JP7073982B2 - Thermosetting composition - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention can be used to form an insulating material in an electronic component, a passion film in a semiconductor device, a buffer coat film, an interlayer insulating film, a flattening film, an interlayer insulating film in a liquid crystal display element, a protective film for a color filter, and the like. The present invention relates to a curable composition, a transparent film thereof, and an electronic component having the film.

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

In addition to the above-mentioned properties, recently, there is an increasing demand for properties that reduce the elution of underlying components (hereinafter, also referred to as barrier properties) in addition to heat resistance and flatness. Behind this, especially in the field of color filters, there is a response to widening the color gamut, and each color filter manufacturer uses dyes that have good color but are easy to elute and decompose, and photo-curing treatment to prevent fading. There is a tendency to minimize. As a result, in the conventional protective film that does not correspond to these tendencies, the elution of the base cannot be sufficiently suppressed, and the elution component is mixed when forming the panel, which deteriorates the display quality of the display. As a result, there is a problem that the yield is lowered.

In response to this requirement, as specific measures required for the protective film, prevention of circulation of the solvent of the alignment film solution at the time of forming the alignment film, and gas component from the color filter during firing in the process after forming the protective film. Traps and the like are required.

Examples of these excellent protective film materials include a thermosetting polymer composition (Patent Document 3) in addition to the thermosetting resin composition (Patent Document 1 and Patent Document 2) shown above. On the other hand, the compositions of Patent Document 1 and Patent Document 3 have a problem that they have good resistance to various treatments, but have insufficient flatness and, in some cases, have low barrier properties. Further, the composition of Patent Document 2 also has a problem that the resistance to various treatments and the flatness are good, but the barrier property is low.

JP-A-2005-105264 Japanese Patent Application Laid-Open No. 2008-156546 Japanese Patent Application Laid-Open No. 2006-282995

An object of the present invention is to provide a thermosetting composition that prevents elution of underlying components and provides a cured film having excellent flatness, and a cured film formed by the thermosetting composition. The present invention provides an electronic component having the cured film.

As a result of diligent studies to solve the above problems, the present inventors have made tetracarboxylic acid dianhydrides, polyesteramidic acids which are reaction products of diamines and polyvalent hydroxy compounds, polymers of cyclic ether compounds, and curing agents. It has been found that the above-mentioned object can be achieved by a cured film obtained by curing a composition containing the above-mentioned substances, and the present invention has been completed.
The present invention includes the following configurations.

[1] A thermosetting composition containing a polyester amic acid (A), a polymer (B) of a cyclic ether compound, and a curing agent (C).
The polyesteramidic acid (A) is an X-mol tetracarboxylic acid dianhydride, a Y-mol diamine and a Z-mol polyvalent hydroxy compound, so that the relationships of the following formulas (1) and (2) are established. It is a reaction product from the raw material contained in the ratio,

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

The polymer (B) of the cyclic ether compound is a homopolymer of the compound (b1) having an oxetanyl group, a copolymer of compounds (b1) having an oxetanyl group, and a compound (b1) having an oxetanyl group and an oxylanyl group. A thermosetting composition which is at least one selected from the copolymer of the compound (b2) having.

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

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

[3] The compound (b1) having an oxetane group is at least one selected from (3-ethyloxetane-3-yl) methyl acrylate and (3-ethyloxetane-3-yl) methyl methacrylate. The thermosetting composition according to item 1] or item [2].

[4] Item [1] or item [2], wherein the compound (b2) having an oxylanyl group is at least one selected from glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether. The thermosetting composition according to.

[5] Any one of [1] to [4], wherein the content of the polymer (B) of the cyclic ether compound is 20 to 400 parts by weight with respect to 100 parts by weight of the polyesteramidic acid (A). The thermosetting composition according to.

[6] A cured film obtained by curing the thermosetting composition according to any one of [1] to [5].

[7] A color filter having the cured film according to item [6] as a transparent protective film.

The thermosetting composition according to a preferred embodiment of the present invention is a material that prevents elution of underlying components and has excellent flatness, and when used as a color filter protective film for a color liquid crystal display element, improves display quality. be able to. In particular, it is useful as a protective film for color filters manufactured by a dyeing method, a pigment dispersion method, an electrodeposition method and a printing method. It can also be used as a protective film and a transparent insulating film for various optical materials.

1. 1. Thermocurable Composition of the Present Invention The thermocurable composition of the present invention is a reaction product from a raw material containing a tetracarboxylic acid dianhydride, a diamine and a polyvalent hydroxy compound, polyesteramidic acid (A), a cyclic ether. A composition containing the polymer (B) of the compound and the curing agent (C), wherein the polymer (B) of the cyclic ether compound has an oxetanyl group, which is a homopolymer of the compound (b1) having an oxetanyl group. It is a thermosetting composition which is at least one selected from a copolymer of compounds (b1) and a copolymer of a compound (b1) having an oxetanyl group and a compound (b2) having an oxylanyl group.

1-1. Polyester amidoic acid (A)
Polyester amide acid is a reaction product from raw materials containing tetracarboxylic acid dianhydride, diamines and polyvalent hydroxy compounds. More specifically, from a raw material containing X mol of tetracarboxylic acid dianhydride, Y mol of diamine and Z mol of polyvalent hydroxy compound in a ratio such that the relationships of the following formulas (1) and (2) are established. Reaction product of.

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

The polyesteramidic acid (A) preferably has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4).

In formulas (3) and (4), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic acid dianhydride, and is preferably an organic group having 2 to 30 carbon atoms. .. R ² is a residue obtained by removing two -NH ₂ from the diamine, and is preferably an organic group having 2 to 30 carbon atoms. R ³ is a residue obtained by removing two -OH from the polyvalent hydroxy compound, and is preferably an organic group having 2 to 20 carbon atoms.

At least a solvent is required for the synthesis of the polyesteramidic acid (A), and the solvent may be left as it is to form a liquid or gel-like thermosetting composition in consideration of handleability and the like, or the solvent may be removed. It may be a solid composition in consideration of transportability and the like. Further, the synthesis of the polyesteramidic acid (A) may contain, if necessary, one or more compounds selected from a monohydroxy compound and a styrene-maleic anhydride copolymer as a raw material, particularly. It preferably contains a monohydroxy compound. Further, in the synthesis of the polyesteramidic acid (A), other compounds other than the above may be contained as a raw material as long as the object of the present invention is not impaired.

1-1-1. Tetracarboxylic acid dianhydride In the present invention, tetracarboxylic acid dianhydride is used as a material for obtaining the polyesteramidic acid (A). Specific examples of preferred tetracarboxylic acid dianhydrides are 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 2, 3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfonate tetracarboxylic acid dianhydride, 2,2', 3,3'-diphenylsulfone tetracarboxylic acid Dianoxide, 2,3,3', 4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2', 3,3' -Diphenyl ether tetracarboxylic acid dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, ethylene glycol bis (anhydrotrimeritate) (trade name; TMEG-100, Shin Nihon Rika Co., Ltd.), cyclobutanetetracarboxylic acid dianhydride, methyl Cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, ethanetetracarboxylic acid dianhydride, and butanetetracarboxylic acid dianhydride. One or more of these can be used.

