TWI783941B - Thermosetting compositions, cured film, and color filter - Google Patents

Abstract

The present invention relates to a thermosetting composition, a cured film and a color filter. The thermosetting composition includes a polyester amide acid (A), an epoxy compound (B) and a compound having a polymerizable double bond ( C). The composition is characterized in that the polyester amide acid (A) contains X moles of tetracarboxylic dianhydride, Y moles of The compound (C) having a polymerizable double bond is a compound having two or more polymerizable double bonds per molecule as a reaction product of diamine and a raw material of a polyhydric hydroxyl compound of Z mole. According to the thermosetting composition of the present invention, it is possible to form a cured film which is preferably used in electronic parts and is excellent in flatness and scratch resistance. 0.2≦Z/Y≦8.0·······(1) 0.2≦(Y+Z)/X≦5.0···(2)

Description

Thermosetting composition, cured film and color filter

The invention relates to an insulating material that can be used to form an insulating material in electronic parts, a passivation film in a semiconductor device, a buffer coating film, an interlayer insulating film, a planarization film, an interlayer insulating film in a liquid crystal display element, and a 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 forming wiring electrodes 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 above-mentioned general manufacturing steps. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to base substrates such as glass, transparency, scratch resistance, coating properties, 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 (Patent Document 1). Furthermore, as the flatness required for high-definition and thinned liquid crystal display elements has improved in recent years, thermosetting compositions with good heat resistance and good flatness have been proposed (Patent Document 2).

With the reduction in power consumption of display elements in recent years, a color filter having pixels including red (R), green (G), blue (B), and white (W) may be used. The W part is a part where there is no photoresist layer such as R, G, B, etc. on the support substrate, so the color filter with pixels containing W is better than the color filter without pixels containing W The surface step difference becomes larger. If the surface level difference is large, the display quality will be lowered, so further improvement in flatness becomes a problem for the thermosetting material.

Moreover, along with the increase in size of display elements in recent years, in-plane unevenness tends to occur in each manufacturing step. For example, in the manufacture of a large liquid crystal display element, in-plane unevenness of the contact pressure of the rubbing roller against the color filter substrate is likely to occur during rubbing of the alignment film. For this reason, the protective film may be scratched at the portion where the contact pressure is high. If the protective film is scratched, the display quality will be lowered, so the improvement of the scratch resistance is a problem for the thermosetting composition. [Prior Art Documents] [Patent Documents]

[Patent Document 1] Japanese Patent Laid-Open No. 2005-105264 [Patent Document 2] Japanese Patent Laid-Open No. 2008-156546

[Problems to be Solved by the Invention] The subject of the present invention is to provide a thermosetting composition that provides a cured film excellent in flatness and scratch resistance, and a cured film formed from the thermosetting composition, and to provide a cured film having The electronic parts of the hardened film. [Technical means to solve the problem]

The inventors of the present invention have conducted diligent research to solve the above-mentioned problems, and as a result, have found that the object can be achieved by using a cured film comprising tetracarboxylic dianhydride, di It is obtained by hardening a composition of polyester amide acid, an epoxy compound, and a compound having two or more polymerizable double bonds per molecule, which are reaction products of amines and polyhydroxy compounds. The present invention includes the following configurations.

[1] A thermosetting composition comprising polyester amide acid (A), an epoxy compound (B) and a compound (C) having a polymerizable double bond, the thermosetting composition is characterized in that: The polyester amide acid (A) contains X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyhydric acid in a ratio established by the following formula (1) and formula (2). Reactants of raw materials of hydroxy compounds, 0.2≦Z/Y≦8.0·······(1) 0.2≦(Y+Z)/X≦5.0···(2) Compounds having polymerizable double bonds ( C) is a compound having two or more polymerizable double bonds per molecule.

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。[2] The thermosetting composition according to item [1], wherein the polyester amide acid (A) includes a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4) .

In formula (3) and formula (4), R ¹ is a residue obtained by removing two -CO-O-CO- from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two -NH ₂ from diamine. The resulting residue, ^R3 is a residue obtained by removing two -OH from the polyhydric hydroxy compound.

[3] The thermosetting composition according to [1], wherein the compound (C) having a polymerizable double bond includes a compound having three or more polymerizable double bonds per molecule.

[4] The thermosetting composition according to item [3], wherein the compound having three or more polymerizable double bonds per molecule is selected from the group consisting of isocyanurate oxirane-modified triacrylate, In the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and carboxyl-containing polyfunctional (meth)acrylate at least one compound.

[5] The thermosetting composition according to [1], wherein the compound (C) having a polymerizable double bond is selected from the group consisting of isocyanuric acid oxirane-modified diacrylate and isocyanuric acid ring A mixture of oxyethane-modified triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and carboxyl-containing polyfunctional (methyl base) at least one compound in the group consisting of acrylates.

[6] The thermosetting composition according to any one of [1] to [4], wherein the content of the epoxy compound (B) is 20 parts by weight with respect to 100 parts by weight of the polyesteramic acid (A). 1 to 400 parts by weight, and the content of the compound (C) having a polymerizable double bond is 1 to 400 parts by weight with respect to 100 parts by weight of the polyesteramic acid (A).

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

[8] A color filter having the cured film according to item [7] 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 flatness and scratch resistance, and when used as a color filter protective film for 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. Moreover, it can also be used as a protective film and a transparent insulating film of various optical materials.

