JP2018016786A - Thermosetting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured film having excellent transparency and heat resistance required for a protective film, and further having no threshold shift in switching caused by specific electric characteristics in a liquid crystal display device, that is, giving no adverse influences on display quality, and a composition that gives the cured film.SOLUTION: A thermosetting composition and a cured film obtained from the composition are provided, and the composition comprises a polyester amide acid and an epoxy compound. The polyester amide acid is a reaction product of raw materials comprising a tetracarboxylic acid dianhydride, diamine and polyvalent hydroxy compound. A cured film obtained from the above composition shows a dielectric loss tangent of 0.007 or less at 20 Hz.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting composition used for a liquid crystal display element, a cured film formed from the thermosetting composition, a color filter, an insulating film, or a protective film using the cured film, and the The present invention relates to an electronic component having a film. More specifically, a thermosetting composition containing a polyester amide acid having an excellent dielectric loss tangent, a cured film that does not adversely affect the switching performance of liquid crystal formed from the thermosetting composition, and the cured film The present invention relates to a used color filter, an insulating film, or a protective 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 process of the liquid crystal display element, chemical treatment or high temperature heat treatment is usually applied to the surface of the element. Therefore, a protective film is provided to prevent the surface of the element from being deteriorated, damaged, or altered. The protective film is required to have heat resistance, chemical resistance, adhesion to the substrate, transparency, and flatness.

  On the other hand, in recent years, there is a high demand for high image quality in liquid crystal display elements, and there are various new types of liquid crystal display elements having a high viewing angle and high-speed response. Among these, the horizontal electric field method (In Plane Switching = IPS method, Fringe Field Switching = FFS method) is widely used mainly in mobile communication devices because of excellent display quality such as viewing angle and contrast ratio.

  However, the liquid crystal used in the horizontal electric field type, particularly the FFS type liquid crystal display device, has excellent characteristics such as being able to be driven at a low voltage, but it has performance depending on the electrical characteristics of the members inherent in the liquid crystal display device. Has a problem of being easily lowered. In fact, various display defects such as switching threshold shift due to the electrical characteristics of the color filter and the alignment film and the elution of components from them occur. For these problems, studies focusing on color filters and alignment films have been performed, but studies focusing on protective films have not been performed.

  In a semiconductor device such as a TFT, a protective film is usually formed on the uppermost wiring for the purpose of wiring protection. By forming the protective film, the quality of the semiconductor device can be improved and the characteristics can be stabilized, and the semiconductor device is hardly affected by the outside world. Highly heat-resistant resin polyimide, which is one of protective film materials, has been extensively studied for use in protective films and insulating films of semiconductor devices, and some of them have been put into practical use. In the development of these polyimides, although several attempts have already been made to lower the dielectric constant, polyimide that satisfies the characteristics of low dielectric constant and low dielectric loss tangent and can be put to practical use, as well as transparency and heat resistance No polyimide has been developed to provide an excellent protective film.

JP 2006-208580 A JP 2006-243594 A

  The object of the present invention is excellent in various properties such as transparency and heat resistance required for a protective film, and further, there is no switching threshold deviation due to unique electrical characteristics in a liquid crystal display device, that is, it adversely affects display quality. It is providing the cured film which does not give, and the composition which gives this cured film.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polyester amide acid, which is a reaction product of a raw material containing a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound, an epoxy compound, and optionally an epoxy It is a thermosetting composition containing a curing agent or a solvent, and the cured film obtained by curing the composition has a low dielectric loss tangent, and further, the cured film is excellent in transparency and heat resistance. As a result, the present invention has been completed. The present invention includes the following configurations.

[1] A thermosetting composition comprising a polyester amide acid (A) and an epoxy compound (B),
In the polyester amic acid (A), X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compounds are such that the relationship of the following formulas (1) and (2) is established. It is a reaction product of raw materials included in a ratio,
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
The content of the epoxy compound (B) is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amic acid (A),
A thermosetting composition, wherein the cured film obtained from the composition has a dielectric loss tangent at 20 Hz of 0.007 or less.

[2] The thermosetting composition according to [1], wherein the polyester amide acid (A) includes a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). .
In Formula (3) and Formula (4), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two —NH ₂ from diamine. R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound.

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

[4] The above monohydroxy compound is one or more selected from isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. 3].

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

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

[7] The thermosetting according to any one of [1] to [6], including 0.1 to 60 parts by weight of the epoxy curing agent (C) with respect to 100 parts by weight of the epoxy compound (B). Sex composition.

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

[9] The phenol-based curing agent (H) is 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 In the above [8], which is at least one selected from the group consisting of 5-trimethyl-1,1-cyclohexanediyl) bis (phenol) and 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane The thermosetting composition as described.

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

[11] The tetracarboxylic dianhydride includes 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2 , 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate) At least one compound selected from the group consisting of:
The diamine is at least one compound selected from the group consisting of 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone,
The polyvalent hydroxy compound includes ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and isocyanuric At least one compound selected from the group consisting of acid tris (2-hydroxyethyl),
The epoxy compound (B) is 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1. .0] heptane, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl ] Propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl]- 1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- ( [2,3-D Xylpropoxy] phenyl)] ethyl] phenyl] propane, 1,1,1-tris (4-hydroxyphenyl) ethanetriglycidyl 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) of 2,2-bis (hydroxymethyl) -1-butanol At least one compound selected from the group consisting of a cyclohexane adduct and a copolymer having a weight average molecular weight of 1,000 to 200,000 obtained by reacting 3-glycidoxypropyltrimethoxysilane as a raw material component And
The epoxy curing agent (C) is 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 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane At least one compound selected from the group consisting of:
The solvent (D) contains at least one selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate.
The thermosetting composition as described in [10] above.

[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 device having the color filter according to [13].

