TWI783001B - Thermosetting compositions, hardened film and color filter - Google Patents

Abstract

The present invention relates to a thermosetting composition, a cured film and a color filter, which include a polymerizable double bond-containing polyester amide acid (A), an epoxy compound (B) and optional additives. The polyester amide acid (A) having a polymerizable double bond contains X moles of tetracarboxylic dianhydride and Y moles of diamine in such a ratio that the relationship of the following formula (1) and formula (2) holds. And the reaction product of the raw material of the polyhydric hydroxyl compound containing the compound which has a polymerizable double bond of Z mole. According to the thermosetting composition of the present invention, a cured film excellent in scratch resistance and barrier properties can be provided, and a highly reliable electronic component having the cured film can be provided. 0.2≦Z/Y≦8.0·······(1) 0.2≦(Y+Z)/X≦5.0···(2).

Description

Thermosetting composition, cured film and color filter

The present invention relates to a kind of insulating material which can be used to form electronic components, passivation film in semiconductor device, buffer coating film, interlayer insulating film, planarization film, interlayer insulating film in liquid crystal display element, color filter ( color filter), a thermosetting composition such as a protective film, a transparent film formed of the thermosetting composition, 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 sometimes performed, or when wiring electrodes are formed into films by sputtering (sputtering), the surface is partially exposed to high temperature. heating. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and deterioration of the surface of various elements. These protective films are required to have various properties that can withstand various treatments in the manufacturing steps as described above. Specifically, heat resistance, solvent resistance, chemical resistance such as acid resistance and alkali resistance, water resistance, adhesion to base substrates such as glass, transparency, scratch resistance, coatability, flatness, Light fastness etc. In the process of increasing the heat resistance required for display element components as the reliability and characteristics required for display elements increase, thermosetting compositions containing polyester amide acid and epoxy compounds with good heat resistance are advocated. matter (for example, refer to Patent Document 1).

In the production of display elements in recent years, in-plane unevenness of the substrate tends to occur in the manufacturing process along with the increase in the size of the production line and the substrate. For example, when rubbing an alignment film in the manufacture of a large liquid crystal display element, in-plane unevenness in the contact pressure of the rubbing roller with respect to the color filter substrate tends to occur. In the part where the contact pressure is high, the protective film may be scratched, and if the protective film is scratched, the display quality will be lowered. Therefore, the improvement of scratch resistance is a problem for the thermosetting composition.

In addition, with the widening of the color gamut of display elements in recent years, color filters having pixels containing higher-density pigments than before may be used. In a color filter having pixels containing a pigment with a high concentration, the pigment component is more likely to be eluted when forming a protective film or the like as an upper layer of the color filter than before. In particular, the red pigment has a high concentration and is easily eluted when the upper layer is formed into a film. If the pigment component is eluted to the upper layer, the display quality will be lowered, so the improvement of the barrier properties of the material forming the upper layer with respect to the elution of the pigment component is a problem. In Patent Document 1, a thermosetting composition excellent in heat resistance is provided, but scratch resistance and barrier properties are not sufficiently satisfactory, and further improvement is required. [Prior art literature]

[Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2005-105264

[Problems to be Solved by the Invention] The subject of the present invention is to provide a thermosetting composition providing a cured film excellent in scratch resistance and barrier properties, and a cured film formed of the thermosetting composition, and further to provide a An electronic component having the cured film. [Technical means to solve the problem]

The inventors of the present invention conducted diligent research to solve the above-mentioned problems, and as a result found that the object can be achieved by using a cured film made of polyester having a polymerizable double bond. It is obtained by hardening the composition of amide acid and epoxy compound. The present invention includes the following configurations.

[1] A thermosetting composition comprising a polymerizable double bond polyester amide acid (A) and an epoxy compound (B), the polyester amide acid (A) being derived from the following formula: (1) and formula (2) The ratio of the established relationship includes the reaction product of the raw materials of X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyhydric hydroxyl compounds, at least one of the raw materials Has a polymeric double bond. 0.2≦Z/Y≦8.0·······(1) 0.2≦(Y+Z)/X≦5.0···(2)

[2] A thermosetting composition comprising a polymerizable double bond polyester amide acid (A) and an epoxy compound (B), the polyester amide acid (A) being derived from the following formula: (1) and the ratio of formula (2) established include the reaction product of raw materials of X moles of tetracarboxylic dianhydride, Y moles of diamine, Z moles of polyhydric hydroxyl compounds and monohydroxy compounds. 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)

在式（3）及式（4）中，R¹ 是自四羧酸二酐除去兩個-CO-O-CO-而成的殘基，R² 是自二胺除去兩個-NH₂ 而成的殘基，R³ 是自多元羥基化合物除去兩個-OH而成的殘基，R³ 的至少一個具有聚合性雙鍵。[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) Structural units.

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. The resulting residue, R ³ is a residue obtained by removing two -OH from a polyhydric hydroxy compound, and at least one of R ³ has a polymerizable double bond.

在式（3）、式（4）及式（5）中，R¹ 是自四羧酸二酐除去兩個-CO-O-CO-而成的殘基，R² 是自二胺除去兩個-NH₂ 而成的殘基，R³ 是自多元羥基化合物除去兩個-OH而成的殘基，R⁴ 是自單羥基化合物除去一個-OH而成的殘基，R³ 及R⁴ 的至少一個具有聚合性雙鍵。[4] The thermosetting composition according to item [2], wherein the polyester amide acid (A) includes a structural unit represented by the following formula (3), a structural unit represented by the following formula (4) A structural unit and a structural unit represented by the following 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 a residue obtained by removing two -CO-O-CO- from diamine. One -NH ₂ residue, R ³ is a residue obtained by removing two -OH from a polyhydroxy compound, R ⁴ is a residue obtained by removing one -OH from a monohydroxy compound, R ³ and R ⁴ At least one of has a polymerizable double bond.

在式（3）、式（4）及式（5）中，R¹ 是自四羧酸二酐除去兩個-CO-O-CO-而成的殘基，R² 是自二胺除去兩個-NH₂ 而成的殘基，R³ 是自多元羥基化合物除去兩個-OH而成的殘基，R⁴ 是自單羥基化合物除去一個-OH而成的殘基，R³ 的至少一個具有聚合性雙鍵。[5] The thermosetting composition according to item [2], wherein the polyester amide acid (A) includes a structural unit represented by the following formula (3), a structural unit represented by the following formula (4) A structural unit and a structural unit represented by the following 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 a residue obtained by removing two -CO-O-CO- from diamine. ^A residue formed by one _-NH2 , ^R3 is a residue obtained by removing two -OH from a polyhydroxy compound, R4 is a residue obtained by removing one -OH from a monohydroxy compound, at least one of ^R3 Has a polymeric double bond.

在式（3）、式（4）及式（5）中，R¹ 是自四羧酸二酐除去兩個-CO-O-CO-而成的殘基，R² 是自二胺除去兩個-NH₂ 而成的殘基，R³ 是自多元羥基化合物除去兩個-OH而成的殘基，R⁴ 是自單羥基化合物除去一個-OH而成的殘基，R⁴ 的至少一個具有聚合性雙鍵。[6] The thermosetting composition according to item [2], wherein the polyester amide acid (A) includes a structural unit represented by the following formula (3), a structural unit represented by the following formula (4) A structural unit and a structural unit represented by the following 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 a residue obtained by removing two -CO-O-CO- from diamine. ^A residue formed by one _-NH2 , ^R3 is a residue obtained by removing two -OH from a polyhydroxy compound, R4 is a residue obtained by removing one ^-OH from a monohydroxy compound, at least one of R4 Has a polymeric double bond.

[7] The thermosetting composition according to any one of [1] to [5], wherein the polyhydric hydroxyl compound is selected from the group consisting of 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'-dihydroxy Dicyclohexyl, tris(2-hydroxyethyl) isocyanurate, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-(4-hydroxyphenyl)ethanol, and polyhydric hydroxyl compounds with polymerizable double bonds At least one compound in the group formed must contain a polyhydric hydroxyl compound having a polymerizable double bond.

[8] The thermosetting composition according to item [6], wherein the polyhydric hydroxyl compound is selected from the group consisting of 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, isocyanurate At least one compound selected from the group consisting of tris(2-hydroxyethyl)acid, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol and 2-(4-hydroxyphenyl)ethanol.

