TW202010769A - Thermosetting compositions, cured film, and color filter - Google Patents

Abstract

The present invention relates to a thermocuring composition, a cured film, and a color filter, which includes a polyester acyl amine acid (A), a polymer of a cyclic ether compound (B), and a cationic polymerization initiator (C). The polyester acyl amine acid (A) is a reaction product derived from a raw material including X mole of tetracarboxylic dianhydride, Y mole of diamine and Z mole of polyhydroxy compound at a ratio established by the relationship of the following formula (1) and formula (2), wherein the polymer of the cyclic ether compound (B) is a polymer derived from a monomer containing a compound (b1) having an oxetanyl group. The thermocuring composition of the present invention can form a cured film that prevents elution of the base component, has excellent flatness, and has good adhesion to the base substrate. 0.2 ≤ Z/Y ≤ 8.0·······(1) 0.2 ≤(Y+Z)/X ≤ 5.0···(2).

Description

Thermosetting composition, cured film and color filter

The present invention relates to an insulating material that can be used to form an electronic component, a passivation film in a semiconductor device, a buffer coating film, an interlayer insulating film, a planarizing film, an interlayer insulating film in a liquid crystal display element, and a color filter ) A thermosetting composition such as a protective film, a transparent film formed from the thermosetting composition, and an electronic component having the film.

In the manufacturing process of devices such as liquid crystal display devices, various chemicals such as organic solvents, acids, and alkaline solutions are sometimes treated, or when forming wiring electrodes by sputtering, the surface is partially exposed to high temperatures Under heating. Therefore, a surface protection film is sometimes provided for the purpose of preventing deterioration, damage, or deterioration of the surface of various elements. These protective films are required to withstand the characteristics of various treatments in the manufacturing steps described above. 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, flatness, and light resistance are required Wait. With the improvement of the required characteristics of the reliability required for display elements and the improvement of the heat resistance required for display element members, a thermosetting composition containing polyester amidic acid and epoxy compounds with good heat resistance is advocated Thing (Patent Literature 1). Furthermore, in recent years, as the flatness required for high-definition and thinned liquid crystal display elements has been improved, thermosetting compositions in which the molecular weight of the epoxy compound of the invention has been adjusted are proposed, in addition to good heat resistance. The flatness is also improved (Patent Document 2).

Recently, the requirements for reducing the elution of the base component (hereinafter also referred to as barrier properties) other than heat resistance and flatness have been strengthened. Against this background, especially in the field of color filters, there is a response to wide color gamut. Among the color filter manufacturers, it is obvious to use pigments with good color and easy to dissolve or decompose, or to prevent discoloration. The process of hardening the light is the minimum trend. The influence on the color filter and the surface protective film caused by these trends is particularly remarkable when forming the alignment film.

The alignment film laminated on the side of the color filter is usually coated on the surface protective film, and has a function of controlling the arrangement of liquid crystal molecules (hereinafter also referred to as alignment). In order to develop the alignment, polyimide is used as the main component, but in order to dissolve the polyimide, it is necessary to use a solvent having high resin solubility such as N-methylpyrrolidone (hereinafter also referred to as a strong solvent). Although the conventional color filter has resistance to the strong solvent used in the step of forming the alignment film, the resistance of the color filter to the strong solvent is reduced due to the above-mentioned trend, and it is likely to be dissolved in the strong solvent. The color filter components elute to the alignment film layer and the liquid crystal layer. As a result, in the conventional protective film that does not respond to these trends, there is a problem that when forming the panel, the color filter components are mixed into the alignment film layer and the liquid crystal layer, thereby degrading the display quality of the display, resulting in a decrease in yield, and the like.

In response to the above-mentioned problems, as a specific countermeasure required for the protective film, it is required that the degassed components such as the decomposition products of the color filter generated during the thermosetting step when forming the protective film and the alignment film are not aligned The film layer and the liquid crystal layer are shielded by flying; when the alignment film is formed, the strong solvent is prevented from infiltrating into the color filter, so that the pigment component of the color filter or the decomposition product is not eluted to the alignment film layer and the liquid crystal layer, etc. .

Various studies have been actively conducted to meet these requirements, but in addition to the thermosetting resin compositions shown above (Patent Document 1 and Patent Document 2), they contain polyester amide acid and N-substituted maleimide An amine thermosetting polymer composition (Patent Document 3) is also an example. On the other hand, the compositions of Patent Literature 1 and Patent Literature 3 may have a good resistance to various treatments, but the flatness is insufficient, and the barrier properties are required to be improved depending on the situation. In addition, the composition of Patent Document 2 also has good resistance to various treatments and flatness, but there is room for improvement in barrier properties. [Prior Art Literature]

[Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 2005-105264 [Patent Document 2] Japanese Patent Laid-Open No. 2008-156546 [Patent Document 3] Japanese Patent Laid-Open No. 2006-282995

[Problems to be solved by the invention] The problem of the present invention is to provide a thermosetting composition that provides a cured film that prevents elution of the base component, has excellent flatness, and has good adhesion to the base substrate, and a cured film formed from the thermosetting composition, and Provided is an electronic part having the hardened film.

[Technical means to solve the problem] The inventors of the present invention have made intensive studies in order to solve the above-mentioned problems, and as a result, have found that the above-mentioned object can be achieved by using the following cured film, which contains the tetracarboxylic dianhydride, The reaction product of the diamine and the polyhydric hydroxy compound is obtained by hardening the composition of the polyester amide acid, the polymer of the cyclic ether compound, and the cationic polymerization initiator. The present invention includes the following configurations.

[1] A thermosetting composition comprising polyester amide acid (A), a polymer (B) of a cyclic ether compound, and a cationic polymerization initiator (C), and the thermosetting composition , The polyester amide acid (A) is derived from a tetracarboxylic dianhydride containing X moles, a diamine of Y moles, and a Z mole from the ratio established by the relationship of the following formula (1) and formula (2) The reaction product of the raw materials of polyhydroxy compounds, 0.2≦Z/Y≦8.0······(1) 0.2≦（Y+Z）/X≦5.0··（2） The polymer (B) of the cyclic ether compound is a homopolymer selected from a compound (b1) having an oxetanyl group, a copolymer of a compound (b1) having an oxetanyl group, and having an oxa At least one of a copolymer of a cyclobutyl compound (b1) and an oxetanyl-containing compound (b2).

式（3）及式（4）中，R¹ 為自四羧酸二酐除去兩個-CO-O-CO-而成的殘基，R² 為自二胺除去兩個-NH₂ 而成的殘基，R³ 為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 formula represented by the following formula (4) Structural units.

In formula (3) and formula (4), R ¹ is a residue obtained by removing two -CO-O-CO- from tetracarboxylic dianhydride, and R ² is obtained by removing two -NH ₂ from a diamine R ³ is a residue obtained by removing two -OH groups from a polyhydroxy compound.

[3] The thermosetting composition according to item [1] or [2], wherein the compound (b1) having an oxetanyl group is selected from acrylic acid (3-ethyloxetane At least one of -3-yl) methyl ester and (3-ethyloxetan-3-yl) methyl methacrylate.

[4] The thermosetting composition according to item [1] or [2], wherein the compound (b2) having an oxetanyl group is selected from glycidyl acrylate and glycidyl methacrylate At least one of methyl glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether.

[5] The thermosetting composition according to any one of [1] to [4], wherein the polymer (B) of the cyclic ether compound is relative to 100 parts by weight of the polyester amide acid (A) ) Content is 20 parts by weight to 400 parts by weight.

[6] The thermosetting composition according to any one of [1] to [5], wherein the cationic polymerization initiator (C) is an anionic antimony-free cationic polymerization initiator.

[7] The thermosetting composition according to any one of [1] to [6], wherein the cationic polymerization initiator (C) is an anionic species that does not contain antimony and the cationic species is a cationic polymer starting from the samium salt system. Initial agent.

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

[9] A color filter having the cured film according to [8] as a transparent protective film.