In this specification, the smaller the step difference of the cured film of the present invention is, the more "excellent in flatness" 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. Thermosetting composition of the present invention The thermosetting composition of the present invention contains polyester amide acid, epoxy compound, And the composition of the compound with polymerizable double bond, and it is characterized in that: with respect to 100 weight parts of polyester amide acid, epoxy compound is 20 weight part～400 weight part, the compound with polymerizable double bond is 1 weight part parts to 400 parts by weight.

1-1. Polyester amide acid (A) Polyester amide acid is a reaction product containing the raw material of tetracarboxylic dianhydride, diamine, and a polyhydric hydroxyl compound. More specifically, the polyester amide acid contains X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of diamine at a ratio established by the following formula (1) and formula (2). The reaction product of the raw materials of the polyhydroxy compound. 0.2≦Z/Y≦8.0·······(1) 0.2≦(Y+Z)/X≦5.0···(2)

The polyester amide acid (A) preferably 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, and is preferably an organic group having 2 to 30 carbon atoms. R ² is a residue obtained by removing two -NH ₂ from diamine, and is preferably an organic group having 2 to 30 carbon atoms. R ³ is a residue obtained by removing two -OH groups from a polyhydric hydroxyl compound, and is preferably an organic group having 2 to 20 carbon atoms.

At least a solvent is required in the synthesis of polyester amide acid (A), and the solvent can be left as it is to prepare a liquid or gel thermosetting composition in consideration of handling, etc., or the solvent can be removed Instead, it is made into a solid composition in consideration of transportability and the like. In addition, the synthesis of polyester amide acid (A) may contain one or more compounds selected from monohydroxy compounds and styrene-maleic anhydride copolymers as raw materials if necessary, and it is particularly preferable to contain monohydroxy compounds. Moreover, the synthesis|combination of polyester amide acid (A) may contain other compounds other than the above-mentioned as a raw material as needed within the range which does not impair the object of this invention.

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 preferred tetracarboxylic dianhydrides are: 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid Dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2',3, 3'-Diphenylenetetracarboxylic dianhydride, 2,3,3',4'-Diphenylenetetracarboxylic dianhydride, 3,3',4,4'-Diphenylether tetracarboxylic acid 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(dehydrated trimellitate) (trade name; TMEG- 100, Nippon Chemical Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, ethane Tetracarboxylic dianhydride, and butanetetracarboxylic dianhydride. More than one of these may be used.

Among these tetracarboxylic dianhydrides, 3,3',4,4'-diphenyl tetracarboxylic dianhydride and 3,3',4,4'-diphenyl ether which impart good transparency are more preferable. Tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, and ethylene glycol bis (dehydrated trimellitate), and more preferably 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dicarboxylic acid anhydride 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). Specific examples of preferred diamines are: 4,4'-diaminodiphenylphenyl, 3,3'-diaminodiphenyl, 3,4'-diaminodiphenyl, bis [4-(4-Aminophenoxy)phenyl]Phenyl, Bis[4-(3-Aminophenoxy)phenyl]Phenyl, Bis[3-(4-Aminophenoxy)phenyl ]Phenyl, [4-(4-Aminophenoxy)phenyl][3-(4-Aminophenoxy)phenyl]Phenyl, [4-(3-Aminophenoxy)phenyl] [3-(4-aminophenoxy)phenyl]pyridine, and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. More than one of these may be used.

Among these diamines, 3,3'-diaminodiphenylphenone and bis[4-(3-aminophenoxy)phenyl]pyrone, which impart good transparency, are more preferred, and 3,3'- '-Diaminodiphenylsulfone.

1-1-3. Polyvalent hydroxy compound In the present invention, a polyvalent hydroxy compound is used as a material for obtaining the polyester amide acid (A). Specific examples of preferred polyhydric hydroxyl compounds are: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, Tetrapropylene glycol, polypropylene glycol with a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol Diol, 2,4-pentanediol, 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-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, Tris(2-hydroxyethyl)isocyanurate, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol S (bis(4-hydroxyphenyl)sulfone), bisphenol F (bis(4-hydroxyphenyl)methane), diethanolamine, and triethanolamine. More than one of these may be used.

Among these polyhydric hydroxyl compounds, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7 - Heptanediol, 1,8-octanediol, and tris(2-hydroxyethyl) isocyanurate, further preferably 1,4-butanediol, 1,5-pentanediol and 1,6 - hexanediol.

1-1-4. Monohydroxy compound In the present invention, a monohydroxy compound can be used as a material for obtaining the polyester amide acid (A). The storage stability of the thermosetting composition improves by using the monohydroxy compound. Specific examples of preferred monohydroxy compounds are: methanol, ethanol, 1-propanol, isopropanol, allyl 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 monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltol, linalool , terpineol (terpineol), dimethyl benzyl carbinol (dimethyl benzyl carbinol), and 3-ethyl-3-hydroxymethyl oxetane. More than one of these may be used.

Among these monohydroxyl compounds, isopropanol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane is more preferable. Considering the compatibility when mixing polyester amide acid (A) formed using these monohydroxy compounds with epoxy compounds and epoxy hardeners, or when a thermosetting composition is used on a color filter For coating properties, it is more preferable to use benzyl alcohol as a monohydroxy compound.

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, diamine, and a polyhydric hydroxyl compound, and to react. More preferably, it is 5 to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer Also, the polyester amide acid (A) used in the present invention can also be synthesized by adding a compound having three or more acid anhydride groups to the raw material. . Since improvement in transparency of the polyester amide acid (A) synthesize|combined by adding the compound which has three or more acid anhydride groups is expected, it is preferable. An example of a compound having three or more acid anhydride groups is a styrene-maleic anhydride copolymer. 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. The molar ratio of styrene/maleic anhydride is more preferably 1 or 2, still more preferably 1.

