JP2019147858A - Thermosetting composition - Google Patents

Abstract

To provide a thermosetting composition providing a cured film achieving various properties of heat resistance, transparency, flatness and substrate adhesiveness at high level, a cured film formed by the thermosetting composition, and an electronic component having the cured layer.SOLUTION: There is provided a thermosetting composition containing a modified polymer (A) by thermally opening an acid anhydride part derived from a monomer (a) of a copolymer which is a reaction product from a monomer (a) represented by the following formula (1) and a monomer (b) other than (a) by a compound having 2 or more hydroxyl groups, a compound having 2 or more epoxy (B) and a solvent (C). In the formula (1), Rand Rare independently hydrogen, alkyl having 1 to 3 carbon atoms, and phenyl.SELECTED DRAWING: None

Description

  The present invention can be used for forming an insulating material in an electronic component, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a planarizing film, an interlayer insulating film in a liquid crystal display element, a protective film for a color filter, and the like. The present invention relates to a curable composition, a transparent film thereby, and an electronic component having the film.

  The manufacturing process of an element such as a liquid crystal display element includes a process of forming an organic thin film having various functions. For example, black matrix resist film formation / patterning / heat treatment process, color filter resist film formation / patterning / heat treatment process, color filter protective film formation / patterning / heat treatment process, ITO conductive film formation process, for ITO patterning Photoresist film formation / patterning / wet etching / resist stripping process, ITO annealing process, alignment film formation / heat treatment / rubbing (polarization exposure) process, and the like. In these various processes, the device has an opportunity to contact various chemicals such as organic solvents, acids, alkaline solutions, etc., and when the electrode is formed by sputtering, the surface is locally exposed to high temperature. In some cases. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and alteration of the surface of various elements. These protective films are required to have various characteristics that can withstand various treatments during the manufacturing process as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, scratch resistance, applicability, flatness, light resistance Etc. are required. In particular, as the required characteristics of reliability required for display elements improve, the heat resistance required for display element members, specifically, the reduction of outgas during heat treatment has been regarded as important. This is because when the various organic thin films described above are formed, the thin film is subjected to a cross-linking reaction and densification by heat treatment, so that heat is applied to the element several times throughout the process. For this reason, when a protective film that generates a large amount of outgas is used, the formation of the upper layer thin film is affected by the outgas from the lower layer, resulting in deterioration of display quality and reliability.

  So far, in order to provide a protective film having high heat resistance, a proposal has been made to use a polyimide material as a protective film (Patent Document 1). A protective film using a siloxane material characterized by high heat resistance and transparency has also been proposed (Patent Documents 2 and 3). Alternatively, a protective film using an epoxy resin and a melamine resin, and a protective film using an acrylic resin or a polyester resin have been proposed (Patent Documents 4, 5, and 6).

  However, in a protective film using a polyimide material, in order to prepare a polyimide or polyimide precursor (polyamic acid) solution, it is necessary to use a so-called polyimide solvent having a strong dissolving power such as N-methylpyrrolidone or γ-butyrolactone. There is a problem that the underlying organic thin film is dissolved. This is a serious problem particularly when used as a protective film for a color filter. In addition, polyimide also has a problem of coloring because the bottom of the light absorption band extends in the visible light region due to charge transfer interaction (CT interaction). On the other hand, when a siloxane material (sol-gel material) is used, the heat resistance and transparency are sufficient, but the temperature required for completing the reaction of the silanol group is 300 ° C. or higher, so that the underlying organic thin film There is also a problem that causes deterioration and a problem that cracks occur in the thin film due to curing shrinkage during thermal curing. In addition, there is a difficulty that the -Si-O-Si- bond of the siloxane material is easily hydrolyzed by the alkaline solution. In the case of a material using an epoxy resin and a melamine resin, although there is no problem in the solvent used and the heat treatment temperature, the heat resistance is not sufficient, and the problem of yellowing also occurs. Even when an acrylic material or a polyester resin is used, the heat resistance of the acrylic part / polyester part, which is the basic skeleton, is not sufficient, resulting in an outgas problem.

  From the above situation, there has been a demand for a material that achieves both high heat resistance and other characteristics, particularly adhesion to a base substrate, flatness, and transparency.

Patent Document 1 JP-A-62-163016
Patent Document 2 Japanese Patent Laid-Open No. 62-242918
Patent Document 3 Japanese Patent Laid-Open No. 7-331178
Patent Document 4 JP 63-131103 A
Patent Document 5 JP-A-8-50289
Patent Document 6 JP2013-253263A

  An object of the present invention is to provide a thermosetting composition that gives a cured film satisfying heat resistance (low outgassing), adhesion, flatness, and transparency, and a cured film formed by the thermosetting composition. Furthermore, it is to provide an electronic component having the cured film.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a copolymer obtained by copolymerizing a monomer having an acid anhydride group and another monomer, and at least two or more. The present invention is completed by using a thermosetting composition containing a copolymer obtained by thermally reacting a compound having a hydroxyl group, a compound having at least two epoxy groups, and a solvent capable of dissolving them. It came to do. The present invention includes the following configurations.