Among these, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, which give good transparency, 2, 2- [Bis (3,4-dicarboxyphenyl)] Hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and ethylene glycol bis (anhydrotrimeritate) are more Preferably, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride and 1,2,3,4-butanetetracarboxylic acid Acid dianhydride is more preferred.

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

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

1-1-3. Multivalent hydroxy compound In the present invention, the polyvalent hydroxy compound is used as a material for obtaining the polyester amidoic acid (A).

Specific examples of preferable polyhydric hydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and weight. Polypropylene glycol with an average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentane Glycol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1, 7-Heptanediol, 1,2,7-Heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 1,2-nonanediol , 1,9-nonandiol, 1,2,9-nonantriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decantriol, 1,2-dodecanediol, 1,12 -Dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, tris isocyanurate (2-hydroxyethyl), bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4) -Hydroxyphenyl) sulfone), bisphenol F (bis (4-hydroxyphenyl) methane), 4,4'-isopropylidenebis (2-phenoxyethanol), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4 '-Dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethanol, diethanolamine, triethanolamine,

Glycerin monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, dipentaerythritol monoallyl ether, dipentaerythritol diallyl ether, dipentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, Sorbitol monoallyl ether, sorbitol diallyl ether, sorbitol triallyl ether, sorbitol tetraallyl ether, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate , Dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, sorbitol di (meth) acrylate , Sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, (meth) acrylic acid modified product of ethylene glycol diglycidyl ether, (meth) acrylic acid modified product of propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether (Meta) acrylic acid modified product, (meth) acrylic acid modified product of glycerin diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, (meth) acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether. (Meta) acrylic acid modified product of bisphenol S diglycidyl ether, (meth) acrylic acid modified product of bisphenol S diglycidyl ether, (meth) acrylic acid modified product of bisphenol F diglycidyl ether, propylene oxide modified product. Bisphenol F diglycidyl ether (meth) acrylic acid modified product, bixylenel diglycidyl ether (meth) acrylic acid modified product, biphenol diglycidyl ether (meth) acrylic acid modified product, full orange phenol diglycidyl ether (meth) ) Acrylic acid modified product, (meth) acrylic acid modified product of cyclohexane-1,4-dimethanol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether (me) T) Acrylic acid modified products, (meth) acrylic acid modified products of tricyclodecanedimethanol diglycidyl ether, and (meth) acrylic acid modified products of other compounds containing two or more epoxy groups per molecule. can.

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

Of methacrylic acid modified product of ethylene glycol diglycidyl ether, acrylic acid modified product of propylene glycol diglycidyl ether, acrylic acid modified product of tripropylene glycol diglycidyl ether, acrylic acid modified product of glycerin diglycidyl ether, bisphenol A diglycidyl ether The following commercially available products are available as methacrylic acid modified products, acrylic acid modified products of bisphenol A diglycidyl ether, methacrylic acid modified products of propylene oxide modified bisphenol A diglycidyl ether, and acrylic acid modified products of propylene oxide modified bisphenol A diglycidyl ether. Can be used.

A specific example of the methacrylic acid modified product of ethylene glycol diglycidyl ether is epoxy ester 40EM (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid modified product of propylene glycol diglycidyl ether is epoxy ester 70PA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid modified product of tripropylene glycol diglycidyl ether is epoxy ester 200PA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid modified product of glycerin diglycidyl ether is epoxy ester 80MFA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the methacrylic acid modified product of bisphenol A diglycidyl ether is epoxy ester 3000MK (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid modified product of bisphenol A diglycidyl ether is epoxy ester 3000A (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of a methacrylic acid-modified product of propylene oxide-modified bisphenol A diglycidyl ether is epoxy ester 3002M (N) (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of propylene oxide-modified bisphenol A diglycidyl ether is epoxy ester 3002A (N) (trade name; Kyoeisha Chemical Co., Ltd.).

1-1-4. Monohydroxy compound In the present invention, a monohydroxy compound may be used as a material for obtaining the polyester amidoic acid (A). By using the monohydroxy compound, the storage stability of the thermosetting composition is improved. Specific examples of preferred monohydroxy compounds include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and the like. Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltor, linalol, terpineol, dimethylbenzylcarbinol, and 3-ethyl-3-hydroxymethyloxetane. One or more of these can be used.

Of these, isopropyl alcohol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane is more preferable. The compatibility of the polyester amic acid (A) produced by using these, the polymer (B) of the cyclic ether compound, and the curing agent (C), and the thermosetting composition on the color filter. Considering the coatability, it is more preferable to use benzyl alcohol as the monohydroxy compound.

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

1-1-5. Styrene-maleic anhydride copolymer Further, the polyesteramidic acid (A) used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups to the above-mentioned raw materials. Polyester amide acid (A) synthesized by adding a compound having three or more acid anhydride groups is preferable because it is expected to improve transparency. An example of a compound having three or more acid anhydride groups is a styrene-maleic anhydride copolymer. Regarding the ratio of each component constituting the styrene-maleic anhydride copolymer, the molar ratio of styrene / maleic anhydride is 0.5 to 4, preferably 1 to 3. The molar ratio of styrene / maleic anhydride is more preferably 1 or 2, and even more preferably 1.

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

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

1-1-6. The synthesis of the aminosilane compound polyesteramidoic acid (A) having one amino group may contain other raw materials other than the above as necessary as long as the object of the present invention is not impaired. An example of such other raw materials is an aminosilane compound having one amino group. The aminosilane compound having one amino group is used to react with the acid anhydride group at the terminal of the polyesteramidic acid (A) to introduce a silyl group at the terminal. When the thermosetting composition of the present invention containing the polyesteramidic acid (A) obtained by adding and reacting an aminosilane compound having one amino group is used, the acid resistance of the obtained cured film is improved. Will be done. Further, when the reaction is carried out with the above-mentioned monomer composition, both a monohydroxy compound and an aminosilane compound having one amino group can be added for the reaction.

Specific examples of the aminosilane compound having one preferable amino group used in the present invention are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxy. Silane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane , P-Aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. One or more of these can be used.

Among these, 3-aminopropyltriethoxysilane and p-aminophenyltriethoxysilane, which improve the acid resistance of the cured film, are more preferable, and 3-aminopropyltriethoxysilane is further preferable from the viewpoint of acid resistance and compatibility.

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

1-1-7. Solvent used in the synthesis reaction of polyesteramidic acid (A) Specific examples of the solvent used in the synthesis reaction to obtain polyesteramide acid (A) (hereinafter, may be referred to as "reaction solvent") are diethylene glycol dimethyl ether and diethylene glycol. Methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl- 2-pyrrolidone and N, N-dimethylacetamide. Of these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ethyl ether are preferable.

1-1-8. Method for Synthesizing Polyesteramide Acid (A) The polyesteramide acid (A) used in the present invention is obtained by reacting X mol of tetracarboxylic acid dianhydride, Y mol of diamine, and Z mol of polyvalent hydroxy compound in the above solvent. At this time, it is preferable that X, Y and Z are set at a ratio such that the relationship of the following formulas (1) and (2) is established between them. Within this range, the polyester amic acid (A) has high solubility in a solvent, and therefore the coatability of the composition is improved, and as a result, a cured film having excellent flatness can be obtained.

