KR20150089919A - Thermosetting compositions and cured products using the same - Google Patents

Abstract

The present invention relates to a thermosetting composition and a cured film obtained by using the same, the composition comprising: a low molecular epoxy compound (A) comprising at least three epoxy groups, with the weight average molecular weight of less than 5000; a high molecular epoxy compound (B) comprising at least three epoxy groups, with the weight average molecular weight of more than or equal to 30000; and a carboxylic compound (C) comprising at least three carboxylic groups. A cured film with excellent both properties of flatness and compliance of foreign substances can be obtained by using the thermosetting composition of the present invention.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermosetting composition and a cured product using the thermosetting composition.

The present invention relates to a thermosetting composition and a cured film obtained by heating the same.

In the manufacturing process of an element such as a liquid crystal display element, various chemical treatments such as an organic solvent, an acid, and an alkali solution are performed, and when the wiring electrode is formed by sputtering, the surface is sometimes locally heated to a high temperature. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and deterioration of the surface of various devices. These protective films are required to have various characteristics that can withstand various treatments in the above-described manufacturing process. Concretely, deterioration such as chemical resistance such as solvent resistance, acid resistance and alkali resistance, water resistance, heat resistance, adhesion to a base substrate such as glass, transparency, resistance to scratches, coating property, Light resistance and the like are required. Particularly, in recent years, as a characteristic when used as a protective film for a color filter, flatness and foreign matter followability have become important.

A color filter used for a display element typified by a liquid crystal display element is composed of pixels of a plurality of colors, and a step is present on the surface of the color filter. Particularly, when a color filter is used for a liquid crystal display element, there is a difference in cell gap at each place due to the step difference of the color filter, and the inclination of the liquid crystal compound to the substrate is not uniform at every place. The step of the color filter can be made small by forming a protective film. In this specification, the smaller the step after formation of the protective film, the better the "flatness" of the protective film or the material for forming the protective film. The " flatness " greatly affects the display quality of a display element using a color filter.

In the manufacturing process of the color filter, foreign matter may adhere to the surface of the substrate unintentionally. At this time, when the thermosetting composition is coated on the substrate on which the foreign substance exists and dried, the film thickness around the foreign substance is confused. As a result, the reflected light around the foreign substance is disturbed, So that foreign substances tend to become conspicuous. The characteristic of alleviating the phenomenon that the foreign substance becomes conspicuous is called " foreign matter followability ". In the present specification, the "excellent foreign matter followability" of the protective film or the material for forming the protective film means that the phenomenon does not easily occur and the foreign matter is not conspicuous. Foreign matter followability greatly affects the yield of the color filter.

Conventionally, a method of using a thermosetting composition containing an epoxy compound having a relatively small molecular weight (see, for example, Patent Document 1) has been proposed in order to improve flatness. Further, a method of using a thermosetting composition containing an epoxy compound having a relatively large molecular weight (for example, see Patent Document 2) has been proposed in order to improve foreign matter followability. By changing the molecular weight of the epoxy compound, it was possible to control the flatness and follow-up property of the foreign substance, but if one property is improved, the other property is deteriorated. Flatness and foreign matter followability are contradictory characteristics, and it has been a very difficult problem to achieve compatibility between flatness and foreign matter followability.

Japanese Patent Application Laid-Open No. 2008-156546 Japanese Patent Application Laid-Open No. 2005-105264

In consideration of the above-mentioned situation, development of a thermosetting composition capable of achieving both flatness and foreign matter followability is required.

The inventors of the present invention have made various studies to solve the above-mentioned problems. As a result, they have found that a low molecular weight epoxy compound containing three or more epoxy groups and having a weight average molecular weight of less than 5,000 and an epoxy group containing three or more epoxy groups, A high molecular weight epoxy compound, and a carboxyl compound containing at least three carboxyl groups, and has completed the present invention.

The present invention has the following configuration.

(A) a low molecular weight epoxy compound (A) containing three or more epoxy groups and having a weight average molecular weight of less than 5,000, a high molecular weight epoxy compound (B) containing three or more epoxy groups and having a weight average molecular weight of 30,000 or more, A thermosetting composition comprising a carboxyl compound (C) containing three or more.

[2] The epoxy resin composition according to any one of [1] to [3], wherein the weight of the low molecular weight epoxy compound (A) is 50 to 99% by weight and the molecular weight of the low molecular weight epoxy compound (A) The thermosetting composition according to [1], wherein the weight of the carboxyl compound (C) is 30 to 200 parts by weight based on 100 parts by weight of the total of the compound (B).

[3] The epoxy resin composition according to any one of [1] to [3], wherein the weight of the low molecular weight epoxy compound (A) is 70 to 95% by weight and the weight of the low molecular weight epoxy compound (A) The thermosetting composition according to item [1], wherein the weight of the carboxyl compound (C) is 40 to 120 parts by weight based on 100 parts by weight of the total amount of the compound (B).

[4] the carboxyl compound (C) is at least one selected from a polyester amide acid (Ca) and a carboxyl group-containing polymer (Cb);

Wherein the polyester amide acid (Ca) is a reaction product obtained by reacting tetracarboxylic dianhydride (ca1), diamine (ca2), and polyhydric hydroxy compound (ca3) as essential components, (C-11) and (C-12) are satisfied with respect to tetracarboxylic dianhydride (ca1), Y mol diamine (ca2), and Z mol polyhydric hydroxy compound (ca3) A ratio;

0.2? Z / Y? 8.0 (C-11)

0.2? (Y + Z) /X? 1.5 (C-12)

1] to [3], wherein the carboxyl group-containing polymer (Cb) is obtained by polymerizing a mixture of a radically polymerizable monomer having a carboxyl group and a radically polymerizable monomer containing another radically polymerizable monomer (cb2) A thermosetting composition according to any one of the preceding claims.

[5] The process according to [1], wherein the polyester amide acid (Ca) is reacted with a monohydric alcohol (ca4) in addition to a tetracarboxylic dianhydride (ca1), a diamine (ca2), and a polyhydric hydroxy compound (ca3) Wherein the thermosetting composition is the thermosetting composition according to item [4].

[6] The thermosetting composition according to any one of [4] or [5], wherein the polyester amide acid (Ca) is a reaction product obtained by reacting a styrene / maleic anhydride copolymer (cb5).

[7] The thermosetting resin composition according to any one of [1] to [3], wherein the radically polymerizable monomer (cb1) having a carboxyl group is at least one selected from (meth) acrylic acid and (meth) acrylate having a carboxyl group, and the other radically polymerizable monomer (cb2) The thermosetting composition according to (4), wherein the thermosetting composition is at least one selected from the group consisting of (meth) acrylate having a hydroxyl group, (meth) acrylate having an aliphatic group, (meth) acrylate having an aromatic group, and N-substituted maleimide.

[8] The positive photosensitive resin composition according to any one of [1] to [5], wherein the (meth) acrylate having an epoxy group is at least one selected from glycidyl (meth) acrylate and the (meth) acrylate having an aliphatic group is methyl (meth) (Meth) acrylate having at least one aromatic group selected from dicyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate and dicyclopentenyloxyethyl Is at least one selected from benzyl (meth) acrylate, and the N-substituted maleimide is at least one selected from N-cyclohexylmaleimide and N-phenylmaleimide. Composition.

[9] The thermosetting resin composition according to any one of [1] to [8], wherein the low molecular weight epoxy compound (A) is an epoxy compound having three or more epoxy groups and a weight average molecular weight of less than 5,000, Composition.

[10] The epoxy resin composition according to any one of [1] to [4], wherein the low molecular weight epoxy compound (A) is a bisphenol A novolak type epoxy compound, 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) - [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2- propanol, ) Phenyl] -2- [4- [1,1-bis [4 - ([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane. Composition.

[11] An epoxy group-containing polymer obtained by polymerizing a mixture of a high molecular weight epoxy compound (B), a radically polymerizable monomer having an epoxy group (b1), and another radically polymerizable monomer (b2) Ba). [10] The thermosetting composition according to any one of [1] to [10].

[12] The thermosetting resin composition according to any one of [1] to [12], wherein the radically polymerizable monomer (b1) having an epoxy group is at least one selected from glycidyl (meth) acrylate and the other radically polymerizable monomer (b2) (Meth) acrylate having a structure represented by the following formula (B-11), and N-substituted maleimide in an amount of 50% by weight or more based on the total weight of the other radically polymerizable monomer (b2) Or more of the thermosetting composition.