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

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

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

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

1. Thermosetting composition The thermosetting composition of the present invention is a polyester amic acid (A), an epoxy compound (B), which is a reaction product of a raw material containing tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound, and A composition containing an epoxy curing agent (C) or a solvent (D) depending on the case, and a dielectric loss tangent at 20 Hz of a cured film obtained from the composition is 0.007 or less. The thermosetting composition of the present invention may further contain other components other than those described above as long as the effects of the present invention are obtained.

1-1. Polyester amide acid (A)
In the polyester amic acid (A), X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compounds are such that the relationship of the following formulas (1) and (2) is established. It is a reaction product of the raw material included in a ratio.
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)

The polyester amic acid (A) preferably has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4).
In Formula (3) and Formula (4), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, preferably an organic group having 2 to 30 carbon atoms. . R ² is a residue obtained by removing two —NH ₂ from a diamine, and is preferably an organic group having 2 to 30 carbon atoms. R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound, and is preferably an organic group having 2 to 20 carbon atoms.

  The synthesis of the polyester amic acid (A) requires at least a solvent. The solvent may be left as it is, and a liquid or gel thermosetting composition considering handling properties may be used, or the solvent may be removed. Thus, a solid composition may be used in consideration of transportability. In addition, the synthesis of the polyester amic acid (A) may include one or more compounds selected from a monohydroxy compound and a styrene-maleic anhydride copolymer as a raw material, if necessary. In particular, it preferably contains a monohydroxy compound. Moreover, the synthesis | combination of the said polyester amide acid (A) may contain other compounds other than the above as a raw material in the range which does not impair the objective of this invention as a raw material.

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

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

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

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

1-1-3. In the present invention, a polyvalent hydroxy compound is used as a material for obtaining the polyester amic acid (A). Specific examples of preferable polyvalent hydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, weight Polypropylene glycol having an average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentane Diol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1, 7 Heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 1,2-nonanediol, 1 , 9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecane Diol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, isocyanuric acid tris (2-hydroxyethyl), bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxy Phenyl) sulfone), bisphenol F (bis (4-hydro) Ciphenyl) methane), 4,4′-isopropylidenebis (2-phenoxyethanol), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4′-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl Alcohol, 2- (4-hydroxyphenyl) ethanol, diethanolamine, triethanolamine, glycerol monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, dipentaerythritol monoallyl ether, dipenta Erythritol diallyl ether, dipentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, sorbitol monoallyl Ether, sorbitol diallyl ether, sorbitol triallyl ether, sorbitol tetraallyl ether, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipenta Erythritol mono (meth) acrylate, dipentaerythritol di (meth) 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 diglycidyl ether ( T) Acrylic acid modified product, (meth) acrylic acid modified product of propylene glycol diglycidyl ether, (meth) acrylic acid modified product of tripropylene glycol diglycidyl ether, (meth) acrylic acid modified product of glycerin diglycidyl ether, bisphenol (Meth) acrylic acid modified product of A diglycidyl ether, (meth) acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether, (meth) acrylic acid modified product of bisphenol S diglycidyl ether, propylene oxide modified bisphenol S di (Meth) acrylic acid modification of glycidyl ether, (meth) acrylic acid modification of bisphenol F diglycidyl ether, (meth) acrylic acid modification of propylene oxide modified bisphenol F diglycidyl ether , (Meth) acrylic acid modified product of bixylenol diglycidyl ether, (meth) acrylic acid modified product of biphenol diglycidyl ether, (meth) acrylic acid modified product of full orange phenol diglycidyl ether, cyclohexane-1,4- (Meth) acrylic acid modification of dimethanol diglycidyl ether, (meth) acrylic acid modification of hydrogenated bisphenol A diglycidyl ether, (meth) acrylic acid modification of tricyclodecane dimethanol diglycidyl ether, and epoxy group (Meth) acrylic acid modified products of other compounds containing 2 or more per molecule. One or more of these can be used.

  Among these, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- Heptanediol, 1,8-octanediol, tris (2-hydroxyethyl) isocyanurate, 2,2-bis (4-hydroxycyclohexyl) propane, 4,4′-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxy Benzyl alcohol, 2- (4-hydroxyphenyl) ethanol, 4,4′-isopropylidenebis (2-phenoxyethanol), (meth) acrylic acid modified product of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ester (Meth) acrylic acid modification of Tell (meth) acrylic acid, (meth) acrylic acid modification of glycerin diglycidyl ether, (meth) acrylic acid modification of bisphenol A diglycidyl ether, (meth) acrylic of propylene oxide modified bisphenol A diglycidyl ether Acid-modified products, (meth) acrylic acid-modified products of bisphenol S diglycidyl ether, (meth) acrylic acid-modified products of propylene oxide-modified bisphenol S diglycidyl ether, (meth) acrylic acid-modified products of bisphenol F diglycidyl ether, and A (meth) acrylic acid modified product of propylene oxide modified bisphenol F diglycidyl ether is preferred. Further, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 4,4′-isopropylidenebis ( 2-phenoxyethanol), 2- (4-hydroxyphenyl) ethanol, (meth) acrylic acid modification of ethylene glycol diglycidyl ether, (meth) acrylic acid modification of propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether (Meth) acrylic acid modified product, (meth) acrylic acid modified product of glycerin diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, and propylene oxide modified bisphenol Of A diglycidyl ether (meth) acrylic acid modified product it is more preferable.

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

  Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane is more preferable. In consideration of the compatibility when the polyester amic acid (A), an epoxy compound, and an epoxy curing agent, which are formed by using these, are mixed, and the applicability of the thermosetting composition on a color filter, monohydroxy The use of benzyl alcohol is particularly preferred for the compound.

  The monohydroxy compound is preferably reacted in an amount of 0 to 300 parts by weight with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound. More preferably, it is 5-200 weight part.

