TW201422719A - Thermosetting resin composition, hardened film, color filter, liquid crystal display device, solid state image device and light emitting diode luminous body - Google Patents

Abstract

This invention provides a thermosetting resin composition with excellent chemical resistance after a precalcination, and further with excellent evenness, heat resistance, adhesion to base substrates such as glass, and transparence. The resin composition includes specific amounts of the following: a polyester amid acid obtained from a reaction of a compound including a tetracarboxylic dianhydride, a diamine and a polyhydroxy compound; an epoxy resin with each molecule including 3-20 epoxy groups and having a weight-average molecular weight of less than 5, 000; and a polymer (A) configured by a radical copolymerization of a radical-polymerizable compound (a1) represented by the following general formula (3), a radical-polymerizable compound (a2) with an alkoxysilane group, and a radical-polymerizable compound (a3) with at least one of an epoxy group, carboxyl and hydroxyphenyl.

Description

Thermosetting resin composition

The present invention relates to an insulating material that can be used in forming an electronic component, a passivation film in a semiconductor device, a buffer coating film, an interlayer insulating film, or a planarization film, or an interlayer insulating film or color filter in a liquid crystal display element. A thermosetting resin composition such as a sheet protective film, a transparent film using the thermosetting resin composition, and an electronic component having the film.

In the manufacturing process of an element such as a liquid crystal display element, when a plurality of chemicals such as an organic solvent, an acid, or an alkali solution are treated, or a film is formed as a wiring electrode by sputtering, the surface may be locally heated to a high temperature. Therefore, there is a case where a surface protective film is provided for the purpose of preventing deterioration, damage, and deterioration of the surface of various elements. For these protective films, characteristics that can withstand various treatments in the manufacturing steps as described above are required. Specifically, heat resistance and solvent resistance are required. Acid resistance. Chemical resistance such as alkali resistance, water resistance, adhesion to a base substrate such as glass, transparency, scratch resistance, coating properties, flatness, light resistance, and the like. In addition, when high-performance viewing angle, high-speed response, and high definition of a liquid crystal display element are used, when it is used as a color filter protective film, a material which improves planarization characteristics and a sputtering step are expected. High heat resistance with less volatile components in various steps of heating to high temperature, such as a calcination step material.

The types of these protective films can be roughly classified into a photocurable resin composition and a thermosetting resin composition. The photocurable resin composition contains a polymer or oligomer having a photopolymerizable group or a monomer and a photopolymerization initiator, and is hardened by causing a chemical reaction by energy of light represented by ultraviolet rays. The photocurable resin composition has the advantages of not requiring high-temperature heating, and is hardened by reacting at room temperature for a short period of time, and can easily form a scribe line used for manufacturing panel division; The problem is as follows: Unreacted monomers which are not reacted at the time of light irradiation generate a large amount of volatile components due to subsequent heating, and it is necessary to change the amount of irradiation light depending on the formed film thickness, resulting in an increase in development for forming a scribe line. , cleaning, drying and other steps. In addition, since the general photocurable resin composition utilizes radical polymerization of an acrylate material, the hardenability of the surface of the film may be insufficient due to oxygen inhibition, and if the curing is insufficient, the subsequent heating may be performed. A large amount of volatile components are generated in the step of high temperature, and heat resistance is deteriorated.

On the other hand, since the thermosetting resin composition is completely cured by heating at a high temperature during film formation, even if it is heated to a high temperature in the subsequent step, the amount of volatile components generated is small, and the heat resistance is excellent. The thermosetting protective film material having excellent properties is a polyester phthalic acid composition (see Patent Document 1). In recent years, there is an increasing demand for a protective film that requires heat resistance, and a photocurable resin composition is being replaced with a thermosetting resin composition.

In general, the manufacturing equipment is changed as the photocurable resin composition is replaced with a thermosetting resin composition, but conventional equipment is often used as it is. The situation In other cases, it is necessary to pass the steps of development, washing, and the like which are not required for the thermosetting resin composition, and the developer or the organic solvent is brought into contact with the surface after the pre-calcination of the thermosetting resin composition, thereby causing stains or unevenness. problem.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-156546

An object of the present invention is to provide a cured film which is excellent in chemical resistance after pre-baking, and which is excellent in flatness, heat resistance, adhesion to a base substrate such as glass, and transparency, and an electronic component having the cured film.

In order to solve the above problems, the inventors of the present invention have conducted active research, and have found that the above object can be attained by the following resin composition and a cured film obtained by curing the resin composition, thereby completing the present invention. The composition comprises: a polyester proline which is obtained by a reaction of a compound comprising a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound; the epoxy resin comprising 3 to 20 rings per molecule The oxy group having a weight average molecular weight of less than 5,000; and the polymer (A) which is a radically polymerizable compound (a1) represented by the following formula (3) and a radical polymerizable compound having an alkoxyalkyl group (a2) and a radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group are subjected to radical copolymerization.

The present invention includes the following constitutions.

[1] A thermosetting resin composition comprising a polyester proline, a ring An oxygen resin and a polymer (A) which is a radically polymerizable compound (a1) represented by the following formula (3) and a radically polymerizable compound having an alkoxyalkyl group ( A2) and a radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group, which is obtained by radical copolymerization; and the above thermosetting resin composition is characterized by: polyester oxime The amine acid is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components, and is made by the ratio of the relationship of the following formula (1) and formula (2). X-mole tetracarboxylic dianhydride, Y-mole diamine, and Z-mole polyhydroxy compound are obtained by reaction, 0.2≦Z/Y≦8.0············· 1)

0.2≦(Y+Z)/X≦5.0····(2)

The epoxy resin is an epoxy resin containing 3 to 20 epoxy groups per molecule and having a weight average molecular weight of less than 5,000, and the epoxy resin is 20 parts by weight to 400 parts by weight based on 100 parts by weight of the polyester phthalic acid. The weight average molecular weight of the polymer (A) is from 1,000 to 50,000, and the polymer (A) is from 0.1 part by weight to 50 parts by weight relative to 100 parts by weight of the polyester phthalic acid; [Chemical Formula 1]

(R ¹ is hydrogen or methyl, R ² to R ⁵ are alkyl groups having 1 to 5 carbon atoms, R ⁶ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 1 to 10, and n is 1 to 150. Integer).

[2] The thermosetting resin composition according to [1], wherein the epoxy curing agent is contained in an amount of from 1 part by weight to 60 parts by weight per 100 parts by weight of the epoxy resin.

[3] The thermosetting resin composition according to [1], wherein the raw material component of the polyester phthalic acid further comprises a monohydric alcohol.

[4] The thermosetting resin composition according to [3], wherein the monohydric alcohol is selected from the group consisting of isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethylidene One or more kinds of -3-hydroxymethyloxetane.

[5] The thermosetting resin composition according to any one of [1] to [4] wherein the raw material component of the polyester phthalic acid further comprises a styrene-maleic anhydride copolymer.

[6] The thermosetting resin composition according to any one of [1] to [5] wherein the polyester phthalic acid has a composition represented by the following formula (4) and formula (5) Unit: [Chemical 2]

(R ⁷ is a tetracarboxylic dianhydride residue, R ⁸ is a diamine residue, and R ⁹ is a residue of a polyvalent hydroxy compound).

[7] The thermosetting resin composition according to any one of [1] to [6] wherein the polyester glutamic acid has a weight average molecular weight of 1,000 to 200,000.

[8] The thermosetting resin composition according to any one of [1], wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4'-diphenylfluorene Carboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, and ethylene One or more of the alcohols (dehydrated trimellitate).

[9] The thermosetting resin composition according to any one of [1] to [8] wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium and bis[4-( One or more of 3-aminophenoxy)phenyl]indoles.

