JP2017061680A - Thermosetting composition - Google Patents

Abstract

An object of the present invention is to provide excellent heat resistance, flatness, heat resistance, chemical resistance such as solvent resistance, acid resistance and alkali resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, scratch resistance, and coating. To provide a cured film which is excellent in properties and a composition which gives the cured film. A composition comprising a polyester amide acid, an epoxy compound having a siloxane bonding site, an epoxy compound having no siloxane bonding site, and an epoxy curing agent, wherein the polyester amide acid is a tetracarboxylic dianhydride, a diamine, And a thermosetting composition obtained by reacting a polyvalent hydroxy compound as an essential raw material component. [Selection diagram] None

Description

  The present invention relates to thermosetting 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, or a protective film for a color filter. The present invention relates to a conductive composition, a transparent film thereby, and an electronic component having the film.

  During 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 when the wiring electrode is formed by sputtering, the surface is locally heated to a high temperature. Sometimes. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and 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 underlying substrates such as glass, transparency, scratch resistance, applicability, flatness, light resistance Etc. are required. In addition, liquid crystal display elements are required to have improved planarization characteristics when used as a color filter protective film as the performance of liquid crystal display elements increases, such as higher viewing angle, faster response, and higher definition. .

  With respect to light resistance, UV ozone treatment has been carried out for cleaning the surface of the protective film so far. However, in particular, in recent years, the color filter protective film for the transverse electric field mode requires higher energy UV ozone treatment to improve the coating property of the photo spacer. Ultraviolet exposure processes such as a photo-alignment process of an alignment film are increasing, and light resistance is a very important characteristic.

  Examples of the protective film material having these excellent properties include a silicon-containing polyamic acid composition (see Patent Document 1) and a polyester amic acid composition (see Patent Document 2 and Patent Document 3). Although the silicon-containing polyamic acid composition has good flatness, the heat resistance is insufficient and the alkali resistance is inferior. The polyester amide acid composition of Patent Document 2 has a drawback of insufficient flatness and heat resistance. The polyester amide acid composition of Patent Document 3 is a material with excellent flatness, heat resistance, and chemical resistance, but has insufficient light resistance, and transparency is lowered in UV ozone treatment and ultraviolet exposure process. There was a drawback of doing. Accordingly, none of the materials satisfy the light resistance, flatness, heat resistance, chemical resistance, and other characteristics as protective film materials.

JP-A-9-291150 JP 2005-105264 A JP 2008-156546 A

  The object of the present invention is excellent in heat resistance, chemical resistance such as solvent resistance / acid resistance / alkali resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, scratch resistance, and coatability. An object of the present invention is to provide an electronic component having a cured film excellent in flatness and light resistance and a composition that provides the cured film.

As a result of intensive studies to solve the above problems, the inventors of the present invention have obtained a polyester amic acid obtained from the reaction of a compound containing tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound, an epoxy compound having a siloxane bonding site, It has been found that the above object can be achieved by a composition containing an epoxy compound having no siloxane bonding site and an epoxy curing agent, and a cured film obtained by curing the composition, and has completed the present invention. .
The present invention includes the following configurations.

（Ｒ^１はテトラカルボン酸二無水物残基であり、Ｒ^２はジアミン残基であり、Ｒ^３は多価ヒドロキシ化合物残基である。） [1] A composition comprising a polyester amide acid, an epoxy compound having a siloxane bond site, an epoxy compound having no siloxane bond site, and an epoxy curing agent;
The polyester amic acid is a reaction product from a raw material which essentially comprises a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound,
The raw material contains X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compounds in a ratio such that the relationship of the following formulas (1) and (2) is satisfied,
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
The polyester amide acid has structural units represented by the following general formulas (3) and (4);
The total of the epoxy compound having the siloxane bond site and the epoxy compound not having the siloxane bond site is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amic acid;
0 to 60 parts by weight of the epoxy curing agent for a total of 100 parts by weight of the epoxy compound; and
The thermosetting composition whose ratio of the epoxy compound which has the said siloxane bond part in the total amount of the said epoxy compound is 0.5 to 70 weight%.

(R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue.)

[2] The thermosetting composition according to item [1], wherein the raw material of the polyester amide acid further contains a monohydric alcohol.

[3] The monohydric alcohol is one or more selected from isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane, [2] The thermosetting composition according to item.

[4] The thermosetting composition according to any one of [1] to [3], wherein the raw material of the polyester amide acid further contains a styrene-maleic anhydride copolymer.

[5] The thermosetting composition according to any one of [1] to [4], wherein the polyesteramidic acid has a weight average molecular weight of 1,000 to 200,000.

[6] The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2, Selected from 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate) The thermosetting composition according to any one of [1] to [5], which is one or more of the above.

[7] Any one of [1] to [6], wherein the diamine is at least one selected from 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone. The thermosetting composition described in 1.

[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, And the thermosetting composition according to any one of [1] to [7], which is at least one selected from tris (2-hydroxyethyl) isocyanurate.

（Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立して水素、水酸基、炭素数１〜２６の有機基、またはエポキシ基を有する有機基であり、Ｒ^７はそれぞれ独立して水素、炭素数１〜２６の有機基、またはエポキシ基を有する有機基であり、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７の少なくとも１つがエポキシ基を有する有機基であり、ｍは２以上の整数であり、Ｒ^４またはＲ^５が異なるＳｉに結合したＲ^４またはＲ^５と結合してシロキサン環を形成していてもよく、そして、Ｒ^６及びＲ^７が結合してシロキサン環を形成していてもよい。）

（Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１はそれぞれ独立して水素または炭素数１〜２６の有機基であり、Ｒ^１２及びＲ^１３はそれぞれ独立して水素、炭素数１〜２６の有機基またはエポキシ基を有する有機基であり、Ｒ^１２及びＲ^１３の少なくとも１つがエポキシ基を有する有機基であり、ｎは１以上の整数であり、Ｒ^８またはＲ^９が異なるＳｉに結合したＲ^８、Ｒ^９、Ｒ^１０、またはＲ^１１と結合してシロキサン環を形成していてもよく、そして、Ｒ^１０またはＲ^１１が異なるＳｉに結合したＲ^８、Ｒ^９、Ｒ^１０、またはＲ^１１と結合してシロキサン環を形成していてもよい。） [9] The epoxy compound having a siloxane bond site is at least one selected from the group of compounds represented by the following formulas (5) and (6), according to any one of [1] to [8] Thermosetting composition.

(R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, a hydroxyl group, an organic group having 1 to 26 carbon atoms, or an organic group having an epoxy group, and R ⁷ is independently hydrogen, 1 to carbon atoms, 26 organic groups having an epoxy group, at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is an organic group having an epoxy group, m is an integer of 2 or more, and R ⁴ Alternatively, R ⁵ may be bonded to R ⁴ or R ⁵ bonded to different Si to form a siloxane ring, and R ⁶ and R ⁷ may be bonded to form a siloxane ring.)

(R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently hydrogen or an organic group having 1 to 26 carbon atoms, and R ¹² and R ¹³ are each independently hydrogen, an organic group having 1 to 26 carbon atoms. or an organic group having an epoxy group, at least one of R ¹² and R ¹³ is an organic group having an epoxy group, n is an integer of 1 or more, R ⁸ where R ⁸ or R ⁹ is bonded to different Si may form a siloxane ring bonded to ^{R 9, R 10} or ^{R 11,, and, R} 8 ^{to R 10} or ^{R 11} are bonded to different ^Si, R ^{9, R 10} or ^{R 11,} and It may be bonded to form a siloxane ring.)

[10] The epoxy compound having a siloxane bonding site is 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane, 1,3-bis (3-glycidoxypropyl) tetramethyl. A copolymer which is a reaction product from a raw material comprising disiloxane, 3-glycidoxypropyltrimethoxysilane, and a raw material comprising 3-glycidoxypropyltrimethoxysilane, phenyltrimethoxysilane and trimethylmethoxysilane. The thermosetting composition according to any one of [1] to [9], which is at least one selected from the group consisting of copolymers that are reaction products.

