeners Agent, pyrazole hardener.

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

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

Specific examples of imidazole-based hardeners are: 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro-1H -Pyrrolo[1,2-a]benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-benzyl-2-methylimidazole and 1-benzyl -2-phenylimidazole. Among these imidazole-based hardeners, 2-undecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenyl, which have a good balance of hardenability and solubility in solvents, are preferred Imidazole.

Specific examples of pyrazole-based hardeners are: pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, and 3-methyl-5-pyrazolone. It is preferably 3,5-dimethylpyrazole which has a good balance between curability and solubility in solvents.

Specific examples of triazole hardeners are: 4-amino-1,2,4-triazole, 1,2,4-triazole, 1,2,3-triazole, 1-hydroxybenzotriazole, 3-mercapto-1,2,4-triazole. It is preferably 1-hydroxybenzotriazole, which has a good balance between curability and solubility in solvents.

Specific examples of phenolic hardeners include: α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 1,1,1-tris(4-hydroxybenzene Group) ethane, 9,9-bis(4-hydroxy-3-methylphenyl) stilbene, 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-tetra(4-hydroxyphenyl)ethane. Among these phenolic hardeners, α,α,α'-tri(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 1, which has a good balance of heat resistance and compatibility are preferred 1,1-tris(4-hydroxyphenyl)ethane and 9,9-bis(4-hydroxy-3-methylphenyl) stilbene.

When a hardener is used, it is preferably 0.1 part by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the epoxy compound (B).

1-4-2. Solvent In the thermosetting composition of the present invention, a solvent can also be used. The solvent optionally added to the thermosetting composition of the present invention is preferably a solvent that can dissolve the polyester amide acid (A), the epoxy compound (B), and the polyfunctional acrylamide compound (C). Specific examples of the solvent are: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, third 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, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, 3-methoxypropionate 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, pyruvate Methyl ester, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl 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 ether Ester, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, 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 1,000 or less Alcohol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol with a weight average molecular weight of 1,000 or less. The solvent may be one of these solvents, or a mixture of two or more of these solvents.

The content of the solvent is preferably 65% by weight 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 be added to improve coating uniformity. Specific examples of surfactants are: Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (the above are trade names; Kyoeisha Chemical Co., Ltd.), Disperbyk -161, Disperbyk -162, Disperbyk -163, Disperbyk -164, Disperbyk-166, Disperbyk-170, Disperbyk-180, Disperbyk-181, Disperbyk (Disperbyk)-181 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 602A, Ftergent 650A, FTX-218 (the above are trade names; Nios ( Neos) Co., Ltd., Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-410 475, 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, Mega(ac) fac) RS-72-K, Megafac RS-76-NS, Megafac DS-21 (the above are trade names; DIC Co., Ltd.), TEGO Twin ) 4000, TEGO Twin (4100), TEGO Flow (370), TEGO Glide (440), TEGO Glide (450), TEGO Glide (450), TEGO Glide (TEGO) Rad) 2200N (the above are trade names; Evonik Japan Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl iodide Ammonium, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amino sulfonate, polyoxyethylene nonyl Phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl wax 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 Alkyd 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 compounds.

If these surfactants 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, fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl trimethylammonium At least one of a salt and a fluoroalkylamine sulfonate is preferable because the uniformity of coating of the thermosetting composition becomes high.

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

1-4-4. Adhesion improver 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 (JNC) Co., Ltd.), 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane (for example, Sala-Ace) (Sila-Ace) S530; trade name; JNC (JNC) Co., Ltd., 3-mercaptopropyltrimethoxysilane (for example, Sila-Ace) S810; trade name; JNC) Co., Ltd.), a copolymer of 3-glycidoxypropyltrimethoxysilane (for example, trade name; COATOSIL MP200, Momentive Performance Materials Japan) Co., Ltd. ) And other silane-based coupling agents, aluminum acetyl diisopropoxide and other aluminum-based coupling agents, and tetraisopropyl bis (dioctyl phosphite) titanate and other titanate-based coupling agents.

Among these adhesion improving agents, 3-glycidoxypropyltrimethoxysilane has a large effect of improving adhesion 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 relative to the total amount of the thermosetting composition.