式（１）において、Ｒ^１及びＲ^２は独立して水素、炭素数１〜３のアルキル又はフェニルである。 [1] The copolymer derived from the monomer (a), which is a reaction product from the monomer (a) represented by the following formula (1) and the monomer (b) other than (a) Thermosetting containing a modified polymer (A) in which an acid anhydride moiety is thermally opened with a compound having two or more hydroxyl groups, a compound (B) having two or more epoxy groups, and a solvent (C) Composition.

In the formula (1), R ¹ and R ² are independently hydrogen, alkyl having 1 to 3 carbon atoms, or phenyl.

式（２）において、Ｒ^１及びＲ^２は独立して水素、炭素数１〜３のアルキル又はフェニルであり、Ｒ^３は１価の有機基である。 [2] The thermosetting composition according to item [1], wherein the monomer (b) is at least one selected from a compound represented by the following formula (2) and indene.

In Formula (2), R ¹ and R ² are independently hydrogen, alkyl having 1 to 3 carbons or phenyl, and R ³ is a monovalent organic group.

式（３−１）において、Ｒ^４は、単結合、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、又は−Ｏ−であり、ｍ及びｎは独立して、１〜２０の整数であり、そして、ベンゼン環の水素は独立して、炭素数１〜３のアルキルで置換されていてもよい。 [3] The thermosetting according to item [1], wherein the compound having two or more hydroxyl groups is at least one selected from compounds represented by the following formulas (3-1) to (3-4): Sex composition.

In Formula (3-1), R ⁴ is a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, or —O—, and m and n are each independently 1 It is an integer of -20, and hydrogen of a benzene ring may be independently substituted by C1-C3 alkyl.

[4] The thermosetting composition according to item [1], wherein the compound (B) having two or more epoxy groups is a compound having an aromatic ring.

式（４）において、Ｒ^５〜Ｒ^８は独立して水素又は炭素数１〜５のアルキルである。 [5] The thermosetting according to the item [1], wherein the compound (B) having two or more epoxy groups includes at least one selected from compounds represented by the following formulas (4) and (5). Sex composition.

In the formula (4), R ^{5 to} R ⁸ are independently hydrogen or alkyl having 1 to 5 carbons.

[6] A cured film formed from the thermosetting composition according to any one of [1] to [5].

[7] A color filter having the cured film according to the item [6] as a transparent protective film.

  The thermosetting composition according to a preferred embodiment of the present invention is a material particularly excellent in heat resistance, and can improve display quality when used as a color filter protective film of a color liquid crystal display element. 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 of the present invention The thermosetting composition of the present invention comprises a modified polymer (A) obtained by thermally reacting a polyfunctional acid anhydride and a compound having two or more hydroxyl groups, and two or more epoxy groups. And a compound (B) having two or more epoxy groups in an amount of 10 to 500 parts by weight based on 100 parts by weight of the modified polymer. It is a thermosetting composition.

1-1. Modified polymer (A)
The modified polymer (A) is a compound selected from the compound represented by the formula (1) as the monomer (a), the compound represented by the formula (2) as the other monomer (b), and an indene. The polyfunctional acid anhydride obtained by radical copolymerization in the presence of an azo initiator is necessarily contained and obtained by thermally reacting a compound having two or more hydroxyl groups. Itaconic anhydride may be used for the compound of the formula (1), and the other monomer (b) may contain compounds other than the above compounds.

  In the other monomer (b), when a compound represented by the formula (2) and a compound other than indene are used, from the viewpoint of heat resistance, preferably 0 to 40 wt% of the whole monomer used for radical polymerization More preferably, the addition amount is 0 to 20 wt%.

  Further, at least a solvent is required for the synthesis of the modified polymer (A). The solvent may be left as it is, and it may be a liquid or gel composition considering handling properties, or the solvent may be removed and a solid composition considering transportability may be used.

  Other compounds than the above may be contained within a range not impairing the object of the present invention. Examples of other raw materials may include a radical polymerizable monomer and a chain transfer agent.

1-1-1. Monomer (a) and monomer (b)
In the present invention, the material for obtaining the modified polymer (A) includes a compound represented by the formula (1) as the monomer (a). In addition, the other monomer (b) preferably contains one or more compounds selected from the compound represented by the formula (2) and indene. Specific examples of Formula (1) include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, phenylmaleic anhydride, and 2,3-diphenylmaleic anhydride. Specific examples of the compound represented by the formula (2) include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide. Moreover, in the range which does not impair the characteristic of this invention, you may also contain monomers (b) other than the compound represented by Formula (2), and indene, As a specific example in that case, methacrylic acid, methyl methacrylate, Ethyl methacrylate, propyl methacrylate, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, 2-phenylethyl methacrylate, isobornyl methacrylate, dicyclopentanyl methacrylate, 2,2 , 2-trifluoroethyl methacrylate.