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

It is preferable to contain 0 weight part - 500 weight part of styrene-maleic anhydride copolymers with respect to 100 weight part of total amounts of tetracarboxylic dianhydride, diamine, and a polyhydric hydroxyl compound. More preferably, it is 10 weight part - 300 weight part.

1-1-6. Aminosilane compound having one amino group In the synthesis of polyester amide acid (A), other compounds other than those mentioned above may be included as needed within the scope not to impair the object of the present invention. Raw Materials As raw materials, examples of such other raw materials are aminosilane compounds having one amine group. The aminosilane compound having an amino group is used to react with the anhydride group at the end of the polyester amide acid (A) to introduce a silyl group at the end. The acid resistance of the obtained cured film can be improved by using the thermosetting composition of the present invention containing polyester amide acid (A) having one amine group The aminosilane compound is obtained by reacting. Furthermore, when reacting with the structure of the said monomer, you may add both a monohydroxyl compound and the aminosilane compound which has one amino group, and may react.

Specific examples of preferred aminosilane compounds having an amino group used in the present invention are: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, Propylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-amine butylbutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyl Diethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. More than one of these may be used.

Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane, which have good acid resistance of the cured film, are more preferable from the viewpoint of acid resistance and compatibility. 3-Aminopropyltriethoxysilane.

It is preferable that the aminosilane compound which has one amino group contains 0 weight part - 300 weight part with respect to 100 weight part of total amounts of tetracarboxylic dianhydride, diamine, and a polyhydric hydroxyl compound. More preferably, it is 5 to 200 parts by weight.

1-1-7. The solvent used in the synthesis reaction of polyester amide acid (A) The solvent used in the synthesis reaction of polyester amide acid (A) (hereinafter sometimes referred to as "reaction Solvent") specific examples are: diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone, and N,N- Dimethylacetamide. Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ether are preferred.

1-1-8. Synthetic method of polyester amide acid (A) The polyester amide acid (A) used in the present invention is preferably prepared by making tetracarboxylic dianhydride X mole, The molar reaction of diamine Y and polyhydric hydroxyl compound Z is synthesized, and at this time, X, Y, and Z are determined to be ratios in which the relationship of the following formula (1) and formula (2) holds among them. If it is this range, since the solubility to a solvent of a polyester amide acid (A) will be high, the applicability of a composition will improve, and as a result, the cured film excellent in flatness can be obtained. 0.2≦Z/Y≦8.0·······(1) 0.2≦(Y+Z)/X≦5.0···(2) Formula (1) is preferably 0.7≦Z/Y≦7.0, more Preferably, 1.0≦Z/Y≦5.0. Also, the formula (2) is preferably 0.5≦(Y+Z)/X≦4.0, more preferably 0.6≦(Y+Z)/X≦2.0.

It can be considered that the polyester amide acid (A) used in the present invention is stronger than a molecule having an amino group or a hydroxyl group at the terminal under the condition that X is used in excess relative to (Y+Z) under the above reaction conditions. Molecules having an anhydride group (-CO-O-CO-) at the end are produced in excess. In the case of reacting with such a monomer configuration, the above-mentioned monohydroxy compound may be added as necessary in order to react with the acid anhydride group at the molecular terminal to esterify the terminal. The polyester amide acid (A) obtained by adding and reacting a monohydroxy compound can improve the compatibility with epoxy compounds and epoxy hardeners, and can improve the thermosetting composition of the present invention containing these compounds. Coatability.

When using 100 weight part or more of reaction solvents with respect to a total of 100 weight part of tetracarboxylic dianhydride, diamine, and a polyhydric hydroxyl compound, since reaction will progress smoothly, 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 the reaction 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 polyhydroxy compound to the reaction solvent; dissolving diamine and polyhydroxy compound in the 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 the method of adding tetracarboxylic dianhydride and diamine to the reaction product after pre-reacting Methods of polyhydroxy compounds, etc.

In the case of reacting the aminosilane compound having one amino group, after the reaction of tetracarboxylic dianhydride, diamine, and polyhydric hydroxyl compound is completed, the reacted solution is cooled to below 40°C, and then added For the aminosilane compound having one amine group, it is preferable to react at 10° C. to 40° C. for 0.1 hour to 6 hours. Also, the monohydroxy compound can be added at any point in time of the reaction.

The polyester amide acid (A) synthesized as above contains the structural unit represented by formula (3) and the structural unit represented by formula (4), and its terminal is derived from tetracarboxylic dianhydride, An acid anhydride group, an amine group, or a hydroxyl group of a diamine or a polyhydric hydroxy compound, or an additive other than these compounds constitutes the terminal. Curability becomes favorable by including such a structure.

The weight average molecular weight of the obtained polyester amide acid (A) is preferably from 1,000 to 200,000, more preferably from 3,000 to 50,000. If it exists in these ranges, flatness and heat resistance will become favorable.

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 645-132900 (for example, the polystyrene calibration kit (calibration kit) PL2010-0102 of Agilent Technologies Co., Ltd.), and the column uses PLgel MIXED-D ( Agilent Technologies (Agilent Technologies Inc.), can use tetrahydrofuran (Tetrahydrofuran, THF) as the mobile phase for measurement. In addition, the weight average molecular weight of the commercially available item in this specification is a catalog (catalogue) description value.

