TWI663187B - Thermosetting compositions, cured films, color filters, liquid crystal display elements, solid-state imaging elements and led luminous bodies - Google Patents

Abstract

The present invention is a thermosetting composition, which comprises polyester amidate, a polymer containing an epoxy group, an epoxy compound, and an epoxy hardener. Anhydride, diamine, and polyhydroxy compound are necessary raw material components to be obtained by reaction. The epoxy group-containing polymer is obtained by using glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw materials. The components are obtained by reaction. The thermosetting composition of the present invention is excellent in coatability, and the cured film formed from the thermosetting composition of the present invention is particularly excellent in light resistance and flatness, and is excellent in heat resistance, solvent resistance, acid resistance, and alkali resistance. It is also excellent in chemical resistance, water resistance, adhesion to base substrates such as glass, transparency, and scratch resistance.

Description

Thermosetting composition, cured film, color filter, liquid crystal display element, solid-state imaging element, and light-emitting diode light-emitting body

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

In the manufacturing steps of elements such as liquid crystal display elements, various chemicals such as organic solvents, acids, and alkali solutions are sometimes treated, or when a wiring electrode is formed by sputtering, the surface is locally heated to a high temperature. Therefore, in order to prevent deterioration, damage, and deterioration of the surface of various elements, a surface protective film may be provided. These protective films are required to have characteristics that can withstand various processes in the manufacturing steps described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to a base substrate such as glass, transparency, and scratch resistance are required. Damage, coating, flatness, light resistance, etc. In addition, under the current situation of increasing performance such as high viewing angle, high-speed response, and high definition of liquid crystal display elements, when used as a color filter protective film, materials having improved planarization characteristics are desired.

Regarding light resistance, it has hitherto been important to perform ultraviolet (UV) ozone treatment for cleaning the surface of the protective film. However, especially in recent years, in order to improve the coating property of a photo spacer in a color filter protective film for a transverse electric field mode, higher-energy ultraviolet ozone treatment has been required, and polymerization has increased. In photo-polymerization steps such as Polymer Sustained Alignment (PSA) mode or ultraviolet exposure steps such as photo-alignment steps of alignment films, light resistance becomes a very important characteristic.

As a protective film material having these excellent characteristics, there are a polyfluorinated acid composition containing silicon (see Patent Document 1) and a polyester fluorinated acid composition (see Patent Documents 2 and 3). The polyamic acid composition containing silicon is a very excellent material in terms of flatness, but has the disadvantages of insufficient heat resistance and poor alkali resistance. The polyester amidate composition of patent document 2 has the disadvantage that flatness and heat resistance are insufficient. The polyester amidate composition of Patent Document 3 is a material having excellent flatness, heat resistance, and chemical resistance, but has the disadvantages that the light resistance is insufficient, and the transparency is reduced in the ultraviolet ozone treatment or the ultraviolet exposure step. . Therefore, as the protective film material, none of the above materials satisfies light resistance, flatness, heat resistance, chemical resistance, and other characteristics.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 9-291150

[Patent Document 2] Japanese Patent Laid-Open No. 2005-105264

[Patent Document 3] Japanese Patent Laid-Open No. 2008-156546

The object of the present invention is to provide chemical resistance, water resistance, acid resistance, alkali resistance, and other chemical resistance, water resistance, adhesion to base substrates such as glass, transparency, scratch resistance, and coating properties. In particular, a cured film excellent in flatness and light resistance and an electronic component including a composition providing the cured film.

The present inventors conducted diligent research in order to solve the above problems, and as a result, they found that the object can be achieved by the following composition and a cured film obtained by curing the composition, and have completed the present invention. The product includes polyester amidate, an epoxy-containing polymer, and an epoxy hardener. The polyester amidate is obtained by a reaction of a compound containing a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound. The epoxy group-containing polymer is obtained by reacting glycidyl (meth) acrylate and a bifunctional (meth) acrylate as essential raw material components.

The present invention includes the following configurations.

[1] A thermosetting composition, which is a composition comprising polyester amidate, a polymer containing an epoxy group, an epoxy compound, and an epoxy hardener, wherein the polyester amidate is By using tetracarboxylic dianhydride, diamine, and polyhydroxy compound It is obtained by reacting the necessary raw material components. Polyesteramine is obtained by making the X mol tetracarboxylic dianhydride, the Y mol diamine, and the Z mol polyhydric hydroxy compound into the following formula (1) and formula (2) The ratio of the relationship established is obtained by reaction, and has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4); the epoxy group-containing polymer is (meth) acrylic acid Glycidyl ester and bifunctional (meth) acrylate are obtained by reacting as essential raw material components, and the weight average molecular weight is 1,000 to 50,000; the epoxy compound contains 2 to 10 epoxy groups per molecule, and the weight average The molecular weight is less than 3,000; the total amount of the epoxy-containing polymer and the epoxy compound is 20 to 400 parts by weight based on 100 parts by weight of the polyester amidamic acid, and the epoxy-containing polymer and the epoxy compound are total The total amount of the compound is 100 parts by weight, and the epoxy hardener is 0.1 to 60 parts by weight; 0.2 ≦ Z / Y ≦ 8.0… (1)

0.2 ≦ (Y + Z) /X≦5.0… (2)

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

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

[3] The thermosetting composition according to [2], wherein the monohydroxy compound is selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl One or more types of 3-hydroxymethyloxetane.

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

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

[6] The thermosetting composition according to [1] or [2], wherein the tetracarboxylic dianhydride is selected from 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3 , 3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4- One or more types of butanetetracarboxylic dianhydride and ethylene glycol bis (anhydrotrimellitate).

[7] The thermosetting composition according to [1] or [2], wherein the diamine is selected from 3,3'-diaminodiphenylphosphonium and bis [4- (3-aminophenoxy) Group) One or more kinds of phenyl] fluorene.

[8] The thermosetting composition according to [1] or [2], wherein the polyhydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1 One or more of 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and tris (2-hydroxyethyl) isocyanurate.

[9] The thermosetting composition according to [1] or [2], wherein the bifunctional (meth) acrylate is selected from ethylene glycol di (meth) acrylate and diethylene glycol di (methyl) Base) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane One or more types of alkanedimethanol di (meth) acrylate.

[10] The thermosetting composition according to [1] or [2], wherein the epoxy group-containing polymer is obtained by further including a raw material component selected from glycidyl (meth) acrylate and a bifunctional ( It is obtained by reacting a radically polymerizable monomer other than a compound of the group consisting of a meth) acrylate.

[11] The thermosetting composition according to [10], which is a radically polymerizable monomer other than a compound selected from the group consisting of glycidyl (meth) acrylate and a bifunctional (meth) acrylate The body is selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid 2-Hydroxyethyl, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, ethylene Triethoxysilane, (meth) acryloxypropyl-3-trimethylsilyl Alkoxysilane, (meth) acryloxyorganopolysiloxane, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetrahydrofurfur (meth) acrylate Ester, γ-butyrolactone (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, (meth) acrylic acid-2,2,2-trifluoroethyl One or more of esters, (meth) acrylic acid, and 4-hydroxyphenylvinyl ketone.