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

[10] The thermosetting composition according to item [7], wherein the polyhydric hydroxyl compound having a polymerizable double bond is selected from glycerol mono(meth)acrylate, trimethylolpropane mono(methyl) ) acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate ester, dipentaerythritol tetra(meth)acrylate, sorbitol mono(meth)acrylate, sorbitol di(meth)acrylate, sorbitol tri(meth)acrylate, sorbitol tetra( Meth)acrylate, modified (meth)acrylic acid of ethylene glycol diglycidyl ether, modified (meth)acrylic acid of propylene glycol diglycidyl ether, modified (meth)acrylic acid of tripropylene glycol diglycidyl ether , (meth)acrylic modified substance of glycerol diglycidyl ether, (meth)acrylic modified substance of bisphenol A diglycidyl ether, (meth)acrylic modified substance of bisphenol A diglycidyl ether modified with propylene oxide At least one compound in the group consisting of (meth)acrylic modified substances of compounds containing two or more epoxy groups per molecule.

[11] The thermosetting composition according to [2], [4], [5] or [6], wherein the monohydroxy compound is selected from isopropanol, benzyl alcohol, propylene glycol mono At least one compound selected from the group consisting of diethyl ether, 3-ethyl-3-hydroxymethyloxetane, and a monohydroxy compound having a polymerizable double bond.

[12] The thermosetting composition according to item [5], wherein the monohydroxy compound is selected from the group consisting of isopropanol, benzyl alcohol, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl oxetane At least one compound from the group consisting of butane.

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

[14] The thermosetting composition according to item [11], wherein the monohydroxyl compound having a polymerizable double bond is selected from furfuryl alcohol, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, aniline p-hydroxy(meth)acrylate, 1,4-cyclohexanedimethanol mono( Meth)acrylate, 3-(2-Hydroxyphenyl)(meth)acrylate, Glycerin Di(meth)acrylate, Trimethylolpropane Di(meth)acrylate, Pentaerythritol Tri(methyl) At least one compound selected from the group consisting of acrylate, dipentaerythritol penta(meth)acrylate, and a modified (meth)acrylic acid compound containing one epoxy group per molecule.

[15] The thermosetting composition according to any one of [1] to [4], wherein the epoxy compound (B ) content is 20 to 400 parts by weight.

[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 item [16] as a transparent protective film. [Effect of the invention]

The thermosetting composition according to a preferred embodiment of the present invention is a material particularly excellent in scratch resistance and barrier properties, and when used as a color filter protective film of a color liquid crystal display element, the display quality can be improved. In particular, it is effective as a protective film for color filters produced by dyeing, pigment dispersion, electrodeposition, and printing. In addition, 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 of the present invention, the more "excellent scratch resistance" the cured film and the thermosetting composition for forming the cured film exhibit.

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

1. The thermosetting composition of the present invention The thermosetting composition of the present invention is a composition containing a polyester amide acid having a polymerizable double bond and an epoxy compound. The polyester amide acid having a polymerizable double bond is a reaction product derived from raw materials including a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound, at least one of which has a polymerizable double bond. The thermosetting composition of this invention contains 20 weight part - 400 weight part of epoxy compounds with respect to 100 weight part of polyester amide acids.

In addition, the thermosetting composition of this invention may contain other components other than the above-mentioned in the range which acquires the effect of this invention.

1-1. Polyester amide acid (A) having a polymerizable double bond Polyester amide acid (A) is obtained by using tetracarboxylic dianhydride, diamine, polyhydroxy compound and monohydroxy compound as essential raw material components. And react to get. Furthermore, polyester amide acid (A) is obtained by making X mole of tetracarboxylic dianhydride, Y mole of diamine, and Z mole of obtained by the reaction of polyhydric hydroxyl compounds.

In addition, the polyester amide 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 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 a residue obtained by removing two -CO-O-CO- from diamine. One -NH ₂ residue, R ³ is a residue obtained by removing two -OH from a polyhydroxy 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.

In the synthesis of polyester amide acid (A), at least a solvent is required. The solvent can be left as it is to prepare a liquid or gel thermosetting composition in consideration of workability, etc., and the solvent can be removed to form a solid composition in consideration of transportability and the like. Composition.

In addition, in the synthesis of the polyester amide acid (A), a styrene-maleic anhydride copolymer may be included as a raw material if necessary, and other materials other than those mentioned above may also be included within the range that does not impair the object of the present invention. other compounds as raw materials. 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 dianhydrides include 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter, sometimes abbreviated as ODPA), 1 ,2,3,4-butanetetracarboxylic dianhydride (hereinafter, sometimes abbreviated as BT-100).

In addition, as said tetracarboxylic dianhydride, other than the above-mentioned ones, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride, 2,2', 3,3' -Benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylphenone tetracarboxylic dianhydride , 2,2',3,3'-diphenylenetetracarboxylic dianhydride, 2,3,3',4'-diphenylenetetracarboxylic dianhydride, 2,2',3,3' -Diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoro Propane dianhydride, ethylene glycol bis(dehydrated trimellitate) (trade name; TMEG-100, Shin Nippon Chemical Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic di Anhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, and ethane tetracarboxylic dianhydride, at least one of the above-mentioned tetracarboxylic dianhydrides can be used.

Among these tetracarboxylic dianhydrides, those that impart good transparency to the cured film are more preferably 3,3',4,4'-diphenylenetetracarboxylic dianhydride, 3,3',4,4' -Diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride and TMEG-100, particularly preferably 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylene tetracarboxylic dianhydride and 1, 2,3,4-Butanetetracarboxylic dianhydride.

1-1-2. Diamine In the present invention, a diamine is used as a material for obtaining the polyester amide acid (A). As a specific example of diamine, it is preferable to mention 3,3'- diaminodiphenylsulfone (it may abbreviate as DDS hereafter) used in an Example.

Furthermore, as specific examples of the diamine, in addition to the above-mentioned ones, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, bis[4-( 4-aminophenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, bis[3-(4-aminophenoxy)phenyl]pyridine, [4-( 4-aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl]pyridine, [4-(3-aminophenoxy)phenyl][3-(4-aminophenoxy) ) phenyl]pyridine and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, at least one of the diamines can be used.

Among these diamines, diamines that impart good transparency to the cured film are more preferably 3,3'-diaminodiphenylphenone and bis[4-(3-aminophenoxy)phenyl]sulfone, especially Preferably it is 3,3'-diaminodiphenylsulfone.

1-1-3. Polyvalent hydroxyl compound In the present invention, a polyhydric hydroxyl compound having no polymerizable double bond and/or a polyhydric hydroxyl compound having a polymerizable double bond are used as a material for obtaining the polyester amide acid (A). compound. Regarding specific examples of polyhydric hydroxyl compounds, it is preferable to enumerate 1,4-butanediol, epoxy ester 70PA (trade name: Kyoeisha Chemical Co., Ltd.), epoxy ester 80MFA (trade name : Kyorongsha Chemical Co., Ltd.), epoxy ester 3002A (N) (trade name: Kyorongsha Chemical Co., Ltd.).

Furthermore, examples of the polyhydric hydroxyl compound not having a polymerizable double bond include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a weight average molecular weight of 1,000 or less, propylene glycol , dipropylene glycol, 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 Alcohol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6- Hexatriol, 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 3,6- Octanediol, 1,2,8-octanediol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanediol, 1,2-decanediol, 1, 10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, iso Tris(2-hydroxyethyl)cyanurate, 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-hydroxybenzyl alcohol, 2 -(4-Hydroxyphenyl)ethanol, diethanolamine and triethanolamine.

Among these polyhydric hydroxyl compounds, those having good solubility in the reaction solvent are more preferably ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 ,7-heptanediol, 1,8-octanediol, tris(2-hydroxyethyl)isocyanurate, 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxy Dicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol and 2-(4-hydroxyphenyl)ethanol. In addition, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol and 2-(4-hydroxyphenyl ) ethanol.