[13] The thermosetting resin composition according to any one of [1] to [10], wherein the radically polymerizable monomer (b1) having an epoxy group is at least one selected from glycidyl (meth) acrylate and the other radically polymerizable monomer (b2) , (Meth) acrylate having a structure represented by the following formula (B-11), and N-substituted maleimide.

[14] The positive resist composition as described in any one of [1] to [10], wherein the (meth) acrylate having an aliphatic group is at least one compound selected from the group consisting of methyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (Meth) acrylate having a structure represented by the formula (B-11) is at least one selected from the group consisting of 3- [tris (trimethylsilyloxy) silyl] propyl (meth) Acrylate, and mono (meth) acryloxypropyl modified polydimethylsiloxane, wherein the N-substituted maleimide is N-cyclohexylmaleimide. The thermosetting resin composition according to any one of [12] Composition.

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

[16] A color filter having the cured film described in [15].

The thermosetting composition of the present invention is compatible with both flatness and foreign matter followability. According to the present invention, there is provided a thermosetting composition capable of forming a cured film having a high display quality and a high yield.

In the present specification, the term "(meth) acrylic acid" may be used to denote one or both of acrylic acid and methacrylic acid. Likewise, "(meth) acrylate" may be used to denote either or both of acrylate and methacrylate.

<1. The thermosetting composition of the present invention>

The first aspect of the present invention relates to a low molecular weight epoxy compound (A) having three or more epoxy groups and having a weight average molecular weight of less than 5,000, a high molecular weight epoxy compound (B) having three or more epoxy groups and having a weight average molecular weight of 30,000 or more ), And a carboxyl compound (C) containing three or more carboxyl groups.

(A), a high molecular weight epoxy compound (B), a high molecular weight epoxy compound (B) and a low molecular weight epoxy compound (B) in the thermosetting composition containing the low molecular weight epoxy compound (A), the high molecular weight epoxy compound (A) in the total weight of the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B) is preferably from 50 to 99 wt%, and the weight ratio of the low molecular weight epoxy compound More preferably 70 to 95% by weight. Within this range, both the flatness of the thermosetting composition of the present invention and the property of following foreign matter become good.

The weight of the carboxyl compound (C) is preferably 30 to 200 parts by weight, more preferably 40 to 120 parts by weight, based on 100 parts by weight of the total amount of the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B) More preferable. Within this range, the curing property of the thermosetting composition of the present invention becomes favorable.

The thermosetting composition of the present invention is not particularly limited to the present description but can be applied to two phenomena caused by the heat flow of the composition upon heating, that is, (1) a phenomenon of improving the flatness by heat flow of the low- , And (2) a high molecular weight epoxy compound having a high melting point is balanced with a phenomenon of improving the foreign matter followability by suppressing the heat flow, whereby both flatness and foreign matter followability can be achieved. In order to develop this subtle balance, it is important to use two or more epoxy compounds which differ greatly in molecular weight and to blend them in a specific ratio.

<1-1. The low molecular weight epoxy compound (A)

The low molecular weight epoxy compound (A) used in the present invention is an epoxy compound containing three or more epoxy groups and having a weight average molecular weight of less than 5,000. The low molecular weight epoxy compound (A) may be a monomer or a polymer of a compound having a polymerizable group other than an epoxy group. The polydispersity (weight average molecular weight / number average molecular weight) of the polymer of the compound having a polymerizable group other than the epoxy group is preferably 1.4 to 4.0, more preferably 1.6 to 3.5.

The low molecular weight epoxy compound (A) may be used alone, or two or more thereof may be used in combination.

Examples of the low molecular weight epoxy compound (A) include phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, glycidyl ether type epoxy compounds, bisphenol A novolac type epoxy compounds, aliphatic polyglycidyl ethers, There are aliphatic epoxy compounds.

Among them, a glycidyl ether type epoxy compound and a bisphenol A novolak type epoxy compound are preferable, and a glycidyl ether type epoxy compound is more preferable. The thermosetting composition using these low molecular weight epoxy compounds (A) has a high ability to planarize the steps.

Preferred examples of the glycidyl ether type epoxy compound are 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -2- [2- (4-fluorophenyl) 4- [1,1-bis [4 - ([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane.

As the low molecular weight epoxy compound (A), commercially available products such as the following may be used. Specific examples of the phenol novolak type epoxy compound are EPPN-201 (trade name, manufactured by Nippon Yakuza Co., Ltd.), jER 152 and 154 (all trade names, Mitsubishi Kagaku K.K.). Specific examples of the cresol novolak-type epoxy compound include EOCN-102S, 103S, 104S and 1020 (all trade names, manufactured by Nippon Kayaku Co., Ltd.). Specific examples of the glycidyl ether type epoxy compound include Teckmor VG3101L (trade name, manufactured by PRINTECH), EPPN-501H and 502H (all trade names, manufactured by Nippon Yakuza Kogyo K.K.) and jER 1032H60 (trade name, Ltd.). Specific examples of the bisphenol A novolac epoxy compound (Ab) include jER 157S65 and 157S70 (all trade names, Mitsubishi Kagaku Co., Ltd.). A specific example of the alicyclic aliphatic epoxy compound is EHPE-3150 (trade name, Daicel K.K.). TECHMORE VG3101L, which is a glycidyl ether type epoxy compound, is a copolymer of 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1- Ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol.

<1-2. The high molecular weight epoxy compound (B)

The high molecular weight epoxy compound (B) used in the present invention is an epoxy compound containing three or more epoxy groups and having a weight average molecular weight of 30,000 or more. The high molecular weight epoxy compound (B) is a polymer of a compound having a polymerizable group other than an epoxy group. The polydispersity (weight average molecular weight / number average molecular weight) of the polymer is preferably 1.5 to 5.0, more preferably 1.8 to 4.0.

The high molecular weight epoxy compound (B) may be used alone, or two or more thereof may be used in combination.

Examples of the high molecular weight epoxy compound (B) include an epoxy group-containing polymer (Ba) obtained by polymerizing a mixture of a radically polymerizable monomer (b1) having an epoxy group and a radically polymerizable monomer containing another radically polymerizable monomer (b2) )All.

<1-2-1. Radical polymerizable monomer (b1) having an epoxy group>

The radically polymerizable monomer (b1) having an epoxy group which is a raw material of the epoxy group-containing polymer (Ba) is not particularly limited as long as it has at least one epoxy group and at least one radically polymerizable group. Examples of the radically polymerizable monomer (b1) having an epoxy group are glycidyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

Of these, glycidyl (meth) acrylate is preferred. A thermosetting composition containing an epoxy group-containing polymer (Ba) obtained by polymerizing a mixture containing at least one selected from these is good in curability.

The radically polymerizable monomer (b1) having an epoxy group may be used alone, or two or more thereof may be used in combination.

<1-2-2. Other radical polymerizable monomer (b2)>

Another radically polymerizable monomer (b2) copolymerized with a radically polymerizable monomer (b1) having an epoxy group is a radically polymerizable monomer which does not have a carboxyl group and an epoxy group and can be copolymerized with a radically polymerizable monomer (b1) having an epoxy group , And is not particularly limited. Examples of such radically polymerizable monomers include (meth) acrylate having an aliphatic group, (meth) acrylate having an aromatic group, (meth) acrylate having a structure represented by the following formula (B-11) Acrylate, N-substituted maleimide, macromonomer, styrene, methylstyrene, vinyltoluene, chloromethylstyrene, indene, (meth) acrylamide and N-acryloylmorpholine.

Specific examples of the (meth) acrylate having an aliphatic group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclohexyl (meth) acrylate, (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate. Examples of the (meth) acrylate having an aromatic group are phenyl (meth) acrylate and benzyl (meth) acrylate. Specific examples of the (meth) acrylate having the structure represented by the formula (B-11) include 3- [tris (trimethylsilyloxy) silyl] propyl (meth) acrylate, and mono (meth) Dimethylsiloxane. Specific examples of other (meth) acrylates include methoxypolyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and glycerol mono Rate. Examples of N-substituted maleimides are N-phenylmaleimide and N-cyclohexylmaleimide. Specific examples of the macromonomer are polystyrene macromonomer and polymethyl methacrylate macromonomer.

