JP7119677B2 - thermosetting composition - Google Patents

Description

The present invention provides a thermal barrier that can be used to form insulating materials in electronic parts, passivation films, buffer coat films, interlayer insulating films, planarizing films in semiconductor devices, interlayer insulating films in liquid crystal display elements, protective films for color filters, and the like. A curable composition, a transparent film therefrom, and an electronic component comprising 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 the surface is locally heated to a high temperature when wiring electrodes are formed by sputtering. Sometimes. Therefore, in some cases, a surface protective film is provided for the purpose of preventing deterioration, damage, and alteration 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, chemical resistance such as solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to the underlying substrate such as glass, transparency, scratch resistance, coatability, flatness, and light resistance. etc. is required. As the required properties of reliability required for display elements improve, the heat resistance required for display element members is also improving. proposed (see, for example, Patent Document 1).

In the production of display elements in recent years, as production lines and substrates have become larger, unevenness within the substrate surface has become more likely to occur in the manufacturing process. For example, in-plane unevenness in the contact pressure of the rubbing roll against the color filter substrate tends to occur during the rubbing of the alignment film in the manufacture of a large-sized liquid crystal display device. In places where the contact pressure is high, the protective film may be scratched, and if the protective film is scratched, the display quality will deteriorate, so improving the scratch resistance of the thermosetting composition has been an issue. .

In addition, with the recent widening of the color gamut of display elements, color filters having pixels containing pigments at a higher density than in the past are sometimes used. In a color filter having pixels containing a high-concentration pigment, the pigment component is more likely to be eluted during the formation of a protective film or the like, which is the upper layer of the color filter, compared to the conventional art. In particular, the red pigment has a high concentration and is easily eluted during the formation of the upper layer. Since the display quality deteriorates when the pigment components are eluted into the upper layer, improvement of the barrier property against the elution of the pigment components of the material forming the upper layer has been a problem. Although Patent Document 1 provides a thermosetting composition having excellent heat resistance, the scratch resistance and barrier properties are not sufficiently satisfactory, and further improvements are desired.

JP 2005-105264

An object of the present invention is to provide a thermosetting composition that provides a cured film having excellent scratch resistance and barrier properties, and a cured film formed from the thermosetting composition, and further having the cured film It is to provide electronic components.

The present inventors have made intensive studies to solve the above problems, and found that the above objects can be achieved by a cured film obtained by curing a composition containing a polyesteramic acid having a polymerizable double bond and an epoxy compound. I found that it can be done, and came to complete the present invention.
The present invention includes the following configurations.

[1] A thermosetting composition containing a polyesteramic acid (A) having a polymerizable double bond and an epoxy compound (B),
The polyesteramic acid (A) is composed of X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyvalent hydroxy compound, and the relationship of the following formulas (1) and (2) is established. is a reaction product from raw materials in proportions such that
A thermosetting composition wherein at least one of said raw materials has a polymerizable double bond.

0.2≤Z/Y≤8.0 (1)
0.2≦(Y+Z)/X≦5.0 (2)

[2] A thermosetting composition containing a polyesteramic acid (A) having a polymerizable double bond and an epoxy compound (B),
The polyesteramic acid (A) comprises X moles of tetracarboxylic dianhydride, Y moles of diamine, Z moles of polyvalent hydroxy compound, and monohydroxy compound, the following formulas (1) and (2) ) is a reaction product from raw materials in a ratio such that the relationship of
A thermosetting composition wherein at least one of said raw materials has a polymerizable double bond.

0.2≤Z/Y≤8.0 (1)
0.2≦(Y+Z)/X≦5.0 (2)

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を除いた残基であり、Ｒ^３の少なくとも１つは重合性二重結合を有する。 [3] The thermosetting composition according to item [1], wherein the polyesteramic 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 a tetracarboxylic dianhydride, and R ² is a residue obtained by removing two —NH ₂ from a diamine. R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound, and at least one of R ³ has a polymerizable double bond.

式（３）、式（４）及び式（５）において、Ｒ^１はテトラカルボン酸二無水物から２つの－ＣＯ－Ｏ－ＣＯ－を除いた残基であり、Ｒ^２はジアミンから２つの－ＮＨ_２を除いた残基であり、Ｒ^３は多価ヒドロキシ化合物から２つの－ＯＨを除いた残基であり、Ｒ^４はモノヒドロキシ化合物から１つの－ＯＨを除いた残基であり、Ｒ^３及びＲ^４の少なくとも１つは重合性二重結合を有する。 [4] The polyesteramic acid (A) comprises a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a structural unit represented by the following formula (5). The thermosetting composition according to item [2].

In formulas (3), (4) and (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two _—NH2 is the residue, R3 is the residue of the polyhydroxy compound with ^two —OH removed, ^R4 is the residue of the monohydroxy compound with one —OH removed, At ^least one of R3 and ^R4 has a polymerizable double bond.

式（３）、式（４）及び式（５）において、Ｒ^１はテトラカルボン酸二無水物から２つの－ＣＯ－Ｏ－ＣＯ－を除いた残基であり、Ｒ^２はジアミンから２つの－ＮＨ_２を除いた残基であり、Ｒ^３は多価ヒドロキシ化合物から２つの－ＯＨを除いた残基であり、Ｒ^４はモノヒドロキシ化合物から１つの－ＯＨを除いた残基であり、Ｒ^３の少なくとも１つは重合性二重結合を有する。 [5] The polyesteramic acid (A) comprises a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a structural unit represented by the following formula (5). The thermosetting composition according to item [2].

In formulas (3), (4) and (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two _—NH2 is the residue, R3 is the residue of the polyhydroxy compound with ^two —OH removed, ^R4 is the residue of the monohydroxy compound with one —OH removed, ^At least one of R3 has a polymerizable double bond.

式（３）、式（４）及び式（５）において、Ｒ^１はテトラカルボン酸二無水物から２つの－ＣＯ－Ｏ－ＣＯ－を除いた残基であり、Ｒ^２はジアミンから２つの－ＮＨ_２を除いた残基であり、Ｒ^３は多価ヒドロキシ化合物から２つの－ＯＨを除いた残基であり、Ｒ^４はモノヒドロキシ化合物から１つの－ＯＨを除いた残基であり、Ｒ^４の少なくとも１つは重合性二重結合を有する。 [6] The polyesteramic acid (A) comprises a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a structural unit represented by the following formula (5). The thermosetting composition according to item [2].

In formulas (3), (4) and (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two _—NH2 is the residue, R3 is the residue of the polyhydroxy compound with ^two —OH removed, ^R4 is the residue of the monohydroxy compound with one —OH removed, At least one of ^R4 has a polymerizable double bond.

[7] The polyhydric hydroxy compound includes ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. , 2,2-bis(4-hydroxycyclohexyl)propane, 4,4′-dihydroxydicyclohexyl, tris(2-hydroxyethyl) isocyanurate, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-(4-hydroxy At least one compound selected from the group consisting of phenyl)ethanol and a polyhydroxy compound having a polymerizable double bond, which necessarily contains a polyhydroxy compound having a polymerizable double bond, [1] to [ 5], the thermosetting composition according to any one of the above items.

[8] The polyhydric hydroxy compound includes ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. , 2,2-bis(4-hydroxycyclohexyl)propane, 4,4′-dihydroxydicyclohexyl, tris(2-hydroxyethyl) isocyanurate, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, and 2-(4- The thermosetting composition according to item [6], which is at least one compound selected from the group consisting of hydroxyphenyl)ethanol.

[9] The thermosetting composition according to [7], wherein the polyhydroxy compound having a polymerizable double bond has a vinyl group, an allyl group, or a (meth)acryloxy group.