On the other hand, as specific examples of the polyhydric hydroxyl compound having a polymerizable double bond, glycerin monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, pentaerythritol diene Propyl ether, dipentaerythritol monoallyl ether, dipentaerythritol diallyl ether, dipentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, sorbitol monoallyl ether, sorbitol diene Propyl ether, Sorbitan triallyl ether, Sorbitan tetraallyl ether, Glycerin mono(meth)acrylate, Trimethylolpropane mono(meth)acrylate, Pentaerythritol mono(meth)acrylate Acrylates, Pentaerythritol Di(meth)acrylate, Dipentaerythritol Mono(meth)acrylate, Dipentaerythritol Di(meth)acrylate, Dipentaerythritol Tri(meth)acrylate, Dipentaerythritol Tetra(meth)acrylate ester, sorbitol mono(meth)acrylate, sorbitol di(meth)acrylate, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, ethylene glycol di Glycidyl ether modified (meth)acrylic acid, propylene glycol diglycidyl ether (meth)acrylic modified, tripropylene glycol diglycidyl ether (meth)acrylic modified, glycerin diglycidyl ether (methyl) ) modified acrylic acid, modified (meth)acrylic acid of bisphenol A diglycidyl ether, modified (meth)acrylic acid of bisphenol A diglycidyl ether modified with propylene oxide, and modified bisphenol S diglycidyl ether (Meth)acrylic modified product, (meth)acrylic modified product of bisphenol S diglycidyl ether modified with propylene oxide, (meth)acrylic modified product of bisphenol F diglycidyl ether, modified with propylene oxide (Meth)acrylic modified product of bisphenol F diglycidyl ether, (meth)acrylic modified product of bisphenol diglycidyl ether, (meth)acrylic modified product of biphenol diglycidyl ether, fluorene di (Meth)acrylic modified product of phenol diglycidyl ether, (meth)acrylic modified product of cyclohexane-1,4-dimethanol diglycidyl ether, (meth)acrylic modified product of hydrogenated bisphenol A diglycidyl ether Acrylic modified substances, (meth)acrylic modified substances of tricyclodecane dimethanol diglycidyl ether, and (meth)acrylic modified substances of other compounds containing two or more epoxy groups per molecule can use these at least one of polyhydric hydroxyl compounds.

Among these polyhydric hydroxyl compounds, the compound having good solubility in the reaction solvent is more preferably a (meth)acrylic modified product of ethylene glycol diglycidyl ether, a (meth)acrylic modified product of propylene glycol diglycidyl ether, glycerin Modified (meth)acrylic acid of diglycidyl ether, modified (meth)acrylic acid of bisphenol A diglycidyl ether, modified (meth)acrylic acid of propylene oxide modified bisphenol A diglycidyl ether, (Meth)acrylic modified product of bisphenol S diglycidyl ether, (meth)acrylic modified product of bisphenol S diglycidyl ether modified with propylene oxide, (meth)acrylic acid modified product of bisphenol F diglycidyl ether Modifiers and (meth)acrylic acid modifiers of propylene oxide modified bisphenol F diglycidyl ether. Also, particularly preferred are (meth)acrylic modified products of ethylene glycol diglycidyl ether, (meth)acrylic modified products of propylene glycol diglycidyl ether, and (meth)acrylic modified products of tripropylene glycol diglycidyl ether. , (meth)acrylic acid modification of glycerol diglycidyl ether, (meth)acrylic modification of bisphenol A diglycidyl ether and (meth)acrylic modification of propylene oxide modified bisphenol A diglycidyl ether Pledge.

Modified methacrylic acid of ethylene glycol diglycidyl ether, modified acrylic acid of propylene glycol diglycidyl ether, modified acrylic acid of tripropylene glycol diglycidyl ether, modified acrylic acid of glycerin diglycidyl ether, bisphenol A Glycidyl ether modified methacrylic acid, bisphenol A diglycidyl ether acrylic modified, propylene oxide modified bisphenol A diglycidyl ether methacrylic modified and propylene oxide modified bisphenol A di As the acrylic modified substance of glycidyl ether, the following commercial products can be used.

A specific example of the methacrylic acid-modified substance of ethylene glycol diglycidyl ether is epoxy ester 40EM (trade name: Kyoeisha Chemical Co., Ltd.). A specific example of an acrylic modified product of propylene glycol diglycidyl ether is epoxy ester 70PA (trade name: Kyoeisha Chemical Co., Ltd.). A specific example of an acrylic modified product of tripropylene glycol diglycidyl ether is epoxy ester 200PA (trade name: Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic modified product of glycerol diglycidyl ether is epoxy ester 80MFA (trade name: Kyoeisha Chemical Co., Ltd.). A specific example of the methacrylic acid-modified substance of bisphenol A diglycidyl ether is epoxy ester 3000MK (trade name: Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic modified product of bisphenol A diglycidyl ether is epoxy ester 3000A (trade name: Kyoeisha Chemical Co., Ltd.). A specific example of a methacrylic acid-modified product of propylene oxide-modified bisphenol A diglycidyl ether is epoxy ester 3002M(N) (trade name: Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic 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, as a material for obtaining the polyester amide acid (A), a monohydroxy compound having no polymerizable double bond and/or one having a polymerizable double bond can also be used. monohydroxy compound.

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 Chemicals Co., Ltd.).

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

Specific examples of the monohydroxyl compound not having a polymerizable double bond are preferably: isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, terpineol, 3-ethyl-3-hydroxymethyl oxetane and dimethyl Dimethyl benzyl carbinol.

Among these monohydroxyl compounds, benzyl alcohol, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane are more preferable. Considering the compatibility when mixing polyester amide acid (A) formed by using these monohydroxyl compounds with epoxy group-containing polymers, epoxy compounds (B) and epoxy hardeners, or thermal For the coatability of the curable composition on a color filter, it is particularly preferable to use benzyl alcohol as a monohydroxy compound having no polymerizable double bond.

Specific examples of the monohydroxyl compound having a polymerizable double bond include, preferably, furfuryl alcohol, allyl alcohol, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate. ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, aniline p-hydroxy(meth)acrylate, 1,4-cyclohexanedimethanol mono( Meth)acrylate, 3-(2-Hydroxyphenyl)(meth)acrylate, Glycerin Di(meth)acrylate, Trimethylolpropane Di(meth)acrylate, Pentaerythritol Tri(methyl) Acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylic modified substance of phenyl glycidyl ether, (meth)acrylic modified substance of tertiary butylphenyl glycidyl ether, and each molecule contains As the (meth)acrylic modified substance of other compounds with one epoxy group, at least one of these monohydroxy compounds can be used.

Among these monohydroxyl compounds, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxy (meth)acrylate are more preferred. Propyl ester, (meth)acrylic acid=4-hydroxyphenyl ester, aniline p-hydroxy(meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, (meth)acrylic acid=3- (2-Hydroxyphenyl) ester. Considering the compatibility when mixing polyester amide acid (A) formed by using these monohydroxyl compounds with epoxy group-containing polymers, epoxy compounds (B) and epoxy hardeners, or thermal For the coatability of the curable composition on the color filter, it is particularly preferable to use a monohydroxyl compound having a polymerizable double bond such as (meth)hydroxyethyl acrylate, (meth)hydroxypropyl acrylate, (meth) ) hydroxybutyl acrylate, 4-hydroxyphenyl (meth)acrylate, aniline p-hydroxy (meth)acrylate and 1,4-cyclohexanedimethanol mono(meth)acrylate.

As methacrylate=4-hydroxyphenyl ester, aniline p-hydroxymethacrylate, and 1,4-cyclohexanedimethanol monoacrylate, the following commercial items can be used. A specific example of methacrylic acid=4-hydroxyphenyl is HQMA (trade name; Osaka Organic Chemical Industry Co., Ltd.). A specific example of p-hydroxymethacrylic aniline 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 Chemicals Co., Ltd.).

It is preferable to contain 0 weight part - 300 weight part of monohydroxyl compounds with respect to 100 weight part of total amounts of a tetracarboxylic dianhydride, a diamine, and a polyhydric hydroxyl compound, and it reacts. More preferably, it is 5 weight part - 200 weight part.

