JP6988566B2 - Thermosetting composition - Google Patents

Description

The present invention relates to a thermosetting composition used for various elements, a cured film formed from the thermosetting composition, and a color filter, an insulating film or a protective film using the cured film.

In the manufacturing process of elements such as liquid crystal display elements, various chemical treatments such as organic solvents, acids, and alkaline solutions are performed, and when the wiring electrodes are formed by sputtering, the surface is locally heated to a high temperature. Sometimes. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and deterioration of the surface of various elements. These protective films are required to have various properties capable of withstanding various treatments during the manufacturing process as described above. Specifically, it has heat resistance, solvent resistance, acid resistance, alkali resistance, and other chemical resistance, water resistance, adhesion to underlying substrates such as glass, transparency, scratch resistance, coatability, flatness, and light resistance. Etc. are required. As the required reliability required for the display element is improved, the heat resistance required for the display element member is improved, and a thermosetting composition containing a polyesteramidic acid and an epoxy compound having good heat resistance is being used. It has been proposed (Patent Document 1). Further, as the flatness required for high-definition and thin liquid crystal display elements has improved in recent years, a thermosetting composition having good flatness in addition to good heat resistance has been proposed. (Patent Document 2).

In recent years, liquid crystal display elements have been narrowed in frame in order to expand the display area, and the materials constituting the display element, such as sealants, spacers, color filters, and protective films for color filters, are made of different materials. High adhesion is required. Further, since the liquid crystal material generally has low moisture resistance, the material is required to have low hygroscopicity, that is, excellent moisture resistance.

Patent Document 1 Japanese Patent Application Laid-Open No. 2016-103010
Patent Document 2 Japanese Patent Application Laid-Open No. 2010-250059

An object of the present invention is to provide a thermosetting composition that provides a cured film having excellent adhesion and moisture resistance, and to provide a cured film formed by the thermosetting composition, and further to have the cured film. To provide electronic components.

As a result of diligent studies to solve the above problems, the present inventors have made a reaction from a polyvalent hydroxy compound in which one or more selected from tetracarboxylic acid dianhydride, diamine, polyester polyol and polycaprolactone polyol is essential. The present invention has been completed by finding that the above object can be achieved by a cured film obtained by curing a composition containing a polyester amic acid, an epoxy compound, and an additive such as an epoxy curing agent if necessary. I came to do.

[1] A thermosetting composition containing a polyester amic acid (A) and an epoxy compound (B).
The polyesteramide acid (A) is an X-mol tetracarboxylic dianhydride, a Y-mol diamine and a Z-mol polyvalent hydroxy compound, such that the following formulas (1) and (2) are established. It is a reaction product from the raw material contained in the ratio,

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

The polyvalent hydroxy compound contains at least one selected from a polyester polyol and a polycaprolactone polyol, and the proportion of the polyester polyol and the polycaprolactone polyol in the polyvalent hydroxy compound is 25 mol% or more. thing.

式（３）及び式（４）において、Ｒ^１はテトラカルボン酸二無水物から２つの−ＣＯ−Ｏ−ＣＯ−を除いた残基であり、Ｒ^２はジアミンから２つの−ＮＨ_２を除いた残基であり、Ｒ^３は多価ヒドロキシ化合物から２つの−ＯＨを除いた残基である。 [2] The thermosetting composition according to item [1], wherein the polyester amic acid (A) contains 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 thermosetting composition according to item [1], wherein the polyester polyol and the polycaprolactone polyol have a weight average molecular weight of less than 5,000.

[4] The thermosetting composition according to any one of [1] to [3], wherein the raw material component of the polyester amic acid (A) further contains a monohydroxy compound.

[5] The polyester polyol is ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl. A reaction product from adipic acid with at least one selected from glycol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol.
The thermosetting composition according to any one of [1] to [4], wherein the polycaprolactone polyol is at least one selected from polycaprolactone diol and polycaprolactone triol.

[6] The tetracarboxylic acid dianhydride is 3,3', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2 , 2- [Bis (3,4-dicarboxyphenyl)] Hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and ethylene glycol bis (anhydrotrimeritate) At least one to be chosen,
The diamine is at least one selected from 3,3'-diaminodiphenyl sulfone and bis [4- (3-aminophenoxy) phenyl] sulfone.
Polyvalent hydroxy compounds other than the polyester polyol and the polycaprolactone polyol are ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane. Acrylate, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, tris isocyanurate (2-) Hydroxyethyl), 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethanol, glycerin mono (meth) acrylate, trimethylol propane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, Pentaerythritol di (meth) acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate , Solbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, 4,4'-isopropylidenebis (2-phenoxyethanol), (meth) acrylic acid modified product of ethylene glycol diglycidyl ether, (Meta) 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 glycerin diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether. ) Acrylate-modified product, propylene oxide-modified bisphenol A diglycidyl ether (meth) acrylic acid-modified product, and (meth) acrylic acid-modified product of a compound containing two or more epoxy groups per molecule. The thermosetting composition according to any one of [1] to [5].

[7] The monohydroxy compound is isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, 3-ethyl-3-hydroxymethyloxetane, furfuryl alcohol, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2 -Hydroxy-3-phenoxypropyl (meth) acrylate, (meth) acrylic acid 4-hydroxyphenyl, p-hydroxy (meth) acrylic anilide, 1,4-cyclohexanedimethanol mono (meth) acrylate, (meth) acrylic acid 3 -(2-Hydroxyphenyl), glycerindi (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and one epoxy group per molecule. Item 3. The thermosetting composition according to item [4], which is at least one selected from (meth) acrylic acid modified products of the compound containing the compound.

[8] The thermosetting composition according to any one of [1] to [7], wherein the polyester amic acid (A) has a weight average molecular weight of 1,000 to 200,000.

[9] The item according to any one of [1] to [8], wherein the content of the epoxy compound (B) is 20 to 400 parts by weight with respect to 100 parts by weight of the polyesteramidic acid (A). Thermosetting composition.

[10] A cured film obtained from the thermosetting composition according to any one of [1] to [9].

[11] A color filter having the cured film according to item [10] as a transparent protective film.

The cured film formed by using the thermosetting composition according to the present invention is excellent in heat resistance, transparency, flatness, adhesion and moisture resistance. This cured film can be applied to various applications such as a color filter, a protective film, and an insulating film.

1. 1. Thermo-curable composition The thermo-curable composition according to the present invention is a polyester amic acid (A) or an epoxy compound obtained by reacting a tetracarboxylic acid dianhydride, a diamine, or a polyvalent hydroxy compound as an essential raw material component. (B), and if necessary, a composition containing an additive, which comprises at least one selected from a polyester polyol and a polycaprolactone polyol as the polyvalent hydroxy compound, and the polyester polyol and the poly in the polyvalent hydroxy compound. The proportion of caprolactone polyol is 25 mol% or more. The total amount of the epoxy compound (B) is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amic acid (A).

The thermosetting composition according to the present invention may further contain components other than the above as long as the effects of the present invention can be obtained.

1-1. Polyester amidoic acid (A)
The polyesteramide acid (A) is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components. Specifically, the polyesteramide acid (A) is an X-mol tetracarboxylic dianhydride, a Y-mol diamine and a Z-mol polyvalent hydroxy compound, so that the relationships of the formulas (1) and (2) are established. It is obtained by reacting at various ratios.

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

Further, the polyester amic acid (A) has a structural unit represented by the formula (3) and a structural unit represented by the 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.

At least a solvent is required for the synthesis of the polyesteramidic acid (A). The solvent may be left as it is to form a liquid or gel-like composition in consideration of handleability and the like, or the solvent may be removed to form a solid composition in consideration of transportability and the like.

Further, in the synthesis of the polyesteramidic acid (A), a styrene-maleic anhydride copolymer may be contained as a raw material, if necessary, and other than the above, as long as the object of the present invention is not impaired. May contain the compound of. Examples of other raw materials include silicon-containing monoamines.

1-1-1. Tetracarboxylic acid dianhydride In the present invention, tetracarboxylic acid dianhydride is used as a material for obtaining polyesteramidic acid (A). Specific examples of the tetracarboxylic dianhydride include 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride used in the examples (hereinafter, may be abbreviated as ODPA), 1, 2, and 2. Examples thereof include 3,4-butanetetracarboxylic dianhydride (hereinafter, may be abbreviated as BT-100).

