TW201809172A - Thermosetting composition, cured film, color filter, liquid crystal display element, and touch panel device excellent in transparency or heat resistance required for a protective film and the display quality is not adversely affected by not having variations in switching threshold caused by specific electrical characteristics of a liquid crystal display device - Google Patents

Abstract

To provide a cured film that is excellent in transparency or heat resistance required for a protective film and that the display quality is not adversely affected by not having variations in switching threshold caused by specific electrical characteristics of a liquid crystal display device; a composition for making the cured film, a color filter comprising the cured film, a liquid crystal display element, and a touch panel device. A thermosetting composition and a cured film obtained therefrom, the thermosetting composition being a composition containing a polyester amic acid and an epoxy compound, the polyester amic acid being a reactant containing raw materials of a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound, and the dielectric loss tangent at 20 Hz of the cured film obtained from the composition is 0.007 or less.

Description

Thermosetting composition, cured film, color filter, liquid crystal display element, and touch panel device

The present invention relates to a thermosetting composition used in a liquid crystal display element and the like, a cured film formed from the thermosetting composition, and a color filter, an insulating film using the cured film, or A protective film, and an electronic component having the film. In more detail, the present invention relates to a thermosetting composition containing polyester lysine, which has excellent dielectric loss tangent, and does not have a switching property to liquid crystals formed from the thermosetting composition. A hardened film that causes adverse effects, and a color filter, an insulating film, or a protective film using the hardened film, and an electronic component having the film.

Liquid crystal display elements are widely used in computer terminal display devices, television image display devices, mobile communication devices, and the like. In the manufacturing step of the liquid crystal display element, the surface of the element is usually subjected to chemical treatment or high-temperature heating treatment. Therefore, a protective film is provided in order to prevent surface deterioration, damage, and deterioration of the element. The protective film is required to have heat resistance, chemical resistance, adhesion to a substrate, transparency, and flatness.

On the other hand, in recent years, liquid crystal display elements include various new-type liquid crystal display elements that have high requirements for image quality, have high viewing angles, and have high-speed response. Among them, the lateral electric field method (in-plane switching (IPS) method, fringe field switching (FFS) method) has been widely popularized around mobile communication devices because of its excellent display quality such as viewing angle and contrast.

However, the liquid crystal used in the liquid crystal display device of the lateral electric field method, especially the FFS method, has excellent characteristics such as being capable of being driven at a low voltage. Reduced problems. Actually, various display failures such as the electrical characteristics of a color filter or an alignment film, or variations in switching thresholds caused by the elution of components derived from these, are caused. In response to these problems, researches focusing on color filters or alignment films have been performed, but researches have not focused on protective films.

Furthermore, in semiconductor devices such as thin film transistors (TFTs), a protective film is usually formed on the uppermost wiring for the purpose of wiring protection. By forming the protective film, it is possible to achieve high quality and stable characteristics of the semiconductor device, and the semiconductor device is less susceptible to external influences. Polyimide, which is a highly heat-resistant resin that is one of the materials for protective films, is often used for protective films or insulating films of semiconductor devices, and some of them have been put into practical use. Regarding the development of these polyimides, although several attempts have been made to achieve a low dielectric constant, there has not yet been developed a polyimide that meets the characteristics of low dielectricity, low dielectric loss tangent, and is resistant to practical use. Amine, and polyimide that provides a protective film excellent in transparency or heat resistance. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-208580 [Patent Document 2] Japanese Patent Laid-Open No. 2006-243594

[Problems to be Solved by the Invention] An object of the present invention is to provide an excellent transparency, heat resistance, and other characteristics required for a protective film, and further, there is no switching threshold deviation due to specific electrical characteristics of a liquid crystal display device, that is, A cured film that does not adversely affect display quality, and a composition that provides the cured film. [Technical means to solve the problem]

The inventors of the present invention conducted diligent research in order to solve the above-mentioned problems, and as a result, they found that a thermosetting composition contains a polyester amine acid, an epoxy compound, and optionally an epoxy hardener or a solvent, etc. The polyester amidate is a reactant of a raw material containing a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound, and it has been found that a cured film obtained by hardening the composition has a low dielectric loss tangent, and further the hardening The film was excellent in transparency or heat resistance, and completed the present invention. The present invention includes the following configurations.

[1] A thermosetting composition comprising a polyester sulfamic acid (A) and an epoxy compound (B), wherein the thermosetting composition is characterized in that: the polyester glutamic acid (A) It is a reaction product of a raw material of a polyvalent hydroxy compound containing X Moore's tetracarboxylic dianhydride, Y Moore's diamine, and Z Moore in a ratio established by the relationship of the following formulae (1) and (2), 0.2 ≦ Z / Y ≦ 8.0 ······ (1) 0.2≤ (Y + Z) /X≦5.0 ··· (2) The content of the epoxy compound (B) relative to the polyester amidamine The acid (A) is 100 parts by weight and 20 to 400 parts by weight, and the dielectric loss tangent at 20 Hz of the cured film obtained from the thermosetting composition is 0.007 or less.

[2] The thermosetting composition according to the above [1], wherein the polyester amidate (A) includes a structural unit represented by the following formula (3) and a formula (4) Building blocks. In formulas (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and R ² is obtained by removing two -NH ₂ from a diamine. R ³ is a residue formed by removing two -OH groups from a polyhydroxy compound.

[3] The thermosetting composition according to the above [1] or [2], wherein the raw material of the polyester amidate (A) further contains a monohydroxy compound.

[4] The thermosetting composition according to the above [3], wherein the monohydroxy compound is selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and One or more of 3-ethyl-3-hydroxymethyloxetane.

[5] The thermosetting composition according to any one of the above [1] to [4], wherein the raw material of the polyester amidate (A) further comprises styrene-maleic anhydride copolymerization Thing.

[6] The thermosetting composition according to any one of the above [1] to [5], wherein the polyester amidine (A) has a weight average molecular weight of 1,000 to 200,000.

[7] The thermosetting composition according to any one of [1] to [6], which contains 0.1 to 60 parts by mass of 100 parts by mass of the epoxy compound (B). Epoxy hardener (C).

[8] The thermosetting composition according to the above [7], wherein the epoxy hardener (C) contains a material selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, 2-undecylimidazole, and a phenolic hardener (H) at least one compound in the group.

[9] The thermosetting composition according to the above [8], wherein the phenolic hardener (H) is selected from the group consisting of α, α, α'-tris (4-hydroxyphenyl) -1-ethyl 4-Isopropylbenzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 4,4 '-(3,3,5-trimethyl-1,1-cyclohexanediyl) bis (phenol), and At least one of the group consisting of 1,1,2,2-tetra (4-hydroxyphenyl) ethane.

[10] The thermosetting composition according to any one of the above [1] to [9], which contains a solvent (D).

[11] The thermosetting composition according to the above [10], wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3 , 3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4- At least one compound in the group consisting of butanetetracarboxylic dianhydride and ethylene glycol bis (anhydrotrimellitate); the diamine is selected from the group consisting of 3,3'-diaminodiphenyl At least one compound in the group consisting of fluorene and bis [4- (3-aminophenoxy) phenyl] fluorene; the polyhydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butane Diols, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and tris (2-hydroxyethyl) isocyanurate At least one compound in the group consisting of; the epoxy compound (B) is selected from the group consisting of 3,4-epoxycyclohexanecarboxylic acid-3 ', 4'-epoxycyclohexylmethyl ester, 1-methyl 4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane, 2- [4- (2,3-glycidoxy) phenyl] -2 -[4- [1,1-bis [4-([2,3-glycidoxy] 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 A mixture of phenyl] phenoxy] -2-propanol, 2- [4- (2,3-glycidoxy) phenyl] -2- [4- [1,1-bis [4-([ 2,3-glycidoxy] phenyl)] ethyl] phenyl] propane, 1,1,1-tris (4-hydroxyphenyl) ethane triglycidyl ether, 1,3-bis (cyclo Oxyethanemethyl) -5- (2-propenyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,2-bis (hydroxymethyl) 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol), and by using 3-glycidyloxypropyltrimethoxysilane as At least one compound in the group consisting of copolymers having a weight average molecular weight of 1,000 to 200,000 obtained by reacting raw material components; the epoxy hardener (C) is selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-eleven Alkyl imidazole, α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 9 , 9-bis (4-hydroxy-3-methylphenyl) fluorene, 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- At least one compound in the group consisting of (4-hydroxyphenyl) ethane; the solvent (D) contains a group selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate At least one of the group.

[12] A cured film obtained by curing the thermosetting composition according to any one of [1] to [11].

[13] A color filter having the cured film according to [12] as a transparent protective film.

[14] A liquid crystal display element including the color filter according to [13].

[15] A liquid crystal display element having the cured film according to the above [12] as a transparent insulating film formed between a TFT and a transparent electrode.

[16] A liquid crystal display element having the cured film according to the above [12] as a transparent insulating film formed between a transparent electrode and an alignment film.