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

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

The polyesteramidic acid (A) used in the present invention has an acid anhydride group (-CO-O-CO-) at the terminal under the condition that X is excessively used with respect to (Y + Z) in the above reaction conditions. It is considered that the molecule having the molecule is excessively generated than the molecule having an amino group or a hydroxyl group at the terminal. When reacting with such a monomer composition, the above-mentioned monohydroxy compound can be added, if necessary, in order to react with the acid anhydride group at the molecular terminal to esterify the terminal. The polyesteramidic acid (A) obtained by adding and reacting the monohydroxy compound has improved compatibility with the polymer (B) and the curing agent (C) of the cyclic ether compound, and contains them. The coatability of the thermosetting composition of the present invention is improved.

It is preferable to use 100 parts by weight or more of the reaction solvent with respect to 100 parts by weight of the total of tetracarboxylic acid dianhydride, diamine and polyvalent hydroxy compound because the reaction proceeds smoothly. The reaction is preferably carried out at 40 ° C. to 200 ° C. for 0.2 to 20 hours.

The order of adding the reaction raw materials to the reaction system is not particularly limited. That is, a method of adding a tetracarboxylic acid dianhydride, a diamine and a polyvalent hydroxy compound to the reaction solvent at the same time, a method of dissolving the diamine and the polyvalent hydroxy compound in the reaction solvent, and then adding the tetracarboxylic acid dianhydride. A method of pre-reacting a tetracarboxylic acid dianhydride with a polyvalent hydroxy compound and then adding a diamine to the product, or a method of pre-reacting a tetracarboxylic acid dianhydride and a diamine and then polyvalently in the product. Any method such as a method of adding a hydroxy compound can be used.

In the case of reacting the aminosilane compound having one amino group, after the reaction of the tetracarboxylic acid dianhydride, the diamine and the polyvalent hydroxy compound is completed, the solution after the reaction is cooled to 40 ° C. or lower. , An aminosilane compound having one amino group may be added, and the reaction may be carried out at 10 to 40 ° C. for 0.1 to 6 hours. Further, the monohydroxy compound may be added at any time of the reaction.

The polyesteramidic acid (A) synthesized in this manner contains a structural unit represented by the formula (3) and a structural unit represented by the formula (4), and the terminal thereof is a tetracarboxylic acid dianhydride which is a raw material. , Diamine or an acid anhydride group derived from a polyvalent hydroxy compound, an amino group or a hydroxy group, or an additive other than these compounds constitutes the terminal thereof. By including such a configuration, the curability becomes good.

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

The weight average molecular weight in the present specification is a value in terms of polystyrene obtained by the GPC method (column temperature: 35 ° C., flow velocity: 1 ml / min). Polystyrene having a molecular weight of 645 to 132900 (for example, polystyrene calibration kit PL2010-0102 of Agilent Technologies, Ltd.) is used as the standard polystyrene, and PLgel MIXED-D (Agilent Technologies, Inc.) is used as the column as the mobile phase. It can be measured using THF. In addition, the weight average molecular weight of the commercial product in this specification is a value published in the catalog.

1-2. Polymer of cyclic ether compound (B)
The polymer (B) of the cyclic ether compound used in the present invention is a homopolymer of the compound (b1) having an oxetanyl group, a copolymer of compounds (b1) having an oxetanyl group, and a compound having an oxetanyl group ( It is at least one selected from the copolymer of b1) and the compound (b2) having an oxylanyl group. The polymer (B) of the cyclic ether compound may be used alone or in combination of two or more.

When the compound having an oxetanyl group (b1) and the compound having an oxylanyl group (b2) are copolymerized, the ratio of the compound having an oxetanyl group (b1) is 50 to 90% by weight in the polymer (B) of the cyclic ether compound. Is preferable from the viewpoint of barrier property. When the ratio of the compound (b1) having an oxetanyl group is 70 to 90% by weight, the barrier property is further improved.

Specific examples of the compound (b1) having an oxetane group include (3-ethyloxetane-3-yl) methyl acrylate (for example, trade name; OXE-10, Osaka Organic Chemical Industry Co., Ltd.), (3-ethyloxetane-). 3-Il) Methyl methacrylate (for example, trade name; OXE-30, Osaka Organic Chemical Industry Co., Ltd.) can be mentioned.

Specific examples of the compound (b2) having an oxylanyl group include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether.

1-3. Ratio of the polymer (B) of the cyclic ether compound to the polyester amic acid (A) The ratio of the total amount of the polymer (B) of the cyclic ether compound to 100 parts by weight of the polyester amic acid (A) in the thermosetting composition of the present invention. Is 20 to 400 parts by weight. When the ratio of the total amount of the polymer (B) of the cyclic ether compound is in this range, the balance between barrier property, flatness and heat resistance is good.

1-4. Hardener (C)
In the thermosetting composition of the present invention, a curing agent (C) may be used in order to improve flatness and chemical resistance. Examples of the curing agent (C) include acid anhydride-based curing agents, carboxylic acid-containing polymers, amine-based curing agents, phenol-based curing agents, imidazole-based curing agents, catalytic curing agents, and sulfonium salts and benzothiazolium salts. Although there are heat-sensitive acid generators such as ammonium salts and phosphonium salts, acid anhydride-based curing agents or imidazole-based curing agents are preferable from the viewpoint of avoiding coloring of the cured film and heat resistance of the cured film.

Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimeric acid anhydride; Aromatic polyvalent carboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride, and styrene-maleic anhydride copolymers. Among these, trimellitic acid anhydride and hexahydrotrimellitic acid anhydride, which have a good balance between heat resistance and solubility in a solvent, are preferable.

Specific examples of the carboxylic acid-containing polymer include ARUFON UC-3000, ARUFON UC-3090 (all trade names; Toagosei Co., Ltd.), Marproof MA-0215Z, Marproof MA-0217Z, and Marproof MA-0221Z. (Both are product names; NOF CORPORATION). Among these, ARUFON UC-3000, which has a good balance between heat resistance, solubility in a solvent, and flatness, is preferable.

Specific examples of the imidazole-based curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2,3-dihydro-1H-pyrrolo [1,2-. a] Benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate. Among these, 2-undecylimidazole, which has a good balance between curability and solubility in a solvent, is preferable.

Specific examples of the phenolic curing agent include α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 4,4'-(3,3,5-trimethyl-) Examples include 1,1-cyclohexanediyl) bis (phenol) and 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane. Among these, α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and 1,1,1-tris (4-hydroxyphenyl) have a good balance of heat resistance and compatibility. ) Ethane and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene are preferred.

When the curing agent (C) is used, the ratio of the curing agent (C) to 100 parts by weight of the polymer (B) of the cyclic ether compound is 0.1 to 60 parts by weight. Regarding the amount of the curing agent (C) added when the acid anhydride-based curing agent is used, more specifically, the carboxylic acid anhydride group or the carboxyl group in the curing agent is 0.1 with respect to the oxetanyl group and the oxylanyl group. It is preferable to add the mixture in an amount of up to 1.5 times. At this time, the carboxylic acid anhydride group is calculated as divalent. It is more preferable to add the carboxylic acid anhydride group or the carboxyl group in an equivalent amount of 0.15 to 0.8 times because the chemical resistance is further improved.

