JP2019035068A - Thermosetting composition - Google Patents

Abstract

To provide a thermosetting composition that gives a cured film having excellent scratch resistance and barrier properties, and a cured film formed of the thermosetting composition, and provide an electronic component having the cured film.SOLUTION: A thermosetting composition contains a polyester amide acid (A) having a polymerizable double bond, an epoxy compound (B), and optionally, an additive. The polyester amide acid (A) having a polymerizable double bond is produced from a reaction of raw materials that comprise X mol of a tetracarboxylic acid dianhydride, Y mol of a diamine, and Z mol of a polyvalent hydroxy compound comprising a compound having a polymerizable double bond, at such a rate that the following relationships of formula (1) and formula (2) are established: 0.2≤Z/Y≤8.0 (1) and 0.2≤(Y+Z)/X≤5.0 (2).SELECTED DRAWING: None

Description

  The present invention can be used for forming an insulating material in an electronic component, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a planarizing 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 thereby, 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 alkali solutions are performed, and the surface is locally heated to a high temperature when forming a wiring electrode by sputtering. Sometimes. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and alteration of the surface of various elements. These protective films are required to have various characteristics that can withstand various treatments during the manufacturing process as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, scratch resistance, applicability, flatness, light resistance Etc. are required. As the required characteristics of reliability required for display elements improve, the heat resistance required for display element members has improved, and a thermosetting composition containing polyesteramidic acid and an epoxy compound with good heat resistance (For example, refer to Patent Document 1).

  In the production of display elements in recent years, as the production line and the substrate increase in size, unevenness in the substrate surface in the manufacturing process is likely to occur. For example, when the alignment film is rubbed in the manufacture of a large liquid crystal display element, in-plane unevenness of the contact pressure of the rubbing roll with respect to the color filter substrate is likely to occur. In places where the contact pressure is high, the protective film may be scratched, and if the protective film is scratched, the display quality deteriorates, so improving the scratch resistance has been an issue for thermosetting compositions. .

  In addition, with the recent widening of the color gamut of display elements, color filters having pixels that contain a pigment having a higher concentration than conventional ones may be used. In a color filter having a pixel containing a high-concentration pigment, the pigment component is more easily eluted when a protective film or the like, which is an upper layer of the color filter, is formed as compared with the conventional color filter. In particular, the red pigment has a high concentration and is likely to be eluted when the upper layer is formed. When the pigment component is eluted into the upper layer, the display quality is lowered. Therefore, it has been a problem to improve the barrier property of the material forming the upper layer against the dissolution of the pigment component. Patent Document 1 gives a thermosetting composition having excellent heat resistance, but scratch resistance and barrier properties are not fully satisfactory, and further improvements are required.

JP 2005-105264 A

  An object of the present invention is to provide a thermosetting composition that gives a cured film excellent in scratch resistance and barrier properties, and a cured film formed by the thermosetting composition, and further has the cured film. To provide electronic components.

As a result of intensive studies to solve the above problems, the inventors of the present invention can achieve the above object by using a cured film obtained by curing a composition containing a polyesteramide acid having an polymerizable double bond and an epoxy compound. The present inventors have found that this can be done and have completed the present invention.
The present invention includes the following configurations.

[1] A thermosetting composition comprising a polyester amide acid (A) having a polymerizable double bond and an epoxy compound (B),
The polyester amic acid (A) is composed of X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyvalent hydroxy compound in the relationship of the following formulas (1) and (2). Is a reaction product from the raw material containing in such a ratio,
A thermosetting composition in which at least one of the 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 comprising a polyester amide acid (A) having a polymerizable double bond and an epoxy compound (B),
The polyester amic acid (A) comprises X moles of tetracarboxylic dianhydride, Y moles of diamine, Z moles of a polyhydroxy compound, and a monohydroxy compound, represented by the following formulas (1) and (2): ) Is a reaction product from a raw material that is contained in such a ratio that the relationship of
A thermosetting composition in which at least one of the 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 polyester amide acid (A) includes a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

In Formula (3) and Formula (4), 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 —NH ₂ from 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 polyester amic 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 Formula (3), Formula (4), and Formula (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is ^two residues from diamine. -NH ₂ is a residue, R ³ is a residue obtained by removing two -OH from a polyvalent hydroxy compound, R ⁴ is a residue obtained by removing one -OH from a monohydroxy compound, At least one of R ³ and R ⁴ 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 polyester amic 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 Formula (3), Formula (4), and Formula (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is ^two residues from diamine. -NH ₂ is a residue, R ³ is a residue obtained by removing two -OH from a polyvalent hydroxy compound, R ⁴ is a residue obtained by removing one -OH from a monohydroxy compound, 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^４の少なくとも１つは重合性二重結合を有する。 [6] The polyester amic 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 Formula (3), Formula (4), and Formula (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is ^two residues from diamine. -NH ₂ is a residue, R ³ is a residue obtained by removing two -OH from a polyvalent hydroxy compound, R ⁴ is a residue obtained by removing one -OH from a monohydroxy compound, At least one of R ⁴ has a polymerizable double bond.

[7] The polyvalent hydroxy compound is 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-hydroxy [1] to [1], which is at least one compound selected from the group consisting of (phenyl) ethanol and a polyvalent hydroxy compound having a polymerizable double bond, and necessarily contains a polyvalent hydroxy compound having a polymerizable double bond. [5] The thermosetting composition according to any one of [5].