As the tetracarboxylic acid dianhydride, in addition to the above compounds, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, , 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2', 3,3'-diphenylsulfone Tetracarboxylic acid dianhydride, 2,3,3', 4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2', 3,3'-diphenyl ether tetracarboxylic acid dianhydride, 2,3,3' , 4'-Diphenyl ether tetracarboxylic acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimeritate) (trade name; TMEG) -100, Shin Nihon Rika Co., Ltd.), Cyclobutanetetracarboxylic acid dianhydride, Methylcyclobutanetetracarboxylic acid dianhydride, Cyclopentanetetracarboxylic acid dianhydride, Cyclohexanetetracarboxylic acid dianhydride, and Etantetracarboxylic acid dianhydride. Anhydrous can be mentioned. At least one of the above-mentioned tetracarboxylic dianhydrides can be used.

Among these, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride and 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, which give good transparency to the cured film, , 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and TMEG-100 are preferred, 3, 3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride and 1,2,3,4-butanetetracarboxylic acid dianhydride Is more preferable.

1-1-2. Diamine In the present invention, diamine is used as a material for obtaining polyesteramidic acid (A). Specific examples of the diamine include 3,3'-diaminodiphenyl sulfone (hereinafter, may be abbreviated as DDS) used in the examples.

As diamines, in addition to the above compounds, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-amino) Phenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, [4- (3- (3-aminophenoxy) phenyl] sulfone Aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane can be mentioned. At least one of the above diamines can be used.

Among these, 3,3'-diaminodiphenyl sulfone and bis [4- (3-aminophenoxy) phenyl] sulfone, which give good transparency to the cured film, are preferable, and 3,3'-diaminodiphenyl sulfone is more preferable. preferable.

1-1-3. Multivalent hydroxy compound The present invention uses a polyvalent hydroxy compound as a material for obtaining the polyester amidoic acid (A). It is essential that the polyvalent hydroxy compound contains at least one selected from polyester polyol and polycaprolactone polyol, and that the proportion of the polyester polyol and polycaprolactone polyol in the polyvalent hydroxy compound is 25 mol% or more. Specific examples of the polyester polyol include the reaction product of 1,4-butanediol and adipic acid (polylite OD-X-240; trade name; DIC Corporation), 3-methyl-1,5-pentane used in the examples. Reaction product of diol and adipic acid (Polylite OD-X-2420; trade name; DIC Corporation), Reaction product of 1,6-hexanediol and adipic acid (Polylite OD-X-2640; trade name; DIC Corporation) Company) can be mentioned. Specific examples of the polycaprolactone polyol include the polycaprolactone triol (Polylite OD-X-2586; trade name; DIC Corporation) used in the examples. Specific examples of the polyvalent hydroxy compound other than the polyester polyol and the polycaprolactone polyol include 1,4-butanediol, triethylene glycol, and diethylene glycol used in the examples.

As the polyvalent hydroxy compound selected from the polyester polyol and the polycaprolactone polyol, in addition to the above-mentioned compound, a reaction product of ethylene glycol and adipic acid having a weight average molecular weight of less than 5,000, and a reaction product of diethylene glycol and adipic acid. Product, reaction product of 1,2-propanediol and adipic acid, reaction product of 1,3-butanediol and adipic acid, reaction product of 1,4-butanediol and adipic acid (eg, Tesslac 2464; Commodity) Name; Hitachi Kasei Co., Ltd.), Reaction product of 1,5-pentanediol and adipic acid, Reaction product of 1,6-hexanediol and adipic acid (eg, Tesslac 2461; Trade name; Hitachi Kasei Co., Ltd.), Reaction products of neopentyl glycol and adipic acid, reaction products of 2-methyl-1,3-propanediol and adipic acid, reaction products of 3-methyl-1,5-pentanediol and adipic acid (eg, teslac). 2462; Trade name; Hitachi Chemical Co., Ltd.), and ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- A reaction product of adipic acid with two or more selected from hexanediol, neopentaneglycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, polycaprolactone diol (eg, Praxel 220N). ; Product name; Daicel Co., Ltd.), polycaprolactone triol (for example, Praxel 320; trade name; Daicel Co., Ltd.) can be mentioned.

Among these, the reaction product of diethylene glycol and adipic acid, the reaction product of 1,4-butanediol and adipic acid, which has good solubility in the reaction solvent and has a weight average molecular weight of less than 3,000, 3- Reaction product of methyl-1,5-pentanediol and adipic acid, reaction product of 1,6-hexanediol and adipic acid, ethylene glycol and reaction product of 1,4-butanediol and adipic acid, ethylene glycol and Reaction products of diethylene glycol and adipic acid, polycaprolactone diols and polycaprolactone triols are preferred.

As polyvalent hydroxy compounds other than polyester polyols and polycaprolactone polyols, in addition to the above compounds, ethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, etc. Tetrapropylene glycol, polypropylene glycol with a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-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-Nonandiol, 1,2,9-Nonantriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanthriol, 1,2-dodecanediol, 1,12-dodecane Diol, glycerin, trimethylol propane, pentaerythritol, dipentaerythritol, tris isocyanurate (2-hydroxyethyl), bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxy) Phenyl) sulfone), bisphenol F (bis (4-hydroxyphenyl) methane), 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 trial Luether, sorbitol tetraallyl ether, 4,4'-isopropyridenebis (2-phenoxyethanol), glycerin mono (meth) acrylate, trimethylol propane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) ) Acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, sorbitol di (meth) ) Acrylic, 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 (Meta) acrylic acid modified product of ether, (meth) acrylic acid modified product of glycerin diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, (meth) acrylic of propylene oxide modified bisphenol A diglycidyl ether Acid-modified product, (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, propylene Oxide-modified bisphenol F diglycidyl ether (meth) acrylic acid modified product, bixirenol diglycidyl ether (meth) acrylic acid modified product, biphenol diglycidyl ether (meth) acrylic acid modified product, full orange phenol diglycidyl ether (Meta) acrylic acid modified product, (meth) acrylic acid modified product of cyclohexane-1,4-dimethanol diglycidyl ether, (meth) acrylic acid modified product of hydrogenated bisphenol A diglycidyl ether, tricyclodecane dimethanol di. Examples thereof include (meth) acrylic acid modified products of glycidyl ether and (meth) acrylic acid modified products of other compounds containing two or more epoxy groups per molecule.

Among these, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexanediol, which have good solubility in the reaction solvent, 7-heptanediol, 1,8-octanediol, tris isocyanurate (2-hydroxyethyl), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4 -Hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethanol, 4,4'-isopropylidenebis (2-phenoxyethanol), (meth) acrylic acid modified product of ethylene glycol diglycidyl ether, ((meth) acrylic acid modified product of propylene glycol diglycidyl ether ( Meta) 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 , (Meta) acrylic acid modified product of bisphenol S diglycidyl ether, (meth) acrylic acid modified product of bisphenol S diglycidyl ether, (meth) acrylic acid modified product of bisphenol F diglycidyl ether, and propylene oxide modified product. A modified (meth) acrylic acid of bisphenol F diglycidyl ether is preferred. In addition, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 4,4'-isopropylene bis ( 2-Phenoxyethanol), 2- (4-hydroxyphenyl) ethanol, (meth) acrylic acid modified product of ethylene glycol diglycidyl ether, (meth) acrylic acid modified product of propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether (Meta) acrylic acid modified product, (meth) acrylic acid modified product of glycerin diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, and (meth) acrylic acid of propylene oxide modified bisphenol A diglycidyl ether. Modified products are particularly preferred.

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

In the synthesis of the polyesteramidic acid (A), an acid anhydride group (-CO-) is used at the terminal under the condition that the monohydroxy compound is not used and X is excessively used with respect to Y + Z within the range of the above formula (2). It is considered that the molecule having O-CO-) is excessively generated than the molecule having an amino group or a hydroxyl group at the terminal. On the other hand, when the reaction is carried out with the composition of such a monomer, if a monohydroxy compound is added, it can react with the acid anhydride group at the molecular terminal and esterify the terminal. The polyesteramidic acid (A) obtained by adding and reacting the monohydroxy compound has improved compatibility with the epoxy compound (B), improves the storage stability of the thermosetting composition, and has heat. The coatability of the curable composition is improved.