1-5. Other Ingredients Various additives can be added to the thermosetting composition of the present invention in order to improve film physical characteristics such as flatness, scratch resistance, coating uniformity, and adhesiveness. Additives include epoxy compounds other than the compound having an oxylanyl group (b2), compounds having a polymerizable double bond, solvents, anionic, cationic, nonionic, fluorine-based or silicon-based leveling agents / surfactants. , Adhesion improvers such as silane coupling agents, and antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds are mainly mentioned.

1-5-1. Epoxy compound In the thermosetting composition of the present invention, an epoxy compound other than the compound (b2) having an oxylanyl group may be used. The epoxy compound optionally used in the thermosetting composition of the present invention is a compound having two or more epoxy groups per molecule. One epoxy compound may be used, or two or more epoxy compounds may be used.

Examples of the above epoxy compounds include bisphenol A type epoxy compound, bisphenol F type epoxy compound, glycidyl ether type epoxy compound, glycidyl ester type epoxy compound, biphenyl type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, and bisphenol A. It is a novolak type epoxy compound, an aliphatic polyglycidyl ether compound, a cyclic aliphatic epoxy compound, a copolymer of a monomer having an epoxy group and another monomer, and an epoxy compound having a siloxane bond site.

Specific examples of commercially available bisphenol A type epoxy compounds are jER 828, 1004, 1009 (all trade names; Mitsubishi Chemical Co., Ltd.); specific examples of commercially available bisphenol F type epoxy compounds are jER 806, 4005P. (Both are trade names; Mitsubishi Chemical Co., Ltd.); Specific examples of commercially available glycidyl ether type epoxy compounds are TECHMORE VG3101L (trade name; Printec Co., Ltd.) and EHPE-3150 (trade name; Daicel Co., Ltd.). , EPPN-501H, 502H (all trade names; Nippon Kayaku Co., Ltd.), and jER 1032H60 (trade name; Mitsubishi Chemical Co., Ltd.); specific examples of commercially available glycidyl ester type epoxy compounds are Denacol EX-. 721 (trade name; Nagase Chemtex Co., Ltd.) and diglycidyl 1,2-cyclohexanedicarboxylate (trade name; manufactured by Tokyo Kasei Kogyo Co., Ltd.); specific examples of commercially available biphenyl type epoxy compounds are jER YX4000, YX4000H, YL6121H (trade name; Mitsubishi Chemical Co., Ltd.), and NC-3000, NC-3000-L, NC-3000-H, NC-3100 (trade name; Nippon Kayaku Co., Ltd.); Specific examples of commercially available phenol novolac type epoxy compounds are EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), jER 152, 154 (both trade names; Mitsubishi Chemical Co., Ltd.) and the like; cresol novolak type. Specific examples of commercially available epoxy compounds are EOCN-102S, 103S, 104S, 1020 (all trade names; Nippon Kayaku Co., Ltd.); specific examples of commercially available bisphenol A novolak type epoxy compounds are jER. 157S65, 157S70 (both trade names; Mitsubishi Chemical Co., Ltd.); specific examples of commercial products of cyclic aliphatic epoxy compounds are seroxide 2021P, 3000 (both trade names; Daicel Co., Ltd.); siloxane bond. Specific examples of commercially available products of epoxy compounds having a moiety include 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane (trade name; Jerest Incorporated), TSL9906 (trade name;). Momentive Performance Materials Japan GK), COATOSIL MP-200 (trade name; Momentive Performance Materials Japan) Capan GK), Composelan SQ506 (trade name; Arakawa Chemical Co., Ltd.), ES-1023 (trade name; Shin-Etsu Chemical Industry Co., Ltd.).

In addition, TECHMORE VG3101L (trade name; Printec Co., Ltd.) is 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxy) epoxy). Propoxy) phenyl] ethyl] phenyl] propane, and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,2) 3-Epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol is a mixture; EHPE-3150 (trade name; Daicel Co., Ltd.) is 2,2-bis (hydroxymethyl)-. It is a 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 1-butanol; seroxide 2021P (trade name; Daicel Co., Ltd.) is 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane. It is a carboxylate; seroxide 3000 (trade name; Daicel Co., Ltd.) is 1-methyl-4- (2-methyloxylanyl) -7-oxabicyclo [4.1.0] heptan; COATOSIL MP-200. (Product name; Momentive Performance Materials Japan LLC) is a polymer of 3-glycidoxypropyltrimethoxysilane.

As the epoxy compound, the above compound may be used alone, or two or more of them may be mixed and used.

1-5-2. Percentage of Epoxy Compounds Other Than Compound (b2) Having Oxylanyl Group to Polyesteramide Acid (A) Other than Compound (b2) Having Oxylanyl Group to 100 Parts by Weight of Polyesteramide Acid (A) in the Thermocurable Composition of the Present Invention The proportion of the total amount of the epoxy compound in the above is 0 to 100 parts by weight. When the ratio of the total amount of the epoxy compounds other than the compound (b2) having an oxylanyl group is in this range, the balance of flatness, heat resistance, chemical resistance, adhesion and barrier property is good. When the barrier property is more important, the total amount of the epoxy compounds other than the compound (b2) having an oxylanyl group is preferably in the range of 0 to 50 parts by weight.

1-5-3. A compound having a polymerizable double bond A compound having a polymerizable double bond may be used in the thermosetting composition of the present invention. The compound having a polymerizable double bond used in the thermosetting composition of the present invention is not particularly limited as long as it has two or more polymerizable double bonds per molecule.

Among the compounds having a polymerizable double bond, specific examples of the compound having two polymerizable double bonds per molecule are ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (). Meta) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin-modified ethylene glycol di (meth) acrylate, epichlorohydrin-modified diethylene glycol di (meth) acrylate, epichlorohydrin-modified triethylene glycol di (meth) acrylate. , Epichlorohydrin modified tetraethylene glycol di (meth) acrylate, epichlorohydrin modified polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene Glycoldi (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin-modified propylene glycol di (meth) acrylate, epichlorohydrin-modified dipropylene glycol di (meth) acrylate, epichlorohydrin-modified tripropylene glycol di (meth) acrylate, epichlorohydrin-modified tetra. Ethylene glycol di (meth) acrylate, epichlorohydrin-modified polypropylene glycol di (meth) acrylate, glycerol acrylate methacrylate, glycerol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin-modified 1,6-hexanediol di (Meta) acrylate, carboxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypyruccinate neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalate neopentyl glycol di (meth) acrylate, stearer. Acid-modified pentaerythritol di (meth) acrylate, allylated cyclohexyldi (meth) acrylate, bis [(meth) acryloxineopentyl glycol] adipate, bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, Bisphenol F di (meth) acrylate, ethylene oxide change Sex bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, ethylene oxide modified bisphenol S di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate , Dicyclopentanyl diacrylate, ethylene oxide modified di (meth) acrylate, caprolactone / ethylene oxide modified di (meth) acrylate, epichlorohydrin modified di (meth) phthalate, tetrabromobisphenol A di (meth) acrylate, Triglycerol di (meth) acrylate, neopentyl glycol-modified trimethyl propandi (meth) acrylate, and isocyanuric acid ethylene oxide-modified diacrylate.