1-1-5. Styrene-maleic anhydride copolymer The polyester amic acid (A) used in the present invention may be synthesized by adding a compound having 3 or more acid anhydride groups to the above raw material. Polyester amide acid (A) synthesized by adding a compound having 3 or more acid anhydride groups is preferable because improvement in transparency is expected. Examples of the compound having 3 or more acid anhydride groups include a styrene-maleic anhydride copolymer. About the ratio of each component which comprises a styrene-maleic anhydride copolymer, the molar ratio of styrene / maleic anhydride is 0.5-4, Preferably it is 1-3. Furthermore, 1 or 2 is more preferable, and 1 is particularly preferable.

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

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

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

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

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

  The aminosilane compound having one amino group is preferably contained in an amount of 0 to 300 parts by weight with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound. More preferably, it is 5-200 weight part.

1-1-7. Solvents used in the synthesis reaction of the polyester amic acid (A) Specific examples of the solvent used in the synthesis reaction for obtaining the polyester amic acid (A) include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and 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 Can be mentioned. Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ethyl ether is preferable.

1-1-8. Method for synthesizing polyester amic acid (A) The polyester amic acid (A) used in the present invention is prepared by reacting X mol of tetracarboxylic dianhydride, Y mol of diamine, and Z mol of polyvalent hydroxy compound in the above solvent. In this case, it is preferable that X, Y, and Z are determined in such a ratio that the relationship of the following formulas (1) and (2) is established between them. If it is this range, the solubility to the solvent of the said polyester amide acid (A) is high, Therefore The applicability | paintability of a composition improves, As a result, the cured film excellent in flatness can be obtained.
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
Formula (1) is preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.0 ≦ Z / Y ≦ 5.0. In the formula (2), 0.5 ≦ (Y + Z) /X≦4.0 is preferable, and 0.6 ≦ (Y + Z) /X≦2.0 is more preferable.

  The polyester amic acid (A) used in the present invention has an acid anhydride group (—CO—O—CO—) at the terminal under the above reaction conditions under the condition that X is excessively used relative to (Y + Z). It is considered that a molecule having an excess is generated more than a molecule having an amino group or a hydroxyl group at the terminal. In the case of reacting in such a monomer structure, the monohydroxy compound described above can be added, if necessary, in order to react with the acid anhydride group at the molecular terminal to esterify the terminal. The polyester amide acid (A) obtained by adding and reacting a monohydroxy compound has improved compatibility with an epoxy compound and an epoxy curing agent, and includes the thermosetting composition of the present invention containing them. The applicability of is improved.

  The reaction solvent is preferably used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound, since the reaction proceeds smoothly. The reaction is preferably carried out at 40 to 200 ° C. for 0.2 to 20 hours.

  The order of adding the reaction raw materials to the reaction system is not particularly limited. That is, a method of simultaneously adding a tetracarboxylic dianhydride and a diamine and a polyvalent hydroxy compound to the reaction solvent, a method of adding the tetracarboxylic dianhydride after dissolving the diamine and the polyvalent hydroxy compound in the reaction solvent, After reacting tetracarboxylic dianhydride and polyvalent hydroxy compound in advance, diamine is added to the reaction product, or after reacting tetracarboxylic dianhydride and diamine in advance, Any method such as a method of adding a polyvalent hydroxy compound can be used.

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

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

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

  The weight average molecular weight in the present specification is a value in terms of polystyrene determined by GPC method (column temperature: 35 ° C., flow rate: 1 ml / min). Standard polystyrene is polystyrene having a molecular weight of 645 to 132900 (for example, polystyrene calibration kit PL2010-0102 of Agilent Technologies, Inc.), and PLgel MIXED-D (Agilent Technology, Inc.) is used as the column, and as a mobile phase. It can be measured using THF. In addition, the weight average molecular weight of the commercial item in this specification is a catalog publication value.

1-2. Epoxy compound (B)
By adding the epoxy compound (B) to the thermosetting composition of the present invention, the heat resistance and solvent resistance of the 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 preferably an epoxy compound having no siloxane bond site is used. It is done.

1-2-1. Epoxy compound having no siloxane bond site The epoxy compound having no siloxane bond site used in the present invention is particularly limited as long as it has good compatibility with other components forming the thermosetting composition of the present invention. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin , An aliphatic polyglycidyl ether compound, or a cyclic aliphatic epoxy resin, a polymer of a monomer having an epoxy group, a copolymer of a monomer having an epoxy group and another monomer, and the like.

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

  As for the epoxy compound which does not have a siloxane bond part, it is preferable that the ratio in an epoxy compound (B) is 50 to 100 weight%, and it is more preferable that it is 80 to 100 weight%. If it exists in these ranges, flatness, heat resistance, an electrical property, and tackiness will become favorable.