[10] The thermosetting resin composition according to any one of [1] to [9] wherein the polyhydric hydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1, 5 One or more of pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol, and tris(2-hydroxyethyl) isocyanurate.

The thermosetting composition according to any one of the above-mentioned (1), wherein R ¹ is a methyl group, in the radically polymerizable compound (a1) represented by the above formula (3), R ² to R ⁵ are a methyl group, R ⁶ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 1 to 5, and n is an integer of 1 to 150.

[12] The thermosetting composition according to any one of [1] to [11] wherein the radically polymerizable compound (a2) having an alkoxyalkyl group is selected from the group consisting of 3-(methyl) Propylene methoxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, 3-(meth)acryloxypropylmethyldimethoxydecane, 3 -1 in a group consisting of -(meth)acryloxypropylmethyldiethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, p-styryltrimethoxydecane More than one species.

The thermosetting composition according to any one of the above aspects, wherein the radical polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group and a hydroxyphenyl group It is one or more selected from the group consisting of glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl ether, (meth)acrylic acid, and 4-hydroxyphenyl vinyl ketone. .

The thermosetting resin composition according to any one of the above aspects, wherein the epoxy curing agent is one or more selected from the group consisting of trimellitic anhydride and hexahydrotrimellitic anhydride. .

[15] The thermosetting resin composition according to [2], wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, and the diamine is 3 , 3'-diaminodiphenylanthracene, the above polyvalent hydroxy compound is 1,4-butanediol, and the above has an alkoxy group The radical polymerizable compound (a2) of the alkylene group is 3-(meth)acryloxypropyltrimethoxydecane, and the weight average molecular weight of the polymer (A) obtained by radical copolymerization is 1,000~ 50,000, the above epoxy hardener is trimellitic anhydride, and further contains methyl 3-methoxypropionate as a solvent.

[16] The thermosetting resin composition according to [3], wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, and the diamine is 3 3'-diaminodiphenylanthracene, the above polyvalent hydroxy compound is 1,4-butanediol, the monohydric alcohol is benzyl alcohol, and the above-mentioned radically polymerizable compound (a2) having an alkoxyalkyl group is 3-(meth)acryloxypropyltrimethoxydecane, wherein the radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group and a hydroxyphenyl group is glycidyl methacrylate, The polymer (A) obtained by radical copolymerization described above has a weight average molecular weight of 1,000 to 50,000, the epoxy curing agent is trimellitic anhydride, and further contains methyl 3-methoxypropionate as a solvent.

[17] A cured film obtained by the thermosetting resin composition according to any one of [1] to [16].

[18] A color filter using the cured film according to [17] as a protective film.

[19] A liquid crystal display element using the color filter according to [18].

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

[21] A liquid crystal display element using the cured film according to [17] It is a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode.

[22] A liquid crystal display element using the cured film according to [17] as a transparent insulating film formed between the transparent electrode and the alignment film.

[23] A light-emitting diode (LED) light-emitting body using the cured film according to [17] as a protective film.

The thermosetting resin composition of the preferred embodiment of the present invention is a material which is particularly excellent in chemical resistance, flatness, and heat resistance after pre-baking, and is used as a color filter protective film as a color liquid crystal display element. In this case, display quality and reliability can be improved. In addition, the cured film obtained by heating the thermosetting resin composition of the preferred embodiment of the present invention is balanced in transparency, adhesion, and sputter resistance, and has high practicality. In particular, it can be used as a protective film for a color filter manufactured by a dyeing method, a pigment dispersion method, a plating method, and a printing method. Moreover, it can also be used as a protective film of various optical materials, and a transparent insulating film.

1. The thermosetting composition of the present invention

The thermosetting resin composition of the present invention comprises: polyester proline which is obtained by using tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound as essential raw materials. Obtained by carrying out a reaction; an epoxy resin comprising 3 to 20 epoxy groups per molecule and having a weight average molecular weight of less than 5,000; and a polymer (A) represented by the following formula (3) a radically polymerizable compound (a1), a radically polymerizable compound (a2) having an alkoxyalkyl group, and a radical polymerizable compound having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group (a3) The thermosetting resin composition is characterized in that the epoxy resin is 20 parts by weight to 400 parts by weight based on 100 parts by weight of the polyester phthalic acid, and the polymer (A) It is from 0.1 part by weight to 50 parts by weight.

(R ¹ is hydrogen or methyl, R ² to R ⁵ are alkyl groups having 1 to 5 carbon atoms, R ⁶ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 1 to 10, and n is 1 to 150. Integer)

1-1. Polyester proline

The polyester proline is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components. More specifically, X-molar tetracarboxylic dianhydride, Y-mole diamine, and Z-mole polyvalent hydroxy compound are carried out at a ratio established by the relationship of the following formulas (1) and (2). Obtained by reaction.

0.2≦Z/Y≦8.0··············(1)

0.2≦(Y+Z)/X≦5.0···(2)

When the polyester phthalic acid is synthesized, at least a solvent is required, and the solvent can be directly left to form a liquid or gel-like thermosetting resin composition in consideration of workability, etc., and the solvent can be removed. A solid-shaped composition such as portability is considered. Further, in the case of synthesizing the polyester phthalic acid, one or more kinds of raw materials selected from the group consisting of a monohydric alcohol and a styrene-maleic anhydride copolymer may be contained as a raw material, and among them, a monohydric alcohol is preferable. Further, in the case of synthesizing the polyester phthalic acid, the raw material may be contained as a raw material, and may contain other raw materials other than the above, as long as the object of the present invention is not impaired. Examples of such other raw materials include monoamine-containing amines.

1-1-1. Tetracarboxylic dianhydride

In the present invention, tetracarboxylic dianhydride is used as a material for obtaining polyester proline. Preferred tetracarboxylic dianhydrides are selected from the group consisting of 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-di Benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic 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'-di Phenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2 ,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, and ethylene glycol bis(dehydrated trimellitate) (trade name, TMEG-100, New Japan Physical and Chemical Co., Ltd.) , cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, etc.: aliphatic tetracarboxylic dianhydride, for example Ethane tetracarboxylic dianhydride and butane tetracarboxylic dianhydride. Some of these One or more kinds of the compounds can be used.

Among these compounds, 3,3',4,4'-diphenylstilbene tetracarboxylic dianhydride and 3,3',4,4'-diphenyl ether which are excellent in transparency are preferable. Tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, TMEG-100, particularly preferably 3,3',4,4'-diphenyl ether Tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride.

1-1-2. Diamine

In the present invention, a diamine is used as a material for obtaining a polyester proline. Preferred diamines are: 4,4'-diaminodiphenyl fluorene, 3,3'-diaminodiphenyl fluorene, 3,4'-diaminodiphenyl fluorene, bis[4 -(4-Aminophenoxy)phenyl]indole, bis[4-(3-aminophenoxy)phenyl]indole, bis[3-(4-aminophenoxy)phenyl]indole , [4-(4-Aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl]indole, [4-(3-aminophenoxy)phenyl][3 -(4-Aminophenoxy)phenyl]indole, and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. One or more of these compounds may be used.

Among these compounds, 3,3'-diaminodiphenylanthracene and bis[4-(3-aminophenoxy)phenyl]anthracene, which are excellent in transparency, are more preferable. It is 3,3'-diaminodiphenylphosphonium.

1-1-3. Polyols

In the present invention, a polyvalent hydroxy compound is used as a material for obtaining polyester proline. Preferred examples of the polyvalent hydroxy compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol. Polypropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5- having a weight average molecular weight of 1,000 or less Pentandiol, 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-decanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-triol, 1,2-dodecanediol, 1,12-dodecanediol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol , tris(2-hydroxyethyl) isocyanurate, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol S (bis(4-hydroxyphenyl)fluorene), Bisphenol F (bis(4-hydroxyphenyl)methane), diethanolamine, triethanolamine, and the like. One or more of these compounds may be used.