1-1-5. Styrene-maleic anhydride copolymer The polyester amide acid used in the present invention can also be synthesized by using a compound having three or more acid anhydride groups as the raw material. Thereby, since the transparency of a cured film improves, it is preferable. As an example of the compound which has three or more acid anhydride groups, a styrene-maleic anhydride copolymer is mentioned. In the case of using styrene-maleic anhydride copolymers as raw materials to synthesize polyester amide acid, the molar number of the tetracarboxylic dianhydride and the molar number of the styrene-maleic anhydride copolymer The total of is converted to "X" in formula (2). The molar ratio of styrene/maleic anhydride is 0.5-4, Preferably it is 1-3 about the ratio of each component which comprises a styrene-maleic anhydride copolymer. Furthermore, 1 or 2 is more preferable, and 1 is especially preferable.

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

1-1-6. Silicon-containing monoamine In the synthesis of polyester amide acid, other raw materials other than those mentioned above may be included as raw materials as needed, as other raw materials Examples of silicon-containing monoamines can be cited.

Regarding specific examples of silicon-containing monoamines used in the present invention, it is preferable to enumerate: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane Methoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxy Silane and m-aminophenylmethyldiethoxysilane. At least one of these silicon-containing monoamines can be used.

Among these silicon-containing monoamines, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane, which have good acid resistance for the hardened film, are more preferred in terms of acid resistance and compatibility. , particularly preferably 3-aminopropyltriethoxysilane.

It is preferable to contain 0 weight part - 300 weight part of silicon-containing monoamines with respect to 100 weight part of total amounts of tetracarboxylic dianhydride, diamine, and polyhydric hydroxyl compound. More preferably, it is 5 weight part - 200 weight part.

1-1-7. Solvent used in synthesis reaction of polyester amide acid (A) Specific details of the solvent used in the synthesis reaction of polyester amide acid (A) having a polymerizable double bond Examples include: diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone. Among these solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ether is preferable.

1-1-8. Synthesis method of polyester amide acid (A) The synthesis method of the polyester amide acid (A) with polymerizable double bonds used in the present invention is to make X mole of tetracarboxylic acid di Anhydride, Y moles of diamine, Z moles of polyhydroxy compound and monohydroxy compound are reacted in the solvent. At this time, it is preferable to determine X, Y, and Z as ratios in which the relationship of the following formula (1) and formula (2) holds among them. If it is the said range, the solubility to a solvent of a polyester amide acid will become high, and the applicability of a composition will improve. 0.2≦Z/Y≦8.0·······(1) 0.2≦(Y+Z)/X≦5.0···(2)

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

It is considered that in the synthesis of polyester amide acid (A), under the condition that X is used in excess relative to Y+Z within the range of the above-mentioned formula (2) without using a monohydroxy compound, the ratio at the end has A molecule having an amino group or a hydroxyl group is more excessively produced as a molecule having an acid anhydride group (-CO-O-CO-) at the terminal. On the other hand, when reacting with the structure of such a monomer, when a monohydroxy compound is added, it can react with the acid anhydride group of a molecular terminal, and can esterify a terminal. Since the polyester amide acid (A) used in the present invention can be obtained by adding and reacting a monohydroxy compound, the compatibility with the epoxy compound (B) is improved, and the coatability of the thermosetting composition is improved.

In addition, in the case of reacting with the above monomer configuration, a silicon-containing monoamine may be added in order to introduce a silyl group at the terminal to react with the acid anhydride group at the terminal of the molecule. The acid resistance of the cured film is improved by using a thermosetting composition containing polyester amide acid obtained by adding and reacting silicon-containing monoamine.

Since reaction will progress smoothly when using 100 weight part or more of reaction solvents with respect to 100 weight part of total amounts of tetracarboxylic dianhydride, diamine, and a polyvalent hydroxyl compound, it is preferable. The reaction is preferably carried out at 40° C. to 200° C. for 0.2 hours to 20 hours.

The order of adding raw materials to the reaction system is not particularly limited. That is, any of the following methods may be used: a method of simultaneously adding tetracarboxylic dianhydride, diamine, and a polyhydroxy compound to a reaction solvent; dissolving the diamine and a polyhydroxy compound in a reaction solvent, and then adding tetracarboxylic acid The method of dianhydride; the method of adding diamine to the reaction product after pre-reacting tetracarboxylic dianhydride and polyhydroxy compound; or adding diamine to the reaction product after pre-reacting tetracarboxylic dianhydride and diamine Methods of polyhydroxy compounds, etc. The monohydroxy compound can be added at any point in the reaction.

In the case of reacting the silicon-containing monoamine, after the reaction of the tetracarboxylic dianhydride, diamine, and polyhydroxy compound, the reaction solution is cooled to below 40°C, and then the silicon-containing monoamine is added to the It is advisable to react at 10°C to 40°C for 0.1 hour to 6 hours. Additionally, the monohydroxy compound can be added at any point in the reaction.

The polyester amide acid (A) synthesized in the described manner comprises the structural unit represented by formula (3), the structural unit represented by formula (4) and the structural unit represented by formula (5), and its end contains source An acid anhydride group, an amino group, a hydroxyl group, or a monovalent organic group derived from a tetracarboxylic dianhydride, a diamine, a polyhydric hydroxy compound, or a monohydroxy compound as a raw material, or an additive other than these compounds. Curability becomes favorable by including such a structure.

The obtained polyester amide has a weight average molecular weight of preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000. Scratch resistance and flatness are favorable in these ranges.

The weight average molecular weight in this specification is a polystyrene conversion value calculated|required by the gel permeation chromatography (Gel Permeation Chromatography, GPC) method (column temperature: 35 degreeC, flow rate: 1 ml/min). The standard polystyrene uses polystyrene with a molecular weight of 645-132,900 (for example, the polystyrene calibration kit (calibration kit) PL2010-0102 from Agilent Technologies Inc.), and the column uses PL gel mixed (PLgel MIXED)-D (Agilent Technologies Inc.), can be measured using tetrahydrofuran (Tetrahydrofuran, THF) as the mobile phase. The weight average molecular weights of commercially available items in this specification are values described in catalogs.

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, bisphenol type epoxy compound, phenol novolac Polymerization of varnish-type epoxy compounds, cresol novolak-type epoxy compounds, bisphenol A novolak-type epoxy compounds, aliphatic polyglycidyl ether compounds, cycloaliphatic epoxy compounds, monomers having epoxy groups Compounds, copolymers of monomers with epoxy groups and other monomers, and epoxy compounds with siloxane bonding sites.

Specific examples of commercially available bisphenol A epoxy compounds are jER 828, jER 1004, and jER 1009 (all trade names; Mitsubishi Chemical Corporation); specific examples of commercially available bisphenol F epoxy compounds jER 806, jER 4005P (both trade names; Mitsubishi Chemical Co., Ltd.); a specific example of a commercially available glycidyl ether type epoxy compound is Tekemo (TECHMORE) VG3101L (trade name; Printec ( Printec) Co., Ltd.), EHPE3150 (trade name; Daicel Co., Ltd.), EPPN-501H, EPPN-502H (both trade names; Nippon Kayaku Co., Ltd.), and jER 1032H60 (trade name; Mitsubishi Chemical Co., Ltd.); a specific example of a commercially available product of a glycidyl ester type epoxy compound is Dana Kaur (Denacol) EX-721 (trade name; Nagase Chemical Industry (Nagase chemteX) Co., Ltd.), and 1 , 2-cyclohexanedicarboxylic acid diglycidyl ester (trade name; Tokyo Chemical Industry Co., Ltd.); specific examples of commercially available bisphenol-type epoxy compounds are jER YX4000, jER YX4000H, jER YL6121H (both are trade name; Mitsubishi Chemical Corporation), and NC-3000, NC-3000-L, NC-3000-H, NC-3100 (all trade names; Nippon Kayaku Co., Ltd.); phenol novolak type epoxy Specific examples of commercially available compounds include EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), jER 152 and jER 154 (both trade names; Mitsubishi Chemical Co., Ltd.); Specific examples of commercially available oxygen compounds include EOCN-102S, EOCN-103S, EOCN-104S, and EOCN-1020 (all trade names; Nippon Kayaku Co., Ltd.); Specific examples of commercially available products are jER 157S65 and jER 157S70 (both trade names; Mitsubishi Chemical Corporation); specific examples of commercially available products of cycloaliphatic epoxy compounds are Celloxide 2021P, Celloxide Celloxide 3000 (both trade names; Daicel Co., Ltd.); 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; Gelest Incorporated), TSL9906 (trade name; Momentive Performance Materials Japan) Co., Ltd.), COATOSIL (COATOSIL) MP-2 00 (trade name; Momentive Performance Materials Japan Co., Ltd.), Conpoceran (Conpoceran) SQ506 (trade name; Arakawa Chemical Co., Ltd.), ES-1023 (trade name; Shin-Etsu Chemical Industry limited company).