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

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

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

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

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

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

Specific examples of such groups in which any methylene (—CH ₂ —) is replaced with a group containing O, NH or Si are acetoxymethyl, 3-methoxy-3-oxopropyl, 3- (2-methoxyethoxy) Propyl, 2,5,8,11-tetraoxatetradecan-14-yl, 2,5,8,11-tetraoxaheptadecan-17-yl, 11,11-dimethoxyundecyl, 2- (dimethylamino) ethyl 2- (diethylamino) ethyl, tetrahydrofuran-3-yl, tetrahydro-2H-pyran-4-yl, 3-((tetrahydrofuran-3-yl) methoxy) propyl, 10- (1,3-dioxolan-2-yl ) Decyl, 10- (1,3-dioxan-2-yl) decyl, morpholino, 4-methoxy-3,5-dimethylbenzyl, hydride Ximethyl, 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-tetraoxatetrasiloca-2-yl) ethyl, 2- (dimethyl (phenyl) silyl) Ethyl, methoxy, ethoxy, propoxy, isopropoxy, prop-1-en-2-yloxy, butoxy, tert-butoxy, sec-butoxy, isobutoxy, tert-pentyloxy, hexyloxy, 2-ethylbutoxy, (3-methyl Pentyl) oxy, (2-methylhexane-2-yl) oxy, octi Ruoxy, (2-ethylhexyl) oxy, decyloxy, 2-methoxyethoxy, 2-ethoxyethoxy, (1-methoxypropan-2-yl) oxy, 2- (2-methoxyethoxy) ethoxy, 2-butoxyethoxy, 3-ethylhexanoyl) oxy, dodecyloxy, tridecyloxy, hexadecyloxy, octadecyloxy, stearoyloxy, (butan-2-ylideneamino) oxy, (diethylamino) oxy, cyclohexyloxy, cyclooctyloxy, bicyclo [2. 2.1] Heptan-2-ylmethoxy, cyclononyloxy, (2-isopropyl-5-methylcyclohexyl) oxy, ((5-methyl-2- (prop-1-en-2-yl) cyclohexyl) oxy, ( Octahydro-1H-4,7-me Noinden-5-yl) oxy, phenoxy, p-tolyloxy, m-tolyloxy, o-tolyloxy, o-carboxyphenoxy, benzyloxy, phenoxy, 3-phenylpropoxy, cinnamyloxy, 1-phenyl- (2-ethoxy-) 2-oxo) ethoxy, (2-methyl-1-oxo-1-phenylpropan-2-yl) oxy, 2-ethoxy-2-oxo-1- (o-tolyl) ethoxy, 2-ethoxy-1- ( 2-methoxyphenyl) -2-oxoethoxy, (4-ethoxy-4-oxo-1-phenylbut-2-en-1-yl) oxy, (1-benzoylcyclohexyl) oxy, and 2-hydroxyethoxy.

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

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

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

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

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

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

Specific examples of such groups in which any methylene (—CH ₂ —) is replaced with a group containing O, NH or Si are acetoxymethyl, 3-methoxy-3-oxopropyl, 3- (2-methoxyethoxy) Propyl, 2,5,8,11-tetraoxatetradecan-14-yl, 2,5,8,11-tetraoxaheptadecan-17-yl, 11,11-dimethoxyundecyl, 2- (dimethylamino) ethyl 2- (diethylamino) ethyl, tetrahydrofuran-3-yl, tetrahydro-2H-pyran-4-yl, 3-((tetrahydrofuran-3-yl) methoxy) propyl, 10- (1,3-dioxolan-2-yl ) Decyl, 10- (1,3-dioxan-2-yl) decyl, morpholino, 4-methoxy-3,5-dimethylbenzyl, hydride Ximethyl, 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-tetraoxatetrasiloca-2-yl) ethyl and 2- (dimethyl (phenyl) silyl ) Ethyl.

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

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

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

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

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

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

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

  When the epoxy compound having a siloxane bond site is used, the proportion in the epoxy compound (B) is 0.5 to 50% by weight, preferably 0.5 to 20% by weight. Within these ranges, the balance of flatness, transparency, heat resistance, electrical characteristics, and tackiness will be good.

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

1-2-3. Specific Example of Epoxy Compound (B) Specific examples of the epoxy compound (B) include 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (for example, trade name: Celoxide 2021P, Daicel Corporation) ), 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane (for example, trade name: Celoxide 3000, Daicel Corporation), 2- [4- (2 , 3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane and 1,3-bis [4- [ 1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl ] Phenyl] ethyl] phenoxy] -2-propanol, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3- Epoxypropoxy) phenyl] ethyl] phenyl] propane (for example, trade name: TECHMORE VG3101L, Printec Co., Ltd.), 1,1,1-tris (4-hydroxyphenyl) ethanetriglycidyl ether (for example, trade name: JER 1032H60) , Mitsubishi Chemical Corporation), 1,3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, And 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (e.g. , Trade name; EHPE3150, Ltd. Daicel), and the like.

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

  Preferred examples of the radical polymerizable compound having no epoxy group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate (for example, trade name: NK ester 2G, Shin-Nakamura Chemical), 1,4- Butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, Inden can be mentioned. These are preferable because the compatibility of the epoxy compound obtained by reacting with glycidyl (meth) acrylate with the polyester amide acid (A) becomes good.

  In addition, for example, a silane compound having an epoxy group, such as a polymer of 3-glycidyloxypropyltrimethoxysilane, which is known as a trade name COATOSIL MP 200 (Momentive Performance Materials Co., Ltd.) is also preferably used. Can do. Since such a compound has an alkoxysilyl group in the molecule, an effect of improving the adhesion between the cured film to be formed and the substrate is expected as an “adhesion improver” described later.

1-3. Ratio of components (A) and (B) The ratio of the total amount of the epoxy compound (B) to 100 parts by weight of the polyester amide acid (A) in the thermosetting composition of the present invention is 20 to 400 parts by weight. When the proportion of the total amount of the epoxy compound (B) is within this range, the balance of flatness, heat resistance, chemical resistance, and adhesion is good. The total amount of the epoxy compound (B) is preferably in the range of 50 to 300 parts by weight.

1-4. Other Components Various additives can be added to the thermosetting composition of the present invention in order to improve coating uniformity and adhesion. Additives include epoxy curing agents, solvents, anionic, cationic, nonionic, fluorine or silicon leveling agents / surfactants, adhesion improvers such as silane coupling agents, hindered phenols, hindered amines. Mainly mentioned are antioxidants such as those based on phosphorus, phosphorus and sulfur.

1-4-1. Epoxy curing agent (C)
In the thermosetting composition of the present invention, the epoxy curing agent (C) may be used in order to improve flatness and chemical resistance. Examples of the epoxy curing agent (C) include an acid anhydride curing agent, an amine curing agent, a phenol curing agent (hereinafter also referred to as “phenol curing agent (H)”), an imidazole curing agent, and catalytic curing. Agents, and heat-sensitive acid generators such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts. From the viewpoint of avoiding coloring of the cured film and the heat resistance of the cured film, acid anhydrides A curing agent or an imidazole curing agent is preferred.