Of these, preferred are methyl (meth) acrylate, n-butyl (meth) acrylate, dicyclopentanyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate, 3- [tris (trimethylsilyloxy) Methyl (meth) acrylate, n-butyl (meth) acrylate, 3- (dimethylamino) ethyl More preferred are tris (trimethylsilyloxy) silyl] propyl (meth) acrylate, mono (meth) acryloxypropyl modified polydimethylsiloxane, and N-cyclohexylmaleimide. The thermosetting composition containing an epoxy group-containing polymer (Ba) obtained by polymerizing a mixture containing at least one selected from the foregoing, has good foreign matter followability.

As the other radically polymerizable monomer (b2), the above-described compounds may be used alone, or two or more of them may be used in combination.

In the polymerization of the epoxy group-containing polymer (Ba) contained in the thermosetting composition of the present invention, among the total weight of the radically polymerizable monomer (b1) having an epoxy group and the other radically polymerizable monomer (b2) The amount of the monomer (b1) is preferably 40 to 95% by weight, more preferably 60 to 90% by weight. Within this range, the thermosetting composition of the present invention has good curability.

In the method of adding the epoxy group-containing polymer (Ba) to the thermosetting composition of the present invention, the solution after the polymerization reaction may be added as it is, or the solids may be extracted by concentrating the solution to add solids only.

<1-3. The carboxyl compound (C)

As described above, the carboxyl compound (C) used in the present invention is a carboxyl compound containing three or more carboxyl groups.

The carboxyl compound (C) may be used alone or in admixture of two or more.

Examples of the carboxyl compound (C) include polyester amide acid (Ca) obtained by reacting tetracarboxylic dianhydride (ca1), diamine (ca2) and polyhydric hydroxy compound (ca3) as essential components, Containing copolymer (Cb) obtained by polymerizing a mixture of a radically polymerizable monomer (cb1) and another radically polymerizable monomer (cb2). These carboxyl compounds (C) are easily obtained from raw materials and compounds, and the curing properties of the thermosetting composition containing the carboxyl compound (C) are good.

<1-3-1. Polyester amide acid (Ca)>

The polyester amide acid (Ca) is obtained by reacting tetracarboxylic dianhydride (ca1), diamine (ca2), and polyhydric hydroxy compound (ca3) as essential components. In addition to these, at least one selected from a monohydric alcohol (ca4) and a styrene-maleic anhydride copolymer (ca5) may be reacted.

In the method of adding the polyester amide acid (Ca) to the thermosetting composition of the present invention, the solution after the polymerization reaction may be added as it is, or the solid may be extracted by concentrating the solution to add solids only.

<1-3-1-1. Tetracarboxylic dianhydride (ca1)>

Examples of the tetracarboxylic dianhydride (ca1) used in the present invention are aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aliphatic tetracarboxylic dianhydride.

Specific examples of the aromatic tetracarboxylic dianhydride include 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3, 3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylsulfone tetracarboxylic dianhydride Water, 2,3,3 ', 4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylether tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA"), 2,2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4- Carboxyphenyl)] hexafluoropropane dianhydride, and ethylene glycol bis (anhydrotrimellitate) (TMEG-100, New Japan Ewha Womans). Specific examples of the alicyclic tetracarboxylic dianhydride are cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride. Examples of the aliphatic tetracarboxylic dianhydride are ethanetetracarboxylic dianhydride, and butanetetracarboxylic dianhydride.

Among these, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, ODPA, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (Anhydrotrimellitate) (trade name: TMEG-100, manufactured by Shin-Etsu Chemical Co., Ltd.) and butane tetracarboxylic dianhydride are preferable, and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride Water, ODPA, and butane tetracarboxylic dianhydride are particularly preferred. A cured film produced using a thermosetting composition containing a polyester amide acid (Ca) containing at least one selected from these as a raw material has high light transmittance

As the tetracarboxylic dianhydride (ca1), the above-described compounds may be used alone, or two or more of them may be used in combination.

<1-3-1-2. Diamine (ca2)>

Specific examples of the diamine (ca2) used in the present invention include 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone (hereinafter abbreviated as "DDS"), 3,4 ' (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [ Sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] Phenyl] sulfone, and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane.

Among these, DDS and bis [4- (3-aminophenoxy) phenyl] sulfone are preferable, and DDS is particularly preferable. A cured film produced using a thermosetting composition containing a polyester amide acid (Ca) containing at least one selected from these as a raw material has high light transmittance

As the diamine (ca2), the above-described compounds may be used alone, or two or more of them may be used in combination.

<1-3-1-3. Polyhydric hydroxy compound (ca3)>

Specific examples of the polyhydric hydroxy compound (ca3) used in the present invention 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, Glycol, tetrapropylene glycol, polypropylene glycol having a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, Pentanediol, 1,2-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6- Heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8- , 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanthiol, 1,2-decanediol, 1,10-decanediol, 1,2,10- , 2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, Dipentaerythritol, bisphenol A, bisphenol S, bisphenol F, diethanolamine, and triethanolamine.

Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8- -Butanediol, 1,5-pentanediol, and 1,6-hexanediol are particularly preferred. The polyester amide acid (Ca) containing at least one selected from these as a raw material has good solubility in a solvent.

As the polyhydric hydroxy compound (ca3), the above-described compounds may be used alone, or two or more of them may be used in combination.

<1-3-1-4. Monohydric alcohol (ca4)>

The synthesis of the polyester amide acid (Ca) may be carried out by reacting a monohydric alcohol (ca4) in addition to the tetracarboxylic dianhydride (ca1), the diamine (ca2), and the polyhydric hydroxy compound (ca3).

Specific examples of monohydric alcohols (ca4) include alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, 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, Phenethyl, dimethylbenzylcarbinol, 3-ethyl-3-hydroxymethyloxetane.

Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane are preferable, and benzyl alcohol is particularly preferable. The polyester amide acid (Ca) containing at least one selected from these as a raw material has good compatibility with the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B).

As the monohydric alcohol (ca4), the above-described compounds may be used alone, or two or more of them may be used in combination.

<1-3-1-5. Styrene-maleic anhydride copolymer (ca5) >

In the synthesis of the polyester amide acid (Ca), a compound having three or more acid anhydride groups may be reacted in addition to tetracarboxylic acid dianhydride (ca1), diamine (ca2), and polyhydric hydroxy compound (ca3).

A specific example of the compound having three or more acid anhydride groups is styrene-maleic anhydride copolymer (ca5). By adding the styrene-maleic anhydride copolymer (ca5), compatibility with the high molecular weight epoxy compound (B) can be improved. The molar ratio of styrene / maleic anhydride is 0.5 to 4, preferably 1 to 3, more preferably about 1, about 2 or about 3, even more preferably about 1 or about 2, Particularly preferred.

Examples of commercially available styrene-maleic anhydride copolymer (ca5) are SMA1000, SMA2000, and SMA3000 (all trade names, manufactured by Kawahara Yuka Co., Ltd.). Of these, SMA1000 having good solubility in a solvent is particularly preferable.

As the styrene-maleic anhydride copolymer (ca5), the above-described compounds may be used alone, or two or more of them may be used in combination.

<1-3-2. The carboxyl group-containing copolymer (Cb)

The carboxyl group-containing copolymer (Cb) is a polymer obtained by polymerizing a mixture of a radically polymerizable monomer (cb1) having a carboxyl group and another radically polymerizable monomer (cb2).

In the polymerization of the carboxyl group-containing polymer (Cb) contained in the thermosetting composition of the present invention, among the total weight of the radically polymerizable monomer (cb1) having a carboxyl group and the other radically polymerizable monomer (cb2) The monomer (cb1) is preferably used in an amount of from 10 to 70% by weight, more preferably from 20 to 50% by weight. Within this range, compatibility of the carboxyl group-containing polymer (Cb) with the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B) is enhanced, and the curing property of the thermosetting composition containing the carboxyl group- do.

In the method of adding the carboxyl group-containing polymer (Cb) to the thermosetting composition of the present invention, the solution after the polymerization reaction may be added as it is, or the solid may be extracted by concentrating the solution to add solids only.

<1-3-2-1. Radically polymerizable monomer (cb1) having carboxyl group>

The radically polymerizable monomer (cb1) having a carboxyl group is a compound having at least one carboxyl group in one molecule and at least one radically polymerizable group.

Specific examples of the radically polymerizable monomer (cb1) having a carboxyl group used in the present invention include (meth) acrylic acid, itaconic acid, citraconic acid, fumaric acid, and maleic acid.

Among these, (meth) acrylic acid and itaconic acid are preferable, and (meth) acrylic acid is particularly preferable. A thermosetting composition containing a carboxyl group-containing polymer (Cb) obtained by polymerizing a mixture containing at least one selected from these is good in curability.