[11] The epoxy curing agent according to any one of [1] to [9], wherein the epoxy curing agent is at least one selected from trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole. Thermosetting composition.

[12] The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride or 1,2,3,4-butanetetracarboxylic dianhydride;
The diamine is 3,3′-diaminodiphenyl sulfone;
The polyvalent hydroxy compound is 1,4-butanediol;
A copolymer having a weight average molecular weight of 1,000 to 200,000, wherein the epoxy compound having a siloxane bonding site is a reaction product from a raw material containing 3-glycidoxypropyltrimethoxysilane;
An epoxy compound having no siloxane bonding site is 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4-1,1-bis [4-([2,3-epoxypropoxy] phenyl) ethyl. ] Phenyl] propane;
The epoxy curing agent is trimellitic anhydride or 2-undecylimidazole;
The thermosetting composition according to item [1], further containing methyl 3-methoxypropionate or propylene glycol monomethyl ether acetate as a solvent.

[13] A cured film obtained from the thermosetting composition according to any one of [1] to [12].

[14] A color filter using the cured film according to the item [13] as a protective film.

[15] A liquid crystal display device using the color filter according to the item [14].

[16] A solid-state imaging device using the color filter according to the item [14].

[17] A liquid crystal display device using the cured film according to the item [13] as a transparent insulating film formed between the TFT and the transparent electrode.

[18] A liquid crystal display device using the cured film according to the item [13] as a transparent insulating film formed between the transparent electrode and the alignment film.

[19] A touch panel device using the cured film according to the item [13] as a transparent insulating film formed on the transparent electrode.

[20] An LED light emitter using the cured film according to the item [13] as a protective film.

  The thermosetting composition according to a preferred embodiment of the present invention is a material particularly excellent in flatness and light resistance, and improves the display quality and reliability when used as a color filter protective film of a color liquid crystal display element. Can do. Further, the cured film obtained by heating the thermosetting composition according to a preferred embodiment of the present invention is well balanced in transparency, chemical resistance, adhesion and sputtering resistance, and is very It is highly practical. 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.

1. Thermosetting composition The thermosetting composition of the present invention is a polyester amic acid obtained by reacting tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound as essential raw material components, an epoxy having a siloxane bonding site. A composition comprising a compound, an epoxy compound having no siloxane bond site, and an epoxy curing agent. In this composition, the total of the epoxy compound having a siloxane bond site and the epoxy compound having no siloxane bond site is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amide acid, On the other hand, the epoxy curing agent is 0 to 60 parts by weight, and the ratio of the epoxy compound having a siloxane bonding site in the total amount of the epoxy compound is 0.5 to 70% by weight. The thermosetting composition of the present invention may further contain other components other than those described above as long as the effects of the present invention are obtained.

1-1. Polyester amide acid Polyester amide acid is obtained by reacting tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound as essential raw material components. More specifically, X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compound are reacted at a ratio such that the relationship of the following formulas (1) and (2) is established. Is obtained.

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、好ましくは炭素数２〜３０の有機基である。Ｒ^２はジアミンから２つの−ＮＨ_２を除いた残基であり、好ましくは炭素数２〜３０の有機基である。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、好ましくは炭素数２〜２０の有機基である。 The polyester amide acid has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4).

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

  At least a solvent is required for the synthesis of the polyester amide acid, and this solvent may be left as it is, and it may be a liquid or gel thermosetting composition in consideration of handling properties. It is good also as a solid composition which considered etc. In addition, the synthesis of the polyester amide acid may contain, as necessary, one or more compounds selected from a monohydroxy compound and a styrene-maleic anhydride copolymer as a raw material. It preferably contains a hydroxy compound. In addition, the synthesis of the polyester amic acid may contain other compounds than the above as a raw material as necessary, as long as the object of the present invention is not impaired.

1-1-1. Tetracarboxylic dianhydride In the present invention, tetracarboxylic dianhydride is used as a material for obtaining the polyester amide acid. Specific examples of preferred tetracarboxylic dianhydrides include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2, 3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfonetetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Diphenyl ether tetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1 2,3,4-butanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, Shin Nippon Rika Co., Ltd.), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetra Mention may be made of carboxylic dianhydrides, cyclopentanetetracarboxylic dianhydrides, cyclohexanetetracarboxylic dianhydrides, ethanetetracarboxylic dianhydrides, and butanetetracarboxylic dianhydrides. One or more of these can be used.

  Among these, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, which gives good transparency, 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and TMEG-100 are more preferred, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride are particularly preferred. .

1-1-2. Diamine In the present invention, a diamine is used as a material for obtaining a polyester amide acid. Specific examples of preferred diamines include 4,4′-diaminodiphenylsulfone, 3,3′-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, Mention may be made of [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane. One or more of these can be used.

  Among these, 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone that give good transparency are more preferable, and 3,3′-diaminodiphenylsulfone is particularly preferable.

1-1-3. Polyvalent hydroxy compound In the present invention, a polyvalent hydroxy compound is used as a material for obtaining polyester amide acid. Specific examples of preferable polyvalent hydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, weight Polypropylene glycol having an average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentane Diol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1, 7 Heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-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-dodecane Diol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, isocyanuric acid tris (2-hydroxyethyl), bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxy Phenyl) sulfone), bisphenol F (bis (4-hydro) Shifeniru) methane) can be exemplified diethanolamine, and triethanolamine. One or more of these can be used.

  Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 have good solubility in solvents. -Octanediol and tris (2-hydroxyethyl) isocyanurate are more preferred, and 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol are particularly preferred.

1-1-4. Monohydroxy Compound In the present invention, a monohydroxy compound may be used as a material for obtaining polyester amide acid. By using a monohydroxy compound, the storage stability of the thermosetting composition is improved. Specific examples of preferable monohydroxy compounds include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene. Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltol, linalool, terpineol, dimethylbenzyl carbinol, and 3-ethyl-3-hydroxymethyloxetane Can be mentioned. One or more of these can be used.

  Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane is more preferable. Compatibility with polyester amic acid produced using these, epoxy compounds with siloxane bonding sites, epoxy compounds without siloxane bonding sites, and epoxy curing agents, and on color filters of thermosetting compositions In consideration of applicability to benzyl alcohol, it is particularly preferable to use benzyl alcohol for the monohydroxy compound.

  The monohydroxy compound is preferably reacted 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 polyesteramic acid used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups to the above raw material. Polyester amide acid synthesized by adding a compound having 3 or more acid anhydride groups is preferred because improvement in transparency is expected. Examples of the compound having 3 or more acid anhydride groups include a styrene-maleic anhydride copolymer. About the ratio of each component which comprises a styrene-maleic anhydride copolymer, the molar ratio of styrene / maleic anhydride is 0.5-4, Preferably it is 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 having good heat resistance and alkali resistance is particularly preferable.

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

1-1-6. Aminosilane compound having one amino group In the synthesis of the polyester amide acid, other raw materials other than those described above may be included as necessary within the range not impairing the object of the present invention. Examples of the raw material include aminosilane compounds having one amino group. The aminosilane compound having one amino group is used to introduce a silyl group at the terminal by reacting with the terminal acid anhydride group of the polyester amic acid. When the thermosetting composition of the present invention containing the polyester amide acid obtained by adding and reacting an aminosilane compound having one amino group is used, the acid resistance of the obtained coating film is improved. Furthermore, when making it react by the structure of the monomer mentioned above, both the monohydroxy compound and the aminosilane compound which has one amino group can also be added and made to react.

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

  Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane that improve the acid resistance of the coating film are more preferable, and 3-aminopropyltriethoxysilane is particularly preferable from the viewpoint of acid resistance and compatibility. .

  The aminosilane compound having one amino group is preferably contained in an amount of 0 to 300 parts by weight 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.

1-1-7. Solvents used in the synthesis reaction of polyester amide acid Specific examples of solvents used in the synthesis reaction to obtain polyester amide acid include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether. Mention may be made of acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetamide. Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ethyl ether is preferable.