[8] The polyvalent hydroxy compound is 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- 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 item [7], wherein the polyvalent hydroxy 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, (meth) acrylic acid modified product of ethylene glycol diglycidyl ether, propylene glycol di (Meth) acrylic acid modified product of ricidyl ether, (meth) acrylic acid modified product of tripropylene glycol diglycidyl ether, (meth) acrylic acid modified product of glycerin diglycidyl ether, (meth) acrylic of bisphenol A diglycidyl ether At least one selected from the group consisting of acid-modified products, (meth) acrylic acid-modified products of propylene oxide-modified bisphenol A diglycidyl ether, and (meth) acrylic acid-modified products of compounds containing two or more epoxy groups per molecule The thermosetting composition according to item [7], which is a compound.

[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 a monohydroxy compound having a polymerizable double bond. The thermosetting composition according to item [2], [4], [5], or [6], which is one compound.

[12] The 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, and (meth). 4-hydroxyphenyl acrylate, p-hydroxy (meth) acrylanilide, 1,4-cyclohexanedimethanol mono (meth) acrylate, (meth) acrylic acid 3- (2-hydroxyphenyl), glycerin di (meth) acrylate, Trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and a (meth) acrylic acid modified product of a compound containing one epoxy group per molecule It is more least one compound selected, [11] The thermosetting composition according to item.

[15] Any of [1] to [4], wherein the content of the epoxy compound (B) is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amide acid (A) having a polymerizable double bond. 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 the item [16] as a transparent protective film

  The thermosetting composition according to a preferred embodiment of the present invention is a material particularly excellent in scratch resistance and barrier properties, and can improve display quality when used as a color filter protective film of a color liquid crystal display element. In particular, it is useful as a protective film for a color filter 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 and a transparent insulating film for various optical materials.

  In the present specification, the higher the pencil hardness of the cured film according to the present invention, the higher the cured film and the thermosetting composition for forming the cured film are expressed as “excellent scratch resistance”.

  In this specification, in order to show one or both of “acrylate” and “methacrylate”, it may be expressed as “(meth) acrylate”. Similarly, in order to indicate one or both of “acryloxy” and “methacryloxy”, it may be expressed as “(meth) acryloxy”.

1. Thermosetting composition of the present invention The thermosetting composition of the present invention is a composition comprising a polyester amide acid having an polymerizable double bond and an epoxy compound. The polyester amic acid having a polymerizable double bond is a reaction product from a raw material containing 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 with respect to 100 parts by weight of polyester amide acid.

  In addition, the thermosetting composition which concerns on this invention may further contain other components other than the above in the range in which the effect of this invention is acquired.

1-1. Polyester amide acid having a polymerizable double bond (A)
The polyester amic acid (A) is obtained by reacting tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound, and monohydroxy compound as essential raw material components. Further, the polyester amic acid (A) is prepared by combining X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyhydroxy compound with the above formulas (1) and (2). It is obtained by reacting at a proper ratio.

The polyester amic acid (A) has a structural unit represented by the formula (3), a structural unit represented by the formula (4), and a structural unit represented by the formula (5). In Formula (3), Formula (4), and Formula (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is ^two residues from diamine. It is a residue obtained by removing —NH ₂ , R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound, and R ⁴ is a residue obtained by removing one —OH from a monohydroxy compound. At least one of R ³ and R ⁴ has a polymerizable double bond.

  At least a solvent is required for the synthesis of the polyester amide acid (A). The solvent may be left as it is, and it may be a liquid or gel-like thermosetting composition in consideration of handling properties, or may be a solid composition in consideration of transportability by removing this solvent.

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

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

  As the tetracarboxylic dianhydride, in addition to those described 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 ( Hydrotrimellitate) (trade name; TMEG-100, Shin Nippon Rika Co., Ltd.), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic Examples thereof include acid dianhydride, butanetetracarboxylic dianhydride, and ethanetetracarboxylic dianhydride, and at least one of the aforementioned tetracarboxylic dianhydrides can be used.

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

1-1-2. Diamine In the present invention, a diamine is used as a material for obtaining the polyester amide acid (A). Specific examples of diamines preferably include 3,3′-diaminodiphenyl sulfone (hereinafter sometimes abbreviated as DDS) used in the examples.

  Specific examples of the diamine include, in addition to those described 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, At least one of diamines can be used.

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

1-1-3. The present invention relates to a polyhydric hydroxy compound having no polymerizable double bond and / or a polyvalent hydroxy compound having a polymerizable double bond as a material for obtaining the polyester amic acid (A). Use. Specific examples of the polyvalent hydroxy compound are preferably 1,4-butanediol, epoxy ester 70PA (trade name; Kyoeisha Chemical Co., Ltd.), epoxy ester 80MFA (trade name; Kyoeisha Chemical Co., Ltd.) used in the examples, Epoxy ester 3002A (N) (trade name; Kyoeisha Chemical Co., Ltd.) can be mentioned.

  As polyvalent hydroxy compounds having no polymerizable double bond, 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, polypropylene glycol having 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-Hep Diol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 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-hydroxyphenol) Nyl) methane), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4′-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethanol, diethanolamine, And triethanolamine.

  Among these, compounds having good solubility in the reaction solvent are ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 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. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, and 2- (4-hydroxyphenyl) ethanol are particularly preferable.