[17] A touch panel device having the cured film according to [12] as a transparent insulating film formed on a transparent electrode. [Effect of the invention]

The thermosetting composition according to a preferred embodiment of the present invention is a particularly excellent material that does not adversely affect display quality in a liquid crystal display device. When used as a color filter protective film for a color liquid crystal display element, , Can improve display quality and reliability. In addition, the cured film obtained by heating the thermosetting composition according to the preferred embodiment of the present invention has low dielectric loss tangent, excellent transparency and heat resistance required as a protective film, and is very practical. High hardened film. In particular, it is useful as a protective film of a color filter manufactured by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. It can also be used as a protective film and a transparent insulating film of various optical materials.

1. Thermosetting composition The thermosetting composition of the present invention contains polyester amine (A), an epoxy compound (B), and optionally an epoxy curing agent (C) or a solvent (D). And the like, the polyester amidate (A) is a reactant containing a raw material of a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound, and the thermosetting composition is characterized by the composition The dielectric loss tangent at 20 Hz of the obtained cured film was 0.007 or less. The thermosetting composition of the present invention may further contain components other than those described above within a range in which the effects of the present invention are obtained.

1-1. Polyester amidate (A) The polyester amidate (A) is a ratio of the following formula (1) and formula (2), which contains X mol tetracarboxylic dianhydride, A reactant for Y Mol's diamine and Z Mol's polyhydroxy compound. 0.2 ≦ Z / Y ≦ 8.0 (1) 0.2 ≦ (Y + Z) /X≦5.0 (2)

It is preferable that the said polyester amidate (A) has a structural unit represented by following formula (3), and a structural unit represented by formula (4). In formulas (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from a 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.

At least a solvent is required for the synthesis of the polyester glutamic acid (A), and the solvent may be left directly to form a liquid or gel-like thermosetting composition in consideration of workability or the like. The said solvent is removed and it is set as the solid composition which considers portability etc. In addition, in the synthesis of the polyester amidine (A), one or more compounds selected from the group consisting of a monohydroxy compound and a styrene-maleic anhydride copolymer may be optionally included as a raw material, and it is particularly preferable to include a monohydroxy group. Compound. In addition, in the synthesis of the polyester amidine (A), other compounds than those described above may be included as a raw material as needed, as long as the object of the present invention is not impaired.

1-1-1. Tetracarboxylic dianhydride In the present invention, a tetracarboxylic dianhydride is used as a material for obtaining the polyester amidate (A). Specific examples of the preferred tetracarboxylic dianhydride include: 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid Acid dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2 ', 3 , 3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid 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 (anhydrotrimellitic acid ester) (trade name: TMEG -100, New Japan Physical and Chemical Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, ethyl Alkyltetracarboxylic dianhydride and butanetetracarboxylic dianhydride. One or more of these tetracarboxylic dianhydrides can be used.

Among these tetracarboxylic dianhydrides, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride and 3,3', 4,4'-diphenyl ether which provide 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 trimellitic acid ester), particularly preferably 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid di 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 amidate (A). Specific examples of preferred diamines include 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 3,4'-diaminodiphenylphosphonium, and bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [3- (4-aminophenoxy) phenyl ] 碸, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] 碸, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] fluorene, and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane. One or more of these diamines can be used.

Among these diamines, 3,3'-diaminodiphenylfluorene and bis [4- (3-aminophenoxy) phenyl] fluorene which provide good transparency are more preferred, and 3,3 is particularly preferred. '-Diaminodiphenylphosphonium.

1-1-3. Polyhydroxy compound In the present invention, a polyhydroxy compound is used as a material to obtain the polyester amidate (A). Specific examples of the preferred polyhydroxy compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, and tripropylene glycol. , Tetrapropylene glycol, polypropylene glycol having 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, 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-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3, 6-octanediol, 1,2,8-octantriol, 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, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol , Tris (2-hydroxyethyl) isocyanurate, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxyphenyl) 碸), Bisphenol F (bis (4-hydroxyphenyl) methane), 4,4'-isopropylidene bis (2-phenoxyethanol), 2,2-bis (4-hydroxy (Cyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethanol, diethanolamine, triethanolamine, glyceryl monoallyl Ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, dipentaerythritol monoallyl ether, dipentaerythritol diallyl ether, dipentaerythritol triallyl ether , Dipentaerythritol tetraallyl ether, sorbitol monoallyl ether, sorbitol diallyl ether, sorbitol triallyl ether, sorbitol tetraallyl ether, glycerol mono (methyl ) Acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol di (methyl) Base) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, sorbitol di (meth) acrylate, sorbitol Tri (meth) acrylate, sorbitol tetra (meth) acrylate, ethylene glycol di shrink (Meth) acrylic acid modified product of oil ether, (meth) acrylic acid modified product of propylene glycol diglycidyl ether, (meth) acrylic acid modified product of tripropylene glycol diglycidyl ether, (glyceryl diglycidyl ether) (Meth) acrylic acid modified product, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, (meth) acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether, bisphenol S Modified (meth) acrylic acid of diglycidyl ether, Modified (meth) acrylic acid of propylene oxide modified bisphenol S diglycidyl ether, Modified (meth) acrylic acid of bisphenol F diglycidyl ether Properties, (meth) acrylic acid modified products of propylene oxide modified bisphenol F diglycidyl ether, (meth) acrylic acid modified products of bixylenol diglycidyl ether, and biphenol diglycidyl ether (Meth) acrylic acid modified product, hydroquinone diglycidyl ether (meth) acrylic acid modified product, cyclohexane-1,4-dimethanol diglycidyl ether (meth) acrylic acid modified product, 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 two or more epoxy groups per molecule. One or more of these polyhydroxy compounds can be used.

Among these polyhydric hydroxy compounds, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,5 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) 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 the glycerol diglycidyl ether , (Meth) acrylic acid modified product of bisphenol A diglycidyl ether, (meth) acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether, (formaldehyde of bisphenol S diglycidyl ether Group) acrylic acid modified product, propylene oxide modified bisphenol S diglycidyl ether (meth) acrylic acid modified product, bisphenol F diglycidyl ether (meth) acrylic acid modified product, and propylene oxide Modified (meth) acrylic acid of modified bisphenol F diglycidyl ether. Furthermore, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 4 , 4'-isopropylidene bis (2-phenoxyethanol), 2- (4-hydroxyphenyl) ethanol, (meth) acrylic acid modified product of ethylene glycol diglycidyl ether, propylene glycol diglycidyl (Meth) acrylic acid modified product of ether, (meth) acrylic acid modified product of tripropylene glycol diglycidyl ether, (meth) acrylic acid modified product of glycerol diglycidyl ether, bisphenol A diglycidyl ether A (meth) acrylic acid modified product and a propylene oxide-modified bisphenol A diglycidyl ether (meth) acrylic acid modified product.

1-1-4. Monohydroxy compound In the present invention, a monohydroxy compound can be used as a material for obtaining the polyester amidate (A). By using a monohydroxy compound, the storage stability of a thermosetting composition can be improved. Specific examples of preferred monohydroxy compounds include methanol, ethanol, 1-propanol, isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, and dipropylene glycol monoamine. Diethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltol , Linalol, terpineol, dimethyl benzylcarbinol, and 3-ethyl-3-hydroxymethyloxetane. One or more of these monohydroxy compounds may be used.

Among these monohydroxy compounds, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane are more preferable. Considering the compatibility of the polyester amidate (A) formed by using these monohydroxy compounds with an epoxy compound and an epoxy hardener, or a thermosetting composition in a color filter For coating properties, benzyl alcohol is particularly preferably used as 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, and containing 0 to 300 parts by weight of a monohydroxy compound. More preferably, it is 5 to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer In addition, in the polyester amidine (A) used in the present invention, a compound having three or more acid anhydride groups may be added to the raw material While synthesized. The polyester amido acid (A) synthesized by adding a compound having three or more acid anhydride groups is preferred because transparency can be improved. Examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. As for the ratio of each component constituting the styrene-maleic anhydride copolymer, the molar ratio of styrene / maleic anhydride is 0.5 to 4, and preferably 1 to 3. Furthermore, 1 or 2 is more preferable, and 1 is especially preferable.

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

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

1-1-6. In the synthesis of the polyester amidinic acid (A) of the amine silane compound having one amine group, other than those mentioned above may be included as needed within a range that does not impair the object of the present invention. Other raw materials are used as raw materials, and examples of such other raw materials include aminosilane compounds having one amine group. An amine silane compound having one amine group is used to introduce a silane group at the terminal by reacting with an acid anhydride group at the terminal of the polyester amido acid (A). The use of the thermosetting composition of the present invention containing the polyester amidate (A) can improve the acid resistance of the obtained cured film by adding an amine having one amine group. It is obtained by reacting a silyl compound. Furthermore, when reacting with the said monomer structure, it is also possible to add both a monohydroxy compound and the amino silane compound which has one amine group, and to perform a reaction.

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

Among these amine silane compounds having one amine group, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane, which improve the acid resistance of the cured film, are more preferable. From the viewpoint of compatibility, 3-aminopropyltriethoxysilane is particularly preferred.

It is preferably an amine silane compound having one amine group in an amount of 0 to 300 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, diamine, and polyhydroxy compound. More preferably, it is 5 to 200 parts by weight.