1-1-8. Polyester amide acid synthesis method In the polyester amide acid synthesis method used in the present invention, tetracarboxylic dianhydride X mole, diamine Y mole, and polyhydric hydroxy compound Z mole are reacted in the solvent. At this time, it is preferable that X, Y, and Z are set to such a ratio that the relationship of the following formulas (1) and (2) is established between them. Within this range, the solubility of the polyester amide acid in the solvent is high, so that the coating property of the composition is improved, and as a result, a cured film having excellent flatness can be obtained.

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

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 polyester amic acid used in the present invention, the molecule having an acid anhydride group (—CO—O—CO—) at the terminal is formed at the terminal under the condition where X is excessively used relative to Y + Z in the above reaction conditions. It is thought that it is produced in excess of molecules having amino groups or hydroxyl groups. In the case of reacting in such a monomer structure, the monohydroxy compound described above can be added, if necessary, in order to react with the acid anhydride group at the molecular terminal to esterify the terminal. The polyester amic acid obtained by adding and reacting the monohydroxy compound has improved compatibility with the epoxy compound and the epoxy curing agent, and the applicability of the thermosetting composition of the present invention containing them is improved. 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 of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound, since 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 reaction raw materials to the reaction system is not particularly limited. That is, a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound are simultaneously added to the reaction solvent. After the diamine and the polyvalent hydroxy compound are dissolved in the reaction solvent, the tetracarboxylic dianhydride is added. After reacting acid dianhydride and polyvalent hydroxy compound in advance, diamine is added to the reaction product, or after reacting tetracarboxylic dianhydride and diamine in advance, polyhydric hydroxy is added to the reaction product. Any method such as adding a compound can be used.

  When the aminosilane compound having one amino group is reacted, after the reaction of the tetracarboxylic dianhydride, the diamine and the polyvalent hydroxy compound is completed, the reaction solution is cooled to 40 ° C. or lower, An aminosilane compound having one group may be added and reacted at 10 to 40 ° C. for 0.1 to 6 hours. The monohydroxy compound may be added at any point in the reaction.

  The polyester amide acid synthesized in this way contains the structural unit represented by the formula (3) and the structural unit represented by the formula (4), and the terminal thereof is a tetracarboxylic dianhydride or diamine as a raw material. Alternatively, it is an acid anhydride group, amino group or hydroxy group derived from a polyvalent hydroxy compound, or an additive other than these compounds constitutes the terminal. By including such a configuration, curability is improved.

  The resulting polyester amic acid preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 3,000 to 50,000. If it exists in these ranges, flatness and heat resistance will become favorable.

  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). Standard polystyrene is polystyrene having a molecular weight of 645 to 132900 (for example, polystyrene calibration kit PL2010-0102 of Agilent Technologies), and PLgel MIXED-D (Agilent Technology) is used for the column as a mobile phase. It can be measured using THF. In addition, the weight average molecular weight of the commercial item in this specification is a catalog publication value.

1-2. Epoxy Compound As the epoxy compound used in the present invention, an epoxy compound having a siloxane bond site and an epoxy compound having no siloxane bond site are used. The epoxy compound having a siloxane bond site is an epoxy compound having no siloxane bond site, which will be described later, without impairing the effects of the present invention, that the ratio of the epoxy compound in the total amount of the epoxy compound is 0.5 to 70% by weight. This is preferable from the viewpoint of developing the characteristics.

1-2-1. Epoxy compound having a siloxane bond site The epoxy compound having a siloxane bond site used in the present invention is not particularly limited as long as it is compatible with the other components forming the thermosetting composition of the present invention. The epoxy compound having a siloxane bonding site is preferably at least one selected from the group of compounds represented by the following formulas (5) and (6).

In formula (5), R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, a hydroxyl group, an organic group having 1 to 26 carbon atoms, or an organic group having an epoxy group, and R ⁷ is independently hydrogen. , An organic group having 1 to 26 carbon atoms, or an organic group having an epoxy group, and at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is an organic group having an epoxy group. m is an integer of 2 or more, and R ⁴ or R ⁵ may be bonded to R ⁴ or R ⁵ bonded to different Si to form a siloxane ring, and R ⁶ and R ⁷ are bonded to each other. A siloxane ring may be formed.

The organic group having 1 to 26 carbon atoms in R ⁴ , R ⁵ and R ⁶ is linear alkyl, branched alkyl, cyclic alkyl, alkyl containing cyclic alkyl, aromatic ring, group containing aromatic ring, etc. Any methylene (CH ₂ ) in these groups may be replaced with a group containing O, NH, N, or a group containing Si, and any hydrogen in these groups may be replaced with fluorine. Also good.

  Specific examples of linear alkyl and branched alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert-pentyl, hexyl, 2,3-dimethylbutan-2-yl, octyl, 6-methylheptyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl.

  Specific examples of cyclic alkyl and alkyl including cyclic alkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, bicyclo [2.2.1] heptan-2-yl, bicyclo [2.2.1] hept. -5-en-2-yl, 2-cyclohexylethyl, 2- (cyclohex-3-en-1-yl) ethyl, 2-cycloheptylethyl, 2- (bicyclo [2.2.1] hept-5 -En-2-yl) ethyl, 3-cyclohexylpropyl, 4- (tert-butyl) cyclohexyl, and adamantyl.

  Specific examples of the aromatic ring and the group containing an aromatic ring are phenyl, benzyl, phenethyl, 4-isopropylphenyl, mesityl, 3,5-diethylphenyl, 4-isobutylphenyl, 2,6-diethylphenyl, naphthalen-2-yl 1,1′-biphenyl, 4 ′-(tert-butyl)-[1,1′-biphenyl] -4-yl, 2,4,6-triisopropylphenyl, 4′-heptyl- [1,1 ′ -Biphenyl] -4-yl, 12-((2-benzoylbenzoyl) oxy) dodecyl, and anthracen-9-yl.

Specific examples of said groups in which any methylene (CH ₂ ) is replaced with a group comprising O, N or Si are acetoxymethyl, 3-methoxy-3-oxopropyl, 3- (2-methoxyethoxy) propyl, 2,5,8,11-tetraoxatetradecan-14-yl, 2,5,8,11-tetraoxaheptadecan-17-yl, 11,11-dimethoxyundecyl, 2- (dimethylamino) ethyl, 2 -(Diethylamino) ethyl, tetrahydrofuran-3-yl, tetrahydro-2H-pyran-4-yl, 3-((tetrahydrofuran-3-yl) methoxy) propyl, 10- (1,3-dioxolan-2-yl) decyl 10- (1,3-dioxan-2-yl) decyl, morpholino, 4-methoxy-3,5-dimethylbenzyl, hydroxy Methyl, 2-hydroxyethyl, 3-hydroxypropyl, 1-carboxyethyl, 4-hydroxybutyl, 4-hydroxy-3-oxobutyl, trimethylsilyl, (trimethylsilyl) methyl, 3- (trimethylsilyl) propyl, 2- (2,4 , 4,6,6,8,8-heptamethyl-1,3,5,7-tetraoxa-2,4,6,8-tetrasilacyclooctane-2-yl) ethyl, 2- (dimethyl (phenyl) silyl ) Ethyl, methoxy, ethoxy, propoxy, isopropoxy, prop-1-en-2-yloxy, butoxy, tert-butoxy, sec-butoxy, isobutoxy, tert-pentyloxy, hexyloxy, 2-ethylbutoxy, (3- Methylpentyl) oxy, (2-methylhexane-2-yl) oxy Octyloxy, (2-ethylhexyl) oxy, decyloxy, 2-methoxyethoxy, 2-ethoxyethoxy, (1-methoxypropan-2-yl) oxy, 2- (2-methoxyethoxy) ethoxy, 2-butoxyethoxy, (3-ethylhexanoyl) oxy, dodecyloxy, tridecyloxy, hexadecyloxy, octadecyloxy, stearoyloxy, (butan-2-ylideneamino) oxy, (diethylamino) oxy, cyclohexyloxy, cyclooctyloxy, bicyclo [2 2.1] heptan-2-ylmethoxy, cyclononyloxy, (2-isopropyl-5-methylcyclohexyl) oxy, ((5-methyl-2- (prop-1-en-2-yl) cyclohexyl) oxy, (Octahydro-1H-4 7-methanoinden-5-yl) oxy, phenoxy, p-tolyloxy, m-tolyloxy, o-tolyloxy, o-carboxyphenoxy, benzyloxy, phenoxy, 3-phenylpropoxy, cinnamyloxy, 1-phenyl- (2- Ethoxy-2-oxo) ethoxy, (2-methyl-1-oxo-1-phenylpropan-2-yl) oxy, 2-ethoxy-2-oxo-1- (o-tolyl) ethoxy, 2-ethoxy-1 -(2-methoxyphenyl) -2-oxoethoxy, (4-ethoxy-4-oxo-1-phenylbut-2-en-1-yl) oxy, (1-benzoylcyclohexyl) oxy, and 2-hydroxyethoxy is there.