[Effect of invention] The thermosetting composition of the preferred embodiment of the present invention is a material that prevents elution of the base component and has excellent flatness, and when used as a color filter protective film for a color liquid crystal display element, can improve display quality . In particular, it is effectively used as a protective film for color filters manufactured by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. In addition, it can also be used as a protective film and transparent insulating film for various optical materials.

1. The thermosetting composition of the present invention The thermosetting composition of the present invention is a composition containing a polyester amide acid (A), a polymer (B) of a cyclic ether compound, and a cationic polymerization initiator (C), the polyester amide acid (A) is a reaction product derived from a raw material containing tetracarboxylic dianhydride, diamine, and polyhydroxy compound, and the polymer (B) of the cyclic ether compound is selected from compounds having oxetanyl group (b1) Homopolymers, copolymers of oxetanyl compound (b1) and copolymers of oxetanyl compound (b1) and oxetanyl compound (b2) One kind.

1-1. Polyester amide acid (A) Polyesteramide acid is a reaction product derived from raw materials containing tetracarboxylic dianhydride, diamine, and polyhydroxy compound. More specifically, the polyester amide acid is derived from a tetracarboxylic dianhydride containing X moles, a diamine of Y moles, and Z from the ratio established by the relationship of the following formula (1) and formula (2) The reaction product of the raw material of polyhydric hydroxy compound of Mohr. 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 a 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 polyhydroxy compound, and is preferably an organic group having 2 to 20 carbon atoms.

In the synthesis of the polyester amide acid (A), at least a solvent is required, and the solvent can be left directly to form a liquid or gel-like thermosetting composition in consideration of operability and the like. The solvent is removed to produce a solid composition in consideration of transportability and the like. In addition, in the synthesis of polyester amide acid (A), if necessary, one or more compounds selected from a monohydroxy compound and a styrene-maleic anhydride copolymer may be included as a raw material, particularly preferably a monohydroxy compound . In addition, in the synthesis of the polyester amide acid (A), other compounds than the above may be included as a raw material as necessary within a range that does not impair the object of the present invention.

1-1-1. Tetracarboxylic dianhydride In the present invention, as a material for obtaining polyester amide acid (A), tetracarboxylic dianhydride is used. Specific examples of preferred tetracarboxylic dianhydride 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'-diphenyl ash tetracarboxylic dianhydride, 2,2',3, 3'-diphenyl sulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether 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-butane tetracarboxylic dianhydride, ethylene glycol bis (dehydrated trimellitate) (trade name; TMEG- 100, New Japan Physical and Chemical Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, ethane Tetracarboxylic dianhydride and butane tetracarboxylic dianhydride. One or more of these tetracarboxylic dianhydrides can be used.

Among these tetracarboxylic dianhydrides, 3,3',4,4'-diphenyl sulfide 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), further preferably 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid di Anhydride and 1,2,3,4-butane tetracarboxylic dianhydride.

1-1-2. Diamine In the present invention, as a material for obtaining polyester amide acid (A), diamine is used. Specific examples of preferred diamines are: 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl ash, 3,4'-diaminodiphenyl ash, bis [4-(4-Aminophenoxy)phenyl] phenanthrene, bis[4-(3-aminophenoxy)phenyl] phenanthrene, bis[3-(4-aminophenoxy)phenyl ] 碸, [4-(4-aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl] 碸, [4-(3-aminophenoxy)phenyl] [3-(4-Aminophenoxy)phenyl] benzene and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. One or more of these diamines can be used.

Among these diamines, 3,3′-diaminodiphenyl sulfone and bis[4-(3-aminophenoxy)phenyl] benzene, which impart good transparency, are more preferred, and 3, 3'-diaminodiphenyl sulfone.

1-1-3. Polyhydroxy compounds In the present invention, as a material for obtaining the polyester amide acid (A), a polyhydroxy compound is used.

Specific examples of preferred polyhydric hydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, Tetrapropylene glycol, polypropylene glycol with a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol Alcohol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6- Hexatriol, 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6- Octanediol, 1,2,8-octanetriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1, 10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, iso Tris (2-hydroxyethyl) cyanurate, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxyphenyl) ash), bisphenol F (Bis(4-hydroxyphenyl)methane), 4,4'-isopropylidenebis(2-phenoxyethanol), 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'- Dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-(4-hydroxyphenyl) ethanol, diethanolamine, triethanolamine,

Glycerol monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, dipentaerythritol monoallyl ether, dipentaerythritol diallyl ether, dipentaerythritol Triallyl ether, dipentaerythritol tetraallyl ether, sorbitol monoallyl ether, sorbitol diallyl ether, sorbitol triallyl ether, sorbitol tetraallyl ether, Glycerin mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol mono(meth)acrylate, Dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, sorbitol mono(meth)acrylate, sorbitol di(meth)acrylate Ester, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, (meth)acrylic acid modified product of ethylene glycol diglycidyl ether, (methyl) of propylene glycol diglycidyl ether Acrylic acid modified product, (meth)acrylic acid modified product of tripropylene glycol diglycidyl ether, (meth)acrylic acid modified product of glycerol diglycidyl ether, (meth)acrylic acid modified product of bisphenol A diglycidyl ether, cyclic Oxypropane modified bisphenol A diglycidyl ether (meth)acrylic modified product, bisphenol S diglycidyl ether (meth)acrylic modified product, propylene oxide modified bisphenol S diglycidyl ether ( Methacrylic acid modified product, (meth)acrylic acid modified product of bisphenol F diglycidyl ether, (meth)acrylic acid modified product of propylene oxide modified bisphenol F diglycidyl ether, bixylenol diglycidyl Modified (meth)acrylic acid of glyceryl ether, modified (meth)acrylic acid of diphenol diglycidyl ether, modified (meth)acrylic acid of stilbene diglycidyl ether, cyclohexane-1,4- Modified (meth)acrylic acid of dimethanol diglycidyl ether, modified (meth)acrylic acid of hydrogenated bisphenol A diglycidyl ether, modified (meth)acrylic acid of tricyclodecane dimethanol diglycidyl ether And (meth)acrylic acid modified products of other compounds containing more than two epoxy groups in each molecule.

Among these polyhydric hydroxy compounds, preferred are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1 which have good solubility in the reaction solvent. ,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, tris(2-hydroxyethyl) isocyanurate, 2,2-bis(4-hydroxycyclohexyl)propane , 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-(4-hydroxyphenyl)ethanol, 4,4'-isopropylidenebis(2-phenoxy (Ethyl alcohol), (meth)acrylic acid modified product of ethylene glycol diglycidyl ether, (meth)acrylic acid modified product of propylene glycol diglycidyl ether, (meth)acrylic acid modified product of glycerol diglycidyl ether, bisphenol (Meth)acrylic acid modified product of A diglycidyl ether, (meth)acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether, (meth)acrylic acid modified product of bisphenol S diglycidyl ether , (Meth)acrylic acid modified product of propylene oxide modified bisphenol S diglycidyl ether, (meth)acrylic acid modified product of bisphenol F diglycidyl ether, and propylene oxide modified bisphenol F diglycidyl ether Modified (meth)acrylic acid. Furthermore, particularly preferred are diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol (Meth)acrylic acid modified product of alcohol, 4,4'-isopropylidenebis(2-phenoxyethanol), 2-(4-hydroxyphenyl)ethanol, ethylene glycol diglycidyl ether, propylene glycol di (Meth)acrylic acid modified product of glycidyl ether, (meth)acrylic acid modified product of tripropylene glycol diglycidyl ether, (meth)acrylic acid modified product of glycerol diglycidyl ether, and bisphenol A diglycidyl ether ( (Meth)acrylic acid modified product and propylene oxide modified bisphenol A diglycidyl ether (meth)acrylic acid modified product.

Modified methacrylic acid as ethylene glycol diglycidyl ether, modified acrylic acid as propylene glycol diglycidyl ether, modified acrylic acid as tripropylene glycol diglycidyl ether, modified acrylic acid as glycerol diglycidyl ether, bisphenol A Modified methacrylic acid of glycidyl ether, modified acrylic acid of bisphenol A diglycidyl ether, modified methacrylic acid of propylene oxide modified bisphenol A diglycidyl ether, and modified bisphenol A dipropylene oxide As the acrylic acid-modified product of glycidyl ether, the following commercially available products can be used.