Furthermore, TECHMORE VG3101L (trade name; Printec Co., Ltd.) is 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4 -[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane and 1,3-bis[4-[1-[4-(2,3 -Glycidyloxy)phenyl]-1-[4-[1-[4-(2,3-Glycidoxy)phenyl]-1-methylethyl]phenyl]ethyl] Mixture of phenoxy]-2-propanol; EHPE3150 (trade name; Daicel Co., Ltd.) is the 1,2-epoxy group of 2,2-bis(hydroxymethyl)-1-butanol -4-(2-Oxiranyl)cyclohexane adduct; Celloxide 2021P (trade name; Daicel Co., Ltd.) is a 3',4'-epoxy ring Hexylmethyl-3,4-epoxycyclohexanecarboxylate; Celloxide 3000 (trade name; Daicel Co., Ltd.) is 1-methyl-4-(2-methyl Oxycyclopropyl)-7-oxabicyclo[4.1.0]heptane; Coat Oslo (COATOSIL) MP-200 (trade name; Momentive Performance Materials Japan Co., Ltd.) is A polymer based on 3-glycidoxypropyltrimethoxysilane.

The epoxy compound (B) may be used alone or in combination of two or more.

1-2-2. Ratio of epoxy compound (B) to polyester amide acid (A) With respect to 100 parts by weight of polyester amide acid (A) in the thermosetting composition of the present invention, epoxy The ratio of the total amount of the compound (B) is 20 to 400 parts by weight. When the ratio of the total amount of the epoxy compound (B) is within the above-mentioned range, the balance of flatness, heat resistance, chemical resistance, and adhesiveness will be favorable. The total amount of the epoxy compound (B) is preferably in the range of 50 parts by weight to 300 parts by weight.

1-3. Other components Various additives may be added to the thermosetting composition of the present invention to improve coating uniformity, adhesiveness, transparency, flatness and chemical resistance. Additives mainly include: epoxy hardener, solvent, anionic, cationic, nonionic, fluorine or silicon-based leveling agent x surfactant, silane coupling agent and other adhesion enhancers, hindered phenolic, Hindered amine-based, phosphorus-based, sulfur-based compounds and other antioxidants, molecular weight modifiers.

1-3-1. Surfactant In the thermosetting composition of the present invention, a surfactant may be added to improve coating uniformity. Concrete examples of surfactants include: Polyflow No.75, Polyflow No.90, Polyflow No.95 (all trade names; a total of Rongshe Chemical Co., Ltd.), Disperbyk (Disperbyk)-161, Disperbyk (Disperbyk)-162, Disperbyk (Disperbyk)-163, Disperbyk (Disperbyk)- 164, Disperbyk-166, Disperbyk-170, Disperbyk-180, Disperbyk-181, Disperbyk Gram (Disperbyk)-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (all commodities Name; BYK Chemie Japan Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF-50-100CS (the above are trade names; Shin-Etsu Chemical Industry Co., Ltd.), Surflon S611 (trade name; AGC Seimi Chemical Co., Ltd.), Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, FTX-218 (all trade names; Neos Co., Ltd.), Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F-477, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac Megafac F-558, Megafac F-559, Megafac R-94, Megafac RS-75, Megafac RS-72-K, Meg afac) RS-76-NS, Megafac (Megafac) DS-21 (all trade names; DIC Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (all trade names; Evonik Japan (Evonik Japan Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonic acid salt, diglyceride tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl sulfamate, 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, Sorbitol Anhydride oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oil Ester, polyoxyethylene naphthyl ether, alkylbenzene sulfonate and alkyl diphenyl ether disulfonate. It is preferable to use at least one kind selected from these surfactants.

Among these surfactants, if selected from BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surflon S611, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac F-559, Megafac RS-72-K, Megafac DS-21, Tego Twin 4000, Fluoroalkylbenzene Sulfonate, Fluoroalkyl Carboxylate, Fluoroalkyl Polyoxyethylene At least one of ether, fluoroalkylsulfonate, fluoroalkyltrimethylammonium salt, and fluoroalkylsulfamate is preferred because the coating uniformity of the thermosetting composition will be high.

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

1-3-2. Coupling agent From the viewpoint of further improving the adhesion between the formed cured film and the substrate, the thermosetting composition of the present invention may further contain a coupling agent.

As such a coupling agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, examples include: 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxy Silane (e.g., trade name; Sara-Ace (Sila-Ace) S510, JNC Co., Ltd.), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (e.g., name; Sarah Ace (Sila-Ace) S530, JNC (JNC) Co., Ltd.), 3-mercaptopropyltrimethoxysilane (for example, trade name; Sarah Ace (Sila-Ace) S810, JNC Enzhi (JNC) Co., Ltd.), polymers of 3-glycidoxypropyltrimethoxysilane (for example, trade name; Coat Oslo (COATOSIL) MP-200, Momentive Performance Materials Japan ) Co., Ltd.) and other silane-based coupling agents, aluminum-based coupling agents such as acetyl alkoxy diisopropoxide, and titanate-based coupling agents such as tetraisopropyl bis(dioctyl phosphite) titanate coupling agent.

Among these coupling agents, 3-glycidoxypropyltrimethoxysilane is preferable because of its large effect of improving adhesion.

From the viewpoint of improving the adhesion between the formed cured film and the substrate, the content of the coupling agent is preferably 0.01% by weight or more and 10% by weight or less based on the total amount of the thermosetting composition.

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.

In the thermosetting composition of the present invention, antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added. Among these, hindered phenols are preferred from the viewpoint of weather resistance. Specific examples include: Irganox 1010, Irganox 1010FF, Irganox 1035, Irganox 1035FF, and Irganox Irganox 1076, Irganox 1076FD, Irganox 1098, Irganox 1135, Irganox 1330, Yilujia Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Irganox 245FF, Yilu Irganox 259, Irganox 3114, Irganox 565, Irganox 565DD (all trade names; shares of BASF Japan) Co., Ltd.), Addie Costa (ADK STAB) AO-20, Addie Costa (ADK STAB) AO-30, Addie Costa (ADK STAB) AO-50, Addie Costa (ADK STAB) AO-60, ADK STAB AO-80 (both trade names; ADEKA Co., Ltd.). Among them, Irganox 1010 and ADK STAB AO-60 are more preferred.

The antioxidant is added in an amount of 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 to suppress an increase in molecular weight due to polymerization and to exhibit excellent storage stability. Examples of the molecular weight modifier include mercaptans, xanthic acids, quinones, hydroquinones, 2,4-diphenyl-4-methyl-1-pentene, and the like.

Specific examples of molecular weight regulators include: 1,4-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, methyl-p-benzoquinone, anthraquinone, hydroquinone, methylhydroquinone, tertiary butyl hydroquinone, 2,5-di-tertiary butyl hydroquinone, 2,5-di-tertiary pentyl hydroquinone, 1,4-dihydroxynaphthalene, 3,6-dihydroxybenzonor Bornane, 4-methoxyphenol, 2,2',6,6'-tetra-tert-butyl-4,4'-dihydroxybiphenyl, 3-(3,5-di-tert-butyl -4-Hydroxyphenyl)propionate stearyl, 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,4,6-tris(3',5' -Di-tert-butyl-4'-hydroxybenzyl) mesitylene, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4-th Tributylcatechol, n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, berydodecanylmercaptan, thioglycolic acid, dimethylxanthogen Acid thioether, diisopropyl xanthate disulfide, 2,6-di-tert-butyl-p-cresol, 4,4'-butylene bis(6-tert-butyl-m-cresol) , 4,4'-thiobis(6-tert-butyl-m-cresol), 2,4-diphenyl-4-methyl-1-pentene, phenothiazine, 2-hydroxyl-1, 4-Naphthoquinone.