  Specific examples of such groups in which any hydrogen is replaced by fluorine are 3,3,3-trifluoropropyl, perfluorooctyl, 5,5,6,6,7,7,8,8,8-nonafluoro- 4,4-bis (trifluoromethyl) octyl, 11- (perfluorophenoxy) undecyl, 2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl, 3-phenoxybenzyl, 4′-methoxy- [1,1′-biphenyl] -4-yl, 4- (octyloxy) phenyl, fluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,2-trifluoroacetoxy, 2,2 , 3,3-tetrafluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, (1,1,1,3,3,3-hexafluoropropoxy 2-yl) oxy, and perfluoro phenoxy.

  Among the above, preferred groups from the viewpoint of excellent compatibility in the composition of the compound and good transparency and flatness of the formed cured film are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert -Butyl, pentyl, tert-pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, phenyl, benzyl, phenethyl, 4-isopropylphenyl, mesityl, 3,5-diethylphenyl, 4-isobutylphenyl, 2,6-diethylphenyl, acetoxymethyl, 3-methoxy-3-oxopropyl, 3- (2-methoxyethoxy) propyl, 4-methoxy-3,5-dimethylbenzyl, trimethylsilyl, (trimethylsilyl) methyl, 3- ( Trimethylsilyl Propyl, methoxy, ethoxy, propoxy, isopropoxy, prop-1-en-2-yloxy, butoxy, tert-butoxy, sec-butoxy, isobutoxy, tert-pentyloxy, hexyloxy, 2-ethylbutoxy, cyclohexyloxy, cyclo Octyloxy, phenoxy, p-tolyloxy, m-tolyloxy, o-tolyloxy, benzyloxy, and 3-phenylpropoxy, more preferred groups are methyl, ethyl, propyl, phenyl, benzyl, acetoxymethyl, trimethylsilyl, (trimethylsilyl) ) Methyl, methoxy, ethoxy, and propoxy.

The organic group having 1 to 26 carbon atoms in R ⁷ is also linear alkyl, branched alkyl, cyclic alkyl, alkyl containing cyclic alkyl, aromatic ring, group containing aromatic ring, etc., and any methylene of these groups (CH ₂ ) may be replaced with a group containing O, NH, N, or a group containing Si, and any hydrogen of these groups may be replaced with fluorine, but R ⁷ is Since it is linked to O, the specific examples are limited as compared to R ⁴ , R ⁵ and R ⁶ .

  Specific examples of linear alkyl and branched alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert-pentyl, hexyl, 2,3-dimethylbutan-2-yl, octyl, 6-methylheptyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl.

  Specific examples of cyclic alkyl and alkyl including cyclic alkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, bicyclo [2.2.1] heptan-2-yl, bicyclo [2.2.1] hept. -5-en-2-yl, 2-cyclohexylethyl, 2- (cyclohex-3-en-1-yl) ethyl, 2-cycloheptylethyl, 2- (bicyclo [2.2.1] hept-5 -En-2-yl) ethyl, 3-cyclohexylpropyl, 4- (tert-butyl) cyclohexyl, and adamantyl.

  Specific examples of the aromatic ring and the group containing an aromatic ring are phenyl, benzyl, phenethyl, 4-isopropylphenyl, mesityl, 3,5-diethylphenyl, 4-isobutylphenyl, 2,6-diethylphenyl, naphthalen-2-yl 1,1′-biphenyl, 4 ′-(tert-butyl)-[1,1′-biphenyl] -4-yl, 2,4,6-triisopropylphenyl, 4′-heptyl- [1,1 ′ -Biphenyl] -4-yl, 12-((2-benzoylbenzoyl) oxy) dodecyl, and anthracen-9-yl.

Specific examples of said groups in which any methylene (CH ₂ ) is replaced with a group comprising O, N or Si are acetoxymethyl, 3-methoxy-3-oxopropyl, 3- (2-methoxyethoxy) propyl, 2,5,8,11-tetraoxatetradecan-14-yl, 2,5,8,11-tetraoxaheptadecan-17-yl, 11,11-dimethoxyundecyl, 2- (dimethylamino) ethyl, 2 -(Diethylamino) ethyl, tetrahydrofuran-3-yl, tetrahydro-2H-pyran-4-yl, 3-((tetrahydrofuran-3-yl) methoxy) propyl, 10- (1,3-dioxolan-2-yl) decyl 10- (1,3-dioxan-2-yl) decyl, morpholino, 4-methoxy-3,5-dimethylbenzyl, hydroxy Methyl, 2-hydroxyethyl, 3-hydroxypropyl, 1-carboxyethyl, 4-hydroxybutyl, 4-hydroxy-3-oxobutyl, trimethylsilyl, (trimethylsilyl) methyl, 3- (trimethylsilyl) propyl, 2- (2,4 , 4,6,6,8,8-heptamethyl-1,3,5,7-tetraoxa-2,4,6,8-tetrasilacyclooctan-2-yl) ethyl and 2- (dimethyl (phenyl) Silyl) ethyl.

  Specific examples of such groups in which any hydrogen is replaced by fluorine are 3,3,3-trifluoropropyl, perfluorooctyl, 5,5,6,6,7,7,8,8,8-nonafluoro- 4,4-bis (trifluoromethyl) octyl, 11- (perfluorophenoxy) undecyl, 2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl, 3-phenoxybenzyl, 4′-methoxy- [1,1′-biphenyl] -4-yl and 4- (octyloxy) phenyl.

  Among the above, preferred groups from the viewpoint of excellent compatibility in the composition of the compound and good transparency and flatness of the formed cured film are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert -Butyl, pentyl, tert-pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, phenyl, benzyl, phenethyl, 4-isopropylphenyl, mesityl, 3,5-diethylphenyl, 4-isobutylphenyl, 2,6-diethylphenyl, acetoxymethyl, 3-methoxy-3-oxopropyl, 3- (2-methoxyethoxy) propyl, 4-methoxy-3,5-dimethylbenzyl, trimethylsilyl, (trimethylsilyl) methyl, and 3- (Trimethyl Le) propyl, and more preferred groups are methyl, ethyl, propyl, phenyl, benzyl, acetoxymethyl, trimethylsilyl, and (trimethylsilyl) methyl.

Specific examples of the organic group having an epoxy group in R ⁴ , R ⁵ , R ⁶ , and R ⁷ include oxirane-2-ylmethyl, 2- (oxiran-2-yl) ethyl, and 4- (oxirane-2-yl). ) Butyl, 3- (oxiran-2-ylmethoxy) propyl, 7-oxabicyclo [4.1.0] heptan-3-yl, 2- (7-oxabicyclo [4.1.0] heptan-2-yl ) Ethyl, dimethyl (4- (oxiran-2-ylmethoxy) butyl) silyl, 3- (7-oxabicyclo [4.1.0] heptan-3-yl) propyl, and 8- (oxiran-2-yl) Octyl.