  On the other hand, as specific examples of the polyvalent hydroxy compound having a polymerizable double bond, preferably 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, glycerol 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 modification of ethylene glycol diglycidyl ether, (meth) acrylic acid modification of propylene glycol diglycidyl ether, tripropylene (Meth) acrylic acid modified product of glycol diglycidyl ether, (meth) acrylic acid modified product of glycerin diglycidyl ether, bisphenol A diglycidyl (Meth) acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether, (meth) acrylic acid modified product of bisphenol S diglycidyl ether, propylene oxide modified bisphenol S diglycidyl ether (Meth) acrylic acid modified product, (meth) acrylic acid modified product of bisphenol F diglycidyl ether, (meth) acrylic acid modified product of propylene oxide modified bisphenol F diglycidyl ether, (meth) acrylic acid of bixylenol diglycidyl ether Modified product, (meth) acrylic acid modified product of biphenol diglycidyl ether, (meth) acrylic acid modified product of full orange phenol diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether (Meth) acrylic acid modified product of hydrogen, hydrogenated bisphenol A diglycidyl ether (meth) acrylic acid modified product, tricyclodecane dimethanol diglycidyl ether (meth) acrylic acid modified product, and epoxy group per molecule The (meth) acrylic acid modified material of the other compound containing 2 or more can be mentioned, At least 1 sort (s) can be used among these.

  Among these, compounds having good solubility in the reaction solvent include (meth) acrylic acid modified products of ethylene glycol diglycidyl ether, (meth) acrylic acid modified products of propylene glycol diglycidyl ether, and glycerin diglycidyl ether. (Meth) acrylic acid modified product, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, (meth) acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether, (meth) acrylic acid of bisphenol S diglycidyl ether Modified product, (meth) acrylic acid modified product of propylene oxide modified bisphenol S diglycidyl ether, (meth) acrylic acid modified product of bisphenol F diglycidyl ether, and propylene oxide modified bisphenol F diglycidyl ether Of (meth) acrylic acid modified product are more preferable. Also, (meth) acrylic acid modified product of ethylene glycol diglycidyl ether, (meth) acrylic acid modified product of propylene glycol diglycidyl ether, (meth) acrylic acid modified product of tripropylene glycol diglycidyl ether, glycerin diglycidyl ether Particularly preferred are (meth) acrylic acid modified products, (meth) acrylic acid modified products of bisphenol A diglycidyl ether, and (meth) acrylic acid modified products of propylene oxide modified bisphenol A diglycidyl ether.

  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 As methacrylic acid modified products, acrylic acid modified products of bisphenol A diglycidyl ether, propylene oxide modified bisphenol A diglycidyl ether methacrylic acid modified products, and propylene oxide modified bisphenol A diglycidyl ether acrylic acid modified products 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 the 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 having no polymerizable double bond and / or a monohydroxy compound having a polymerizable double bond may be used as a material for obtaining the polyester amic acid (A). Good.

  As specific examples of the monohydroxy compound, benzyl alcohol, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxyphenyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate (hereinafter, (May be abbreviated as CHDMMA.) (Trade name; Nippon Kasei Co., Ltd.).

  When a monohydroxy compound is used, the storage stability of the thermosetting composition is improved.

  Specific examples of the monohydroxy compound 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 preferable. Compatibility when polyester amide acid (A), epoxy group-containing polymer, epoxy compound (B), and epoxy curing agent are mixed, and application property of thermosetting composition onto color filter In view of the above, it is particularly preferable to use benzyl alcohol for a monohydroxy compound having no polymerizable double bond.

  Specific examples of the monohydroxy compound 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, (meth) acrylic acid 4-hydroxyphenyl, p-hydroxy (meth) acrylanilide, 1,4-cyclohexanedimethanol mono (meth) acrylate, (meth) acrylic acid 3- (2 -Hydroxyphenyl), glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglyci Mention of (meth) acrylic acid modified products of diether, (meth) acrylic acid modified products of t-butylphenylglycidyl ether, and (meth) acrylic acid modified products of other compounds containing one epoxy group per molecule And at least one of them can be used.

  Among these, hydroxyethyl (meth) acrylate, 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, (meth) acrylic acid = 3- (2-hydroxyphenyl) are more preferable. Compatibility when polyester amide acid (A), epoxy group-containing polymer, epoxy compound (B), and epoxy curing agent are mixed, and application property of thermosetting composition onto color filter In view of the above, monohydroxy compounds having a polymerizable double bond include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylic acid = 4-hydroxyphenyl, p The use of hydroxy- (meth) acrylanilide and 1,4-cyclohexanedimethanol mono (meth) acrylate is particularly preferred.

  The following commercially available products can be used as methacrylic acid = 4-hydroxyphenyl, p-hydroxymethacrylanilide, and 1,4-cyclohexanedimethanol monoacrylate. A specific example of methacrylic acid = 4-hydroxyphenyl 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.).

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

1-1-5. Styrene-maleic anhydride copolymer The polyester amide acid used in the present invention may be synthesized using a compound having 3 or more acid anhydride groups in the above raw material. This is preferable because the transparency of the cured film is improved. Examples of the compound having 3 or more acid anhydride groups include styrene-maleic anhydride copolymer. 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 ) Is converted 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 preferable, and 1 is particularly preferable.

  Specific examples of the styrene-maleic anhydride copolymer include SMA3000P, SMA2000P, and SMA1000P (all trade names: Kawa Crude Chemical Co., Ltd.). Among these, SMA1000P, in which the cured film has good heat resistance and alkali resistance, is particularly preferable.

1-1-6. Silicon-containing monoamine In the synthesis of polyester amic acid, as a raw material, other raw materials other than the above may be included as necessary, as long as the object of the present invention is not impaired. A monoamine is mentioned.

  Specific examples of the silicon-containing monoamine 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, which have good acid resistance of the cured film, are more preferable, and 3-aminopropyltriethoxysilane is particularly preferable from the viewpoints 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 with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound.

1-1-7. Solvents used in the synthesis reaction of polyester amic acid (A) Specific examples of solvents 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. And 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, or diethylene glycol methyl ethyl ether is preferable.