1-1-7. Solvents used in the synthesis reaction of polyester amidate (A) Specific examples of solvents used in the synthesis reaction to obtain the polyester amidate (A) include diethyl Dimethyl glycol 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, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide. Among these solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ethyl ether is preferred.

1-1-8. Method for synthesizing polyester amidate (A) The polyester amidate (A) used in the present invention is obtained by making tetracarboxylic dianhydride X mole in the solvent, The diamine Y mole and the polyhydroxy compound Z mole are synthesized by reaction, and in this case, X, Y, and Z are preferably determined by a ratio in which the relationship of the following formula (1) and formula (2) holds. If it is the said range, since the solubility of the said polyester amidamic acid (A) in a solvent is high, the coating property of a composition improves, 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) Formula (1) is preferably 0.7 ≦ Z / Y ≦ 7.0, more It is preferably 1.0 ≦ Z / Y ≦ 5.0. In addition, Expression (2) is preferably 0.5 ≦ (Y + Z) /X≦4.0, and more preferably 0.6 ≦ (Y + Z) /X≦2.0.

It can be considered that the polyester amidine (A) used in the present invention has an amine group or a hydroxyl group at the terminal under the reaction conditions and an excess of X with respect to (Y + Z). Molecules are more excessively formed into molecules having an acid anhydride group (-CO-O-CO-) at the end. 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 monohydroxy compound may be added as necessary. The polyester amido acid (A) obtained by adding a monohydroxy compound for reaction can improve compatibility with epoxy compounds and epoxy hardeners, and can improve the thermosetting composition of the present invention containing these compounds. Coating.

It is preferable to use 100 parts by weight or more of the reaction solvent with respect to 100 parts by weight of the total of tetracarboxylic dianhydride, diamine, and polyhydroxy compound, since the reaction proceeds smoothly. The reaction is preferably performed 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 in which tetracarboxylic dianhydride is simultaneously added to a reaction solvent with a diamine and a polyhydroxy compound; a diamine and a polyhydroxy compound are dissolved in the reaction solvent, and then tetracarboxylic acid is added A method of dianhydride; a method of adding a diamine to a reaction product of a tetracarboxylic dianhydride and a polyhydroxy compound in advance; or a method of adding a tetracarboxylic dianhydride and a diamine to a reaction product in advance Method of polyhydric hydroxy compound and the like.

In the case where the amine silane compound having one amine group is reacted, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyhydroxy compound is completed, the reaction solution is cooled to 40 ° C. or lower, and then an amine having one The amino-based silane compound is preferably reacted at 10 ° C to 40 ° C for 0.1 to 6 hours. Moreover, a monohydroxy compound may be added at an arbitrary time point of the reaction.

The polyester amidine (A) synthesized as described above includes the structural unit represented by the formula (3) and the structural unit represented by the formula (4), and its terminal is derived from tetracarboxylic acid as a raw material. An acid dianhydride, a diamine, or an acid anhydride group, an amine group, or a hydroxyl group of a polyhydroxy compound, or an additive other than these compounds constitutes a terminal thereof. By including such a structure, hardenability becomes favorable.

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

The weight average molecular weight in this specification is a polystyrene-equivalent value calculated by a gel permeation chromatography (GPC) method (column temperature: 35 ° C, flow rate: 1 ml / min). Standard polystyrene uses polystyrene with a molecular weight of 645-132900 (for example, the polystyrene calibration kit of Agilent Technologies Co., Ltd. PL2010-0102), and the column is mixed with PL gel (PLgel MIXED) -D (Agilent Technology Co., Ltd.) can be measured using tetrahydrofuran (THF) as a mobile phase. In addition, the weight average molecular weight of the commercial item in this specification is a catalogue value.

1-2. Epoxy compound (B) By adding an epoxy compound (B) to the thermosetting composition of this invention, the heat resistance and solvent resistance of a cured film can be improved.

As the epoxy compound (B) used in the present invention, an epoxy compound having a siloxane bond site and an epoxy compound having no siloxane bond site can be used, and it is preferred to use an epoxy compound without a siloxane bond site. An epoxy compound at the bonding site.

1-2-1. Epoxy compound without a siloxane bond site The epoxy compound without a siloxane bond site used in the present invention need only be related to other components forming the thermosetting composition of the present invention. The compatibility is not particularly limited, and examples include bisphenol A epoxy resin, bisphenol F epoxy resin, glycidyl ether epoxy resin, glycidyl ester epoxy resin, and biphenyl ring. Epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, aliphatic polyglycidyl ether compound, or cyclic aliphatic epoxy resin, with epoxy resin Polymers of monomers based on radicals, copolymers of monomers having epoxy groups and other monomers, and the like.

Examples of the bisphenol A epoxy resin include jER 828, jER 1004, and jER 1009 (both trade names; Mitsubishi Chemical Corporation) and the like. Examples of bisphenol F-type epoxy resins: jER 806, jER 4005P (both are trade names; Mitsubishi Chemical Corporation) and the like. Glycidyl ether type epoxy resins can be enumerated: TECHMORE VG3101L (trade name; Printec Co., Ltd.), EHPE-3150 (trade name; Daicel Co., Ltd.), EPPN- 501H, EPPN-502H (all are trade names; Nippon Kayaku Co., Ltd.), jER 1032H60 (trade names; Mitsubishi Chemical Co., Ltd.), etc. Examples of the glycidyl ester epoxy resin include: Denacol EX-721 (trade name; Nagase ChemteX Co., Ltd.); 1,2-cyclohexanedicarboxylic acid diglycidyl ester (Trade name; manufactured by Tokyo Chemical Industry Co., Ltd.), etc. Examples of biphenyl epoxy resins: jER YX4000, jER YX4000H, jER YL6121H (both trade names; Mitsubishi Chemical Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3100 ( Are trade names; Nippon Kayaku Co., Ltd.). Examples of phenol novolac epoxy resins include EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), jER 152, jER 154 (both trade names; Mitsubishi Chemical Corporation) and the like. Examples of cresol novolac epoxy resins include EOCN-102S, EOCN-103S, EOCN-104S, and EOCN-1020 (both trade names; Nippon Kayaku Co., Ltd.) and the like. Examples of the bisphenol A novolac epoxy resin include jER 157S65, jER 157S70 (both trade names; Mitsubishi Chemical Corporation), and the like. Cycloaliphatic epoxy resins can be exemplified: Celloxide 2021P, Celloxide 3000 (both trade names; Daicel Co., Ltd.), and the like.

The proportion of the epoxy compound having no siloxane bonding site in the epoxy compound (B) is preferably 50% by weight to 100% by weight, and more preferably 80% by weight to 100% by weight. If it exists in these ranges, flatness, heat resistance, electrical characteristics, and tackiness will become favorable.

1-2-2. Epoxy compound having a siloxane bond site The epoxy compound having a siloxane bond site used in the present invention is only required to be compatible with other components forming the thermosetting composition of the present invention. The solubility is not particularly limited. The epoxy compound having a siloxane bond site is preferably at least one selected from the group consisting of a compound represented by the following formula (5) and a compound represented by the formula (6).

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

R ⁴ , R ⁵ and R ⁶ having 1 to 26 carbon organic groups are a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an alkyl group including a cyclic alkyl group, an aromatic ring, and an aromatic ring Any of these methyl groups (-CH _2- ) may be substituted with a group containing O, NH, N, or a group containing Si, and any hydrogen of these groups may be substituted with fluorine.

Specific examples of the linear alkyl group and the branched alkyl group are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, third pentyl, hexyl, 2 , 3-dimethylbutane-2-yl, octyl, 6-methylheptyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecane base.

Specific examples of the cyclic alkyl group and the alkyl group including a cyclic alkyl group are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and bicyclo [2.2.1] heptane-2- Base, bicyclo [2.2.1] hept-5-en-2-yl, 2-cyclohexylethyl, 2- (cyclohex-3-en-1-yl) ethyl, 2-cycloheptylethyl, 2- (Bicyclo [2.2.1] hept-5-en-2-yl) ethyl, 3-cyclohexylpropyl, 4- (thirdbutyl) cyclohexyl, and adamantyl.

Specific examples of the aromatic ring and the group containing the aromatic ring are phenyl, benzyl, phenethyl, 4-isopropylphenyl, mesityl, 3,5-diethylphenyl, and 4-isobutyl Phenyl, 2,6-diethylphenyl, naphthalene-2-yl, 1,1'-biphenyl, 4 '-(third butyl)-[1,1'-biphenyl] -4 -Yl, 2,4,6-triisopropylphenyl, 4'-heptyl- [1,1'-biphenyl] -4-yl, 12-((2-benzylidene benzamidine Group) oxy) dodecyl, and anthracene-9-yl.