  Among the above, preferred groups from the viewpoint of good transparency and heat resistance of the cured film formed are oxirane-2-ylmethyl, 2- (oxiran-2-yl) ethyl, and 4- (oxirane-2-yl). ) Butyl, 3- (oxiran-2-ylmethoxy) propyl, 7-oxabicyclo [4.1.0] heptan-3-yl, and 2- (7-oxabicyclo [4.1.0] heptane-2- Yl) ethyl, more preferred groups are oxiran-2-ylmethyl, 2- (oxiran-2-yl) ethyl, 4- (oxiran-2-yl) butyl, 3- (oxiran-2-ylmethoxy) propyl is there.

In the formula (6), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently hydrogen or an organic group having 1 to 26 carbon atoms, and R ¹² and R ¹³ are each independently hydrogen, carbon number 1 -26 organic group or an organic group having an epoxy group, and at least one of R ¹² and R ¹³ is an organic group having an epoxy group. n is an integer of 1 or more, and R ⁸ or R ⁹ may be bonded to R ⁸ , R ⁹ , R ¹⁰ , or R ¹¹ bonded to different Si to form a siloxane ring, and R ¹⁰ Alternatively, R ¹¹ may be bonded to R ⁸ , R ⁹ , R ¹⁰ , or R ¹¹ bonded to different Si to form a siloxane ring.

As the organic group having an organic group having 1 to 26 carbon atoms and an epoxy group in R ^{8 to} R ^13, the groups exemplified for R ⁴ , R ⁵ and R ⁶ in the above formula (5) can be mentioned in the same manner, and is preferable. The same applies to groups and more preferable groups.

  The weight average molecular weight of the epoxy compound having a siloxane bonding site is preferably 200 to 10,000, more preferably 200 to 5,000. If it exists in these ranges, flatness will become favorable. Therefore, the value of m in the above formula (5) is preferably 2 to 50, more preferably 2 to 25, and the value of n in the above formula (6) is preferably 1 to 74, more preferably. 1-36.

  The ratio of the epoxy compound having a siloxane bonding site to the total amount of the epoxy compound having no siloxane bonding site and the epoxy compound having a siloxane bonding site is 0.5 to 70% by weight, preferably 1 to 50% by weight. is there. If it exists in these ranges, the balance of flatness, transparency, heat resistance, and tackiness will become favorable.

  Specific examples of the epoxy compound having a siloxane bond site include an organosilicon compound having an epoxy group and no further siloxane bond can be formed by condensation, and one kind that has an epoxy group and can generate a siloxane bond by condensation A copolymer of the above organosilicon compounds, or one or more types of organosilicon compounds having an epoxy group and capable of producing a siloxane bond by condensation, and an epoxy group capable of producing a siloxane bond by condensation. It is a copolymer with an organosilicon compound that does not. If it is a commercial product, 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane (trade name; manufactured by Jerest Technologies Inc.), TSL 9906 (trade name; Momentive Performance Materials Co., Ltd.) CoatOsil MP-200 (trade name; manufactured by Momentive Performance Material Co., Ltd.), Composelan SQ506 (trade name; manufactured by Arakawa Chemical Co., Ltd.), ES-1023 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) And so on.

1-2-2. Epoxy compound having no siloxane bond site The epoxy compound having no siloxane bond site used in the present invention is not particularly limited as long as it has good compatibility with other components forming the thermosetting composition of the present invention. Glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, aliphatic polyglycidyl ether compound, or cyclic aliphatic epoxy resin, epoxy group And a polymer of a monomer having an epoxy group, a copolymer of a monomer having an epoxy group and another monomer, and the like.

  As the glycidyl ether type epoxy resin, TECHMORE VG3101L (trade name; Printtech Co., Ltd.), EHPE-3150 (trade name; Daicel Corporation), EPPN-501H, 502H (all trade names; Nippon Kayaku Co., Ltd.), And JER 1032H60 (trade name; Mitsubishi Chemical Corporation). Examples of glycidyl ester type epoxy resins include Denacol EX-721 (trade name; Nagase ChemteX Corporation), 1,2-cyclohexanedicarboxylic acid diglycidyl (trade name; manufactured by Tokyo Chemical Industry Co., Ltd.), and phenol novolac type epoxy resins. EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), JER 152, 154 (both trade names: Mitsubishi Chemical Corporation), and the like. Examples of the cresol novolac type epoxy resin include EOCN-102S, 103S, 104S, and 1020 (all trade names: Nippon Kayaku Co., Ltd.). Examples of the bisphenol A novolac type epoxy resin include JER 157S65 and 157S70 (both trade names: Mitsubishi Chemical Corporation). Examples of the cycloaliphatic epoxy resin include Celoxide 2021P and 3000 (both trade names: Daicel Corporation).

1-3. Epoxy curing agent An epoxy curing agent may be used in the thermosetting composition of the present invention 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, benzothiazolium salts, ammonium salts, phosphonium salts, etc. 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 curing agent include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrotrimellitic anhydride Aromatic carboxylic 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.

1-4. Ratio of polyester amic acid, epoxy compound, and epoxy curing agent The ratio of the total amount of the epoxy compound to 100 parts by weight of the polyester amic acid in the thermosetting composition of the present invention is 20 to 400 parts by weight. When the ratio of the total amount of the epoxy compound is within this range, the balance of flatness, heat resistance, chemical resistance, and adhesion is good. The total amount of the epoxy compound is preferably in the range of 50 to 300 parts by weight.

  When using an epoxy hardening | curing agent in the thermosetting composition of this invention, the ratio of the epoxy hardening | curing agent with respect to 100 weight part of epoxy compounds is 0.1-60 weight part. More specifically, regarding the addition amount when the epoxy curing agent is an acid anhydride curing agent, the carboxylic acid anhydride group or carboxyl group in the epoxy curing agent is 0.1 to 1.5 times the epoxy group. It is preferable to add so that it may become 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.

1-5. Other Components Various additives can be added to the thermosetting composition of the present invention in order to improve coating uniformity and adhesiveness. Additives include solvents, anionic, cationic, nonionic, fluorine or silicon leveling agents / surfactants, adhesion improvers such as silane coupling agents, hindered phenols, hindered amines, phosphorus And antioxidants such as sulfur compounds.

1-5-1. Solvent A solvent may be added to the thermosetting composition of the present invention. The solvent that is optionally added to the thermosetting composition of the present invention is preferably a solvent that can dissolve the polyester amic acid, epoxy compound, epoxy curing agent, and the like. Specific examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, acetone, 2-butanone, ethyl acetate, butyl acetate, propyl acetate, Butyl propionate, ethyl lactate, methyl hydroxyacetate, hydroxyethyl acetate, hydroxybutyl acetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-hydroxypropionate Ethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, 2-hydroxypropionate Propyl onate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, aceto Ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, triplicate Pyrene glycol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobuty Ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, γ-butyrolactone, or N, N-dimethylacetamide, and cyclohexanone. One of these may be sufficient as a solvent, and these 2 or more types of mixtures may be sufficient as it.

1-5-2. 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 are trade names: Kyoeisha Chemical Co., Ltd.), Disperbak 161, Dispersake 162, Dispersake 163, Dispersake 164, Dispersake 166, Dispersake 170, Dispersake 180, Dispersake 181 and Dispers Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (all of these are trade names; BIC Chemie Japan KK), KP-341, KP-358, KP- 368, KF-96-50CS, KF-50-100CS (all are trade names; Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon K -40, Surflon S611 (all are trade names; AGC Seimi Chemical Co., Ltd.), Aftergent 222F, Aftergent 208G, Aftergent 251, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, Aftergent 602A , TF 650A, FTX-218 (all are trade names; Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 Name: Mitsubishi Materials Corporation), Megafuck F-171, Megafuck F-177, Megafuck F-410, Megafuck F-430, Megafuck F-444, Megafuck F-4 72SF, Megafuck F-475, Megafuck F-477, Megafuck F-552, Megafuck F-553, Megafuck F-554, Megafuck F-555, Megafuck F-556, Megafuck F-558, Megafuck F-559, Megafuck R-30, Megafuck R-94, Megafuck RS-75, Megafuck RS-72-K, Megafuck RS-76-NS, Megafuck DS-21 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 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 steer 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, BYK306, BYK342, BYK346, KP-341, KP-358, KP-368, Surflon S611, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 650A, Megafuck F-477 , Megafuck F-556, Megafuck RS-72-k, TEGO Twin 4000, Fluoroalkylbenzenesulfonate, Fluoroalkylcarboxylate, Fluoroalkylpolyoxyethylene ether, Fluoroalkylsulfonate, Fluoroalkyltrimethylammonium salt, And at least one selected from fluoroalkylaminosulfonates are preferred because the coating 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.