[12] The thermosetting composition according to [1] or [2], wherein the epoxy compound is selected from 3,4-epoxycyclohexanecarboxylic acid-3 ', 4'-epoxycyclohexylmethyl Ester, 2- [4- (2,3-glycidoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-glycidoxy] phenyl) )] Ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-glycidyloxy) phenyl] -1- [4- [1- [4- A mixture of (2,3-glycidoxyphenyl) -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol, and 2- [4- (2,3- Glycidoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-glycidoxy] phenyl)] ethyl] phenyl] propane the above.

[13] The thermosetting composition according to [1] or [2], wherein the epoxy hardener is one or more members selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole.

[14] The thermosetting composition according to [1], wherein the tetracarboxylic dianhydride is selected from 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 1,2,3 One or more of 1,4-butanetetracarboxylic dianhydride; diamine is 3,3'-diaminodiphenylphosphonium; polyhydroxy compound is 1,4-butanediol; polymer containing epoxy group The reaction is based on glycidyl methacrylate, diethylene glycol dimethacrylate and tetrahydrofurfuryl methacrylate as raw materials. The obtained copolymer having a weight average molecular weight of 1,000 to 50,000; the epoxy compound is 3,4-epoxycyclohexanecarboxylic acid-3 ', 4'-epoxycyclohexyl methyl ester; the epoxy hardener is selected from trimellitic anhydride And one or more kinds of 2-undecylimidazole; and one or more kinds selected from methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent.

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

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

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

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

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

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

[21] A light emitting diode (Light Emitting Diode, LED) light emitting body using the cured film as described in [15] as a protective film.

The thermosetting composition according to a preferred embodiment of the present invention is flat and A material having particularly excellent light resistance can improve display quality and reliability when used as a color filter protective film for a color liquid crystal display element. Furthermore, the cured film obtained by heating the thermosetting composition according to the preferred embodiment of the present invention is also balanced in terms of transparency, chemical resistance, adhesion, and sputtering resistance, and has extremely high practicality. In particular, it is effectively used as a protective film for a color filter manufactured by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. It can also be used as a protective film and a transparent insulating film of various optical materials.

Thermosetting composition

The thermosetting composition of the present invention includes polyester amidine (the polyester amidate is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound as essential raw material components), containing Epoxy group-containing polymer (the epoxy group-containing polymer is obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw materials), an epoxy compound And an epoxy hardener composition, characterized in that the epoxy compound is 20 parts by weight to 400 parts by weight relative to 100 parts by weight of polyester glutamic acid, and 100 parts by weight relative to an epoxy-containing polymer, The epoxy hardener is 0.1 to 60 parts by weight. The thermosetting composition of the present invention may further contain components other than those described above within a range in which the effects of the present invention are obtained.

1-1. Polyesteramine

Polyester amidate is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound as essential raw material components. More specifically, the reaction is carried out by reacting a X mol tetracarboxylic dianhydride, a Y mol diamine, and a Z mol polyhydroxy compound at a ratio where the relationship of the following formula (1) and formula (2) is established. obtain.

0.2 ≦ Z / Y ≦ 8.0… (1)

0.2 ≦ (Y + Z) /X≦5.0… (2)

The polyester amidate has a structural unit represented by the following 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 a tetracarboxylic dianhydride, and is preferably an organic group having 2 to 30 carbon atoms. R ² is a residue obtained by removing two -NH ₂ from the diamine, and is preferably an organic group having 2 to 30 carbon atoms. R ³ is a residue obtained by removing two -OH groups from a polyhydroxy compound, and is preferably an organic group having 2 to 20 carbon atoms.

At least a solvent is required for the synthesis of polyester glutamic acid. The solvent can be left as it is, and it can be made into a liquid or gel-like thermosetting composition in consideration of handling properties, or the solvent can be removed and made into consideration. To a solid composition such as portability. Moreover, the synthesis | combination of polyester glutamic acid may contain 1 or more types of compounds selected from a monohydroxy compound and a styrene-maleic anhydride copolymer as a raw material as needed, Among these, it is preferable to contain a monohydroxy compound. Moreover, the synthesis | combination of polyester glutamic acid can also contain other compounds as mentioned above as a raw material as needed, without impairing the objective of this invention. Examples of such other raw materials include silicon-containing monoamines.

1-1-1. Tetracarboxylic dianhydride

In the present invention, the material used to obtain polyester amidate is tetracarboxylic dianhydride. Specific examples of the preferred tetracarboxylic dianhydride include 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride Anhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2 ', 3,3 '-Diphenylphosphonium tetracarboxylic dianhydride, 2,3,3', 4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dicarboxylic acid Anhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3 (3 , 4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100 , Nippon Physico Chemical Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, ethane tetra Carboxylic dianhydride and butanetetracarboxylic dianhydride. One or more of these tetracarboxylic dianhydrides can be used.

Among these tetracarboxylic dianhydrides, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride and 3,3', 4,4'-diphenyl ether tetra, which provide good transparency, are more preferred. Carboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and TMEG-100, especially Preferred are 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride and 1,2,3,4-butane Alkyltetracarboxylic dianhydride.

1-1-2. Diamine

In the present invention, a diamine is used as a material for obtaining polyester amidate. Specific examples of preferred diamines include 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 3,4'-diaminodiphenylphosphonium, and bis [ 4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [3- (4-aminophenoxy) phenyl]碸, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] 碸, [4- (3-aminophenoxy) phenyl] [ 3- (4-aminophenoxy) phenyl] fluorene, and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane. One or more of these diamines can be used.

Among these diamines, 3,3'-diaminodiphenylfluorene and bis [4- (3-aminophenoxy) phenyl] fluorene which provide good transparency are more preferable, and 3,3'- Diaminodiphenylphosphonium.

1-1-3. Polyhydroxy compounds

In the present invention, a polyhydroxy compound is used as a material for obtaining polyester amidate. Specific examples of preferred polyhydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, and tetraethylene glycol. Propylene glycol, polypropylene glycol with a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentane Alcohol, 1,5-pentanediol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanedidiol Alcohol, 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-octantriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1, 2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerol, trimethylol Propane, pentaerythritol, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxy Phenyl) ii), bisphenol F (bis (4-hydroxyphenyl) methane), diethanolamine, and triethanolamine. One or more of these polyhydroxy compounds can be used.

Among these polyhydric hydroxy compounds, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- Heptanediol, 1,8-octanediol, and tris (2-hydroxyethyl) isocyanurate, particularly 1,4-butanediol, 1,5-pentanediol, and 1,6- Hexanediol.

1-1-4. Monohydroxy compounds

In the present invention, a monohydroxy compound can be used as a material for obtaining polyester amidate. By using a monohydroxy compound, the storage stability of a thermosetting composition can be improved. Specific examples of preferred monohydroxy compounds include methanol, ethanol, 1-propanol, isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, and dipropylene glycol monoethyl ether. , Dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, phenol, borneol, maltol, Linalol, terpineol, dimethyl benzylcarbinol and 3- Ethyl-3-hydroxymethyloxetane. One or more of these monohydroxy compounds can be used.