式（３−１）において、Ｒ^４は、単結合、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、又は−Ｏ−であり、ｍ及びｎは独立して、１〜２０の整数であり、そして、ベンゼン環の水素は独立して、炭素数１〜３のアルキルで置換されていてもよい。 1-1-2.2 Compound having two or more hydroxyl groups In the present invention, a compound having two or more hydroxyl groups is used as a material for obtaining the modified polymer (A). Preferably, 1,4-bis (hydroxyethoxy) benzene, 1,3-bis (hydroxyethoxy) benzene, 4,4′-isopropylidenebis (2-phenoxyethanol), bis [4- (2-hydroxyethoxy) phenyl Sulfone, 2,2 ′-[(1,1′-biphenyl) -4,4′-diylbis (oxy)] bisethanol. Other compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2 -Pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,3,5-pentanetriol, 2,3,4-pentanetriol, 1,2-hexane Diol, 1,6-hexanediol, 2,5-hexanediol, 1,2,3-hexanetriol, 1,2,5-hexanetriol, 1,2,6-hexanetriol (of formula (3-2) Compound), 1,2-heptanediol, 1,7-he Tandiol, 1,2,5-heptanetriol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2- Dodecanediol, 1,12-dodecanediol, glycerin, 1,3,6-hexanetriol, trimethylolpropane (compound of formula (3-3)), isocyanuric acid tris (2-hydroxyethyl), pentaerythritol (formula ( Compound of 3-4), dipentaerythritol, and a compound represented by the following formula (3-1). .

In Formula (3-1), R ⁴ is a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, or —O—, and m and n are each independently 1 It is an integer of -20, and hydrogen of a benzene ring may be independently substituted by C1-C3 alkyl.

  A plurality of these compounds can be used in combination.

1-1-3. Solvents used in the synthesis of the modified polymer (A) Specific examples of solvents used in the synthesis to obtain the modified polymer (A) include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, methoxyacetic acid Ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- D Ethyl toxipropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyrubin Methyl acetate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexane Sanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether . One of these may be sufficient as a solvent, and these 2 or more types of mixtures may be sufficient as it.

1-1-4. Molecular weight regulator used for the synthesis of the modified polymer (A) When synthesizing the modified polymer (A), a molecular weight regulator may be further contained in order to suppress an increase in the molecular weight and to exhibit excellent storage stability. Good. Examples of the molecular weight modifier include mercaptans, xanthogens, quinones, hydroquinones, and 2,4-diphenyl-4-methyl-1-pentene.

  Specific examples of the molecular weight modifier include 2-hydroxy-1,4-naphthoquinone, benzoquinone, 1,4-naphthoquinone, 1,4-dihydroxynaphthalene, 2,5-di-t-butylhydroquinone, hydroquinone, methylhydroquinone, t-butylhydroquinone, methoquinone, p-benzoquinone, methyl-p-benzoquinone, t-butyl-p-benzoquinone, anthraquinone, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid Dimethyl xanthogen sulfide, diisopropyl xanthogen disulfide, 2,4-diphenyl-4-methyl-1-pentene, and the like.

  A molecular weight modifier may be used independently and may be used in combination of 2 or more.

1-1-5. Method for synthesizing modified polymer (A) The modified polymer (A) used in the present invention comprises a compound represented by the formula (1), a compound represented by the formula (2), and a monomer selected from indene. Is polymerized in the above solvent in the presence of a thermal radical initiator. At this time, the number of moles per functional group of the compound represented by the formula (1) and the number of moles per functional group of the compound having two or more hydroxyl groups need to be in the following ranges. Here, the functional group means an acid anhydride group in the compound represented by the formula (1) and a hydroxyl group in a compound having two or more hydroxyl groups.

0.5 ≦ X ≦ 5.0, X = (number of moles of acid anhydride / number of moles of hydroxyl group)

  Within this range, the solubility of the modified polymer (A) in the solvent is high, and the composition has good heat resistance, flatness, and adhesion, and more preferably 0.7 ≦ X ≦ 4.0. Yes, and more preferably 1.0 ≦ X ≦ 3.0.

  In the synthesis of the modified polymer (A), in the first-stage radical polymerization, the monomers of the formulas (1) and (2) are copolymerized, so that the polymerization heat is large. When the polymerization control is difficult due to the polymerization heat, the heat of polymerization can be reduced by using a chain transfer agent. The chain transfer agent is not particularly limited, but 2,4-diphenyl-4-methyl-1-pentene is preferably used.

  The reaction solvent is preferably used in an amount of 80 parts by weight or more with respect to 100 parts by weight of the solute since the reaction proceeds smoothly. The reaction is carried out at 40 to 200 ° C. for 0.2 to 20 hours.