As the radically polymerizable monomer (cb1) having a carboxyl group, the above-described compounds may be used alone, or two or more of them may be used in combination.

<1-3-2-2. Other radically polymerizable monomer (cb2)>

The other radically polymerizable monomer (cb2) is not particularly limited as long as it is a radically polymerizable monomer that does not have a carboxyl group and can be copolymerized with a radically polymerizable monomer (cb1) having a carboxyl group.

As the other radically polymerizable monomer (cb2) used in the present invention, one or more selected from among those exemplified as the radically polymerizable monomer (b1) having an epoxy group or the other radically polymerizable monomer (b2) can be used.

Among these, glycidyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N-phenylmaleimide, Hexylmaleimide is preferred. The carboxyl group-containing polymer (Cb) obtained by polymerizing a mixture containing at least one member selected therefrom has good compatibility with the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B), and the carboxyl group- (Cb), a cured film having a good flatness can be formed.

As the other radical polymerizable monomer (cb2) used in the present invention, the above-described compounds may be used alone, or two or more of them may be used in combination.

<1-4. Solvent (D)>

The solvent (D) used in the present invention is preferably at least one compound having a boiling point of 100 to 200 캜, or a mixed solvent containing 20% by weight or more of the compound. Specific examples of the compound having a boiling point of 100 to 200 캜 include water, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxyacetate, , Methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate (hereinafter abbreviated as MMP), ethyl 3-methoxypropionate, Propoxy propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, ethyl 2-ethoxypropionate, Ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Methyl propionate, ethyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol monomethyl ether (hereinafter abbreviated as "PGME"), propylene glycol monomethyl ether (hereinafter abbreviated as "PGME"), propylene glycol monomethyl ether (Hereinafter abbreviated as &quot; PGMEA &quot;), 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 moiety Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether (hereinafter referred to as "EDM" ), Toluene, xylene,? -Butyrolactone, and N, N-dimethylacetamide.

Among them, ethyl lactate, MMP, ethyl 3-ethoxypropionate, PGME, PGMEA, propylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and EDM are preferable, Ethyl 3-ethoxypropionate, PGME, PGMEA and EDM are particularly preferred. By using at least one selected from these, the uniformity of application becomes good.

The solvent (D) may be a solvent used for the polymerization reaction of the epoxy group-containing polymer (Ba), the polyester amide acid (Ca) or the carboxyl group-containing polymer (Cb) as a solution in the thermosetting composition as it is, In addition, a diluting solvent (a solvent for adjusting the solid content concentration) may be added. When only the solid component extracted and concentrated from the solution after the polymerization reaction is used for the thermosetting composition with respect to the epoxy group-containing polymer (Ba), the polyester amide acid (Ca) or the carboxyl group-containing polymer (Cb), the solvent (D) Upon preparation of the composition, the total amount thereof is added together with the components (A) to (C).

<1-5. Additives>

The thermosetting composition of the present invention may contain an additive in view of improving the properties of the thermosetting composition in the present invention such as coating uniformity, adhesion, stability, and the like. Examples of the additives include polymer dispersing agents such as acrylic type, styrene type, polyethylene imine type and urethane type; Surfactants such as anionic, cationic, nonionic, and fluoric surfactants; Silicone polymerization system application property improving agent; Adhesion-improving agents such as silane-based coupling agents and aluminum-based coupling agents; Ultraviolet absorbers such as alkoxybenzophenones; An anti-aggregation agent such as sodium polyacrylate; An epoxy compound other than the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B); Thermosetting agents such as oxetanyl compounds, melamine compounds and bisazide compounds; Epoxy curing agents such as carboxyl compounds other than the carboxyl compound (C), carboxylic anhydrides, phenol compounds and imidazole compounds; And an antioxidant such as a hindered phenol.

If the amount of the additive added is 20 parts by weight or less based on 100 parts by weight of the total of the low molecular weight epoxy compound (A), the high molecular weight epoxy compound (B) and the carboxyl compound (C), the object of the present invention is not impaired, It is preferable to improve the properties of the composition.

Specific examples of the polymer dispersing agent, surfactant, and coating property improving agent are Polyflow No.45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 Disperbyk 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) BYK-346 and BYK-346 (all trade names, manufactured by Big Chemical Japan K.K.), KP-341 (trade name, , KP-358, KP-368, KF-96-50CS and KF-50-100CS (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Surplon S-611, Surplon SC- , EFTOP EF-351, EFTOP EF-35 (all trade names, product of AGC Seiyaku Chemical Co., Ltd.), Phtogent 222 F, Ptagent 251, DFX-18 and FTX- 352, EFTOP EF-601, EFTOP EF-801, and EFTOP EF-802 (all trade names, manufactured by Mitsubishi Materials Corporation), Megapack F-444, Megapack F-430, Megapack F- F-551, Megafac F-551, Megapac F-555, Megapac F-556, Megapac F-557, Megapac F- MegaPack RS-76, RS-76, RS-76, RS-76, RS-76, 77 (all trade names, manufactured by DIC K.K.), fluoroalkylbenzenesulfonic acid salts, fluoroalkylcarboxylic acid salts, fluoroalkyl polyoxyethylene ethers, fluoroalkylammonium iodides, fluoroalkyl betaines, (Fluoroalkylpolyoxyethylene ether), a fluoroalkyltrimethylammonium salt, a fluoroalkylaminosulfonate salt, a polyoxyethylene nonylphenyl ether, a polyoxyethylene octylphenyl ether, a polyoxyethyl Alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, poly Polyoxyethylene laurylamine, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan Palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonate.

Specific examples of the adhesion improver include 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, and 3-glycidyloxypropyltrimethoxysilane, which are silane-based coupling agents; And tetraisopropyl bis (dioctylphosphite) titanate, which is an aluminum-based coupling agent, acetoalkoxyaluminum diisopropylate, and a titanate-based coupling agent.

Specific examples of the epoxy compound other than the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B) are a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, and a bifunctional alicyclic aliphatic epoxy compound.

As the epoxy compounds other than the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B), commercially available products such as the following may be used. Specific examples of the bisphenol A type epoxy compound are jER 828, 1004, and 1009 (all trade names, Mitsubishi Kagaku Kogyo Co.). Specific examples of the bisphenol F type epoxy compound are jER 806 and 4005P (both trade names, Mitsubishi Kagaku Kogyo Co.). A specific example of the bifunctional alicyclic aliphatic epoxy compound is Celloxide 2021P (trade name, Daicel K.K.).

Specific examples of the epoxy curing agent include a carboxyl compound other than the carboxyl compound (C), such as succinic acid, maleic acid, itaconic acid, citraconic acid, 2,3-dimethylmaleic acid, 1,2-cyclohexanedicarboxylic acid, Cyclohexene-1,2-dicarboxylic acid, 4-methylhexane-1,2-dicarboxylic acid, 4-methyl-4-cyclohexene- Dicarboxylic acid, 3-methyl-4-cyclohexene-1,2-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, bicyclo [2.2.2] 3-methylphthalic acid, 2,3-naphthalenedicarboxylic acid, 1,2-naphthalic acid, glutaric acid, 3-methylglutaric acid, 3,3-dicarboxylic acid, Dimethylglutaric acid, 2,2-dimethylglutaric acid, 1,1-cyclopentanediacetic acid, and N-phthaloyl-DL-glutamic acid; Examples of the carboxylic anhydrides include succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, 2,3-dimethyl maleic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-methyl- Cyclohexene-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, Cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, bicyclo [2.2.2] 3-methylphthalic anhydride, 2,3-naphthalene dicarboxylic anhydride, 1,2-naphthalic anhydride, glutaric anhydride, 3-methylglutaric anhydride, 3-dicarboxylic anhydride, phthalic anhydride, Acid anhydride, 3,3-dimethylglutaric anhydride, 2,2-dimethylglutaric anhydride, 1,1-cyclopentanedic acetic anhydride, N-phthaloyl-DL-glutamic acid anhydride, and trimellitic anhydride; And imidazole compounds such as 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro- 2-a] benzimidazole, and 1-cyanoethyl-2-undecylimidazolium trimellitate.

Examples of the antioxidant such as a hindered phenol include a compound having tert-butyl at the ortho position of the phenol OH and having a substituent such as an alkyl group and a compound capable of having a substituent at the para position via a para- Known compounds such as 2- to 4-mer are used. An example of a commercially available product is adecastab AO-60 (trade name, ADEKA).