1-4-5. Antioxidants From the viewpoints of improving transparency and preventing yellowing when the cured film is exposed to high temperature, the thermosetting composition of the present invention may further contain an antioxidant.

Antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added to the thermosetting composition of the present invention. Among these, from the viewpoint of light resistance, hindered phenols are preferred. Specific examples are: Irganox 1010, Irganox 1010FF, Irganox 1035, Irganox 1035FF, Irganox (Irganox) 1035FF Irganox) 1076, Irganox 1076FD, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1330, Irganox (Irganox) Irganox) 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox (Irganox) 245FF Irganox) 259, Irganox 3114, Irganox 565, Irganox 565DD (all 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 (ADK STAB) AO-80 (both trade names; ADEKA). Among them, better is Irganox 1010 and ADK STAB AO-60.

The 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 adjuster to suppress the increase in molecular weight due to polymerization and exhibit excellent storage stability. Examples of the molecular weight modifier include thiols, xanthogen acids, quinones, hydroquinones, and 2,4-diphenyl-4-methyl-1-pentene.

Specific examples of the molecular weight modifier include 1,4-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, methyl-p-benzoquinone, anthraquinone, hydroquinone, methylhydroquinone, Third butyl hydroquinone, 2,5-di-third butyl hydroquinone, 2,5-di-third pentyl hydroquinone, 1,4-dihydroxynaphthalene, 3,6-dihydroxybenzophenone 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 tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4- Tributylcatechol, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary-dodecyl mercaptan, thioglycolic acid, dimethyl yellow Original acid sulfide, diisopropyl xanthogen acid disulfide, 2,6-di-t-butyl-p-cresol, 4,4'-butylene bis(6-t-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 modifier may be used alone or in combination of two or more. Among the molecular weight modifiers, a naphthoquinone-based molecular weight modifier is preferred in terms of showing excellent storage stability.

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

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

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

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

1-4-8. Anti-agglomerating agent The thermosetting composition of the present invention may contain an anti-agglomerating agent from the viewpoint of preventing fusion of the polyester amidic acid (A) or epoxy compound (B) with a solvent and preventing aggregation.

Specific examples of anti-agglomerating 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 trade names; BYK Chemie Japan Co., Ltd.), FTX-218, Ftergent 710FM, Ftergent 710FS (all trade names ; Neos (Neos) Co., Ltd.), Floren (Flowlen) G-600, and Floren (Flowlen) G-700 (both trade names; Gongrongshe Chemical Co., Ltd.).

The anti-agglomeration agent is used in an amount of 0.01 to 10 parts by weight relative to the total amount of the thermosetting composition.

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

Specific examples of the thermal cross-linking agent are: Nikalak (Nikalac) MW-30HM, Nikalak (MW) 100LM, Nikalak (MX) 270, Nikalak (MX-280), Nikalak (MX-280) Nikalac MX-290, Nikalac MW-390, and Nikalac MW-750LM (both trade names; Sanwa Chemical Co., Ltd.).

The thermal crosslinking agent is used 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)acryloyl groups per molecule.

Specific examples of the compound having two (meth)acryloyl groups per molecule in the (meth)acrylate compound are: ethylene glycol di(meth)acrylate, diethylene glycol di(methyl) Acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, epichlorohydrin modified ethylene glycol di(meth) Base) acrylate, epichlorohydrin modified diethylene glycol di(meth)acrylate, epichlorohydrin modified triethylene glycol di(meth)acrylate, epichlorohydrin modified tetraethylene glycol di( Methacrylic acid ester, epichlorohydrin modified polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylic acid 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, glycerol acrylic acid Ester methacrylate, glycerol 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, hydroxytrimethyl acetate neopentyl glycol di(meth)acrylate, caprolactone modification Hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, bis[(methyl ) Acryloyl neopentyl glycol) adipate, bisphenol A di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, bisphenol F di(methyl) ) 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 di(meth)acrylate Ester, caprolactone·ethylene oxide modified 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 isocyanurate ethylene oxide modified diacrylate.