[10] The polyvalent hydroxy compound having a polymerizable double bond includes glycerin mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, di Pentaerythritol 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, ethylene glycol diglycidyl ether (meth)acrylic acid modified product, propylene glycol diglycidyl ether (meth)acrylic acid modified product, tripropylene glycol diglycidyl ether (meth) ) modified acrylic acid, (meth)acrylic acid modified glycerol diglycidyl ether, (meth)acrylic acid modified bisphenol A diglycidyl ether, (meth)acrylic acid modified propylene oxide modified bisphenol A diglycidyl ether, and a (meth)acrylic acid-modified compound containing two or more epoxy groups per molecule, the thermosetting composition according to item [7].

[11] The monohydroxy compound is at least one selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, 3-ethyl-3-hydroxymethyloxetane, and monohydroxy compounds having a polymerizable double bond. The thermosetting composition according to item [2], item [4], item [5], or item [6], which is one compound.

[12] Item [5], wherein the monohydroxy compound is at least one compound selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. thermosetting composition.

[13] The thermosetting composition according to item [11], wherein the monohydroxy compound having a polymerizable double bond has a vinyl group, an allyl group, or a (meth)acryloxy group.

[14] The monohydroxy compound having a polymerizable double bond includes furfuryl alcohol, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, (meth) 4-hydroxyphenyl acrylate, p-hydroxy(meth)acrylanilide, 1,4-cyclohexanedimethanol mono(meth)acrylate, 3-(2-hydroxyphenyl)(meth)acrylate, glycerin di(meth)acrylate, selected from the group consisting of trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and (meth)acrylic acid-modified compounds containing one epoxy group per molecule; The thermosetting composition according to item [11], which is at least one compound.

[15] Any one of [1] to [4], wherein the content of the epoxy compound (B) is 20 to 400 parts by weight relative to 100 parts by weight of the polyesteramic acid (A) having a polymerizable double bond 2. The thermosetting composition according to item 1.

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

[17] A color filter having the cured film according to [16] as a transparent protective film

The thermosetting composition according to a preferred embodiment of the present invention is a material having particularly excellent scratch resistance and barrier properties, and can improve display quality when used as a color filter protective film for a color liquid crystal display device. In particular, it is useful as a protective film for color filters produced by a dyeing method, a pigment dispersion method, an electrodeposition method and a printing method. It can also be used as a protective film for various optical materials and as a transparent insulating film.

In this specification, the higher the pencil hardness of the cured film according to the present invention, the more excellent the scratch resistance of the cured film and the thermosetting composition for forming the cured film.

In this specification, "(meth)acrylate" may be used to indicate one or both of "acrylate" and "methacrylate". Similarly, "(meth)acryloxy" may be used to indicate one or both of "acryloxy" and "methacryloxy."

1. Thermosetting Composition of the Present Invention The thermosetting composition of the present invention is a composition containing a polyesteramic acid having a polymerizable double bond and an epoxy compound. The polyester amic acid having a polymerizable double bond is a reaction product from raw materials including a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound, and at least one of the raw materials has a polymerizable double bond. . The thermosetting composition of the present invention contains 20 to 400 parts by weight of an epoxy compound per 100 parts by weight of polyesteramic acid.

In addition, the thermosetting composition according to the present invention may further contain other components other than the above within the range in which the effects of the present invention can be obtained.

1-1. Polyesteramic acid having a polymerizable double bond (A)
The polyesteramic acid (A) is obtained by reacting a tetracarboxylic dianhydride, a diamine, a polyhydric hydroxy compound, and a monohydroxy compound as essential raw materials. Furthermore, the polyesteramic acid (A) contains X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyhydroxy compound so that the relationships of the above formulas (1) and (2) are established. It is obtained by reacting at a ratio of

Moreover, the polyesteramic acid (A) has a structural unit represented by formula (3), a structural unit represented by formula (4), and a structural unit represented by formula (5). In formulas (3), (4) and (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two R ³ is the residue of the multivalent hydroxy compound with _two —OH removed, and R ⁴ is the residue of the monohydroxy compound with one —OH removed. At ^least one of R3 and ^R4 has a polymerizable double bond.

At least a solvent is required for the synthesis of the polyesteramic acid (A). The solvent may be left as it is to form a liquid or gel thermosetting composition in consideration of handling properties, etc., or the solvent may be removed to form a solid composition in consideration of transportability.

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

1-1-1. Tetracarboxylic dianhydride In the present invention, a tetracarboxylic dianhydride is used as a material for obtaining the polyesteramic acid (A). Specific examples of the tetracarboxylic dianhydride are preferably 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride (hereinafter sometimes abbreviated as ODPA) used in the examples, 1 , 2,3,4-butanetetracarboxylic dianhydride (hereinafter sometimes abbreviated as BT-100).

As the tetracarboxylic dianhydride, in addition to the above, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 2,2′,3,3′-benzophenonetetracarboxylic dianhydride anhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2′,3,3′- diphenylsulfonetetracarboxylic dianhydride, 2,3,3′,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2′,3,3′-diphenylethertetracarboxylic dianhydride, 2,3, 3′,4′-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(anhydrotrimellitate) (trade name) ; TMEG-100, New Japan Chemical Co., Ltd.), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, butanetetracarboxylic acid Dianhydrides and ethanetetracarboxylic dianhydrides can be mentioned, and at least one of the tetracarboxylic dianhydrides described above can be used.

Among these, acid anhydrides that give good transparency to cured films are 3,3′,4,4′-diphenylsulfonetetracarboxylic acid dianhydride, 3,3′,4,4′-diphenyl ether tetracarboxylic acid dianhydride, carboxylic acid dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and TMEG-100 More preferably, 3,3′,4,4′-diphenylethertetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride Carboxylic dianhydrides are particularly preferred.

1-1-2. Diamine In the present invention, a diamine is used as a material for obtaining the polyesteramic acid (A). A specific example of the diamine is preferably 3,3′-diaminodiphenylsulfone (hereinafter sometimes abbreviated as DDS) used in the examples.

Specific examples of the diamine include, in addition to those mentioned above, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 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 can be mentioned, At least one diamine can be used.

Among these, the diamine that gives good transparency to the cured film is more preferably 3,3′-diaminodiphenyl sulfone and bis[4-(3-aminophenoxy)phenyl] sulfone, and 3,3′-diaminodiphenyl Sulfones are particularly preferred.

1-1-3. Polyvalent hydroxy compound The present invention uses a polyvalent hydroxy compound having no polymerizable double bond and/or a polyvalent hydroxy compound having a polymerizable double bond as a material for obtaining polyesteramic acid (A). use. Specific examples of polyhydric hydroxy compounds are preferably 1,4-butanediol, Epoxy Ester 70PA (trade name; Kyoeisha Chemical Co., Ltd.), Epoxy Ester 80MFA (trade name; Kyoeisha Chemical Co., Ltd.), Epoxy ester 3002A (N) (trade name; Kyoeisha Chemical Co., Ltd.) can be mentioned.

Examples of polyhydroxy compounds having no polymerizable double bond 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, and tripropylene. Glycol, tetrapropylene glycol, polypropylene glycol with a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentane diol, 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-octanediol, 1,2-nonanediol , 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12 - dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, tris(2-hydroxyethyl)isocyanurate, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol S (bis(4 -hydroxyphenyl) sulfone), bisphenol F (bis(4-hydroxyphenyl)methane), 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxy Mention may be made of benzyl alcohol, 2-(4-hydroxyphenyl)ethanol, diethanolamine, and triethanolamine.