Among these compounds, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-g, which are excellent in solubility in a solvent, are more preferable. a diol, 1,8-octanediol, and tris(2-hydroxyethyl) isocyanurate, particularly preferably 1,4-butanediol, 1,5-pentanediol, and 1,6 - hexanediol.

1-1-4. Monohydric alcohol

In the present invention, monohydric alcohol is preferably used as a material for obtaining polyester proline. By using a monohydric alcohol, storage stability is improved. Preferred monohydric alcohols include methanol, ethanol, 1-propanol, isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, phenol, borneol, maltol, linalool (linalool), terpineol, dimethyl benzyl carbinol, 3-ethyl-3-hydroxymethyl oxetane, and the like. Among these compounds Use one or more types.

Among these compounds, more preferred are isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl oxetane. Considering the compatibility in the case where the polyester phthalic acid formed by using these compounds is mixed with an epoxy resin and an epoxy curing agent, or the thermosetting resin composition as a final product in a color filter In the coating property, it is particularly preferred to use a benzyl alcohol in the monohydric alcohol.

It is preferable to contain 0 to 300 parts by weight of monohydric alcohol 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 parts by weight to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer

Further, the polyester phthalic acid used in the present invention may be subjected to a synthesis reaction by adding a compound having three or more acid anhydride groups. Thereby, transparency is improved, so it is preferable. Specific examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. The molar ratio of the styrene/maleic anhydride to the styrene/maleic anhydride copolymer is from 0.5 to 4, preferably from 1 to 3, and more preferably more preferably 1 Or 2, especially good 1.

Specific examples of the styrene-maleic anhydride copolymer include commercially available products such as SMA3000P, SMA2000P, and SMA1000P supplied by Chuan crude oil refining Co., Ltd. Among these compounds, SMA1000P which is excellent in heat resistance and alkali resistance is particularly preferred.

It is preferred to contain 0 parts by weight to 500 parts by weight of styrene-cis-butyl group based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. A enedic anhydride copolymer. More preferably, it is 10 weight part - 300 weight part.

1-1-6. Monoamine containing hydrazine

In the case of synthesizing the polyester phthalic acid, the raw material may be contained as a raw material, and other raw materials other than the above may be contained as needed within the scope of the object of the present invention. Examples of such other raw materials include fluorene-containing monoamine.

Preferred monoamine-containing amines for use in the present invention include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-aminopropylmethyldimethoxydecane. , 3-aminopropylmethyldiethoxydecane, 4-aminobutyltrimethoxydecane, 4-aminobutyltriethoxydecane, 4-aminobutylmethyldiethoxydecane, P-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, p-aminophenylmethyldimethoxydecane, p-aminophenylmethyldiethoxydecane, m-amino group Phenyltrimethoxynonane, m-aminophenylmethyldiethoxydecane, and the like. One or more of these compounds may be used.

Among these compounds, 3-aminopropyltriethoxydecane which is excellent in acid resistance of a coating film, and aminophenyltrimethoxydecane are preferable in terms of acid resistance and compatibility. Particularly preferred is 3-aminopropyltriethoxydecane.

It is preferably contained in an amount of from 0 part by weight 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 parts by weight to 200 parts by weight.

1-1-7. Solvent used in the synthesis reaction of polyester proline

The solvent used in the synthesis reaction for obtaining the polyester proline may, for example, be diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether or diethylene glycol alone. Ethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone, and N,N-dimethylacetamide.

Among these compounds, preferred are propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ether.

These solvents may be used singly or as a mixture of two or more kinds. Further, in the case of a ratio of 30% by weight or less, other solvents may be used in addition to the above solvent.

1-1-8. Method for synthesizing polyester proline

The polyester proline which is used in the present invention is synthesized by reacting tetracarboxylic dianhydride X mole, diamine Y mole, and polyvalent hydroxy compound Z mole in the above solvent. In this case, X, Y, and Z are preferably set to a ratio at which the relationship between the following formulas (1) and (2) is established. When it is this range, since the solubility of a polyester lysine in a solvent is high, the coating property of a composition improves, and it is set as the cured film which is excellent in planarity.

0.2≦Z/Y≦8.0··············(1)

0.2≦(Y+Z)/X≦5.0···(2)

The relationship of the formula (1) is preferably 0.7 ≦ Z / Y ≦ 7.0, more preferably 1.0 ≦ Z / Y ≦ 5.0. Further, the relationship of the formula (2) is preferably 0.5 ≦ (Y + Z) / X ≦ 4.0, more preferably 0.6 ≦ (Y + Z) / X ≦ 2.0.

When the polyester phthalic acid used in the present invention has an acid anhydride group at the molecular terminal, the above monohydric alcohol may be added as needed to carry out the reaction. The polyester phthalic acid obtained by the reaction by adding a monohydric alcohol not only improves the compatibility with the epoxy resin and the epoxy hardener, but also improves the heat hardening of the present invention comprising the epoxy resin and the epoxy hardener. The coatability of the resin composition.

Further, in the case where the above-mentioned fluorene-containing monoamine is reacted with a polyester phthalic acid having an acid anhydride group at a molecular terminal, the acid resistance of the obtained coating film is improved. Further, the monohydric alcohol may be reacted with the hydrazine monoamine and the polyester valine.

When 100 parts by weight or more of the reaction solvent is used per 100 parts by weight of the total 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 hours to 20 hours. When the reaction of the hydrazine monoamine is carried out, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyvalent hydroxy compound is completed, it is preferred to cool the reaction liquid to 40 ° C or lower, and then add the hydrazine monoamine to 10 The reaction is carried out at °C~40 °C for 0.1 hour to 6 hours. Alternatively, a monohydric alcohol can be added at any point in the reaction.

The order of addition of the reaction raw materials to the reaction system is not particularly limited. That is, any one of the following methods may be used: a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound are simultaneously added to a reaction solvent; after dissolving a diamine and a polyhydric hydroxy compound in a reaction solvent, tetracarboxylic acid is added. a dianhydride; a tetracarboxylic dianhydride and a polyvalent hydroxy compound are reacted in advance, and a diamine is added to the reaction product; or a tetracarboxylic dianhydride and a diamine are reacted in advance, and a polyhydric hydroxyl group is added to the reaction product. Compound.

The polyester phthalic acid synthesized in the above manner preferably comprises a constituent unit including the above formula (4) and formula (5), and the terminal is derived from a tetracarboxylic dianhydride, a diamine or a polyhydric hydroxyl group as a raw material. An acid anhydride group, an amine group or a hydroxyl group of the compound, or an additive other than the compounds constitutes the terminal. By including the above configuration, the hardenability becomes good.

In the general formula (4) and the general formula (5), R ⁷ is a tetracarboxylic dianhydride residue, and preferably an organic group having 2 to 30 carbon atoms. R ⁸ is a diamine residue, preferably an organic group having 2 to 30 carbon atoms. R ⁹ is a residue of a polyvalent hydroxy compound, preferably an organic group having 2 to 20 carbon atoms. Here, the tetracarboxylic dianhydride residue, the diamine residue, and the polyvalent hydroxy compound residue mean a polyester formed by reacting a tetracarboxylic dianhydride as a raw material with a diamine or a polyvalent hydroxy compound. Residues derived from various starting materials in valine. The tetracarboxylic dianhydride residue is a group obtained by removing two acid anhydride groups of a tetracarboxylic dianhydride, and the diamine residue is a group obtained by removing two amine groups of a diamine, and a polyhydric hydroxyl group. The compound residue refers to a group obtained by removing two hydroxyl groups among a plurality of hydroxyl groups of the polyvalent hydroxy compound.