Specific examples of the monohydroxy compound include isopropyl 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, and diethylene glycol. Monoethyl ether, diethylene glycol monomethyl ether, terpineol, 3-ethyl-3-hydroxymethyloxetane, dimethylbenzylcarbinol, furfuryl alcohol, allyl alcohol, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) ) Acrylate, 2-Hydroxy-3-phenoxypropyl (meth) acrylate, (meth) acrylic acid 4-hydroxyphenyl, p-hydroxy (meth) acrylic anilide, 1,4-cyclohexanedimethanol mono (meth) acrylate, (meth) ) Acrylic acid 3- (2-Hydroxyphenyl), glycerindi (meth) acrylate, trimethylolpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl ether ( Examples thereof include (meth) acrylic acid modified products, (meth) acrylic acid modified products of t-butylphenylglycidyl ether, and (meth) acrylic acid modified products of other compounds containing one epoxy group per molecule.

Among these, isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, which have good compatibility between the polyesteramidic acid (A) obtained by adding and reacting the monohydroxy compound and the epoxy compound (B), 3-Ethyl-3-hydroxymethyloxetane, furfuryl alcohol, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate. , P-Hydroxy (meth) acrylic anilide, 1,4-cyclohexanedimethanol mono (meth) acrylate, (meth) acrylic acid 3- (2-hydroxyphenyl), glycerindi (meth) acrylate, trimethyl propandi (meth) ) Acrylic, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and (meth) acrylic acid-modified compounds containing one epoxy group per molecule are preferred.

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

式（３）、式（４）及び式（５）において、Ｒ^１はテトラカルボン酸二無水物から２つの−ＣＯ−Ｏ−ＣＯ−を除いた残基であり、Ｒ^２はジアミンから２つの−ＮＨ_２を除いた残基であり、Ｒ^３は多価ヒドロキシ化合物から２つの−ＯＨを除いた残基であり、Ｒ^４はモノヒドロキシ化合物から１つの−ＯＨを除いた残基である。式中のＲ^１、Ｒ^２、Ｒ^３、及びＲ^４は独立して、１つの構造でもよく、２つ以上の構造を含んでいてもよい。 The polyesteramidic acid (A) synthesized in this manner contains a structural unit represented by the formula (3), a structural unit represented by the formula (4), and a structural unit represented by the formula (5). , The terminal thereof is an acid anhydride group, an amino group, a hydroxy group, or a monovalent organic group derived from a tetracarboxylic acid dianhydride, a diamine, a polyvalent hydroxy compound, or a monohydroxy compound, which is a raw material, or a monovalent organic group thereof. It is composed of additives other than compounds. By including such a configuration, the curability becomes good.

In formulas (3), (4) and (5), R ¹ is a residue obtained by removing two -CO-O-CO- from tetracarboxylic acid dianhydride, and R ² is two diamines. It is a residue excluding −NH ₂ ^{, R 3} is a residue obtained by removing two −OH from a polyvalent hydroxy compound, and R ⁴ is a residue excluding one −OH from a monohydroxy compound. ^{R 1} , R ² , R ³ and R ⁴ in the formula may independently have one structure or may include two or more structures.

1-1-5. Styrene-maleic anhydride copolymer The polyesteramidic acid (A) used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups to the above-mentioned raw materials. This is preferable because the transparency of the cured film is improved. Specific examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. The ratio of each component constituting the styrene-maleic anhydride copolymer is preferably 0.5 to 4 in terms of the molar ratio of styrene / maleic anhydride.

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

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

1-1-6. Silicon-Containing Monoamine In the present invention, a silicon-containing monoamine may be used as a material for obtaining the polyester amidoic acid (A). When a thermosetting composition containing polyesteramidic acid (A) obtained by adding and reacting a silicon-containing monoamine is used, the acid resistance of the cured film is improved.

Specific examples of the silicon-containing monoamine used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 4-aminobutyl. Trimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyl Examples thereof include diethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. At least one 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 particularly preferable from the viewpoint of acid resistance and compatibility. preferable.

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

1-1-7. Solvent used in the synthesis reaction of polyesteramidic acid (A) Specific examples of the solvent used in the synthesis reaction to obtain polyesteramide acid (A) include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and diethylene glycol monoethyl ether acetate. Examples thereof include ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, and cyclohexanone. Of these, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ethyl ether is preferable.

1-1-8. Method for synthesizing polyester amide acid In the method for synthesizing polyester amide acid (A) used in the present invention, X mol of tetracarboxylic acid dianhydride, Y mol of diamine, and Z mol of polyvalent hydroxy compound are mixed in the above solvent. React. At this time, it is preferable that X, Y and Z are set at a ratio such that the relations of the following equations (1) and (2) are established between them. Within this range, the solubility of the polyester amic acid (A) in the solvent is high, and the coatability of the composition is improved. As a result, a cured film having excellent flatness can be obtained.

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

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

The order of adding the raw materials to the reaction system is not particularly limited. That is, a method of simultaneously adding a tetracarboxylic acid dianhydride, a diamine and a polyvalent hydroxy compound to a reaction solvent, a method of dissolving a diamine and a polyvalent hydroxy compound in a reaction solvent, and then adding a tetracarboxylic acid dianhydride, tetra. A method in which a carboxylic acid dianhydride and a polyvalent hydroxy compound are reacted in advance and then a diamine is added to the reaction product, or a tetracarboxylic acid dianhydride and a diamine are previously reacted and then a large amount is added to the reaction product. Any method can be used, such as a method of adding a valent hydroxy compound.

The monohydroxy compound and the styrene-maleic anhydride copolymer may be added at any point in the reaction. When the above-mentioned silicon-containing monoamine is reacted, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyvalent hydroxy compound, the reaction solution is cooled to 40 ° C. or lower, and then the silicon-containing monoamine is added to obtain 10 to 40. It is advisable to react at ° C for 0.1 to 6 hours.

The weight average molecular weight of the obtained polyester amidoic acid (A) is preferably 1,000 to 200,000, more preferably 3,000 to 50,000. Within these ranges, flatness and heat resistance are good.

The weight average molecular weight in the present specification is a value in terms of polystyrene obtained by the GPC method (column temperature: 35 ° C., flow rate: 1 ml / min). Standard polystyrene is polystyrene with a molecular weight of 645-132,900 (eg, polystyrene calibration kit PL2010-012; trade name; Agilent Technologies, Inc.), and column is PLgel MIXED-D (trade name; Agilent Technologies). It can be measured using THF as a mobile phase using (Co., Ltd.). The weight average molecular weights of commercially available products in the present specification are the values listed in the catalog.

1-2. Epoxy compound (B)
By adding the epoxy compound (B) to the thermosetting composition of the present invention, the heat resistance and solvent resistance of the cured film can be enhanced.

Examples of the epoxy compound (B) are 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (eg, seroxide 2021P; trade name; Daicel Co., Ltd.), 1-methyl-4- (2-). Methyloxylanyl) -7-oxabicyclo [4.1.0] heptane (eg, seroxide 3000; trade name; Daicel Co., Ltd.), 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy)) Phenyl] -1- [4- [1- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-Propanol mixture (eg, TECHMORE VG3101L; Commodity Name; Printec Co., Ltd.), 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] Phenyl] Propane, 1,1,1-Tris (4-hydroxyphenyl) ethanetriglycidyl ether, 1,3-bis (oxylanylmethyl) -5- (2-propenyl) -1,3,5-triazine- 1,2,4,6 (1H, 3H, 5H) -trione, 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (eg, EHPE3150; Product name; Daicel Co., Ltd.), 3,3', 5,5'-tetramethyl-4,4'-biphenol diglycidyl ether (for example, YX4000H; product name; Mitsubishi Chemical Co., Ltd.), 4,4'-isopropoxy Redendiphenol and 1-chloro-2,3-epoxypropane polycondensate hydroxide (eg YX8034; trade name; Mitsubishi Chemical Co., Ltd.), α-2,3-epoxypropoxyphenyl-ω-hydropoly [2-( 2,3-Epoxypropoxy) benziliden-2,3-epoxypropoxyphenylene] (for example, EPPN-501H; trade name; Nippon Kayaku Co., Ltd.) can be mentioned.

The epoxy compound (B) used in the present invention may be an epoxy group-containing polymer. This epoxy group-containing polymer contains glycidyl (meth) acrylate alone, 4-hydroxybutyl (meth) acrylate glycidyl ether alone, glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate as radically polymerizable compounds having an epoxy group. It is obtained by reacting one or more selected from glycidyl ether with a radically polymerizable compound having no epoxy group. By using the epoxy group-containing polymer, the transparency of the cured film obtained from the thermosetting composition is increased, and the decrease in transparency in the UV ozone treatment step and the ultraviolet exposure step can be suppressed, which is preferable. In the case of the copolymer, the radical polymerizable compound having an epoxy group is contained in an amount of 50 to 99% by weight in all the monomers constituting the epoxy group-containing polymer from the viewpoint of flatness, heat resistance and solvent resistance. Is preferable.