1-5-3. Adhesion improver The thermosetting composition of the present invention may further contain an adhesion improver from the viewpoint of further improving the adhesion between the formed cured film and the substrate.

  As such an adhesion improver, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, Silaace S510; trade name: JNC Corporation), 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane (eg, Silaace S530; trade name; JNC Corporation), 3-mercaptopropyltrimethoxysilane (eg, Silaace S810; trade name; JNC Corporation) Agents, aluminum coupling agents such as acetoalkoxyaluminum diisopropylate, and titanate coupling agents such as tetraisopropylbis (dioctyl phosphite) titanate.

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

  The content of the adhesion improver is preferably 10% by weight or less based on the total amount of the thermosetting composition. On the other hand, it is preferable that it is 0.01 weight% or more.

1-5-4. Antioxidant The thermosetting composition of the present invention may further contain an antioxidant from the viewpoint of improving transparency and preventing yellowing when the cured film is exposed to a high temperature.

  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, IrganoxFF, 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 AO-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 5 parts by weight with respect to the total amount of the thermosetting composition.

1-5-7. Other Additives When the above-mentioned polyester amide acid does not contain a styrene-maleic anhydride copolymer as a raw material, a styrene-maleic anhydride copolymer may be added as another component.

1-6. 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 with time of the composition is good, which is preferable. A storage temperature of −20 ° C. to 10 ° C. is more preferable because there is no precipitate.

2. Cured film obtained from thermosetting composition The thermosetting composition of the present invention comprises a polyester amic acid, an epoxy compound having a siloxane bonding site, an epoxy compound having no siloxane bonding site, and an epoxy curing agent. Depending on the properties to be obtained, a solvent, a coupling agent, a surfactant, and other additives may be selected and added as necessary, and they may be uniformly mixed and dissolved.

  When the thermosetting composition prepared as described above (after being dissolved in a solvent in the case of a solid state without a solvent) is applied to the surface of the substrate and the solvent is removed by heating, for example, the coating film Can be formed. Conventionally known methods such as spin coating, roll coating, dipping, and slit coating can be used to apply the thermosetting composition to the substrate surface. Next, this coating film is heated (prebaked) with a hot plate or an oven. The heating 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, in order to cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 250 ° C., for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.

  When heated, the cured film thus obtained is heated when 1) the polyamic acid portion of the polyester amic acid is dehydrated to form an imide bond, and 2) the carboxylic acid of the polyester amic acid reacts with the epoxy compound to increase the 3) Since the epoxy compound is cured and has a high 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 or a solid-state image sensor can be produced using this color filter. The cured film of the present invention is effective when used as a transparent insulating film formed between the TFT and the transparent electrode or a transparent insulating film formed between the transparent electrode and the alignment film, in addition to the protective film for the color filter. It is. 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, a reference example, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples. First, a polyester amic acid solution composed of a reaction product of tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound was synthesized as shown below (Synthesis Examples 1, 2, 3, and 4).

Synthesis Example 1 Synthesis of Polyesteramide Acid Solution (A1) In a four-necked flask equipped with a stirrer, dehydrated and purified methyl 3-methoxypropionate (hereinafter abbreviated as “MMP”), 3, 3 ′, 4, 4 ′ -Diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA"), 1,4-butanediol, and benzyl alcohol were charged in the following weights, and stirred at 130 ° C for 3 hours in a dry nitrogen stream.
MMP 446.96g
ODPA 183.20g
31.93 g of 1,4-butanediol
Benzyl alcohol 25.54g
Thereafter, the reaction solution was cooled to 25 ° C., 3,3′-diaminodiphenylsulfone (hereinafter abbreviated as “DDS”) and MMP were added in the following weights, and stirred at 20 to 30 ° C. for 2 hours. Stir at 1 ° C. for 1 hour.
DDS 29.33g
MMP 183.04g

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

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

[Synthesis Example 2] Synthesis of polyester amic acid solution (A2) In a four-necked flask equipped with a stirrer, dehydrated and purified propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMEA”), 1,2,3,4-butanetetra Carboxylic dianhydride (hereinafter abbreviated as “BT-100”), SMA1000P (trade name; styrene / maleic anhydride copolymer, Kawa Crude Oil Co., Ltd.), 1,4-butanediol, benzyl alcohol And stirred at 125 ° C. for 3 hours under a stream of dry nitrogen.
PGMEA 324.00g
BT-100 30.64g
SMA1000P 145.88g
1,4-butanediol 9.29g
Benzyl alcohol 44.59g
Thereafter, the reaction solution was cooled to 25 ° C., DDS and PGMEA were added at the following weights, stirred at 20-30 ° C. for 2 hours, and then stirred at 125 ° C. for 2 hours.
DDS 9.60g
PGMEA 36.00g

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

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

[Synthesis Example 3] Synthesis of polyester amic acid solution (A3) In a four-necked flask equipped with a stirrer, dehydrated and purified PGMEA, BT-100, SMA1000P, 1,4-butanediol, and benzyl alcohol were charged in the following weights in this order: The mixture was stirred at 125 ° C. for 3 hours under a dry nitrogen stream.
PGMEA 324.00g
BT-100 30.04g
SMA1000P 143.05g
9.11 g of 1,4-butanediol
Benzyl alcohol 54.66g
Thereafter, the reaction solution was cooled to 25 ° C., DDS and PGMEA were added at the following weights, stirred at 20-30 ° C. for 2 hours, and then stirred at 125 ° C. for 2 hours.
DDS 3.14g
PGMEA 36.00g

[Z / Y = 8.0, (Y + Z) /X=0.8]

  The solution was cooled to room temperature to obtain a 30% by weight solution (A3) of a pale yellow transparent polyester amide acid. A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A3) was 9,000.

Synthesis Example 4 Synthesis of Polyesteramide Acid Solution (A4) In a four-necked flask equipped with a stirrer, dehydrated and purified PGMEA, diethylene glycol methyl ethyl ether (hereinafter abbreviated as “EDM”), ODPA, SMA1000P, 1,4-butane Diol and benzyl alcohol were charged in the order of the following weights and stirred at 120 ° C. for 3 hours under a dry nitrogen stream.
PGMEA 504.00g
EDM 96.32g
ODPA 47.7g
SMA1000P 144.97g
1,4-butanediol 9.23g
Benzyl alcohol 55.40 g
Thereafter, the reaction solution was cooled to 25 ° C., DDS and MMP were added at the following weights, stirred at 20 to 30 ° C. for 2 hours, and then stirred at 120 ° C. for 2 hours.
DDS 12.72g
EDM 29.68g

[Z / Y = 2.0, (Y + Z) /X=1.0]

  The solution was cooled to room temperature to obtain a 30% by weight solution (A4) of a pale yellow transparent polyester amide acid. A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A4) was 21,000.

  Next, as an epoxy compound having a siloxane bond site, a copolymer obtained by reacting as a raw material component one or more organosilicon compounds having an epoxy group and capable of generating a siloxane bond by condensation is shown below. Synthesis was performed as shown (Synthesis Examples 5 and 6).