  Specific examples of the acid anhydride curing agent include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrotrimellitic anhydride Aromatic carboxylic anhydrides such as phthalic anhydride and trimellitic anhydride, and styrene-maleic anhydride copolymers. Among these, trimellitic anhydride and hexahydrotrimellitic anhydride having a good balance between heat resistance and solubility in solvents are preferable.

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

  In the epoxy curing agent (C) of the present invention, a phenolic curing agent (H) may be used for the purpose of lowering the dielectric loss tangent in addition to the function of curing the epoxy. Specific examples of the phenolic curing agent (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. Among these, α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,1,1-tris (4-hydroxyphenyl) having a good balance between heat resistance and compatibility ) Ethane and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene are preferred.

  When using the said epoxy hardening | curing agent (C), the ratio of the said epoxy hardening | curing agent (C) with respect to 100 weight part of said epoxy compounds (B) is 0.1-60 weight part. Regarding the addition amount when the epoxy curing agent (C) is an acid anhydride curing agent and a phenol curing agent (H), more specifically, the carboxylic acid anhydride in the epoxy curing agent with respect to the epoxy group. The group, carboxyl group or phenolic hydroxyl group is preferably added in an amount of 0.1 to 1.5 times equivalent. At this time, the carboxylic acid anhydride group is calculated as divalent. If the carboxylic acid anhydride group, carboxyl group or phenolic hydroxyl group is added in an amount of 0.15 to 0.8 times equivalent, the chemical resistance is further improved, which 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) optionally added to the thermosetting composition of the present invention is preferably a solvent capable of dissolving the polyester amide acid (A), the epoxy compound (B), the epoxy curing agent (C) and the like. Specific examples of the solvent (D) include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, acetone, 2-butanone, ethyl acetate, butyl acetate, Propyl acetate, butyl propionate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3 -Ethyl hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, 2-hydroxy Propyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, aceto Ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, Ripropylene 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 Nobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, γ-butyrolactone, or N, N-dimethylacetamide, cyclohexanone, ethylene glycol, diethylene glycol, triethylene glycol Ethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and polypropylene glycol having a weight average molecular weight of 1,000 or less. One of these may be sufficient as a solvent, and these 2 or more types of mixtures may be sufficient as it.

  It is preferable that content of a solvent is 65 to 95 weight% with respect to the thermosetting composition whole quantity. More preferably, it is 70 to 90% by weight.

1-4-3. Surfactant A surfactant may be added to the thermosetting composition of the present invention in order to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (all are trade names: Kyoeisha Chemical Co., Ltd.), Disperbak 161, Dispersake 162, Dispersake 163, Dispersake 164, Dispersake 166, Dispersake 170, Dispersake 180, Dispersake 181 and Dispers Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (all of these are trade names; BIC Chemie Japan KK), KP-341, KP-358, KP- 368, KF-96-50CS, KF-50-100CS (all are trade names; Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon K -40, Surflon S611 (all are trade names; AGC Seimi Chemical Co., Ltd.), Aftergent 222F, Aftergent 208G, Aftergent 251, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, Aftergent 602A , TF 650A, FTX-218 (all are trade names; Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 Name: Mitsubishi Materials Corporation), Megafuck F-171, Megafuck F-177, Megafuck F-410, Megafuck F-430, Megafuck F-444, Megafuck F-4 72SF, Megafuck F-475, Megafuck F-477, Megafuck F-552, Megafuck F-553, Megafuck F-554, Megafuck F-555, Megafuck F-556, Megafuck F-558, Megafuck F-559, Megafuck R-30, Megafuck R-94, Megafuck RS-75, Megafuck RS-72-K, Megafuck RS-76-NS, Megafuck DS-21 Name: DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N Japan Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether) ), Fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene Tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene steer Ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan Examples include laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these.

  Among these surfactants, BYK306, BYK342, BYK346, KP-341, KP-358, KP-368, Surflon S611, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 650A, Megafuck F-477 , Megafuck F-556, Megafuck RS-72-k, TEGO Twin 4000, Fluoroalkylbenzenesulfonate, Fluoroalkylcarboxylate, Fluoroalkylpolyoxyethylene ether, Fluoroalkylsulfonate, Fluoroalkyltrimethylammonium salt, And at least one selected from fluoroalkylaminosulfonates are preferred because the coating uniformity of the thermosetting composition is increased.

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

1-4-4. Adhesion improver The thermosetting composition of the present invention may further contain an adhesion improver from the viewpoint of further improving the adhesion between the formed cured film and the substrate. As such an adhesion improver, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, Silaace S510; trade name: JNC Corporation), 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane (eg, Silaace S530; trade name; JNC Corporation), 3-mercaptopropyltrimethoxysilane (eg, Silaace S810; trade name; JNC Corporation) Agents, aluminum coupling agents such as acetoalkoxyaluminum diisopropylate, and titanate coupling agents such as tetraisopropylbis (dioctyl phosphite) titanate. In addition, although it is COATOSIL MP200 mentioned above as an epoxy compound, it can be used similarly to the said adhesive improvement agent under the classification | category with the silane coupling agent which has an epoxy group.

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

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

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

  You may add antioxidants, such as a hindered phenol type | system | group, a hindered amine type | system | group, a phosphorus type | system | group, and a sulfur type compound, to the thermosetting composition of this invention. Of these, hindered phenols are preferred from the viewpoint of weather resistance. Specific examples, Irganox1010, IrganoxFF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox295 (both product Name: BASF Japan Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, DK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80 (trade names; Ltd ADEKA) and the like. Among these, Irganox 1010 and ADK STAB AO-60 are more preferable.

  The antioxidant is used by adding 0.1 to 5 parts by weight with respect to the total amount of the thermosetting composition.

1-4-6. Other additives When the polyester amic acid (A) does not contain a styrene-maleic anhydride copolymer as a raw material, a styrene-maleic anhydride copolymer may be added as another component.

1-5. Storage of Thermosetting Composition When the thermosetting composition of the present invention is stored in the range of −30 ° C. to 25 ° C., the stability with time of the composition is good, which is preferable. A storage temperature of −20 ° C. to 10 ° C. is more preferable because there is no precipitate.