Among these compounds, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol have good solubility in reaction solvents. , 1,8-octanediol, tris(2-hydroxyethyl)isocyanurate, 2,2-bis(4-hydroxycyclohexyl)propane, 4,4′-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol , and 2-(4-hydroxyphenyl)ethanol are more preferred. Also particularly preferred are 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, and 2-(4-hydroxyphenyl)ethanol.

On the other hand, specific examples of polyvalent hydroxy compounds having a polymerizable double bond are preferably glycerin monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, and 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, di Pentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, ethylene glycol diglycidyl ether (meth) acrylic acid modified product, (Meth)acrylic acid-modified propylene glycol diglycidyl ether, (meth)acrylic acid-modified tripropylene glycol diglycidyl ether, (meth)acrylic acid-modified glycerol diglycidyl ether, bisphenol A diglycidyl ether (meth) ) acrylic acid-modified, propylene oxide-modified bisphenol A diglycidyl ether (meth)acrylic acid-modified, bisphenol S diglycidyl ether (meth)acrylic acid-modified, propylene oxide-modified bisphenol S diglycidyl ether (meth)acryl Acid-modified products, (meth)acrylic acid-modified bisphenol F diglycidyl ether, (meth)acrylic acid-modified propylene oxide-modified bisphenol F diglycidyl ether, (meth)acrylic acid-modified bixylenol diglycidyl ether, biphenol (Meth)acrylic acid-modified diglycidyl ether, (meth)acrylic acid-modified fluorenediphenol diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether (meth)acrylic acid-modified hydrogenated bisphenol A diglycidyl ether, (meth)acrylic acid-modified tricyclodecane dimethanol diglycidyl ether, and epoxy groups per molecule Other compounds containing two or more (meth)acrylic acid-modified products can be mentioned, and at least one of these can be used.

Among these, compounds with good solubility in the reaction solvent are ethylene glycol diglycidyl ether modified with (meth)acrylic acid, propylene glycol diglycidyl ether modified with (meth)acrylic acid, glycerin diglycidyl ether (Meth)acrylic acid-modified products, bisphenol A diglycidyl ether modified (meth)acrylic acid products, propylene oxide-modified bisphenol A diglycidyl ether modified (meth)acrylic acid products, bisphenol S diglycidyl ether (meth)acrylic acid products Modified products, (meth)acrylic acid-modified propylene oxide-modified bisphenol S diglycidyl ether, (meth)acrylic acid-modified bisphenol F diglycidyl ether, and (meth)acrylic acid-modified propylene oxide-modified bisphenol F diglycidyl ether things are more preferred. In addition, ethylene glycol diglycidyl ether modified (meth)acrylic acid, propylene glycol diglycidyl ether modified (meth)acrylic acid, tripropylene glycol diglycidyl ether modified (meth)acrylic acid, glycerin diglycidyl ether A (meth)acrylic acid-modified product, a (meth)acrylic acid-modified bisphenol A diglycidyl ether, and a (meth)acrylic acid-modified propylene oxide-modified bisphenol A diglycidyl ether are particularly preferred.

Methacrylic acid-modified ethylene glycol diglycidyl ether, acrylic acid-modified propylene glycol diglycidyl ether, acrylic acid-modified tripropylene glycol diglycidyl ether, acrylic acid-modified glycerol diglycidyl ether, bisphenol A diglycidyl ether 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, the following commercial products are available. can be used.

A specific example of the methacrylic acid-modified ethylene glycol diglycidyl ether is Epoxy Ester 40EM (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of acrylic acid-modified propylene glycol diglycidyl ether is Epoxy Ester 70PA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified tripropylene glycol diglycidyl ether is Epoxy Ester 200PA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of acrylic acid-modified glycerin diglycidyl ether is Epoxy Ester 80MFA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the methacrylic acid-modified bisphenol A diglycidyl ether is Epoxy Ester 3000MK (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of acrylic acid-modified bisphenol A diglycidyl ether is Epoxy Ester 3000A (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the methacrylic acid-modified propylene oxide-modified bisphenol A diglycidyl ether is Epoxy Ester 3002M (N) (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of acrylic acid-modified 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 having no polymerizable double bond and/or a monohydroxy compound having a polymerizable double bond may be used as the material for obtaining the polyesteramic acid (A). good.

Specific examples of monohydroxy compounds preferably include benzyl alcohol, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxyphenyl methacrylate, and 1,4-cyclohexanedimethanol monoacrylate (hereinafter referred to as It may be abbreviated as CHDMMA.) (trade name; Nippon Kasei Co., Ltd.).

Using a monohydroxy compound improves the storage stability of the thermosetting composition.

Specific examples of monohydroxy compounds having no polymerizable double bond are preferably isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, Mention may be made of ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, terpineol, 3-ethyl-3-hydroxymethyloxetane, and dimethylbenzyl carbinol.

Among these, benzyl alcohol, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane are more preferred. Compatibility in the case of mixing the polyesteramic acid (A) obtained by using these, the epoxy group-containing polymer, the epoxy compound (B) and the epoxy curing agent, and the applicability of the thermosetting composition on the color filter , the use of benzyl alcohol is particularly preferred for monohydroxy compounds that do not have polymerizable double bonds.

Specific examples of monohydroxy compounds having a polymerizable double bond are preferably furfuryl alcohol, allyl alcohol, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2-hydroxy- 3-phenoxypropyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, p-hydroxy (meth)acrylanilide, 1,4-cyclohexanedimethanol mono (meth)acrylate, 3-(2) (meth)acrylic acid -hydroxyphenyl), glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylic acid-modified phenyl glycidyl ether, Examples include (meth)acrylic acid-modified t-butylphenyl glycidyl ether and (meth)acrylic acid-modified other compounds containing one epoxy group per molecule, at least one of which is used. be able to.

Among these, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, (meth)acrylic acid = 4-hydroxyphenyl, More preferred are p-hydroxy(meth)acrylanilide, 1,4-cyclohexanedimethanol mono(meth)acrylate, and (meth)acrylic acid = 3-(2-hydroxyphenyl). Compatibility in the case of mixing the polyesteramic acid (A) obtained by using these, the epoxy group-containing polymer, the epoxy compound (B) and the epoxy curing agent, and the applicability of the thermosetting composition on the color filter , monohydroxy compounds with polymerizable double bonds include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylic acid = 4-hydroxyphenyl, p -Hydroxy(meth)acrylanilide and 1,4-cyclohexanedimethanol mono(meth)acrylate are particularly preferred.

As 4-hydroxyphenyl methacrylate, p-hydroxymethacrylanilide, and 1,4-cyclohexanedimethanol monoacrylate, the following commercial products can be used. A specific example of 4-hydroxyphenyl methacrylate is HQMA (trade name; Osaka Organic Chemical Industry Co., Ltd.). A specific example of p-hydroxymethacrylanilide is HMAd (trade name; Osaka Organic Chemical Industry Co., Ltd.). A specific example of 1,4-cyclohexanedimethanol monoacrylate is 1,4-cyclohexanedimethanol monoacrylate (CHDMMA) (trade name; Nippon Kasei Co., Ltd.).

It is preferable that the monohydroxy compound is added in an amount of 0 to 300 parts by weight for the total amount of 100 parts by weight of the tetracarboxylic dianhydride, the diamine and the polyhydric hydroxy compound. More preferably 5 to 200 parts by weight.

1-1-5. Styrene-Maleic Anhydride Copolymer The polyester amic acid used in the present invention may be synthesized by using a compound having three or more acid anhydride groups as the raw material described above. This is preferable because it improves the transparency of the cured film. Examples of compounds having 3 or more acid anhydride groups include styrene-maleic anhydride copolymers. When synthesizing polyester amic acid using a styrene-maleic anhydride copolymer as a raw material, the sum of the number of moles of the tetracarboxylic dianhydride and the number of moles of the styrene-maleic anhydride copolymer is expressed by the formula (2 ) as "X". As for the ratio of each component constituting the styrene-maleic anhydride copolymer, the molar ratio of styrene/maleic anhydride is 0.5-4, preferably 1-3. Furthermore, 1 or 2 is more preferred, and 1 is particularly preferred.