  The reaction sequence of the raw materials was obtained by radically polymerizing the monomer (a) and the other monomer (b) in the presence of a solvent and an azo initiator, and then obtaining a polyfunctional acid anhydride copolymer. A compound having one or more hydroxyl groups is added and heated.

  In the radical polymerization, a reaction temperature of 40 ° C. to 120 ° C. is preferable, and a reaction temperature of 60 ° C. to 80 ° C. is more preferable. After completion of radical polymerization, the mixture is cooled to room temperature, a compound having two or more hydroxyl groups is added, and reacted at 100 to 200 ° C. for 0.1 to 6 hours.

  In the modified polymer (A) synthesized in this way, even when the compound having two or more hydroxyl groups has low solubility in the copolymer or the solvent used, it becomes a uniform transparent liquid after the thermal reaction, resulting in defects. It is possible to form a uniform thin film without any defects. On the other hand, when a compound having two or more hydroxyl groups is simply added to the system without thermal reaction after polymerization of the radical copolymer, it forms a thin film even if it is soluble in the solvent and becomes a transparent solution. After evaporation of the solvent, a compound having two or more hydroxyl groups precipitates due to poor compatibility, and it is often impossible to form a uniform thin film. For this reason, by guiding to the multibranched polyester, not only the heat resistance is improved, but also a thin film having no defect can be formed.

  The weight average molecular weight of the obtained modified polymer is preferably 1,000 to 1,000,000, and more preferably 3,000 to 500,000. If it exists in these ranges, applicability | paintability and flatness will be 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). For standard polystyrene, polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 of Agilent Technologies) is used, and PLgel MIXED-D (Agilent Technology, Inc.) is used for the column. It can be measured using THF as the mobile phase. The weight average molecular weight of the commercial product in this specification is a catalog publication value.

1-2. Compound (B) having two or more epoxy groups
The epoxy compound used in the present invention is a compound having two or more epoxy groups per molecule. The compound (B) having two or more epoxy groups may be one type or two or more types.

1-2. A compound (B) having at least two epoxy groups
Examples of the compound (B) having two or more epoxy groups are bisphenol A type epoxy compound, bisphenol F type epoxy compound, glycidyl ether type epoxy compound, glycidyl ester type epoxy compound, biphenyl type epoxy compound, phenol novolac type epoxy compound , Cresol novolac type epoxy compound, bisphenol A novolak type epoxy compound, aliphatic polyglycidyl ether compound, cycloaliphatic epoxy compound, polymer of monomer having epoxy group, copolymerization of monomer having epoxy group and other monomer An epoxy compound having a coalescence and a siloxane bonding site. The compound (B) having two or more epoxy groups is preferably a compound having an aromatic ring.

  Specific examples of commercial products of bisphenol A type epoxy compounds are jER 828, 1004 and 1009 (all trade names are Mitsubishi Chemical Corporation); specific examples of commercial products of bisphenol F type epoxy compounds are jER 806 and 4005P. Specific examples of commercially available glycidyl ether type epoxy compounds are TECHMORE VG3101L (trade name, Printec Co., Ltd.), EHPE3150 (trade name, Daicel Corporation), EPPN. -501H, 502H (both trade names, Nippon Kayaku Co., Ltd.), and jER 1032H60 (trade name, Mitsubishi Chemical Corporation); specific examples of commercially available glycidyl ester type epoxy compounds include Denacol EX-721 ( Product name, Nagase ChemteX Corporation ), And diglycidyl 1,2-cyclohexanedicarboxylate (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.); specific examples of commercially available biphenyl type epoxy compounds are 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.); Specific examples are EPPN-201 (trade name, Nippon Kayaku Co., Ltd.) and jER 152, 154 (both trade names, Mitsubishi Chemical Co., Ltd.) and the like; specific examples of commercial products of cresol novolac type epoxy compounds are , EOCN-102S, 103S, 104S, 1020 (all trade names, Nippon Kayaku shares Specific examples of commercial products of bisphenol A novolac type epoxy compounds are jER 157S65 and 157S70 (both are trade names, Mitsubishi Chemical Corporation); specific examples of commercial products of cycloaliphatic epoxy compounds Is Celoxide 2021P, 3000 (both trade names, Daicel Corporation); a specific example of a commercially available epoxy compound having a siloxane bonding site is 1,3-bis [2- (3,4-epoxycyclohexyl) Ethyl] tetramethyldisiloxane (trade name, Jerest Incorporated), TSL 9906 (trade name, Momentive Performance Materials LLC), COATOSIL MP-200 (trade name, Momentive Performance Materials LLC), Composeran SQ506 (quotient Name, Arakawa Chemical Co., Ltd.), ES-1023 (trade name, is a Shin-Etsu Chemical Co., Ltd.).