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

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

1-3-5. Epoxy curing agent In order to improve flatness and chemical resistance, the thermosetting composition of the present invention may further contain an epoxy curing agent. As epoxy curing agents, there are acid anhydride-based curing agents, amine-based curing agents, phenol-based curing agents, imidazole-based curing agents, pyrazole-based curing agents, triazine-based curing agents, catalyst-type curing agents and cobalt salts, benzo Thermosensitive acid generators such as thiazolium salts, ammonium salts, and phosphonium salts are preferably acid anhydride-based curing agents or imidazole-based curing agents from the viewpoint of avoiding coloring of the cured film and heat resistance of the cured film.

Specific examples of the acid anhydride hardener are 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 acid anhydride-based curing agents, trimellitic anhydride and hexahydrotrimellitic anhydride have a good balance of heat resistance and solubility in solvents.

Specific examples of the imidazole hardener are 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 imidazole-based curing agents, 2-undecylimidazole having a good balance between curing properties and solubility in solvents is preferable.

Specific examples of the pyrazole-based hardener include pyrazole, 3,5-dimethylpyrazole, 3-amino-5-methylpyrazole, and 3-amino-5-hydroxypyrazole. Among these pyrazole-based curing agents, 3,5-dimethylpyrazole having a good balance between curability and solubility in solvents is preferable.

Specific examples of the triazine hardener include 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3-mercapto- 1,2,4-triazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 1,2, 3-Benzotriazole, 5-methyl-1H-benzotriazole, methyl-1H-benzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole. Among these triazine-based curing agents, 1,2,3-benzotriazole having a good balance between curing properties and solubility in solvents is preferable.

When using an epoxy curing agent, the ratio of an epoxy curing agent is 0.1 weight part - 60 weight part with respect to 100 weight part of epoxy compounds (B). When the epoxy curing agent is an acid anhydride-based curing agent, in more detail, it is preferable that the carboxylic acid anhydride group or carboxyl group in the epoxy curing agent becomes 0.1 equivalent to 1.5 times the epoxy group. Add in an equivalent amount. At this time, the carboxylic acid anhydride group is calculated as divalent. When adding a carboxylic acid anhydride group or a carboxyl group so that it may become 0.15 times equivalent - 0.8 times equivalent, since chemical resistance will improve more, it is more preferable.

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

Specific examples of ultraviolet absorbers include TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN (TINUVIN) 326, TINUVIN 571, TINUVIN 765 (all trade names; BASF Japan Co., Ltd.).

The ultraviolet absorber is added and used in an amount of 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 property of the present invention does not fuse the polyester amide acid (A) or epoxy compound (B) having a polymerizable double bond with a solvent to prevent aggregation. The composition may also contain an anti-agglomeration agent.

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

0.01 to 10 parts by weight of an anti-aggregation agent is added to the total amount of the thermosetting composition and used.

1-3-8. Thermal crosslinking agent From the viewpoint of further improving heat resistance, chemical resistance, in-plane uniformity, flexibility, flexibility, and elasticity, the thermosetting composition of the present invention may contain thermal crosslinker.

Specific examples of thermal crosslinking agents are Nikalac (Nikalac) MW-30HM, Nikalac (Nikalac) MW-100LM, Nikalac (Nikalac) MX-270, Nikalac (Nikalac) MX-280, Nikalac Nikalac MX-290, Nikalac MW-390, Nikalac MW-750LM (all trade names; Sanwa Chemical Co., Ltd.).

The thermal crosslinking agent is added and used in an amount of 0.1 to 10 parts by weight based on the total amount of the thermosetting composition.

在式（6）中，R⁵ 為氫或甲基，R⁶ ～R⁹ 為碳數1～5的烷基，R¹⁰ 為碳數1～10的烷基，m為1～10的整數，n為1～150的整數。1-3-9. Other additives The thermosetting composition of the present invention may further contain a radically polymerizable compound (P1) represented by the following formula (6), a radically polymerizable compound having an alkoxysilyl group Compound (P2) and a radically polymerizable compound (P3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group are radically copolymerized polymers (hereinafter sometimes referred to as "radical copolymerization polymers") ).

In formula (6), R ⁵ is hydrogen or methyl, R ⁶ to R ⁹ are alkyl groups with 1 to 5 carbons, R ¹⁰ is an alkyl group with 1 to 10 carbons, m is an integer of 1 to 10, n is an integer of 1-150.

1-3-9-1. Radical polymerizable compound (P1) represented by formula (6) Since the radically polymerizable compound (P1) represented by formula (6) functions as a surfactant, by adding ( P1) When used as a raw material, the radical copolymer functions as a surfactant, and even without adding a surfactant separately, the flatness, adhesion to the base substrate, and coatability are improved. By adding the radically polymerizable compound (P1), the radical copolymerization polymer is easily manifested on the film surface.

In the present invention, in the radically polymerizable compound (P1) represented by formula (6), it is preferable that R ⁵ is hydrogen or methyl, R ⁶ to R ⁹ are methyl groups, and R ¹⁰ is carbon number 1 to 10. A compound wherein m is an integer of 1 to 5, and n is an integer of 1 to 150. More preferably, R ⁵ is a methyl group, R ⁶ to R ⁹ are methyl groups, R ¹⁰ is a butyl group, m is 3, and n is an integer of 1 to 150. In addition, it is more preferable that n is 30 to 150 An integer of 70, particularly preferably n is an integer of 50-70. The weight average molecular weight of the radically polymerizable compound (P1) represented by formula (6) is preferably 500 to 8,000.

The radically polymerizable compound (P1) represented by formula (6) can be produced by a known method. In addition, commercially available items can also be used. For example, FM-0711, FM-0721, FM-0725 (all are trade names; JNC Co., Ltd.) etc. are mentioned.

1-3-9-2. Radical polymerizable compound (P2) having an alkoxysilyl group In the present invention, a compound having an alkoxysilyl group is used as a raw material for obtaining the radical copolymer Radical polymerizable compound (P2). A preferred radical polymerizable compound (P2) is selected from 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3 -(Meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethyl One or more of the group consisting of oxysilane and p-styryltrimethoxysilane. Among these radically polymerizable compounds, 3-(meth)acryloxypropyltrimethoxysilane and 3-(meth)acryloxypropyltriethoxysilane are preferable because of their good flatness. By using (P2), transparency, chemical resistance, etc. improve. In addition, due to the silane coupling effect, the adhesion to the base material is improved.

1-3-9-3. Radical polymerizable compound (P3) having at least one of epoxy group, carboxyl group, and hydroxyphenyl group In the present invention, as a raw material for obtaining the radical copolymerization polymer, A radically polymerizable compound (P3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group. A preferred free radical polymerizable compound (P3) is selected from glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, (meth)acrylic acid, 4-hydroxyphenylethylene More than one of the group consisting of base ketones. (P3) functions as a polymer crosslinking agent, and contributes to improvement of heat resistance, chemical resistance, and the like.

1-3-9-4. The method for producing a radical copolymer polymer. The radical copolymer polymer is obtained by combining a radical polymerizable compound (P1) represented by formula (6) and a free radical having an alkoxysilyl group. It is obtained by radical copolymerization of a radically polymerizable compound (P2) and a radically polymerizable compound (P3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group. The method for producing the radical copolymer is not particularly limited, and the radical copolymer can be produced by heating the above radical polymerizable compounds in the presence of a radical initiator. As a radical initiator, an organic peroxide, an azo compound, etc. can be used. The reaction temperature of the radical copolymerization is not particularly limited, but is usually in the range of 50°C to 150°C. The reaction time is also not particularly limited, and is usually in the range of 1 hour to 48 hours. In addition, the reaction can also be carried out under any pressure of increased pressure, reduced pressure or atmospheric pressure.

The solvent used in the radical copolymerization reaction is preferably a solvent that dissolves the produced polymer. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl Methyl oxyacetate, 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, methyl 2-methoxypropionate, 2-methoxy ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, 2 -Hydroxy-2-methylpropionate ethyl ester, 2-methoxy-2-methylpropionate methyl ester, 2-ethoxy-2-methylpropionate ethyl ester, methyl pyruvate, ethyl pyruvate Esters, Propyl pyruvate, Methyl acetoacetate, Ethyl acetoacetate, Methyl 2-oxobutyrate, Ethyl 2-oxobutyrate, 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, two Ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ether. The solvent may be one of these solvents, or a mixture of two or more of these solvents.