Specific examples of the methyl group (-CH _2- ) substituted with a group containing O, NH or Si are ethoxymethyl, 3-methoxy-3-oxopropyl, 3 -(2-methoxyethoxy) propyl, 2,5,8,11-tetraoxatetradecane-14-yl, 2,5,8,11-tetraoxatetradecane-17- Group, 11,11-dimethoxyundecyl, 2- (dimethylamino) ethyl, 2- (diethylamino) ethyl, tetrahydrofuran-3-yl, tetrahydro-2H- Pyran-4-yl, 3-((tetrahydrofuran-3-yl) methoxy) propyl, 10- (1,3-dioxolane-2-yl) decyl, 10- (1, 3-dioxane-2-yl) decyl, morpholinyl, 4-methoxy-3,5-dimethylbenzyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, -Carboxyethyl, 4-hydroxybutyl, 4-hydroxy-3-oxobutyl, trimethylsilyl, (trimethylsilyl) methyl, 3- (trimethylsilyl) propyl, 2- (2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-cyclotetrasiloxane-2-yl) ethyl, 2- (dimethyl (phenyl) silyl) ethyl, methoxy, ethoxy, propoxy, isopropoxy, prop-1-en-2-yloxy, butoxy, cap Tributoxy, second butoxy, isobutoxy, third pentyl Methyl, hexyloxy, 2-ethylbutoxy, (3-methylpentyl) oxy, (2-methylhexane-2-yl) oxy, octyloxy, (2-ethyl Hexyl) oxy, decyloxy, 2-methoxyethoxy, 2-ethoxyethoxy, (1-methoxypropane-2-yl) oxy, 2- (2-methoxy Ethoxy) ethoxy, 2-butoxyethoxy, (3-ethylhexyl) oxy, dodecyloxy, tridecyloxy, cetyloxy , Octadecyloxy, stearylyloxy, (butane-2-ylideneamino) oxy, (diethylamino) oxy, cyclohexyloxy, cyclooctyloxy, Bicyclo [2.2.1] heptane-2-ylmethoxy, cyclononyloxy, (2-isopropyl-5-methylcyclohexyl) oxy, (5-methyl-2- (propyl- 1-en-2-yl) cyclohexyl) oxy, (octahydro-1H-4,7-methyl bridge inden-5-yl) oxy, phenoxy, p-tolyloxy, m-tolyloxy , O-tolyloxy, o-carboxyphenoxy, benzyloxy, phenethyloxy, 3-phenylpropoxy, cinnamyloxy, 1-phenyl- (2-ethoxy-2- (Oxo) ethoxy, (2-methyl-1-oxo-1-phenylpropane-2-yl) oxy, 2-ethoxy-2-oxo-1- (o-tolyl) ethyl Methyl, 2-ethoxy-1- (2-methoxyphenyl) -2-oxoethoxy, (4-ethoxy-4-oxo-1-phenylbut-2-ene- 1-yl) oxy, (1-benzylidenecyclohexyl) oxy, and 2-hydroxyethoxy.

Specific examples of the group in which arbitrary hydrogen is substituted with fluorine are 3,3,3-trifluoropropyl, perfluorooctyl, 5,5,6,6,7,7,8,8,8-ninefluoro -4,4-bis (trifluoromethyl) octyl, 11- (perfluorophenoxy) undecyl, 2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl , 3-phenoxybenzyl, 4'-methoxy- [1,1'-biphenyl] -4-yl, 4- (octyloxy) phenyl, fluoromethoxy, difluoromethyl Oxy, 2,2,2-trifluoroethoxy, 2,2,2-trifluoroacetamidooxy, 2,2,3,3-tetrafluoropropoxy, 2,2,3,3, 3-pentafluoropropoxy, (1,1,1,3,3,3-hexafluoropropane-2-yl) oxy, and perfluorophenoxy.

Among these groups, from the viewpoints of excellent compatibility in the composition of the compound and good transparency and flatness of the formed cured film, preferred groups are methyl, ethyl, propyl, and isopropyl. , Butyl, isobutyl, third butyl, pentyl, third pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, phenyl, benzyl , Phenethyl, 4-isopropylphenyl, mesityl, 3,5-diethylphenyl, 4-isobutylphenyl, 2,6-diethylphenyl, ethoxyl Methyl, 3-methoxy-3-oxopropyl, 3- (2-methoxyethoxy) propyl, 4-methoxy-3,5-dimethylbenzyl, trimethyl Silyl, (trimethylsilyl) methyl, 3- (trimethylsilyl) propyl, methoxy, ethoxy, propoxy, isopropoxy, prop-1-ene-2- Ethoxy, butoxy, third butoxy, second butoxy, isobutoxy, third pentyloxy, hexyloxy, 2-ethylbutoxy, cyclohexyloxy, cyclo Octyloxy, phenoxy, p-tolyloxy, m-tolyloxy, o-tolyloxy, benzyloxy, and 3-phenylpropoxy More preferred groups are methyl, ethyl, propyl, phenyl, benzyl, ethoxymethyl, trimethylsilyl, (trimethylsilyl) methyl, methoxy, ethoxy , And propoxy.

The organic group having 1 to 26 carbon atoms in R ⁷ is also a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an alkyl group including a cyclic alkyl group, an aromatic ring, a group including an aromatic ring, etc. Any of the methyl groups (-CH _2- ) may be substituted by a group containing O, NH, N, or a group containing Si, and any hydrogen of these groups may be substituted by fluorine, but since R ^{7 is} bonded to O Therefore, compared with R ⁴ , R ⁵ and R ⁶ , specific examples are limited.

Specific examples of the linear alkyl group and the branched alkyl group are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, third pentyl, hexyl, 2 , 3-dimethylbutane-2-yl, octyl, 6-methylheptyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecane base.

Specific examples of the cyclic alkyl group and the alkyl group including a cyclic alkyl group are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and bicyclo [2.2.1] heptane-2- Base, bicyclo [2.2.1] hept-5-en-2-yl, 2-cyclohexylethyl, 2- (cyclohex-3-en-1-yl) ethyl, 2-cycloheptylethyl, 2- (Bicyclo [2.2.1] hept-5-en-2-yl) ethyl, 3-cyclohexylpropyl, 4- (thirdbutyl) cyclohexyl, and adamantyl.

Specific examples of the aromatic ring and the group containing the aromatic ring are phenyl, benzyl, phenethyl, 4-isopropylphenyl, mesityl, 3,5-diethylphenyl, and 4-isobutyl Phenyl, 2,6-diethylphenyl, naphthalene-2-yl, 1,1'-biphenyl, 4 '-(third butyl)-[1,1'-biphenyl] -4 -Yl, 2,4,6-triisopropylphenyl, 4'-heptyl- [1,1'-biphenyl] -4-yl, 12-((2-benzylidene benzamidine Group) oxy) dodecyl, and anthracene-9-yl.

Specific examples of the methyl group (-CH _2- ) substituted with a group containing O, NH or Si are ethoxymethyl, 3-methoxy-3-oxopropyl, 3 -(2-methoxyethoxy) propyl, 2,5,8,11-tetraoxatetradecane-14-yl, 2,5,8,11-tetraoxatetradecane-17- Group, 11,11-dimethoxyundecyl, 2- (dimethylamino) ethyl, 2- (diethylamino) ethyl, tetrahydrofuran-3-yl, tetrahydro-2H- Pyran-4-yl, 3-((tetrahydrofuran-3-yl) methoxy) propyl, 10- (1,3-dioxolane-2-yl) decyl, 10- (1, 3-dioxane-2-yl) decyl, morpholinyl, 4-methoxy-3,5-dimethylbenzyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1 -Carboxyethyl, 4-hydroxybutyl, 4-hydroxy-3-oxobutyl, trimethylsilyl, (trimethylsilyl) methyl, 3- (trimethylsilyl) propyl, 2- (2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-cyclotetrasiloxane-2-yl) ethyl, And 2- (dimethyl (phenyl) silyl) ethyl.

Specific examples of the group in which arbitrary hydrogen is substituted with fluorine are 3,3,3-trifluoropropyl, perfluorooctyl, 5,5,6,6,7,7,8,8,8-ninefluoro -4,4-bis (trifluoromethyl) octyl, 11- (perfluorophenoxy) undecyl, 2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl , 3-phenoxybenzyl, 4'-methoxy- [1,1'-biphenyl] -4-yl, and 4- (octyloxy) phenyl.

Among these groups, from the viewpoints of excellent compatibility in the composition of the compound and good transparency and flatness of the formed cured film, preferred groups are methyl, ethyl, propyl, and isopropyl. , Butyl, isobutyl, third butyl, pentyl, third pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, phenyl, benzyl , Phenethyl, 4-isopropylphenyl, mesityl, 3,5-diethylphenyl, 4-isobutylphenyl, 2,6-diethylphenyl, ethoxyl Methyl, 3-methoxy-3-oxopropyl, 3- (2-methoxyethoxy) propyl, 4-methoxy-3,5-dimethylbenzyl, trimethyl Silyl, (trimethylsilyl) methyl, and 3- (trimethylsilyl) propyl, more preferably methyl, ethyl, propyl, phenyl, benzyl, ethoxy Methyl, trimethylsilyl, and (trimethylsilyl) methyl.

The organic group having an epoxy group of R ⁴ , R ⁵ , R ⁶ , and R ⁷ is specifically oxetan-2-ylmethyl, 2- (oxetan-2-yl) ethyl, 4- (Oxetan-2-yl) butyl, 3- (oxetan-2-ylmethoxy) propyl, 7-oxabicyclo [4.1.0] heptane-3-yl, 2- (7-oxabicyclo [4.1.0] heptane-2-yl) ethyl, dimethyl (4- (oxetan-2-ylmethoxy) butyl) silyl, 3- (7 -Oxabicyclo [4.1.0] heptane-3-yl) propyl, and 8- (oxetan-2-yl) octyl.