The obtained polyester glutamic acid preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 3,000 to 50,000. If it is these ranges, flatness and heat resistance will become favorable.

The weight average molecular weight in the present specification is a value in terms of polystyrene obtained by a gel permeation chromatography (GPC) method (column temperature: 35 ° C, flow rate: 1 ml/min). Standard polystyrene uses polystyrene with a molecular weight of 645 to 132,900 (for example, VARIAN polystyrene calibration kit PL2010-0102), and PLGL is used for the column. MIXED-D (VARIAN Corporation) can be measured using tetrahydrofuran (THF) as a mobile phase. Further, the weight average molecular weight of the commercially available product in the present specification is a catalogue revealed value.

1-2. Epoxy resin

The epoxy resin containing 3 to 20 epoxy groups per molecule and having a weight average molecular weight of less than 5,000 used in the present invention has good compatibility with other components forming the thermosetting resin composition of the present invention. There is no special limit. The number of epoxy groups per molecule contained in the epoxy resin is preferably from 3 to 15, more preferably from 3 to 6, and particularly preferably three. If it is in these ranges, heat resistance will become favorable. The weight average molecular weight of the epoxy resin is preferably from 200 to 3,000, more preferably from 200 to 2,000, still more preferably from 200 to 1,000. If it is in these ranges, flatness will become favorable.

Preferred examples of the epoxy resin are: phenol novolak type epoxy resin, cresol novolak type epoxy resin, glycidyl ether type epoxy resin, bisphenol A novolak type epoxy resin, aliphatic polycondensation water A glyceryl ether, a cyclic aliphatic epoxy resin, or the like. Among these compounds, a glycidyl ether type epoxy resin, a bisphenol A novolak type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolak type epoxy resin are particularly excellent in heat resistance.

A specific example of the epoxy resin is particularly preferably: 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3- Epoxypropoxy]phenyl]]ethyl]phenyl]propane with 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[ a mixture of 4-[1-[4-(2,3-epoxypropoxyphenyl)-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol, and 2- [4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]benzene) Base)]ethyl]phenyl]propane. Further, as the epoxy resins, commercially available products as described below can be used.

A glycidyl ether type epoxy resin containing 3 to 20 epoxy groups per molecule and having a weight average molecular weight of less than 5,000 can be exemplified by TECHMORE VG3101L (trade name, Printec Co., Ltd.), EPPN-501H. 502H (trade name, Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name, Mitsubishi Chemical Corporation), etc., and bisphenol A novolac type epoxy resin: JER 157S65, JER 157S70 (trade name, Mitsubishi) (Chemical Co., Ltd.), etc., the phenol novolac type epoxy resin, for example, EPPN-201 (trade name, Nippon Kayaku Co., Ltd.), JER 152, JER 154 (trade name, Mitsubishi Chemical Corporation), etc. Examples of the phenol novolac type epoxy resin include EOCN-102S, EOCN-103S, EOCN-104S, and EOCN-1020 (trade name, Nippon Kayaku Co., Ltd.).

1-3. Polymers obtained by radical copolymerization (A)

The mixing ratio of the radically polymerizable compound in the above-mentioned radical copolymerized polymer (A) used in the present invention from the viewpoint of the chemical resistance and the flatness after the pre-calcination ((a1), (a2) The weight ratio in the case where the total of (a3) is 100 is preferably (a1) is 0.1 to 5, (a2) is 1 to 95, and (a3) is 1 to 95. The weight ratio is preferably a1: a2: a3 = 0.1 to 3: 15 to 79: 20 to 84, and particularly preferably a1: a2: a3 = 0.5 to 2.5: 20 to 74: 25 to 79.

In the present invention, by using the radical copolymerized polymer (A), after pre-calcination, the polymer is apparently present on the surface of the coating film by surface segregation, and thus chemical resistance Improvement in properties, flatness, heat resistance, and scratch resistance.

1-3-1. Radical polymerizable compound (a1)

In the present invention, the radically polymerizable compound (a1) represented by the following formula (3) is used as a raw material for obtaining the above-mentioned radical copolymerized polymer (A).

(R ¹ is hydrogen or methyl, R ² to R ⁵ are alkyl groups having 1 to 5 carbon atoms, R ⁶ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 1 to 10, and n is 1 to 150. Integer)

Since the radically polymerizable compound (a1) functions as a surfactant, the polymer (A) acts as a surfactant by using (a1) as a raw material, and flatness is not required without adding a surfactant. The adhesion to the base substrate and the coating property are also improved. By adding the radically polymerizable compound (a1), the polymer (A) is easily present on the surface of the film.

In the present invention, in the radically polymerizable compound (a1) represented by the formula (3), R ¹ is preferably hydrogen or a methyl group, R ² to R ⁵ are a methyl group, and R ⁶ is a carbon 1 to 10. An alkyl group, m is an integer of 1 to 5, and n is a compound of an integer of 1 to 150. More preferably, R ¹ is a methyl group, R ² to R ⁵ are a methyl group, R ⁶ is a butyl group, m is 3, and n is an integer of 1 to 150, and particularly preferably n is 30 to 70. An integer compound, particularly preferably a compound having an integer of 50 to 70.

The weight average molecular weight of the radically polymerizable compound (a1) is preferably from 500 to 8,000.

The radically polymerizable compound (a1) can be produced by a known method. In addition, commercially available compounds can also be used. For example, FM-0711 (JN), FM-0721 (JNC Co., Ltd.), FM-0725 (JNC Co., Ltd.), etc. are mentioned.

1-3-2. Radical polymerizable compound having an alkoxyalkyl group (a2)

In the present invention, a radically polymerizable compound (a2) having an alkoxyalkylalkyl group is used as a raw material for obtaining the above-mentioned radical copolymerized polymer (A). The preferred radically polymerizable compound (a2) is selected from the group consisting of 3-(meth)acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, and 3 -(Meth)acryloxypropylmethyldimethoxydecane, 3-(meth)acryloxypropylmethyldiethoxydecane, vinyltrimethoxydecane, vinyl triethyl One or more of the group consisting of oxydecane and p-styryltrimethoxydecane. Among these compounds, 3-(meth)acryloxypropyltrimethoxydecane and 3-(meth)acryloxypropyltriethoxydecane are preferred because of good flatness. By using (a2), transparency, chemical resistance, and the like are improved. Further, the adhesion to the substrate is improved by the decane coupling effect.

1-3-3. A radically polymerizable compound having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group (a3)

In the present invention, at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group is used. The radically polymerizable compound (a3) is used as a raw material for obtaining the above-mentioned radical copolymerized polymer (A). The preferred radically polymerizable compound (a3) is selected from the group consisting of glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl ether, (meth)acrylic acid, 4-hydroxyphenylvinyl One or more of the groups consisting of ketones. (a3) The function as a crosslinking agent of a polymer is especially useful for improving heat resistance, chemical resistance, etc. after pre-baking.

1-3-4. Method for producing radical copolymerized polymer (A)

The radically polymerizable polymer (A) is a radically polymerizable compound (a1) represented by the above formula (3), a radically polymerizable compound (a2) having an alkoxyalkyl group, and a ring. The radically polymerizable compound (a3) of at least one of an oxy group, a carboxyl group, and a hydroxyphenyl group is obtained by radical copolymerization. The method for producing the radical copolymerized polymer (A) is not particularly limited, and the radically polymerizable polymer (A) can be produced by heating the above radical polymerizable compound 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 hour to 48 hours. Further, the reaction can be carried out under any pressure of pressurization, reduced pressure or atmospheric pressure.