The radical copolymer used in the present invention can be prepared as a radical copolymer solution in consideration of operability etc. by leaving the solvent used in the polymerization as it is, or it can be prepared by removing the solvent. Solid free radical copolymers ranging from portability etc.

When the weight-average molecular weight of the radical copolymer polymer obtained by GPC analysis using polystyrene as a standard is in the range of 1,000 to 50,000, film-forming properties are good, which is preferable. Furthermore, if the weight average molecular weight is the range of 2,500-20,000, since the flatness of a cured film becomes favorable, it is more preferable. Furthermore, since the flatness and chemical resistance of a cured film are favorable in the range of 2,500-15,000 weight average molecular weights, it is especially preferable.

Other additives are added and used in an amount of 0.1 to 20 parts by weight based on the total amount of the thermosetting composition.

1-4. Solvent A solvent may also 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 polyester amide acid (A), epoxy compound (B), and the like. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl Methyl oxyacetate, ethyl ethoxyacetate, 3-methoxybutyl acetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2 -Methyl methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate , methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 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 mono Butyl 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 ether, polyethylene glycol, polypropylene glycol. The solvent may be one of these solvents, or a mixture of two or more of these solvents.

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 of the composition over time becomes good. If the storage temperature is -20°C to 10°C, no precipitates will exist, which is more preferable.

2. Cured film of thermosetting composition The thermosetting composition of the present invention can be obtained by mixing polyester amide acid (A) having a polymerizable double bond and epoxy compound (B), According to the target characteristics, epoxy hardeners, solvents, surfactants, adhesion enhancers, antioxidants and other additives are optionally added, and these compounds are uniformly mixed and dissolved.

When the thermosetting composition prepared as described above (in the case of a solvent-free solid state, after being dissolved in a solvent) is applied on the surface of a substrate, and the solvent is removed by heating, for example, a coating film can be formed . Coating of the thermosetting composition on the surface of the substrate can be performed by conventionally known methods such as spin coating, roll coating, dipping, and slit coating to form a coating film. Next, the coating film is temporarily fired on a hot plate, an oven, or the like. Temporary firing conditions vary depending on the type and blending ratio of each component, usually at 70°C to 150°C, for 5 minutes to 15 minutes if an oven is used, and for 1 minute to 5 minutes if a heating plate is used. Thereafter, main firing is carried out in order to harden the coating film. The formal firing conditions vary depending on the type and blending ratio of each component, usually at 180°C to 250°C, preferably at 200°C to 250°C, for 30 minutes to 90 minutes if an oven is used, and for 30 minutes if a heating plate is used. A cured film can be obtained by heat-processing for 5 minutes - 30 minutes.

When the cured film obtained in the above manner is heated, further, 1) the polyamic acid part of the polyesteramic acid (A) is dehydrated and cyclized to form an imide bond, and 2) the carboxylic acid of the polyesteramic acid It reacts with epoxy group-containing polymers to increase its molecular weight, so it is very tough, and has excellent transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and sputtering resistance. Therefore, when the cured film of this invention is used as a protective film for color filters, it is effective, and a liquid crystal display element or a solid-state imaging element can be manufactured using a color filter. In addition to the protective film for color filters, if the cured film of the present invention is used as a transparent insulating film formed between a thin film transistor (Thin Film Transistor, TFT) and a transparent electrode or a transparent insulating film formed between a transparent electrode and an alignment film Film and use, it is effective. Furthermore, even if the cured film of this invention is used as a protective film of a light emitting diode (Light Emitting Diode, LED) light-emitting body, it is effective. [Example]

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

The components indicated by the abbreviations in Tables 1 to 4 are as follows. PGMEA: Propylene glycol monomethyl ether acetate as solvent MMP: Methyl 3-methoxypropionate as 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; Chuanyuan Chemical Co., Ltd.) Epoxy ester 70PA: Acrylic modified propylene glycol diglycidyl ether Substance (trade name; Kyoeisha Chemical Co., Ltd.) DDS: 3,3'-diaminodiphenylsulfone M-402: Aronix M-402 (commercial product) which is a compound having a polymerizable double bond Toagosei Co., Ltd.) VG3101L: TECHMORE VG3101L (trade name; Printec Co., Ltd.) as an epoxy compound TMA: trimellitic anhydride as an epoxy hardener C11Z: as a ring 2-Undecylimidazole 2P4MZ as an oxygen hardener: 2-Phenyl-4-methylimidazole S510 as an epoxy hardener: Sila-Ace S510 (trade name; JNC Co., Ltd.) MP-200: COATOSIL MP-200 (trade name; Momentive Performance Materials Japan Co., Ltd.) as an epoxy compound AO-60: ADK STAB AO-60 (trade name; ADEKA Co., Ltd.) as an antioxidant DS-21: Megafac DS-21 (trade name) as a surfactant ; Di Aisheng (DIC) Co., Ltd.

[Synthesis Example 1] Synthesis of Polyester Amino Acid (A1) Solution In a four-necked flask with a stirrer, dehydrated and purified PGMEA, BT-100, SMA1000P, benzyl alcohol, methanol 2-hydroxyethyl acrylate and 1,4-butanediol were stirred under dry nitrogen flow at 125°C for 2 hours (the first stage of synthesis). PGMEA 42.81 g BT-100 3.04 g SMA1000P 14.45 g Benzyl Alcohol 3.31 g 2-Hydroxyethyl Methacrylate 1.33 g 1,4-Butanediol 0.92 g

Thereafter, the reaction liquid was cooled to 25° C., DDS and PGMEA were charged in the following weights, stirred at 20° C. to 30° C. for 2 hours, and then stirred at 125° C. for 1 hour (the second stage of synthesis). DDS 0.95 g PGMEA 7.02 g [Z/Y=2.7, (Y+Z)/X=0.9]

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

[Synthesis Example 2～Synthesis Example 6] The synthesis of polyester amide acid (A2)～polyester amide acid (A6) solution is based on the method of synthesis example 1, with the temperature, time and ratio recorded in Table 1 (unit: g) Each component is reacted to obtain a polyester amide acid solution.

Table 1

[Comparative Synthesis Example 1 and Comparative Synthesis Example 2] The synthesis of polyester amide acid (a1) and polyester amide acid (a2) solution is based on the method of synthesis example 1, with the temperature, time and ratio recorded in Table 2 ( Unit: g) Each component was reacted to obtain a polyester amide acid solution.

各試劑及溶劑的裝入量的單位為克（g）Table 2

The unit of loading amount of each reagent and solvent is gram (g)

[Example 1] The 30% by weight solution of polyester amide acid (A1) obtained in Synthesis Example 1, 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.

[Example 2-Example 8 and Comparative Example 1-Comparative Example 3] According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) described in Table 3 and Table 4 to obtain a thermosetting composition thing.

裝入量的單位為克（g）table 3

The unit of load is grams (g)

裝入量的單位為克（g）Table 4

The unit of load is grams (g)

Using the thermosetting compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3, a cured film was produced by the method described below, and scratch resistance, barrier properties, transparency, flatness. Table 5 shows the evaluation results of the cured films of Examples 1 to 8, and Table 6 shows the evaluation results of the cured films of Comparative Examples 1 to 3.

[Evaluation method of scratch resistance] A thermosetting composition 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. Then, it 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 the 8.4.1 pencil scratch test of JIS K-5400-1990 to measure the pencil hardness of the cured film, and the results are shown in Table 5 and Table 6 . When the pencil hardness was 3H or more, it was evaluated as scratch resistance ◯, and when it was 2H or less, it was evaluated as scratch resistance ×.