Preferred examples of the radically polymerizable compound having no epoxy group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-hydroxyl. Ethyl (meth) acrylate, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-((meth) acryloyloxy) propyltris (Trimethylsiloxy) silane, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di ( Examples thereof include meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and inden. These are preferable because they have good compatibility with the polyesteramidic acid (A) of the epoxy compound obtained by reacting with glycidyl (meth) acrylate.

1-3. Additives Various additives can be added to the thermosetting composition of the present invention in order to improve coating uniformity, adhesiveness, transparency, resolution, flatness, and chemical resistance. Additives include anionic, cationic, nonionic, fluorine-based or silicon-based leveling agents / surfactants, coupling agents such as silane coupling agents, hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based additives. Mainly examples thereof include antioxidants such as compounds, compounds having a polymerizable double bond, epoxy curing agents, ultraviolet absorbers, anti-aggregation agents, heat cross-linking agents, and film surface exposed radical copolymerized polymers.

1-3-1. Surfactant A surfactant may be added to the thermosetting composition of the present invention in order to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (trade name; Kyoeisha Chemical Co., Ltd.), Disperbyk-161, Disperbake-162, Disperbake-163, Disperbake-164, Disperbake-166, Disperbake-170, Disperbake-180. , Disper Bake-181, Disper Bake-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (All product names; Big Chemie Japan Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF-50-100CS (All product names; Shin-Etsu Chemical Industry Co., Ltd.), Surflon-S611 (Products) Name; AGC Seimi Chemical Co., Ltd.), Futtergent 222F, Futtergent 208G, Futtergent 251, Futtergent 710FL, Futtergent 710FM, Futtergent 710FS, Futtergent 601AD, Futtergent 650A, FTX-218 (all trade names; Neos Co., Ltd.), Mega Fuck F-410, Mega Fuck F-430, Mega Fuck F-444, Mega Fuck F-472SF, Mega Fuck F-475, Mega Fuck F-477, Mega Fuck F-552, Mega Fuck F -553, Mega Fuck F-554, Mega Fuck F-555, Mega Fuck F-556, Mega Fuck F-558, Mega Fuck F-559, Mega Fuck R-94, Mega Fuck RS-75, Mega Fuck RS-72 -K, Mega Fuck RS-76-NS, Mega Fuck DS-21 (all trade names; DIC Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N , (All trade names; Ebonic Japan Co., Ltd.), Fluoroalkylbenzene sulfonate, Fluoroalkylcarboxylate, Fluoroalkylpolyoxyethylene ether, Fluoroalkylammonium iodide, Fluoroalkylbetaine, Fluoroalkylsulfonate, Diglycerin Tetrax (fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfon Acid, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxy Ethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxy Examples thereof include ethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonates, and alkyldiphenyl ether disulfonates. It is preferable to use at least one selected from these.

Among these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surflon-S611, Footergent 710FL, Footergent 710FM, Footergent 710FS, Footergent 601AD, Footergent 650A, Megafuck F-477, Megafuck F-556, Megafuck F-559, Megafuck RS-72-K, Megafuck DS-21, TEGO Twin 4000, Fluoroalkylbenzene Sulfonate, Fluoroalkylcarboxylate, At least one selected from fluoroalkylpolyoxyethylene ether, fluoroalkylsulfonate, fluoroalkyltrimethylammonium salt, and fluoroalkylaminosulfonate enhances the coating uniformity of the thermosetting composition. Therefore, it is preferable.

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

1-3-2. Coupling Agent The thermosetting composition of the present invention may further contain a coupling agent from the viewpoint of further improving the adhesion between the cured film to be formed and the substrate.

As such a coupling agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, Silaace S510; trade name; JNC Co., Ltd.), 2- (3). , 4-Epoxycyclohexyl) ethyltrimethoxysilane (eg, Silaace S530; trade name; JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane (eg, Silaace S810; trade name; JNC Co., Ltd.), 3-glycidyl-oxy Silane-based coupling agents such as a copolymer of propyltrimethoxysilane (for example, COATOSIL MP200; trade name; Momentive Performance Materials Japan LLC), aluminum-based coupling agents such as acetalkoxyaluminum diisopropyrate, And titanate-based coupling agents such as tetraisopropylbis (dioctylphosphite) titanate can be mentioned.

Among these, 3-glycidyloxypropyltrimethoxysilane and its copolymer are preferable because they have a large effect of improving adhesion.

When the content of the coupling agent is 0.01% by weight or more and 10% by weight or less with respect to the total amount of the thermosetting composition, the adhesion between the formed cured film and the substrate is improved. preferable.

1-3-3. Antioxidant The thermosetting composition of the present invention may further contain an antioxidant from the viewpoint of improving transparency and preventing yellowing when the cured film is exposed to a high temperature.

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. Of these, the hindered phenolic system is preferable from the viewpoint of weather resistance. As a specific example, Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox259, Irganox3114, Irganox565, Irganox565DD (all trade name; BASF Japan stock (Company), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-80 (all trade names; ADEKA Corporation). Of these, Irganox 1010 and ADK STAB AO-60 are more preferable.

The antioxidant is added in an amount of 0.1 to 10 parts by weight based on the total amount of the thermosetting composition.

1-3-4. Compounds with Polymerizable Double Bonds The thermosetting composition of the present invention may further contain a compound having a polymerizable double bond from the viewpoint of improving scratch resistance.

Specific examples of the thermosetting composition of the present invention include ethylene oxide-modified bisphenol A diacrylate (for example, Funkryl FA-324A; trade name; Hitachi Kasei Co., Ltd.) and isocyanuric acid ethylene oxide-modified diacrylate (for example, Aronix M). -215; trade name; Toa Synthetic Co., Ltd.), isocyanuric acid ethylene oxide-modified triacrylate, trimethyl propanetriacrylate (for example, Aronix M-309; trade name; Toa Synthetic Co., Ltd.), pentaerythritol triacrylate and pentaerythritol tetraacrylate. Mixtures of (eg, Aronix M-306 (65-70% by weight), M-305 (55-63% by weight), M-303 (40-60% by weight), M-452 (25-40% by weight) and M-450 (less than 10% by weight); trade name; Toa Synthetic Co., Ltd., the content in parentheses is the value listed in the catalog for the content of pentaerythritol triacrylate in the mixture), dipentaerythritol pentaacrylate and dipentaerythritol hexa. Acrylate (eg, Aronix M-403 (50-60% by weight), M-400 (40-50% by weight), M-402 (30-40% by weight), M-404 (30-40% by weight), M. -406 (25 to 35% by weight), and M-405 (10 to 20% by weight); trade name; Toa Synthetic Co., Ltd., the content in parentheses is listed in the catalog of the content of dipentaerythritol pentaacrylate in the mixture. Value), carboxyl group-containing polyfunctional acrylate (eg, Aronix M-510; trade name; Toa Synthetic Co., Ltd.), reaction product of isophorone diisocyanate and pentaerythritol triacrylate (eg, UA-306I; trade name; Kyoeisha Chemical Co., Ltd.) ), A reaction product of hexamethylene diisocyanate and phenylglycidyl ether acrylate (AH-600, trade name; Kyoeisha Chemical Co., Ltd.), a reaction product of hexamethylene diisocyanate and dipentaerythritol pentaacrylate (UA-510H, trade name; Kyoeisha Chemical Co., Ltd.) (Co., Ltd.), U-15HA (trade name; Shin-Nakamura Chemical Co., Ltd.), a reaction product of polyisocyanurate and dipentaerythritol tetraacrylate, which is a reaction product of hexamethylenediamine and isocyanuric acid, acrylic of a phenol novolac type epoxy compound. Acid-modified product (for example, TEA-100; trade name; KES M Co., Ltd.), acrylic acid-modified products of cresol novolak type epoxy compounds (for example, CNEA-100; trade name; KSM Co., Ltd.) and the like can be mentioned.