1-1-8. Method for Synthesizing Polyester Amic Acid (A) The method for synthesizing the polyester amic acid (A) having a polymerizable double bond used in the present invention comprises X moles of tetracarboxylic dianhydride, Y moles of diamine, Z moles of A polyhydroxy compound and a monohydroxy compound are reacted in the solvent. At this time, it is preferable that X, Y, and Z are determined in such a ratio that the relationship of the following formulas (1) and (2) is established between them. If it is this range, the solubility to the solvent of a polyester amide acid is high, and the applicability | paintability of a composition improves.

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

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

  In the synthesis of the polyester amide acid (A), a monohydroxy compound is not used, and an acid anhydride group (—CO— is formed at the terminal under the condition where X is excessively used with respect to Y + Z within the range of the formula (2). It is considered that molecules having (O—CO—) are generated in excess of molecules having an amino group or a hydroxyl group at the terminal. On the other hand, when reacting with such a monomer structure, if a monohydroxy compound is added, it can react with an acid anhydride group at the molecular end to esterify the end. Since the polyester amide acid (A) used in the present invention is obtained by adding a monohydroxy compound and reacting with it, the compatibility with the epoxy compound (B) is improved and the applicability of the thermosetting composition is improved. Improve.

  Moreover, when making it react with the structure of the monomer mentioned above, in order to make it react with the acid anhydride group of a molecular terminal and introduce | transduce a silyl group at the terminal, a silicon-containing monoamine can be added. When the thermosetting composition containing the polyester amide acid obtained by adding and reacting a silicon-containing monoamine is used, the acid resistance of the cured film is improved.

  The reaction solvent is preferably used in an amount of 100 parts by weight or more based on 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound because the reaction proceeds smoothly. The reaction is preferably carried out at 40 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 tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound to the reaction solvent, a method of adding tetracarboxylic dianhydride after dissolving diamine and polyvalent hydroxy compound in the reaction solvent, tetra After reacting carboxylic dianhydride and polyvalent hydroxy compound in advance, add diamine to the reaction product, or after reacting tetracarboxylic dianhydride and diamine in advance, Any technique such as a technique of adding a divalent hydroxy compound can be used. The monohydroxy compound may be added at any point in the reaction.

  In the case of reacting the silicon-containing monoamine, after the reaction of the tetracarboxylic dianhydride, the diamine and the polyvalent hydroxy compound, the reaction liquid is cooled to 40 ° C. or lower, and then the silicon-containing monoamine is added, and 10 to 40 ° C. For 0.1 to 6 hours. The monohydroxy compound may be added at any point in the reaction.

  The polyester amic acid (A) synthesized in this way includes a structural unit represented by the formula (3), a structural unit represented by the formula (4), and a structural unit represented by the formula (5). The terminal is an acid anhydride group, an amino group, a hydroxy group, or a monovalent organic group derived from a tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound, or monohydroxy compound as a raw material, or these Consists of additives other than compounds. By including such a configuration, curability is improved.

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

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

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. The epoxy compound (B) may be one type or two or more types.

  Examples of the epoxy compound (B) are 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, Bisphenol A novolak type epoxy compound, aliphatic polyglycidyl ether compound, cycloaliphatic epoxy compound, polymer of monomer having epoxy group, copolymer of monomer having epoxy group and other monomer, and siloxane bonding site It is an epoxy compound having.

  Specific examples of commercial products of bisphenol A type epoxy compounds are jER 828, 1004 and 1009 (all trade names; Mitsubishi Chemical Corporation); specific examples of commercial products of bisphenol F type epoxy compounds are jER 806 and 4005P. (All are trade names; Mitsubishi Chemical Corporation); Specific examples of commercially available glycidyl ether type epoxy compounds are TECHMORE VG3101L (trade name; Printec Co., Ltd.), EHPE-3150 (trade name; Daicel Corporation). EPPN-501H, 502H (all trade names; Nippon Kayaku Co., Ltd.) and jER 1032H60 (trade names; Mitsubishi Chemical Corporation); specific examples of commercially available glycidyl ester type epoxy compounds are Denacol EX- 721 (trade name; Nagase ChemteX Corporation) Company), and diglycidyl 1,2-cyclohexanedicarboxylate (trade name; Tokyo Chemical Industry Co., Ltd.); specific examples of commercially available biphenyl type epoxy compounds are jER YX4000, YX4000H, YL6121H (all trade names; Mitsubishi) Chemical Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3100 (all trade names; Nippon Kayaku Co., Ltd.); specific examples of commercially available phenol novolac epoxy compounds Examples are EPPN-201 (trade name; Nippon Kayaku Co., Ltd.) and jER 152, 154 (both trade names: Mitsubishi Chemical Co., Ltd.) and the like; specific examples of commercially available cresol novolac epoxy compounds are as follows: EOCN-102S, 103S, 104S, 1020 (all trade names; Nippon Kayaku Co., Ltd.) Specific examples of commercial products of bisphenol A novolac type epoxy compounds are jER 157S65 and 157S70 (both trade names; Mitsubishi Chemical Corporation); specific examples of commercial products of cycloaliphatic epoxy compounds Is Celoxide 2021P, 3000 (both trade names; Daicel Corporation); a specific example of a commercially available epoxy compound having a siloxane bonding site is 1,3-bis [2- (3,4-epoxycyclohexyl) Ethyl] tetramethyldisiloxane (trade name; Gerest Incorporated), TSL 9906 (trade name; Momentive Performance Materials LLC), COATOSIL MP-200 (trade name; Momentive Performance Materials LLC), Composeran SQ506 (quotient Name; is a Shin-Etsu Chemical Co., Ltd.); Arakawa Chemical Co., Ltd.), ES-1023 (trade names.