  TECHMORE VG3101L (trade name, Printec Co., Ltd.) is 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3- Epoxypropoxy) phenyl] ethyl] phenyl] propane, and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2 , 3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol; EHPE3150 (trade name, Daicel Corporation) is 2,2-bis (hydroxymethyl) -1 -1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of butanol; Celoxide 2021P (trade name, Daicel Corporation) is 3 ' 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; Celoxide 3000 (trade name, Daicel Corporation) is 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4 .1.0] heptane; COATOSIL MP-200 (trade name, Momentive Performance Materials LLC) is a polymer containing 3-glycidoxypropyltrimethoxysilane as a raw material component.

1-2-2. Ratio of compound (B) having two or more epoxy groups to modified polymer (A) Compound (B) having two or more epoxy groups to 100 parts by weight of modified polymer (A) in the thermosetting composition of the present invention The ratio of the total amount is 10 to 500 parts by weight. When the ratio of the total amount of the compound (B) having two or more epoxy groups is within this range, the balance of flatness, heat resistance, chemical resistance, and base adhesion is good. The total amount of the compound (B) having two or more epoxy groups is preferably in the range of 50 to 300 parts by weight, but this is determined by adjusting the molar ratio of the multibranched polyester and the epoxy curing agent.

1-3. Other Components Various additives can be added to the thermosetting composition of the present invention in order to improve coating uniformity, adhesion, transparency, flatness, and chemical resistance. 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 phosphorous, phosphorus and sulfur compounds, molecular weight modifiers, and epoxy curing agents.

1-3-1. 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. 75, Polyflow No. 90, polyflow no. 95 (all trade names, Kyoeisha Chemical Co., Ltd.), Disperbak-161, Disperbak-162, Disperbak-163, Dispersake-164, Dispersake-166, Dispersake-170, Dispersake-180 , Disper Bake-181, Disper Bake-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (All trade names, Big Chemie Japan Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF-50-100CS (all trade names, Shin-Etsu Chemical Co., Ltd.), Surflon-S611 (Products) Name AGC Seimi Chemical Co., Ltd.), Aftergent 222F, Aftergent 208G, Aftergent 251, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, Aftergent 650A, FTX-218 (all trade names and stocks) Company Neos), Mega Fuck F-410, Mega Fuck F-430, Mega Fuck F-444, Mega Fuck F-472SF, Mega Fuck F-475, Mega Fuck F-477, Mega Fuck F-552, Mega Fuck F- 553, Megafuck F-554, Megafuck F-555, Megafuck F-556, Megafuck F-558, Megafuck F-559, Megafuck R-94, Megafuck RS-75, Megafuck RS-7 -K, Megafuck RS-76-NS, Megafuck DS-21 (all trade names, DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (All are trade names, Evonik Japan Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (Fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxy Ethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, poly Oxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, Polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, poly Alkoxy polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonates, and alkyl diphenyl ether disulfonic acid salts. It is preferable to use at least one selected from these.

  Among these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surflon-S611, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, Aftergent 650A, Megafuck F-477, Megafuck F-556, Megafuck F-559, Megafuck RS-72-K, Megafuck DS-21, TEGO Twin 4000, Fluoroalkylbenzenesulfonate, Fluoroalkylcarboxylate, When it is at least one selected from fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl trimethyl ammonium salt, and fluoroalkyl amino sulfonate The coating uniformity of the thermosetting composition is preferably 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.

1-3-2. Coupling Agent The thermosetting composition of the present invention may further contain a coupling agent from the viewpoint of further improving the adhesion between the formed cured film and the substrate.

  As such a coupling agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, trade name, Silaace S510, JNC Corporation), 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name, Silaace S530, JNC Corporation), 3-mercaptopropyltrimethoxysilane (for example, trade name, Silaace S810, JNC Corporation), 3-glycidyloxypropyl Silane coupling agents such as trimethoxysilane copolymer (for example, trade name, CoatOSil MP200, Momentive Performance Materials Japan GK), acetoalkoxyaluminum diiso Aluminum coupling agents such as Ropireto, and tetraisopropyl bis (dioctyl phosphite) can be mentioned titanate coupling agents such as titanates.

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

  Since the content of the coupling agent is 0.01% by weight or more and 10% by weight or less with respect to the total amount of the thermosetting composition, the adhesion between the formed cured film and the substrate is improved. preferable.

1-3-3. 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. As a specific example, Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox259, Irganox3114, Irganox565, Irganox565DD (all trade name, BASF Japan stock Company), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-80 (all are trade names) ADEKA Co., Ltd.). Among these, Irganox 1010 and ADK STAB AO-60 are more preferable.

  The antioxidant is used by adding 0.1 to 10 parts by weight with respect to the total amount of the thermosetting composition.