2. Cured film obtained from thermosetting composition
2-1. Manufacturing method of cured film The thermosetting composition of the present invention is a mixture of the polyester amide acid (A) and the epoxy compound (B). Depending on the intended properties, an epoxy curing agent, a solvent, and a coupling agent , Surfactants, and other additives may be selected as necessary, and mixed and dissolved uniformly.

  When the thermosetting composition prepared as described above (after dissolving in a solvent in the case of a solid state without a solvent) is applied to the surface of the substrate and the solvent is removed, for example, by heating, a cured film is obtained. Can be formed. Conventionally known methods such as spin coating, roll coating, dipping, and slit coating can be used to apply the thermosetting composition to the substrate surface. Next, this coating film is heated (prebaked) with a hot plate or an oven. The heating conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 150 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Then, in order to cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 250 ° C., for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.

  The cured film obtained in this manner was, when heated, 1) the polyamic acid part of the polyester amic acid (A) was dehydrated to form an imide bond, and 2) the carboxylic acid of the polyester amic acid (A). Reacts with the epoxy compound (B) to increase the molecular weight. 3) Since the epoxy compound (B) is cured to increase the molecular weight, it is very tough and has transparency, heat resistance, chemical resistance, and flatness. Excellent in adhesion, adhesion, light resistance, and sputtering resistance. Therefore, the cured film is a protective film formed on an upper layer of a semiconductor layer, an electrode, a wiring, etc. in a semiconductor device, a liquid crystal display element or a circuit material, for example, a protective film for a color filter, a passivation film, an α-ray blocking film It is effective when used as a buffer coat film.

2-2. Cured film dielectric tangent The cured film obtained from the thermosetting composition of the present invention has an excellent dielectric loss tangent, for example, 0.007 or less, preferably 0.006 or less, more preferably 0.005 or less. . When a cured film having a dielectric loss tangent at 20 Hz of 0.007 or less is used as a transparent protective film, for example, in a color filter, a switching threshold shift due to a specific electrical characteristic in a liquid crystal display device does not occur. It is particularly excellent in that it does not have an adverse effect.

  Further, the cured film of the present invention includes 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, in addition to the protective film for the color filter, Or it is effective even if it uses as a transparent insulating film formed on a transparent electrode.

  As a specific example, a glass substrate on which a TFT, a transparent electrode (pixel electrode) and an alignment film are 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, and between them. In a TFT liquid crystal display device manufactured by sandwiching a liquid crystal composition, further attaching a polarizing plate to the outside of both glass substrates, and arranging a backlight light source on the back surface, the cured film of the present invention is on a color filter. Used as protective film, transparent insulating film formed between TFT and transparent electrode, transparent insulating film formed between transparent electrode and alignment film, and transparent insulating film formed on transparent electrode can do.

  The color filter is prepared by forming filter segments of each color on the substrate using a red, green, and blue coloring composition by a known inkjet method, printing method, photoresist method, etching method, or the like. Can do. Among them, in consideration of high definition, controllability and reproducibility of spectral characteristics, each color coloring composition in which a pigment is dispersed in a composition containing a transparent resin, a precursor monomer, and a photopolymerization initiator. A photoresist method is preferred in which a color filter is prepared by applying a colored resist material on a substrate and then repeating pattern exposure and development to form a color filter segment for each color.

  Next, although a synthesis example, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples.

  First, solutions of polyester amide acids (A1) to (A4) and (A5) comprising reaction products of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound were synthesized as shown below.

[Synthesis Example A-1] Preparation of Polyesteramide Acid (A1) Solution In a four-necked flask equipped with a stirrer, dehydrated and purified methyl 3-methoxypropionate (hereinafter abbreviated as “MMP”), 3, 3 ′, 4 , 4′-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as “ODPA”), 1,4-butanediol, and benzyl alcohol were charged in the following weights and stirred at 125 ° C. for 2 hours under a dry nitrogen stream ( First stage of synthesis).
MMP 49.00g
ODPA 20.36g
1,4-butanediol 3.55 g
Benzyl alcohol 2.84g

Thereafter, the reaction solution was cooled to 25 ° C., 3,3′-diaminodiphenylsulfone (hereinafter abbreviated as “DDS”) and MMP were added in the following weights, and stirred at 20 to 30 ° C. for 2 hours. The mixture was stirred at 125 ° C. for 1 hour (synthesis stage 2).
DDS 3.26g
MMP 21.00g

  The solution was cooled to room temperature to obtain a 30% by weight solution of pale yellow transparent polyester amide 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 Polyesteramide Acid (A2) Solution In a four-necked flask equipped with a stirrer, dehydrated purified propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMEA”), 1, 2, 3, 4 -Butanetetracarboxylic dianhydride (hereinafter abbreviated as "BT-100"), SMA-1000P (trade name; styrene / maleic anhydride copolymer, Kawa Crude Oil Co., Ltd.), 1,4-butanediol, And benzyl alcohol in the order of the following weights, and stirred at 125 ° C. for 2 hours under a dry nitrogen stream (first stage of synthesis).
PGMEA 53.49g
BT-100 3.83g
SMA-1000P 18.23g
1,4-butanediol 1.16 g
Benzyl alcohol 5.57g

Thereafter, the reaction solution was cooled to 25 ° C., DDS and PGMEA were added in the following weights, stirred at 20-30 ° C. for 2 hours, and then stirred at 125 ° C. for 1 hour (2nd stage of synthesis).
DDS 1.20g
PGMEA 16.51g

  The solution was cooled to room temperature to obtain a 30% by weight solution of a pale yellow transparent polyester amide acid (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 Examples A-3 and 4] Preparation of Polyesteramide Acid (A3) or (A4) Solution According to the method of Synthesis Example A-2, the temperatures, times, and ratios shown in Table 1 (unit: g) Each component was reacted to obtain a solution of polyester amide acid (A3) or (A4). Further, the weight average molecular weight of the obtained polymer was measured in the same manner. In Table 1, “Bis-A-2EOH” represents 4,4′-isopropylidenebis (2-phenoxyethanol).