  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)- 1,2-Epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol; Celoxide 2021P (trade name; Daicel Corporation) is 3 ′ 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; 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 containing 3-glycidoxypropyltrimethoxysilane as a raw material component.

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

1-2-2. Ratio of epoxy compound (B) to polyester amic acid (A) The ratio of the total amount of epoxy compound (B) to 100 parts by weight of polyester amic acid (A) in the thermosetting composition of the present invention is 20 to 400 parts by weight. is there. When the proportion of the total amount of the epoxy compound (B) is within this range, the balance of flatness, heat resistance, chemical resistance, and adhesion is good. The total amount of the 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, adhesion, transparency, flatness, and chemical resistance. Additives include epoxy curing agents, solvents, anionic, cationic, nonionic, fluorine or silicon leveling agents / surfactants, adhesion improvers such as silane coupling agents, hindered phenols, hindered amines. Mainly mentioned are antioxidants and molecular weight modifiers such as system, phosphorus and sulfur compounds.

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 the surfactant include Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (all trade names: Kyoeisha Chemical Co., Ltd.), Disperbeek 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181 and Disper Bake 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (all trade names; Big 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-S -101, Surflon-KH-40, Surflon-S611 (all trade names; AGC Seimi Chemical Co., Ltd.), Aftergent 222F, Aftergent 208G, Aftergent 251, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, After Gento 601AD, Aftergent 602A, Aftergent 650A, FTX-218 (all trade names; Neos Corporation), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 ( All are trade names; Mitsubishi Materials Corporation), Megafuck F-171, Megafuck F-177, Megafuck F-410, Megafuck F-430, Megafuck 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, Megafuck F-559, Megafuck R-30, Megafuck R-94, Megafuck RS-75, Megafuck RS-72-K, Megafuck RS-76-NS, Megafuck DS-21 (whichever Product name; 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 (all trade names; Japan Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether) ), Fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene Tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl Ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan Examples include laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonate. 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, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, Aftergent 650A, Megafuck F-477, Megafuck F-556, Megafuck F-559, Megafuck RS-72-K, Megafuck DS-21, TEGO Twin 4000, Fluoroalkylbenzenesulfonate, Fluoroalkyl At least selected from among carboxylates, fluoroalkylpolyoxyethylene ethers, fluoroalkylsulfonates, fluoroalkyltrimethylammonium salts, and fluoroalkylaminosulfonates 1 is also preferable because the application uniformity of the thermosetting composition is increased.

  The content of the surfactant in the thermosetting composition of the present invention is preferably 0.01 to 10% by weight with respect to the total amount 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 formed cured film 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: Silaace S510, JNC Corporation), 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name: Silaace S530, JNC Corporation), 3-mercaptopropyltrimethoxysilane (for example, trade name: Silaace S810, JNC Corporation), Momentive Performance Materials Co., Ltd. Company) and other silane coupling agents, aluminum coupling agents such as acetoalkoxyaluminum diisopropylate, and titanates such as tetraisopropylbis (dioctylphosphite) titanate Mention may be made of a door-based coupling agent.

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

  Since 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, the adhesion 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 when the cured film is exposed to high temperatures.

  You may add antioxidants, such as a hindered phenol type | system | group, a hindered amine type | system | group, a phosphorus type | system | group, and a sulfur type compound, to the thermosetting composition of this invention. Of these, hindered phenols are preferred from the viewpoint of weather resistance. Specific examples, Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox295 (none Product name: BASF Japan Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB A -50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80 (trade names; Ltd ADEKA) and the like. 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 with respect to the total amount of the thermosetting composition.

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

  Specific examples of the molecular weight modifier include 2-hydroxy-1,4-naphthoquinone, benzoquinone, 1,4-naphthoquinone, 1,4-dihydroxynaphthalene, 2,5-di-t-butylhydroquinone, hydroquinone, methylhydroquinone, t-butylhydroquinone, methoquinone, p-benzoquinone, methyl-p-benzoquinone, t-butyl-p-benzoquinone, anthraquinone, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid Dimethyl xanthogen sulfide, diisopropyl xanthogen disulfide, 2,4-diphenyl-4-methyl-1-pentene, and the like.

  A molecular weight modifier may be used independently and may be used in combination of 2 or more. Among molecular weight regulators, naphthoquinone molecular weight regulators are preferred from the standpoint of exhibiting excellent storage stability.

  Among the 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 curing agents, amine curing agents, phenol curing agents, imidazole curing agents, catalytic curing agents, and sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, and the like. Although there exist a heat-sensitive acid generator etc., an acid anhydride type hardening | curing agent or an imidazole type hardening | curing agent is preferable from a viewpoint of avoiding coloring of a cured film and the heat resistance of a cured film.

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

  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 having a good balance between curability and solubility in a solvent is preferable.

  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. About the addition amount in case an epoxy hardening agent is an acid anhydride type hardening | curing agent, in detail, the carboxylic acid anhydride group or carboxyl group in an epoxy hardening agent is 0.1-1.5 with respect to an epoxy group. It is preferable to add so that it may become a double equivalent. At this time, the carboxylic acid anhydride group is calculated as divalent. If the carboxylic acid anhydride group or carboxyl group is added so as to have an equivalent amount of 0.15 to 0.8 times, the chemical resistance is further improved, which is more preferable.

1-3-6. 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.

1-3-7. Anti-agglomeration agent The thermosetting composition of the present invention may contain an anti-agglomeration agent from the viewpoint of blending the polyester amide acid (A) or epoxy compound (B) having a polymerizable double bond with a solvent to prevent aggregation. Good.