Specific examples of the styrene-maleic anhydride copolymer include SMA3000P, SMA2000P, and SMA1000P (all trade names; Kawakuro Kagaku Co., Ltd.). Among these, SMA1000P is particularly preferable because the heat resistance and alkali resistance of the cured film are good.

1-1-6. In the synthesis of the silicon-containing monoamine polyester amic acid, as raw materials, other raw materials than the above may be included as necessary as long as the object of the present invention is not impaired. Examples of other raw materials include silicon-containing Monoamines are mentioned.

Specific examples of silicon-containing monoamines used in the present invention are preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4 -aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p- Mention may be made of aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. At least one of these can be used.

Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane are more preferable because the acid resistance of the cured film is good, and 3-aminopropyltriethoxysilane is particularly preferable from the viewpoint of acid resistance and compatibility. preferable.

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

1-1-7. Solvent Used in Synthesis Reaction of Polyester Amic Acid (A) Specific examples of the solvent used in the synthesis reaction for obtaining polyester amic acid (A) having a polymerizable double bond include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and 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, and cyclohexanone. Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ethyl ether are preferred.

1-1-8. Method for synthesizing polyesteramic acid (A) The method for synthesizing the polyesteramic acid (A) having a polymerizable double bond used in the present invention is X moles of tetracarboxylic dianhydride, Y moles of diamine, Z moles of A polyhydric hydroxy compound and a monohydroxy compound are reacted in the above solvent. At this time, it is preferable to set X, Y and Z to a ratio such that the relationships of the following formulas (1) and (2) are established among them. Within this range, the solubility of the polyesteramic acid in the solvent is high, and the coating properties of the composition are improved.

0.2≤Z/Y≤8.0 (1)
0.2≦(Y+Z)/X≦5.0 (2)

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

In the synthesis of polyesteramic acid (A), without using a monohydroxy compound, under the condition that X is excessively used with respect to Y + Z within the range of the above formula (2), an acid anhydride group (-CO- O--CO--) is thought to be produced in excess from molecules having terminal amino groups or hydroxyl groups. On the other hand, when a monohydroxy compound is added to react with such a monomer structure, it reacts with the acid anhydride group at the terminal of the molecule, and the terminal can be esterified. The polyesteramic acid (A) used in the present invention is obtained by adding and reacting a monohydroxy compound, so it improves the compatibility with the epoxy compound (B) and improves the applicability of the thermosetting composition. Improve.

In addition, when reacting with the above-described monomer composition, a silicon-containing monoamine can be added in order to react with the acid anhydride group at the terminal of the molecule and introduce a silyl group at the terminal. When a thermosetting composition containing a polyesteramic acid obtained by adding and reacting with a silicon-containing monoamine is used, the acid resistance of the cured film 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 amount of the tetracarboxylic dianhydride, the diamine and the polyhydric 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 raw materials to the reaction system is not particularly limited. That is, a method of simultaneously adding a tetracarboxylic dianhydride, a diamine and a polyhydroxy compound to a reaction solvent, a method of dissolving a diamine and a polyhydroxy compound in a reaction solvent and then adding a tetracarboxylic dianhydride, a method of adding a tetracarboxylic dianhydride, A method of pre-reacting a carboxylic dianhydride and a polyvalent hydroxy compound and then adding a diamine to the reaction product, or a method of pre-reacting a tetracarboxylic dianhydride and a diamine and then adding a large amount to the reaction product. Any method such as a method of adding a hydroxy compound can be used. The monohydroxy compound may be added at any point during the reaction.

When the silicon-containing monoamine is reacted, after the reaction of the tetracarboxylic dianhydride, the diamine and the polyhydric hydroxy compound, the reaction solution is cooled to 40°C or less, and then the silicon-containing monoamine is added and the temperature is adjusted to 10 to 40°C. for 0.1 to 6 hours. Also, the monohydroxy compound may be added at any point in the reaction.

The polyesteramic acid (A) thus synthesized contains a structural unit represented by formula (3), a structural unit represented by formula (4), and a structural unit represented by formula (5). , its terminal is an acid anhydride group, an amino group, a hydroxy group, or a monovalent organic group derived from the raw material tetracarboxylic dianhydride, diamine, polyhydroxy compound, or monohydroxy compound, or these It is composed of additives other than compounds. By including such a configuration, the curability is improved.

The weight average molecular weight of the resulting polyesteramic acid is preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000. Within these ranges, the scratch resistance and flatness are good.

The weight-average molecular weight in this specification is a value in terms of polystyrene obtained by the GPC method (column temperature: 35° C., flow rate: 1 ml/min). For standard polystyrene, polystyrene with a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 of Agilent Technologies Inc.), PLgel MIXED-D (Agilent Technologies Inc.) is used for the column, It can be measured using THF as a mobile phase. The weight-average molecular weights of commercial products in this specification are catalog values.

1-2. Epoxy compound (B)
The epoxy compound (B) used in the present invention is a compound having two or more epoxy groups per molecule. Epoxy compounds (B) may be of one type or two or more types.

Examples of the epoxy compound (B) include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, biphenyl type epoxy compounds, phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, Bisphenol A novolac epoxy compounds, aliphatic polyglycidyl ether compounds, cycloaliphatic epoxy compounds, polymers of monomers having epoxy groups, copolymers of monomers having epoxy groups and other monomers, and siloxane binding sites It is an epoxy compound with

Specific examples of commercially available bisphenol A type epoxy compounds are jER 828, 1004 and 1009 (all trade names; Mitsubishi Chemical Corporation); specific examples of commercially available bisphenol F type epoxy compounds are jER 806 and 4005P. (both are trade names; Mitsubishi Chemical Corporation); specific examples of commercially available glycidyl ether type epoxy compounds are TECHMORE VG3101L (trade name; Printec Co., Ltd.) and EHPE-3150 (trade name; Daicel Corporation). , EPPN-501H, 502H (both trade names; Nippon Kayaku Co., Ltd.), and jER 1032H60 (trade name; Mitsubishi Chemical Corporation); specific examples of commercially available glycidyl ester type epoxy compounds are Denacol EX- 721 (trade name; Nagase ChemteX Corporation), and diglycidyl 1,2-cyclohexanedicarboxylate (trade name; Tokyo Chemical Industry Co., Ltd.); specific examples of commercially available biphenyl type epoxy compounds are jER YX4000 and YX4000H. , YL6121H (all trade names; Mitsubishi Chemical Corporation), and NC-3000, NC-3000-L, NC-3000-H, and NC-3100 (all trade names; Nippon Kayaku Co., Ltd.); phenol Specific examples of commercially available novolac epoxy compounds include EPPN-201 (trade name; Nippon Kayaku Co., Ltd.) and JER 152 and 154 (both trade names; Mitsubishi Chemical Co., Ltd.); Specific examples of commercially available compounds include EOCN-102S, 103S, 104S, and 1020 (all trade names; Nippon Kayaku Co., Ltd.); specific examples of commercially available bisphenol A novolac epoxy compounds include jER 157S65. , 157S70 (both trade names; Mitsubishi Chemical Corporation); specific examples of commercially available cycloaliphatic epoxy compounds are Celoxide 2021P and 3000 (both trade names; Daicel Corporation); Specific examples of commercially available epoxy compounds having・Performance Materials G.K.), COATOSIL MP-200 (trade name: Momentive Performance Materials G.K.), Poselan SQ506 (trade name; Arakawa Chemical Co., Ltd.) and ES-1023 (trade name; Shin-Etsu Chemical Co., Ltd.).