<1-6. Process for producing epoxy group-containing polymer (Ba) or carboxyl group-containing polymer (Cb)

The polymerization method of the epoxy group-containing polymer (Ba) or the carboxyl group-containing polymer (Cb) is not particularly limited, but radical polymerization in a solution using a solvent is preferred. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator to be used, but is usually in the range of 50 to 150 캜. The polymerization time is not particularly limited, but is usually in the range of 1 to 24 hours. The polymerization can be carried out under any pressure of a pressure, a reduced pressure or an atmospheric pressure.

<1-6-1. Solvent used for polymerization reaction of epoxy group-containing polymer (Ba) or carboxyl group-containing polymer (Cb)

The solvent used in the polymerization reaction of the epoxy group-containing polymer (Ba) is preferably a solvent which dissolves the radically polymerizable monomer (b1) having an epoxy group to be used, the other radically polymerizable monomer (b2), and the epoxy group- Solvents are preferred. The solvent used in the polymerization reaction of the carboxyl group-containing polymer (Cb) is preferably a solvent which dissolves the radically polymerizable monomer (cb1) having a carboxyl group to be used, the other radically polymerizable monomer (cb2) and the resulting carboxyl group-containing polymer (Cb) Solvents are preferred. Hereinafter, the solvent used in the polymerization reaction may be referred to as a &quot; polymerization solvent &quot;.

Specific examples of the solvent to be used for the polymerization reaction of the epoxy group-containing polymer (Ba) or the carboxyl group-containing polymer (Cb) include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, But are not limited to, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, MMP, methyl 3-ethoxypropionate, ethylene glycol monoethyl ether, PGME, PGMEA, diethylene glycol dimethyl ether, EDM, cyclopentanone, Hexanone, N-methyl-2-pyrrolidone, and N, N-dimethylformamide. The polymerization solvent may be used alone or in admixture of two or more.

Of these, MMP, PGME, PGMEA and EDM are preferred.

<1-6-2. Polymerization initiator used in the polymerization reaction of the epoxy group-containing polymer (Ba) or the carboxyl group-containing polymer (Cb)

For polymerization of the epoxy group-containing polymer (Ba) or the carboxyl group-containing polymer (Ca), known polymerization initiators can be used. The polymerization initiator used in the polymerization of the epoxy group-containing polymer (Ba) and the polymerization initiator used in the polymerization of the carboxyl group-containing polymer (Ca) used in the present invention include a compound capable of generating a radical by heat, azobisisobutyronitrile Based initiator, and an peroxide-based initiator such as benzoyl peroxide. In the radical polymerization, a chain transfer agent such as thioglycolic acid may be added in an appropriate amount to control the molecular weight of the resulting epoxy group-containing polymer (Ba) and the carboxyl group-containing polymer (Cb).

<1-6-3. Weight average molecular weight of epoxy group-containing polymer (Ba) or carboxyl group-containing polymer (Cb)>

The weight-average molecular weight of the obtained epoxy group-containing polymer (Ba) is preferably 30,000 to 300,000, and more preferably 40,000 to 100,000. Within the above-mentioned range, foreign matter followability becomes better.

The weight average molecular weight of the carboxyl group-containing polymer (Cb) is preferably 1,000 to 100,000, more preferably 3,000 to 20,000. Within the above-mentioned range, the film thickness uniformity after coating becomes better.

The weight average molecular weight in the present specification is a value in terms of polystyrene determined by GPC method (column temperature: 35 ° C, flow rate: 1 mL / min). Polystyrene having a molecular weight of 645 to 132,900 (for example, Agilent S-M2-10 polystyrene calibration kit PL2010-0102 (trade name, manufactured by Agilent Technologies, Inc.)) as the standard polystyrene, PLgel MIXED-D (trade name, (Manufactured by Rent Technology Co., Ltd.) and THF as a mobile phase. The weight average molecular weight of a commercial product in the present specification is a catalog value.

When the thermosetting composition of the present invention is shaded and stored at a temperature in the range of -30 to 25 占 폚, the stability of the composition over time is satisfactory. When the storage temperature is -20 to 10 占 폚, the stability over time is better.

<1-7. Process for producing polyester amide acid (Ca)

In the production method of the polyester amide acid (Ca), X mole of tetracarboxylic dianhydride (ca1), Y mole of diamine (ca2), and Z mole of polyhydric hydroxy compound (ca3) are reacted in a solvent. In this case, it is preferable that X, Y, and Z are defined as a ratio in which the relationship of the following formulas (C-11) and (C-12) is established between them. Within this range, the solubility of the polyester amide acid (Ca) in the solvent becomes better, and thus the coatability of the composition is improved, and as a result, a cured film having more uniform film thickness can be obtained.

0.2? Z / Y? 8.0 (C-11)

0.2? (Y + Z) /X? 1.5 (C-12)

The relationship of the formula (C-11) is preferably 0.7? Z / Y? 7.0, more preferably 1.3? Z / Y? 7.0. The relationship of the formula (C-12) is preferably 0.5? (Y + Z) / X? 1.2, more preferably 0.7? (Y + Z) / X? 1.0.

Hereinafter, a part or all of the tetracarboxylic acid dianhydride (ca1), diamine (ca2), polyhydric hydroxy compound (ca3), monohydric alcohols (ca4) and (ca5), which are raw materials of the polyester amide acid May be referred to as &quot; reaction raw materials &quot;.

When the polyester amide acid (Ca) has an acid anhydride group at the molecular end, the reaction can be carried out by adding the above-described monohydric alcohol (ca4), if necessary. The polyester amide acid (Ca) obtained by reacting with a monohydric alcohol (ca4) is not only improved in compatibility with the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B) The applicability of the thermosetting composition of the present invention is improved.

The preferable range of the solvent used in the polymerization reaction of the polyester amide acid (Ca) is 100 parts by weight based on 100 parts by weight of the total of tetracarboxylic dianhydride (ca1), diamine (ca2), and polyhydric hydroxy compound (ca3) Parts by weight or more. Within this range, the reaction proceeds smoothly, which is preferable. The preferred reaction temperature and reaction time for the polymerization reaction of the polyester amide acid (Ca) are 40 to 200 占 폚 and 0.2 to 20 hours, respectively. The monohydric alcohol (cb4) may 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, a method of simultaneously adding a tetracarboxylic dianhydride (ca1), a diamine (ca2), and a polyhydroxy compound (ca3) to a reaction solvent, a method of dissolving a diamine (ca2) and a polyhydric hydroxy compound (ca3) (Ca1), tetracarboxylic dianhydride (ca1) and polyhydric hydroxy compound (ca3) are preliminarily reacted with a tetracarboxylic dianhydride (ca1) and then a diamine (ca2) is added to the reaction product , Or a method in which tetracarboxylic dianhydride (ca1) and diamine (ca2) are preliminarily reacted and then a polyhydric hydroxy compound (ca3) is added to the reaction product.

The polyester amide acid (Ca) thus synthesized contains a constitutional unit comprising the following general formula (C-13) and the general formula (C-14), and its terminal is a tetracarboxylic dianhydride (ca1 , An amino group, or a hydroxy group derived from a diamine (c), a diamine (ca2), or a polyhydric hydroxy compound (ca3), or an additive other than these compounds constitute the terminal. In the general formulas (C-13) and (C-14), R ¹¹ is a residue of a tetracarboxylic dianhydride (ca1), preferably an organic group having 2 to 30 carbon atoms. R ¹² is a diamine (ca 2) residue, preferably an organic group having 2 to 30 carbon atoms. R ¹³ is a residue of a polyhydric hydroxy compound (ca 3), preferably an organic group having 2 to 20 carbon atoms.

<1-8-1. Solvent used for polymerization reaction of polyester amide acid (Ca)

Specific examples of the solvent used in the polymerization reaction for obtaining the polyester amide acid (Ca) used in the present invention include ethyl lactate, MMP, methyl 3-ethoxypropionate, PGMEA, diethylene glycol dimethyl ether, EDM, diethylene Glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, cyclohexanone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide.

Of these, MMP, PGMEA and EDM are preferable.

The solvent used in the polymerization reaction may be used alone or in combination of two or more. If the proportion is 30% by weight or less, a solvent other than the above-mentioned solvent may be mixed and used.

<1-8-2. Weight average molecular weight of polyester amide acid (Ca) >

The weight average molecular weight of the resulting polyester amide acid (Ca) is preferably 1,000 to 50,000, more preferably 3,000 to 25,000. Within the above-mentioned range, the film thickness uniformity after coating becomes good.