  Specific examples of the anti-agglomeration agent include Disperbak-145, Disperbak-161, Disperbak-162, Disperbak-163, Dispersake-164, Dispersake-182, Dispersake-184, Dispersake-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, Footent 710FM, It is a footent 710FS (all are brand names; Neos Co., Ltd.), Floren G-600, and Floren G-700 (all are brand names; Kyoeisha Chemical Co., Ltd.).

  The aggregation inhibitor is used by adding 0.01 to 10 parts by weight with respect 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-film uniformity, flexibility, flexibility, and elasticity.

  Specific examples of the thermal crosslinking agent include Nicarak MW-30HM, Nicarak MW-100LM, Nicarak MW-270, Nicarak MW-280, Nicarac MW-290, Nicarac MW-390, Nicarac MW-750LM (all trade names; stocks) Company Sanwa Chemical).

  The thermal crosslinking agent is used by adding 0.1 to 10 parts by weight with respect to 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 includes a radical polymerizable compound (P1) represented by the following formula (6), a radical polymerizable compound (P2) having alkoxysilyl, and epoxy, carboxyl, and hydroxyphenyl. A polymer obtained by radical copolymerization of a radically polymerizable compound (P3) having at least one of the above (hereinafter also referred to as “radical copolymer”) may be further contained.

In the 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 of 1 to 150.

1-3-9-1. Radical polymerizable compound represented by formula (6) (P1)
Since the radically polymerizable compound (P1) represented by the formula (6) acts as a surfactant, the radical copolymerized polymer acts as a surfactant by using (P1) as a raw material. Even if a surfactant is not added separately, the flatness, adhesion to the base substrate, and coatability are improved. By adding the radically polymerizable compound (P1), the radical copolymerized polymer is easily revealed on the film surface.

In the present invention, in the radical polymerizable compound (P1) represented by the 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 The compound whose integer of -5 and n is an integer of 1-150 is preferable. 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, and n is more preferably an integer of 30 to 70. , N is preferably an integer of 50 to 70. The weight average molecular weight of the radically polymerizable compound (P1) represented by the formula (6) is preferably 500 to 8,000.

  The radically polymerizable compound (P1) represented by the formula (6) can be produced by a known method. A commercially available product may also be used. For example, FM-0711, FM-0721, FM-0725 (all are brand names; JNC Corporation) etc. are mentioned.

1-3-9-2. Radical polymerizable compound having alkoxysilyl (P2)
In the present invention, a radical polymerizable compound (P2) having alkoxysilyl is used as a raw material for obtaining the radical copolymer. Preferred radical 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 good flatness. By using (P2), transparency, chemical resistance and the like are improved. Moreover, adhesiveness with a base material improves by the silane coupling effect.

1-3-9-3. Radical polymerizable compound having at least one of epoxy, carboxyl and hydroxyphenyl (P3)
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. The preferred radically polymerizable compound (P3) is at least one 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 crosslinking agent for the polymer and contributes to improvement in heat resistance, chemical resistance, and the like.

1-3-9-4. Method for Producing Radical Copolymer The radical copolymer is composed of a radical polymerizable compound (P1) represented by formula (6), a radical polymerizable compound (P2) having alkoxysilyl, and epoxy, carboxyl and hydroxyphenyl. It can be obtained by radical copolymerization of 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 radical polymerizable compounds in the presence of a radical initiator. As the radical initiator, organic peroxides, azo compounds and the like can be used. Although the reaction temperature of radical copolymerization is not specifically limited, Usually, it is the range of 50 to 150 degreeC. The reaction time is not particularly limited, but is usually in the range of 1 to 48 hours. In addition, the reaction can be performed under any pressure of pressure, reduced pressure, or atmospheric pressure.

  The solvent used for the above radical copolymerization reaction is preferably a solvent in which the polymer to be produced 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- Ethyl loxy-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 Recall 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. One of these may be sufficient as a solvent, and these 2 or more types of mixtures may be sufficient as it.

  The radical copolymer used in the present invention may be a radical copolymer solution that takes into account handling properties while leaving the solvent used in the polymerization as it is, or a solid copolymer that takes into account transportability by removing this solvent. It may be a radical copolymer having a shape.

  A radical copolymer having a weight average molecular weight in the range of 1,000 to 50,000 determined by GPC analysis using polystyrene as a standard is preferable because of good film formability. 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 and 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 good, which is particularly preferable.

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

1-4. Solvent You may use a solvent for the thermosetting composition of this invention. The solvent arbitrarily added to the thermosetting composition of the present invention is preferably a solvent capable of dissolving the polyester amide 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, 2-hydroxy-2-methylpropyl Methyl pionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, aceto Methyl acetate, 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 of these.

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 stability over time of the composition becomes good. If the storage temperature is −20 ° C. to 10 ° C., there is no precipitate and it is more preferable.

2. Cured film of thermosetting composition The thermosetting composition of the present invention comprises a polyester amide 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 they can be obtained by uniformly mixing and dissolving them.

  When the thermosetting composition prepared as described above (after dissolving 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, the coating film Can be formed. Application of the thermosetting composition to the substrate surface can form a coating film by a conventionally known method such as spin coating, roll coating, dipping, or slit coating. Next, this coating film is temporarily baked by a hot plate or an oven. Temporary baking 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. Then, this baking is performed in order to cure the coating film. The main firing conditions vary depending on the types and blending ratios of the respective components, but are usually 180 to 250 ° C., preferably 200 to 250 ° C., 30 to 90 minutes for an oven, 5 to 30 minutes for a hot plate, and heat treatment. Thus, a cured film can be obtained.