[Synthesis Example A-5] Preparation of polyester amic acid (A5) solution A four-necked flask equipped with a stirrer was charged with dehydrated and purified MMP, ODPA, 1,4-butanediol, and benzyl alcohol at the following weights and dried. The mixture was stirred at 130 ° C. for 3 hours under a nitrogen stream (first synthesis step).
MMP 446.96g
ODPA 183.20g
31.93 g of 1,4-butanediol
Benzyl alcohol 25.54g

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

  The solution was cooled to room temperature to obtain a 30% by weight solution of pale yellow transparent polyester amide 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.

  Next, a solution of epoxy group-containing polymers (B1) to (B4) and (B5) comprising a reaction product of a radically polymerizable compound having an epoxy group and a radically polymerizable compound having no epoxy group is shown below. Synthesized as shown.

[Synthesis Example B-1] Preparation of Epoxy Group-Containing Polymer (B1) Solution In a four-necked flask with a stirrer, PGMEA dehydrated and purified as a polymerization solvent, glycidyl methacrylate (hereinafter referred to as a radical polymerizable compound having an epoxy group) Abbreviated as “GMA”), and V-601 (trade name; dimethyl-2,2′-azobis (2-methylpropionate), Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were charged at the following weights: The mixture was stirred at 110 ° C. for 2 hours under a dry nitrogen stream.
PGMEA 31.50g
GMA 13.50g
V-601 1.35g

  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 with a stirrer, MMP, GMA dehydrated and purified as a polymerization solvent, 2G as a radical polymerizable compound having no epoxy group (Diethylene glycol dimethacrylate (trade name; NK ester 2G), Shin-Nakamura Chemical Co., Ltd.) and V-601 as a polymerization initiator were charged in the following weights and stirred at 110 ° C. for 2 hours under a dry nitrogen stream.
MMP 31.50g
GMA 12.15g
2G 1.35g
V-601 2.03g

  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 4] Preparation of Solution of Epoxy Group-Containing Polymer (B3) or (B4) According to the method of Synthesis Example B-2, the temperature, time, and ratio shown in Table 2 (unit: Each component was reacted in g) to obtain an epoxy group-containing polymer (B3) or (B4). Further, the weight average molecular weight of the obtained epoxy group-containing polymer was measured in the same manner. In Table 2, “NPM” represents N-phenylmaleimide, and “CHMI” represents N-cyclohexylmaleimide.

[Synthesis Example B-5] Preparation of Epoxy Group-Containing Polymer (B5) Solution In a four-necked flask equipped with a stirrer, PGMEA as a polymerization solvent, GMA as a radical polymerizable compound having an epoxy group, and other polymerizable compounds , Dicyclopentenyloxyethyl methacrylate (hereinafter abbreviated as “CMA”), methacrylic acid (hereinafter abbreviated as “MA”), and V-601 as a polymerization initiator were charged in the following composition at 80 ° C. for 3 hours. After heating, it was heated at 90 ° C. for 1 hour.
GMA 103.20g
CMA 12.00g
MA 4.80g
V-601 18.00g
PGMEA 280.00g

  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.

[Example 1]
Next, a thermosetting composition was prepared using the solution of the polyester amide acid (A1) obtained in Synthesis Example A-1, a commercially available epoxy compound, and an epoxy curing agent as shown below. Moreover, the cured film was obtained from the said thermosetting composition and this cured film was evaluated. These details are summarized in Table 3A.

  A 500 ml separable flask equipped with a stirring blade was purged with nitrogen, and 100.00 g of polyester amic acid (A1) and TECHMORE VG3101L (trade name; Printec Co., Ltd.) 58.50 g as an epoxy compound (B5) were added to the flask. Trimellitic anhydride (hereinafter abbreviated as “TMA”) 6.00 g as an epoxy curing agent, ADK STAB AO-60 (trade name; manufactured by ADEKA Corporation, hereinafter abbreviated as “AO-60”) as an additive 0.57.4 g, 367.4 g of dehydrated and purified MMP as a solvent, and 109.3 g of diethylene glycol methyl ethyl ether (hereinafter abbreviated as “EDM”) were charged, and stirred at room temperature for 3 hours to dissolve uniformly. Next, 0.2 g of MegaFuck F-556 (trade name; manufactured by DIC Corporation) was added, stirred for 1 hour at room temperature, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a coating solution.

[Evaluation of cured film electrical characteristics (dielectric loss tangent)]
The coating solution was spin-coated for 10 seconds on a chromium-deposited glass substrate for electrodes, 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 in an oven at 230 ° C. for 30 minutes to obtain a cured film having a thickness of 1.5 μm. On the obtained cured film, aluminum for electrodes was vapor-deposited to prepare a sample in which the cured film was sandwiched between a chromium electrode and an aluminum electrode. The dielectric loss tangent at 20 Hz of the obtained sample was measured using an LCR meter (trade name; E4980A, Agilent Technologies).

[Evaluation of transparency and heat resistance of 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 thickness of 1.0 μm. The cured film thus obtained was evaluated for transparency and heat resistance.

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

[Evaluation method of heat resistance]
After the obtained glass substrate with a cured film was reheated at 230 ° C. for 1 hour, the film thickness before heating and the film thickness after heating were measured, and the remaining film ratio was calculated by the following formula. For the measurement of the film thickness, the step, surface roughness, and fine shape measuring apparatus (trade name: P-15, KLA TENCOR Co., Ltd.) was used. The case where the residual film ratio after heating was 96% or more was rated as “◯”, and the case where the residual film ratio after heating was less than 95% was evaluated as “poor”.