Among these monohydroxy compounds, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane are more preferable. Considering the compatibility of the polyester amidate formed using these monohydroxy compounds with epoxy-containing polymers, epoxy compounds, and epoxy hardeners, or the thermosetting composition in color filters For coating properties on optical sheets, benzyl alcohol is particularly preferably used as the monohydroxy compound.

The reaction is preferably performed with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyhydroxy compound, and containing 0 to 300 parts by weight of a monohydroxy compound. It is more preferably 5 parts by weight to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer

In addition, the polyester amidine used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups to the raw material. It is preferable to perform transparency as mentioned above because transparency can be improved. Examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. As for the ratio of each component constituting the styrene-maleic anhydride copolymer, the molar ratio of styrene / maleic anhydride is 0.5 to 4, and preferably 1 to 3. Furthermore, 1 or 2 is more preferable, and 1 is especially preferable.

Specific examples of the styrene-maleic anhydride copolymer include SMA3000P, SMA2000P, and SMA1000P (all are trade names; Sichuan Crude Chemical Co., Ltd.). Among these commercially available products, SMA1000P having good heat resistance and alkali resistance is particularly preferred.

It is preferably used in combination with tetracarboxylic dianhydride, diamine, and polyhydroxy compound. 100 parts by weight is measured to contain 0 to 500 parts by weight of a styrene-maleic anhydride copolymer. It is more preferably 10 to 300 parts by weight.

1-1-6. Silicon monoamine

In the synthesis of polyester glutamic acid, other raw materials other than those described above may be included as raw materials, as long as the object of the present invention is not impaired. Examples of such other raw materials include silicon-containing monoamines.

Specific examples of the preferred silicon-containing monoamine used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropylmethyldiamine. Methoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethyl Oxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane , M-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. One or more of these silicon-containing monoamines can be used.

Among these silicon-containing monoamines, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane, which are excellent in acid resistance of the coating film, are more preferable, and from the viewpoint of acid resistance and compatibility, they are particularly preferable. 3-aminopropyltriethoxysilane.

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

1-1-7. Solvents used in the synthesis of polyester amidine

Specific examples of the solvent used in the synthesis reaction for obtaining the polyester amidate may be Examples include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether B Acid esters, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamidine amine. Among these solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ethyl ether is preferable.

1-1-8. Synthesis method of polyester lysine

The method for synthesizing the polyester sulfamic acid used in the present invention is to react a tetracarboxylic dianhydride X mole, a diamine Y mole, and a polyhydroxy compound Z mole in the solvent. In this case, X, Y, and Z are preferably set to a ratio in which the relationship of the following formula (1) and formula (2) is established between these X, Y, and Z. If the content is within this range, the solubility of the polyester amidino acid in the solvent is high, so that the coating property of the composition is improved, and as a result, a cured film having excellent flatness can be obtained.

0.2 ≦ Z / Y ≦ 8.0… (1)

0.2 ≦ (Y + Z) /X≦5.0… (2)

In the formula (1), 0.7 ≦ Z / Y ≦ 7.0 is preferred, and 1.0 ≦ Z / Y ≦ 5.0 is more preferred. Further, in the formula (2), 0.5 ≦ (Y + Z) /X≦4.0 is preferred, and 0.6 ≦ (Y + Z) /X≦2.0 is more preferred.

The polyester amidine used in the present invention is a component having an amine group or a hydroxyl group at the terminal under the reaction conditions described above under conditions where X is excessively used with respect to Y + Z. The molecule is more excessively generated to have a molecule having an acid anhydride group (-CO-O-CO-) at the terminal. When reacting with such a monomer structure, in order to react with an acid anhydride group at the molecular terminal to esterify the terminal, the monohydroxy compound may be added as necessary. The polyester glutamic acid obtained by adding a monohydroxy compound for reaction can improve compatibility with epoxy compounds and epoxy hardeners, and can improve coatability of the thermosetting composition of the present invention containing these compounds.

Further, when the reaction is performed with the above-mentioned monomer configuration, a silicon-containing monoamine may be added in order to introduce a silane group at the terminal in order to react with an acid anhydride group at the molecular terminal. The use of the thermosetting composition of the present invention containing a polyester amidic acid obtained by adding a silicon-containing monoamine to a reaction can improve the acid resistance of the resulting coating film. In the case where the reaction is carried out with the configuration of the monomer, both a monohydroxy compound and a silicon-containing monoamine may be added to perform the reaction.

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

The order in which the reaction raw materials are added to the reaction system is not particularly limited. That is, any of the following methods can be used: tetracarboxylic dianhydride is simultaneously added to the reaction solvent with the diamine and the polyhydroxy compound; the diamine and the polyhydroxy compound are dissolved in the reaction solvent, and then the tetracarboxylic dianhydride is added. After the tetracarboxylic dianhydride and the polyhydroxy compound are reacted in advance, a diamine is added to the reaction product; or after the tetracarboxylic dianhydride and the diamine are reacted in advance, a polyhydroxy compound is added to the reaction product.

In the case of reacting the silicon-containing monoamine, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyhydroxy compound is completed, the reaction solution is cooled to 40 ° C or lower, and then the silicon-containing monoamine is added at 10 ° C. It is appropriate to react at ~ 40 ° C for 0.1 to 6 hours. Moreover, a monohydroxy compound may be added at an arbitrary time point of the reaction.

The polyester amidine synthesized as described above includes the structural unit represented by the formula (3) and the structural unit represented by the formula (4), and its terminal is derived from tetracarboxylic dianhydride and dicarboxylic acid as raw materials. An acid anhydride group, an amine group, or a hydroxyl group of an amine or a polyhydroxy compound, or an additive other than these compounds constitutes a terminal thereof. By including such a structure, hardenability becomes favorable.

The weight average molecular weight of the obtained polyester amidine is preferably 1,000 to 200,000, and more preferably 3,000 to 50,000. If it exists in these ranges, flatness and heat resistance will become favorable.

The weight average molecular weight in this specification is a polystyrene conversion value calculated | required by the Gel Permeation Chromatography (GPC) method (column temperature: 35 degreeC, flow rate: 1 ml / min). Standard polystyrene uses polystyrene with a molecular weight of 645 ~ 132900 (such as the Agilent Technologies polystyrene calibration kit PL2010-0102), and the column uses PLgel MIXED-D ( (Agilent Technology Co., Ltd.), Tetrahydrofuran (THF) can be used as the mobile phase for measurement. In addition, the weight average molecular weight of the commercial item in this specification is a catalogue value.

1-2. Epoxy-containing polymers

The epoxy group-containing polymer used in the present invention is obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw material components. The epoxy group-containing polymer is not particularly limited as long as it has good compatibility with other components forming the thermosetting composition of the present invention. Moreover, the bifunctional (meth) acrylate which reacts with glycidyl (meth) acrylate may be 1 type, and may be 2 or more types.

The thermosetting composition of the present invention containing an epoxy-group-containing polymer obtained by using one type of glycidyl (meth) acrylate as a raw material monomer has the advantage of transparency of a cured film obtained therefrom. When it becomes high, the fall of transparency in a ultraviolet ozone treatment process or a ultraviolet exposure process can be suppressed. From the viewpoints of flatness, heat resistance, and chemical resistance, it is preferable to contain 40 parts by weight to 99 parts by weight of glycidyl (meth) acrylate in all of the monomers that serve as a raw material for the epoxy group-containing polymer. .