<1-9. Storage of epoxy group-containing copolymer (Ba), polyester amide acid (Ca), carboxyl group-containing copolymer (Cb), and thermosetting composition>

When the epoxy group-containing copolymer (Ba), the polyester amide acid (Ca), the carboxyl group-containing copolymer (Cb) and the thermosetting composition are stored at a temperature in the range of -30 to 25 占 폚, desirable. If the storage temperature is -20 to 10 占 폚, no precipitate is more preferable.

<1-10. Effect of thermosetting composition >

The thermosetting composition of the present invention has various properties such as high light transmittance, high chemical resistance, and high adhesion with the base portion which are generally required for a cured film, for example.

The cured film obtained by curing the thermosetting composition of the present invention has high flatness and high foreign matter followability. Therefore, the thermosetting composition of the present invention can obtain the effect of improving the yield at the time of production while maintaining the display quality of the display device.

<2. The cured film of the present invention>

The cured film of the present invention is obtained by heating the thermosetting composition of the present invention. The thermosetting composition of the present invention is suitable for forming a cured film having a high ability of flattening a level difference and capable of following foreign substances, and can be used for a color filter. For example, it is preferably used as a protective film of a color filter.

The color filter is a filter that does not pass a specific wavelength region while passing a specific wavelength region of visible light. The color filter used in the display element is formed by forming pixels (red (R), green (G), and blue (B)) of at least three primary colors and a light shielding region (black matrix) In some cases, a protective film and a transparent electrode are laminated. The color filter can be obtained by a known method.

The cured film obtained by heating and curing the thermosetting composition of the present invention can be formed by a conventional method for forming a polymer film in a resist field, and is formed, for example, as follows.

<2-1. Formation of Coating Film>

First, the thermosetting composition of the present invention is coated on a substrate such as glass by a known method such as spin coating, roll coating, or slit coating to form a coating film. Next, the coating film of the thermosetting composition on the substrate is dried in a hot plate or an oven. Normally, it is dried at 60 to 150 DEG C for 1 to 10 minutes. As the substrate, for example, a transparent glass substrate such as a white plate glass, a glass plate glass, a CRT glass plate glass, or the like, a polycarbonate, a polyether sulfone, a polyester, an acrylic polymer, a vinyl chloride polymer, an aromatic polyamide polymer, a polyamideimide, A film or a substrate, a metal plate such as an aluminum plate, a copper plate, a nickel plate, or a stainless plate, or a semiconductor plate having a ceramic plate or a photoelectric conversion element. These substrates can be subjected to pretreatment such as chemical treatment such as silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, etc., as desired.

<2-2. Firing>

The film on the substrate is finally baked at 100 to 250 DEG C for 10 to 120 minutes. By heating in the firing step, a cured film can be obtained. The firing conditions are preferably carried out at 130 to 240 캜 for 15 to 40 minutes.

[Example]

Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited thereto.

Compounds used in Synthesis Examples, Comparative Synthesis Examples, Reference Examples, Examples, and Comparative Examples are listed in each component.

Low molecular weight epoxy compound (A):

A-1: TECHMORE VG3101L (trade name, PRINTECH Co., Ltd.)

A-2: jER 157 S65 (trade name, manufactured by Mitsubishi Kagaku K.K.)

Radically polymerizable monomer (b1) having an epoxy group:

b1-1: glycidyl methacrylate

Other radically polymerizable monomers (b2):

b2-1: n-butyl methacrylate

b2-2: monomethacryloxypropyl modified polydimethylsiloxane (trade name: SILLA PLAIN FM-0721 (number average molecular weight catalog: 5,000, abbreviated as "FM-0721"

b2-3: N-Cyclohexylmaleimide

b2-4: N-phenylmaleimide

Polymerization initiator used in polymerization reaction of epoxy group-containing copolymer (Ba):

Dimethyl 2,2'-azobis (2-methylpropionic acid) (V-601, abbreviated as "V-601" manufactured by Wako Pure Chemical Industries, Ltd.)

Solvent used in the polymerization reaction of the epoxy group-containing polymer (Ba)

MMP

Tetracarboxylic dianhydride (ca1):

ca1-1: ODPA

ca1-2: Butane tetracarboxylic dianhydride (Rikacid BT-100, abbreviated as "BT-100", New Japan Ewha Womans'

Diamine (ca2):

ca2-1: DDS

Polyhydric hydroxy compound (ca3):

ca3-1: 1,4-butanediol

Monohydric alcohol (ca4):

ca4-1: benzyl alcohol

Styrene-maleic anhydride copolymer (ca5):

ca5-1: SMA-1000

Solvent used for reaction of polyester amide acid (Ca)

MMP

Radically polymerizable monomer (cb1) having carboxyl group:

cb1-1: methacrylic acid

Other radically polymerizable monomer (cb2):

cb2-1: benzyl methacrylate

cb2-2: N-phenylmaleimide

Polymerization initiator used in the polymerization reaction of the carboxyl group-containing copolymer (Cb):

V-601

Solvent used in the polymerization reaction of the carboxyl group-containing polymer (Cb)

PGMEA

Dilution solvent:

MMP

PGMEA

PGME

EDM

Additive-1: carboxylic acid anhydride, trimellitic anhydride

Additive-2: 3-glycidyloxypropyltrimethoxysilane (trade name SILLAACE S-510, JNC Corporation, hereinafter abbreviated as "S-510") which is a silane coupling agent,

Additive-3: Celloxide 2021P (trade name, Daicel Corporation) which is an epoxy compound other than the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B)

Additive-4: 2-undecyl imidazole (trade name: Cueazol C11Z, manufactured by Shikoku Kasei Kogyo K.K., hereinafter abbreviated as "C11Z"), which is an imidazole compound,

Additive-5: BYK-342 (trade name, manufactured by Japan Chemical Industry Co., Ltd.), which is a silicone surfactant,

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

In a four-necked flask equipped with a stirrer, MMP as a polymerization solvent, n-butyl methacrylate as a radically polymerizable monomer (b2) as a radically polymerizable monomer (b1) having a carboxyl group, And V-601 were charged into the following composition (composition), heated at 80 占 폚 for 3 hours, and then heated at 90 占 폚 for 3 hours.

Glycidyl methacrylate (b1) 24,000 g

n-butyl methacrylate (b2) 6.000 g

V-601 (Polymerization initiator) 0.120 g

MMP (Polymerization solvent) 70,000 g

After completion of the reaction, the solution was cooled to room temperature to obtain a 30 wt% solution of the epoxy group-containing polymer (Ba-1). The weight average molecular weight determined by GPC analysis was 78,000 and the polydispersity was 2.6.

The term &quot; 30 wt% solution of epoxy group-containing polymer (Ba-1) &quot; as used herein refers to a solution containing 30 wt% of the solids and a concentration calculated from the weight of the solvent, Lt; / RTI &gt; The same applies to the following synthesis examples and comparative synthesis examples.

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

The following components were charged in the following amounts by the same method as in Synthesis Example 1, and polymerization was carried out.

Glycidyl methacrylate (b1) 24,000 g

n-butyl methacrylate (b2) 5.700 g

FM-0721 (b2) 0.300 g

V-601 (Polymerization initiator) 0.120 g

MMP (Polymerization solvent) 70,000 g

The same treatment as in Synthesis Example 1 was carried out to obtain a 30 wt% solution of the epoxy group-containing polymer (Ba-2). The weight average molecular weight determined by GPC analysis was 80,000.

[Synthesis Example 3] Synthesis of epoxy group-containing polymer (Ba-3)

The following components were charged in the following amounts by the same method as in Synthesis Example 1, and polymerization was carried out.

Glycidyl methacrylate (b1) 21,000 g

n-butyl methacrylate (b2) 3.000 g

N-cyclohexylmaleimide (b2) 6.000 g

V-601 (Polymerization initiator) 0.240 g

MMP (Polymerization solvent) 70,000 g

The same treatment as in Synthesis Example 1 was carried out to obtain a 30 wt% solution of the epoxy group-containing polymer (Ba-3). The weight average molecular weight determined by GPC analysis was 38,000.

[Synthesis Example 4] Synthesis of epoxy group-containing polymer (Ba-4)

The following components were charged in the following amounts by the same method as in Synthesis Example 1, and polymerization was carried out.