[Evaluation method of barrier properties] The 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. Using a proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.), 70 mJ/cm ² was irradiated with all radiometers. Post-baking in an oven at 200° C. for 20 minutes to obtain a glass substrate with a color resist. Then, using a UV ashing device (PHOTO SURFACE PROCESSOR) (abbreviated as PSP) PL2003N-12 manufactured by Sen (SEN) Special Light Source Co., Ltd., low-pressure mercury lamp), the color resist was treated. The glass substrate was cleaned by UV irradiation. The amount of UV irradiation here was 1000 mJ/cm ² . The thermosetting composition was spin-coated on the glass substrate with the color resist at 400 rpm for 10 seconds, and prebaked on a heating plate at 90° C. for 2 minutes. Then, it post-baked in oven at 230 degreeC for 30 minutes, and obtained the glass substrate which laminated|stacked the cured film and the color resist with a film thickness of 1.0 micrometers. The obtained laminated substrate was heated on a hot plate at 80° C., and 0.2 mL of NMP was added dropwise. Immediately after the dropwise addition, it was covered with a cover glass, and heated for 40 minutes with an 80° C. hot plate in this state. Take out the stacked substrate and recover NMP. In addition, the used laminated substrate was washed with 10 mL of NMP, and the cleaning solution was also collected. The separately recovered NMPs were collected, and the transmittance was measured with a UV-Vis-NIR spectrophotometer (trade name: V-670, JASCO Corporation). A baseline was drawn at 400 nm to 800 nm, and within the above range, a case where the extremely small transmittance was 90% or more was evaluated as a barrier property ○, and a case where the transmittance was less than 90% was evaluated as a barrier property ×.

[Evaluation method of transparency] A thermosetting composition 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. Then, it 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 a cured film, the transmittance of the cured film alone at a wavelength of 400 nm was measured using a UV-Vis-NIR spectrophotometer (trade name; V-670, JASCO Corporation) . The case where the transmittance was 95% or more was evaluated as transparency (circle), and the case where the transmittance was less than 95% was evaluated as transparency x.

[Evaluation method of flatness] Spin-coat a thermosetting composition at 300 rpm for 10 seconds on a color filter substrate without a hardened film having pixels including R, G, and B pixels, and heat it on a heating plate at 90°C Pre-bake for 2 minutes. Then, it post-baked in an oven at 230° C. for 30 minutes to obtain a color filter substrate with a cured film having an average film thickness of the protective film of 1.5 μm. Then, about the obtained color filter board|substrate with a cured film, the surface level difference was measured using the micro shape measuring apparatus, and Table 5 and Table 6 show the result. The case where the maximum step difference was 0.2 μm or less was evaluated as flatness ◯, and the case where the maximum step difference was 0.21 μm or more was evaluated as flatness ×. In addition, for color filter substrates without a hardened film, those with a maximum step difference of 1 μm are used.

table 5

Table 6

From the results shown in Table 5, it is clear 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 turned out that the scratch resistance of the cured film produced from the thermosetting composition of the comparative example 1 which used the polyester amide acid which does not contain the compound which has a polymerizable double bond was inferior. In addition, it was found that the scratch resistance and barrier properties of the cured films prepared from the thermosetting compositions of Comparative Example 2 and Comparative Example 3 to which a compound having a polymerizable double bond was subsequently added were insufficient.

INDUSTRIAL APPLICABILITY The cured film obtained from the thermosetting composition of the present invention has high flatness and high scratch resistance, and can be used as a color filter, an LED light-emitting element, and a light-receiving film. Protective films for various optical materials such as devices, and insulating films formed between TFTs and transparent electrodes and between transparent electrodes and alignment films.

none

none

Claims (11)

A kind of thermosetting composition, it is characterized in that, comprises and is made up of polyester amide acid (A), epoxy compound (B), solvent and additive by polymerizable double bond, and described additive is made of surfactant, even At least one of the group consisting of coupling agent, antioxidant and epoxy hardener, and the polyester amide acid (A) is derived from the following formula (1) and formula (2). A reaction product of raw materials of molar tetracarboxylic dianhydride, Y molar diamine, and Z molar polyhydroxy compound, at least one of which has a polymerizable double bond, 0.2≦Z/Y≦8.0. ． ． ． ． ． ． (1) 0.2≦(Y+Z)/X≦5.0． ． ． (2), described polyester amide acid (A) comprises the structural unit represented by following formula (3) and the structural unit represented by 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. ^R3 is a residue formed by removing two -OH from a polyhydric hydroxyl compound, at least one of ^R3 has a polymerizable double bond, wherein compared to the polyester amide acid (A ) 100 parts by weight, the content of the epoxy compound (B) is 20 parts by weight ~ 400 parts by weight. A kind of thermosetting composition, it is characterized in that, comprises and is made up of polyester amide acid (A), epoxy compound (B), solvent and additive by polymerizable double bond, and described additive is made of surfactant, even At least one of the group consisting of coupling agent, antioxidant and epoxy hardener, and the polyester amide acid (A) is derived from the following formula (1) and formula (2). A reaction product of raw materials of molar tetracarboxylic dianhydride, Y molar diamine, Z molar polyhydroxy compound and monohydroxy compound, at least one of which has a polymerizable double bond, 0.2≦Z/Y ≦8.0． ． ． ． ． ． ． (1) 0.2≦(Y+Z)/X≦5.0． ． ． (2), the polyester amide acid (A) comprises the structural unit represented by the following formula (3), the structural unit represented by the following formula (4) and the structural unit represented by the following 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 a residue obtained by removing two -CO-O-CO- from diamine. ^A residue formed by one _-NH2 , ^R3 is a residue obtained by removing two -OH from a polyhydroxy compound, R4 is a residue obtained by removing one -OH from a monohydroxy compound, at least one of ^R3 It has a polymerizable double bond, wherein the content of the epoxy compound (B) is 20 parts by weight to 400 parts by weight relative to 100 parts by weight of polyester amide acid (A) having a polymerizable double bond. The thermosetting composition according to claim 2, wherein R ⁴ has a polymerizable double bond. The thermosetting composition as described in any one of items 1 to 3 in the scope of the patent application, wherein the polyhydric hydroxyl compound is selected from the group consisting of 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'-bis Hydroxydicyclohexyl, tris(2-hydroxyethyl)isocyanurate, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-(4-hydroxyphenyl)ethanol and polyhydric hydroxyl groups with polymerizable double bonds At least one compound in the group consisting of compounds must contain a polyhydric hydroxyl compound having a polymerizable double bond. The thermosetting composition according to claim 4, wherein the polyhydric hydroxyl compound having a polymerizable double bond has a vinyl group, an allyl group or a (meth)acryloxy group. The thermosetting composition as described in item 4 of the scope of the patent application, wherein the polyhydric hydroxyl compound having a polymerizable double bond is selected from glycerin mono(meth)acrylate, trimethylolpropane mono(methyl ) acrylate, pentaerythritol mono(meth)propylene ester, pentaerythritol di(meth)acrylate, dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate ester, sorbitol mono(meth)acrylate, sorbitol di(meth)acrylate, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, ethylene glycol di Glycidyl ether modified (meth)acrylic acid, propylene glycol diglycidyl ether (meth)acrylic modified, tripropylene glycol diglycidyl ether (meth)acrylic modified, glycerin diglycidyl ether (methyl) ) acrylic modified substance, (meth)acrylic modified substance of bisphenol A diglycidyl ether, (meth)acrylic modified substance of bisphenol A diglycidyl ether modified with propylene oxide, and each molecule contains two or more At least one compound in the group consisting of (meth)acrylic modified substances of epoxy-based compounds. The thermosetting composition as described in item 2 or item 3 of the scope of the patent application, wherein the monohydroxy compound is selected from isopropanol, benzyl alcohol, propylene glycol monoethyl ether, 3-ethyl-3-hydroxymethyl At least one compound selected from the group consisting of oxetane and a monohydroxyl compound having a polymerizable double bond. The thermosetting composition according to claim 7, wherein the monohydroxyl compound having a polymerizable double bond has a vinyl group, an allyl group or a (meth)acryloxy group. The thermosetting composition as described in item 7 of the scope of the patent application, wherein the monohydroxyl compound having a polymerizable double bond is selected from furfuryl alcohol, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, aniline p-hydroxy(meth)acrylate, 1,4- Cyclohexanedimethanol mono(meth)acrylate, 3-(2-hydroxyphenyl)(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate , pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and (meth)acrylic modified substances of compounds containing one epoxy group per molecule at least one compound. A cured film, characterized in that it is a cured film of a thermosetting composition as described in any one of claims 1 to 9. A color filter characterized in that it has the hardened film as described in claim 10 as a transparent protective film.