TECHMORE VG3101L (trade name; Printec Co., Ltd.) is 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxy propoxy)phenyl]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; EHPE-3150 (trade name; Daicel Corporation) is 2,2-bis(hydroxymethyl)- It is a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 1-butanol; Celoxide 2021P (trade name; Daicel Corporation) is 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane. carboxylate; Celoxide 3000 (trade name; Daicel Corporation) is 1-methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4.1.0]heptane; COATOSIL MP-200 (trade name; Momentive Performance Materials LLC) is a polymer whose raw material is 3-glycidoxypropyltrimethoxysilane.

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

1-2-2. Ratio of epoxy compound (B) to polyesteramic acid (A) The ratio of the total amount of epoxy compound (B) to 100 parts by weight of polyesteramic acid (A) in the thermosetting composition of the present invention is 20 to 400 parts by weight. be. When the proportion of the total amount of the epoxy compound (B) is within this range, the flatness, heat resistance, chemical resistance, and adhesion are well balanced. The total amount of epoxy compound (B) is preferably in the range of 50 to 300 parts by weight.

1-3. Other Components Various additives can be added to the thermosetting composition of the present invention in order to improve coating uniformity, adhesiveness, transparency, flatness and chemical resistance. Additives include epoxy curing agents, solvents, anionic, cationic, nonionic, fluorine-based or silicon-based leveling agents/surfactants, adhesion improvers such as silane coupling agents, hindered phenols, and hindered amines. Antioxidants such as system, phosphorus, and sulfur compounds, and molecular weight modifiers are mainly included.

1-3-1. Surfactant A surfactant may be added to the thermosetting composition of the present invention in order to improve coating uniformity. Specific examples of surfactants include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (both trade names; Kyoeisha Chemical Co., Ltd.), Disperbake 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181, Disperbake 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (both product names: BYK-Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all trade names; Shin-Etsu Chemical Co., Ltd.), Surflon-SC-101, Surflon -KH-40, Surflon-S611 (both trade names; AGC Seimi Chemical Co., Ltd.), Futergent 222F, Futergent 208G, Futergent 251, Futergent 710FL, Futergent 710FM, Futergent 710FS, Futergent 601AD, Futer EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all trade names; Neos Co., Ltd.) ; Mitsubishi Materials Corporation), Megafuck F-171, Megafuck F-177, Megafuck F-410, Megafuck F-430, Megafuck F-444, Megafuck F-472SF, Megafuck F-475, Mega Fakfuck F-477, Megafuck F-552, Megafuck F-553, Megafuck F-554, Megafuck F-555, Megafuck F-556, Megafuck F-558, Megafuck F-559, Megafuck R -30, Megafac R-94, Megafac RS-75, Megafac RS-72-K, Megafac RS-76-NS, Megafac DS-21 (all trade names; DIC Corporation), TEGO Twin 4000 , TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (both trade names: Evonik Japan Ltd.), fluoroalkylbenzenesulfonate, 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, polyoxy Ethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate , 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 sulfonates, and alkyl diphenyl ether disulfonates. It is preferable to use at least one selected from these.

Among these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-358, KP-368, Surflon-S611, Futergent 710FL, Futergent 710FM, Futergent 710FS, Futergent 601AD, Futergent 650A, Megafac F-477, Megafac F-556, Megafac F-559, Megafac RS-72-K, Megafac DS-21, TEGO Twin 4000, Fluoroalkylbenzenesulfonate, Fluoroalkyl At least one selected from carboxylates, fluoroalkylpolyoxyethylene ethers, fluoroalkylsulfonates, fluoroalkyltrimethylammonium salts, and fluoroalkylaminosulfonates ensures uniform application of the thermosetting composition. This is preferable because it increases the durability.

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 weight of the thermosetting composition.

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

As such a coupling agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, trade name: Sila Ace S510, JNC Corporation), 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane (for example, trade name; Sila Ace S530, JNC Corporation), 3-mercaptopropyltrimethoxysilane (for example, trade name; Sila Ace S810, JNC Corporation), Momentive Performance Materials Co., Ltd. company), aluminum coupling agents such as acetoalkoxyaluminum diisopropylate, and titanate 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 coupling agent is 0.01% by weight or more and 10% by weight or less with respect to the total amount of the thermosetting composition, because the adhesiveness between the formed cured film and the substrate is improved. preferable.

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

Antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added to the thermosetting composition of the present invention. Among these, hindered phenols are preferred from the viewpoint of weather resistance.具体例としては、Ｉｒｇａｎｏｘ１０１０、Ｉｒｇａｎｏｘ１０１０ＦＦ、Ｉｒｇａｎｏｘ１０３５、Ｉｒｇａｎｏｘ１０３５ＦＦ、Ｉｒｇａｎｏｘ１０７６、Ｉｒｇａｎｏｘ１０７６ＦＤ、Ｉｒｇａｎｏｘ１０７６ＤＷＪ、Ｉｒｇａｎｏｘ１０９８、Ｉｒｇａｎｏｘ１１３５、Ｉｒｇａｎｏｘ１３３０、Ｉｒｇａｎｏｘ１７２６、Ｉｒｇａｎｏｘ１４２５ ＷＬ、Ｉｒｇａｎｏｘ１５２０Ｌ、Ｉｒｇａｎｏｘ２４５、Ｉｒｇａｎｏｘ２４５ＦＦ、Ｉｒｇａｎｏｘ２４５ＤＷＪ、Ｉｒｇａｎｏｘ２５９、Ｉｒｇａｎｏｘ３１１４、Ｉｒｇａｎｏｘ５６５、Ｉｒｇａｎｏｘ５６５ＤＤ、Ｉｒｇａｎｏｘ２９５（いずれもBASF Japan 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 Co., Ltd.). Among these, Irganox 1010 and ADK STAB AO-60 are more preferable.

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

1-3-4. Molecular Weight Modifier The thermosetting composition of the present invention may further contain a molecular weight modifier in order to suppress an increase in molecular weight due to polymerization and to exhibit excellent storage stability. Examples of molecular weight modifiers include mercaptans, xantogens, quinones, hydroquinones and 2,4-diphenyl-4-methyl-1-pentene.

Specific examples of molecular weight modifiers include 2-hydroxy-1,4-naphthoquinone, benzoquinone, 1,4-naphthoquinone, 1,4-dihydroxynaphthalene, 2,5-di-t-butylhydroquinone, hydroquinone, methylhydroquinone, t-butyl hydroquinone, methoquinone, p-benzoquinone, methyl-p-benzoquinone, t-butyl-p-benzoquinone, anthraquinone, n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, thioglycolic acid , dimethyl xanthogen sulfide, diisopropyl xanthogen disulfide, 2,4-diphenyl-4-methyl-1-pentene and the like.

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

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

1-3-5. Epoxy Curing Agent The thermosetting composition of the present invention may further contain an epoxy curing agent in order to improve flatness and chemical resistance. Epoxy curing agents include acid anhydride-based curing agents, amine-based curing agents, phenol-based curing agents, imidazole-based curing agents, catalyst-type curing agents, and sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, and the like. Among heat-sensitive acid generators and the like, acid anhydride-based curing agents and imidazole-based curing agents are preferred from the viewpoint of avoiding coloration of the cured film and heat resistance of the cured film.

Specific examples of the acid anhydride curing agent include aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride; aromatic polycarboxylic anhydrides such as phthalic anhydride and trimellitic anhydride; and styrene-maleic anhydride copolymers. Among these, trimellitic anhydride and hexahydrotrimellitic anhydride are preferred because they have a good balance of heat resistance and solubility in solvents.