Preferred examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate. , 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate. These examples are preferable because the epoxy group-containing polymer obtained by reacting with glycidyl (meth) acrylate has good compatibility with polyester amidate. From the viewpoints of flatness, heat resistance, and chemical resistance, it is preferable to contain 1 to 30 parts by weight of a bifunctional (meth) acrylate in all of the monomers that serve as a raw material for the epoxy group-containing polymer. .

The monomer which becomes the raw material of the epoxy group-containing polymer may include A radical polymerizable monomer other than a compound of the group consisting of glycidyl (meth) acrylate and a bifunctional (meth) acrylate is used as a raw material component. In this specification, such a monomer is called "other radically polymerizable monomer." From the viewpoint of exhibiting the characteristics of the other radically polymerizable monomer without impairing the effects of the present invention, it is preferable to contain 0 parts by weight to all the monomers that are the raw material of the epoxy-containing polymer. 40 parts by weight of other radical polymerizable monomers.

Specific examples of other radical polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic ring Hexyl ester, 2-hydroxyethyl (meth) acrylate, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, (meth) acryloxypropyl-3-trimethylsilyloxysilane, (meth) acryloxyorganopolysiloxane, Dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, γ-butyrolactone (meth) acrylate, N-cyclohexyl Maleimide, N-phenylmaleimide, -2,2,2-trifluoroethyl (meth) acrylate, (meth) acrylic acid, 4-hydroxyphenylvinyl ketone, and the like.

The other radical polymerizable monomers may be one type or two or more types.

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

1-2-1. Solvents used in the synthesis of epoxy-containing polymers

The synthesis of an epoxy-group-containing polymer obtained by reacting glycidyl (meth) acrylate and a bifunctional (meth) acrylate as an essential raw material component requires at least a solvent.

Specific examples of the solvent used in the polymerization reaction for obtaining an epoxy group-containing polymer include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and diethyl ether. Glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclic Hexanone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide. Among these solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ethyl ether are preferable.

These solvents can be used alone or as a mixed solvent of two or more kinds. Moreover, if it is a ratio of 30 weight% or less with respect to the total amount of a solvent, you may mix and use other solvents other than the said solvent.

1-2-2. Synthesis method of epoxy-containing polymer

The method for synthesizing the epoxy group-containing polymer is not particularly limited, but radical polymerization in a solution using a solvent is preferred. If a reaction solvent of 100 parts by weight or more is used with respect to 100 parts by weight of the total of glycidyl (meth) acrylate, bifunctional (meth) acrylate, and other radical polymerizable monomers used as necessary, The reaction proceeds smoothly and is therefore preferred. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated from the polymerization initiator to be used, and is usually in the range of 50 ° C to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 1 hour to 24 hours. Moreover, the polymerization can be performed under any pressure of pressure, reduced pressure, or atmospheric pressure. get on.

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

The epoxy group-containing polymer may be left as a solvent used in the synthesis to form an epoxy compound solution in consideration of handling properties, or the solvent may be removed to form a solid ring in consideration of handling properties. Oxygen compound.

1-3. Epoxy compounds

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

Preferable examples of the epoxy compound are preferably a phenol novolak type epoxy compound, a cresol novolac type epoxy compound, a glycidyl ether type epoxy compound, a bisphenol A novolac type epoxy compound, an aliphatic polyglycidyl ether compound, Or cyclic aliphatic epoxy compounds. As these epoxy compounds, commercially available products described below can be used.

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

1-4. Epoxy hardener

In the thermosetting composition of the present invention, an epoxy curing agent is used in order to improve flatness and chemical resistance. Epoxy hardeners include acid anhydride-based hardeners, amine-based hardeners, phenol-based hardeners, imidazole-based hardeners, catalyst-based hardeners, and thermostable acids such as sulfonium salts, benzothiazolium salts, ammonium salts, and sulfonium salts. The generator and the like are preferably an acid anhydride-based hardener or an imidazole-based hardener from the viewpoint of avoiding the coloration of the cured film and the heat resistance of the cured film.

Specific examples of the acid anhydride-based hardener include aliphatic dicarboxylic acid anhydrides (e.g., maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic acid). Dicarboxylic anhydride, hexahydrotrimellitic anhydride, etc.), aromatic polycarboxylic anhydride (such as phthalic anhydride, trimellitic anhydride, etc.), and styrene-maleic anhydride copolymer. Among these acid anhydride-based hardeners, trimellitic anhydride and hexahydrotrimellitic anhydride, which have a good balance between heat resistance and solubility in solvents, are particularly preferred.

Specific examples of the imidazole-based hardener 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. Among these imidazole-based hardeners, 2-undecylimidazole, which has a good balance between curability and solubility in solvents, is particularly preferred.

1-5. Proportion of polyester lysine, epoxy-containing polymer, epoxy compound, and epoxy hardener

In the thermosetting composition of the present invention, the ratio of the total amount of the epoxy group-containing polymer and the epoxy compound to 100 parts by weight of the polyester amidate is 20 to 400 parts by weight. When the ratio of the total amount of the epoxy group-containing polymer and the epoxy compound is within this range, the balance of flatness, heat resistance, chemical resistance, and adhesion is good. The total amount of the epoxy group-containing polymer and the epoxy compound is more preferably in a range of 50 parts by weight to 300 parts by weight.

The ratio of the epoxy hardener to the total amount of the epoxy-containing polymer and the epoxy compound is 100 parts by weight with respect to the total amount of the epoxy-containing polymer and the epoxy compound, and the epoxy hardener is 0.1 weight Parts ~ 60 parts by weight. For example, in the case where the epoxy hardener is an acid anhydride-based hardener, more specifically, it is preferable that the carboxylic anhydride group or carboxyl group in the epoxy hardener is 0.1 relative to the epoxy group. It is added in the manner of double equivalent to 1.5 times equivalent. At this time, the carboxylic acid anhydride group is calculated at a divalent value. When a carboxylic anhydride group or a carboxyl group is added so that it may become 0.15-times equivalent to 0.8-times equivalent, since chemical resistance will improve further, it is more preferable.

1-6. Other ingredients

Various additives can be added to the thermosetting composition of the present invention to improve coating uniformity and adhesion. Examples of additives include solvents, anionic, cationic, non-ionic, fluorine or silicon based leveling agents / surfactants, adhesion improvers such as silane coupling agents, hindered phenols, hindered amines, phosphorus Based, sulfur based compounds and other antioxidants.

1-6-1. 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 polyester amidate, an epoxy group-containing polymer, an epoxy compound, an epoxy hardener, and the like. Specific examples of the solvent are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tertiary butanol, acetone, 2-butanone, ethyl acetate, Butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl glycolate, ethyl acetate, butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid Butyl ester, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, 3-methoxypropionate Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, 2-methoxypropionate propyl, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2-methylpropionic acid Methyl ester, 2-hydroxy-2-methylpropionic acid Ethyl ester, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetamidine Methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, dioxane, ethylene glycol, Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol Monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, Diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, acetonitrile, toluene, xylene, γ-butyrolactone, and N, N- Dimethylacetamide. The solvent may be one kind of these solvents or a mixture of two or more kinds of these solvents.