A specific example of the methacrylic acid modified product of ethylene glycol diglycidyl ether is epoxy ester 40EM (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of propylene glycol diglycidyl ether is epoxy ester 70PA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of tripropylene glycol diglycidyl ether is epoxy ester 200PA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of glycerol diglycidyl ether is epoxy ester 80MFA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the methacrylic acid modified product of bisphenol A diglycidyl ether is epoxy ester 3000MK (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic modified product of bisphenol A diglycidyl ether is epoxy ester 3000A (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of a methacrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether is epoxy ester 3002M (N) (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of propylene oxide-modified bisphenol A diglycidyl ether is epoxy ester 3002A(N) (trade name; Kyoeisha Chemical Co., Ltd.).

1-1-4. Monohydroxy compound In the present invention, as a material for obtaining the polyester amide acid (A), a monohydroxy compound can be used. By using a monohydroxy compound, the storage stability of the thermosetting composition is improved. 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 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 (terpineol), dimethyl benzyl methanol (dimethyl benzyl carbinol) and 3-ethyl-3-hydroxymethyl oxetane. One or more of these monohydroxy compounds can be used.

Among these monohydroxy compounds, isopropyl alcohol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane are more preferred. If the polyester amide acid (A) formed using these monohydroxy compounds is mixed with the polymer (B) of the cyclic ether compound and the cationic polymerization initiator (C), the compatibility, or heat For the coating property of the curable composition on the color filter, benzyl alcohol is preferably used for the monohydroxy compound.

The reaction is preferably carried out with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine and polyhydroxy compound, preferably containing 0 to 300 parts by weight of monohydroxy compound. More preferably, it is 5 to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer In addition, 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. The transparency of the polyester amidic acid (A) synthesized by adding a compound having three or more acid anhydride groups is expected to be improved, so it is preferable. An example of a compound having three or more acid anhydride groups is a styrene-maleic anhydride copolymer. Regarding the ratio of each component constituting the styrene-maleic anhydride copolymer, the mole ratio of styrene/maleic anhydride is 0.5 to 4, preferably 1 to 3. The molar ratio of styrene/maleic anhydride is more preferably 1 or 2, and further preferably 1.

Specific examples of styrene-maleic anhydride copolymers are SMA3000P, SMA2000P, and SMA1000P (all are trade names; Sichuan Crude Oil Chemical Co., Ltd.). Among these styrene-maleic anhydride copolymers, SMA1000P having excellent heat resistance and alkali resistance is particularly preferred.

The styrene-maleic anhydride copolymer preferably contains 0 to 500 parts by weight relative to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyhydroxy compound. More preferably, it is 10 parts by weight to 300 parts by weight.

1-1-6. Aminosilane compounds with one amine group In the synthesis of polyester amide acid (A), other raw materials other than those mentioned above may be included as raw materials as needed within a range that does not impair the object of the present invention. Examples of such other raw materials are having an amine group Of amino silane compounds. The aminosilane compound having one amine group is used to react with the acid anhydride group at the terminal of the polyester amide acid (A) to introduce a silane group at the terminal. If the thermosetting composition of the present invention containing polyester amide acid (A) is used, the acid resistance of the obtained cured film can be improved. The polyester amide acid (A) has one amine group by adding Obtained by reacting the aminosilane compound. Furthermore, when the reaction is carried out with the above-mentioned monomer structure, both a monohydroxy compound and an aminosilane compound having one amine group may be added and reacted.

Specific examples of the preferred aminosilane compound having one amine group used in the present invention are: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-amino group Propylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-amine Butylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyl Diethoxysilane, m-aminophenyltrimethoxysilane and m-aminophenylmethyldiethoxysilane. One or more of these compounds can be used.

Among these compounds, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane with improved acid resistance of the cured film are more preferred. From the viewpoint of acid resistance and compatibility, Furthermore, 3-aminopropyltriethoxysilane is preferable.

The aminosilane compound having one amine group preferably contains 0 to 300 parts by weight relative to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine and polyhydroxy compound. More preferably, it is 5 to 200 parts by weight.

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

1-1-8. Synthesis method of polyester amide acid (A) The polyester amide acid (A) used in the present invention is preferably synthesized by reacting tetracarboxylic dianhydride X mole, diamine Y mole and polyhydroxy compound Z mole in the solvent. At the time, X, Y, and Z are determined as the ratios in which the relationship of the following formula (1) and formula (2) is established. Within the above range, the solubility of the polyester amidic acid (A) in the solvent is high, so the coating property of the composition is improved, and as a result, a cured film excellent in flatness can be obtained. 0.2≦Z/Y≦8.0······(1) 0.2≦（Y+Z）/X≦5.0··（2） In formula (1), preferably 0.7≦Z/Y≦7.0, more preferably 1.0≦Z/Y≦5.0. In addition, in formula (2), 0.5≦(Y+Z)/X≦4.0 is preferable, and 0.6≦(Y+Z)/X≦2.0 is more preferable.

It can be considered that the polyester amide acid (A) used in the present invention is more than the molecule having an amine group or a hydroxyl group at the terminal under the reaction conditions under the excessive use of X relative to (Y+Z) A molecule having an acid anhydride group (-CO-O-CO-) at the end is excessively generated. When reacting with such a monomer structure, in order to react with an acid anhydride group at the molecular terminal to esterify the terminal, the above-mentioned monohydroxy compound may be added as necessary. The polyester amide acid (A) obtained by adding a monohydroxy compound to the reaction can improve the compatibility with the polymer (B) of the cyclic ether compound and the cationic polymerization initiator (C), and can improve the inclusion of these The coatability of the thermosetting composition of the present invention of the compound.

If 100 parts by weight or more of a reaction solvent is used with respect to a total of 100 parts by weight of tetracarboxylic dianhydride, diamine, and polyhydroxy compound, the reaction proceeds smoothly, which 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 also be used: a method of adding tetracarboxylic dianhydride, diamine, and polyhydroxy compound to the reaction solvent at the same time; after dissolving the diamine and polyhydroxy compound in the reaction solvent, adding tetracarboxylic acid The method of dianhydride; the method of adding the diamine to the reaction product after reacting the tetracarboxylic dianhydride with the polyhydroxy compound in advance; or the method of adding the diamine to the reaction product after reacting the tetracarboxylic dianhydride and the diamine in advance Methods of polyhydric hydroxy compounds, etc.

In the case of reacting the amine silane compound having one amine group, after the reaction of the tetracarboxylic dianhydride, diamine and polyhydric hydroxy compound is completed, the solution after the reaction is cooled to 40°C or less, and then added The aminosilane compound having one amine group is preferably reacted at 10°C to 40°C for 0.1 to 6 hours. In addition, the monohydroxy compound may be added at any stage of the reaction.

The polyester amide acid (A) synthesized in the above manner includes the structural unit represented by the formula (3) and the structural unit represented by the formula (4), and its terminal is derived from the tetracarboxylic dianhydride as a raw material, The anhydride group, amine group or hydroxyl group of the diamine or polyhydroxy compound, or additives other than these compounds constitute the terminal. By including such a structure, curability becomes good.

The weight average molecular weight of the obtained polyester amide acid (A) is preferably 1,000 to 200,000, and more preferably 2,000 to 50,000. Within these ranges, flatness and heat resistance become good.

The weight-average molecular weight in this specification is a polystyrene conversion value obtained by gel permeation chromatography (Gel Permeation Chromatography, GPC) method (column temperature: 35°C, flow rate: 1 ml/min). For standard polystyrene, use polystyrene with a molecular weight of 645 to 132900 (for example, Agilent Technologies Co., Ltd. polystyrene calibration kit (PL2010-0102), and use PL gel for column mixing (PLgel MIXED)-D (Agilent Technologies Co., Ltd.) can be measured using tetrahydrofuran (Tetrahydrofuran, THF) as the mobile phase. In addition, the weight average molecular weight of the commercial item in this specification is the value described in a catalog.