Glycidyl methacrylate (b1) 21,000 g

n-butyl methacrylate (b2) 3.000 g

N-phenylmaleimide (b2) 6.000 g

V-601 (Polymerization initiator) 0.240 g

MMP (Polymerization solvent) 70,000 g

The same treatment as in Synthesis Example 1 was carried out to obtain a 30 wt% solution of the epoxy group-containing polymer (Ba-4). The weight average molecular weight determined by GPC analysis was 39,000.

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

The following components were charged in the following amounts by the same method as in Synthesis Example 1, and polymerization was carried out.

Glycidyl methacrylate (b1) 24,000 g

n-butyl methacrylate (b2) 6.000 g

V-601 (Polymerization initiator) 0.600 g

MMP (Polymerization solvent) 70,000 g

The same treatment as in Synthesis Example 1 was carried out to obtain a 30 wt% solution of the epoxy group-containing polymer (Ba'-1). The weight average molecular weight determined by GPC analysis was 23,000 and the polydispersity was 2.0.

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

The following components were charged in the following amounts by the same method as in Synthesis Example 1, and polymerization was carried out.

Glycidyl methacrylate (b1) 24,000 g

n-butyl methacrylate (b2) 6.000 g

V-601 (Polymerization initiator) 3.000 g

MMP (Polymerization solvent) 70,000 g

The same treatment as in Synthesis Example 1 was carried out to obtain a 30 wt% solution of the epoxy group-containing polymer (Ba'-2). The weight average molecular weight determined by GPC analysis was 8,100 and the polydispersity was 1.8.

[Synthesis Example 5] Synthesis of polyester amide acid (Ca-1)

A 1,000-mL four-necked flask equipped with a thermometer, a stirrer, a feed inlet and a nitrogen gas inlet was charged with 446.96 g of MMP dehydrated and purified as a solvent used in the polymerization reaction, 1,4-butanediol (ca3) as a polyhydric hydroxy compound 31.53 g of benzyl alcohol as a monohydric alcohol (ca4) and 183.20 g of tetracarboxylic dianhydride (ca1) as O3 were fed into a flask and stirred at 130 DEG C for 3 hours in a dry nitrogen stream. Thereafter, the solution after the reaction was cooled to 25 DEG C, 29.33 g of DDS and 183.04 g of MMP were added as a diamine (ca2), stirred at 20 to 30 DEG C for 2 hours and then stirred at 115 DEG C for 1 hour, Lt; 0 &gt; C or lower to obtain a 30 wt% solution of pale yellow and transparent polyester amide acid (Ca-1). The weight average molecular weight measured by GPC was 4,200.

Z / Y = 3, (Y + Z) /X=0.8

[Synthesis Example 6] Synthesis of polyester amide acid (Ca-2)

To a 1,000 mL four-necked flask equipped with a thermometer, a stirrer, a feed inlet and a nitrogen gas inlet, 600.32 g of PGMEA dehydrated and purified as a solvent for use in the polymerization reaction, 47.68 g of ODPA as tetracarboxylic dianhydride (ca1) , 144.97 g of SMA1000 as a styrene-maleic anhydride copolymer (ca5), 55.40 g of benzyl alcohol as a monohydric alcohol (ca4), 9.23 g of 1,4-butanediol as a polyhydric hydroxy compound (ca3) And the mixture was stirred at 130 캜 for 3 hours under a nitrogen stream. Thereafter, the solution after the reaction was cooled to 25 DEG C, 12.72 g of DDS and 29.68 g of PGMEA were added as a diamine (ca2), and the mixture was stirred at 20 to 30 DEG C for 2 hours and then at 115 DEG C for 1 hour. Lt; 0 &gt; C or lower to obtain a 30 wt% solution of pale yellow and transparent polyester amide acid (Ca-2). The weight average molecular weight measured by GPC was 21,000.

Z / Y = 2, (Y + Z) / X = 1

[Synthesis Example 7] Synthesis of polyester amide acid (Ca-3)

604.80 g of dehydrated and purified PGMEA as a solvent for use in the polymerization reaction and BT-100 as a tetracarboxylic dianhydride (ca1) were placed in a 1,000 mL four-necked flask equipped with a thermometer, a stirrer, a feed inlet and a nitrogen gas inlet 164.11 g of SMA1000 as a styrene-maleic anhydride copolymer (ca5), 50.17 g of benzyl alcohol as a monohydric alcohol (ca4) and 10.45 g of 1,4-butanediol as a polyhydric hydroxy compound (ca3) , And the mixture was stirred at 130 캜 for 3 hours in a dry nitrogen stream. Thereafter, the solution after the reaction was cooled to 25 DEG C, 10.80 g of DDS and 25.20 g of PGMEA were added as a diamine (ca2), stirred at 20 to 30 DEG C for 2 hours and then stirred at 115 DEG C for 1 hour, Lt; 0 &gt; C or lower to obtain a 30 wt% solution of pale yellow and transparent polyester amide acid (Ca-3). The weight average molecular weight measured by GPC was 10,000.

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

[Synthesis Example 8] Synthesis of carboxyl group-containing polymer (Cb-1)

The following components were charged in the following amounts by the same method as in Synthesis Example 1, and polymerization was carried out.

Methacrylic acid (cb1) 9.000 g

Benzyl methacrylate (cb2) 18,000 g

N-phenylmaleimide (cb2) 3.000 g

V-601 (Polymerization initiator) 1.500 g

PGMEA (Polymerization solvent) 70,000 g

The same treatment as in Synthesis Example 1 was carried out to obtain a 30 wt% solution of the carboxyl group-containing polymer (Cb-1). The weight average molecular weight determined by GPC analysis was 4,700.

[Table 1]

[Table 1] (Continued)

[Example 1]

(Ba-1) as a high molecular weight epoxy compound (B), a polyester amide acid (Ca-1) as a carboxyl compound as a low molecular weight epoxy compound (A), TECHMORE VG3101L as a low molecular weight epoxy compound , Trimellitic anhydride, S-510, and BYK-342 as additives, MMP and EDM as diluting solvents were mixed and dissolved in the following composition to obtain a thermosetting composition. The viscosity of this thermosetting composition was 5.6 mPa..

Techmore VG3101L 5.700 g

A 30 wt% solution of the epoxy group-containing polymer (Ba-1) 0.500 g

A 30 wt% solution of polyester amide acid (Ca-1) 10.000 g

Trimellitic anhydride 0.600 g

S-510 0.473 g

BYK-342 0.021 g

MMP 17.783 g

EDM 6.284 g

The total amount of the solvent (D) contained in the composition is such that the amount of the solvent (D) contained in the 30 wt% solution of the polyester amide acid (Ca-1) contained in the 30 wt% solution of the epoxy group- MMP, and the amount of MMP and EDM added for dilution, in which the solids concentration was adjusted to be approximately 24% by weight. Example 2 The same applies to the following and comparative examples.

The thermosetting composition was spin-coated on a glass substrate at 600 rpm for 10 seconds and prebaked on a hot plate at 80 DEG C for 3 minutes to form a coating film. Thereafter, the coated film was cured by heating in an oven at 230 DEG C for 30 minutes to obtain a glass substrate with a cured film having a thickness of 2.0 mu m.

The thickness of the cured film of the glass substrate with a cured film was measured by cutting out a part of the cured film and using a step, surface roughness, fine shape measuring device P-16 + (trade name, manufactured by Tencor Corporation).

A color filter substrate with a cured film was obtained by coating and heating the above-mentioned thermosetting composition on a color filter substrate in accordance with a method of forming a glass substrate with a cured film.

The color filter substrate used in this evaluation is a color filter substrate in which pixels of R, G, and B are formed on a glass substrate and black matrixes are formed, and the maximum value (Hereinafter abbreviated as &quot; maximum step &quot;) is 1.1 to 1.2 mu m.

The flatness of the thus obtained color filter substrate with a cured film was evaluated. The evaluation results of the flatness are shown in Table 2.

The measurement methods of the physical properties and evaluation methods of the respective properties performed in this example and this comparative example are shown below.

[Measurement method of maximum step difference, evaluation method of flatness]

The maximum step of the surface of the color filter substrate was measured using a step, surface roughness, fine shape measuring device P-16 + (trade name, manufactured by Tencor Corporation). This measured value will be referred to as &quot; maximum step difference (CF) &quot;.

Subsequently, a cured film was formed on the color filter substrate as described above, and the maximum step of the surface of the cured film of the obtained color filter substrate with the cured film was measured under the same conditions. This measured value will be referred to as &quot; maximum step (CF + OC) &quot;.

The planarization ratio (DOP) was calculated from the following formula (DOP-1). The evaluation of the flatness was expressed as "? &Quot; when the DOP was 80% or more, and "x" when the DOP was less than 80%.