1-2. Epoxy compound (B) The epoxy compound (B) used in this invention is a compound which has two or more epoxy groups per molecule. The epoxy compound (B) may be one kind or two or more kinds.

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 Novolak-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 Polymers, 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.), EHPE-3150 (trade name; Daicel Co., Ltd.), EPPN-501H, EPPN-502H (both trade names; Nippon Kayaku Co., Ltd.), and jER 1032H60 (trade name 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; manufactured by Tokyo Chemical Industry Co., Ltd.); specific examples of commercially available bisphenol-type epoxy compounds are jER YX4000, jER YX4000H, and jER YL6121H (all trade names; Mitsubishi Chemical Corporation), and NC-3000, NC-3000-L, NC-3000-H, NC-3100 (all trade names; Nippon Kayaku Co., Ltd.); phenol novolac Specific examples of commercially available products of the type epoxy compound are EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), and jER 152, jER 154 (both trade names; Mitsubishi Chemical Co., Ltd.); cresol novolac Specific examples of commercially available varnish-type epoxy compounds are EOCN-102S, EOCN-103S, EOCN-104S, and EOCN-1020 (all are trade names; Nippon Kayaku Co., Ltd.); Specific examples of commercially available oxygen compounds are jER 157S65 and jER 157S70 (both trade names; Mitsubishi Chemical Corporation); specific examples of commercially available cycloaliphatic epoxy compounds are Celloxide 2021P, 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 Advanced Materials ( Momentive Performance Materials) Co., Ltd.), COATOSIL (COATOSIL) MP-200 (commodity name; Momentive Performance Materials Co., Ltd.), Conpoceran (Conpoceran) SQ506 (trade name; Arakawa Chemical Co., Ltd.), ES-1023 (trade name; Shin-Etsu Chemical Co., Ltd.).

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-Glycidyloxy)phenyl]-1-methylethyl]phenyl]ethyl ]phenoxy]-2-propanol; EHPE-3150 (trade name; Daicel Co., Ltd.) is 1,2-bis(hydroxymethyl)-1-butanol Epoxy-4-(2-oxiranyl) cyclohexane adduct; Celloxide 2021P (trade name; Daicel Co., Ltd.) is 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; Celloxide 3000 (trade name; Daicel Co., Ltd.) is 1-methyl- 4-(2-Methyloxiranyl)-7-oxabicyclo[4.1.0]heptane; COATOSIL (COATOSIL) MP-200 (trade name; shares of Momentive Performance Materials) Ltd.) is a polymer of 3-glycidoxypropyltrimethoxysilane.

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

1-3. 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 compound ( The ratio of the total amount of B) is 20 to 400 parts by weight. When the ratio of the total amount of the epoxy compound (B) is within this 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.

1-4. Compound (C) having a polymerizable double bond The compound (C) having a polymerizable double bond used in the present invention is not particularly restricted as long as it has two or more polymerizable double bonds per molecule. limited.

Specific examples of compounds having two polymerizable double bonds per molecule of the compound (C) having polymerizable double bonds are: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylic acid ester, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, epichlorohydrin modified ethylene glycol di(meth)acrylate ) acrylate, epichlorohydrin modified diethylene glycol di(meth)acrylate, epichlorohydrin modified triethylene glycol di(meth)acrylate, epichlorohydrin modified tetraethylene glycol di(meth)acrylate base) acrylate, epichlorohydrin modified polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate , tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, epichlorohydrin modified propylene glycol di(meth)acrylate, epichlorohydrin modified dipropylene glycol di(meth)acrylate, Epichlorohydrin modified tripropylene glycol di(meth)acrylate, epichlorohydrin modified tetrapropylene glycol di(meth)acrylate, epichlorohydrin modified polypropylene glycol di(meth)acrylate, glycerol acrylate Methacrylate, glycerol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, epichlorohydrin modified 1,6-hexanediol di(meth)acrylate , Methoxylated cyclohexyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxytrimethyl acetate neopentyl glycol di(meth)acrylate, caprolactone modified hydroxyl Neopentyl glycol trimethyl acetate di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, bis[(meth) Acryloxy neopentyl glycol] adipate, bisphenol A di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate Acrylate, ethylene oxide modified bisphenol F di(meth)acrylate, bisphenol S di(meth)acrylate, ethylene oxide modified bisphenol S di(meth)acrylate, 1, 4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, dicyclopentyl diacrylate, ethylene oxide modified phosphate di(meth)acrylate , Caprolactone·ethylene oxide modified phosphate di(meth)acrylate, epichlorohydrin modified phthalate di(meth)acrylate, tetrabromobisphenol A di(meth)acrylate, Triglycerol di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, and isocyanurate-ethylene oxide-modified diacrylate.

Specific examples of compounds having three or more polymerizable double bonds per molecule of the compound (C) having polymerizable double bonds are: trimethylolpropane tri(meth)acrylate, ethylene oxide modified three Methylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, epichlorohydrin modified trimethylolpropane tri(meth)acrylate, glycerol Alcohol tri(meth)acrylate, epichlorohydrin modified glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, epoxy Ethane-modified phosphoric acid tri(meth)acrylate, caprolactone/ethylene oxide modified phosphoric acid tri(meth)acrylate, caprolactone-modified tris[(meth)acryloxyethyl] Isocyanurate, di-trimethylolpropane tetra(meth)acrylate, diglycerol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and alkyl modified dipentaerythritol tetra(meth)acrylate base) acrylate, dipentaerythritol penta(meth)acrylate, alkyl modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate ) acrylates, and carboxyl-containing multifunctional (meth)acrylates.