1-2. Polymer of cyclic ether compound (B) The polymer (B) of the cyclic ether compound used in the present invention is a copolymer selected from a homopolymer of a compound (b1) having an oxetanyl group and a compound (b1) having an oxetanyl group. And at least one copolymer of an oxetanyl group-containing compound (b1) and an oxetanyl group-containing compound (b2). The polymer (B) of the cyclic ether compound may be one kind, or two or more kinds may be used.

In the case where the compound (b1) having an oxetanyl group is copolymerized with the compound (b2) having an oxetanyl group, if the ratio of the compound (b1) having an oxetanyl group is From 50% by weight to 90% by weight in the polymer (B), it is preferable from the viewpoint of barrier properties. If the ratio of the compound (b1) having an oxetanyl group is 70% by weight to 90% by weight, the barrier property is further improved.

Specific examples of the compound (b1) having an oxetanyl group include: (3-ethyloxetan-3-yl)methyl acrylate (for example, trade name; OXE-10, Osaka Organic Chemistry Industrial Co., Ltd.), (3-ethyloxetan-3-yl) methyl methacrylate (for example, trade name; OXE-30, Osaka Organic Chemical Industry Co., Ltd.).

Specific examples of the compound (b2) having an oxetanyl group include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether. .

1-3. Ratio of polymer (B) of cyclic ether compound to polyester amide (A) The ratio of the total amount of the polymer (B) of the cyclic ether compound relative to 100 parts by weight of the polyester amide acid (A) in the thermosetting composition of the present invention is 20 parts by weight to 400 parts by weight. When the ratio of the total amount of polymers (B) of the cyclic ether compound is within the above range, the balance of barrier properties, flatness, and heat resistance is good.

1-4. Cationic polymerization initiator (C) In the thermosetting composition of the present invention, a cationic polymerization initiator (C) is used. The cationic polymerization initiator (C) used in the present invention is an onium salt, and as a cationic species, an ammonium salt, a monium salt, an iodonium salt, and a phosphonium salt are used, and as an anionic species, antimony hexafluoride or phosphorus hexafluoride is used Wait. Among these cationic polymerization initiators, from the viewpoint of safety, it is desirable to use a cationic polymerization initiator whose anionic species is phosphorus hexafluoride.

Specific examples of the ammonium salt-based cationic polymerization initiator include: K-PURE CXC-1612, K-PURE CXC-1613, K-PURE CXC-1615, K-PURE TAG2172, K-PURE TAG-2678 , K-PURE TAG2713 (both trade names; KING INDUSTRIES Co., Ltd.).

As specific examples of the cationic salt-based cationic polymerization initiators, Sun-aid SI-110, Sun-aid SI-150, Sun-aid SI-300 (all trade names; Sanxin Chemical Industry Co., Ltd.); CPI-100P, CPI-200K (all trade names; Sanapro Co., Ltd.).

Specific examples of the iodonium salt-based cationic polymerization initiator include Irgacure 250 and Irgacure 270 (both trade names; BASF Europe).

Specific examples of the phosphonium salt-based cationic polymerization initiator include ethyltriphenylphosphonium hexafluorophosphate, ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium hexafluorophosphate, Tetrabutylphosphonium hexafluoroantimonate.

Among these cationic polymerization initiators (C), Sun-aid SI-150, which is a cationic polymerization initiator using antimony hexafluoride, exhibits very good flatness and barrier properties. On the other hand, antimony is a toxic substance, and from the viewpoint of safety, it is preferable to add a cationic polymerization initiator containing no antimony to the composition. If it is selected from cationic polymerization initiators that do not contain antimony, from the viewpoint of flatness, barrier properties, safety, and added amount, it is preferably a cationic polymerization initiator of the saline salt type.

When the cationic polymerization initiator (C) is used, the ratio of the cationic polymerization initiator (C) is 0.1 to 60 parts by weight with respect to 100 parts by weight of the polymer (B) of the cyclic ether compound.

1-5. Hardener The thermosetting composition of the present invention may include an acid anhydride-based hardener, a carboxylic acid-containing polymer, an imidazole-based hardener, and a phenol-based hardener from the viewpoint of further improving heat resistance and chemical resistance. Etc. hardener.

Specific examples of the acid anhydride-based hardener are: maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride and other aliphatic Dicarboxylic anhydride; aromatic polycarboxylic anhydrides such as phthalic anhydride and trimellitic anhydride; and styrene-maleic anhydride copolymers. Among these acid anhydride-based curing agents, preferred are trimellitic anhydride and hexahydrotrimellitic anhydride, which have a good balance between heat resistance and solubility in solvents.

Specific examples of the carboxylic acid-containing polymer include: ARUFON UC-3000, ARUFON UC-3090, ARUFON UC-3900 (all are trade names ; East Asia Synthetic Co., Ltd.), Marproof MA-0215Z, Marproof MA-0217Z and Marproof MA-0221Z (both trade names; Nippon Oil Co., Ltd. the company). Among these carboxylic acid-containing polymers, ARUFON UC-3900 having good heat resistance, solubility in solvents and flatness is preferred.

Specific examples of the imidazole-based hardener are: 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro -1H-pyrrolo[1,2-a]benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-benzyl-2-methylimidazole and 1- Benzyl-2-phenylimidazole. Among these imidazole-based hardeners, 2-undecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenyl, which have a good balance of hardenability and solubility in solvents, are preferred Imidazole.

Specific examples of phenolic hardeners include: α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 1,1,1-tris(4-hydroxybenzene Group) ethane, 9,9-bis(4-hydroxy-3-methylphenyl) stilbene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 4,4 '-(3,3,5-trimethyl-1,1-cyclohexanediyl)bis(phenol) and 1,1,2,2-tetra(4-hydroxyphenyl)ethane. Among these phenolic hardeners, α,α,α'-tri(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 1, which has a good balance of heat resistance and compatibility are preferred 1,1-tris(4-hydroxyphenyl)ethane and 9,9-bis(4-hydroxy-3-methylphenyl) stilbene.

When a hardener is used, it is preferably 0.1 part by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the polymer (B) of the cyclic ether compound.

1-6. Other ingredients In the thermosetting composition of the present invention, various additives may be added to improve film properties such as flatness, scratch resistance, coating uniformity, and adhesion. Additives mainly include: epoxy compounds other than oxetanyl compound (b2), compounds having polymerizable double bonds, solvents, anionic, cationic, nonionic, fluorine or silicon leveling Agents/surfactants, adhesion improvers such as silane coupling agents, antioxidants such as hindered phenols, hindered amines, phosphorus, and sulfur compounds.

1-6-1. Epoxy compound In the thermosetting composition of the present invention, an epoxy compound other than the compound (b2) having an oxetanyl group can also be used. The epoxy compound used arbitrarily in the thermosetting composition of the present invention is a compound having two or more epoxy groups per molecule. The epoxy compound may be one kind, or two or more kinds may be used.

Examples of the epoxy compound are: bisphenol A epoxy compound, bisphenol F epoxy compound, glycidyl ether epoxy compound, glycidyl ester epoxy compound, biphenyl epoxy compound, phenol novolac Varnish-type epoxy compounds, cresol novolac-type epoxy compounds, bisphenol A novolac-type epoxy compounds, aliphatic polyglycidyl ether compounds, cyclic aliphatic epoxy compounds, monomers with epoxy groups and others Copolymers of monomers and epoxy compounds with siloxane bond sites.