Synthesis Example 5 Synthesis of Epoxy Compound (S1) Having Siloxane Bonding Site In a 1000 ml four-necked flask, 109.24 g of dehydrated and purified toluene, 21.62 g of purified water, and tetramethylammonium hydroxide having a concentration of 25% by weight 2.92 g of an aqueous solution (hereinafter abbreviated as “TMAH”) was charged, and stirring was started. In addition, as a dropping solution, a 300 ml cylindrical dropping funnel was charged with 53.78 g of dehydrated and purified toluene, 3-glycidoxypropyltrimethoxysilane (trade name: Silaace S510; manufactured by JNC Corporation, hereinafter abbreviated as “S510”). 94.54 g was charged, and the entire amount was poured into the 1000 ml four-necked flask charged with the raw material over 1 hour, and then the mixture was stirred for 2 hours for condensation. The reaction solution was separated using purified water, and toluene was distilled off from the obtained organic layer using a rotary evaporator to obtain an epoxy compound (S1) having a siloxane bond site. The weight average molecular weight measured by GPC of this solution was 3,200 (in terms of polystyrene).

Synthesis Example 6 Synthesis of Epoxy Compound (S2) Having Siloxane Bonding Site In a 1000 ml four-necked flask, 137.64 g of dehydrated and purified toluene, 32.44 g of purified water, and tetramethylammonium hydroxide having a concentration of 25% by weight 4.38 g of an aqueous solution (hereinafter abbreviated as “TMAH”) was charged, and stirring was started. In addition, as a dropping solution, in a 300 ml cylindrical dropping funnel, 67.76 g of dehydrated and purified toluene, 28.36 g of 3-glycidoxypropyltrimethoxysilane (S510), 59.48 g of phenyltrimethoxysilane, trimethylmethoxysilane The whole amount was poured into the 1000 ml four-necked flask charged with 31.26 g and charged with raw materials over 1 hour, and then stirred for 2 hours for condensation. The reaction solution was separated using purified water, and toluene was distilled off from the obtained organic layer using a rotary evaporator to obtain an epoxy compound (S2) having a siloxane bond site. The weight average molecular weight measured by GPC of this solution was 1,900 (in terms of polystyrene).

  Next, as an epoxy compound having no siloxane bonding site, a copolymer obtained by reacting a monomer having an epoxy group and another monomer copolymerized with the monomer as a raw material component is synthesized as shown below. (Synthesis Examples 7 and 8).

[Synthesis Example 7] Synthesis of epoxy compound solution (E1) having no siloxane bond site In a 1000 ml four-necked flask equipped with a thermometer, stirrer, raw material inlet and nitrogen gas inlet, 300.00 g of dehydrated and purified MMP, 160.00 g of glycidyl methacrylate (hereinafter abbreviated as “GMA”), 40.00 g of butyl methacrylate (hereinafter abbreviated as “BMA”), 2,2′-azobis (2,4-dimethylvaleronitrile) 8 as a polymerization initiator 0.000 g was charged and polymerization was carried out by heating at a polymerization temperature of 90 ° C. for 2 hours. The reaction solution was cooled to 30 ° C. or less to obtain a 40% by weight epoxy compound solution (E1) having no siloxane bonding site. The weight average molecular weight measured by GPC of this solution was 78,000 (polystyrene conversion).

[Synthesis Example 8] Synthesis of epoxy compound solution (E2) having no siloxane bonding site In a 1000 ml four-necked flask equipped with a thermometer, stirrer, raw material inlet and nitrogen gas inlet, 420.00 g of dehydrated and purified MMP, 162.00 g of glycidyl methacrylate, 18.00 g of diethylene glycol dimethacrylate, and 27.00 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator were charged and heated at a polymerization temperature of 110 ° C. for 2 hours. Polymerization was performed. The reaction solution was cooled to 30 ° C. or lower to obtain a 30% by weight epoxy compound solution (E2) having no siloxane bonding site. The weight average molecular weight measured by GPC of this solution was 3,600 (polystyrene conversion).

  Next, the polyester amide acid (A1, A2, A3, and A4) obtained in Synthesis Examples 1, 2, 3, and 4, the epoxy compound having a siloxane bonding site obtained in Synthesis Examples 5 and 6, and Synthesis Example Thermal curing using epoxy compounds having no siloxane bonding sites, commercially available epoxy resins (epoxy compounds having siloxane bonding sites or epoxy compounds having no siloxane bonding sites), and epoxy curing agents obtained in 7 and 8 The composition was prepared as shown below. A cured film was obtained from the thermosetting composition, and the cured film was evaluated (Examples 1 to 11 and Comparative Examples 1 to 6).

[Example 1]
A 500 ml separable flask equipped with a stirring blade was purged with nitrogen, and 100.00 g of the polyester amide acid (A1) obtained in Synthesis Example 1 and CoatOsil MP-200 (hereinafter referred to as an epoxy compound having a siloxane bonding site) were added to the flask. "S3" abbreviated as 1.50 g, TECHMORE VG3101L as an epoxy compound having no siloxane bond site (trade name; Printec, Inc., abbreviated as "E3" hereinafter) 58.50 g, trimellitic anhydride as an epoxy curing agent Product (hereinafter abbreviated as “TMA”) 6.00 g, ADK STAB AO-60 (trade name; manufactured by ADEKA) 0.48 g as additive, dehydrated and purified MMP367.38 g and EDM 109.34 g as a solvent. The mixture was stirred at room temperature for 3 hours and dissolved uniformly. Next, 0.17 g of Megafac F-556 (trade name; manufactured by DIC Corporation) was added, stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a coating solution.

  Next, this coating solution was spin-coated on a glass substrate and a color filter substrate at 800 rpm for 10 seconds, and then pre-baked on a hot plate at 80 ° C. for 3 minutes to form a coating film. Thereafter, the coating film was cured by heating at 230 ° C. for 30 minutes in an oven to obtain a cured film having a thickness of 1.0 μm.

  The cured film thus obtained was evaluated for its transparency, light resistance, flatness, and heat resistance.

[Transparency evaluation method]
In the obtained glass substrate with a cured film, the transmittance of the cured film alone at a wavelength of 400 nm was measured by an ultraviolet-visible near-infrared spectrophotometer (trade name; V-670, manufactured by JASCO Corporation). . The case where the transmittance was 97% or more was rated as ◯, and the case where the transmittance was less than 97% was rated as ×.

[Method for evaluating light resistance]
The glass substrate with a cured film after the transparency was evaluated in the above [Transparency Evaluation Method] was 1 J / with a UV ozone cleaning device (trade name: PL2003N-12, light source: low-pressure mercury lamp, manufactured by Sen Special Light Source Co., Ltd.). After performing UV ozone treatment of cm ² (254 nm conversion) and heating in an oven at 230 ° C. for 30 minutes, only a cured film is obtained using an ultraviolet-visible infrared spectrophotometer (trade name: V-670, manufactured by JASCO Corporation). The transmittance of light at a wavelength of 400 nm was measured. The case where the transmittance was 95% or more was rated as ○, and the case where the transmittance was less than 95% was rated as ×.

[Evaluation method of flatness]
The step of the cured film surface of the obtained color filter substrate with a cured film was measured using a step / surface roughness / fine shape measuring device (trade name: P-15, KLA TENCOR Co., Ltd.). A case where the maximum value of the step between the R, G and B pixels including the black matrix (hereinafter, abbreviated as the maximum step) is less than 0.25 μm is indicated as “◯”, and a case where it is 0.25 μm or more is indicated as “X”. The color filter substrate used is a pigment dispersion color filter (hereinafter abbreviated as CF) using a resin black matrix having a maximum step of about 0.5 μm.

[Evaluation method of heat resistance]
After the obtained glass substrate with a cured film was reheated at 230 ° C. for 1 hour, the film thickness before heating and the film thickness after heating were measured, and the remaining film ratio was calculated by the following formula. For the measurement of the film thickness, the step, surface roughness, and fine shape measuring apparatus (trade name: P-15, KLA TENCOR Co., Ltd.) was used. The case where the residual film ratio after heating was 96% or more was rated as “◯”, and the case where the residual film ratio after heating was less than 96% was evaluated as “poor”.