The compound (C) having a polymerizable double bond may be used alone or in combination of two or more.

In 100% by weight of the compound (C) having a polymerizable double bond, it is preferable to contain 50% by weight or more of a compound having three or more polymerizable double bonds per molecule from the viewpoint of scratch resistance.

Among the compounds (C) having a polymerizable double bond, it is preferable to use isocyanuric acid oxirane-modified diacrylate, isocyanuric acid epoxy, etc. from the viewpoint of flatness and scratch resistance. Ethane-modified triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and carboxyl-containing polyfunctional (meth)acrylic acid ester.

As the compound (C) having a polymerizable double bond, the following commercial items can be used. Specific examples of isocyanurate oxirane-modified diacrylate are Aronix M-215 (trade name; Toagosei Co., Ltd.); isocyanurate oxirane-modified diacrylate and isocyanuric acid ethylene oxide modified triacrylate specific examples are Aronix (Aronix) M-313 (30% by weight to 40% by weight) and Aronix (Aronix) M-315 (3 % by weight to 13% by weight, hereinafter abbreviated as "M-315") (both are trade names; Toagosei Co., Ltd., the content in parentheses is isocyanurate oxirane-modified diacrylate in the mixture The catalog record value of content rate); specific examples of trimethylolpropane triacrylate are Aronix (Aronix) M-309 (trade name; Toagosei Co., Ltd.); pentaerythritol triacrylate and pentaerythritol tetraacrylate Specific examples of the mixture are Aronix (Aronix) M-306 (65% by weight to 70% by weight), Aronix (Aronix) M-305 (55% by weight to 63% by weight), Aronix (Aronix) M-303 (30% by weight to 60% by weight), Aronix M-452 (25% by weight to 40% by weight), and Aronix M-450 (less than 10% by weight) ( Both are trade names; Toa Gosei Co., Ltd., the content in parentheses is the catalog record value of the content of pentaerythritol triacrylate in the mixture); specific examples of the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are Aronix M-403 (50% to 60% by weight), Aronix M-400 (40% to 50% by weight), Aronix M-402 (30% by weight % to 40% by weight, hereinafter abbreviated as "M-402"), Aronix M-404 (30% to 40% by weight), Aronix M-406 (25% to 35% by weight % by weight), and Aronix (Aronix) M-405 (10% by weight to 20% by weight) (both trade names; Toagosei Co., Ltd., the content in parentheses is the dipentaerythritol pentaacrylate in the mixture content rate recorded in the catalog); specific examples of carboxyl-containing multifunctional acrylates are Aronix M-510 and Aronix M-520 (hereinafter abbreviated as "M-520") (both is a trade name; Toa Gosei Co., Ltd.).

1-5. The ratio of the compound (C) having a polymerizable double bond to the polyester amide acid (A) per 100 parts by weight of the polyester amide acid (A) in the thermosetting composition of the present invention, The ratio of the total amount of the compound (C) which has a polymerizable double bond is 1 weight part - 400 weight part. When the ratio of the total amount of the compound (C) having a polymerizable double bond is within this range, the balance of flatness, heat resistance, and scratch resistance is favorable. The total amount of the compound (C) having a polymerizable double bond is preferably in the range of 1 to 300 parts by weight.

1-6. Other Components Various additives may be added to the thermosetting composition of the present invention to improve coating uniformity and adhesiveness. Additives mainly include: epoxy hardeners, solvents, anionic, cationic, nonionic, fluorine or silicon-based leveling agents, surfactants, silane coupling agents and other adhesion enhancers, hindered phenols, Antioxidants such as hindered amines, phosphorus and sulfur compounds.

1-6-1. Epoxy curing agent (D) In the thermosetting composition of the present invention, an epoxy curing agent (D) may be used in order to improve flatness and chemical resistance. As the epoxy curing agent (D), there are acid anhydride-based curing agents, amine-based curing agents, phenol-based curing agents, imidazole-based curing agents, catalyst-type curing agents, and columium salts, benzothiazolium salts, ammonium salts, phosphonium The thermosensitive acid generator such as salt is preferably an acid anhydride-based curing agent or an imidazole-based curing agent from the viewpoint of avoiding coloring of the cured film and the heat resistance of the cured film.

Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride. ; Aromatic polycarboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride; and styrene-maleic anhydride copolymer. 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-based hardeners 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.

When using an epoxy curing agent (D), the ratio of an epoxy curing agent (D) is 0.1 weight part - 60 weight part with respect to 100 weight part of epoxy compounds (B). When the epoxy curing agent (D) 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 is 0.1 times the equivalent ~ 1.5 times the equivalent way to add. 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.

1-6-2. Solvent (E) In the thermosetting composition of the present invention, a solvent (E) can also be used. The solvent (E) optionally added to the thermosetting composition of the present invention is preferably a soluble polyester amide acid (A), an epoxy compound (B), a compound having a polymerizable double bond (C), a ring Solvent for oxygen hardener (D), etc. Specific examples of the solvent (E) are: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tertiary butanol, acetone, 2-butanone, Ethyl acetate, Butyl acetate, Propyl acetate, Butyl propionate, Ethyl lactate, Methyl glycolate, Ethyl glycolate, Butyl glycolate, Methyl methoxyacetate, Ethyl methoxyacetate, Butyl Methoxyacetate, Methyl Ethoxyacetate, Ethyl Ethoxyacetate, 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-Methoxypropionate Methyl 2-methoxypropionate, 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 acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 4-hydroxy-4 -Methyl-2-pentanone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol mono Diethyl 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 monomethyl ether Butyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, γ-butyrolactone, or N,N-dimethylacetamide, and cyclohexanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethers having a weight average molecular weight of 1,000 or less Ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and polypropylene glycol with a weight average molecular weight of 1,000 or less. The solvent may be one of these solvents, or a mixture of two or more of these solvents.