[Examples 2 to 15 and 16]
According to the method of Example 1, each component was uniformly mixed and dissolved at the ratio (unit: g) shown in Tables 3A and 3B to obtain a thermosetting composition. Moreover, about the obtained thermosetting composition, preparation of the cured film and evaluation of each characteristic were performed similarly. These details are summarized in Tables 3A and 3B.

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

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

[Acid anhydride epoxy curing agent]
TMA: trimellitic anhydride

[Epoxy curing agent having phenolic hydroxyl group (phenolic curing agent)]
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 Corporation)
AO-60: ADK STAB AO-60 (trade name; Adeka Corporation)
F-556: Megafuck F-556 (trade name; DIC Corporation)
F-559: Megafuck F-559 (trade name; DIC Corporation)

[solvent]
MMP: methyl 3-methoxypropionate EDM: diethylene glycol ethyl methyl ether PGMEA: propylene glycol monomethyl ether acetate
PEG: Polyethylene glycol PPG: Polypropylene glycol

[Comparative Examples 1 to 5 and 6]
According to the method of Example 1, each component was uniformly mixed and dissolved in the proportions (unit: g) shown in Table 4 to obtain a thermosetting composition. Moreover, about the obtained thermosetting composition, preparation of the cured film and evaluation of each characteristic were performed similarly. These details are summarized in Table 4.

  When the obtained cured film was used as a protective film on the color filter to produce a horizontal electric field type liquid crystal display device, the color filter produced using the thermosetting compositions of Examples 1 to 15 and 16 was obtained. In the liquid crystal display device used, since the dielectric loss tangent of the protective film (cured film) is low, there is little electric loss, the rising and falling shapes of the rectangular wave of the liquid crystal driving signal are smoothed, and the threshold deviation of the driving voltage is generated. As a result, a lateral electric field type liquid crystal display device excellent in display performance was obtained. On the other hand, in the liquid crystal display device using the color filter produced using the thermosetting compositions of Comparative Examples 1 to 5 and 6, since the pixel flicker is conspicuous and the electric loss is large, Since the signal could not be transmitted well, severe alignment failure was observed.

  As can be seen from the above results, the cured film of the present invention is an excellent cured film having excellent electrical characteristics and particularly low electrical loss, and is therefore free from liquid crystal alignment disorder and switching threshold deviation. In addition, the cured films obtained from the thermosetting compositions of Examples 1 to 15 and 16 were excellent in heat resistance and transparency required for the protective film.

  The cured film obtained from the thermosetting composition according to a preferred embodiment of the present invention is not only excellent in transparency and heat resistance required for a protective film, but also particularly excellent in that it does not adversely affect display quality in a liquid crystal display device. Since it is a material, it can be used as a protective film of various optical materials such as a color filter, and a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (17)

A thermosetting composition comprising a polyester amic acid (A) and an epoxy compound (B),
In the polyester amic acid (A), X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compounds are such that the relationship of the following formulas (1) and (2) is established. It is a reaction product of raw materials included in a ratio,
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
The content of the epoxy compound (B) is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amic acid (A),
A thermosetting composition, wherein the cured film obtained from the composition has a dielectric loss tangent at 20 Hz of 0.007 or less. The thermosetting composition according to claim 1, wherein the polyester amic acid (A) includes a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).
In Formula (3) and Formula (4), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two —NH ₂ from diamine. R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound.   The thermosetting composition according to claim 1 or 2, wherein the raw material of the polyester amic acid (A) further contains a monohydroxy compound.   The monohydroxy compound is one or more selected from isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. Thermosetting composition.   The thermosetting composition according to any one of claims 1 to 4, wherein the raw material of the polyester amic acid (A) further contains a styrene-maleic anhydride copolymer.   The thermosetting composition according to any one of claims 1 to 5, wherein the polyester amic acid (A) has a weight average molecular weight of 1,000 to 200,000.   The thermosetting composition according to any one of claims 1 to 6, comprising 0.1 to 60 parts by weight of an epoxy curing agent (C) with respect to 100 parts by weight of the epoxy compound (B).   The epoxy curing agent (C) contains at least one compound selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, 2-undecylimidazole, and phenolic curing agent (H). The thermosetting composition according to claim 7.   The phenolic curing agent (H) is 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) The thermosetting according to claim 8, which is at least one selected from the group consisting of -1,1-cyclohexanediyl) bis (phenol) and 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane. Sex composition.   The thermosetting composition according to any one of claims 1 to 9, comprising a solvent (D). The tetracarboxylic dianhydride includes 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [Bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate) At least one compound selected,
The diamine is at least one compound selected from the group consisting of 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone,
The polyvalent hydroxy compound includes ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and isocyanuric At least one compound selected from the group consisting of acid tris (2-hydroxyethyl),
The epoxy compound (B) is 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1. .0] heptane, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl ] Propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl]- 1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- ( [2,3-D Xylpropoxy] phenyl)] ethyl] phenyl] propane, 1,1,1-tris (4-hydroxyphenyl) ethanetriglycidyl 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) of 2,2-bis (hydroxymethyl) -1-butanol At least one compound selected from the group consisting of a cyclohexane adduct and a copolymer having a weight average molecular weight of 1,000 to 200,000 obtained by reacting 3-glycidoxypropyltrimethoxysilane as a raw material component And
The epoxy curing agent (C) is 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 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane At least one compound selected from the group consisting of:
The solvent (D) contains at least one selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate.
The thermosetting composition according to claim 10.   The cured film obtained by hardening the thermosetting composition of any one of Claims 1-11.   A color filter comprising the cured film according to claim 12 as a transparent protective film.   A liquid crystal display device comprising the color filter according to claim 13.   The liquid crystal display element which has a cured film of Claim 12 as a transparent insulating film formed between TFT and a transparent electrode.   A liquid crystal display element having the cured film according to claim 12 as a transparent insulating film formed between the transparent electrode and the alignment film.   A touch panel device having the cured film according to claim 12 as a transparent insulating film formed on the transparent electrode.