Specific examples of commercially available products of bisphenol A type epoxy compounds are jER 828, jER 1004, and jER 1009 (all trade names; Mitsubishi Chemical Corporation); specific examples of commercially available products of bisphenol F type epoxy compounds JER 806, jER 4005P (both trade names; Mitsubishi Chemical Co., Ltd.); a specific example of a commercially available product of a glycidyl ether epoxy compound is TECHMORE VG3101L (trade name; Plintech ( Printec) Co., Ltd.), EHPE3150 (trade name; Daicel) Co., Ltd., EPPN-501H, EPPN-502H (both trade names; Nippon Kayaku Co., Ltd.), and jER 1032H60 (trade name; Mitsubishi Chemical Corporation); specific examples of commercially available products of glycidyl ester epoxy compounds are Denacol EX-721 (trade name; 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 products of biphenyl-type epoxy compounds are jER YX4000, jER YX4000H, and jER YL6121H (all Is a trade name; Mitsubishi Chemical Co., Ltd.), and NC-3000, NC-3000-L, NC-3000-H, NC-3100 (all trade names; Nippon Kayaku Co., Ltd.); phenol novolak type ring Specific examples of commercially available products of oxygen compounds are EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), and jER 152, jER 154 (both trade names; Mitsubishi Chemical Co., Ltd.), etc.; cresol novolac type Specific examples of commercially available products of epoxy compounds are EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all are trade names; Nippon Kayaku Co., Ltd.), etc.; bisphenol A novolac epoxy compound Specific examples of commercially available products are jER 157S65, jER 157S70 (both trade names; Mitsubishi Chemical Co., Ltd.); specific examples of commercially available products of cycloaliphatic epoxy compounds are Celloxide 2021P, Celloxide 3000 (both trade names; Daicel) Co., Ltd.; a specific example of a commercial product of an epoxy compound having a siloxane bond site is 1,3-bis[2 -(3,4-epoxycyclohexyl)ethyl]tetramethyldisilaxane (trade name; Gelest Incorporated), TSL9906 (trade name; Momentive, Japan) Performance Materials Japan) Co., Ltd., COATOSIL MP 200 (trade name; Momentive Performance Materials Japan), Conpoceran SQ506 (trade name; Arakawa Chemical Co., Ltd.), ES-1023 (trade name; Shin-Etsu Chemical Industry) 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 -Glycidoxy)phenyl]-1-[4-[1-[4-(2,3-glycidoxy)phenyl]-1-methylethyl]phenyl]ethyl] Phenoxy]-2-propanol mixture; EHPE3150 (trade name; Daicel Corporation) is 1,2-epoxy of 2,2-bis(hydroxymethyl)-1-butanol -4-(2-oxiranyl) cyclohexane adduct; Celloxide 2021P (trade name; Daicel Corporation) is 3', 4'- Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate; Celloxide 3000 (trade name; Daicel Corporation) is 1-methyl-4-( 2-methyloxirane)-7-oxabicyclo[4.1.0]heptane; COATOSIL MP200 (trade name; Momentive Performance Materials Japan Co., Ltd.) It is a polymer of 3-glycidoxypropyltrimethoxysilane.

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

1-6-2. Ratio of epoxy compound other than oxetanyl compound (b2) to polyester amide (A) The ratio of the total amount of epoxy compounds other than the oxetanyl group-containing compound (b2) to 0 parts by weight of the polyester amidic acid (A) in the thermosetting composition of the present invention is 0 parts by weight Parts to 100 parts by weight. If the ratio of the total amount of epoxy compounds other than the oxetanyl compound (b2) is within the above range, the balance of flatness, heat resistance, chemical resistance, adhesion, and barrier properties is good. When the barrier property is more important, the total amount of epoxy compounds other than the oxetanyl-containing compound (b2) is preferably in the range of 0 parts by weight to 50 parts by weight.

1-6-3. Compounds with polymerizable double bonds In the thermosetting composition of the present invention, a compound having a polymerizable double bond can also be used. The compound having a polymerizable double bond used in the thermosetting composition of the present invention is not particularly limited as long as it has two or more polymerizable double bonds per molecule.

Specific examples of the compound having two polymerizable double bonds per molecule in the compound having a polymerizable double bond 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 ) Acrylic ester, epichlorohydrin modified diethylene glycol di(meth)acrylate, epichlorohydrin modified triethylene glycol di(meth)acrylate, epichlorohydrin modified tetraethylene glycol di(meth) 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 Trimethylacetic acid neopentyl glycol di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, bis[(methyl) Acryloyl neopentyl glycol] adipate, bisphenol A di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, bisphenol F di(methyl) 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 di(meth)acrylate , Caprolactone·ethylene oxide modified 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 the compound having three or more polymerizable double bonds in each molecule of the compound having a polymerizable double bond are: trimethylolpropane tri(meth)acrylate, ethylene oxide modification Trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, epichlorohydrin modified trimethylolpropane tri(meth)acrylate, propylene Triol tri(meth)acrylate, epichlorohydrin modified glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, cyclic Oxyethane modified tri(meth)acrylate, caprolactone·ethylene oxide modified tri(meth)acrylate, caprolactone modified tri[(meth)acryloyloxyethyl ] Isocyanurate, di-trimethylolpropane tetra (meth) acrylate, diglycerol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and alkyl modified di pentaerythritol tetra (meth) Base) acrylate, dipentaerythritol penta(meth)acrylate, alkyl modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate ) Acrylic esters and polyfunctional (meth)acrylates containing carboxyl groups.

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

From the viewpoint of scratch resistance, 100% by weight of the compound having a polymerizable double bond is preferably a compound containing 50% by weight or more of three or more polymerizable double bonds per molecule.

Among the compounds having a polymerizable double bond, from the viewpoint of flatness and scratch resistance, isocyanurate ethylene oxide is preferably used to modify diacrylate, isocyanurate ethylene oxide Alkane modified triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and carboxyl group-containing multifunctional (meth)acrylate.

As the compound having a polymerizable double bond, commercially available products as described below can be used. A specific example of isocyanuric acid ethylene oxide modified diacrylate is Aronix (Aronix) M-215 (trade name; East Asia Synthetic Co., Ltd.); isocyanuric acid ethylene oxide modified diacrylate Specific examples of mixtures of isocyanuric acid ethylene oxide modified triacrylates are Aronix M-313 (30% by weight to 40% by weight) and Aronix M-315 (3 % By weight to 13% by weight, hereinafter abbreviated as "M-315") (all are trade names; East Asia Synthetic Co., Ltd., the content in parentheses is isocyanuric acid ethylene oxide modified diacrylate in the mixture Contents listed in the catalogue); the specific examples of trimethylolpropane triacrylate are Aronix M-309 (trade name; East Asia Synthetic Co., Ltd.); pentaerythritol triacrylate and pentaerythritol tetraacrylate Specific examples of the mixture of Aronix (Aronix) M-306 (65 wt% ~ 70 wt%), Aronix (Aronix) M-305 (55 wt% ~ 63 wt%), Aronix (Aronix) M-303 (30% to 60% by weight), Aronix M-452 (25% to 40% by weight) and Aronix M-450 (less than 10% by weight) (both It is a trade name; East Asia Synthetic Co., Ltd., the content rate in parentheses is the cataloged value of the content rate of pentaerythritol triacrylate in the mixture); the specific example of the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is sub Aronix M-403 (50% to 60% by weight), Aronix M-400 (40% to 50% by weight), Aronix M-402 (30% by weight) ～40% by weight, hereinafter abbreviated as “M-402”), Aronix M-404 (30%-40%), Aronix M-406 (25%～35% %) and Aronix (Aronix) M-405 (10% by weight to 20% by weight) (both trade names; East Asia Synthetic Co., Ltd., the content in parentheses is the content of dipentaerythritol pentaacrylate in the mixture Catalogue value); Specific examples of carboxyl-containing polyfunctional (meth)acrylates are Aronix (Aronix) M-510 and Aronix (Aronix) M-520 (hereinafter abbreviated as "M-520") (All are trade names; East Asia Synthetic Co., Ltd.).

1-6-4. Ratio of compound with polymerizable double bond to polyester amide (A) The ratio of the total amount of the compound having a polymerizable double bond is 100 parts by weight to 100 parts by weight with respect to 100 parts by weight of the polyester amide acid (A) in the thermosetting composition of the present invention. If the ratio of the total amount of the compound having a polymerizable double bond is within the above range, the balance of flatness, heat resistance, scratch resistance, and barrier properties is good. When the barrier property is more important, the total amount of the compound having a polymerizable double bond is preferably in the range of 0 parts by weight to 50 parts by weight.