In the present invention, the compound having a polymerizable double bond is used in an amount of 20 to 150 parts by weight based on 100 parts by weight of the polyesteramidic acid (A). When the compound having a polymerizable double bond is 50 to 120 parts by weight, it is preferable from the viewpoint of adhesion and scratch resistance.

In the present invention, it is more preferable from the viewpoint of scratch resistance to contain 50% by weight or more of the compound having 3 or more polymerizable double bonds per molecule in 100% by weight of the compound having a polymerizable double bond.

1-3-5. Epoxy curing agent The thermosetting composition of the present invention may further contain an epoxy curing agent in order to improve flatness and chemical resistance. As the epoxy curing agent, an acid anhydride-based curing agent, an amine-based curing agent, a phenol-based curing agent, an imidazole-based curing agent, a pyrazole-based curing agent, a triazole-based curing agent, a catalytic curing agent, a sulfonium salt, and a benzothiazo. There are heat-sensitive acid generators such as nium salt, ammonium salt, and phosphonium salt, but an acid anhydride-based curing agent or an imidazole-based curing agent is preferable from the viewpoint of avoiding coloring of the cured film and heat resistance of the cured film. ..

Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride. Examples thereof include aromatic polyvalent carboxylic acid anhydrides such as phthalic anhydride and trimellitic acid anhydride. Among these, trimellitic acid anhydride and hexahydrotrimellitic acid anhydride, which can improve the heat resistance of the cured film without impairing the solubility of the thermosetting composition in a solvent, are particularly preferable.

Specific examples of the imidazole-based curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2,3-dihydro-1H-pyrrolo [1,2- a] Benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-benzyl-2-methylimidazole and 1-benzyl-2-phenylimidazole can be mentioned. Among these, 2-undecylimidazole and 2-phenyl-4-methylimidazole and 1-benzyl-, which can improve the curability of the cured film without impairing the solubility of the thermosetting composition in a solvent. 2-Phenylimidazole is particularly preferred.

The ratio of the epoxy curing agent to the epoxy compound (B) is 0.1 to 60 parts by weight of the epoxy curing agent with respect to 100 parts by weight of the epoxy compound (B). For example, regarding the amount added when the epoxy curing agent is an acid anhydride-based curing agent, more specifically, the carboxylic acid anhydride group or the carboxyl group in the epoxy curing agent is 0.1 to 1.5 times as much as the epoxy group. It is preferable to add it in an equivalent amount. At this time, the carboxylic acid anhydride group is calculated as divalent. It is more preferable to add the carboxylic acid anhydride group or the carboxyl group in an equivalent amount of 0.15 to 0.8 times because the chemical resistance is further improved.

1-3-6. Ultraviolet absorber The thermosetting composition of the present invention may contain an ultraviolet absorber from the viewpoint of improving light resistance.

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 Ltd.).

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

1-3-7. Anti-aggregation agent The thermosetting composition of the present invention may contain an anti-aggregation agent from the viewpoint of blending the solid content with the solvent and preventing aggregation.

Specific examples of the anti-aggregation agent include Disperbake-145, Disperbake-161, Disperbake-162, Disperbake-163, Disperbake-164, Disperbake-182, Disperbake-184, Disperbake-185. , Disper Bake-2163, Disper Bake-2164, BYK-220S, Disper Bake-191, Disper Bake-199, Disper Bake-2015 (all trade names; Big Chemie Japan Co., Ltd.), FTX-218, Footergent 710FM, Futergent 710FS (trade name; Neos Co., Ltd.), Floren G-600, Floren G-700 (trade name; Kyoeisha Chemical Co., Ltd.).

The anti-aggregation agent is used by adding 0.01 to 10 parts by weight with respect to the total amount of the thermosetting composition.

1-3-8. Thermosetting agent The thermosetting composition of the present invention may contain a thermosetting agent from the viewpoint of further improving heat resistance, chemical resistance, in-film uniformity, flexibility, flexibility, and elasticity.

Specific examples of the thermal cross-linking agent include Nicarac MW-30HM, Nicarac MW-100LM, Nicarac MX-270, Nicarac MX-280, Nicarac MX-290, Nicarac MW-390, and Nicarac MW-750LM (all trade names; Sanwa Chemical).

The thermosetting agent is used by adding 0.1 to 10 parts by weight to the total amount of the thermosetting composition.

式（６）において、Ｒ^５は水素又はメチルであり、Ｒ^６〜Ｒ^９は炭素数１〜５のアルキルであり、Ｒ^１０は炭素数１〜１０のアルキルであり、ｍは１〜１０の整数であり、ｎは１〜１５０の整数である。 1-3-9. Membrane surface exposed radical copolymer polymer The thermosetting composition of the present invention comprises a radical polymerizable compound (P1) represented by the following formula (6), a radical polymerizable compound having an alkoxysilyl (P2), and an epoxy. A polymer obtained by radically copolymerizing a radically polymerizable compound (P3) having at least one of carboxyl and hydroxyphenyl (hereinafter, may be referred to as “radical copolymerized polymer”) may be further contained.

In formula (6), R ⁵ is hydrogen or methyl, R ^{6 to} R ⁹ are alkyls having 1 to 5 carbon atoms, R ¹⁰ is an alkyl having 1 to 10 carbon atoms, and m is 1 to 10 carbon atoms. It is an integer, and n is an integer of 1 to 150.

1-3-9-1. Radical polymerizable compound (P1)
Since the radically polymerizable compound (P1) represented by the formula (6) acts as a surfactant, the radical copolymerized polymer acts as a surfactant by using (P1) as a raw material. Flatness, adhesion to the underlying substrate, and coatability are improved without adding a separate surfactant. By adding the radically polymerizable compound (P1), the radical copolymerized polymer is easily exposed on the film surface.

In the present invention, among the radically polymerizable compounds (P1) represented by the formula (6), R ⁵ is hydrogen or methyl, R ^{6 to} R ⁹ are methyl, R ¹⁰ is an alkyl of carbons 1 to 10, and m is 1. Compounds having an integer of ~ 5 and n being an integer of 1 to 150 are preferable. Compounds in which R ⁵ is methyl, R ^{6 to} R ⁹ are methyl, R ¹⁰ is butyl, m is 3, and n is an integer of 1-150 are more preferable, and compounds in which n is an integer of 30 to 70 are even more preferable. , N is an integer of 50 to 70, which is particularly preferable. The weight average molecular weight of the radically polymerizable compound (P1) represented by the formula (6) is preferably 500 to 8,000.

The radically polymerizable compound (P1) can be produced by a known method. Further, a commercially available product may be used. For example, FM-0711, FM-0721, FM-0725 (all trade names; JNC Corporation) and the like can be mentioned.

1-3-9-2. Radical polymerizable compound with alkoxysilyl (P2)
In the present invention, a radically polymerizable compound (P2) having an alkoxysilyl is used as a raw material for obtaining the radical copolymerized polymer. Preferred radically polymerizable compounds (P2) are 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth). ) One or more selected from the group consisting of acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane. Among these, 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane are preferable because they have good flatness. By using (P2), transparency, chemical resistance and the like are improved. In addition, the silane coupling effect improves the adhesion to the base material.

1-3-9-3. Radical polymerizable compound (P3) having at least one of epoxy, carboxyl and hydroxyphenyl
In the present invention, a radically polymerizable compound (P3) having at least one of epoxy, carboxyl, and hydroxyphenyl is used as a raw material for obtaining the radical copolymerized polymer. The preferred radically polymerizable compound (P3) is one or more selected from the group consisting of glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylic acid, and 4-hydroxyphenylvinyl ketone. .. (P3) functions as a cross-linking agent for the polymer and contributes to improvement of heat resistance, chemical resistance and the like.

1-3-9-4. Method for Producing Radical Copolymerization Polymer with Exposed Film Surface The radical copolymerizable polymer with exposed film surface is a radically polymerizable compound (P1) represented by the formula (6), a radically polymerizable compound having an alkoxysilyl (P2), and a radically polymerizable compound (P2). It is obtained by radical polymerization of a radically polymerizable compound (P3) having at least one of epoxy, carboxyl and hydroxyphenyl. The method for producing the radical copolymerized polymer exposed on the film surface is not particularly limited, but the radically polymerizable compounds can be produced by heating in the presence of a radical initiator. As the radical initiator, an organic peroxide, an azo compound or the like can be used. The reaction temperature of the radical copolymerization is not particularly limited, but is usually in the range of 50 ° C. to 150 ° C. The reaction time is also not particularly limited, but is usually in the range of 1 to 48 hours. In addition, the reaction can be carried out under any pressure of pressurization, depressurization or atmospheric pressure.