The solvent used in the above radical copolymerization reaction is preferably a solvent which dissolves the produced polymer. Specific examples of the solvent are: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, acetone, 2-butanone, ethyl acetate , butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl methoxyacetate, methoxy Ethyl acetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxopropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate , 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, 2-hydroxypropionic acid methyl ester, 2-hydroxypropionic acid propyl ester, 2-methyl Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxyl Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropanoate, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2-methylpropionic acid Ethyl ester, methyl pyruvate, ethyl pyruvate, propyl pyruvate, 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 Methyl 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, C Alcohol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol single Ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ether, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, γ-butyrolactone, or N,N-dimethylacetamide, cyclohexanone. The solvent may be one of the solvents, or a mixture of two or more of the solvents.

The radical copolymerized polymer (A) used in the present invention can directly form a solvent which is used in the polymerization to form a radical copolymerized polymer solution in consideration of workability and the like, and can also be considered as a solvent. Solid shape to portability Free radical copolymerization of polymers.

When the weight average molecular weight determined by GPC analysis using polystyrene standards is in the range of 1,000 to 50,000, the radical copolymerized polymer (A) is preferred because it has good film formability. Further, when the weight average molecular weight is in the range of 2,500 to 20,000, the flatness of the film is good, and therefore it is more preferable. Further, when the weight average molecular weight is in the range of 2,500 to 15,000, the chemical resistance after pre-baking is good, which is particularly preferable.

1-4. Epoxy hardener

In the thermosetting resin composition of the present invention, an epoxy curing agent may be added in order to improve flatness, heat resistance, and chemical resistance. The epoxy resin is an acid anhydride-based curing agent, an amine-based curing agent, a phenol-based curing agent, and a catalyst-type curing agent, and is preferably an acid anhydride-based curing agent in terms of coloring and heat resistance.

Specific examples of the acid anhydride-based curing agent include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride. One or more of phthalic anhydride, trimellitic anhydride, and styrene-maleic anhydride copolymer. Among these compounds, trimellitic anhydride and hexahydrotrimellitic anhydride are particularly preferable in terms of balance between heat resistance and solubility in a solvent.

1-5. Proportion of polyester proline, epoxy resin, radical copolymerized polymer (A), epoxy hardener

In the thermosetting resin composition of the present invention, the ratio of the epoxy resin is from 20 parts by weight to 400 parts by weight based on 100 parts by weight of the polyester phthalic acid. If epoxy When the ratio is in this range, the balance between flatness, heat resistance, chemical resistance, and adhesion is good. It is especially preferable if the epoxy resin is in the range of 50 parts by weight to 300 parts by weight.

The radical copolymerized polymer (A) is added for the purpose of improving chemical resistance and flatness after pre-calcination. In the thermosetting resin composition of the present invention, the ratio of the radical copolymerized polymer (A) is from 0.1 part by weight to 50 parts by weight based on 100 parts by weight of the polyester phthalic acid. When the ratio of the radical copolymerized polymer (A) is in this range, the balance of flatness, heat resistance, chemical resistance, and adhesion is good, which is preferable. It is particularly preferable that the radical copolymerized polymer (A) is in the range of 0.2 part by weight to 30 parts by weight.

In the case where an epoxy curing agent is added for the purpose of improving flatness, heat resistance, and chemical resistance, the ratio of the epoxy resin to the epoxy curing agent is: epoxy hardening with respect to 100 parts by weight of the epoxy resin The agent is from 1 part by weight to 60 parts by weight, preferably from 5 parts by weight to 25 parts by weight. More specifically, the amount of the epoxy curing agent to be added is preferably 0.1 to 1.5 equivalents based on the carboxylic acid anhydride group or the carboxyl group in the epoxy curing agent. At this time, the carboxylic anhydride group is calculated by 2 yuan. When the carboxylic anhydride group or the carboxyl group is added in an amount of from 0.15 equivalents to 0.8 equivalents, the chemical resistance is further improved, which is particularly preferable.

1-6. Other ingredients

In the thermosetting resin composition of the present invention, various additives may be added in order to improve coating uniformity and adhesion. The additives mainly include solvents, anionic, cationic, nonionic, fluorine or lanthanide leveling agents. Interfacial adhesion improver such as surfactant, decane coupling agent, hindered phenolic, hindered amine, phosphorus, and sulfur An antioxidant such as a compound, a hardening accelerator, and a thermosensitive acid generator.

1-6-1. Solvent

The solvent used in the polymerization reaction in the case of synthesizing the polyester phthalic acid and the radical copolymerization polymer (A) can be used as it is as the solvent used for the thermosetting resin composition of the present invention. The solid content concentration of the thermosetting resin composition is selected according to the film thickness of the coating film, and usually includes a solid component in a range of 5 parts by weight to 50 parts by weight in 100 parts by weight of the resin composition. Further, the amount of the solvent can be appropriately determined in consideration of problems such as the operation of the resin composition. In some cases, for example, a thermosetting resin composition in a solid state may be formed by removing a solvent from the thermosetting resin composition.

1-6-2. Surfactant

In the thermosetting resin composition of the present invention, a surfactant may be added in order to improve coating uniformity. Examples of the surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 (all of which are trade names, Kyoeisha Chemical Industry Co., Ltd.), and Disperbyk 161. , Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Disperbyk 181, Disperbyk 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (above) All are trade names, BYK-Chemie Japan Co., Ltd., KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all of which are trade names, Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40, Surflon S611 (all of which are trade names, AGC Qingmei Chemical Co., Ltd. Company), Ftergent 222F, Ftergent 251, FTX-218 (all of which are trade names, Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all of which are trade names, Mitsubishi Materials Co., Ltd.), Megafac F-171, Megafac F-177, Megafac F-410, Megafac F-430, Megafac F-444, Megafac F- 472SF, Megafac F-475, Megafac F-477, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac F-558, Megafac R-30, Megafac R- 94, Megafac RS-75, Megafac RS-72-K, (all of which are trade names, Dainippon Ink (DIC) Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (all of the above are trade names, Evonik Degussa Japan), fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate , fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetra (fluoroalkyl polyoxyethylene ), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amine sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl Ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxygen Ethylene stearate, polyoxyethylene laurylamine, sorbitol laurate, sorbitol palmitate, sorbitol stearate, sorbitol oleate, sorbitol fatty acid ester, poly Oxyethylene sorbitan laurate, polyoxyethylene sorbitol palmitate, polyoxyethylene sorbitol stearic acid Ester, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, or alkyl diphenyl ether disulfonate. It is preferred to use at least one selected from the above compounds for the above additives.

Among the surfactants, selected from the group consisting of BYK306, BYK342, BYK346, KP-341, KP-358, KP-368, Surflon S611, Megafac F-477, Megafac F-556, TEGO Twin 4000, fluoroalkylbenzene Sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetra (fluoroalkyl ethoxylate) At least one of the fluoroalkyltrimethylammonium salt and the fluoroalkylaminosulfonate is preferred because the coating uniformity of the thermosetting resin composition is improved.

In the case where the above surfactant is contained, the content of the surfactant in the thermosetting composition of the present invention is usually preferably from 0.01% by weight to 10% by weight.

1-6-3. Adhesion improver

The thermosetting resin composition of the present invention may further contain an adhesion improving agent from the viewpoint of further improving the adhesion between the formed cured film and the substrate. From the above viewpoints, the content of the adhesion improving agent is preferably 10% by weight or less based on the total amount of the thermosetting resin composition. On the other hand, it is preferably 0.01% by weight or more.

As such an adhesion improving agent, for example, a decane-based, aluminum-based or titanate-based coupling agent can be used, and specific examples thereof include 3-glycidoxypropyldimethylethoxy decane and 3-glycidyloxygen. a decane coupling agent such as propylmethyldiethoxysilane or 3-glycidoxypropyltrimethoxydecane, an aluminum coupling agent such as acetaloxydiisopropylaluminate, or tetraisopropyl Bis (dioctyl phosphite) titanate A titanate coupling agent such as tetraisopropylbis (dioctylphosphite) titanate.