1-3-4. Epoxy Curing Agent The composition of the present invention may further contain an epoxy curing agent in order to improve flatness and chemical resistance. Epoxy curing agents include acid anhydride curing agents, amine curing agents, phenol curing agents, imidazole curing agents, catalytic curing agents, and sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, and the like. Although there exist a thermosensitive acid generator etc., an acid anhydride type hardening | curing agent or an imidazole type hardening | curing agent, or its combination is preferable from a viewpoint of avoiding coloring of a cured film and the heat resistance of a cured film.

  Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride; Aromatic polyvalent carboxylic acid 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.

  When using an epoxy curing agent, the ratio of the epoxy curing agent to 100 parts by weight of the compound (B) having two or more epoxy groups is 0.1 to 60 parts by weight. About the addition amount in case an epoxy hardening agent is an acid anhydride type hardening | curing agent, in detail, the carboxylic acid anhydride group or carboxyl group in an epoxy hardening agent is 0.1-1.5 with respect to an epoxy group. It is preferable to add so that it may become a double equivalent. At this time, the carboxylic acid anhydride group is calculated as divalent. If the carboxylic acid anhydride group or carboxyl group is added so as to have an equivalent amount of 0.15 to 0.8 times, the chemical resistance is further improved, which is more preferable.

1-3-5. Ultraviolet Absorber The thermosetting composition of the present invention may contain an ultraviolet absorber from the viewpoint of further improving the deterioration preventing ability of the formed transparent film.

  Specific examples of the ultraviolet absorber are TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571, and TINUVIN 765 (all trade names are BASF Japan Ltd.).

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

1-3-6. Anti-flocculating agent The composition of the present invention may contain an anti-flocculating agent from the viewpoint of blending the solid content with a solvent and preventing aggregation.

  Specific examples of the anti-agglomeration agent include Disperbak-145, Disperbak-161, Disperbak-162, Disperbak-163, Dispersake-164, Dispersake-182, Dispersake-184, Dispersake-185 , Disper Bake-2163, Disper Bake-2164, BYK-220S, Disper Bake-191, Disper Bake-199, Disper Bake-2015 (all trade names, Big Chemie Japan Co., Ltd.), FTX-218, Footent 710FM, They are Footgent 710FS (all trade names, Neos Co., Ltd.), Floren G-600, and Floren G-700 (all trade names, Kyoeisha Chemical Co., Ltd)

  The aggregation inhibitor is used by adding 0.01 to 10 parts by weight with respect to the total amount of the thermosetting composition.

1-3-7. Thermal Crosslinker The composition of the present invention may contain a thermal crosslinker from the viewpoint of further improving heat resistance, chemical resistance, in-film uniformity, flexibility, flexibility and elasticity.

  Specific examples of the thermal crosslinking agent include Nicarak MW-30HM, Nicarak MW-100LM, Nicarax MX-270, Nicarac MX-280, Nicarax MX-290, Nicarac MW-390, Nicarac MW-750LM (all are trade names, ( Sanwa Chemical Co., Ltd.).

  The thermal crosslinking agent is used by adding 0.1 to 10 parts by weight with respect to the total amount of the composition.

1-4. Solvent (C)
The thermosetting composition of the present invention contains a solvent (C). The solvent (C) used in the composition of the present invention is preferably a solvent capable of dissolving the modified polymer (A) and the compound (B) having two or more epoxy groups. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxybutyl acetate, 3 -Methyl oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, 2- Propyl hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2-methylpropyl Methyl pionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, aceto Methyl acetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl Ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. The solvent may be one of these, or a mixture of two or more of these.

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 over time of the composition becomes good. If the storage temperature is −20 ° C. to 10 ° C., there is no precipitate and it is more preferable.

2. Cured film formed from thermosetting composition The thermosetting composition of the present invention is a mixture of a modified polymer (A) and a compound (B) having two or more epoxy groups, and depending on the intended properties, Furthermore, an epoxy curing agent, a solvent, a surfactant, an adhesion improver, an antioxidant, and other additives can be selected and added as necessary.

  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 by heating, for example, the coating film Can be formed. Application of the thermosetting composition to the substrate surface can form a coating film by a conventionally known method such as spin coating, roll coating, dipping, or slit coating. Next, this coating film is temporarily baked by a hot plate or an oven. Temporary baking 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, this baking is performed in order to cure the coating film. The main firing conditions vary depending on the types and blending ratios of the respective components, but are usually 180 to 250 ° C., preferably 200 to 250 ° C., 30 to 90 minutes for an oven, 5 to 30 minutes for a hot plate, and heat treatment. Thus, a cured film can be obtained.

  The cured film obtained in this way is very sensitive to 1) the modified polymer (A) reacts with the compound (B) having two or more epoxy groups to form a three-dimensional network during heating. It is tough and excellent in transparency, heat resistance, chemical resistance, flatness and adhesion. Further, regarding light resistance, sputtering resistance, scratch resistance, and coating property, it is expected to be excellent for the same reason. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state imaging element can be produced using this color filter. The cured film of the present invention is effective when used as a transparent insulating film formed between a TFT and a transparent electrode or a transparent insulating film formed between a transparent electrode and an alignment film, in addition to a protective film for a color filter. It is. Furthermore, the cured film of the present invention is also effective when used as a protective film for LED light emitters.