1-6-2. Surfactants

A surfactant may be added to the thermosetting composition of the present invention to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, and Polyflow No. 90. Polyflow No. 95 (the above are all trade names; Gongrongshe Chemical Co., Ltd.), Disperbyk 161, Disperbyk 162, Dis Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Dis Disperbyk 181, Disperbyk 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (The above are all trade names; Japan Bi Chemical (BYK Chemie Japan) Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (the above are all trade names; Shin-Etsu Chemical Industry Co., Ltd.), Surflon SC-101, Surflon KH-40, Surflon S611 (both are trade names; AGC Seimi Chemical Co., Ltd.), Fugit ( Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent ) 602A, Ftergent 650A, FTX-218 (the above are the trade names; Neos Co., Ltd.), Eftop (EFTOP) EF-351, Eftop (EFTOP) EF-352 , Eftop (EFTOP) EF-601, Eftop (EFTOP) EF-801, Eftop (EFTOP) EF-802 (all above are trade names; Mitsubishi Material) Co., Ltd.), Megafac F-171, Megafac F-177, Megafac F-410, Megafac F-430, Megafac F-444, Mega (Megafac) F-472SF, Megafac (F-475), Megafac (F-477), Megafac (F-552), Megafac (F-553), Megafac (F) -554, Megafac F-555, Megafac F-556, Megafac F-558, Megafac R-30, Megafac R-94, Megafac (Megafac) RS-75, Mega (Megafac) RS-72-K, Megafac RS-76-NS (the above are all trade names; DIC Corporation), TEGO Twin 4000, Tegotun ( TEGO Twin) 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, Tego TEGO Rad 2200N, TEGO Rad 2250N (the above are all trade names, Evonik-Degussa Japan Co., Ltd.), fluoroalkylbenzene sulfonate, fluorine Alkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl Trimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene Oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearic acid Ester, polyoxyethylene laurylamine, Alkyd laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitol Anhydride palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyl diphenyl ether disulfonic acid salt. Preferably, at least one selected from these compounds is used.

Among these surfactants, if selected from BYK306, BYK342, BYK346, KP-341, KP-358, KP-368, Surflon S611, Ftergent 710FL, Ftergent 710FM, Fudge (Ftergent) 710FS, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac RS-72-k, TEGO Twin 4000, Among fluoroalkylbenzene sulfonates, fluoroalkyl carboxylates, fluoroalkyl polyoxyethylene ethers, fluoroalkyl sulfonates, fluoroalkyl trimethyl ammonium salts, and fluoroalkyl amine sulfonates At least one type is preferable because the coating uniformity of the thermosetting composition is improved.

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.

1-6-3. Adhesiveness improver

From the viewpoint of further improving the adhesion between the formed cured film and the substrate, the thermosetting composition of the present invention may further contain an adhesion improver.

As such an adhesion improving agent, for example, a silane-based, aluminum-based, or titanate-based coupling agent can be used. Specific examples include 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane ( For example, Sila-Ace S510; trade name; JNC Corporation), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (for example, Sila-Ace) S530; trade name; JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane (such as Sila-Ace S810; trade name; JNC Co., Ltd.) and other silane-based coupling agents Aluminum-based coupling agents such as aluminum alkoxydiisopropoxide, and titanate-based coupling agents such as tetraisopropylbis (dioctylphosphite) titanate.

Among these adhesion promoters, 3-glycidoxypropyltriethoxysilyl Alkanes are preferred because they have a large effect of improving adhesion.

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

1-6-4. Antioxidants

From the viewpoint of improving transparency and preventing yellowing of the cured film when exposed to high temperatures, the thermosetting composition of the present invention may further contain an antioxidant.

Antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added to the thermosetting composition of the present invention. Among them, from the viewpoint of weather resistance, a hindered phenol type is preferred. Specific examples include Irganox 1010, Irganox FF, Irganox 1035, Irganox 1035FF, Yiluganox ( Irganox 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Ilganox ( Irganox 1330, Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Ilganox (Irganox) 245FF, Irganox 245DWJ, Irganox 259, Irganox 3114, Irganox 565, Yiluganox (Irganox) 565DD, Irganox 295 (both trade names; BASF Japan Co., Ltd.), ADK STAB AO-20, ADK STAB) AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80 (both trade names; ADEKA Co., Ltd.). Among them, Irganox 1010 and ADK STAB AO-60 are more preferred.

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

1-6-7. Other additives

When the polyester glutamic acid does not contain a styrene-maleic anhydride copolymer as a raw material, a styrene-maleic anhydride copolymer may be added as another component.

1-7. Storage of thermosetting composition

When the thermosetting composition of the present invention is stored in a range of -30 ° C to 25 ° C, the stability over time of the composition is improved, which is preferable. If the storage temperature is -20 ° C to 10 ° C, no precipitates are present and it is more preferable.

2. A cured film obtained from a thermosetting composition

The thermosetting composition of the present invention can be obtained by mixing polyester amine acid, an epoxy group-containing polymer, an epoxy compound, and an epoxy hardener, and further, if necessary, according to the target characteristics. Solvents, coupling agents, surfactants, and other additives are optionally added to mix and dissolve these compounds uniformly.

A coating film can be formed by applying the thermosetting composition prepared as described above (in the case of a solvent-free solid state, after dissolving in a solvent) to the surface of a substrate and removing the solvent by, for example, heating. . The thermally curable composition can be applied to the substrate surface by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, and a slit coating method. Second, use a hot plate or oven This coating film is heated (pre-baked). The heating conditions vary depending on the type of each component and the blending ratio. Usually at 70 ° C to 150 ° C, it is 5 minutes to 15 minutes if an oven is used, and 1 minute to 5 minutes if a heating plate is used. Thereafter, in order to harden the coating film, a hardened film can be obtained by heat treatment at 180 ° C to 250 ° C, preferably 200 ° C to 250 ° C, and in an oven for 30 minutes to 90 minutes, if If it is a hot plate, it takes 5 minutes to 30 minutes.

When the hardened film obtained as described above is heated, 1) the polyamidic acid of the polyester polyamic acid is partially dehydrated and cyclized to form an imine bond, and 2) the carboxylic acid of the polyester polyamino acid and an epoxy group-containing Polymer reacts to increase molecular weight, and 3) epoxy-containing polymer hardens and polymerizes, so it is very tough, and has transparency, heat resistance, chemical resistance, flatness, adhesion, and light resistance And excellent sputtering 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 imaging element can be manufactured using the color filter. In addition to the protective film for a color filter, the cured film of the present invention is effective if used as a transparent insulating film formed between a TFT and a transparent electrode or a transparent insulating film formed between a transparent electrode and an alignment film. Moreover, the cured film of this invention is effective even if it is used as a protective film of LED light emitting body.