Among these groups, from the viewpoint of good transparency and heat resistance of the formed cured film, preferred groups are oxetan-2-ylmethyl and 2- (oxetan-2-yl). Ethyl, 4- (oxetan-2-yl) butyl, 3- (oxetan-2-ylmethoxy) propyl, 7-oxabicyclo [4.1.0] heptane-3 -And 2- (7-oxabicyclo [4.1.0] heptane-2-yl) ethyl, more preferred are oxetan-2-ylmethyl, 2- (oxetane 2-yl) ethyl, 4- (oxetan-2-yl) butyl, 3- (oxetan-2-ylmethoxy) propyl.

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

The organic groups having 1 to 26 carbons and the organic group having an epoxy group in R ⁸ to R ¹³ can be similarly exemplified by the groups exemplified as R ⁴ , R ^5, and R ⁶ in the formula (5), and are more preferable. The same applies to the bases and the more preferred bases.

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

When using the epoxy compound which has a siloxane bond site | part, the ratio in an epoxy compound (B) is 0.5 weight%-50 weight%, Preferably it is 0.5 weight%-20 weight%. If it exists in these ranges, the balance of flatness, transparency, heat resistance, electrical characteristics, and viscosity will become favorable.

A specific example of the epoxy compound having a siloxane bond site is an organic silicon compound having an epoxy group and which cannot generate a siloxane bond through further condensation; a siloxane compound having an epoxy group and which can generate siloxane by condensation A copolymer of one or more organosilicon compounds having a bond; or one or more organosilicon compounds having an epoxy group and capable of generating a siloxane bond through condensation, and those having one or more siloxane bonds that can be generated through condensation Copolymer of epoxy-based organosilicon compounds. If it is a commercially available product, it can be listed as: 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisilaxane (trade name; Jerester Technology Co., Ltd. (Manufactured by Gelest Technologies Incorporated), TSL9906 (trade name; Momentive Performance Material (manufactured)), COATOSIL MP-200 (trade name; Momentive High-tech Materials (stock) (Manufactured), Conpoceran SQ506 (trade name; manufactured by Arakawa Chemical Co., Ltd.), ES-1023 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

1-2-3. Specific examples of the epoxy compound (B) Specific examples of the epoxy compound (B) include 3,4-epoxycyclohexanecarboxylic acid-3 ', 4'-epoxy ring Hexyl methyl ester (for example, trade name: Celloxide 2021P, Daicel Co., Ltd.), 1-methyl-4- (2-methyloxiranyl) -7-oxyl Heterobicyclo [4.1.0] heptane (for example, trade name: Celloxide 3000, Daicel Co., Ltd.), 2- [4- (2,3-epoxypropoxy) Phenyl] -2- [4- [1,1-bis [4- (2,3-glycidoxy) 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] phenyl] ethyl] phenoxy] -2-propanol mixture, 2- [4- (2,3-glycidoxy) phenyl] -2- [4- [1,1- Bis [4- (2,3-glycidoxy) phenyl] ethyl] phenyl] propane (for example, trade name: TECHMORE VG3101L, Printec Co., Ltd.), 1 , 1,1-tris (4-hydroxyphenyl) ethane triglycidyl ether (for example, trade name: jER 1032H60, Mitsubishi Chemical Corporation), 1,3- (Oxiranylmethyl) -5- (2-propenyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, and 2,2-bis 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of (hydroxymethyl) -1-butanol (for example, trade name: EHPE-3150, Daicel ) Co., Ltd.) and so on.

The epoxy compound (B) used in the present invention may be an epoxy group-containing polymer. The epoxy-group-containing polymer can be obtained by using glycidyl (meth) acrylate alone as a radical polymerizable compound having an epoxy group, or by using glycidyl (meth) acrylate and those having no epoxy group. It is obtained by reacting a radical polymerizable compound. By using an epoxy group-containing polymer, the transparency of the cured film obtained from the thermosetting composition is increased, and the decrease in transparency in the ultraviolet ozone treatment step or the ultraviolet exposure step is suppressed, which is preferable. In the case of a copolymer, from the viewpoints of flatness, heat resistance, and solvent resistance, it is preferred that all monomers constituting the epoxy group-containing polymer contain 50% to 99% by weight of (A Based) glycidyl acrylate.

Preferred examples of the radically polymerizable compound having no epoxy group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate (for example, a trade name: NK ester ( NK ester) 2G, Shin Nakamura Chemical), 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylic acid Ester, tricyclodecane dimethanol di (meth) acrylate, N-phenylcis butene difluorene imide, N-cyclohexyl cis butylene diimide, indene. These examples are preferable because the epoxy compound obtained by reacting with glycidyl (meth) acrylate has good compatibility with polyester amidate (A).

Further, for example, a polymer such as 3-glycidyloxypropyltrimethoxysilane known as the trade name COATOSIL MP 200 (Metco Advanced Materials Co., Ltd.) can be suitably used. Of silane compounds with epoxy groups. Since such a compound has an alkoxysilyl group in the molecule, the effect of improving the adhesion between the formed cured film and the substrate can be expected, as in the "adhesion improver" described later.

1-3. The ratio of the component (A) and the component (B) to 100 parts by weight of the polyester amidine (A) in the thermosetting composition of the present invention, the ratio of the epoxy compound (B) to The proportion of the total amount is 20 to 400 parts by weight. If the ratio of the total amount of the said epoxy compound (B) is the said 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 a range of 50 parts by weight to 300 parts by weight.

1-4. Other ingredients Various additives can be added to the thermosetting composition of the present invention to improve uniformity of coating and adhesion. Examples of additives include epoxy hardeners, solvents, anionic, cationic, nonionic, fluorine or silicon leveling agents / surfactants, adhesion improvers such as silane coupling agents, hindered phenols, Hindered amine-based, phosphorus-based, sulfur-based compounds and other antioxidants.

1-4-1. Epoxy hardener (C) In the thermosetting composition of the present invention, the epoxy hardener (C) may be used in order to improve flatness and chemical resistance. The epoxy hardener (C) includes an acid anhydride-based hardener, an amine-based hardener, a phenol-based hardener (hereinafter also referred to as "phenol-based hardener (H)"), an imidazole-based hardener, and a catalyst-type hardener. And thermosensitive acid generators such as sulfonium salts, benzothiazolium salts, ammonium salts, and sulfonium salts. From the viewpoint of avoiding the coloration of the cured film and the heat resistance of the cured film, an acid anhydride-based curing agent or imidazole is preferred. Department of hardener.

Specific examples of the acid anhydride-based hardener include aliphatic dicarboxylic acid anhydrides (for example, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydro Trimellitic anhydride, etc.), aromatic polycarboxylic anhydride (such as phthalic anhydride, trimellitic anhydride, etc.), styrene-maleic anhydride copolymer. Among these acid anhydride-based hardeners, trimellitic anhydride and hexahydrotrimellitic anhydride, which have a good balance between heat resistance and solubility in solvents, are preferred.

Specific examples of the imidazole-based hardener include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2,3-dihydro-1H. -Pyrrolo [1,2-a] benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate. Among these imidazole-based hardeners, 2-undecylimidazole having a good balance between curability and solubility in a solvent is preferred.

In the epoxy hardener (C) of the present invention, a phenol-based hardener (H) may be used for the purpose of reducing the dielectric loss tangent in addition to the function of hardening the epoxy resin. Specific examples of the phenolic hardener (H) include α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,1,1-tris (4 -Hydroxyphenyl) ethane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 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-tetrakis (4-hydroxyphenyl) ethane . Of these phenolic hardeners (H), α, α, α′-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, which is well-balanced in heat resistance and compatibility, is preferred, 1,1,1-tris (4-hydroxyphenyl) ethane, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.

When the epoxy curing agent (C) is used, the proportion of the epoxy curing agent (C) is 0.1 to 60 parts by weight relative to 100 parts by weight of the epoxy compound (B). In the case where the epoxy curing agent (C) is an acid anhydride-based curing agent and a phenol-based curing agent (H), more specifically, it is preferred that the epoxy curing agent is cured with respect to epoxy groups. The carboxylic anhydride group, carboxyl group, or phenolic hydroxyl group in the agent is added so that it becomes 0.1 to 1.5 times equivalent. At this time, the carboxylic acid anhydride group is calculated as a divalent. If a carboxylic anhydride group, a carboxyl group, or a phenolic hydroxyl group is added so that it becomes 0.15-times equivalent to 0.8-times equivalent, chemical resistance will be improved further, and it is more preferable.

1-4-2. Solvent (D) A solvent (D) may be added to the thermosetting composition of the present invention. The solvent (D) arbitrarily added to the thermosetting composition of the present invention is preferably capable of dissolving the polyester amidate (A), the epoxy compound (B), and the epoxy hardener (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 acetate, 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 ester, ethyl 2-methoxypropionate, ethyl 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 acetate, ethyl acetate, 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 monobutyl 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, two Oxane, toluene, xylene, γ-butyrolactone, or N, N-dimethylacetamide, cyclohexanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, weight Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and tetrapropylene glycol having an average molecular weight of 1,000 or less, and polypropylene glycol having a weight average molecular weight of 1,000 or less. The solvent may be one kind of these solvents or a mixture of two or more kinds of these solvents.