Among the compounds having a polymerizable double bond, specific examples of the compound having three or more polymerizable double bonds per molecule are trimethylol propanetri (meth) acrylate and ethylene oxide-modified trimethylol propanetri (meth) acrylate. , Propylene oxide-modified trimethylol propanetri (meth) acrylate, epichlorohydrin-modified trimethylol propanetri (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, alkyl-modified Dipentaerythritol tri (meth) acrylate, ethylene oxide-modified tri (meth) acrylate, caprolactone / ethylene oxide-modified tri (meth) acrylate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, ditrimethylol propanetetra ( Meta) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth). Acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and carboxyl group-containing polyfunctional (meth) acrylate.

As the compound having a polymerizable double bond, the above compound may be used alone, or two or more of them may be mixed and used.

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

Among the compounds having the above polymerizable double bond, isocyanuric acid ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipenta. It is preferable to use erythritol hexaacrylate and carboxyl group-containing polyfunctional (meth) acrylate from the viewpoint of flatness and scratch resistance.

As the compound having a polymerizable double bond, the following commercially available products can be used. A specific example of isocyanuric acid ethylene oxide-modified diacrylate is Aronix M-215 (trade name; Toa Synthetic Co., Ltd.); a specific example of a mixture of isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate is Aronix M-. 313 (30-40% by weight) and M-315 (3-13% by weight, hereinafter abbreviated as "M-315") (both trade names; Toa Synthetic Co., Ltd., content in parentheses is isocyanuric acid in the mixture (Catalog value of ethylene oxide-modified diacrylate content); A specific example of trimetylolpropanetriacrylate is Aronix M-309 (trade name; Toa Synthetic Co., Ltd.); pentaerythritol triacrylate and pentaerythritol tetraacrylate. Specific examples of the mixture of Aronix M-306 (65 to 70% by weight), M-305 (55 to 63% by weight), M-303 (30 to 60% by weight), M-452 (25 to 40% by weight). ), And M-450 (less than 10% by weight) (both are trade names; Toa Synthetic Co., Ltd., the content in parentheses is the value listed in the catalog for the content of pentaerythritol triacrylate in the mixture); Specific examples of the mixture of pentaacrylate and dipentaerythritol hexaacrylate include Aronix M-403 (50-60% by weight), M-400 (40-50% by weight), M-402 (30-40% by weight, hereinafter "30-40% by weight"). M-402 "), M-404 (30-40% by weight), M-406 (25-35% by weight), and M-405 (10-20% by weight) (trade name; Toa Synthetic Co., Ltd.) The content in parentheses is the catalog value of the content of dipentaerythritol pentaacrylate in the mixture); specific examples of carboxyl group-containing polyfunctional (meth) acrylates are Aronix M-510 and M-520 ( Hereinafter, it is abbreviated as "M-520") (both are trade names; Toa Synthetic Co., Ltd.).

1-5-4. Ratio of Compounds Having Polymerizable Double Bonds to Polyesteramide Acid (A) The ratio of the total amount of compounds having polymerizable double bonds to 100 parts by weight of polyesteramide acid (A) in the thermosetting composition of the present invention is. It is 0 to 100 parts by weight. When the ratio of the total amount of the compound having a polymerizable double bond is in this range, the balance between flatness, heat resistance, scratch resistance and barrier property is good. When the barrier property is more important, the total amount of the compound having a polymerizable double bond is preferably in the range of 0 to 50 parts by weight.

1-5-5. Solvent (D)
The solvent (D) may be used for the thermosetting composition of the present invention. The solvent (D) arbitrarily added to the thermosetting composition of the present invention is preferably a solvent capable of dissolving the polyester amic acid (A), the polymer (B) of the cyclic ether compound, the curing agent (C) and the like. Specific examples of the solvent (D) include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, acetone, 2-butanone, ethyl acetate, butyl acetate, and the like. Propyl acetate, butyl propionate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3 -Ethyl hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, 2- Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Methyl acid, ethyl 2-oxobutate, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate , Cyclopentanone, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monomethyl Ether Acetate, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monoethyl Ether Acetate, Diethylene Glycolmo Nobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, γ-butyrolactone, or N, N-dimethylacetamide, and cyclohexanone, ethylene glycol, diethylene glycol, Triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and polypropylene glycol having a weight average molecular weight of 1,000 or less. The solvent may be one of these or a mixture of two or more of them.

The content of the solvent (D) is preferably 65 to 95% by weight based on the total amount of the thermosetting composition. More preferably, it is 70 to 90% by weight.

1-5-6. Surfactant A surfactant may be added to the thermosetting composition of the present invention in order to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (All of the above are trade names; Kyoeisha Chemical Co., Ltd.), Disperbake 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181 and Disperbake. Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (all of the above are trade names; Big Chemie Japan Co., Ltd.), KP-341, KP-358, KP- 368, KF-96-50CS, KF-50-100CS (all product names; Shinetsu Chemical Industry Co., Ltd.), Surflon SC-101, Surflon KH-40, Surflon S611 (all product names; AGC Seimi Chemical Co., Ltd.) (Company), Futtergent 222F, Futtergent 208G, Futtergent 251, Futtergent 710FL, Futtergent 710FM, Futtergent 710FS, Futtergent 601AD, Futtergent 602A, Futtergent 650A, FTX-218 (all of the above are trade names; stocks). Company Neos), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all of the above are product names; Mitsubishi Material Co., Ltd.), Megafuck F-171, Megafuck F -177, Mega Fuck F-410, Mega Fuck F-430, Mega Fuck F-444, Mega Fuck F-472SF, Mega Fuck F-475, Mega Fuck F-477, Mega Fuck F-552, Mega Fuck F-553 , Mega Fuck F-554, Mega Fuck F-555, Mega Fuck F-556, Mega Fuck F-558, Mega Fuck F-559, Mega Fuck R-30, Mega Fuck R-94, Mega Fuck RS-75, Mega Fuck RS-72-K, Mega Fuck RS-76-NS, Mega Fuck DS-21 (all product names; DIC Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (all of the above are trade names; Ebonic Japan Co., Ltd.) Formula company), Fluoroalkylbenzene sulfonate, Fluoroalkylcarboxylate, Fluoroalkylpolyoxyethylene ether, Fluoroalkylammonium iodide, Fluoroalkylbetaine, Fluoroalkylsulfonate, Diglycerin tetrakis (Fluoroalkylpolyoxyethylene ether) , Fluoroalkyltrimethylammonium salt, Fluoroalkylaminosulfonate, Polyoxyethylene nonylphenyl ether, Polyoxyethylene octylphenyl ether, Polyoxyethylene alkyl ether, Polyoxyethylene lauryl ether, Polyoxyethylene oleyl ether, Polyoxyethylene tri Decyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate , Solbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyl Diphenyl ether disulfonate. It is preferable to use at least one selected from these.

Among these surfactants, BYK306, BYK342, BYK346, KP-341, KP-358, KP-368, Surflon S611, Footergent 710FL, Footergent 710FM, Footergent 710FS, Footergent 650A, Megafuck F-477. , Megafuck F-556, Megafuck RS-72-K, Megafuck DS-21, TEGO Twin 4000, Fluoroalkylbenzene Sulfonate, Fluoroalkyl Sulfate, Fluoroalkyl Polyoxyethylene Ether, Fluoroalkyl Sulfate, At least one selected from the fluoroalkyltrimethylammonium salt and the fluoroalkylaminosulfonate is preferable because the coating uniformity of the thermosetting composition is improved.