Among these compounds, 3-glycidoxypropyltrimethoxydecane is preferred because it has a large effect of improving adhesion.

1-6-4. Antioxidants

The thermosetting resin composition of the present invention may further contain an antioxidant in terms of improving transparency and preventing yellowing in the case where the cured film is exposed to a high temperature. From such a viewpoint, the content of the antioxidant is 0.1 to 5 parts by weight based on the total amount of the thermosetting resin composition.

An antioxidant such as a hindered phenol type, a hindered amine type, a phosphorus type or a sulfur type compound may be added to the thermosetting composition of the present invention. Among them, from the viewpoint of weather resistance, a hindered phenol system is preferred. Specific examples include Irganox 1010, Irganox FF, Irganox 1035, Irganox 1035FF, Irganox 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Irganox 245FF Irganox 245DWJ, Irganox 259, Irganox 3114, Irganox 565, Irganox 565DD, Irganox 295 (trade name, 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 (trade name, ADEKA). More preferably, it is Irganox 1010, ADK STAB AO-60.

1-6-5. Hardening accelerator

Hardening accelerator is used to promote the reaction of epoxy resin with epoxy hardener and improve hard The heat resistance and the chemical resistance of the chemical film are 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the solid component of the thermosetting resin composition (residual component from which the solvent is removed from the resin composition). use.

The hardening accelerator may have any function of promoting the reaction between the epoxy resin and the epoxy curing agent, and examples thereof include an imidazole curing accelerator, a phosphine curing accelerator, an ammonium curing accelerator, and a Lewis acid curing accelerator. Agents and the like are exemplified.

1-6-6. Sensible acid generator

The heat-sensitive acid generator is used for imparting sufficient hardness and chemical resistance to the cured film even when the thermosetting resin composition of the present invention is used under conditions of low temperature curing at less than 200 ° C. 100 parts by weight of the solid component of the thermosetting resin composition (residual component from which the solvent is removed from the resin composition) is added in an amount of 0.001 part by weight to 3 parts by weight.

Examples of the thermosensitive acid generator include an onium salt, a benzothiazolium salt, an ammonium salt, a phosphonium salt and the like.

1-6-7. Other additives

In the case where the polyester phthalic 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. Preservation of thermosetting resin composition

When the thermosetting resin composition of the present invention is stored in a temperature range of -30 ° C to 25 ° C, the composition has a good stability over time, which is preferable. If the storage temperature is -20 ° C ~ 10 ° C, there is no precipitate, better

2. A cured film obtained from a thermosetting resin composition

The thermosetting resin composition of the present invention can be mixed with a polyester phthalic acid, an epoxy resin, and a radical copolymerized polymer (A), and a solvent or an epoxy hardener is optionally added depending on the intended characteristics. The coupling agent, the surfactant, and other additives are obtained by uniformly mixing and dissolving them.

When the thermosetting resin composition prepared in the above manner (after being dissolved in a solvent in a solid state without a solvent) is applied to the surface of the substrate, for example, by removing the solvent by heating or the like, a coating film can be formed. The coating of the thermosetting resin composition on the surface of the substrate can be carried out by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, or a slit coating method. Then, the coating film is pre-calcined by a hot plate or an oven or the like. The pre-baking conditions vary depending on the type of each component and the blending ratio, and are usually from 70 ° C to 150 ° C for 5 minutes to 15 minutes in the case of an oven, and from 1 minute to 5 minutes in the case of a hot plate. Then, in order to harden the coating film, the main baking is performed. The main calcination conditions vary depending on the type of each component and the blending ratio, and are usually from 180 ° C to 250 ° C, preferably from 200 ° C to 250 ° C, and if it is an oven, it is heated for 30 minutes to 90 minutes, and if it is a hot plate Then, heat treatment is performed for 5 minutes to 30 minutes, whereby a cured film can be obtained.

The cured film obtained in the above manner is formed by heating and dehydrating cyclization to form a quinone bond, 2) a carboxylic acid and an epoxy resin of a polyester phthalic acid. The reaction is carried out to obtain a high molecular weight, and 3) the epoxy resin is cured and polymerized, so that it is very strong, and is excellent in transparency, heat resistance, chemical resistance, flatness, and adhesion. In addition, for the same reason, light resistance can be expected Excellent in spatterability, scratch resistance, and coating properties. Therefore, the cured film of the present invention can be effectively used as a protective film for a color filter, and a color filter can be used to manufacture a liquid crystal display element or a solid-state imaging element. In addition, the cured film of the present invention can be effectively used as a transparent insulating film formed between a TFT and a transparent electrode or a transparent insulating film formed between a transparent electrode and an alignment film, in addition to being used as a protective film for a color filter. . Further, the cured film of the present invention can also be effectively used as a protective film for an LED illuminator.

[Examples]

The present invention will be specifically described based on the synthesis examples, examples, and comparative examples, but the present invention is not limited by the examples.

First, a polyester proline solution containing a reaction product of a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound was synthesized in the following manner (Synthesis Example 1 and Synthesis Example 2).

[Synthesis Example 1] Synthesis of Polyester Amidinic Acid Solution (B1)

Hydroxyl-depleted methyl 3-methoxypropionate (hereinafter abbreviated as "MMP"), 3,3',4,4'-diphenyl ether was added to a four-necked flask equipped with a stirrer with the following weight. Tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA"), 1,4-butanediol, and benzyl alcohol were stirred at 130 ° C for 3 hours under a nitrogen stream.

MMP 446.96g

ODPA 183.20g

1,4-butanediol 31.93g

Benzyl alcohol 25.54g

Then, the reaction solution was cooled to 25 ° C, and 3,3'-diaminodiphenyl hydrazine (hereinafter abbreviated as "DDS") and MMP were added under the following weight, and stirred at 20 ° C to 30 ° C 2 After an hour, it was stirred at 115 ° C for 1 hour.

DDS 29.33g

MMP 183.04g

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

The solution was cooled to room temperature to obtain a 30 wt% solution (B1) of pale yellow transparent polyester phthalic acid.

A portion of the solution was collected and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the obtained polymer (B1) had a weight average molecular weight of 4,200.

[Synthesis Example 2] Synthesis of Polyester Amidinic Acid Solution (B2)

In a four-necked flask equipped with a stirrer, dehydrated and purified propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA"), ODPA, SMA1000P (trade name, styrene. Adipic anhydride copolymer, Chuan crude oil Co., Ltd.), 1,4-butanediol, benzyl alcohol, dehydrated purified diethylene glycol methyl ether (hereinafter referred to as "EDM"), under a dry nitrogen stream Stir at 130 ° C for 3 hours.

PGMEA 504.00g

ODPA 47.68g

SMA1000P 144.97g

1,4-butanediol 9.23g

Benzyl alcohol 55.40g

EDM 96.32g

Then, the reaction liquid was cooled to 25 ° C, and DDS and EDM were added in the following weight, and the mixture was stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 115 ° C for 1 hour.

DDS 12.72g

EDM 29.68g

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

The solution was cooled to room temperature to obtain a 30 wt% solution (B2) of pale yellow transparent polyester phthalic acid.

A portion of the solution was collected and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the obtained polymer (B2) had a weight average molecular weight of 21,000.

Then, the radically polymerizable compound (a1) represented by the formula (3), the radically polymerizable compound (a2) having an alkoxyalkyl group, and an epoxy group, a carboxyl group, or a hydroxybenzene group are synthesized in the following manner. A polymer (A) obtained by radically copolymerizing a radically polymerizable compound (a3) of at least one of the groups.