The solvent used for the above radical copolymerization reaction is preferably a solvent in which the polymer to be produced dissolves. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, and the like. Ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -Ethyl methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2- Methyl oxobutate, ethyl 2-oxobutate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. The solvent may be one of these or a mixture of two or more of them.

The film surface-exposed radical copolymer used in the present invention may be in the form of a solution in which the solvent used for the polymerization is left as it is in consideration of handleability and the like, or a solid in which the solvent is removed in consideration of transportability and the like. It may be a shape.

When the weight average molecular weight of the radical copolymer polymer in which the film surface is exposed is in the range of 1,000 to 50,000 obtained by GPC analysis using polystyrene as a standard, the film forming property is good and it is preferable. Further, when the weight average molecular weight is in the range of 2,500 to 20,000, the flatness of the cured film is good, which is more preferable. Further, when the weight average molecular weight is in the range of 2,500 to 15,000, the flatness and chemical resistance of the cured film are good, which is particularly preferable.

The film surface exposed radical copolymer polymer is used by adding 0.1 to 20 parts by weight based on the total amount of the thermosetting composition.

1-4. Solvent A solvent may be added to the thermosetting composition of the present invention. The solvent arbitrarily added to the thermosetting composition of the present invention is preferably a solvent capable of dissolving polyesteramidic acid (A), epoxy compound (B), additives used as necessary, and the like. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, and the like. Ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -Ethyl methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2- Methyl oxobutate, ethyl 2-oxobutate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. The solvent may be one of these or a mixture of two or more of them.

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. When the storage temperature is −20 ° C. to 10 ° C., there is no precipitate and it is more preferable.

2. 2. Cured film of thermosetting composition In the thermosetting composition of the present invention, polyester amide acid (A), epoxy compound (B), and if necessary, additives and solvents are added, and they are uniformly mixed and dissolved. Can be obtained by doing.

The thermosetting composition prepared as described above (after being dissolved in a solvent in the case of a solid state without a solvent) is applied to the surface of the substrate, and the solvent is removed by heating, for example, to obtain a coating film. Can be formed. For the application of the thermosetting composition to the surface of the substrate, conventionally known methods such as a spin coating method, a roll coating method, a dipping method, a flexographic method, a spray method, and a slit coating method can be used. Next, this coating film is heated (prebaked) on a hot plate or an oven. The heating conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 150 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate.

Then, a cured film can be obtained by heat-treating at 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 to completely cure the coating film. ..

In the cured film thus obtained, when heated, 1) the polyamic acid portion of the polyesteramidic acid (A) is dehydrated and cyclized to form an imide bond, and 2) the carboxylic acid of the polyesteramidic acid (A) is formed. Since it has a high molecular weight by reacting with an epoxy group-containing polymer, it is extremely tough and has excellent adhesion, moisture resistance, transparency, heat resistance, chemical resistance, flatness, and light resistance. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state image pickup device can be manufactured by using the color filter. The cured film of the present invention is effective when used as a transparent insulating film formed between the TFT and the transparent electrode or as a transparent insulating film formed between the transparent electrode and the alignment film, in addition to the protective film for the color filter. .. Further, the cured film of the present invention is also effective when used as a protective film for an LED light emitter or a base film for a coated polarizing plate.

Next, the present invention will be specifically described with reference to synthetic examples, examples, and comparative examples, but the present invention is not limited to these examples. First, a polyesteramidic acid solution composed of reaction products such as tetracarboxylic acid dianhydride, diamine, and polyvalent hydroxy compound was synthesized as shown below (Synthesis Examples 1 to 11).

[Synthesis Example 1] Synthesis of polyester amidoic acid (A1) solution In a four-mouthed flask equipped with a stirrer, dehydration-purified methyl 3-methoxypropionate (hereinafter abbreviated as "MMP"), 3,3', 4,4' -Diphenyl ether tetracarboxylic acid dianhydride (hereinafter abbreviated as "ODPA"), polyesterdiol which is a reaction product of 1,4-butanediol and adipic acid (hereinafter abbreviated as "OD-X-240"), 1, 4-Butandiol and benzyl alcohol were charged in the following weights and stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis).
MMP 50.00g
ODPA 12.75g
OD-X-240 12.33g
1,4-Butanediol 1.11g
Benzyl alcohol 1.78g

Then, the reaction solution was cooled to 25 ° C., 3,3'-diaminodiphenyl sulfone (hereinafter abbreviated as "DDS") and MMP were added in the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then 125. The mixture was stirred at ° C. for 1 hour (second stage of synthesis).
DDS 2.04g
MMP 20.00g

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

The solution was cooled to room temperature to give a 30 wt% solution of pale yellow clear polyester amic acid (A1). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A1) was 5,500.

[Synthesis Example 2] Synthesis of polyester amidoic acid (A2) solution Polyester diol, which is a reaction product of dehydrated and purified MMP, ODPA, 3-methyl-1,5-pentanediol and adipic acid, is placed in a four-mouthed flask equipped with a stirrer. Hereinafter, abbreviated as “OD-X-2420”), 1,4-butanediol and benzyl alcohol were charged in the following weights and stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis).
MMP 50.00g
ODPA 9.03g
OD-X-2420 17.47g
1,4-butanediol 0.79g
Benzyl alcohol 1.26g

Then, the reaction solution was cooled to 25 ° C., DDS and MMP were added under the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then at 125 ° C. for 1 hour (second stage of synthesis).
DDS 1.45g
MMP 20.00g

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

The solution was cooled to room temperature to give a 30 wt% solution of pale yellow clear polyester amic acid (A2). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A2) was 7,400.

[Synthesis Example 3] Synthesis of polyester amidoic acid (A3) solution In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, polycaprolactone triol OD-X-2586, 1,4-butanediol, and benzyl alcohol are placed. The mixture was charged with the following weight and stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis).
MMP 50.00g
ODPA 13.58g
OD-X-2586 11.17g
1,4-Butanediol 1.18g
Benzyl alcohol 1.89g

Then, the reaction solution was cooled to 25 ° C., DDS and MMP were added under the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then at 125 ° C. for 1 hour (second stage of synthesis).
DDS 2.17g
MMP 20.00g

[Z / Y = 3.8, (Y + Z) /X=1.0]

The solution was cooled to room temperature to give a 30 wt% solution of pale yellow clear polyester amic acid (A3). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A3) was 18,100.

[Synthesis Example 4] Synthesis of Polyester Amidic Acid (A4) Solution Dehydrated and purified propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA"), 1,2,3,4-butanetetra in a four-mouthed flask equipped with a stirrer. Carboxylic acid dianhydride (hereinafter abbreviated as "BT-100"), SMA1000P which is a styrene-maleic anhydride copolymer, OD-X-2420, 1,4-butanediol, and benzyl alcohol in the following order by weight. The mixture was charged and stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis).
PGMEA 50.00g
BT-100 2.37g
SMA1000P 11.29g
OD-X-2420 11.97g
1,4-butanediol 0.18g
Benzyl alcohol 3.45g

Then, the reaction solution was cooled to 25 ° C., DDS and PGMEA were added under the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then at 125 ° C. for 1 hour (second stage of synthesis).
DDS 0.74g
PGMEA 20.00g

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

The solution was cooled to room temperature to give a 30 wt% solution of pale yellow clear polyester amic acid (A4). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A4) was 9,400.

[Synthesis Example 5] Synthesis of polyester amidoic acid (A5) solution In a four-necked flask equipped with a stirrer, dehydrated and purified PGMEA, BT-100, SMA1000P, which is a styrene-maleic anhydride copolymer, and 1,6-hexanediol are added. A polyester polyol (hereinafter abbreviated as "OD-X-2640"), which is a reaction product of adipic acid,, 1,4-butanediol, and benzyl alcohol are charged in the following weight in this order, and stirred at 125 ° C. for 2 hours under a dry nitrogen stream. (First stage of synthesis).
PGMEA 50.00g
BT-100 2.37g
SMA1000P 11.29g
OD-X-2640 11.97g
1,4-butanediol 0.18g
Benzyl alcohol 3.45g

Then, the reaction solution was cooled to 25 ° C., DDS and PGMEA were added under the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then at 125 ° C. for 1 hour (second stage of synthesis).
DDS 0.74g
PGMEA 20.00g

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

The solution was cooled to room temperature to give a 30 wt% solution of pale yellow clear polyester amic acid (A5). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A5) was 8,600.