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

1-5-7. Adhesion improver The thermosetting composition of the present invention may further contain an adhesion improver from the viewpoint of further improving the adhesion between the cured film to be formed and the substrate. As an example of such an adhesion improver, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, Silaace S510; trade name; JNC Co., Ltd.), 2- (3). , 4-Epoxycyclohexyl) Ethyltrimethoxysilane (eg, Silaace S530; trade name; JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane (eg, Silaace S810; trade name; JNC Co., Ltd.) and other silane couplings. Agents, aluminum-based coupling agents such as acetalkoxyaluminum diisopropylate, and titanate-based coupling agents such as tetraisopropylbis (dioctylphosphite) titanate.

Among these, 3-glycidyloxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.

The content of the adhesion improver is preferably 0.01% by weight or more and 10% by weight or less with respect to the total amount of the thermosetting composition.

1-5-8. Antioxidant The thermosetting composition of the present invention may further contain an antioxidant from the viewpoint of improving transparency and preventing yellowing when the cured film is exposed to a high temperature.

Antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added to the thermosetting composition of the present invention. Of these, the hindered phenolic system is preferable from the viewpoint of light resistance.具体例は、Ｉｒｇａｎｏｘ１０１０、Ｉｒｇａｎｏｘ１０１０ＦＦ、Ｉｒｇａｎｏｘ１０３５、Ｉｒｇａｎｏｘ１０３５ＦＦ、Ｉｒｇａｎｏｘ１０７６、Ｉｒｇａｎｏｘ１０７６ＦＤ、Ｉｒｇａｎｏｘ１０７６ＤＷＪ、Ｉｒｇａｎｏｘ１０９８、Ｉｒｇａｎｏｘ１１３５、Ｉｒｇａｎｏｘ１３３０、Ｉｒｇａｎｏｘ１７２６、Ｉｒｇａｎｏｘ１４２５ＷＬ、Ｉｒｇａｎｏｘ１５２０Ｌ、Ｉｒｇａｎｏｘ２４５、Ｉｒｇａｎｏｘ２４５ＦＦ、Ｉｒｇａｎｏｘ２４５ＤＷＪ、Ｉｒｇａｎｏｘ２５９、Ｉｒｇａｎｏｘ３１１４、Ｉｒｇａｎｏｘ５６５、Ｉｒｇａｎｏｘ５６５ＤＤ、Ｉｒｇａｎｏｘ２９５（いずれも商品名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 (all product names; ADEKA). Of these, Irganox 1010 and ADK STAB AO-60 are more preferable.

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

1-5-9. Molecular Weight Adjusting Agent The thermosetting composition of the present invention may further contain a molecular weight adjusting agent in order to suppress an increase in molecular weight due to polymerization and to exhibit excellent storage stability. Examples of the molecular weight adjusting agent include mercaptans, xanthates, quinones, hydroquinones, 2,4-diphenyl-4-methyl-1-pentene and the like.

Specific examples of the molecular weight modifier include 1,4-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, methyl-p-benzoquinone, anthraquinone, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,5-di. -T-butylhydroquinone, 2,5-di-t-amylhydroquinone, 1,4-dihydroxynaphthalene, 3,6-dihydroxybenzonorbornane, 4-methoxyphenol, 2,2', 6,6'-tetra-t -Butyl-4,4'-dihydroxybiphenyl, 3- (3,5-di-t-butyl-4-hydroxyphenyl) stearyl propionate, 2,2'-methylenebis (6-t-butyl-4-ethylphenol) ), 2,4,6-Tris (3', 5'-di-t-butyl-4'-hydroxybenzyl) mecitylene, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxy) Phenyl) propionate], 4-t-butylpyrocatechol, n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, thioglycolic acid, dimethylxanthogen sulfide, diisopropylxanthogen disulfide, 2,6-di -T-butyl-p-cresol, 4,4'-butylidenebis (6-t-butyl-m-cresol), 4,4'-thiobis (6-t-butyl-m-cresol), 2,4-diphenyl Examples thereof include -4-methyl-1-pentene, phenothiazine, 2-hydroxy-1,4-naphthoquinone and the like.

The molecular weight adjusting agent may be used alone or in combination of two or more. Among the molecular weight adjusting agents, naphthoquinone-based molecular weight adjusting agents are preferable from the viewpoint of exhibiting excellent storage stability.

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

1-5-10. Ultraviolet absorber The thermosetting composition of the present invention may contain an ultraviolet absorber from the viewpoint of further improving the deterioration preventing ability of the formed transparent film.

Specific examples of the ultraviolet absorber are TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571, and TINUVIN 765 (all trade names; BASF Japan Ltd.).

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

1-5-11. Anti-aggregation agent The thermosetting composition of the present invention may contain an anti-aggregation agent from the viewpoint of blending a polyester amic acid (A) or an epoxy compound (B) having a polymerizable double bond with a solvent to prevent aggregation. good.

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

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

1-5-12. Thermosetting agent The thermosetting composition of the present invention may contain a thermosetting agent from the viewpoint of further improving heat resistance, chemical resistance, in-plane uniformity, flexibility, flexibility, and elasticity.

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

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

1-6. Preservation of Thermosetting Composition The thermosetting composition of the present invention is preferably stored in the range of −30 ° C. to 25 ° C. because the stability of the composition over time is good. When the storage temperature is −20 ° C. to 10 ° C., there is no precipitate and it is more preferable.

2. 2. Curing film obtained from a thermosetting composition The thermosetting composition of the present invention comprises a polyesteramidic acid (A), a polymer of a cyclic ether compound (B), a curing agent (C), a solvent (D), and further. Epoxy compounds other than the compound having an oxylanyl group (b2), compounds having a polymerizable double bond, surfactants, adhesion improvers, antioxidants, and other additives are selected and added as necessary, and these are added. Can be obtained by uniformly mixing and dissolving.

The thermosetting composition prepared as described above (after being dissolved in a solvent in the case of a solid state without a solvent) is applied to the surface of the substrate, and the solvent is removed by heating, for example, to obtain a coating film. Can be formed. The thermosetting composition can be applied to the surface of the substrate by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, or a slit coating method. Next, this coating film is temporarily fired on a hot plate, an oven, or the like. The tentative firing conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 150 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. After that, the main firing is performed to cure the coating film. The main firing conditions vary depending on the type and mixing ratio of each component, but are usually 180 to 250 ° C., preferably 200 to 250 ° C., 30 to 90 minutes for an oven, and 5 to 30 minutes for a hot plate, and heat treatment is performed. This makes it possible to obtain a cured film.

The cured film thus obtained has a high molecular weight when 1) the polyamic acid portion of the polyesteramidic acid is dehydrated and cyclized to form an imide bond, and 2) the carboxylic acid of the polyesteramidic acid reacts with the epoxy compound. And 3) Since the epoxy compound is cured and has a high molecular weight, it is extremely tough and has excellent transparency, heat resistance, chemical resistance, flatness and adhesion. Further, the light resistance, spatter resistance, scratch resistance, and coatability are also expected to be excellent for the same reason. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state image pickup device can be manufactured using this color filter. Further, the cured film of the present invention is effective when used as a transparent insulating film formed between the TFT and the transparent electrode or a transparent insulating film formed between the transparent electrode and the alignment film, in addition to the protective film for the color filter. Is. Further, the cured film of the present invention is also effective when used as a protective film for an LED light emitter.