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

1-6-3. Surfactant In the thermosetting composition of the present invention, a surfactant may be added to improve coating uniformity. Specific examples of surfactants are: Polyflow No.45, Polyflow KL-245, Polyflow No.75, Polyflow No. 90. Polyflow (Polyflow) No.95 (the above are trade names; Kyorongsha Chemical Co., Ltd.), Disperbyk (Disperbyk) 161, Disperbyk (Disperbyk) 162, Diss Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Diss Disperbyk (Disperbyk) 181, Disperbyk (Disperbyk) 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (the above are product names; Japanese Bi BYK Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (the above are trade names; Shin-Etsu Chemical Co., Ltd.), Surflon (Surflon) SC-101, Surflon (Surflon) KH-40, and Surflon (Surflon) S611 (the above are trade names; AGC Seimi Chemical Co., Ltd.), Fugit ( Ftergent) 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent ) 602A, Ftergent 650A, FTX-218 (the above are trade names; Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352 , EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (the above are trade names; Mitsubishi Material Co., Ltd.), Megafa (Megafac) F-171, Megafac F-177, Megafac F-410, Megafac F-430, Megafac ac) 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 F-558, Megafac F-559, Megafac ) R-30, Megafac R-94, Megafac RS-75, Megafac RS-72-K, Megafac RS-76-NS, Megafac DS-21 (the above are trade names; DIC Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (The above are trade names; Evonik-Degussa Japan Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl Ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglyceryl tetra(fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl sulfamate, polyoxygen Vinyl 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 Alcohol palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene Ethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyl diphenyl ether disulfonate. It is preferred to use at least one compound selected from these compounds.

Among these surfactants, if selected from BYK306, BYK342, BYK346, KP-341, KP-358, KP-368, Surflon S611, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac RS-72-K, Megafac DS- 21. TEGO Twin 4000, fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyltrimethylammonium salt, And at least one of fluoroalkylsulfamate, since the coating uniformity of the thermosetting composition becomes high, it is preferable.

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.

1-6-4. Adhesive improving agent From the viewpoint of further improving the adhesiveness between the formed cured film and the substrate, the thermosetting composition of the present invention may further contain an adhesive improving agent. As an example of such an adhesion improving agent, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane ( eg Sila-Ace S510; trade name; JNC Inc.), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (eg Sila-Ace Silane-based coupling agents such as S530; trade name; JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane (such as Sara-Ace (Sila-Ace) S810; trade name; JNC Co., Ltd.), acetyl Aluminum-based coupling agents such as alkoxy aluminum diisopropoxide, and titanate-based coupling agents such as tetraisopropylbis(dioctyl phosphite) titanate.

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

The content of the adhesion improving agent is preferably at most 10% by weight relative to the total amount of the thermosetting composition. On the other hand, it is preferably at least 0.01% by weight.

1-6-5. Antioxidant From the viewpoint of improving transparency and preventing yellowing of the cured film when exposed to high temperatures, the thermosetting composition of the present invention may further contain an antioxidant.

Antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added to the thermosetting composition of the present invention. Among these, hindered phenols are preferred from the viewpoint of light resistance. Specific examples are: Irganox 1010, Irganox FF, Irganox 1035, Irganox 1035FF, Irganox ( Irganox) 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Irganox ( Irganox) 1330, Irganox 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox ( Irganox) 245FF, Irganox 245DWJ, Irganox 259, Irganox 3114, Irganox 565, Irganox ( Irganox) 565DD, Irganox 295 (all trade names; BASF Japan Co., Ltd.), ADK STAB AO-20, ADK STAB (ADK STAB) AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB (ADK STAB) AO-80 (both trade names; ADEKA Inc.). Among them, the better ones are Irganox 1010 and ADK STAB AO-60.

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

1-6-6. Other additives As other components, styrene-maleic anhydride copolymer can be added.

1-7. 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, which is preferable. If the storage temperature is -20°C to 10°C, no precipitates are present, which is more preferable.

2. Cured film obtained from the thermosetting composition The thermosetting resin composition of the present invention can be obtained by mixing polyester amide (A), epoxy compound (B) bonded compound (C) is mixed, and epoxy hardener (D), solvent (E), surfactant, adhesion enhancer, antioxidant, and other additives are further selected and added according to the target characteristics, and these compounds are Mix evenly to dissolve.

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 substrate surface can be performed by conventionally known methods such as spin coating, roll coating, dipping, and slit coating to form a coating film. Next, this coating film is once 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 as above is heated, 1) the polyamic acid part of the polyesteramic acid is dehydrated and cyclized to form an imide bond, and 2) the carboxylic acid of the polyesteramic acid reacts with the epoxy compound And high molecular weight, and 3) The epoxy compound hardens and high molecular weight, so it is very tough, and it is excellent in transparency, heat resistance, chemical resistance, flatness, and adhesiveness. Also, for the same reason, it is expected to be excellent in light resistance, sputter resistance, scratch resistance, and coatability. 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 this color filter. Also, 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 as a transparent electrode formed between a transparent electrode and an alignment film It is effective if it is used with a transparent insulating film. 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.