[Synthesis Example 6] Synthesis of polyester amidoic acid (A6) solution In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, OD-X-2420), 1,4-butanediol in this order by weight: The mixture was charged and stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis).
MMP 50.00g
ODPA 7.78g
OD-X-2420 20.07g
1,4-butanediol 0.90g

Then, the reaction solution was cooled to 25 ° C., DDS and MMP were added under the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then at 125 ° C. for 1 hour (second stage of synthesis).
DDS 1.25g
MMP 20.00g

[Z / Y = 4.0, (Y + Z) /X=1.0]

The solution was cooled to room temperature to give a 30 wt% solution of pale yellow clear polyester amic acid (A6). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A6) was 7,400.

[Synthesis Example 7] Synthesis of polyester amidoic acid (A7) solution In a four-necked flask equipped with a stirrer, dehydration-purified MMP, ODPA, OD-X-2586), and 1,4-butanediol are added in the following weight in this order. The mixture was charged and stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis).
MMP 50.00g
ODPA 10.48g
OD-X-2586 17.23g
1,4-butanediol 0.61g

Then, the reaction solution was cooled to 25 ° C., DDS and MMP were added under the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then at 125 ° C. for 1 hour (second stage of synthesis).
DDS 1.68g
MMP 20.00g

[Z / Y = 5.5, (Y + Z) /X=1.3]

The solution was cooled to room temperature to give a 30 wt% solution of pale yellow clear polyester amic acid (A7). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A7) was 23,000.

[Synthesis Example 8] Synthesis of polyester amidoic acid (A8) solution In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, OD-X-2586) and diethylene glycol are charged in the following weight in this order, and a dry nitrogen stream is used. The mixture was stirred at 125 ° C. for 2 hours (first stage of synthesis).
MMP 50.00g
ODPA 12.91g
OD-X-2586 14.14g
Diethylene glycol 0.88g

Then, the reaction solution was cooled to 25 ° C., DDS and MMP were added under the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then at 125 ° C. for 1 hour (second stage of synthesis).
DDS 2.07g
MMP 20.00g

[Z / Y = 4.0, (Y + Z) / X = 0.8]

The solution was cooled to room temperature to give a 30 wt% solution of pale yellow clear polyester amic acid (A8). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A8) was 24,700.

[Synthesis Example 9] Synthesis of polyester amidoic acid (A9) solution In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, 1,4-butanediol, and benzyl alcohol are charged in the following weights, and 125 under a dry nitrogen stream. The mixture was stirred at ° C for 2 hours (first stage of synthesis).
MMP 50.00g
ODPA 20.36g
1,4-Butanediol 3.55g
Benzyl alcohol 2.84g

Then, the reaction solution was cooled to 25 ° C., 3,3'-diaminodiphenyl sulfone (hereinafter abbreviated as "DDS") and MMP were added in the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then 125. The mixture was stirred at ° C. for 1 hour (second stage of synthesis).
DDS 3.26g
MMP 20.00g

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

The solution was cooled to room temperature to give a 30 wt% solution of pale yellow clear polyester amic acid (A9). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A9) was 4,200.

[Synthesis Example 10] Synthesis of polyester amidoic acid (A10) solution In a four-necked flask equipped with a stirrer, dehydrated and purified PGMEA, BT-100, SMA1000P, 1,4-butanediol, and benzyl alcohol are charged in the following weight in this order. The mixture was stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis).
PGMEA 50.00g
BT-100 3.83g
SMA1000P 18.23g
1,4-Butanediol 1.16g
Benzyl alcohol 5.57 g

Then, the reaction solution was cooled to 25 ° C., DDS and PGMEA were added under the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then at 125 ° C. for 1 hour (second stage of synthesis).
DDS 1.20g
PGMEA 20.00g

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

The solution was cooled to room temperature to give a 30 wt% solution of pale yellow clear polyester amic acid (A10). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A10) was 13,000.

[Synthesis Example 11] Synthesis of polyester amidoic acid (A11) solution In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, and 1,4-butanediol are charged in the following order by weight and at 125 ° C. under a dry nitrogen stream. The mixture was stirred for 2 hours (first stage of synthesis).
MMP 50.00g
ODPA 21.54g
1,4-Butanediol 5.01g

Then, the reaction solution was cooled to 25 ° C., DDS and MMP were added under the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then at 125 ° C. for 1 hour (second stage of synthesis).
DDS 3.45g
MMP 20.00g

[Z / Y = 4.0, (Y + Z) /X=1.0]

The solution was cooled to room temperature to give a 30 wt% solution of pale yellow clear polyester amic acid (A11). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A11) was 5,200.

Tables 1-1 and 1-2 show the charged amounts of the compounds of Synthesis Examples 1 to 11 and the reaction conditions.

Next, an epoxy group-containing polymer that can be used as the epoxy compound (B) was synthesized as shown below (Synthesis Examples 12 to 14).

[Synthesis Example 12] Synthesis of Epoxide Group-Containing Polymer (B1) Solution PGMEA dehydrated and purified as a polymerization solvent and glycidyl methacrylate as a radically polymerizable compound having an epoxy group are charged into a four-necked flask equipped with a stirrer by the following weights. Further, dimethyl-2,2'-azobis (2-methylpropionate) (V-601; trade name; Wako Pure Chemical Industries, Ltd.) was charged as a polymerization initiator under the following weight, and the temperature was 110 ° C. under a dry nitrogen stream. Was stirred for 2 hours.
PGMEA 31.50g
Glycidyl methacrylate 13.50 g
V-601 1.35g

The solution was cooled to room temperature to give a 30 wt% solution of the epoxy group-containing polymer (B1). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained epoxy group-containing polymer (B1) was 3,900.

[Synthesis Example 13] Synthesis of Epoxide Group-Containing Polymer (B2) Solution MMP dehydrated and purified as a polymerization solvent, glycidyl methacrylate as a radically polymerizable compound having an epoxy group, and an epoxy group are contained in a four-necked flask equipped with a stirrer. Diethylene glycol dimethacrylate was charged as a non-radical polymerizable compound by the following weight, and V-601 was charged as a polymerization initiator by the following weight, and the mixture was stirred at 110 ° C. for 2 hours under a dry nitrogen stream.
MMP 31.50g
Glycidyl methacrylate 12.15g
Diethylene glycol dimethacrylate 1.35g
V-601 2.03g

The solution was cooled to room temperature to give a 30 wt% solution of the epoxy group-containing polymer (B2). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained epoxy group-containing polymer (B2) was 4,000.

[Synthesis Example 14] Synthesis of Epoxide Group-Containing Polymer (B3) Solution MMP dehydrated and purified as a polymerization solvent, glycidyl methacrylate as a radically polymerizable compound having an epoxy group, and an epoxy group are contained in a four-necked flask equipped with a stirrer. N-cyclohexylmaleimide was charged as a non-radical polymerizable compound under the following weight, and V-601 was charged as a polymerization initiator at the following weight, and the mixture was stirred at 110 ° C. for 2 hours under a dry nitrogen stream.
MMP 31.50g
Glycidyl methacrylate 12.15g
N-cyclohexylmaleimide 1.35g
V-601 2.03g

The solution was cooled to room temperature to give a 30 wt% solution of the epoxy group-containing polymer (B3). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained epoxy group-containing polymer (B3) was 3,800.

Table 2 shows the charged amounts of the compounds of Synthesis Examples 12 to 14, reaction conditions, and the like.

[Example 1]
A 500 ml separable flask equipped with a stirring blade was substituted with nitrogen, and 100.0 g of the polyesteramidic acid (A1) solution obtained in Synthesis Example 1 as polyesteramic acid (A) was added to the flask as the epoxy compound (B). 60.0 g of TECHMORE VG3101L (trade name; Printec Co., Ltd.), 0.3 g of Megafuck DS-21 (trade name; DIC Co., Ltd.) as a surfactant, and COATOSIL MP200 (trade name; Momentive Co., Ltd.) as a coupling agent. Performance Materials Japan LLC) 4.8 g, ADK STAB AO-60 (trade name; ADEKA Co., Ltd.) as an antioxidant, 0.2 g, Trimellitic acid anhydride (hereinafter, "TMA") as an epoxy curing agent. ”) 6.0 g, 2-undecylimidazole 0.2 g, PGMEA dehydrated and purified as a solvent as a solvent, 445.9 g, and propylene glycol monomethyl ether (hereinafter abbreviated as“ PGME ”) 57.4 g. , Stirred at room temperature for 3 hours to dissolve uniformly.
Then, it was filtered through a membrane filter (0.1 μm) to prepare a thermosetting composition.