1-6-5. Solvent (D) In the thermosetting composition of the present invention, a solvent (D) can also be used. The solvent (D) optionally added to the thermosetting composition of the present invention is preferably a polymer (B) capable of dissolving polyester amide acid (A), a cyclic ether compound, and a cationic polymerization initiator (C) And other solvents. Specific examples of the solvent (D) are: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, third 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-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2 -Methyl methyl propionate, ethyl 2-hydroxy-2-methyl propionate, methyl 2-methoxy-2-methyl propionate, ethyl 2-ethoxy-2-methyl propionate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 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 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 mono Butyl ether acetate, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, acetonitrile, dioxane, toluene, Xylene, γ-butyrolactone, or N,N-dimethylacetamide and cyclohexanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, weight average molecular weight of 1,000 or less Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 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 (D) is preferably 65% by weight to 95% by weight relative to the total amount of the thermosetting composition. More preferably, it is 70% by weight to 90% by weight.

1-6-6. 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. 75, Polyflow No. 90, Polyflow No. 95 (the above are trade names; Kyoeisha Chemical Co., Ltd.), Disperbyk -161, Disperbyk -162, Disperbyk -163, Disperbyk -164, Disperbyk-166, Disperbyk-170, Disperbyk-180, Disperbyk-181, Disperbyk (Disperbyk)-181 Disperbyk)-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (the above are trade names ; BYK Chemie Japan Co., Ltd., KP-341, KP-368, KF-96-50CS, KF-50-100CS (the above are trade names; Shin-Etsu Chemical Industry Co., Ltd.), Sha Surflon S611 (trade name; AGC Seimi Chemical Co., Ltd.), Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL , Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 602A, Ftergent 602A, Ftergent 650A, FTX-218 (the above are trade names; Nios ( Neos) Co., Ltd., Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-410 475, Megafac F-477, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac ( Megafac) F-556, Megafac F-558, Megafac F-559, Megafac R-94, Megafac RS-75, Mega(ac) fac) 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 Glide (440), TEGO Glide (450), TEGO Glide (450), TEGO Glide (TEGO) Rad) 2200N (the above are trade names; Evonik Japan Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl iodide Ammonium, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amino sulfonate, polyoxyethylene nonyl Phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl wax Ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan Palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan Alkyd stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate and alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these compounds.

If these surfactants are selected from BYK-306, BYK-342, BYK-346, KP-341, 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, fluoroalkyl trimethylammonium At least one of a salt and a fluoroalkylamine sulfonate is preferable because the uniformity of coating of the thermosetting composition becomes high.

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

1-6-7. Adhesion improver From the viewpoint of further improving the adhesion between the formed cured film and the substrate, the thermosetting composition of the present invention may further contain an adhesion improving agent. Examples of the adhesion improving agent include silane-based, aluminum-based, or titanate-based coupling agents. Specifically: 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane ( For example, Sila-Ace S510; trade name; JNC (JNC) Co., Ltd.), 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane (for example, Sala-Ace) (Sila-Ace) S530; trade name; JNC (JNC) Co., Ltd., 3-mercaptopropyltrimethoxysilane (for example, Sila-Ace) S810; trade name; JNC) Co., Ltd.), a copolymer of 3-glycidoxypropyltrimethoxysilane (for example, trade name; COATOSIL MP200, Momentive Performance Materials Japan) Co., Ltd. ) And other silane-based coupling agents, aluminum acetyl diisopropoxide and other aluminum-based coupling agents, and tetraisopropyl bis (dioctyl phosphite) titanate and other titanate-based coupling agents.

Among these adhesion improving agents, 3-glycidoxypropyltrimethoxysilane has a large effect of improving adhesion and is therefore preferable.

The content of the adhesion improving agent is preferably 0.01% by weight or more and 10% by weight or less relative to the total amount of the thermosetting composition.

1-6-8. Antioxidants From the viewpoints of improving transparency and preventing yellowing when the cured film is exposed to high temperature, 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, from the viewpoint of light resistance, hindered phenols are preferred. Specific examples are: Irganox 1010, Irganox 1010FF, Irganox 1035, Irganox 1035FF, Irganox (Irganox) 1035FF Irganox 1076, Irganox 1076FD, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1330, Irganox (Irganox) Irganox) 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox (Irganox) 245FF Irganox) 259, Irganox 3114, Irganox 565, Irganox 565DD (all trade names; BASF Japan Co., Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO- 60. ADK STAB AO-80 (all trade names; ADEKA) Co., Ltd. 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 relative to the total amount of the thermosetting composition.

1-6-9. Molecular weight regulator The thermosetting composition of the present invention may further contain a molecular weight adjuster to suppress the increase in molecular weight due to polymerization and exhibit excellent storage stability. Examples of the molecular weight modifier include thiols, xanthogen acids, quinones, hydroquinones, 2,4-diphenyl-4-methyl-1-pentene, and the like.

Specific examples of the molecular weight modifier include 1,4-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, methyl-p-benzoquinone, anthraquinone, hydroquinone, methylhydroquinone, Third butyl hydroquinone, 2,5-di-third butyl hydroquinone, 2,5-di-third pentyl hydroquinone, 1,4-dihydroxynaphthalene, 3,6-dihydroxybenzophenone Bornane, 4-methoxyphenol, 2,2',6,6'-tetra-tert-butyl-4,4'-dihydroxybiphenyl, 3-(3,5-di-tert-butyl -4-hydroxyphenyl) stearyl propionate, 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,4,6-tris(3',5' -Di-tert-butyl-4'-hydroxybenzyl) mesitylene, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4- Tributylcatechol, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary-dodecyl mercaptan, thioglycolic acid, dimethyl yellow Original acid sulfide, diisopropyl xanthogen acid disulfide, 2,6-di-t-butyl-p-cresol, 4,4'-butylene bis(6-t-butyl-m-cresol ), 4,4'-thiobis(6-tert-butyl-m-cresol), 2,4-diphenyl-4-methyl-1-pentene, phenothiazine, 2-hydroxy-1 , 4-naphthoquinone, etc.

The molecular weight modifier may be used alone or in combination of two or more. Among the molecular weight modifiers, a naphthoquinone-based molecular weight modifier is preferred in terms of showing excellent storage stability.

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

1-6-10. Ultraviolet absorber From the viewpoint of further improving the deterioration suppression ability of the formed transparent film, the thermosetting composition of the present invention may contain an ultraviolet absorber.

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

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

1-6-11. Anti-agglomerating agent The thermosetting composition of the present invention may contain an anti-agglomerating agent from the viewpoint of not fusing the polyester amidic acid (A) or epoxy compound (B) having a polymerizable double bond with a solvent and preventing aggregation.

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

The anti-agglomeration agent is used in an amount of 0.01 to 10 parts by weight relative to the total amount of the thermosetting composition.

1-6-12. Thermal crosslinking agent From the viewpoint of further improving heat resistance, chemical resistance, film surface uniformity, flexibility, flexibility, and elasticity, the thermosetting composition of the present invention may contain a thermal crosslinking agent.

Specific examples of the thermal cross-linking agent are: Nikalak (Nikalac) MW-30HM, Nikalak (MW) 100LM, Nikalak (MX) 270, Nikalak (MX-280), Nikalak (MX-280) Nikalac MX-290, Nikalac MW-390, Nikalac MW-750LM (all are trade names; Sanwa Chemical Co., Ltd.).

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

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

2. Hardened film obtained from thermosetting composition The thermosetting composition of the present invention can be obtained by optionally adding polyester amide (A), a polymer of a cyclic ether compound (B), a cationic polymerization initiator (C), a solvent (D), and epoxy compounds other than the oxetanyl compound (b2), compounds with polymerizable double bonds, surfactants, adhesion enhancers, antioxidants and other additives, to homogenize these compounds To mix and dissolve.