[Example]

Next, the present invention will be specifically described by way of synthesis examples, reference examples, examples, and comparative examples, but the present invention is not limited to these examples. First, a polyester amidic acid solution containing a reaction product of a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound was synthesized as follows (Synthesis Example 1, Synthesis Example 2, Synthesis Example 3, and Synthesis Example 4).

[Synthesis Example 1] Synthesis of polyester lysine solution (A1)

In a four-necked flask equipped with a stirrer, dehydrated and purified methyl 3-methoxypropionate (hereinafter abbreviated as "MMP"), 3,3 ', 4,4'-dibenzene were charged at the following weight. The ether ether tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA"), 1,4-butanediol, and benzyl alcohol were stirred at 130 ° C for 3 hours under a stream of dry nitrogen.

Thereafter, the reaction solution was cooled to 25 ° C, and 3,3'-diaminodiphenylphosphonium (hereinafter abbreviated as "DDS") and MMP were added at the following weights, and stirred at 20 ° C to 30 ° C for 2 hours. Stir at 115 ° C for 1 hour.

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

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

[Synthesis Example 2] Synthesis of polyester lysine solution (A2)

In a four-necked flask equipped with a stirrer, propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA"), 1,2,3,4-butanetetracarboxylic acid, which had undergone dehydration purification, were charged in the following weight order. Acid dianhydride (hereinafter abbreviated as "BT-100"), SMA1000P (trade name; styrene-maleic anhydride copolymer, Sichuan Crude Chemical Co., Ltd.), 1,4-butanediol, benzyl alcohol, and dry nitrogen The mixture was stirred at 125 ° C for 3 hours while flowing down.

After that, the reaction solution was cooled to 25 ° C., DDS and PGMEA were added at the following weights, and the mixture was stirred at 20 ° C. to 30 ° C. for 2 hours, and then stirred at 125 ° C. for 2 hours.

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

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

[Synthesis Example 3] Synthesis of polyester lysine solution (A3)

In a four-necked flask equipped with a stirrer, PGMEA, BT-100, SMA1000P, 1,4-butanediol, and benzyl alcohol, which had been subjected to dehydration purification, were sequentially loaded at the following weights, and carried out under a dry nitrogen stream at 125 ° C Stir for 3 hours.

After that, the reaction solution was cooled to 25 ° C., DDS and PGMEA were added at the following weights, and the mixture was stirred at 20 ° C. to 30 ° C. for 2 hours, and then stirred at 125 ° C. for 2 hours.

[Z / Y = 8.0, (Y + Z) /X=0.8]

The solution was cooled to room temperature to obtain a 30% by weight solution (A3) of pale yellow transparent polyester amidine. A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A3) was 9,000.

[Synthesis Example 4] Synthesis of polyester lysine solution (A4)

In a four-necked flask equipped with a stirrer, the following weights were charged and removed in order. Water-purified PGMEA, diethylene glycol methyl ethyl ether (hereinafter abbreviated as "EDM"), ODPA, SMA1000P, 1,4-butanediol, and benzyl alcohol, and stirred at 120 ° C for 3 hours under a stream of dry nitrogen. .

After that, the reaction solution was cooled to 25 ° C, and DDS and MMP were charged at the following weights, and the mixture was stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 120 ° C for 2 hours.

[Z / Y = 2.0, (Y + Z) /X=1.0]

The solution was cooled to room temperature to obtain a 30% by weight solution (A4) of a pale yellow transparent polyester amidine. A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A4) was 21,000.

Next, the composition obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw materials was synthesized as follows. Epoxy-based polymers (Synthesis Example 5, Synthesis Example 6, Synthesis Example 7, Synthesis Example 8, and Synthesis Example 9).

[Synthesis Example 5] Synthesis of epoxy group-containing polymer solution (B1)

A 1000-ml four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen introduction port was charged with 420.00 g of dehydrated purified MMP, 162.00 g of glycidyl methacrylate (hereinafter abbreviated as "GMA"), two 18.00 g of ethylene glycol dimethacrylate and 27.00 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator were heated at a polymerization temperature of 110 ° C for 2 hours to Polymerize. The reaction solution was cooled to 30 ° C. or lower to obtain a 30% by weight solution (B1) of the epoxy group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 3,600 (in terms of polystyrene).

[Synthesis Example 6] Synthesis of epoxy group-containing polymer solution (B2)

A 1000-ml four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen introduction port was charged with dehydrated and purified MMP 300.00 g, GMA 180.00 g, 1,4-butanediol dimethacrylate 20.00 g, 20.00 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was polymerized by heating at a polymerization temperature of 90 ° C for 2 hours. The reaction solution was cooled to 30 ° C. or lower to obtain a 40% by weight solution (B2) of the epoxy group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 12,000 (polystyrene equivalent).

[Synthesis Example 7] Synthesis of epoxy group-containing polymer solution (B3)

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

[Synthesis Example 8] Synthesis of epoxy group-containing polymer solution (B4)

A 1000-ml four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen introduction port was charged with dehydrated and purified MMP 420.00 g, GMA 144.00 g, diethylene glycol dimethacrylate 27.00 g, and methacrylic acid. Methoxy organic polysiloxane (trade name; FM-0721, JNC Co., Ltd.) 9.00 g, 2,2'-azobis (2,4-dimethylvaleronitrile) 27.00 g as a polymerization initiator The polymerization was carried out by heating at a polymerization temperature of 110 ° C for 2 hours. The reaction solution was cooled to 30 ° C. or lower to obtain a 30% by weight solution (B4) of the epoxy group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 3,900 (polystyrene equivalent).

[Synthesis Example 9] Synthesis of epoxy group-containing polymer solution (B5)

A 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material input port and a nitrogen inlet port was charged with dehydrated and purified MMP 420.00 g, GMA 126.00 g, diethylene glycol dimethacrylate 18.00 g, and acrylic acid-2 -36.00 g of hydroxyethyl esters and 27.00 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as polymerization initiators were polymerized by heating at a polymerization temperature of 110 ° C for 2 hours. By cooling the reaction to 30 ° C or lower to obtain a 30% by weight solution (B5) of the epoxy-group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 4,500 (polystyrene equivalent).

[Comparative Synthesis Example 1] Synthesis of epoxy group-containing polymer (C1)

A 1000-ml four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen inlet was charged with 300.00 g of dehydrated purified MMP, 180.00 g of GMA, 20.00 g of methyl methacrylate, and 2 as a polymerization initiator. 8.00 g of 2'-azobis (2,4-dimethylvaleronitrile) was polymerized by heating at a polymerization temperature of 90 ° C for 2 hours. The reaction solution was cooled to 30 ° C. or lower to obtain a 40% by weight solution (C1) of the epoxy group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 15,000 (polystyrene equivalent).

[Comparative Synthesis Example 2] Synthesis of epoxy group-containing polymer (C2)

A 1000-ml four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen introduction port was charged with dehydrated and purified MMP 300.00 g, GMA 180.00 g, 1,4-butanediol dimethacrylate 20.00 g, 13.00 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was polymerized by heating at a polymerization temperature of 90 ° C for 2 hours. The reaction solution was cooled to 30 ° C. or lower to obtain a 40% by weight solution (C1) of the epoxy group-containing polymer. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 58,000 (in terms of polystyrene).