[Examples 2 to 21]
According to the method of Example 1, each component was mixed and dissolved at the ratios shown in Tables 3-1 and 3-2 to obtain a thermosetting resin composition.

[Method of manufacturing glass substrate for evaluation]
The prepared thermosetting composition was spin-coated on a glass substrate for 10 seconds and prebaked on a hot plate at 100 ° C. for 2 minutes. Further, it was post-baked in an oven at 230 ° C. for 30 minutes to obtain a glass substrate with a cured film having a film thickness of 1.5 μm.

[Method of manufacturing color filter substrate for evaluation]
The prepared thermosetting composition was spin-coated on a color filter substrate for 10 seconds and prebaked on a hot plate at 100 ° C. for 2 minutes. Further, it was post-baked in an oven at 230 ° C. for 30 minutes to obtain a color filter substrate with a cured film having a film thickness of 1.5 μm. The color filter substrate used is a pigment dispersion color filter using a resin black matrix having a maximum step between the central portions of R, G, and B pixels (hereinafter, abbreviated as step between pixels) of 0.12 μm.

The cured film thus obtained was evaluated for its adhesiveness, hygroscopicity, flatness, and transparency by the method described below. The results are shown in Table 4.

[Evaluation method of substrate adhesion]
A pressure cooker test was carried out on the obtained glass substrate with a cured film and a color filter substrate, and then the adhesion to the substrate was confirmed by a cross-cut test. A PLAMOUNT PM40 (trade name; Hitachi, Ltd.) was used for the pressure cooker test, and the test was carried out for 24 hours under the conditions of a temperature of 120 ° C., a humidity of 100%, and a pressure of 0.2 MPa. For the cross-cut test, cellophane film tape No. 610 (trade name; 3M Japan Ltd.) was used.

The judgment of adhesion is 0; no peeling, 1; peeling within 5% with respect to the area of the cross-cut portion, 2; peeling within 15% with respect to the area of the cross-cut portion, 3; the cross-cut portion. Peeling within 35% with respect to the area of 4; peeling of 35% or more with respect to the area of the cross-cut portion was evaluated on a 5-point scale.

[Evaluation method of sealant adhesion]
A sealant (KAYATORON U-1400; trade name; Kyoritsu) in which 1.0 wt% of 5.0 μm beads (Micropearl SP-205; trade name; Sekisui Chemical Industry Co., Ltd.) is mixed with the obtained glass substrate with a cured film. (Chemical Co., Ltd.) was adhered in an amount of 0.2 mg, a glass substrate was placed on the glass substrate, and then the glass substrate was cured under predetermined curing conditions while being fixed. A indentation test of a sample prepared using a small tabletop tester EZ Graph (trade name; Shimadzu Corporation) was performed, and the indentation amount (N; Newton) required for the sealant to peel off was measured.

[Evaluation method of hygroscopicity]
10.0 mg of the thermosetting resin was scraped off from the obtained glass substrate with a cured film and put into an aluminum pan. Weight loss when heated from 30 ° C to 150 ° C at a rate of 10 ° C / min and then held at 150 ° C for 20 minutes using a thermogravimetric measuring device (TG-DTA 8120; trade name; Rigaku Co., Ltd.) Was measured.

[Evaluation method of flatness]
The step between pixels of the obtained color filter substrate with a cured film was measured using a step / surface roughness / fine shape measuring device (P-17; trade name; KLA; TENCOR Co., Ltd.).

[Transparency evaluation method]
In the obtained glass substrate with a cured film, the transmittance of the light of the cured film alone at a wavelength of 400 nm was measured by an ultraviolet-visible near-infrared spectrophotometer (V-670; trade name; JASCO Corporation).

As is clear from the results shown in Table 4, the cured film of the composition using the polyesteramidic acid (A) containing the polyvalent hydroxy compound selected from the polyester polyol and the polycaprolactone polyol has excellent adhesion and moisture absorption. Good results were obtained with all the properties including flatness and transparency.

The cured film obtained from the heat-curable composition of the present invention is excellent in adhesion, moisture absorption, and transparency, which is a characteristic required as an optical material, and thus is a color filter, an LED light emitting element, and a light receiving element. It can be used as a protective film for various optical materials such as, and as a transparent insulating film formed between a TFT and a transparent electrode and between a transparent electrode and an alignment film.

Claims (10)

A thermosetting composition comprising a polyester amic acid (A) and an epoxy compound (B).
The polyesteramide acid (A) is an X-mol tetracarboxylic dianhydride, a Y-mol diamine and a Z-mol polyvalent hydroxy compound, such that the following formulas (1) and (2) are established. It is a reaction product from the raw material contained in the ratio,

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

The raw material component of the polyesteramidic acid (A) further contains a monohydroxy compound, and the raw material component is further contained.
The polyvalent hydroxy compound contains at least one selected from a polyester polyol and a polycaprolactone polyol, and the proportion of the polyester polyol and the polycaprolactone polyol in the polyvalent hydroxy compound is 25 mol% or more. thing. The thermosetting composition according to claim 1, wherein the polyester amic acid (A) contains 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. The thermosetting composition according to claim 1, wherein the polyester polyol and the polycaprolactone polyol have a weight average molecular weight of less than 5,000. The polyester polyols are ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2 A reaction product from adipic acid with at least one selected from -methyl-1,3-propanediol and 3-methyl-1,5-pentanediol.
The thermosetting composition according to any one of claims 1 to 3 , wherein the polycaprolactone polyol is at least one selected from polycaprolactone diol and polycaprolactone triol. A thermosetting composition comprising a polyester amic acid (A) and an epoxy compound (B).
The polyesteramide acid (A) is an X-mol tetracarboxylic dianhydride, a Y-mol diamine and a Z-mol polyvalent hydroxy compound, such that the following formulas (1) and (2) are established. It is a reaction product from the raw material contained in the ratio,

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

The polyvalent hydroxy compound contains at least one selected from a polyester polyol and a polycaprolactone polyol, and the proportion of the polyester polyol and the polycaprolactone polyol in the polyvalent hydroxy compound is 25 mol% or more. thing.
However, the tetracarboxylic acid dianhydride is 3,3', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2, 2- [Bis (3,4-dicarboxyphenyl)] Hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and ethylene glycol bis (anhydrotrimeritate) At least one
The diamine is at least one selected from 3,3'-diaminodiphenyl sulfone and bis [4- (3-aminophenoxy) phenyl] sulfone.
Polyvalent hydroxy compounds other than the polyester polyol and the polycaprolactone polyol are ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane. Acrylate, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, tris isocyanurate (2-) Hydroxyethyl), 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethanol, glycerin mono (meth) acrylate, trimethylol propane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, Pentaerythritol di (meth) acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate , Solbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, 4,4'-isopropylidenebis (2-phenoxyethanol), (meth) acrylic acid modified product of ethylene glycol diglycidyl ether, (Meta) 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 glycerin diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether. ) Acrylate-modified product, propylene oxide-modified bisphenol A diglycidyl ether (meth) acrylic acid-modified product, and (meth) acrylic acid-modified product of a compound containing two or more epoxy groups per molecule. be. The monohydroxy compound is isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, 3-ethyl-3-hydroxymethyloxetane, furfuryl alcohol, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-. 3-Phenoxypropyl (meth) acrylate, (meth) acrylic acid 4-hydroxyphenyl, p-hydroxy (meth) acrylic anilide, 1,4-cyclohexanedimethanol mono (meth) acrylate, (meth) acrylic acid 3- (2) -Hydroxyphenyl), glycerindi (meth) acrylate, trimethylpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and compounds containing one epoxy group per molecule. The thermosetting composition according to claim 1 , which is at least one selected from (meth) acrylic acid modified products. The thermosetting composition according to any one of claims 1 to 6 , wherein the polyesteramidic acid (A) has a weight average molecular weight of 1,000 to 200,000. The thermosetting composition according to any one of claims 1 to 7 , wherein the content of the epoxy compound (B) is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amic acid (A). .. A cured film obtained from the thermosetting composition according to any one of claims 1 to 8. A color filter having the cured film according to claim 9 as a transparent protective film.