Residual film ratio = (film thickness after heating / film thickness before heating) × 100

[Tacking evaluation method]
The coating solution was spin-coated on a glass substrate at 800 rpm for 10 seconds, and then pre-baked on a hot plate at 80 ° C. for 3 minutes to form a coating film. Then, the presence or absence of tack was determined by palpation. The case where the coating film after pre-baking was touched and there was no shape change by visual observation on the surface of the film was marked with ◯, and the case where there was a shape change was marked with x.

[Examples 2 to 11]
According to the method of Example 1, each component was mixed and dissolved at the ratio (unit: g) described in Tables 1-1 and 1-2 to obtain a thermosetting composition. In addition, about the abbreviation of each compound in the table, S4 is 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane (trade name; Jerest), which is an epoxy compound having a siloxane bonding site. Technologies Incorporated). In the additive column, S510 is an adhesion improver Silaace S510 (trade name; JNC Corporation), AO-60 is an antioxidant ADK STAB AO-60 (trade name; manufactured by ADEKA Corporation), and F-556 is a surface activity. Agent Megafac F-556 (trade name; manufactured by DIC Corporation) is shown.

[Comparative Examples 1-6]
According to the method of Example 1, each component was mixed and dissolved at the ratio (unit: g) shown in Table 2 to obtain a thermosetting composition.

  Moreover, the evaluation result of the cured film of Examples 1-11 was put together in Table 1-1 and 1-2, and the evaluation result of the cured film of Comparative Examples 1-6 was put together in Table 2, respectively.

  As is clear from the results shown in Table 1, the cured films using the epoxy compounds having siloxane bonding sites of Examples 1 to 11 are excellent in flatness, and have all of transparency, light resistance and heat resistance. It can be seen that the points are balanced.

  On the other hand, although the cured film using only the epoxy compounds of Comparative Example 1 and Comparative Examples 5 and 6 is excellent in transparency and heat resistance, the flatness is inferior. When E3 is used for the epoxy compound of Comparative Example 2 and an epoxy compound having a siloxane bond site is used in an amount less than the preferred range, the transparency, light resistance and heat resistance are excellent, but the flatness is poor. It was. On the contrary, when the epoxy compound having a siloxane bonding site of Comparative Examples 3 and 4 was used in an amount larger than the preferred range, the flatness was good, but tack occurred at the pre-baking stage. As described above, all the characteristics could be satisfied only when a certain amount of the epoxy compound having a siloxane bonding site was used as an essential component.

  The cured film obtained from the thermosetting composition of the present invention is excellent in properties as an optical material such as transparency, light resistance, and sputtering resistance, so that it can be used for color filters, LED light emitting elements, light receiving elements, etc. It can be used as a protective film such as various optical materials, and a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (20)

A composition comprising a polyester amide acid, an epoxy compound having a siloxane bond site, an epoxy compound having no siloxane bond site, and an epoxy curing agent;
The polyester amic acid is a reaction product from a raw material which essentially comprises a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound,
The raw material contains X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compounds in a ratio such that the relationship of the following formulas (1) and (2) is satisfied,
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
The polyester amide acid has structural units represented by the following general formulas (3) and (4);
The total of the epoxy compound having the siloxane bond site and the epoxy compound not having the siloxane bond site is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amic acid;
0 to 60 parts by weight of the epoxy curing agent for a total of 100 parts by weight of the epoxy compound; and
The thermosetting composition whose ratio of the epoxy compound which has the said siloxane bond part in the total amount of the said epoxy compound is 0.5 to 70 weight%.

(R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue.)   The thermosetting composition according to claim 1, wherein the raw material of the polyester amide acid further contains a monohydric alcohol.   The monohydric alcohol is at least one selected from isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. Thermosetting composition.   The thermosetting composition according to any one of claims 1 to 3, wherein the raw material of the polyester amic acid further contains a styrene-maleic anhydride copolymer.   The thermosetting composition according to any one of claims 1 to 4, wherein the polyester amic acid has a weight average molecular weight of 1,000 to 200,000.   Tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [ 1 selected from bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate) The thermosetting composition according to any one of claims 1 to 5, which is a seed or more.   The thermosetting according to any one of claims 1 to 6, wherein the diamine is at least one selected from 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone. Sex composition.   Polyhydric hydroxy compounds are ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and isocyanuric acid The thermosetting composition according to any one of claims 1 to 7, wherein the thermosetting composition is one or more selected from tris (2-hydroxyethyl). The thermosetting composition according to any one of claims 1 to 8, wherein the epoxy compound having a siloxane bonding site is at least one selected from the group of compounds represented by the following formulas (5) and (6). .

(R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, a hydroxyl group, an organic group having 1 to 26 carbon atoms, or an organic group having an epoxy group, and R ⁷ is independently hydrogen, 1 to carbon atoms, 26 organic groups having an epoxy group, at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is an organic group having an epoxy group, m is an integer of 2 or more, and R ⁴ Alternatively, R ⁵ may be bonded to R ⁴ or R ⁵ bonded to different Si to form a siloxane ring, and R ⁶ and R ⁷ may be bonded to form a siloxane ring.)

(R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently hydrogen or an organic group having 1 to 26 carbon atoms, and R ¹² and R ¹³ are each independently hydrogen, an organic group having 1 to 26 carbon atoms. or an organic group having an epoxy group, at least one of R ¹² and R ¹³ is an organic group having an epoxy group, n is an integer of 1 or more, R ⁸ where R ⁸ or R ⁹ is bonded to different Si may form a siloxane ring bonded to ^{R 9, R 10} or ^{R 11,, and, R} 8 ^{to R 10} or ^{R 11} are bonded to different ^Si, R ^{9, R 10} or ^{R 11,} and It may be bonded to form a siloxane ring.)   An epoxy compound having a siloxane bonding site is 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane, 1,3-bis (3-glycidoxypropyl) tetramethyldisiloxane, Copolymer which is a reaction product from a raw material containing 3-glycidoxypropyltrimethoxysilane, and a reaction product from a raw material containing 3-glycidoxypropyltrimethoxysilane, phenyltrimethoxysilane and trimethylmethoxysilane The thermosetting composition according to claim 1, wherein the thermosetting composition is at least one selected from the group consisting of copolymers.   The thermosetting composition according to any one of claims 1 to 9, wherein the epoxy curing agent is at least one selected from trimellitic anhydride, hexahydrotrimellitic anhydride and 2-undecylimidazole. object. The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride or 1,2,3,4-butanetetracarboxylic dianhydride;
The diamine is 3,3′-diaminodiphenyl sulfone;
The polyvalent hydroxy compound is 1,4-butanediol;
A copolymer having a weight average molecular weight of 1,000 to 200,000, wherein the epoxy compound having a siloxane bonding site is a reaction product from a raw material containing 3-glycidoxypropyltrimethoxysilane;
An epoxy compound having no siloxane bonding site is 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4-1,1-bis [4-([2,3-epoxypropoxy] phenyl) ethyl. ] Phenyl] propane;
The epoxy curing agent is trimellitic anhydride or 2-undecylimidazole;
The thermosetting composition according to claim 1, further comprising methyl 3-methoxypropionate or propylene glycol monomethyl ether acetate as a solvent. "   The cured film obtained from the thermosetting composition of any one of Claims 1-12.   A color filter using the cured film according to claim 13 as a protective film.   A liquid crystal display element using the color filter according to claim 14.   A solid-state imaging device using the color filter according to claim 14.   The liquid crystal display element using the cured film of Claim 13 as a transparent insulating film formed between TFT and a transparent electrode.   The liquid crystal display element using the cured film of Claim 13 as a transparent insulating film formed between a transparent electrode and alignment film.   A touch panel device using the cured film according to claim 13 as a transparent insulating film formed on the transparent electrode.   The LED light-emitting body which used the cured film of Claim 13 as a protective film.