Next, the polyester amines (A1, A2, A3, and A4) obtained in Synthesis Example 1, Synthesis Example 2, Synthesis Example 3, and Synthesis Example 4, Synthesis Example 5, Synthesis Example 6, Synthesis Example 7, Epoxy group-containing polymerization obtained in Synthesis Example 8 and Synthesis Example 9 (B1, B2, B3, B4, and B5), Comparative Synthesis Example 1, and Epoxy-containing Polymers (C1 and C2) obtained in Comparative Synthesis Example 2, commercially available polyfunctional, and having a weight average molecular weight of less than 3,000 An epoxy compound and an epoxy curing agent were prepared as described below. A cured film was obtained from the thermosetting composition, and evaluation of the cured film was performed (Reference Example 1 to Reference Example 8, Example 1 to Example 4, and Comparative Example 1 to Comparative Example 5).

[Reference Example 1]

A 500 ml separable flask equipped with a stirring wing was purged with nitrogen, and 100.0 g of the polyester amidino acid solution (A1) obtained in Synthesis Example 1 and an epoxy group-containing obtained in Synthesis Example 5 were placed in the flask. 175.0 g of polymer solution (B1), 6.0 g of trimellitic anhydride (hereinafter abbreviated as "TMA") as an epoxy hardener, 4.4 g of 3-glycidyloxypropyltrimethoxysilane as an additive, and Ed Costa 0.4 g of ADK STAB AO-60 (trade name; ADEKA Co., Ltd.), 230.8 g of dehydrated and purified MMP and 105.8 g of EDM as solvents, and stirred at room temperature for 3 hr, so that It dissolves evenly. Next, 0.2 g of Megafac F-477 (trade name; DIC) Co., Ltd. was added, stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a coating solution. .

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

The cured film obtained as described above was evaluated for its characteristics regarding transparency, light resistance, flatness, heat resistance, and chemical resistance.

[Transparency evaluation method]

In the obtained glass substrate with a cured film, the transmittance of light with a wavelength of only 400 nm of the cured film was measured with an ultraviolet-visible near-infrared spectrophotometer (trade name; V-670, Japan Spectroscopy Corporation). A case where the transmittance was 97% or more was evaluated as “○”, and a case where the transmittance was less than 97% was evaluated as “×”.

[Evaluation method of light resistance]

For the glass substrate with a cured film after the transparency was evaluated in the [Transparency Evaluation Method], a UV ozone cleaning device (trade name; PL2003N-12, light source; low-pressure mercury lamp, SEN special light source) Co., Ltd.) UV-ozone treatment at 1J / cm ² (254nm conversion), heating in an oven at 230 ° C for 30 minutes, and then using an ultraviolet-visible near-infrared spectrophotometer (trade name; V-670, Japan Spectrophoton Co., Ltd.) Co., Ltd.) was measured for the transmittance only with light having a wavelength of 400 nm of the cured film. A case where the transmittance was 96% or more was evaluated as “○”, and a case where the transmittance was less than 96% was evaluated as “×”.

[Evaluation method of flatness]

The step difference of the cured film surface of the obtained color filter substrate with a cured film was measured using a step / surface roughness / fine shape measuring device (trade name; P-15, KLA TENCOR Co., Ltd.). . A case where the maximum value of the step difference between R, G, and B elements including the black matrix (hereinafter abbreviated as "maximum step difference") is less than 0.3 µm is evaluated as "○", and a case of 0.3 µm or more is evaluated as "× ". Moreover, The color filter substrate used was a pigment-dispersed color filter (hereinafter abbreviated as “CF”) using a resin black matrix with a maximum step difference of about 0.5 μm.

[Evaluation method of heat resistance]

The obtained glass substrate with a cured film was reheated at 250 ° C. for 1 hour, and the film thickness before heating and the film thickness after heating were measured, and the residual film ratio was calculated by the following calculation formula. The film thickness was measured using the step / surface roughness / fine shape measuring device (trade name; P-15, KLA TENCOR Co., Ltd.). A case where the residual film rate after heating was 95% or more was evaluated as “○”, and a case where the residual film rate after heating was less than 95% was evaluated as “×”.

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

[Evaluation method of chemical resistance]

Each of the obtained glass substrates with a cured film was immersed in a 5% by weight sodium hydroxide aqueous solution at 60 ° C for 10 minutes (hereinafter abbreviated as "NaOH treatment"), and contained 36% hydrochloric acid / 60% nitric acid. / Water = 40/20/40 in a mixed solution (weight ratio) at 50 ° C for 5 minutes (hereinafter referred to as "acid treatment"), and in N-methyl-2-pyrrolidone at 50 ° C After performing an immersion treatment (hereinafter abbreviated as "NMP treatment") for 30 minutes, reheating was performed at 230 ° C for 1 hour. The residual film rate after reheating and the transmittance after reheating were measured. A case where the residual film rate after reheating was 90% or more and the transmittance at 400 nm after reheating was 95% or more was evaluated as "○". Residual film rate after reheating is less than 90% or transmittance after reheating When less than 95%, it was evaluated as "×".

Residual film rate after reheating = (film thickness after reheating / film thickness before reheating) × 100

[Reference Example 2 to Reference Example 8]

According to the method of Reference Example 1, each component was mixed and dissolved at the ratio (unit: g) shown in Table 1 to obtain a thermosetting composition. In addition, regarding the abbreviated names of the additives in Tables 1 to 3, S510 represents the adhesiveness improving agent Sila-Ace S510 (trade name; JNC Co., Ltd.), and AO-60 represents the antioxidant Adikos. ADK STAB AO-60 (trade name; ADEKA Co., Ltd.), F-477, F-556 and RS-72-K respectively represent the surfactant Megafac F-477 , Megafac F-556, and Megafac RS-72-K (both trade names; DIC Corporation).

[Examples 1 to 4]

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

[Comparative Example 1 to Comparative Example 5]

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

Hereinafter, the evaluation results of the cured films of Reference Examples 1 to 8 are collectively described in Table 4, the evaluation results of the cured films of Examples 1 to 4 are collectively described in Table 5, and Comparative Example 1 The evaluation results of the cured film of Comparative Example 5 are collectively described in Table 6.

From the results shown in Tables 5 and 6, it can be seen that the cured films of Examples 1 to 4 are excellent in light resistance and flatness, and have balance in all aspects of transparency, heat resistance, and chemical resistance. On the other hand, Comparative Examples 1 and 2 used epoxy group-containing polymers (the epoxy group-containing polymers were obtained by reacting glycidyl methacrylate and a monofunctional methacrylate). Although the cured film was excellent in light resistance, the flatness was on the selected / unselected line for evaluation, and the heat resistance and chemical resistance were poor. Comparative Example 3 Hardening using an epoxy group-containing polymer obtained by reacting a glycidyl methacrylate and a bifunctional methacrylate having a molecular weight of 50,000 or more The flatness of the film was poor. In addition, the unused comparative examples 4 and 5 contained epoxy It is a polymer based on a cured film using a polyfunctional epoxy compound having a weight average molecular weight of less than 3,000. In Comparative Example 4, the light resistance was poor, and in Comparative Example 5, the heat resistance and chemical resistance were poor. As described above, only epoxy-group-containing polymers (weight average molecular weight; 1,000 ~) obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw materials are used. 50,000) can meet all characteristics.