Specific examples of the imidazole curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo[1,2- a] benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate. Among these, 2-undecylimidazole is preferred because it has a good balance of curability and solubility in solvents.

When using an epoxy curing agent, the ratio of the epoxy curing agent to 100 parts by weight of the epoxy compound (B) is 0.1 to 60 parts by weight. When the epoxy curing agent is an acid anhydride-based curing agent, more specifically, the addition amount is such that the carboxylic anhydride group or carboxyl group in the epoxy curing agent is 0.1 to 1.5 with respect to the epoxy group. It is preferable to add so as to double the equivalent amount. At this time, the carboxylic anhydride group is calculated as divalent. It is more preferable to add 0.15 to 0.8 equivalents of carboxylic acid anhydride groups or carboxyl groups, since the chemical resistance is further improved.

1-3-6. Ultraviolet Absorber The thermosetting composition of the present invention may contain an ultraviolet absorber from the viewpoint of further improving the ability of the formed transparent film to prevent deterioration.

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 based on the total amount of the thermosetting composition.

1-3-7. Anti-aggregation agent The thermosetting composition of the present invention may contain an anti-aggregation agent from the viewpoint of preventing aggregation by blending the polyesteramic acid (A) and the epoxy compound (B) having a polymerizable double bond with a solvent. good.

Specific examples of anti-aggregating agents are Disperbyk-145, Disperbake-161, Disperbake-162, Disperbake-163, Disperbake-164, Disperbake-182, Disperbake-184, Disperbake-185 , Disperbake-2163, Disperbake-2164, BYK-220S, Disperbake-191, Disperbake-199, Disperbake-2015 (both trade names; BYK Chemie Japan Co., Ltd.), FTX-218, Futergent 710FM, They are Ftergent 710FS (both trade names; Neos Co., Ltd.), Floren G-600, and Floren G-700 (both trade names; Kyoeisha Chemical Co., Ltd.).

The aggregation inhibitor is used by adding 0.01 to 10 parts by weight to the total amount of the thermosetting composition.

1-3-8. Thermal Crosslinking Agent The thermosetting composition of the present invention may contain a thermal crosslinking agent from the viewpoint of further improving heat resistance, chemical resistance, in-plane uniformity, flexibility, softness and elasticity.

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

The thermal cross-linking agent is used by adding 0.1 to 10 parts by weight based on the total amount of the thermosetting composition.

式（６）において、Ｒ^５は水素またはメチルであり、Ｒ^６～Ｒ^９は炭素数１～５のアルキルであり、Ｒ^１０は炭素数１～１０のアルキルであり、ｍは１～１０の整数であり、ｎは１～１５０の整数である。 1-3-9. Other additives The thermosetting composition of the present invention comprises a radically polymerizable compound (P1) represented by the following formula (6), a radically polymerizable compound (P2) having alkoxysilyl, and epoxy, carboxyl, hydroxyphenyl may further contain a polymer obtained by radically copolymerizing a radically polymerizable compound (P3) having at least one of (hereinafter sometimes referred to as "radical copolymer").

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

1-3-9-1. Radically polymerizable compound (P1) represented by formula (6)
Since the radically polymerizable compound (P1) represented by formula (6) acts as a surfactant, the use of (P1) as a raw material causes the radical copolymer to act as a surfactant, Flatness, adhesion to the underlying substrate, and coatability are improved without adding a separate surfactant. By adding the radically polymerizable compound (P1), the radical copolymer becomes more likely to emerge on the film surface.

In the present invention, in the radically polymerizable compound (P1) represented by formula (6), R ⁸ is hydrogen or methyl, R ⁹ to R ¹² are methyl, R ¹³ is alkyl having 1 to 10 carbons, and m is 1. Compounds in which n is an integer from 1 to 150 are preferred. Compounds in which R ⁸ is methyl, R ⁹ to R ¹² are methyl, R ¹³ is butyl, m is 3, and n is an integer of 1 to 150 are more preferred, and those in which n is an integer of 30 to 70 are even more preferred. , n is an integer of 50-70 is particularly preferred. The weight average molecular weight of the radically polymerizable compound (P1) represented by formula (6) is preferably 500-8,000.

The radically polymerizable compound (P1) represented by formula (6) can be produced by a known method. Moreover, you may use a commercial thing. For example, FM-0711, FM-0721, FM-0725 (all trade names; JNC Corporation) and the like can be mentioned.

1-3-9-2. Radically polymerizable compound (P2) having alkoxysilyl
In the present invention, a radical polymerizable compound (P2) having alkoxysilyl is used as a raw material for obtaining the radical copolymer. Preferred radically polymerizable compounds (P2) are 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth) ) one or more selected from the group consisting of acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane; Among these, 3-(meth)acryloxypropyltrimethoxysilane and 3-(meth)acryloxypropyltriethoxysilane are preferable because of their good flatness. By using (P2), transparency, chemical resistance, etc. are improved. Also, the silane coupling effect improves the adhesion to the substrate.

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

1-3-9-4. Method for Producing Radical Copolymer The radical copolymer comprises a radically polymerizable compound (P1) represented by formula (6), a radically polymerizable compound (P2) having alkoxysilyl, and epoxy, carboxyl, and hydroxyphenyl. It is obtained by radically copolymerizing a radically polymerizable compound (P3) having at least one. The method for producing the radical copolymer is not particularly limited, but the radical copolymer can be produced by heating the above radically polymerizable compounds in the presence of a radical initiator. Organic peroxides, azo compounds and the like can be used as radical initiators. Although the reaction temperature for radical copolymerization is not particularly limited, it is usually in the range of 50°C to 150°C. The reaction time is also not particularly limited, but is usually in the range of 1 to 48 hours. Moreover, the reaction can be carried out under any pressure of increased pressure, reduced pressure or atmospheric pressure.

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

The radical copolymer used in the present invention may be a radical copolymer solution in which the solvent used in the polymerization is left as it is in consideration of handling properties, etc., or a solid solution in which the solvent is removed and transportability is taken into consideration. It may be a radical copolymerized polymer with a shape.

It is preferable that the radical copolymer has a weight average molecular weight in the range of 1,000 to 50,000 as determined by GPC analysis using polystyrene as a standard, because film formability is good. Furthermore, when the weight-average molecular weight is in the range of 2,500 to 20,000, the flatness of the cured film is good, which is more preferable. Furthermore, when the weight average molecular weight is in the range of 2,500 to 15,000, the flatness and chemical resistance of the cured film are excellent, which is particularly preferred.

Other additives are used by adding 0.1 to 20 parts by weight based on the total amount of the thermosetting composition.

1-4. Solvent A solvent may be used in the thermosetting composition of the present invention. The solvent optionally added to the thermosetting composition of the present invention is preferably a solvent capable of dissolving the polyesteramic acid (A), the epoxy compound (B) and the like. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxybutyl acetate, 3 -methyl oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, 2- propyl hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate , ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, Ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether, polyethylene glycol, polypropylene glycol. The solvent may be one of these or a mixture of two or more thereof.

1-5. Storage of Thermosetting Composition When the thermosetting composition of the present invention is stored in the range of -30°C to 25°C, the composition has good stability over time. A storage temperature of −20° C. to 10° C. is more preferable since there is no precipitate.

2. Cured film of thermosetting composition The thermosetting composition of the present invention is prepared by mixing a polyesteramic acid (A) having a polymerizable double bond and an epoxy compound (B). A curing agent, a solvent, a surfactant, an adhesion improver, an antioxidant, and other additives can be selected and added as necessary, and can be obtained by uniformly mixing and dissolving them.