Compounds used in Synthesis Examples, Examples, and Comparative Examples are described for each component.

Tetracarboxylic dianhydride: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA") 1,2,3,4-butane tetracarboxylic dianhydride (hereinafter Abbreviated as "BT-100") Diamine: 3,3'-diaminodiphenylsulfone (hereinafter abbreviated as "DDS") Polyhydric compound: 1,4-butanediol monohydroxyl compound: benzyl alcohol styrene -Maleic anhydride copolymer: trade name SMA1000P, Chuanyuan Chemical Co., Ltd., hereinafter abbreviated as "SMA1000P" Solvent used in the synthesis reaction of polyester amide acid (A): 3-methoxymethyl propionate ( Hereinafter abbreviated as "MMP") Propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA")

Epoxy compound (B): B1: TECHMORE VG3101L (trade name; Printec Co., Ltd., hereinafter abbreviated as "VG3101L") B2: Celloxide 2021P (trade name name; Daicel Co., Ltd.) B3: COATOSIL MP-200 (trade name; Momentive Performance Materials Co., Ltd.) B4: polyglycidyl methacrylate

Compound (C) having a polymerizable double bond: C1: M-402 (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) C2: M-315 (isocyanurate ethylene oxide modified diacrylate and isocyanuric acid ethylene oxide modified triacrylate mixture) C3: M-520 (carboxyl-containing multifunctional acrylate) C4: M-510 (carboxyl-containing multifunctional acrylate)

Epoxy hardener (D): D1: Trimellitic anhydride D2: Curezole (Curezole) C11Z (imidazole compound) D3: Curezole (Curezole) 2P4MZ (imidazole compound)

Solvent (E): MMP: methyl 3-methoxypropionate PGMEA: propylene glycol methyl ether acetate PEG: polyethylene glycol 400 (trade name; Wako Pure Chemical Industries, Ltd.) PPG: polypropylene glycol, diol Type, 400 (trade name; Wako Pure Chemical Industries, Ltd.)

Additives: Additive-1: 3-glycidyloxypropyltrimethoxysilane (trade name; Sila-Ace S510, JNC Co., Ltd., hereinafter abbreviated as "S510") as a silane-based coupling agent ") Additive-2: Adkstab AO-60 (trade name; ADEKA Co., Ltd., hereinafter abbreviated as "AO-60"), which is a hindered phenolic antioxidant. Additive-3 : Megafac F-556 (trade name; DIC Co., Ltd., hereinafter abbreviated as "F-556") which is a fluorosurfactant

First, a polyester amide acid solution was synthesized from tetracarboxylic dianhydride, diamine, and polyhydric hydroxy compound as shown below (synthesis example 1 and synthesis example 2).

[Synthesis example 1] Synthesis of polyester amide acid solution (A1) In a four-necked flask with a stirrer, dehydrated and purified MMP, ODPA, 1,4-butanediol, and benzyl alcohol were charged at the following weight, The mixture was stirred at 130° C. for 3 hours under a stream of dry nitrogen. MMP 446.96 g ODPA 183.20 g 1,4-Butanediol 31.93 g Benzyl Alcohol 25.54 g

Thereafter, the reacted solution was cooled to 25°C, 3,3'-diaminodiphenylsulfone (hereinafter abbreviated as "DDS") and MMP were added in the following weight, and stirred at 20°C to 30°C for 2 hours Then, stir at 115° C. for 1 hour. DDS 29.33 g MMP 183.04 g [Z/Y=3.0, (Y+Z)/X=0.8]

The solution was cooled to room temperature to obtain a light yellow transparent 30% by weight solution (A1) of polyester amide acid.

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 4,200.

[Synthesis Example 2] Synthesis of Polyester Amino Acid Solution (A2) In a four-neck flask with a stirrer, dehydrated and purified PGMEA, BT-100, SMA1000P, 1,4-butyl were sequentially loaded with the following weights Diol and benzyl alcohol were stirred at 125° C. for 3 hours under a stream of dry nitrogen. PGMEA 487.50 g BT-100 33.51 g SMA1000P 159.55 g 1,4-Butanediol 10.16 g Benzyl Alcohol 48.77 g

Thereafter, the solution after the reaction was cooled to 25° C., DDS and PGMEA were added by the following weights, and stirred at 20° C. to 30° C. for 2 hours, and then at 125° C. for 2 hours. DDS 10.50 g PGMEA 57.69 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 (A2) of polyesteramide.

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 (A2) was 10,000.

[Synthesis Example 3] Synthesis of Polyester Amino Acid (A3) Solution (A3) In a four-necked flask with a stirrer, dehydrated and purified PGMEA, ODPA, SMA1000P, 1,4- Butanediol was stirred at 125° C. for 3 hours under a stream of dry nitrogen. PGMEA 510.00 g ODPA 52.87 g SMA1000P 160.77 g 1,4-Butanediol 10.24 g

Thereafter, the solution after the reaction was cooled to 25° C., DDS and PGMEA were added by the following weights, and stirred at 20° C. to 30° C. for 2 hours, and then at 125° C. for 2 hours. DDS 10.58 g PGMEA 95.00 g [Z/Y=2.7, (Y+Z)/X=0.6]

The solution was cooled to room temperature to obtain a pale yellow transparent 30% by weight solution (A3) of polyesteramide.