If the thermosetting composition prepared in the above manner (in the case of a solvent-free solid state, after being dissolved in a solvent) is applied to the surface of the substrate, and the solvent is removed by, for example, heating, the coating can be formed membrane. The coating of the thermosetting composition on the surface of the substrate can be formed by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, and a slit coating method. Then, the coating film is temporarily calcined using a hot plate, an oven, or the like. The temporary calcination conditions vary depending on the types of ingredients and the mixing ratio. Usually, at 70°C to 150°C, if an oven is used, it is 5 minutes to 15 minutes, and if a hot plate is used, it is 1 minute to 5 minutes. Thereafter, in order to harden the coating film, the main calcination is performed. The formal calcination conditions vary depending on the type of ingredients and the mixing ratio, usually at 180 ℃ ~ 250 ℃, preferably 200 ℃ ~ 250 ℃, if you use an oven, it is 30 minutes to 90 minutes, if you use a hot plate, it is 5 From minutes to 30 minutes, a cured film can be obtained by performing heat treatment.

When the cured film obtained in the above manner is heated, 1) the polyamic acid of the polyester amide acid is partially dehydrated and cyclized to form an amide imine bond, and 2) the carboxylic acid of the polyester amide acid reacts with the epoxy compound The high molecular weight, and 3) the epoxy compound is hardened and the high molecular weight, so it is very tough, and has excellent transparency, heat resistance, chemical resistance, flatness and adhesion. In addition, for the same reason, it is also expected to be excellent in light resistance, sputtering resistance, scratch resistance, and coating properties. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and the color filter can be used to manufacture a liquid crystal display element or a solid-state imaging element. 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 (TFT) and a transparent electrode or formed between a transparent electrode and an alignment film The transparent insulating film is effective. Furthermore, the cured film of the present invention is effective even as a protective film for a light emitting diode (LED) light emitter. [Example]

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

The abbreviations of the compounds used in Synthesis Examples, Examples, and Comparative Examples indicate the following raw materials.

[Tetracarboxylic anhydride] ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride BT-100: 1,2,3,4-butanetetracarboxylic dianhydride Rikacid BT-100 (trade name; New Japan Physical and Chemical Co., Ltd.)

[Diamine] DDS: 3,3'-diaminodiphenyl sulfone

[Polyhydroxy compound] Bis-A-2EOH: 4,4'-isopropylidenebis(2-phenoxyethanol) 70PA: Epoxy ester 70PA (trade name; Kyoeisha Chemical Co., Ltd.)

[Styrene-maleic anhydride copolymer] SMA1000P (trade name; Sichuan Crude Oil Chemical Co., Ltd.)

[Cyclic ether compound] OXE-30: (3-ethyloxetan-3-yl) methyl methacrylate OXE-10: (3-ethyloxetane-3-yl) methyl acrylate GMA: glycidyl methacrylate

[Epoxy compounds other than (b2)] E1: TECHMORE VG3101L (trade name; Printec Co., Ltd.)

[Thermal polymerization initiator] V-601: Dimethyl 2,2'-azobis(2-methylpropionate)

[Cationic polymerization initiator] CPI-100P (trade name; Sanapro Co., Ltd.) CPI-200K (trade name; Sanapro Co., Ltd.) Irgacure 250 (trade name; BASF Europe)

[hardener] TMA: trimellitic anhydride UC-3900: ARUFON UC-3900 (trade name; East Asia Synthetic Co., Ltd.)

[additive] S510: Sila-Ace S510 (trade name; JNC Co., Ltd.); adhesion improver (coupling agent) AO-60: ADK STAB AO-60 (trade name; ADEKA Co., Ltd.); antioxidant DS-21: Megafac DS-21 (trade name; DIC) Co., Ltd.; surfactant

[Solvent] MMP: methyl 3-methoxypropionate PGMEA: propylene glycol monomethyl ether acetate

First, a polyester amide acid solution (Synthesis Example 1 to Synthesis Example 7) as a reaction product of tetracarboxylic dianhydride, diamine, monohydroxy compound, polyhydroxy compound, or the like is synthesized as follows.

[Synthesis Example 1] Synthesis of polyester amide acid (A1) In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, 1,4-butanediol, and benzyl alcohol were charged at the following weights, and the mixture was stirred at 125°C for 2 hours under a stream of dry nitrogen (synthesis The first stage). MMP 49.00 g ODPA 20.36 g 1,4-butanediol 3.55 g Benzyl alcohol 2.84 g

Thereafter, the solution after the reaction was cooled to room temperature, and DDS and MMP were added at the following weights, and the mixture was stirred at 20°C to 30°C for 2 hours, and then stirred at 125°C for 1 hour (second stage of synthesis). DDS 3.26 g MMP 21.00 g [Z/Y=3.0, (Y+Z)/X=0.8]

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

[Synthesis Example 2] Synthesis of polyester amide acid (A2) In a four-necked flask equipped with a stirrer, dehydrated and purified PGMEA, BT-100, SMA1000P, 1,4-butanediol, and benzyl alcohol were sequentially charged at the following weights, under a stream of dry nitrogen and at 125°C Stir for 2 hours (the first stage of synthesis). PGMEA 53.49 g BT-100 3.83 g SMA1000P 18.23 g 1,4-butanediol 1.16 g Benzyl alcohol 5.57 g

Thereafter, the solution after the reaction was cooled to room temperature, and DDS and PGMEA were added at the following weights, stirred at 20°C to 30°C for 2 hours, and then stirred at 125°C for 1 hour (second stage of synthesis). DDS 1.20 g PGMEA 16.51 g [Z/Y=2.7, (Y+Z)/X=0.9]

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

[Synthesis Example 3 to Synthesis Example 7] Synthesis of polyester amide acid (A3) to polyester amide acid (A7) According to the methods of Synthesis Example 1 and Synthesis Example 2, each component was reacted at the temperature, time and ratio (unit: g) described in Table 1-1 to obtain polyester amide acid (A3) to polyester amide acid (A3) A7) Solution.

各試劑及溶劑的裝入量的單位為克（g）Table 1-1

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

Next, a solution of the polymer (B) of the cyclic ether compound (Synthesis Example 8 to Synthesis Example 13) was synthesized as follows.

[Synthesis Example 8] Synthesis of polymer (B1) of cyclic ether compound In a four-necked flask equipped with a stirrer, dehydration-purified PGMEA as a polymerization solvent and OXE-30 as an oxetanyl-containing compound (b1) were charged with the following weight, and further charged with the following weight V-601 as a polymerization initiator was stirred at 110°C for 2 hours under a stream of dry nitrogen. PGMEA 31.50 g OXE-30 13.50 g V-601 1.35 g

The solution was cooled to room temperature to obtain a 30% by weight solution of the polymer (B1) of the cyclic ether compound. A part of the solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (B1) of the obtained cyclic ether compound was 7,200.

[Synthesis Example 9] Synthesis of polymer (B2) of cyclic ether compound In a four-necked flask equipped with a stirrer, PGMEA as a polymerization solvent subjected to dehydration purification, OXE-30 as a compound (b1) having an oxetanyl group, and as a compound having an oxetane are charged at the following weights The GMA of the base compound (b2) was further charged into the polymerization initiator V-601 at the following weight, and stirred at 110° C. for 2 hours under a stream of dry nitrogen. PGMEA 31.500 g OXE-30 10.125 g GMA 3.375 g V-601 1.350 g

The solution was cooled to room temperature to obtain a 30% by weight solution of the polymer (B2) of the cyclic ether compound. A part of the solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (B2) of the obtained cyclic ether compound was 7,300.

[Synthesis Example 10 to Synthesis Example 13] Synthesis of cyclic ether compound polymer (B3) to cyclic ether compound polymer (B6) According to the methods of Synthesis Example 8 and Synthesis Example 9, each component was reacted at the temperature, time and ratio (unit: g) described in Table 1-2 to obtain polymers (B3) to cyclic ether compounds of cyclic ether compounds Polymer (B6) solution.