DOP = 100% × [maximum step difference (CF) - maximum step difference (CF + OC)] / maximum step difference (CF)

[Method of measuring foreign matter size, method of evaluating foreign matter followability]

A glass substrate (hereinafter referred to as "chromium substrate") on which chromium was deposited on the surface was set on a spreader of a bead spacer, and a bead spacer having a diameter of 7 μm was sprayed at a rate of 3 to 5 pieces / cm ² . A chromium substrate with a cured film containing a bead spacer was obtained by coating and heating the above-mentioned thermosetting composition on a chromium substrate to which this bead spacer was attached in the same manner as in the method for producing a glass substrate with a cured film. The surface of the chromium substrate with the cured film containing the bead spacer was observed at 50 times using a differential interference microscope AFX-IIA (trade name, Nikon Corporation), and the surface of the raised portion of the cured film around the bead spacer Diameter (hereinafter referred to as &quot; foreign matter size &quot;) was measured.

The foreign matter followability was evaluated as "? &Quot; when the foreign matter size was 80 占 퐉 or less, and" 占 "when the foreign matter size was 81 占 퐉 or more.

[Examples 2 to 11, Comparative Examples 1 to 4]

Similar to Example 1, a thermosetting composition was prepared according to the composition shown in the following table. The amount of the solvent was adjusted so that the solid concentration became approximately 24% by weight. These thermosetting compositions were spin-coated at a rotational speed of 2.0 to 2.1 占 퐉 after post-baking, and the same evaluations as in Example 1 were carried out. The results of Examples 2 to 11 are shown in Table 2 together with the results of Example 1, and the results of Comparative Examples 1 to 4 are shown in Table 3, respectively.

[Table 2]

[Table 2] (Continued)

[Table 3]

The thermosetting compositions of Examples 1 to 12 contain a low molecular weight epoxy compound (A), a high molecular weight epoxy compound (B), and a carboxyl compound (C). In contrast, the thermosetting composition of Comparative Example 1 did not contain the high molecular weight epoxy compound (B). The thermosetting composition of Comparative Example 2 did not contain the low molecular weight epoxy compound (A). The thermosetting compositions of Comparative Examples 3 and 4 were prepared in the same manner as in Example 1 except that the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B) were not contained and the molecular weight of the low molecular weight epoxy compound (A) and the molecular weight of the high molecular weight epoxy compound (Ba ') having an intermediate molecular weight.

As is clear from the above, in all of Examples 1 to 12, both flatness and foreign matter followability are good. Compared with these, Comparative Example 1, which does not contain the high molecular weight epoxy compound (B), is inferior in foreign matter followability. Comparative Example 2 containing no low molecular weight epoxy compound (A) had poor flatness. Molecular Weight of Low Molecular Weight Epoxy Compound (A) and High Molecular Weight Comparative Examples 3 to 4 containing an epoxy compound (Ba ') having an intermediate molecular weight of the molecular weight of the epoxy compound (B) are poor in flatness and foreign matter followability.

The cured film formed by using the thermosetting composition of the present invention can be used as a protective film for a color filter, so that a color filter having excellent display quality and a high yield can be produced. By using the color filter, the display quality can be improved without lowering the yield particularly in the liquid crystal display element of the transverse electric field mode.

Claims (16)

A low molecular weight epoxy compound (A) having three or more epoxy groups and having a weight average molecular weight of less than 5,000;
A high molecular weight epoxy compound (B) containing three or more epoxy groups and having a weight average molecular weight of 30,000 or more; And
The carboxyl compound (C) containing three or more carboxyl groups
&Lt; / RTI &gt; The method according to claim 1,
(A) and the high molecular weight epoxy compound (B) are contained in the total amount of the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B) ), Wherein the weight of the carboxyl compound (C) is 30 to 200 parts by weight based on 100 parts by weight of the total amount of the thermosetting composition. The method according to claim 1,
(A) and the high molecular weight epoxy compound (B) are contained in the total amount of the low molecular weight epoxy compound (A) and the high molecular weight epoxy compound (B) ), Wherein the weight of the carboxyl compound (C) is 40 to 120 parts by weight based on 100 parts by weight of the total amount of the thermosetting composition. 4. The method according to any one of claims 1 to 3,
The carboxyl compound (C) is at least one selected from a polyester amide acid (Ca) and a carboxyl group-containing polymer (Cb);
Wherein the polyester amide acid (Ca) is a reaction product obtained by reacting tetracarboxylic dianhydride (ca1), diamine (ca2), and polyhydric hydroxy compound (ca3) as essential components, (C-11) and the following formula (C-12) are satisfied for tetracarboxylic dianhydride (ca1), Y mol diamine (ca2) and Z mol polyhydric hydroxy compound ;
0.2? Z / Y? 8.0 (C-11)
0.2? (Y + Z) /X? 1.5 (C-12)
Wherein the carboxyl group-containing polymer (Cb) is obtained by polymerizing a mixture of a radically polymerizable monomer (cb1) having a carboxyl group and a radically polymerizable monomer containing another radically polymerizable monomer (cb2). 5. The method of claim 4,
Wherein the polyester amide acid (Ca) is a reaction product obtained by reacting a monohydric alcohol (ca4) in addition to a tetracarboxylic dianhydride (ca1), a diamine (ca2), and a polyhydric hydroxy compound (ca3) . The method according to claim 4 or 5,
Is a reaction product obtained by reacting a polyester amide acid (Ca) with a styrene / maleic anhydride copolymer (cb5). 5. The method of claim 4,
Wherein the radically polymerizable monomer (cb1) having a carboxyl group is at least one selected from (meth) acrylic acid and (meth) acrylate having a carboxyl group, and the other radically polymerizable monomer (cb2) ) Acrylate, (meth) acrylate having an aliphatic group, (meth) acrylate having an aromatic group, and N-substituted maleimide. 8. The method of claim 7,
(Meth) acrylate having an epoxy group is at least one selected from glycidyl (meth) acrylate and the (meth) acrylate having an aliphatic group is at least one selected from the group consisting of methyl (meth) acrylate, n-butyl (Meth) acrylate having at least one aromatic group selected from cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (Meth) acrylate, and the N-substituted maleimide is at least one selected from N-cyclohexylmaleimide and N-phenylmaleimide. 9. The method according to any one of claims 1 to 8,
Wherein the low molecular weight epoxy compound (A) is an epoxy compound having three or more epoxy groups and a weight average molecular weight of less than 5,000, and having an aromatic group. 10. The method of claim 9,
Wherein the low molecular weight epoxy compound (A) is at least one compound selected from the group consisting of a bisphenol A novolak type epoxy compound, 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] Phenyl] ethyl] phenoxy] -2-propanol and 2- [4- (2,3-epoxypropoxy) phenyl] 2- [4- [1,1-bis [4 - ([2,3-epoxypropoxy] phenyl]] ethyl] phenyl] propane. 11. The method according to any one of claims 1 to 10,
(Ba) obtained by polymerizing a mixture of a high molecular weight epoxy compound (B), a radically polymerizable monomer having an epoxy group (b1), and another radically polymerizable monomer (b2) , Thermosetting composition. 12. The method of claim 11,
Wherein the radically polymerizable monomer (b1) having an epoxy group is at least one selected from glycidyl (meth) acrylate, the other radically polymerizable monomer (b2) is at least one selected from the group consisting of (meth) (Meth) acrylate having a structure represented by the following formula (B-11), and N-substituted maleimide in an amount of 50% by weight or more based on the total weight of the other radically polymerizable monomer (b2) , Thermosetting composition:

. 12. The method of claim 11,
Wherein the radically polymerizable monomer (b1) having an epoxy group is at least one selected from glycidyl (meth) acrylate, the other radically polymerizable monomer (b2) is at least one selected from the group consisting of (meth) (Meth) acrylate having a structure represented by the following formula (B-11), and N-substituted maleimide:

. The method according to claim 12 or 13,
It is preferable that the (meth) acrylate having an aliphatic group is at least one selected from the group consisting of methyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (Meth) acrylate and the (meth) acrylate having a structure represented by the formula (B-11) is at least one selected from the group consisting of 3- [tris (trimethylsilyloxy) , And mono (meth) acryloxypropyl-modified polydimethylsiloxane, wherein the N-substituted maleimide is N-cyclohexylmaleimide. A cured film obtained by heating the thermosetting composition according to any one of claims 1 to 14. A color filter having the cured film according to claim 15.