  The cured film thus obtained is further heated during heating, 1) the polyamic acid portion of the polyester amic acid (A) is dehydrated to form an imide bond, and 2) the carboxylic acid of the polyester amic acid contains an epoxy group. Since it reacts with the polymer to increase the molecular weight, it is very tough and has excellent transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and sputtering resistance. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element and a solid-state imaging element can be manufactured using the color filter. 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 effective even when used as a protective film for LED light emitters.

  Next, although a synthesis example, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples.

The components represented by the abbreviations in Tables 1 to 4 are as follows.
PGMEA: Propylene glycol monomethyl ether acetate as a solvent MMP: Methyl 3-methoxypropionate as a solvent ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride BT-100: 1, 2,3 , 4-butanetetracarboxylic dianhydride SMA1000P: styrene-maleic anhydride copolymer (trade name; Kawa Crude Chemical Co., Ltd.)
Epoxy ester 70PA: Acrylic acid modified product of propylene glycol diglycidyl ether (trade name; Kyoeisha Chemical Co., Ltd.)
DDS: 3,3′-diaminodiphenyl sulfone M-402: Aronix M-402 (trade name; Toagosei Co., Ltd.) which is a compound having a polymerizable double bond
VG3101L: TECHMORE VG3101L (trade name; Printec Co., Ltd.), which is an epoxy compound
TMA: trimellitic anhydride which is an epoxy curing agent,
C11Z: Epoxy curing agent 2-undecylimidazole 2P4MZ: Epoxy curing agent 2-phenyl-4-methylimidazole S510: Adhesion improver Silaace S510 (trade name; JNC Corporation)
MP-200: COATOSIL MP-200 which is an epoxy compound (trade name; Momentive Performance Material Co., Ltd.)
AO-60: ADEKASTAB AO-60 (trade name; ADEKA Corporation) which is an antioxidant,
DS-21: Megafac DS-21, a surfactant (trade name; DIC Corporation)

[Synthesis Example 1] Synthesis of polyester amic acid (A1) solution In a four-necked flask equipped with a stirrer, dehydrated and purified PGMEA, BT-100, SMA1000P, benzyl alcohol, 2-hydroxyethyl methacrylate, and 1,4-butanediol were sequentially added. The mixture was charged with the following weight and stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis).
PGMEA 42.81g
BT-100 3.04g
SMA1000P 14.45g
Benzyl alcohol 3.31 g
1.33 g of 2-hydroxyethyl methacrylate
1,2-butanediol 0.92g

Thereafter, the reaction solution was cooled to 25 ° C., DDS and PGMEA were added in the following weights, stirred at 20-30 ° C. for 2 hours, and then stirred at 125 ° C. for 1 hour (2nd 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 30% by weight solution of pale yellow transparent polyester amide 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 obtained polyester amic acid (A1) had a weight average molecular weight of 22,100.

[Synthesis Examples 2-6] Synthesis of Polyesteramide Acids (A2) to (A6) Solutions According to the method of Synthesis Example 1, each component was reacted at the temperatures, times, and ratios (unit: g) shown in Table 1. To obtain a polyester amic acid solution.

[Comparative Synthesis Examples 1 and 2] Synthesis of Polyester Amic Acid Solutions (a1) and (a2) According to the method of Synthesis Example 1, each component was added at the temperature, time, and ratio (unit: g) shown in Table 2. Reaction was carried out to obtain a polyester amic acid solution.

[Example 1]
The ratio (unit: g) described in Table 3 for 30% by weight solution of polyester amide acid obtained in Synthesis Example 1 (A1), VG3101L, TMA, C11Z, S510, AO-60, DS-21, PGMEA and PGME Were mixed and dissolved, 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, the components were mixed and dissolved at the ratios (unit: g) described in Table 3 and Table 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. The evaluation results of the cured films of Examples 1 to 8 are shown in Table 5, and the evaluation results of the cured films of Comparative Examples 1 to 3 are shown in Table 6.

[Scratch resistance evaluation method]
The thermosetting composition was spin-coated on a glass substrate at 300 rpm for 10 seconds, and pre-baked on a 90 ° C. hot plate for 2 minutes. Then, it post-baked for 30 minutes at 230 degreeC in oven, and obtained the glass substrate with a cured film which is a film thickness of 1.5 micrometers. 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, and the results are shown in Tables 5 and 6. The case where the pencil hardness was 3H or higher was evaluated as scratch resistance x, and the case where the pencil hardness was 2H or lower was evaluated as scratch resistance x.

[Evaluation method for barrier properties]
A color resist was spin coated on a glass substrate at 300 rpm for 10 seconds, and prebaked on a 90 ° C. hot plate for 2 minutes. A proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.) was used, and 70 mJ / cm ² was irradiated on all lines. Post baking was performed at 200 ° C. for 20 minutes in an oven to obtain a glass substrate with a color resist. 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.), UV irradiation cleaning of the glass substrate with a color resist was performed. The UV irradiation amount 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 90 ° C. hot plate for 2 minutes. Subsequently, it was post-baked in an oven at 230 ° C. for 30 minutes to obtain a glass substrate on which a cured film having a thickness of 1.0 μm and a color resist were laminated. The obtained laminated substrate was heated with a hot plate at 80 ° C., and 0.2 mL of NMP was dropped. Immediately after the dropping, a cover glass was put on and heated in an 80 ° C. hot plate for 40 minutes. The laminated substrate was taken out and NMP was collected. Further, the used laminated substrate was washed with 10 mL of NMP, and the washing liquid was also collected. The collected NMPs were collected, 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 the barrier property ◯ was evaluated when the minimum transmittance within the range was 90% or more, and the barrier property × was evaluated when the transmittance was less than 90%.