Next, the present invention will be specifically described with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to these examples.

The abbreviations of the compounds used in Synthesis Examples, Examples, and Comparative Examples indicate the following raw materials.

[Tetracarboxylic acid anhydride]
ODPA: 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride BT-100: 1,2,3,4-butanetetracarboxylic acid dianhydride

[Diamine]
DDS: 3,3'-diaminodiphenyl sulfone

[Multivalent hydroxy compound]
Bis-A-2EOH: 4,4'-isopropylidenebis (2-phenoxyethanol)
70PA: Epoxy ester 70PA (trade name; Kyoeisha Chemical Co., Ltd.)

[Styrene-maleic anhydride copolymer]
SMA1000P (Product name; Kawahara Yuka Co., Ltd.)

[Cyclic ether compound]
OXE-30: (3-ethyloxetane-3-yl) methyl methacrylate OXE-10: (3-ethyloxetane-3-yl) methyl acrylate GMA: glycidyl methacrylate E6: TECHMORE VG3101L (trade name; Printec Co., Ltd.)

[Radical polymerizable compounds other than cyclic ether compounds]
MMA: Methyl Methacrylate NPM: N-Phenyl Maleimide

[Thermal polymerization initiator]
V-601: Dimethyl 2,2'-azobis (2-methylpropionate)

[Curing agent (C)]
TMA: Trimelli acid anhydride UC-3000: ARUFON UC-3000 (trade name; Toagosei Co., Ltd.)

S510: Sila Ace S510 (trade name; JNC Corporation)
AO-60: ADK STAB AO-60 (trade name; ADEKA CORPORATION)
F-556: Megafuck F-556 (trade name; DIC Corporation)

[solvent]
MMP: Methyl 3-methoxypropionate PGMEA: Propylene glycol monomethyl ether acetate

First, a polyesteramidic acid solution which is a reaction product of a tetracarboxylic acid dianhydride, a diamine, a monohydroxy compound, a polyvalent hydroxy compound and the like was synthesized as shown below (Synthesis Examples 1 to 7).

[Synthesis Example 1] Synthesis of polyester amidoic acid (A1) solution In a four-necked flask equipped with a stirrer, dehydration-purified methyl 3-methoxypropionate (hereinafter abbreviated as "MMP"), 3,3', 4,4' -Diphenyl ether tetracarboxylic acid dianhydride (hereinafter abbreviated as "ODPA"), 1,4-butanediol and benzyl alcohol were charged in the following weights and stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis). ).
MMP 49.00g
ODPA 20.36g
1,4-Butanediol 3.55g
Benzyl alcohol 2.84g

Then, the reaction solution was cooled to 25 ° C., 3,3'-diaminodiphenyl sulfone (hereinafter abbreviated as "DDS") and MMP were added in the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then 125. The mixture was stirred at ° C. for 1 hour (second stage of synthesis).
DDS 3.26g
MMP 21.00g

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

The solution was cooled to room temperature to give a 30 wt% solution of pale yellow clear polyester amic acid (A1). A part of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyesteramidic acid (A1) was 4,200.

[Synthesis Example 2] Synthesis of polyester amidoic acid (A2) solution In a four-necked flask equipped with a stirrer, dehydrated and purified propylene glycol monomethyl ether acetate (PGMEA), 1,2,3,4-butanetetracarboxylic acid dianhydride ( BT-100), SMA1000P (trade name; styrene / maleic anhydride copolymer, Kawahara Yuka Co., Ltd.), 1,4-butanediol, and benzyl alcohol are charged in the following order by weight, and at 125 ° C. under a dry nitrogen stream. The mixture was stirred for 2 hours (first stage of synthesis).
PGMEA 53.49g
BT-100 3.83g
SMA1000P 18.23g
1,4-Butanediol 1.16g
Benzyl alcohol 5.57 g

Then, the reaction solution was cooled to 25 ° C., DDS and PGMEA were added under the following weight, and the mixture was stirred at 20 to 30 ° C. for 2 hours and then at 125 ° C. for 1 hour (second stage of synthesis).
DDS 1.20g
PGMEA 16.51g

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

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

[Synthesis Examples 3 to 7] Synthesis of Polyester Amidoic Acids (A3) to (A7) Solutions According to the methods of Synthesis Examples 1 and 2, at the temperature, time, and ratio (unit: g) shown in Table 1-1. Each component was reacted to obtain a polyesteramidic acid (A3) to (A7) solution.

Next, a solution of the polymer (B) of the cyclic ether compound was synthesized as shown below (Synthesis Example 8).

[Synthesis Example 8] Synthesis of Polymer (B1) Solution of Cyclic Ether Compound In a four-necked flask equipped with a stirrer, PGMEA dehydrated and purified as a polymerization solvent and OXE-30 as a compound (b1) having an oxetanyl group are placed in the following weight. Further, V-601 was charged as a polymerization initiator at the following weight, and the mixture was stirred at 110 ° C. for 2 hours under a dry nitrogen stream.
PGMEA 31.50g
OXE-30 13.50g
V-601 1.35g

The solution was cooled to room temperature to give a 30 wt% solution of the polymer (B1) of the cyclic ether compound. A part of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (B1) of the cyclic ether compound was 7,200.

[Synthesis Example 9] Synthesis of Polymer (B2) Solution of Cyclic Ether Compound In a four-necked flask equipped with a stirrer, PGMEA dehydrated and purified as a polymerization solvent, OXE-30 as a compound having an oxetanyl group (b1), and an oxylanyl group are placed. GMA was charged as the compound (b2) having the following weight, and V-601 was charged as the polymerization initiator under the following weight, and the mixture was stirred at 110 ° C. for 2 hours under a dry nitrogen stream.
PGMEA 31.500g
OXE-30 10.125g
GMA 3.375g
V-601 1.350g

The solution was cooled to room temperature to give a 30 wt% solution of the polymer (B2) of the cyclic ether compound. A part of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (B2) of the cyclic ether compound was 7,300.

[Synthesis Examples 10 to 13] Synthesis of Polymers (B3) to (B6) Solutions of Cyclic Ether Compounds The temperature, time, and ratio (units) shown in Table 1-2 are according to the methods of Synthesis Examples 8 and 9. : G) was used to react each component to obtain a polymer (B3) to (B6) solution of the cyclic ether compound.

[Comparative Synthesis Examples 1 to 5] Synthesis of solutions of cyclic ether compounds (E1) to (E5) other than (B) According to the methods of Synthesis Examples 8 and 9, the temperatures, times, and temperatures and times shown in Table 1-3 are shown. Each component was reacted at a ratio (unit: g) to obtain a solution of cyclic ether compounds (E1) to (E5) other than (B).

[Example 1]
A 500 ml separable flask equipped with a stirring blade was substituted with nitrogen, and 100.0 g of the polyesteramidic acid (A1) solution obtained in Synthesis Example 1 as polyesteramidic acid (A) was added to the flask, and the weight of the cyclic ether compound was increased. 100.0 g of the compound (B1), 6.0 g of TMA as a curing agent, 3.3 g of S510 as an adhesion improver, 0.3 g of AO-60 as an antioxidant, and MMP dehydrated and purified as a solvent (D). 41.7 g and 97.6 g of PGMEA were charged and stirred at room temperature for 3 hours to uniformly dissolve.