[Synthesis Example 3] Synthesis of radical copolymerized polymer (A1)

In a four-necked flask equipped with a stirrer, dehydrated purified EDM as a polymerization solvent and FM-0721 as a radically polymerizable compound (a1) were added in the following weight (in the above formula (3), R ¹ ~ R ⁵ is a methyl group, R ⁶ is a butyl group, m = 3, n = 66, a weight average molecular weight: 5,000, JNC Co., Ltd.), 3- as a polymerizable compound (a2) having an alkoxyalkyl group Methyl propylene methoxy propyl trimethoxy decane, glycidyl methacrylate as a radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group, further having the following weight V-601 (Wako Pure Chemical Industries, Ltd.), which was used as a polymerization initiator, was stirred at 90 ° C for 2 hours under a stream of dry nitrogen.

EDM 40.00g

FM-0721 0.20g

Glycidyl methacrylate 8.00g

3-methylpropenyloxypropyltrimethoxydecane 11.80g

V-601 2.00g

The solution was cooled to room temperature to obtain a 33.3 wt% solution of the polymer (A1).

A portion of the solution was collected and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the obtained polymer (A1) had a weight average molecular weight of 5,400.

[Synthesis Example 4] Synthesis of Polymer (A2)

In the same manner as in Synthesis Example 3, the following components were added in the following weights to carry out polymerization.

EDM 40.00g

FM-0721 0.40g

Glycidyl methacrylate 8.00g

3-methylpropenyloxypropyltrimethoxydecane 11.60g

V-601 2.00g

The same treatment as in Synthesis Example 3 was carried out to obtain a 33.3 wt% solution of the polymer (A2). GPC analysis of the obtained polymer (A2) (polystyrene standard) The weight average molecular weight determined was 5,800.

[Comparative Synthesis Example 1] Synthesis of Radical Copolymerized Polymer (C1)

In the same manner as in Synthesis Example 3, the following components were added in the following weights to carry out polymerization.

EDM 40.00g

Glycidyl methacrylate 8.00g

3-methylpropenyloxypropyltrimethoxydecane 12.00g

V-601 2.00g

The same treatment as in Synthesis Example 3 was carried out to obtain a 33.3 wt% solution of the polymer (C1). The weight average molecular weight of the obtained polymer (C1) determined by GPC analysis (polystyrene standard) was 5,500.

[Comparative Synthesis Example 2] Synthesis of Radical Copolymerized Polymer (C2)

In the same manner as in Synthesis Example 3, the following components were added in the following weights to carry out polymerization.

EDM 40.00g

FM-0721 0.20g

Glycidyl methacrylate 9.00g

Benzyl methacrylate 10.80g

V-601 2.00g

The same treatment as in Synthesis Example 3 was carried out to obtain a 33.3 wt% solution of the polymer (C2). The weight average molecular weight of the obtained polymer (C2) determined by GPC analysis (polystyrene standard) was 5,900.

[Comparative Synthesis Example 3] Synthesis of Radical Copolymerized Polymer (C3)

The following components were placed in the same manner as in Synthesis Example 3 under the following weight, and stirred at 110 ° C for 2 hours under a nitrogen stream.

EDM 40.00g

FM-0721 0.20g

Benzyl methacrylate 15.00g

Methacrylic acid 4.80g

V-601 2.00g

The same treatment as in Synthesis Example 3 was carried out to obtain a 33.3 wt% solution of the polymer (C3). The weight average molecular weight of the obtained polymer (C3) determined by GPC analysis (polystyrene standard) was 6,200.

Then, the polyester phthalic acid (B1, B2) obtained in Synthesis Example 1 and Synthesis Example 2, and the radical copolymerized polymers (A1 and A2) obtained in Synthesis Example 3 and Synthesis Example 4 were used, and Comparative Synthesis Example 1 was used. Comparative Synthesis Example 2, the radical copolymerized polymer (C1, C2, C3) obtained in Comparative Synthesis Example 3, and a commercially available polyfunctional epoxy resin having a weight average molecular weight of less than 5,000 were prepared by thermosetting in the following manner. In the resin composition, a cured film was obtained from the thermosetting resin composition, and the cured film was evaluated (Examples 1 to 3, Comparative Example 1 to Comparative Example 5, Tables 1 to 4).

[Example 1]

According to the ratio of Table 1, the polyester proline (B1) and TECHMORE VG3101L (trade name, Printec Co., Ltd.) obtained in Synthesis Example 1 (the number of epoxy groups per molecule: 3, molecular weight: 592.7) , the freedom obtained in Synthesis Example 3 Copolymerized polymer (A1), S510 (trade name, 3-glycidoxypropyltrimethoxydecane (JNC Co., Ltd.)), TMA (trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.)), IRGANOX 1010 (trade name, BASF Japan Co., Ltd.), dehydrated purified MMP, and dehydrated purified EDM were mixed and dissolved, and filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting resin composition.

[Example 2, Example 3, Comparative Example 1 to Comparative Example 5]

Example 2 and Example 3 In the same manner as in Example 1, the components were mixed and dissolved according to the ratio of Table 1, and Comparative Examples 1 to 5 were in the same manner as in Example 1, according to the ratio of Table 2. Each component was mixed and dissolved, and filtered using a membrane filter having a pore size of 0.2 μm to obtain a thermosetting resin composition.

[Evaluation method 1 of thermosetting composition]

1) Chemical resistance after pre-calcination

The obtained thermosetting resin composition was spin-coated on a glass substrate at 500 rpm to 600 rpm for 10 seconds, and then pre-calcined on a hot plate at 130 ° C for 1 minute and 30 seconds to form a coating film. Then, a drop of a 0.05% potassium hydroxide aqueous solution was dropped on the coating film, and after standing for 1 minute, the substrate was washed with pure water for 1 minute, and dried on a hot plate at 100 ° C for 2 minutes. The substrate was heated in an oven at 230 ° C for 30 minutes to cure the coating film to obtain a cured film having a film thickness of 1.5 μm. The obtained cured film was observed with a polarizing microscope, and if no trace of the liquid droplet was observed, it was represented by ○, and when a trace of the liquid droplet was observed, it was represented by ×.

[Evaluation method 2 of thermosetting composition]

The obtained thermosetting resin composition is applied to the glass at 500 rpm to 600 rpm. After spin coating on the substrate and the color filter substrate for 10 seconds, the film was pre-calcined on a hot plate at 130 ° C for 1 minute and 30 seconds to form a coating film. Then, the coating film was cured by heating in an oven at 230 ° C for 30 minutes to obtain a cured film having a film thickness of 1.5 μm. The properties of the cured film obtained in the above manner were evaluated for flatness, heat resistance, transparency, and adhesion. The results of these evaluations are shown in Table 3.

2) Flatness

Use the step difference. Surface roughness. The fine shape measuring device (trade name, P-16+, KLA TENCOR Co., Ltd.) was used to measure the step of the surface of the cured film of the color filter substrate with the obtained cured film. The case where the maximum value of the step difference between the R, G, and B pixels including the black matrix (hereinafter referred to as the maximum step difference) is less than 0.2 μm is denoted by ○, and the case where 0.2 μm or more is used is denoted by ×. Further, the color filter substrate used was a pigment dispersion color filter (hereinafter abbreviated as CF) using a resin black matrix having a maximum step difference of about 1.1 μm.

3) Transparency

For the glass substrate with the obtained cured film, a UV-visible near-infrared spectrophotometer V-670 (trade name, Japan Spectrophoto Co., Ltd.) was used, and a glass substrate not having a transparent film was used as a reference, and light having a wavelength of 400 nm was measured. Penetration rate. The case where the light transmittance is 95% or more is denoted by ○, and the case where the light transmittance is less than 95% is denoted by ×.

4) Heat resistance

After the glass substrate with the obtained cured film was further heated at 250 ° C for 1 hour, the residual film ratio after heating with respect to the film thickness before heating and the transmittance at 400 nm after heating were measured. The residual film rate after heating is 95% or more and 400 nm after heating The case where the transmittance is 95% or more is referred to as ○. The case where the residual film ratio after heating is less than 95% or the transmittance at 400 nm after heating is less than 95% is referred to as ×.