The specific examples of the compound having three or more (meth)acryloyl groups per molecule in the (meth)acrylate compound are: trimethylolpropane tri(meth)acrylate, ethylene oxide Trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, epichlorohydrin modified trimethylolpropane tri(meth)acrylate, Glycerin tri(meth)acrylate, epichlorohydrin modified glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, Ethylene oxide modified tri(meth)acrylate, caprolactone·Ethylene oxide modified tri(meth)acrylate, caprolactone modified tri[(meth)acryloyloxyethyl Base] isocyanurate, di-trimethylolpropane tetra(meth)acrylate, diglycerol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkyl modified dipentaerythritol tetra( Methacrylate, dipentaerythritol penta(meth)acrylate, alkyl modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate Group) acrylate and polyfunctional (meth)acrylate containing carboxyl groups.

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

From the viewpoint of scratch resistance, 100% by weight of the (meth)acrylate compound is preferably a compound containing 50% by weight or more of three or more (meth)acryloyl groups per molecule. .

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

As the (meth)acrylate compound, commercially available products as described below can be used. A specific example of isocyanuric acid ethylene oxide modified diacrylate is Aronix (Aronix) M-215 (trade name; East Asia Synthetic Co., Ltd.); isocyanuric acid ethylene oxide modified diacrylate Specific examples of mixtures of isocyanuric acid ethylene oxide modified triacrylates are Aronix M-313 (30% by weight to 40% by weight) and Aronix M-315 (3 % By weight to 13% by weight, hereinafter abbreviated as "M-315") (all are trade names; East Asia Synthetic Co., Ltd., the content in parentheses is isocyanuric acid ethylene oxide modified diacrylate in the mixture Contents listed in the catalogue); the specific examples of trimethylolpropane triacrylate are Aronix M-309 (trade name; East Asia Synthetic Co., Ltd.); pentaerythritol triacrylate and pentaerythritol tetraacrylate Specific examples of the mixture of Aronix (Aronix) M-306 (65 wt% ~ 70 wt%), Aronix (Aronix) M-305 (55 wt% ~ 63 wt%), Aronix (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) (both It is a trade name; East Asia Synthetic Co., Ltd., the content rate in parentheses is the cataloged value of the content rate of pentaerythritol triacrylate in the mixture); the specific example of the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is sub 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 abbreviated as “M-402”), Aronix M-404 (30%-40%), Aronix M-406 (25%～35% %) and Aronix (Aronix) M-405 (10% by weight to 20% by weight) (both trade names; East Asia Synthetic Co., Ltd., the content in parentheses is the content of dipentaerythritol pentaacrylate in the mixture Catalogue value); Specific examples of carboxyl-containing polyfunctional (meth)acrylates are Aronix (Aronix) M-510 and Aronix (Aronix) M-520 (hereinafter abbreviated as "M-520") (All are trade names; East Asia Synthetic Co., Ltd.).

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

1-4-11. Other additives As other components, 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 of the composition over time becomes good and preferable. If the storage temperature is -20°C to 10°C, no precipitates are generated, which is more preferable.

2. Hardened film obtained from thermosetting composition The thermosetting composition of the present invention can be obtained by mixing a polyester amide acid (A), an epoxy compound (B) and a polyfunctional acrylamide compound (C), and further depending on the target characteristics, if necessary The epoxy hardener, solvent, surfactant, adhesion improver, antioxidant, (meth)acrylate compound, and other additives are selected and added, and these compounds are uniformly mixed and dissolved.

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 the substrate, and the solvent is removed by, for example, heating, the coating can be formed membrane. The coating of the thermosetting composition on the surface of the substrate can be formed by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, and a slit coating method. Then, the coating film is temporarily calcined using a hot plate, an oven, or the like. The temporary calcination conditions vary depending on the types of ingredients and the mixing ratio. Usually, at 70°C to 150°C, if an oven is used, it is 5 minutes to 15 minutes, and if a hot plate is used, it is 1 minute to 5 minutes. Thereafter, in order to harden the coating film, the main calcination is performed. The formal calcination conditions vary depending on the type of ingredients and the mixing ratio, usually at 180 ℃ ~ 250 ℃, preferably 200 ℃ ~ 250 ℃, if you use an oven, it is 30 minutes to 90 minutes, if you use a hot plate, it is 5 From 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 polyamic acid of the polyester amide acid is partially 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 is hardened and the high molecular weight, so it is very tough, 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, sputtering resistance, scratch resistance, and coating properties. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and the color filter can be used to manufacture a liquid crystal display element or a solid-state imaging element. 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 as a protective film for a light emitting diode (LED) light emitter. [Example]

Next, the present invention will be specifically described by the synthesis examples, examples, and comparative examples, but the present invention is not limited by these examples.