  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.

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

[Synthesis Example 1] Synthesis of Modified Polymer (A1) Solution In a four-necked flask equipped with a stirrer, methyl 3-methoxypropionate (MMP), N-cyclohexylmaleimide, maleic anhydride, radical initiator V-65 (Wako Pure Chemical Industries, Ltd.) Manufactured by Kogyo Co., Ltd.) and α-methylstyrene dimer were charged at the following weights and heated and stirred at 80 ° C. for 2 hours under a dry nitrogen stream to obtain a radical copolymer (first stage of synthesis).

MMP 23.333g
N-cyclohexylmaleimide 6.464 g
Maleic anhydride 3.537g
V-65 0.100g
α-methylstyrene dimer 0.050 g

  Thereafter, the reaction solution was cooled to 25 ° C., and 5.669 g of 4,4′-isopropylidenebis (2-phenoxyethanol) was added, followed by stirring at 150 ° C. for 3 hours (the second stage of synthesis).

  The solution was cooled to room temperature to obtain a 30% by weight solution of a pale yellow transparent modified polymer (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 resulting modified polymer (A1) had a weight average molecular weight Mw of 14,000 and a polydispersity Mw / Mn of 3.8. )

[Synthesis Examples 2 to 10] Synthesis of Solutions of Modified Polymers (A2) to (A10) According to the method of Synthesis Example 1, each component was reacted at the temperatures, times, and ratios (unit: g) shown in Table 1. To obtain solutions of modified polymers (A2) to (A10).

[Comparative Synthesis Examples 1 and 2] Synthesis of solutions of polyesters (R1) and (R2) General linear polyesters having no branching structure and not having the specific structure included in the present claims are listed in Table 1, Reaction was carried out at time and in proportion to obtain a solution of polyester (R1) and (R2). However, the reaction temperature was 150 ° C. for 3 hours.

The compounds used in the synthesis examples and comparative synthesis examples indicated by abbreviations in Table 1 are as follows.
CHMI: N-cyclohexylmaleimide NPM: N-phenylmaleimide IN: Indene MAH: Maleic anhydride ODPA: 4,4′-oxydiphthalic anhydride BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride V-65: 2,2′-azobis (2,4-dimethylvaleronitrile); manufactured by Wako Pure Chemical Industries, Ltd. αMSD: α-methylstyrene dimer bisA-2EOH: 4,4′-isopropylidenebis (2- Phenoxyethanol)

BPE-40, 60, 100: New Pole BPE-40, New Pole BPE-60, New Pole BPE-100; manufactured by Sanyo Chemical Industries, Ltd .; diols having the following structures, respectively, having hydroxyl values of 276, 228, 167 Is a compound

HT: 1,2,6-hexanetriol TMP: trimethylolpropane PE: pentaerythritol BD: 1,4-butanediol MMP: methyl 3-methoxypropionate

[Example 1]
30% by weight solution of modified polymer (A1) obtained in Synthesis Example 1 VG3101L as trifunctional epoxy compound, YX4000H as bifunctional epoxy compound, trimellitic anhydride (TMA) as curing agent, S510 as silane coupling agent ADK STAB AO-60 as an antioxidant, F-556 as a surfactant, and propylene glycol monomethyl ether acetate (PGMEA) as a diluent solvent are mixed and dissolved in the proportions (parts by weight) shown in Table 2, and a membrane filter ( The mixture was filtered through a 0.2 μm aperture to obtain a thermosetting composition.

[Examples 2 to 13 and Comparative Examples 1 and 2]
According to the method of Example 1, each component was mixed and dissolved in the proportions (parts by weight) shown in Table 2 to obtain a thermosetting composition.

  Using each of the obtained thermosetting compositions, the heat resistance, planarization rate, and base adhesion were evaluated by the methods described below. The evaluation result of the cured film of Examples 1-13 was put together in Table 3, and was described. Moreover, as Comparative Examples 1 and 2, the heat resistance, planarization rate, and base adhesion of a cured film formed using a thermosetting composition containing a normal polyester having no branched structure were evaluated. The evaluation results are shown in Table 3.