The thermosetting composition prepared as described above (in the case of a solid state without a solvent, after dissolving in a solvent) is applied to the surface of a substrate, and the solvent is removed by, for example, heating to form a coating film. can be formed. The coating of the thermosetting composition on the surface of the substrate can be formed by conventionally known methods such as spin coating, roll coating, dipping and slit coating. This coating film is then calcined on a hot plate, an oven, or the like. The calcination conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 150° C. for 5 to 15 minutes in an oven and 1 to 5 minutes in a hot plate. After that, the main baking is performed to harden the coating film. The main baking conditions vary depending on the type and blending ratio of each component, but are usually 180 to 250 ° C., preferably 200 to 250 ° C., 30 to 90 minutes in an oven, 5 to 30 minutes in a hot plate. A cured film can be obtained by this.

In the cured film thus obtained, when heated, 1) the polyamic acid portion of the polyesteramic acid (A) undergoes cyclodehydration to form an imide bond, and 2) the carboxylic acid of the polyesteramic acid contains an epoxy group. Since it reacts with a polymer to increase its molecular weight, it is very tough and has excellent transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and spatter resistance. Therefore, the cured film of the present invention is effective when used as a protective film for color filters, and liquid crystal display devices and solid-state imaging devices can be manufactured using color filters. The cured film of the present invention is effective when used as a transparent insulating film formed between a TFT and a transparent electrode, or a transparent insulating film formed between a transparent electrode and an alignment film, in addition to a protective film for a color filter. . Furthermore, the cured film of the present invention is also effective as a protective film for LED emitters.

EXAMPLES Next, the present invention will be specifically described by synthesis examples, examples and comparative examples, but the present invention is not limited by these examples.

Components represented by abbreviations in Tables 1 to 4 are as follows.
PGMEA: Solvent propylene glycol monomethyl ether acetate MMP: Solvent methyl 3-methoxypropionate ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride BT-100: 1,2,3 ,4-butanetetracarboxylic dianhydride SMA1000P: Styrene-maleic anhydride copolymer (trade name; Kawase Chemical Co., Ltd.)
Epoxy ester 70PA: acrylic acid-modified propylene glycol diglycidyl ether (trade name; Kyoeisha Chemical Co., Ltd.)
DDS: 3,3'-diaminodiphenylsulfone M-402: Aronix M-402, a compound having a polymerizable double bond (trade name; Toagosei Co., Ltd.)
VG3101L: TECHMORE VG3101L which is an epoxy compound (trade name; Printec Co., Ltd.)
TMA: trimellitic anhydride, an epoxy curing agent;
C11Z: 2-undecylimidazole as an epoxy curing agent 2P4MZ: 2-phenyl-4-methylimidazole as an epoxy curing agent S510: Sila Ace S510 as an adhesion improver (trade name; JNC Corporation)
MP-200: COATOSIL MP-200 which is an epoxy compound (trade name; Momentive Performance Materials Co., Ltd.)
AO-60: ADEKASTAB AO-60 (trade name; ADEKA Co., Ltd.) which is an antioxidant,
DS-21: Megafac DS-21 (trade name; DIC Corporation), a surfactant

[Synthesis Example 1] Synthesis of polyesteramic acid (A1) solution Dehydrated and purified PGMEA, BT-100, SMA1000P, benzyl alcohol, 2-hydroxyethyl methacrylate, and 1,4-butanediol were added in this order to a four-necked flask equipped with a stirrer. The following weights were charged and stirred at 125° C. for 2 hours under a stream of dry nitrogen (first stage of synthesis).
PGMEA 42.81g
BT-100 3.04g
SMA1000P 14.45g
3.31 g of benzyl alcohol
2-hydroxyethyl methacrylate 1.33g
1,4-butanediol 0.92 g

After that, the reaction solution was cooled to 25° C., DDS and PGMEA were added in the following weights, stirred at 20 to 30° C. for 2 hours, and then stirred at 125° C. for 1 hour (second stage of synthesis).
DDS 0.95g
PGMEA 7.02g

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

The solution was cooled to room temperature to obtain a pale yellow, transparent 30% by weight solution of polyesteramic acid (A1). A portion of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyesteramic acid (A1) was 22,100.

[Synthesis Examples 2 to 6] Synthesis of polyesteramic acid (A2) to (A6) solutions In accordance with the method of Synthesis Example 1, each component was reacted at the temperature, time, and ratio (unit: g) shown in Table 1. to obtain a polyesteramic acid solution.

[Comparative Synthesis Examples 1 and 2] Synthesis of polyesteramic acid solutions (a1) and (a2) According to the method of Synthesis Example 1, each component was prepared at the temperature, time, and ratio (unit: g) shown in Table 2. It was reacted to obtain a polyesteramic acid solution.

[Example 1]
The 30% by weight solution (A1) of the polyesteramic acid obtained in Synthesis Example 1, VG3101L, TMA, C11Z, S510, AO-60, DS-21, PGMEA and PGME in the proportions shown in Table 3 (unit: g) and filtered through a membrane filter (0.2 μm) to obtain a thermosetting composition.

[Examples 2 to 8 and Comparative Examples 1 to 3]
According to the method of Example 1, each component was mixed and dissolved in the proportions (unit: g) shown in Tables 3 and 4 to obtain a thermosetting composition.

Using the thermosetting compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3, cured films were prepared by the methods described below, and scratch resistance, barrier properties, transparency, and flatness were evaluated. Table 5 shows the evaluation results of the cured films of Examples 1-8, and Table 6 shows the evaluation results of the cured films of Comparative Examples 1-3.

[Method for evaluating scratch resistance]
The thermosetting composition was spin-coated onto a glass substrate at 300 rpm for 10 seconds and pre-baked 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 film thickness of 1.5 μm. The obtained glass substrate with a cured film was subjected to JIS K-5400-1990 8.4.1 pencil scratch test to measure the pencil hardness of the cured film. Tables 5 and 6 show the results. When the pencil hardness was 3H or more, the scratch resistance was evaluated as ◯, and when the pencil hardness was 2H or less, the scratch resistance was evaluated as x.

[Method for evaluating barrier properties]
A color resist was spin-coated on a glass substrate at 300 rpm for 10 seconds and prebaked on a hot plate at 90° C. for 2 minutes. A proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.) was used to irradiate 70 mJ/cm ² over the entire line. After post-baking in an oven at 200° C. for 20 minutes, a glass substrate with a color resist was obtained. Subsequently, using a UV ashing device (PHOTO SURFACE PROCESSOR (abbreviated as PSP) PL2003N-12, low-pressure mercury lamp manufactured by Sen Special Light Source Co., Ltd.), the glass substrate with the color resist was cleaned by UV irradiation. The UV dose here is 1000 mJ/cm ² . The thermosetting composition was spin-coated on a glass substrate with a color resist at 400 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 laminated with a cured film having a thickness of 1.0 μm and a color resist. The laminated substrate thus obtained was heated with a hot plate at 80° C., and 0.2 mL of NMP was added dropwise. Immediately after dropping, a cover glass was placed on the solution, and the solution was heated on a hot plate at 80°C for 40 minutes. The laminated substrate was taken out and NMP was recovered. Also, the laminated substrate used was washed with 10 mL of NMP, and the washing liquid was also recovered. The collected NMP was put together and the transmittance was measured with an ultraviolet-visible-near-infrared spectrophotometer (trade name: V-670, JASCO Corporation). A base line was drawn at 400 nm to 800 nm, and barrier properties were evaluated as ◯ when the minimum transmittance was 90% or more in that range, and as x when less than 90%.