The following abbreviations refer to 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-butane tetracarboxylic dianhydride, Rikacid BT-100 (trade name; New Japan Physical and Chemical Co., Ltd.) DDS: 3,3'-diaminodiphenyl sulfone Bis-A-2EOH: 4,4'-isopropylidenebis(2-phenoxyethanol) 70PA: Epoxy ester 70PA (trade name; Kyoeisha Chemical Co., Ltd.) SMA1000P: Styrene-maleic anhydride copolymer SMA1000P (trade name; Sichuan Crude Oil 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'-dipropenyl-4,7,10-trioxa-1,13-tridecanediamine (N,N'-diacryloyl-4,7 , 10-trioxa-1, 13-tridecanediamine), FAM-201 (trade name; Fuji Film Co., Ltd.) DEAA: Monofunctional acrylamide compound Diethylacrylamide TMA: Hardener Trimellitic anhydride C11Z: Hardener Curezole C11Z (trade name; Shikoku Chemical Co., Ltd.) MP200: Adhesion improver 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; East Asia Synthetic Co., Ltd.)

First, a polyester amide acid solution (Synthesis Example 1 to Synthesis Example 7) as a reaction product of tetracarboxylic dianhydride, diamine, monohydroxy compound, polyhydroxy compound, or the like is synthesized as follows.

[Synthesis Example 1] Synthesis of polyester amide acid (A1) In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, 1,4-butanediol, and benzyl alcohol were charged at the following weights, and the mixture was stirred at 125°C for 2 hours under a stream of dry nitrogen (synthesis The first stage). 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, and DDS and MMP were added at the following weights, and the mixture was stirred at 20°C to 30°C for 2 hours, and then stirred at 125°C for 1 hour (second stage of synthesis). DDS 3.26 g MMP 21.00 g [Z/Y=3.0, (Y+Z)/X=0.8]

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

[Synthesis Example 2] Synthesis of polyester amide acid (A2) In a four-necked flask equipped with a stirrer, dehydrated and purified PGMEA, BT-100, SMA1000P, 1,4-butanediol, and benzyl alcohol were sequentially charged at the following weights, under a stream of dry nitrogen and at 125°C Stir for 2 hours (the first stage of synthesis). 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, and DDS and PGMEA were added at the following weights, stirred at 20°C to 30°C for 2 hours, and then stirred at 125°C for 1 hour (second stage of synthesis). DDS 1.20 g 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 light yellow transparent polyester amide acid (A2). A part 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 polyester amide acid (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) described in Table 1 to obtain polyester amide acid (A3) to polyester amide acid (A7) Solution.

各試劑及溶劑的裝入量的單位為克（g）Table 1

The unit of the amount of each reagent and solvent is gram (g)

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

[Example 1] A 30% by weight solution of the polyester amide acid (A1) obtained in Synthesis Example 1, VG3101L, FAM-402, TMA, MP200, AO-60, at the ratio (unit: g) described in Table 2-1 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 acid (A1) described in Table 2-1 is the weight of the polymer other than the solvent of the 30% by weight solution.

[Examples 2 to 14 and Comparative Examples 1 to 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 flatness evaluation results are shown in Table 2-1 to Table 2-2 and Table 3.