各試劑及溶劑的裝入量的單位為克（g）Table 1-2

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

[Example 1] A 500 ml separable flask with a stirring wing was replaced with nitrogen, and the flask was charged with 100.0 g of the polyester amide acid obtained in Synthesis Example 1 as polyester amide acid (A) ( A1) Solution, 120.0 g of cyclic ether compound polymer (B1), 3.6 g of CPI-100P as a cationic polymerization initiator (C), 3.7 g of S510 as an adhesion improver, 0.4 g of AO-60 as an antioxidant, 54.9 g of dehydrated MMP as a solvent (D), and 100.8 g of PGMEA were stirred at room temperature for 3 hours to uniformly dissolve.

Then, 1.0 g of Megafac DS-21 (trade name; DIC) Co., Ltd. was added as a surfactant, and stirred at room temperature for 1 hour, using a membrane filter (pore size 0.2 μm ) It is filtered to prepare a thermosetting composition.

[Barrier evaluation method] When measuring with a UV-Vis near-infrared spectrophotometer (trade name; V-670, Japan Spectroscopy Co., Ltd.), the thermosetting composition was spin-coated at 300 rpm for 10 seconds to have absorption near 560 nm and have On the color filter substrate including no R, G, and B pixels without a hardened film, pre-bake on a hot plate at 90°C for 2 minutes. Then, post-bake at 230° C. for 30 minutes in an oven to obtain a color filter substrate with a cured film having a protective film with an average film thickness of 2.0 μm.

Then, 0.5 mL of 1-methyl-2-pyrrolidone was added dropwise to the color filter substrate with a cured film cut into a 10 cm square, and the glass cut into a 9 cm square (hereinafter referred to as cover glass) was statically placed. It was placed on a color filter substrate with a cured film, and heated at 180°C for 5 minutes using a hot plate. After the heating is completed, the cover glass is removed, and 5 mL of 1-methyl-2-pyrrolidone is used to clean the cover glass and the color filter substrate with a hardened film, and the cleaning solution is transferred to a 10 mL measuring flask. 1-Methyl-2-pyrrolidone was added to a graduated cylinder with a cleaning solution and the volume was adjusted to 10 mL, and the mixed solution was used as the eluent of the color filter substrate with a hardened film. Thereafter, using the ultraviolet-visible-near infrared spectrophotometer, using 1-methyl-2-pyrrolidone as a reference sample, the transmittance of the eluate was measured. Based on the measured results, the case where the transmittance at 560 nm is 90% or more is set to ○, and the case where less than 90% is set to x.

[Evaluation method of flatness] The thermosetting composition was spin-coated at 300 rpm for 10 seconds on a micro-shape measuring device (trade name; P-17, KLA TENCOR) Co., Ltd. in advance. The surface level difference was measured with R and G. And B, the non-cured color filter substrate of the pixel is pre-baked on a hot plate at 90°C for 2 minutes. Then, post-bake at 230° C. for 30 minutes in an oven to obtain a color filter substrate with a cured film having a protective film with an average film thickness of 2.0 μm. After that, the obtained color filter substrate with a cured film was measured for the surface level difference.

Calculate the flattening rate based on the maximum value of the surface level difference of the color filter substrate without a cured film and the color filter substrate with a cured film (hereinafter abbreviated as "maximum level difference"), and use the following calculation formula . The case where the flattening rate was 85% or more was evaluated as flatness ○, and the case where less than 85% was evaluated as flatness ×. In addition, the color filter substrate without a cured film has a maximum step difference of 1.5 μm. Flattening rate = [(Maximum step difference of color filter substrate without cured film-Maximum step difference of color filter substrate with cured film)/(Maximum step difference of color filter substrate without cured film )]×100%

[Evaluation method of adhesion] Then, the thermosetting composition was spin-coated on the glass substrate at 800 rpm for 10 seconds, and prebaked on a hot plate at 90°C for 2 minutes. Then, after baking at 230° C. for 30 minutes in an oven, a glass substrate with a cured film having a protective film thickness of 1.0 μm was obtained. The obtained glass substrate with a cured film was tested according to JIS K5600-5-6:1999. The case where the test result shows the adhesion of category 0 to category 2 is ○, and the case of showing the adhesion of categories 3 to 5 is ×.

[Example 2 to Example 16] According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) described in Table 2-1 to Table 2-3 to obtain a thermosetting composition.

裝入量的單位為克（g）table 2-1

The unit of loading is grams (g)

裝入量的單位為克（g）Table 2-2

The unit of loading is grams (g)

裝入量的單位為克（g）Table 2-3

The unit of loading is grams (g)

[Comparative Example 1 to Comparative Example 5] According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) of Table 3 to obtain a thermosetting composition.

裝入量的單位為克（g）table 3

The unit of loading is grams (g)

From the results shown in Tables 2-1 to 2-3, it is clear that the cured films using the cationic polymerization initiators of Examples 1 to 16 are excellent in barrier properties, and have flatness and adhesion Get a balance.

In Comparative Example 1 and Comparative Example 3 described in Table 3, trimellitic anhydride (TMA) was used as a hardener, and its barrier properties were good. On the other hand, Comparative Example 3 has poor flatness, and Comparative Example 1 has poor adhesion in addition to flatness. Although Comparative Example 2, Comparative Example 4, and Comparative Example 5 had good adhesion, they did not exhibit barrier properties at all.

As described above, only when the polyester amide acid (A), the polymer (B) of the cyclic ether compound, and the cationic polymerization initiator (C) are used as essential components, all characteristics can be satisfied. [Industry availability]

The cured film obtained from the thermosetting composition of the present invention has high barrier properties and high flatness, and can be used as a protection for various optical materials such as color filters, LED light-emitting elements, and light-receiving elements. Film, and an insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

no

no

Claims (9)

A thermosetting composition comprising polyester amide acid (A), a polymer (B) of a cyclic ether compound and a cationic polymerization initiator (C), and in the thermosetting composition, The polyester amide acid (A) is derived from a tetracarboxylic dianhydride containing X moles, a diamine of Y moles, and a Z mole from the ratio established by the relationship of the following formula (1) and formula (2) The reaction product of the raw materials of polyhydroxy compounds, 0.2≦Z/Y≦8.0······(1) 0.2≦（Y+Z）/X≦5.0··（2） The polymer (B) of the cyclic ether compound is a homopolymer selected from a compound (b1) having an oxetanyl group, a copolymer of a compound (b1) having an oxetanyl group, and having an oxa At least one of a copolymer of a cyclobutyl compound (b1) and an oxetanyl-containing compound (b2). The thermosetting composition as described in item 1 of the patent application scope, wherein the polyester amide acid (A) includes 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 obtained by removing two -NH ₂ from a diamine R ³ is a residue obtained by removing two -OH groups from a polyhydroxy compound. The thermosetting composition as described in item 1 or item 2 of the patent application scope, wherein the compound (b1) having an oxetanyl group is selected from acrylic acid (3-ethyloxetane-3 -Yl) methyl ester and at least one of (3-ethyloxetan-3-yl) methyl methacrylate. The thermosetting composition as described in item 1 or item 2 of the patent application range, wherein the compound (b2) having an oxetanyl group is selected from glycidyl acrylate, glycidyl methacrylate, methyl alcohol At least one of methyl glycidyl acrylate and 4-hydroxybutyl acrylate glycidyl ether. The thermosetting composition according to any one of items 1 to 4 of the patent application scope, wherein the polymer (B) of the cyclic ether compound is relative to 100 parts by weight of the polyester amide acid (A) ) Content is 20 parts by weight to 400 parts by weight. The thermosetting composition as described in any one of claims 1 to 5, wherein the cationic polymerization initiator (C) is an anionic antimony-free cationic polymerization initiator. The thermosetting composition as described in any one of patent application items 1 to 6, wherein the cationic polymerization initiator (C) is an anionic species that does not contain antimony and the cationic species is a cationic polymer of the samium salt system. Initial agent. A cured film obtained by curing the thermosetting composition according to any one of claims 1 to 7 of the patent application. A color filter having a cured film as described in item 8 of the patent application scope as a transparent protective film.