In addition, as shown in Table 4, the cured films of Reference Examples 1 to 8 in which epoxy compounds were not used, although each evaluation item was "○", a part of the light resistance showed values inferior to the examples. Each of the flatness showed a larger value than the example.

[Industrial availability]

The cured film obtained from the thermosetting composition of the present invention has excellent characteristics as optical materials such as transparency, light resistance, and sputtering resistance. From this aspect, it can be used as a color filter, an LED light-emitting element, and Protective films of various optical materials such as light receiving elements, and transparent insulating films formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (21)

A thermosetting composition is a composition comprising a polyester amidate, a polymer containing an epoxy group, an epoxy compound, and an epoxy hardener, wherein the polyester amidate is passed through A tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound are used as essential raw material components to perform the reaction; the polyester amidate is obtained by making the X-mole tetracarboxylic dianhydride and Y-mole The diamine and the ZMol polyhydric hydroxy compound are obtained by reacting at a ratio where the relationship of the following formula (1) and formula (2) is established, and have a structural unit represented by the following formula (3) and a formula ( The structural unit represented by 4); the epoxy group-containing polymer is obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw materials, and the weight average molecular weight is 3,000 to 50,000; the epoxy compound contains 2 to 10 epoxy groups per molecule, and the weight average molecular weight is less than 3,000; relative to 100 parts by weight of the epoxy group-containing polymer, 1 to 30 parts by weight of the epoxy compound; relative to the polyester amidine 100 parts by weight, the total amount of the epoxy group-containing polymer and the epoxy compound is 20 to 400 parts by weight, relative to the total amount of the epoxy group-containing polymer and the epoxy compound The amount is 100 parts by weight, and the epoxy hardener is 0.1 parts by weight to 60 parts by weight; 0.2 ≦ Z / Y ≦ 8.0… (1) 0.2 ≦ (Y + Z) /X≦5.0… (2) In formulas (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from the tetracarboxylic dianhydride, and R ² is obtained by removing two from the diamine. -NH _{2 is} a residue, and R ³ is a residue obtained by removing two -OH from the polyhydroxy compound. The thermosetting composition according to item 1 of the scope of patent application, wherein a raw material component of the polyester amidate further comprises a monohydroxy compound. The thermosetting composition according to item 2 of the scope of patent application, wherein the monohydroxy compound is selected from the group consisting of isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3- One or more types of ethyl-3-hydroxymethyloxetane. The thermosetting composition according to claim 1 or claim 2, wherein a raw material component of the polyester glutamic acid further comprises a styrene-maleic anhydride copolymer. The thermosetting composition according to item 1 or item 2 of the scope of patent application, wherein the weight average molecular weight of the polyester amidine is 1,000 to 200,000. The thermosetting composition according to claim 1 or claim 2, wherein the tetracarboxylic dianhydride is selected from 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride , 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1, 2, 3, One or more of 4-butanetetracarboxylic dianhydride and ethylene glycol bis (anhydrotrimellitic acid ester). The thermosetting composition according to claim 1 or claim 2, wherein the diamine is selected from 3,3'-diaminodiphenylphosphonium and bis [4- (3-amino One or more types of phenoxy) phenyl] fluorene. The thermosetting composition according to claim 1 or claim 2, wherein the polyhydroxy compound is selected from ethylene glycol, propylene glycol, 1,4-butanediol, and 1,5-pentanediol 1 or more of 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and tris (2-hydroxyethyl) isocyanurate. The thermosetting composition according to claim 1 or claim 2, wherein the bifunctional (meth) acrylate is selected from 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 (meth) acrylate, three One or more types of cyclodecanedimethanol di (meth) acrylate. The thermosetting composition according to claim 1 or claim 2, wherein the epoxy group-containing polymer is obtained by further including, in a raw material component, a member selected from the group consisting of the glycidyl (meth) acrylate It is obtained by reacting with a radically polymerizable monomer other than the compound of the group consisting of the bifunctional (meth) acrylate. The thermosetting composition according to claim 10, wherein the thermosetting composition is selected from compounds other than a compound consisting of the glycidyl (meth) acrylate and the bifunctional (meth) acrylate. The radical polymerizable monomer is selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate , 2-hydroxyethyl (meth) acrylate, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane, (meth) acryloxypropyl-3-trimethylsilyloxysilane, (meth) acryloxyorganopolysiloxane, (methyl (Diyl) dicyclopentyl acrylate, dicyclopentenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, γ-butyrolactone (meth) acrylate, N-cyclohexyl maleate One or more of fluorenimine, N-phenylmaleimide, (meth) acrylic acid-2,2,2-trifluoroethyl ester, (meth) acrylic acid, and 4-hydroxyphenylvinyl ketone . The thermosetting composition according to claim 1 or claim 2, wherein the epoxy compound is selected from 3,4-epoxycyclohexanecarboxylic acid-3 ', 4'-epoxy ring Hexyl methyl ester, 2- [4- (2,3-glycidoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-glycidoxy)] Phenyl)] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-glycidoxy) phenyl] phenyl] -1- [4- [1- [ A mixture of 4- (2,3-glycidoxyphenyl) -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol, and 2- [4- (2, 3-glycidoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-glycidoxy] phenyl)] ethyl] phenyl] propane 1 or more. The thermosetting composition according to claim 1 or claim 2, wherein the epoxy hardener is one or more members selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole. The thermosetting composition according to item 1 of the scope of patent application, wherein the tetracarboxylic dianhydride is selected from 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 1,2 1 or more of 3,4-butanetetracarboxylic dianhydride; the diamine is 3,3'-diaminodiphenylphosphonium; the polyhydroxy compound is 1,4-butanediol; The weight-average molecular weight of the epoxy group-containing polymer obtained by reacting glycidyl methacrylate, diethylene glycol dimethacrylate, and tetrahydrofurfuryl methacrylate as raw materials is 3,000 to 50,000. The epoxy compound is 3,4-epoxycyclohexanecarboxylic acid-3 ', 4'-epoxycyclohexyl methyl ester; the epoxy hardener is selected from trimellitic anhydride and 2-eleven One or more kinds of alkylimidazole; and one or more kinds selected from methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent. A cured film obtained from the thermosetting composition according to any one of claims 1 to 14 in the scope of patent application. A color filter uses a hardened film as described in item 15 of the scope of patent application as a protective film. A liquid crystal display element using the color filter according to item 16 of the patent application scope. A solid-state imaging element using a color filter as described in item 16 of the patent application scope. A liquid crystal display element using a cured film as described in item 15 of the scope of patent application as a transparent insulating film formed between a thin film transistor and a transparent electrode. A liquid crystal display element using a cured film as described in item 15 of the patent application scope as a transparent insulating film formed between a transparent electrode and an alignment film. A light-emitting diode light-emitting body uses a cured film as described in item 15 of the scope of patent application as a protective film.