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 (A3) was 15,000.

Next, using the 30% by weight solutions (A1), (A2) and (A3) of polyester amide obtained in Synthesis Example 1, Synthesis Example 2, and Synthesis Example 3, thermosetting compositions were prepared as follows A cured film was obtained from the thermosetting composition, and the cured film was evaluated.

[Example 1] The 30% by weight solution (A1) of polyester amide acid obtained in Synthesis Example 1, VG3101L, M-402, trimellitic anhydride, and S510 were mixed in the ratio (unit: g) described in Table 1-1. , AO-60, F-556, MMP, and PGMEA were mixed and dissolved, and filtered through a membrane filter (0.2 μm) to obtain a thermosetting composition.

[Table 1-1]

[Table 1-2]

[Table 1-3]

Furthermore, the total amount of the solvent contained in the thermosetting composition is the total amount of the MMP contained in the polyesteramic acid solution (A1), and the MMP and PGMEA of the solvent (E). The solid content concentration was adjusted to about 15% by weight. The same applies to Example 2 and subsequent examples and comparative examples.

[Evaluation method of flatness] Using a step difference, surface roughness, and fine shape measuring device (trade name; P-17, KLA TENCOR Co., Ltd.), the thermosetting property was measured at 300 rpm for 10 seconds. The composition was spin-coated on a color filter substrate without a hardened film having pixels including R, G, B, and W whose surface level difference was measured, 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 color filter substrate with a cured film having an average film thickness of the protective film of 2.0 μm. Then, the surface level difference was measured about the obtained color filter board|substrate with a cured film. Calculate the planarization rate from the maximum value of the surface level of the color filter substrate without a hardening film and the color filter substrate with a hardening film (hereinafter abbreviated as "maximum level difference"), using the following formula , and the results are shown in Table 1-1. The case where the flattening rate was 75% or more was evaluated as flatness (circle), and the case where the flattening rate was less than 75% was evaluated as flatness ×. Furthermore, the color filter substrate without a hardened film is used with a maximum step difference of 2.5 μm. Planarization rate = (maximum step difference of color filter substrate without hardening film - maximum step difference of color filter substrate with hardening film) / (maximum step difference of color filter substrate without hardening film) ×100%

[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. 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 2.0 μm. The pencil hardness of the cured film was measured by performing 8.4.1 pencil scratch test of JIS K-5400-1990 on the obtained glass substrate with the cured film, and the result is shown in Table 1-1. The case where the pencil hardness was 3H or more was evaluated as scratch resistance ◯, and the case where the pencil hardness was 2H or less was evaluated as scratch resistance ×.

[Example 2 to Example 23 and Comparative Example 1] According to the method of Example 1, each component was mixed and dissolved at the ratio (unit: g) described in Table 1-1 to Table 1-3 to obtain a thermosetting composition thing. The planarization rate and pencil hardness were measured according to the method of Example 1, and the evaluation results of flatness and scratch resistance are shown in Tables 1-1 to 1-3.

As is clear from the results shown in Tables 1-1 to 1-3, the thermosetting compositions of Examples 1 to 23 are excellent in flatness and scratch resistance. On the other hand, it can be seen that in Comparative Example 1, which is a thermosetting composition not containing a compound (C) having a polymerizable double bond, flatness and scratch resistance are poor.

[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 Protective films for various optical materials such as light receiving elements, and insulating films formed between TFTs and transparent electrodes and between transparent electrodes and alignment films.

none

none

Claims (7)

A thermosetting composition comprising polyester amide acid (A), an epoxy compound (B) and a compound (C) having a polymerizable double bond, the thermosetting composition is characterized in that: the poly Esteramide acid (A) is a polyhydric hydroxyl compound containing X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyhydric hydroxyl compounds at a ratio established by the following formula (1) and formula (2). The reaction product of raw materials, 0.2≦Z/Y≦8.0. ． ． ． ． ． ． (1) 0.2≦(Y+Z)/X≦5.0...(2) The epoxy compound (B) does not include an epoxy compound having a fluorene skeleton, and the compound (C) having a polymerizable double bond is Multifunctional (meth)acrylic compound, relative to 100 parts by weight of the polyester amide acid (A), the content of the epoxy compound (B) is 200 parts by weight to 400 parts by weight, and the polymerizable The content of the double bond compound (C) is 1 to 400 parts by weight. The thermosetting composition as described in claim 1, wherein the polyester amide acid (A) comprises a structural unit represented by the following formula (3) and a structure represented by the following formula (4) unit,

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 the polyhydric hydroxy compound. The thermosetting composition according to claim 1, wherein the compound (C) having a polymerizable double bond includes a compound having three or more polymerizable double bonds per molecule. The thermosetting composition as described in item 3 of the scope of the patent application, wherein the compound having three or more polymerizable double bonds in each molecule is selected from the group consisting of isocyanuric acid ethylene oxide modified triacrylate , trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and carboxyl-containing polyfunctional (meth)acrylates of at least one compound. The thermosetting composition as described in item 1 of the scope of the patent application, wherein the compound (C) having a polymerizable double bond is selected from isocyanuric acid ethylene oxide modified diacrylate and isocyanuric acid Mixture of ethylene oxide modified triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate At least one compound in the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and carboxyl-containing polyfunctional (meth)acrylate. A cured film obtained by curing the thermosetting composition described in any one of claims 1 to 5. A color filter having the hardened film described in claim 6 as a transparent protective film.