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

[Evaluation method of flatness] The thermosetting composition was spin-coated at 300 rpm for 10 seconds on a pre-use level difference, surface roughness, and fine shape measuring device (trade name; P-17, KLA TENCOR Co., Ltd.) to measure the surface level. On the poor color filter substrate having no cured film including pixels of R, G, and B, pre-bake on a hot plate at 90°C for 2 minutes. Then, post-bake at 230° C. for 30 minutes in an oven to obtain a color filter substrate with a cured film having an average film thickness of 1.5 μm as a protective film. After that, the obtained color filter substrate with a cured film was measured for the surface level difference. Calculate the flattening rate based on the maximum value of the surface level difference of the color filter substrate without a cured film and the color filter substrate with a cured film (hereinafter abbreviated as "maximum level difference"), and use the following calculation formula (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 less than 85.0% was evaluated as flatness ×. In addition, for the color filter substrate without a cured film, a maximum step difference of 1.0 μm is used. Flattening 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 a glass substrate at 300 rpm for 10 seconds, and prebaked on a hot plate at 90°C for 2 minutes. After baking at 230°C for 30 minutes in an oven, a glass substrate with a cured film thickness of 1.5 μm was obtained. The obtained glass substrate with a cured film was subjected to the 8.4.1 pencil scratch test of JIS K-5400-1990, thereby measuring the pencil hardness of the cured film, and the results are shown in Table 1. A case with a pencil hardness of 3H or more was evaluated as scratch resistance ○, and a case with 2H or less was evaluated as scratch resistance ×.

[Transparency evaluation method] 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. After baking at 230°C for 30 minutes in an oven, a glass substrate with a cured film thickness of 1.5 μm was obtained. The obtained glass substrate with a cured film was measured for the transmittance of the cured film using an ultraviolet-visible spectrophotometer, and the results are shown in Table 1. The case where the transmittance at a wavelength of 400 nm was 95.0% or more was evaluated as transparency ○, and the case where less than 95.0% was evaluated as transparency ×.

[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. After baking at 230°C for 30 minutes in an oven, a glass substrate with a cured film thickness of 1.5 μm was obtained. The obtained glass substrate with a cured film was tested according to ISO2409. The case where the test result shows the adhesion of category 0 to category 1 is ○, and the case of showing the adhesion of categories 2 to 5 is ×.

[Evaluation method of 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. After baking at 230°C for 30 minutes in an oven, a glass substrate with a cured film thickness of 1.5 μm was obtained. The obtained hardened film was cut out to make a powder, and the weight loss before and after heating was measured with a thermogravimetric differential thermal analysis device. 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. A case where the amount of weight reduction is 2.0% or less is designated as ○, and a case where the amount of weight reduction is greater than 2.0% is represented 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. After baking at 230°C for 30 minutes in an oven, a glass substrate with a cured film thickness of 1.5 μm was obtained. The obtained hardened film was cut out to make a powder, and the weight loss before and after heating was measured with 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, and then from 150°C to 250°C at 10°C/min. Heat at 250°C for 30 minutes. Here, the weight at the time when the temperature increase from 150°C to 250°C was started was taken as a reference, and the difference from the weight after heating at 250°C for 30 minutes was taken as the weight reduction. A case where the weight reduction amount shows 3.0% or less is ○, and a case where the weight reduction amount shows a value exceeding 3.0% is X.

裝入量的單位為克（g）table 2-1

The unit of loading is grams (g)

裝入量的單位為克（g）Table 2-2

The unit of loading is grams (g)

裝入量的單位為克（g）table 3

The unit of loading is grams (g)

From the results shown in Tables 2-1 to 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 that are thermosetting compositions containing no polyfunctional acrylamide compound (C) have poor flatness. [Industry availability]

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

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Claims (5)

A thermosetting composition comprising polyester amide acid (A), epoxy compound (B) and polyfunctional acrylamide compound (C), and the thermosetting composition is characterized by, The polyester amide acid (A) is a multicomponent including X molar tetracarboxylic dianhydride, Y molar diamine, and Z molar in a ratio established by the relationship of the following formula (1) and formula (2) The reaction product of the raw material of the hydroxy compound, The multifunctional 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 thermosetting composition as described in item 1 of the patent application scope, wherein the polyester amide acid (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 a diamine R ³ is a residue obtained by removing two -OH groups from a polyhydroxy compound. The thermosetting composition according to item 1 or item 2 of the patent application scope, wherein the content of the epoxy compound (B) is 20 parts by weight with respect to 100 parts by weight of the polyester amide acid (A) Parts to 400 parts by weight, and the content of the multifunctional acrylamide compound (C) is 1 part by weight to 100 parts by weight relative to 100 parts by weight of the polyester amide acid (A). A cured film obtained by curing the thermosetting composition according to any one of claims 1 to 3 of the patent application. A color filter having a cured film as described in item 4 of the patent application scope as a transparent protective film.