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

1-4-3. Surfactant A surfactant may be added to the thermosetting composition of the present invention to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, and Polyflow No. 90. Polyflow No. 95 (the above are all trade names; Gongrongshe Chemical Co., Ltd.), Disperbyk 161, Disperbyk 162, Dis Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Dis Disperbyk 181, Disperbyk 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (The above are all trade names; Japan Bi Chemical (BYK Chemie Japan) Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (the above are all trade names; Shin-Etsu Chemical Industry Co., Ltd.), Surfon SC-101, Surflon KH-40, Surflon S611 (all above) Are trade names; AGC Seimi Chemical Co., Ltd.), Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 602A, Ftergent 650A, FTX-218 (the above are all trade names; Neos Co., Ltd.) , Eftop (EFTOP) EF-351, Eftop (EFTOP) EF-352, Eftop (EFTOP) EF-601, Eftop (EFTOP) EF-801, Eftop (EFTOP) EF-802 (The above are trade names; Mitsubishi Material Co., Ltd.), Megafac F-171, Megafac F-177, Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F-477, Megafac F-552, Mega (Megafac) F-553, Megafac (F-554), Megafac 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 all trade names; Di Edison ( (DIC) Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGOGLA TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (the above are all trade names, Japan Evonik Degussa (Evonik-Degussa Japan Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl Sulfonate, diglycerol tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amino sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene Octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene ole alkenyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearin Ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan hard Fatty acid ester, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, poly Oxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyl diphenyl ether disulfonate. It is preferable to use at least one 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, TEGO Twin 4000, fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl trimethylammonium salt, and fluoroalkylamino sulfonate At least one of them is preferred because the uniformity of coating of the thermosetting composition is improved.

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

1-4-4. Adhesiveness 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 improver. As such an adhesiveness improving agent, for example, a silane-based, aluminum-based, or titanate-based coupling agent can be used. Specific examples include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane ( For example, Sila-Ace S510; trade name; JNC Co., Ltd.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (for example, Sala-Ace ( Sila-Ace) S530; trade name; JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane (such as Sila-Ace S810; trade name; JNC shares) Co., Ltd.) and other silane coupling agents, aluminum coupling agents such as acetoxy aluminum diisopropoxide, and titanate coupling agents such as tetraisopropylbis (dioctyl phosphite) titanate联 剂。 Union agent. In addition, although COATOSIL MP-200 is described as an epoxy compound in the foregoing, it can be classified as an epoxy-based silane-based coupling agent and is the same as the adhesion-improving agent. To use.

Among these adhesiveness-improving agents, 3-glycidoxypropyltrimethoxysilane is preferred because it has a large effect of improving adhesiveness.

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

1-4-5. 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, from the viewpoint of weather resistance, a hindered phenol type is preferred. Specific examples include: Irganox 1010, Irganox FF, Irganox 1035, Irganox 1035FF, Yiluganox (Irganox) 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Ilganox (Irganox) 1330, Irganox 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Ilganox (Irganox) 245FF, Irganox 245DWJ, Irganox 259, Irganox 3114, Irganox 565, Yiluganuosi (Irganox) 565DD, Irganox 295 (both trade names; BASF Japan), ADK STAB AO-20, ADK STAB) AO-30, ADK STAB AO-50, ADK STAB AO-60, Ai ADK STAB AO-70, ADK STAB AO-80 (both trade names; ADEKA Co., Ltd.). Among them, more preferred are Irganox 1010 and ADK STAB AO-60.

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

1-4-6. Other additives In the case where the polyester amidate (A) does not contain a styrene-maleic anhydride copolymer as a raw material, a styrene-maleic anhydride copolymer may also be added As other ingredients.

1-5. Preservation of thermosetting composition The thermosetting composition of the present invention is preferably stored within a temperature range of -30 ° C to 25 ° C. If the storage temperature is -20 ° C to 10 ° C, no precipitates are present, so it is more preferable.

2. A cured film obtained from a thermosetting composition 2-1. Method for producing a cured film The thermosetting resin composition of the present invention can be obtained as follows: Polyester (A) and The epoxy compound (B) is mixed, and an epoxy hardener, a solvent, a coupling agent, a surfactant, and other additives are optionally added according to the target characteristics, and these compounds are uniformly mixed and dissolved.

The thermosetting composition prepared as described above (in the case of a solid state without a solvent, after being dissolved in a solvent) is coated on the surface of a substrate, and the solvent is removed by, for example, heating to form a cured film. . The thermally curable composition can be applied to the substrate surface by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, and a slit coating method. Next, the coating film is heated (pre-baked) using a hot plate, an oven, or the like. The heating conditions vary depending on the type of each component and the blending ratio. Usually, it is 70 ° C to 110 ° C. If it is an oven, it is 5 minutes to 15 minutes. If it is a hot plate, it is 1 minute to 5 minutes. Thereafter, in order to harden the coating film, a cured film can be obtained by heat treatment at 180 ° C to 250 ° C, preferably 200 ° C to 250 ° C, and in an oven, for 30 minutes to 90 minutes If it is a hot plate, it is performed for 5 to 30 minutes.

When the cured film obtained as described above is heated, 1) the polyamidic acid of the polyester phosphoamic acid (A) is partially dehydrated and cyclized to form a phosphonium imine bond, and 2) the polyester phosphoamino acid ( A) The carboxylic acid reacts with the epoxy compound (B) to obtain a high molecular weight, and 3) The epoxy compound (B) hardens to form a high molecular weight, so it is very tough, and has transparency, heat resistance, and resistance. Excellent chemical resistance, flatness, adhesion, light resistance, and sputtering resistance. Therefore, if the cured film is used for a semiconductor device, a liquid crystal display element, a circuit material, or the like as a protective film formed on an upper layer of a semiconductor layer, an electrode, wiring, or the like, such as a protective film for a color filter, a passivation film, α A radiation blocking film, a buffer coating film, and the like are effective.

2-2. Dielectric loss tangent of the cured film The cured film obtained from the thermosetting composition of the present invention has an excellent dielectric loss tangent, for example, a dielectric loss of 0.007 or less, preferably 0.006 or less, and more preferably 0.005 or less. Loss tangent. When a hardened film having a dielectric loss tangent at 20 Hz of 0.007 or less is used as a transparent protective film, for example, for a color filter, the switching threshold deviation due to the specific electrical characteristics of a liquid crystal display device does not occur. That is, it is particularly excellent in that it does not adversely affect display quality.

Further, in addition to the protective film for a color filter, the cured film of the present invention is used as a transparent insulating film formed between a TFT and a transparent electrode, a transparent insulating film formed between a transparent electrode and an alignment film, or formed on A transparent insulating film on a transparent electrode is also effective.

As a specific example, a glass substrate on which a TFT, a transparent electrode (pixel electrode), and an alignment film is formed, and a glass substrate on which a color filter, a transparent electrode (counter electrode), and an alignment film are formed are opposed to each other. In the TFT liquid crystal display element manufactured by sandwiching a liquid crystal composition, and further bonding polarizing plates on the outside of two glass substrates, and disposing a backlight light source on the back, the cured film of the present invention can be used as a protective film on a color filter. A transparent insulating film formed between the TFT and the transparent electrode, a transparent insulating film formed between the transparent electrode and the alignment film, and a transparent insulating film formed on the transparent electrode.

In addition, the color filters can be formed by using known inkjet methods, printing methods, photoresist methods, etching methods, etc., using red, green, and blue colored compositions on the substrate to form filter regions of various colors. While making. Among these, in consideration of high-definition, controllability of spectroscopic characteristics, reproducibility, and the like, a photoresist method is preferred in which a pigment is dispersed in a monomer containing a transparent resin and a precursor thereof, and a photopolymerization initiator. Each coloring composition (coloring resist material) obtained from the composition is coated on a substrate for film formation, and then pattern exposure and development are performed to form a one-color filter segment, which is repeated for each color. The steps to make a color filter. [Example]

Next, the present invention will be specifically described with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples at all.

First, polyester amidate (A1) to polyester amidate (A4) and polyester amidate (A5) containing a reaction product of a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound are synthesized as follows. The solution.