Next, 0.2 g of Megafuck F-556 (trade name; DIC Corporation) was added as a surfactant, stirred at room temperature for 1 hour, and filtered through a membrane filter (pore size 0.2 μm) to form a thermosetting composition. Was prepared.

[Barrier evaluation method]
Substrate of a color filter without a cured film having pixels containing R, G, and B having absorption near 560 nm when measured with an ultraviolet-visible near-infrared spectrophotometer (trade name; V-670, JASCO Corporation). The thermocurable composition was spin-coated on top at 300 rpm for 10 seconds and prebaked on a hot plate at 90 ° C. for 2 minutes. Subsequently, it was post-baked in an oven at 230 ° C. for 30 minutes to obtain a color filter substrate with a cured film having an average film thickness of 2.0 μm.

Next, 0.5 mL of 1-methyl-2-pyrrolidone was dropped onto a color filter substrate with a cured film cut out in a 10 cm square, and glass (hereinafter referred to as cover glass) cut out in a 9 cm square was placed on a color filter substrate with a cured film. It was allowed to stand on top and heated at 180 ° C. for 5 minutes using a hot plate. After the heating was completed, the cover glass was removed, the cover glass and the color filter substrate with the cured film were washed with 5 mL of 1-methyl-2-pyrrolidone, and the washing liquid was transferred to a 10 mL volumetric flask. 1-Methyl-2-pyrrolidone was added to a volumetric flask containing a cleaning solution, and the mixture was made up to 10 mL, and the mixed solution was used as an eluate for a color filter substrate with a cured film. Then, with the above-mentioned ultraviolet-visible near-infrared spectrophotometer, 1-methyl-2-pyrrolidone was used as a reference sample, and the transmittance of the eluate was measured. From the measurement results, the case where the transmittance at 560 nm was 90% or more was evaluated as ◯, and the case where the transmittance was less than 90% was evaluated as x.

[Evaluation method of flatness]
The thermosetting composition is placed on a color filter substrate without a curing film having pixels containing R, G, and B whose surface step is measured in advance using a fine shape measuring device (trade name; P-17, KLA TENCOR Co., Ltd.). Was spin coated at 300 rpm for 10 seconds and prebaked on a hot plate at 90 ° C. for 2 minutes. Subsequently, it was post-baked in an oven at 230 ° C. for 30 minutes to obtain a color filter substrate with a cured film having an average film thickness of 2.0 μm. Then, the surface step was measured with respect to the obtained color filter substrate with a cured film.

The flattening rate was calculated from the maximum value of the surface step of the color filter substrate without the cured film and the color filter substrate with the cured film (hereinafter, abbreviated as "maximum step") using the following formula. When the flattening rate was 75% or more, it was evaluated as flatness ◯, and when it was less than 75%, it was evaluated as flatness ×. As the color filter substrate without a cured film, a color filter substrate having a maximum step of 1.5 μm was used.

Flattening rate = [(Maximum step of color filter substrate without cured film-Maximum step of color filter substrate with cured film) / (Maximum step of color filter substrate without cured film)] x 100%

[Evaluation method of heat resistance]
The thermosetting composition was then spin-coated on a glass substrate at 800 rpm for 10 seconds and prebaked on a hot plate at 90 ° C. for 2 minutes. Subsequently, it was post-baked in an oven at 230 ° C. for 30 minutes to obtain a glass substrate with a cured film having a protective film thickness of 1.0 μm. After reheating the obtained glass substrate with a cured film at 230 ° C. for 1 hour, the film thickness before heating and the film thickness after heating were measured, and the residual film ratio was calculated by the following formula. The fine shape measuring device (trade name; P-17, KLA TENCOR Co., Ltd.) was used for measuring the film thickness. The case where the residual film ratio after heating was 95% or more was evaluated as ◯, and the case where the residual film ratio after heating was less than 95% was evaluated as x.

[Examples 2 to 13]
According to the method of Example 1, each component was mixed and dissolved at the ratios (units: g) shown in Tables 2-1 to 2-2 to obtain a thermosetting composition.

[Comparative Examples 1 to 6]
According to the method of Example 1, each component was mixed and dissolved at the ratio (unit: g) shown in Table 3 to obtain a thermosetting composition.

As is clear from the results shown in Tables 2-1 to 2-2, the cured film using the polymer (B) of the cyclic ether compound of Examples 1 to 13 has excellent barrier properties and flatness. And it can be seen that the heat resistance is well-balanced.

It can be seen that the cured film using only the cyclic ether compound (E) other than (B) in Comparative Examples 1 to 6 in Table 3 is excellent in heat resistance. On the other hand, in Comparative Example 1, the barrier property was also good, but the flatness was poor. In Comparative Examples 2 and 3, not only the barrier property but also the flatness was bad. The flatness of Comparative Examples 4 to 6 was good, but the barrier property was not good.

As described above, all the characteristics could be satisfied only when the polymer (B) of the cyclic ether compound was used as an essential component.

The cured film obtained from the heat-curable composition of the present invention has a high barrier property and high flatness, and thus is a protective film for various optical materials such as a color filter, an LED light emitting element and a light receiving element, and a TFT. It can be used as an insulating film formed between the transparent electrode and the transparent electrode and the alignment film.

Claims (7)

A thermosetting composition comprising a polyester amic acid (A), a polymer (B) of a cyclic ether compound, and a curing agent (C).
The polyesteramidic acid (A) is an X-mol tetracarboxylic acid dianhydride, a Y-mol diamine and a Z-mol polyvalent hydroxy compound, so that the relationships of the following formulas (1) and (2) are established. It is a reaction product from the raw material contained in the ratio,

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

The polymer (B) of the cyclic ether compound has a homopolymer by radical polymerization of the compound (b1) having an oxetanyl group, a copolymer by radical polymerization of compounds (b1) having an oxetanyl group, and an oxetanyl group. It is at least one selected from the copolymers of the compound (b1) and the compound (b2) having an oxylanyl group by radical polymerization .
The compound (b1) having an oxetanyl group is a (meth) acrylate compound having an oxetanyl group.
A thermosetting composition in which the compound (b2) having an oxylanyl group is a (meth) acrylate compound having an oxylanyl group . The thermosetting composition according to claim 1, wherein the polyester amic acid (A) contains a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

In formulas (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from tetracarboxylic acid dianhydride, and R ² is a residue obtained by removing two -NH ₂ from diamine. R ³ is a residue obtained by removing two -OH from a polyvalent hydroxy compound. The compound (b1) having an oxetane group is at least one selected from (3-ethyloxetane-3-yl) methyl acrylate and (3-ethyloxetane-3-yl) methyl methacrylate, claim 1 or 2. The thermosetting composition according to 2. The thermosetting composition according to claim 1 or 2, wherein the compound (b2) having an oxylanyl group is at least one selected from glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether. thing. The thermosetting according to any one of claims 1 to 4, wherein the content of the polymer (B) of the cyclic ether compound is 20 to 400 parts by weight with respect to 100 parts by weight of the polyesteramidic acid (A). Sex composition. A cured film obtained by curing the thermosetting composition according to any one of claims 1 to 5. A color filter having the cured film according to claim 6 as a transparent protective film.