[Transparency evaluation method]
The thermosetting composition was spin-coated on a glass substrate at 300 rpm for 10 seconds, and pre-baked on a 90 ° C. hot plate for 2 minutes. Then, it post-baked for 30 minutes at 230 degreeC in oven, and obtained the glass substrate with a cured film which is a film thickness of 1.5 micrometers. The transmittance | permeability in wavelength 400nm of the light of only a cured film was measured with the ultraviolet visible near-infrared spectrophotometer (brand name; V-670, JASCO Corporation) in the obtained glass substrate with a cured film. The case where the transmittance was 95% or more was evaluated as transparency ○, and the case where the transmittance was less than 95% was evaluated as transparency ×.

[Evaluation method of flatness]
The thermosetting composition was spin-coated at 300 rpm for 10 seconds on a color filter substrate without a cured film having pixels including R, G, and B, and prebaked on a 90 ° C. hot plate for 2 minutes. Subsequently, it was post-baked at 230 ° C. for 30 minutes in an oven to obtain a color filter substrate with a cured film having an average protective film thickness of 1.5 μm. Then, the surface level difference was measured using the fine shape measuring apparatus with respect to the obtained color filter substrate with a cured film, and the results are shown in Tables 5 and 6. The case where the maximum step was 0.2 μm or less was evaluated as flatness ○, and the case where it was 0.21 μm or more was evaluated as flatness ×. A color filter substrate without a cured film was used having a maximum step of 1 μm.

  As is clear from the results shown in Table 5, it can be seen that the cured films prepared 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 made from the thermosetting composition of Comparative Example 1 using polyester amide acid not containing a compound having a polymerizable double bond has poor scratch resistance. Moreover, it turns out that the cured film made from the thermosetting composition of the comparative example 2 and the comparative example 3 which added the compound which has a polymerizable double bond later lacks scratch resistance and barrier property. .

  The cured film obtained from the thermosetting composition of the present invention has a high flatness and a high scratch resistance, so that 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 And an insulating film formed between the transparent electrode and between the transparent electrode and the alignment film.

Claims (17)

A thermosetting composition comprising a polyester amide acid (A) having a polymerizable double bond and an epoxy compound (B),
The polyester amic acid (A) is composed of X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyvalent hydroxy compound in the relationship of the following formulas (1) and (2). Is a reaction product from the raw material containing in such a ratio,
A thermosetting composition in which at least one of the 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 comprising a polyester amide acid (A) having a polymerizable double bond and an epoxy compound (B),
The polyester amic acid (A) comprises X moles of tetracarboxylic dianhydride, Y moles of diamine, Z moles of a polyhydroxy compound, and a monohydroxy compound, represented by the following formulas (1) and (2): ) Is a reaction product from a raw material that is contained in such a ratio that the relationship of
A thermosetting composition in which at least one of the 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 polyester amic acid (A) includes a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

In Formula (3) and Formula (4), 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 —NH ₂ from 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 polyester amic acid (A) includes 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 Formula (3), Formula (4), and Formula (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is ^two residues from diamine. -NH ₂ is a residue, R ³ is a residue obtained by removing two -OH from a polyvalent hydroxy compound, R ⁴ is a residue obtained by removing one -OH from a monohydroxy compound, At least one of R ³ and R ⁴ has a polymerizable double bond. The polyester amic acid (A) includes 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 Formula (3), Formula (4), and Formula (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is ^two residues from diamine. -NH ₂ is a residue, R ³ is a residue obtained by removing two -OH from a polyvalent hydroxy compound, R ⁴ is a residue obtained by removing one -OH from a monohydroxy compound, At least one of R ³ has a polymerizable double bond. The polyester amic acid (A) includes 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 Formula (3), Formula (4), and Formula (5), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is ^two residues from diamine. -NH ₂ is a residue, R ³ is a residue obtained by removing two -OH from a polyvalent hydroxy compound, R ⁴ is a residue obtained by removing one -OH from a monohydroxy compound, At least one of R ⁴ has a polymerizable double bond.   The polyvalent hydroxy compound includes 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. The thermosetting composition according to item 1.   The polyvalent hydroxy compound includes 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) The thermosetting composition according to claim 6, which is at least one compound selected from the group consisting of ethanol.   The thermosetting composition according to claim 7, wherein the polyvalent hydroxy 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 is 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, ethylene glycol diglycidyl ether modified with (meth) acrylic acid, propylene glycol diglycidyl (Meth) acrylic acid modification of ether, (meth) acrylic acid modification of tripropylene glycol diglycidyl ether, (meth) acrylic acid modification of glycerin diglycidyl ether, (meth) acrylic acid modification of bisphenol A diglycidyl ether And at least one compound selected from the group consisting of (meth) acrylic acid modified products of propylene oxide-modified bisphenol A diglycidyl ether, and (meth) acrylic acid modified products of compounds containing two or more epoxy groups per molecule The thermosetting composition according to claim 7.   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 a monohydroxy compound having a polymerizable double bond. The thermosetting composition according to claim 2, 4, 5, or 6.   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.   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 is 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, (meth) acrylic acid 3- (2-hydroxyphenyl), glycerin di (meth) acrylate, trimethylolpropane Selected from the group consisting of di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and (meth) acrylic acid modified products of compounds containing one epoxy group per molecule The thermosetting composition according to claim 11, which is at least one compound.   The content of the epoxy compound (B) is 20 to 400 parts by weight based on 100 parts by weight of the polyester amic acid (A) having a polymerizable double bond, according to any one of claims 1 to 4. Thermosetting composition.   The cured film of the thermosetting composition of any one of Claims 1-15.   A color filter having the cured film according to claim 16 as a transparent protective film