[Synthesis example A-1] Preparation of solution of polyester amido acid (A1) In a four-necked flask equipped with a stirrer, methyl 3-methoxypropanoate (methyl 3-methoxy propionate (hereinafter abbreviated as "MMP"), 3,3 ', 4,4'-diphenylether tetracarboxylic dianhydride (3,3', 4,4'-diphenylether tetracarboxylic dianhydride, abbreviated as "ODPA"), 1,4-butanediol, and benzyl alcohol, and stirred at 125 ° C for 2 hours under a stream of dry nitrogen (the first stage of synthesis). NMP 49.00 g ODPA 20.36 g 1,4-butanediol 3.55 g benzyl alcohol 2.84 g

Thereafter, the reaction solution was cooled to 25 ° C, and 3,3'-diamino diphenyl sulfone (hereinafter abbreviated as "DDS") and MMP were charged at the following weights at 20 ° C to 30 ° C. After stirring for 2 hours, stirring was performed at 125 ° C for 1 hour (second stage of synthesis). DDS 3.26 g MMP 21.00 g

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

[Synthesis example A-2] Preparation of solution of polyester amidine (A2) In a four-necked flask equipped with a stirrer, propylene glycol monomethyl ether acetate (dehydrated and purified) was charged in the following order by weight: glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA"), 1,2,3,4-butane tetracarboxylic dianhydride (1,2,3,4-butane tetracarboxylic dianhydride, abbreviated as "BT-100") SMA-1000P (commercial name; styrene-maleic anhydride copolymer, Sichuan Crude Chemical Co., Ltd.), 1,4-butanediol, and benzyl alcohol under a dry nitrogen stream at 125 ° C for 2 hours Stir (the first stage of synthesis). PGMEA 53.49 g BT-100 3.83 g SMA-1000P 18.23 g 1,4-butanediol 1.16 g benzyl alcohol 5.57 g

After that, the reaction solution was cooled to 25 ° C., DDS and PGMEA 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 1.20 g PGMEA 16.51 g

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

[Synthesis Example A-3 and Synthesis Example A-4] Preparation of Polyester Amidate (A3) or Polyester Amidate (A4) Solution According to the method of Synthesis Example A-2, the temperature shown in Table 1 was used. , Time, and ratio (unit: g) react each component to obtain a solution of polyester amidate (A3) or polyester amidate (A4). And the weight average molecular weight of the obtained polymer was measured in the same manner. In addition, "Bis-A-2EOH" in Table 1 means 4,4'-isopropylidenebis (2-phenoxyethanol).

[Synthesis example A-5] Preparation of solution of polyester amidine (A5) In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, and 1,4-butanediol were charged at the following weight. And benzyl alcohol, and stirred at 130 ° C for 3 hours under a stream of dry nitrogen (synthesis first stage). MMP 446.96 g ODPA 183.20 g 1,4-butanediol 31.93 g benzyl alcohol 25.54 g

After that, the reaction solution was cooled to 25 ° C., and DDS and MMP were added at the following weights, followed by stirring at 20 ° C. to 30 ° C. for 2 hours, and then stirring at 115 ° C. for 1 hour (second stage of synthesis). DDS 29.33 g MMP 183.04 g

The solution was cooled to room temperature to obtain a 30% by weight solution of light yellow transparent polyester amido acid (A5). A part of the solution was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A5) was 4,200.

[Table 1]

Next, an epoxy group-containing polymer (B1) to an epoxy group-containing polymer including a reaction product of a radical polymerizable compound having an epoxy group and a reaction product of a radical polymerizable compound having no epoxy group is synthesized as follows. Of polymer (B4) and epoxy-containing polymer (B5).

[Synthesis Example B-1] Preparation of solution of epoxy group-containing polymer (B1) In a four-necked flask equipped with a stirrer, PGMEA which was dehydrated and purified as a polymerization solvent was charged at the following weight as Glycidyl methacrylate (hereinafter abbreviated as "GMA") of an epoxy-based radically polymerizable compound was further charged with V-601 (trade name; 2,2 ') as a polymerization initiator at the following weight. -Azobis (2-methylpropanoic acid) dimethyl, Wako Pure Chemical Industries, Ltd.), and stirred under a dry nitrogen stream at 110 ° C for 2 hours. PGMEA 31.50 g GMA 13.50 g V-601 1.35 g

The solution was cooled to room temperature to obtain a 30% by weight solution of the epoxy group-containing polymer (B1). A part of the solution was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight-average molecular weight of the obtained epoxy-group-containing polymer (B1) was 3,900.

[Synthesis Example B-2] Preparation of solution of epoxy group-containing polymer (B2) In a four-necked flask equipped with a stirrer, MMP, GMA, 2G (diethylene glycol dimethacrylate (trade name; NK ester 2G), Shin Nakamura Chemical) as a radical polymerizable compound having no epoxy group was further charged with V as a polymerization initiator at the following weight -601, stirring at 110 ° C for 2 hours under a stream of dry nitrogen. MMP 31.50 g GMA 12.15 g 2G 1.35 g V-601 2.03 g

The solution was cooled to room temperature to obtain a 30% by weight solution of the epoxy group-containing polymer (B2). A part of the solution was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight-average molecular weight of the obtained epoxy group-containing polymer (B2) was 4,000.

[Synthesis Example B-3 to Synthesis Example B-4] The solution of the epoxy group-containing polymer (B3) or the epoxy group-containing polymer (B4) was prepared according to the method of Synthesis Example B-2. Table 2 Each component was reacted at the temperature, time, and ratio (unit: g) described above to obtain an epoxy group-containing polymer (B3) or an epoxy group-containing polymer (B4). The weight-average molecular weight of the obtained epoxy group-containing polymer was measured in the same manner. In addition, "NPM" in Table 2 represents N-phenyl-cis-butyl diimide, and "CHMI" represents N-cyclohexyl-cis-butyl diimide.

[Synthesis Example B-5] Preparation of solution of epoxy group-containing polymer (B5) In a four-necked flask equipped with a stirrer, PGMEA as a polymerization solvent was added with the following composition, and free radicals having epoxy groups were added. GMA based polymerizable compounds, dicyclopentenyloxy ethyl methacrylate (hereinafter referred to as "CMA") and methacrylic acid (hereinafter referred to as "MA" ") And V-601 as a polymerization initiator, after heating at 80 ° C for 3 hours, and then heating at 90 ° C for 1 hour. GMA 103.20 g CMA 12.00 g MA 4.80 g V-601 18.00 g PGMEA 280.00 g

The solution was cooled to room temperature to obtain a 30% by weight solution of the epoxy group-containing polymer (B5). A part of the solution was sampled, and the weight-average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight-average molecular weight of the obtained epoxy group-containing polymer (B5) was 12,000.

[Table 2]

[Example 1] Next, a thermosetting composition was prepared as described below using a solution of the polyester sulfamic acid (A1) obtained in Synthesis Example A-1, a commercially available epoxy compound, and an epoxy hardener. . A cured film was obtained from the thermosetting composition, and the cured film was evaluated. The details of these are summarized in Table 3A.

A 500 ml separable flask equipped with a stirring wing was purged with nitrogen. In this flask, 100.00 g of a polyester glutamic acid solution (A1) and TECHMORE VG3101L as an epoxy compound (B5) were charged. (Trade name; Printec (stock)) 58.50 g, trimellitic anhydride (hereinafter referred to as "TMA") as epoxy hardener 6.00 g, ADK STAB as an additive AO-60 (trade name; manufactured by ADEKA Co., Ltd., hereinafter abbreviated as "AO-60") 0.5 g, 367.4 g of MMP dehydrated and purified as a solvent, and diethylene glycol methylethyl 109.3 g of diethyleneglycol methyl ethyl ether (hereinafter abbreviated as "EDM") was stirred at room temperature for 3 hours to uniformly dissolve. Next, 0.2 g of Megafac F-556 (trade name; manufactured by DIC) was added, stirred at room temperature for 1 hour, and filtered with a membrane filter having a pore size of 0.2 μm to prepare a coating. liquid.

[Evaluation of the electrical characteristics (dielectric loss tangent) of the cured film] The coating liquid was spin-coated on a glass substrate on which chromium was vapor-deposited for use in electrodes for 10 seconds, and then preheated at 80 ° C for 3 minutes on a hot plate. Bake to form a coating film. Thereafter, the coating film was cured by heating at 230 ° C. for 30 minutes in an oven to obtain a cured film having a film thickness of 1.5 μm. On the obtained cured film, aluminum for electrodes was vapor-deposited, and a sample in which the cured film was sandwiched between a chromium electrode and an aluminum electrode was prepared. The inductance-capacitance-resistance meter (LCR meter) (trade name: E4980A, Agilent Technologies Co., Ltd.) was used to measure the dielectric loss tangent of the obtained sample at 20 Hz.

[Evaluation of the transparency and heat resistance of the cured film] Next, the coating solution was spin-coated on a glass substrate at 800 rpm for 10 seconds, and then pre-baked on a hot plate at 80 ° C for 3 minutes to form a coating film. Thereafter, the coating film was cured by heating at 230 ° C. for 30 minutes in an oven to obtain a cured film having a film thickness of 1.0 μm. With respect to the cured film obtained as described above, transparency and heat resistance were evaluated.

[Evaluation method of transparency] In the obtained glass substrate with a cured film, the wavelength of only the cured film was measured using an ultraviolet-visible near-infrared spectrophotometer (trade name: V-670, manufactured by JASCO Corporation). Transmission at 400 nm light. A case where the transmittance was 97% or more was evaluated as ○, and a case where the transmittance was less than 97% was evaluated as ×.

[Evaluation method of heat resistance] After the obtained glass substrate with a cured film was reheated at 230 ° C for 1 hour, the film thickness before heating and the film thickness after heating were measured, and the residual was calculated from the following calculation formula. Film rate. For the measurement of the film thickness, the step / surface roughness / fine shape measuring device (trade name: P-15, KLA TENCOR Co., Ltd.) was used. A case where the residual film rate after heating was 96% or more was evaluated as ○, and a case where the residual film rate after heating was less than 96% was evaluated as x.