5) Adhesion

The glass substrate with the obtained cured film was evaluated by a mesh peeling test (cross cutting test). The evaluation is the number of remaining meshes after peeling off the tape in 100 meshes of 1 mm square. The case where the residual number /100 is 100/100 is denoted by ○, and the case of 99/100 or less is denoted by ×.

The results obtained by the above evaluation methods for the thermosetting resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Tables 3 and 4.

As is clear from the results shown in Table 4, it is understood that the thermosetting resin compositions of Examples 1 to 3 are excellent in chemical resistance and flatness after pre-baking, and further in transparency, heat resistance, and adhesion. Balance all aspects. On the other hand, the thermosetting resin composition containing no radical copolymerized polymer (A) of Comparative Example 1 and Comparative Example 2 was excellent in flatness, but was inferior in chemical resistance after pre-baking. In addition, the thermosetting resin composition containing the radically polymerizable polymer of the radically polymerizable compound (a1) represented by the formula (3) of Comparative Example 3, and the inclusion of Comparative Example 3 and Comparative Example 4 The thermosetting resin composition of the radical copolymerized polymer containing no radical polymerizable compound (a2) having an alkoxyalkyl group is inferior in chemical resistance and flatness after pre-baking. As described above, the radically polymerizable compound (a1) represented by the formula (3), the radically polymerizable compound (a2) having an alkoxyalkyl group, and the epoxy group are used in a specific amount. When the polymer (A) in which the radically polymerizable compound (a3) of at least one of the carboxyl group and the hydroxyphenyl group is radically copolymerized, all the properties can be satisfied.

[Industrial availability]

The thermosetting resin composition of the present invention is excellent in chemical resistance after pre-baking, and the cured film obtained from the thermosetting resin composition of the present invention is excellent in transparency as well as heat resistance and the like as an optical material. It can be used as a protective film of various optical materials such as a color filter, an LED light-emitting element, and a light-receiving element, and a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (23)

A thermosetting resin composition comprising a polyester phthalic acid, an epoxy resin, and a polymer (A), wherein the polymer (A) is a radical represented by the following formula (3) The polymerizable compound (a1), the radically polymerizable compound (a2) having an alkoxyalkyl group, and the radical polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group are freely available. The polyester phthalic acid is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components by using the following formula (1) and The ratio of the relationship of the formula (2) is such that the polyester phthalic acid obtained by reacting X-mole tetracarboxylic dianhydride, Y-mole diamine, and Z-mole polyvalent hydroxy compound, 0.2 ≦Z/ Y≦8.0············· (1) 0.2≦(Y+Z)/X≦5.0··· (2) The above epoxy resin contains 3 to 20 in each molecule. An epoxy group having an epoxy group and a weight average molecular weight of less than 5,000, and the epoxy resin is 20 parts by weight to 400 parts by weight based on 100 parts by weight of the polyester phthalic acid. Polymer (A) of the weight average molecular weight of 1,000 to 50,000, and the polyester acid amide with respect to 100 parts by weight of the polymer (A) is 0.1 parts by weight to 50 parts by weight; (R ¹ is hydrogen or methyl, R ² to R ⁵ are alkyl groups having 1 to 5 carbon atoms, R ⁶ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 1 to 10, and n is 1 to 150. Integer). The thermosetting resin composition according to claim 1, wherein the epoxy curing agent is contained in an amount of from 1 part by weight to 60 parts by weight per 100 parts by weight of the epoxy resin. The thermosetting resin composition according to claim 1 or 2, wherein the raw material component of the polyester phthalic acid further comprises a monohydric alcohol. The thermosetting resin composition according to claim 3, wherein the monohydric alcohol is selected from the group consisting of isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl One or more kinds of -3-hydroxymethyloxetane. The thermosetting resin composition according to any one of claims 1 to 4, wherein the raw material component of the polyester phthalic acid further comprises a styrene-maleic anhydride copolymer. The thermosetting resin composition according to any one of the items 1 to 5, wherein the polyester phthalic acid has a composition represented by the following formula (4) and formula (5) unit: (R ⁷ is a tetracarboxylic dianhydride residue, R ⁸ is a diamine residue, and R ⁹ is a residue of a polyvalent hydroxy compound). The thermosetting resin composition according to any one of claims 1 to 6, wherein the polyester glutamic acid has a weight average molecular weight of 1,000 to 200,000. The thermosetting resin composition according to any one of claims 1 to 7, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4'-diphenylfluorene Carboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, and ethylene One or more of the alcohols (dehydrated trimellitate). The thermosetting resin composition according to any one of claims 1 to 8, wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium and bis[4-( One or more of 3-aminophenoxy)phenyl]indoles. The thermosetting resin composition according to any one of the preceding claims, wherein the polyhydric hydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, and 1,5 - pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol, One or more of tris(2-hydroxyethyl) isocyanurate. In the thermosetting composition according to any one of the above-mentioned items (3), in the radically polymerizable compound (a1) represented by the above formula (3), R ¹ is a methyl group. R ² to R ⁵ are a methyl group, R ⁶ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 1 to 5, and n is an integer of 1 to 150. The thermosetting composition according to any one of the items 1 to 11, wherein the radically polymerizable compound (a2) having an alkoxyalkyl group is selected from the group consisting of 3-(methyl) Propylene methoxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, 3-(meth)acryloxypropylmethyldimethoxydecane, 3 -1 in a group consisting of -(meth)acryloxypropylmethyldiethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, p-styryltrimethoxydecane More than one species. The thermosetting composition according to any one of the items 1 to 12, wherein the radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group It is one or more selected from the group consisting of glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl ether, (meth)acrylic acid, and 4-hydroxyphenyl vinyl ketone. . The thermosetting resin composition according to any one of the present invention, wherein the epoxy curing agent is one or more selected from the group consisting of trimellitic anhydride and hexahydrotrimellitic anhydride. . The thermosetting resin composition according to claim 2, wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, and the diamine is 3 , 3'- Diaminodiphenylphosphonium, the above polyvalent hydroxy compound is 1,4-butanediol, and the above radical polymerizable compound (a2) having an alkoxyalkyl group is 3-(meth)acryloxypropyl Trimethoxy decane, the above-mentioned radical copolymerization of the polymer (A) has a weight average molecular weight of 1,000 to 50,000, an epoxy hardener is trimellitic anhydride, and further contains methyl 3-methoxypropionate. As a solvent. The thermosetting resin composition according to claim 3, wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, and the diamine is 3 3'-diaminodiphenylanthracene, the above polyvalent hydroxy compound is 1,4-butanediol, the monohydric alcohol is benzyl alcohol, and the above-mentioned radically polymerizable compound (a2) having an alkoxyalkyl group is 3-(meth)acryloxypropyltrimethoxydecane, wherein the radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group and a hydroxyphenyl group is glycidyl methacrylate, The polymer (A) obtained by radical copolymerization described above has a weight average molecular weight of 1,000 to 50,000, an epoxy curing agent of trimellitic anhydride, and a methyl 3-methoxypropionate as a solvent. A cured film obtained by the thermosetting resin composition according to any one of claims 1 to 16. A color filter using the cured film as described in claim 17 as a protective film. A liquid crystal display element using the color filter described in claim 18 of the patent application. A solid-state photographic element using the color filter of claim 18 of the patent application. A liquid crystal display element using the cured film described in claim 17 as a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode. A liquid crystal display element using the cured film according to claim 17 of the invention as a transparent insulating film formed between a transparent electrode and an alignment film. A light-emitting diode (LED) light-emitting body using the cured film described in claim 17 as a protective film.