[Transparency evaluation method]
The thermosetting composition was spin-coated onto a glass substrate at 300 rpm for 10 seconds and pre-baked 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 film thickness of 1.5 μm. For the obtained glass substrate with the cured film, the transmittance of only the cured film at a light wavelength of 400 nm was measured with an ultraviolet-visible-near-infrared spectrophotometer (trade name: V-670, JASCO Corporation). When the transmittance was 95% or more, the transparency was evaluated as ◯, and when the transmittance was less than 95%, the transparency was evaluated as x.

[Method for evaluating flatness]
The thermosetting composition was spin-coated at 300 rpm for 10 seconds on a color filter substrate without a cured film having pixels containing R, G, and B, 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 protective film thickness of 1.5 μm. After that, the surface unevenness of the obtained cured film-attached color filter substrate was measured using a fine shape measuring device, and the results are shown in Tables 5 and 6. When the maximum step was 0.2 μm or less, the flatness was evaluated as ◯, and when it was 0.21 μm or more, the flatness was evaluated as x. The color filter substrate without a cured film used had a maximum level difference of 1 μm.

As is clear from the results shown in Table 5, the cured films produced from the thermosetting compositions of Examples 1 to 8 are excellent in scratch resistance, barrier properties, transparency and flatness. On the other hand, it can be seen that the cured film produced from the thermosetting composition of Comparative Example 1, which uses a polyesteramic acid that does not contain a compound having a polymerizable double bond, has poor scratch resistance. In addition, it can be seen that the cured films prepared from the thermosetting compositions of Comparative Examples 2 and 3, to which a compound having a polymerizable double bond was added later, lacked scratch resistance and barrier properties. .

Since the cured film obtained from the thermosetting composition of the present invention has high flatness and high scratch resistance, it can be used as a protective film for various optical materials such as color filters, LED light emitting elements and light receiving elements, and TFTs. It can be used as an insulating film formed between the transparent electrode and the transparent electrode and the alignment film.

Claims (17)

A thermosetting composition consisting only of a polyesteramic acid (A) having a polymerizable double bond, an epoxy compound (B) , a solvent and additives ,
the additive is at least one selected from the group consisting of only surfactants, coupling agents, antioxidants and epoxy curing agents;
The polyesteramic acid (A) is composed of X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyvalent hydroxy compound, and the relationship of the following formulas (1) and (2) is established. is a reaction product from raw materials in proportions such that
A thermosetting composition wherein at least one of said raw materials has a polymerizable double bond.

0.2≤Z/Y≤8.0 (1)
0.2≦(Y+Z)/X≦5.0 (2) A thermosetting composition consisting only of a polyesteramic acid (A) having a polymerizable double bond, an epoxy compound (B) , a solvent and additives ,
the additive is at least one selected from the group consisting of only surfactants, coupling agents, antioxidants and epoxy curing agents;
The polyesteramic acid (A) comprises X moles of tetracarboxylic dianhydride, Y moles of diamine, Z moles of polyvalent hydroxy compound, and monohydroxy compound, the following formulas (1) and (2) ) is a reaction product from raw materials in a ratio such that the relationship of
A thermosetting composition wherein at least one of said raw materials has a polymerizable double bond.

0.2≤Z/Y≤8.0 (1)
0.2≦(Y+Z)/X≦5.0 (2) The thermosetting composition according to claim 1, wherein the polyesteramic acid (A) comprises 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 a tetracarboxylic dianhydride, and R ² is a residue obtained by removing two —NH ₂ from a diamine. R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound, and at least one of R ³ has a polymerizable double bond. The polyesteramic acid (A) comprises a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a structural unit represented by the following formula (5). Item 3. The thermosetting composition according to item 2.

In formulas (3), (4) and (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two _—NH2 is the residue, R3 is the residue of the polyhydroxy compound with ^two —OH removed, ^R4 is the residue of the monohydroxy compound with one —OH removed, At ^least one of R3 and ^R4 has a polymerizable double bond. The polyesteramic acid (A) comprises a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a structural unit represented by the following formula (5). Item 3. The thermosetting composition according to item 2.

In formulas (3), (4) and (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two _—NH2 is the residue, R3 is the residue of the polyhydroxy compound with ^two —OH removed, ^R4 is the residue of the monohydroxy compound with one —OH removed, ^At least one of R3 has a polymerizable double bond. The polyesteramic acid (A) comprises a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a structural unit represented by the following formula (5). Item 3. The thermosetting composition according to item 2.

In formulas (3), (4) and (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two _—NH2 is the residue, R3 is the residue of the polyhydroxy compound with ^two —OH removed, ^R4 is the residue of the monohydroxy compound with one —OH removed, At least one of ^R4 has a polymerizable double bond. The polyhydric hydroxy compounds include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2, 2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxydicyclohexyl, tris(2-hydroxyethyl)isocyanurate, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-(4-hydroxyphenyl)ethanol , and at least one compound selected from the group consisting of a polyvalent hydroxy compound having a polymerizable double bond, which necessarily contains a polyvalent hydroxy compound having a polymerizable double bond, any one of claims 1 to 5 2. The thermosetting composition according to item 1. The polyhydric hydroxy compounds include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2, 2-bis(4-hydroxycyclohexyl)propane, 4,4′-dihydroxydicyclohexyl, tris(2-hydroxyethyl)isocyanurate, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, and 2-(4-hydroxyphenyl) 7. The thermosetting composition according to claim 6, which is at least one compound selected from the group consisting of ethanol. 8. The thermosetting composition according to claim 7, wherein the polyhydroxy compound having a polymerizable double bond has a vinyl group, an allyl group, or a (meth)acryloxy group. The polyvalent hydroxy compound having a polymerizable double bond includes 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 ) acrylate, sorbitol tetra(meth)acrylate, ethylene glycol diglycidyl ether modified (meth)acrylic acid, propylene glycol diglycidyl ether modified (meth)acrylic acid, tripropylene glycol diglycidyl ether (meth)acrylic acid modified products, (meth)acrylic acid-modified glycerol diglycidyl ether, (meth)acrylic acid-modified bisphenol A diglycidyl ether, (meth)acrylic acid-modified propylene oxide-modified bisphenol A diglycidyl ether, and epoxy groups The thermosetting composition according to claim 7, which is at least one compound selected from the group consisting of (meth)acrylic acid-modified compounds containing two or more per molecule. The monohydroxy compound is at least one compound selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, 3-ethyl-3-hydroxymethyloxetane, and monohydroxy compounds having a polymerizable double bond. 7. The thermosetting composition of claim 2, 4, 5, or 6, wherein a The thermosetting according to claim 5, wherein the monohydroxy compound is at least one compound selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. Composition. 12. The thermosetting composition according to claim 11, wherein the monohydroxy compound having a polymerizable double bond has a vinyl group, an allyl group, or a (meth)acryloxy group. The monohydroxy compound having a polymerizable double bond includes furfuryl alcohol, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, (meth) acrylic acid 4 -hydroxyphenyl, p-hydroxy(meth)acrylanilide, 1,4-cyclohexanedimethanol mono(meth)acrylate, 3-(2-hydroxyphenyl)(meth)acrylic acid, glycerol di(meth)acrylate, trimethylolpropane At least one selected from the group consisting of di(meth)acrylates, pentaerythritol tri(meth)acrylates, dipentaerythritol penta(meth)acrylates, and (meth)acrylic acid-modified compounds containing one epoxy group per molecule 12. The thermosetting composition of claim 11, which is a compound of The content of the epoxy compound (B) is 20 to 400 parts by weight with respect to 100 parts by weight of the polyesteramic acid (A) having a polymerizable double bond, according to any one of claims 1 to 4. Thermosetting composition. A cured film of the thermosetting composition according to any one of claims 1 to 15. A color filter comprising the cured film according to claim 16 as a transparent protective film .