[Example 2 to Example 15 and Example 16] According to the method of Example 1, the components were uniformly mixed and dissolved at the ratios (unit: g) described in Table 3A and Table 3B to obtain a thermosetting composition Thing. In addition, the obtained thermosetting composition was subjected to the production of a cured film and evaluation of each characteristic in the same manner. The details of these are summarized in Tables 3A and 3B.

[Table 3A]

[Table 3B]

The abbreviations in Tables 3A and 3B indicate the following raw materials.

[Epoxy compound] B6: Techmore VG3101L (trade name; Printec Co., Ltd.)

[Acid anhydride hardener] TMA: trimellitic anhydride

[Epoxy hardener having a phenolic hydroxyl group (phenolic hardener)] H1: α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene H2: 1, 1,1-tris (4-hydroxyphenyl) ethane H3: 9,9-bis (4-hydroxy-3-methylphenyl) fluorene H4: 1,3-bis [2- (4-hydroxyphenyl ) -2-propyl] benzene H5: 4,4 '-(3,3,5-trimethyl-1,1-cyclohexanediyl) bis (phenol) H6: 1,1,2,2- Tetrakis (4-hydroxyphenyl) ethane

[Additive] S510: Sila-Ace S510 (trade name; JNC Co., Ltd.) AO-60: ADK STAB AO-60 (trade name; Eddie) (ADEKA) Co., Ltd.) F-556: Megafac F-556 (trade name; DIC) Co., Ltd. F-559: Megafac F-559 (trade name; Di Love Health (DIC) Co., Ltd.)

[Solvent] MMP: methyl 3-methoxypropionate EDM: diethylene glycol methyl ethyl ether PGMEA: propylene glycol monomethyl ether acetate PEG: polyethylene glycol PPG: polypropylene glycol

[Comparative Example 1 to Comparative Example 5 and Comparative Example 6] According to the method of Example 1, the components were uniformly mixed and dissolved at the ratio (unit: g) shown in Table 4 to obtain a thermosetting composition. In addition, the obtained thermosetting composition was subjected to the production of a cured film and evaluation of each characteristic in the same manner. The details of these are summarized in Table 4.

[Table 4]

Using the obtained cured film as a protective film on a color filter, liquid crystal display devices of various lateral electric field methods were produced. As a result, the obtained films were produced using the thermosetting composition of Examples 1 to 15 and 16 In the liquid crystal display device of the color filter, since the dielectric loss tangent of the protective film (cured film) is low, the electrical loss is small, and the rising and falling shapes of the rectangular wave of the liquid crystal driving signal are passivated to generate a driving voltage. The threshold deviation is reduced, and a lateral electric field type liquid crystal display device having excellent display performance can be obtained. On the other hand, in a liquid crystal display device using a color filter manufactured using the thermosetting composition of Comparative Examples 1 to 5 and Comparative Example 6, the pixels flicker significantly, and further, the electrical loss is large, so the electrical signal is large. Failure to communicate smoothly resulted in severe misalignment.

From the above results, it can be seen that the cured film of the present invention is excellent in electrical characteristics, in particular, it has low electrical loss, and therefore there is no disorder of the alignment of the liquid crystal or switching threshold deviation, and it is a very excellent cured film. In addition, the cured films obtained from the thermosetting compositions of Examples 1 to 15 and 16 are also excellent in heat resistance and transparency required for a protective film.

[Industrial Applicability] The cured film obtained from the thermosetting composition according to the preferred embodiment of the present invention is not only excellent in transparency or heat resistance required for a protective film, but also has no effect on a liquid crystal display device. It is a particularly excellent material that adversely affects display quality. Therefore, it can be used as a protective film for various optical materials such as color filters, and a transparent insulating film formed between a TFT and a transparent electrode and between a transparent electrode and an alignment film.

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Claims (17)

A thermosetting composition comprising a polyester sulfamic acid (A) and an epoxy compound (B), wherein the thermosetting composition is characterized in that the polyester fluoramic acid (A) is as follows Ratios where the relationship of formulas (1) and (2) holds: reactants of the raw materials of polyvalent hydroxy compounds containing X mol tetracarboxylic dianhydride, Y mol diamine, and Z mol, 0.2 ≦ Z / Y ≦ 8.0 ····· (1) 0.2 ≦ (Y + Z) /X≦5.0 ··· (2) The content of the epoxy compound (B) relative to the polyester amidine (A ) 100 parts by weight and 20 to 400 parts by weight, and the dielectric loss tangent at 20 Hz of the cured film obtained from the thermosetting composition is 0.007 or less. The thermosetting composition according to item 1 of the scope of patent application, wherein the polyester amidate (A) includes a structural unit represented by the following formula (3) and a structure represented by the following formula (4) unit, In formulas (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and R ² is obtained by removing two -NH ₂ from a diamine. R ³ is a residue formed by removing two -OH groups from a polyhydroxy compound. The thermosetting composition according to claim 1 or claim 2, wherein the raw material of the polyester amidate (A) further contains a monohydroxy compound. The thermosetting composition according to item 3 of the application, wherein the monohydroxy compound is selected from the group consisting of isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3- One or more of ethyl-3-hydroxymethyloxetane. The thermosetting composition according to any one of claims 1 to 4, in which the raw material of the polyester amidate (A) further comprises a styrene-maleic anhydride copolymer. The thermosetting composition according to any one of claims 1 to 5, in which the weight average molecular weight of the polyester amidine (A) is 1,000 to 200,000. The thermosetting composition according to any one of claims 1 to 6, in which the epoxy compound (B) contains 0.1 to 60 parts by mass of epoxy based on 100 parts by mass of the epoxy compound (B). Hardener (C). The thermosetting composition according to item 7 of the scope of patent application, wherein the epoxy hardener (C) contains a material selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, 2-undecylimidazole, and a phenolic hardener (H ) At least one compound in the group. The thermosetting composition according to item 8 of the scope of patent application, wherein the phenolic hardener (H) is selected from the group consisting of α, α, α'-tris (4-hydroxyphenyl) -1-ethyl- 4-Isopropylbenzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis [2 -(4-hydroxyphenyl) -2-propyl] benzene, 4,4 '-(3,3,5-trimethyl-1,1-cyclohexanediyl) bis (phenol), and 1, At least one of the group consisting of 1,2,2-tetrakis (4-hydroxyphenyl) ethane. The thermosetting composition according to any one of claims 1 to 9 of the scope of patent application, further comprising a solvent (D). The thermosetting composition according to claim 10, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butane At least one compound in the group consisting of tetracarboxylic dianhydride and ethylene glycol bis (anhydrotrimellitate); the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium, At least one compound from the group consisting of bis [4- (3-aminophenoxy) phenyl] fluorene; the polyhydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, and 1,4-butanediol , 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and tris (2-hydroxyethyl) isocyanurate At least one compound in the group; the epoxy compound (B) is selected from the group consisting of 3,4-epoxycyclohexanecarboxylic acid-3 ', 4'-epoxycyclohexylmethyl ester, 1-methyl- 4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane, 2- [4- (2,3-glycidoxy) phenyl] -2- [ 4- [1,1-bis [4-([2,3-glycidoxy] phenyl)] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-glycidoxy) phenyl] -1- [4- [1- [4- (2,3-glycidoxy) phenyl] -1-methyl Methylethyl] phenyl] ethyl] phenoxy] -2-propanol mixture, 2- [4- (2,3-glycidoxy) phenyl] -2- [4- [1, 1-bis [4-([2,3-glycidoxy] phenyl)] ethyl] phenyl] propane, 1,1,1-tris (4-hydroxyphenyl) ethane triglycidyl ether 1,3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, and by passing 3-glycidyloxy At least one compound selected from the group consisting of copolymers having a weight average molecular weight of 1,000 to 200,000 obtained by reacting propyltrimethoxysilane as a raw material component; the epoxy hardener (C) is selected from the group consisting of trimellitic anhydride, Hexahydrotrimellitic anhydride, 2-undecylimidazole, α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,1,1-tris (4- Hydroxyphenyl) ethane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 4 , 4 '-(3,3,5-trimethyl-1,1-cyclohexanediyl) bis (phenol), and 1 At least one compound in the group consisting of 1,1,2,2-tetra (4-hydroxyphenyl) ethane; the solvent (D) contains a compound selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl At least one of the group consisting of ether acetate. The cured film obtained by hardening | curing the thermosetting composition as described in any one of Claims 1-11. A color filter has a cured film as described in item 12 of the patent application scope as a transparent protective film. A liquid crystal display element includes the color filter according to item 13 of the scope of patent application. A liquid crystal display element has a cured film as described in item 12 of the scope of patent application as a transparent insulating film formed between a thin film transistor and a transparent electrode. A liquid crystal display element has the cured film according to item 12 of the patent application scope as a transparent insulating film formed between a transparent electrode and an alignment film. A touch panel device has a cured film as described in item 12 of the scope of patent application as a transparent insulating film formed on a transparent electrode.