[Evaluation method of heat resistance]
The obtained thermosetting composition was spin-coated on a glass substrate at 650 rpm for 10 seconds, and prebaked on an 80 ° C. hot plate for 2 minutes. Then, it post-baked (PB) for 30 minutes at 230 degreeC in oven, and obtained the glass substrate with a cured film (this is made into the film thickness after PB). In the obtained glass substrate with a cured film, the film thickness was measured using a step / surface roughness / fine shape measuring device (trade name, P-17, KLA TENCOR Co., Ltd.) to obtain an initial film thickness. Thereafter, the glass substrate with a cured film was post-baked in an oven at 230 ° C. for 60 minutes, and the film thickness was measured in the same manner (this film thickness is referred to as post-EB1 film thickness). Moreover, the glass substrate with a cured film after PB was separately post-baked at 250 ° C. for 60 minutes, and the film thickness was measured in the same manner (this is referred to as the post-EB2 film thickness). The remaining film ratios 1 and 2 are calculated using the following formulas: ○, those with a remaining film ratio of PB-EB1 of 99% or more, Δ with less than 99% to 98%, and × with less than 98%. It was. In addition, a film with a remaining film ratio between PB and EB2 of 99% or more was evaluated as “◯”, a film with less than 99% to 98% was evaluated as “Δ”, and a film with less than 98% was evaluated as “X”.

Residual film ratio 1 (%) = (film thickness after EB1 / film thickness after PB) × 100
Residual film ratio 2 (%) = (film thickness after EB2 / film thickness after PB) × 100

[Evaluation method of flatness]
An uneven substrate (pattern with a line of 100 μm, a space of 50 μm, a film thickness of 1 μm) including a resist pattern in which a surface step is measured using a step / surface roughness / fine shape measuring device (trade name, P-17, KLA Tencor Corporation). The obtained thermosetting composition was spin-coated at 650 rpm for 10 seconds on a substrate and pre-baked on an 80 ° C. hot plate for 2 minutes. Subsequently, it was post-baked at 230 ° C. for 30 minutes in an oven to obtain a color filter substrate with a cured film having an average protective film thickness of 1.5 μm. Then, the surface level | step difference was measured with respect to the obtained color filter substrate with a cured film. The flattening rate was calculated from the maximum surface level difference (hereinafter abbreviated as “maximum level difference”) of the color filter substrate without cured film and the color filter substrate with cured film using the following formula, and the results are shown in Table 3. It was. As a result of flatness, 100 to 80% was evaluated as ◎, 79 to 60% as ◯, and less than 60% as ×.

Flattening rate (%) = ((maximum step of uneven substrate−maximum step of uneven substrate with cured film) / maximum step of uneven substrate) × 100

[Adhesion evaluation method]
The obtained thermosetting composition was spin-coated on an uneven substrate (line: 100 μm, space: 50 μm, film thickness: 1.0 μm) at 650 rpm for 10 seconds, and prebaked on an 80 ° C. hot plate for 2 minutes. Then, it post-baked for 30 minutes at 230 degreeC in oven, and obtained the glass substrate with a cured film. A cross-cut test (JIS K 5400, release tape: 3M No. 361 was used) was performed on both the obtained concavo-convex substrate with a cured film and a similarly prepared glass substrate with a cured film, and the following classifications 0 to 5 were performed. According to the evaluation, the classifications 0 to 1 were evaluated as ◯, the classifications 2 through 3 as Δ, and the classifications 4 through 5 as x. The adhesion evaluation on the concavo-convex substrate with a cured film was “adhesion evaluation 1”, and the adhesion evaluation on the glass substrate with a cured film was “adhesion evaluation 2”.

<Category 0>: The edges of the cut are completely smooth, and there is no peeling to the eyes of any lattice.
<Category 1> ... Small peeling of the coating film at the intersection of cuts. The cross-cut portion is clearly not affected by more than 5%.
<Category 2> The coating film is peeled along the edge of the cut and / or at the intersection. The cross-cut part is clearly affected by more than 5%, but not more than 15%.
<Category 3>: The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eyes are partially or completely peeled off. The cross cut part is clearly affected by more than 15%, but not more than 35%.
<Category 4>: The coating film is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely peeled off. The cross-cut portion is clearly not affected by more than 35%.
<Category 5>... Any of the degree of peeling that cannot be classified even in Category 4.

[Transparency evaluation method]
The obtained thermosetting composition was spin-coated on a glass substrate at 650 rpm for 10 seconds, and prebaked on an 80 ° C. hot plate for 2 minutes. Then, it heat-processed for 30 minutes at 230 degreeC in oven, and obtained the glass substrate with a cured film which is a film thickness of 1.5 micrometers. In the obtained glass substrate with a cured film, the light transmittance at 400 nm of the cured film was measured with an ultraviolet-visible near-infrared spectrophotometer (trade name, V-670, JASCO Corporation). In this case, only the glass substrate was used as a reference, and the light transmittance of the cured film alone was calculated (in this case, interference due to multiple reflection was not considered). The case where the light transmittance was 98% or more was evaluated as transparency ○, the case where the transmittance was less than 95% was evaluated as transparency ×, and the space between them was evaluated as Δ.

As is clear from the results shown in Table 3, it can be seen that the thermosetting compositions of Examples 1 to 13 satisfy heat resistance, flatness, and adhesion. On the other hand, Comparative Examples 1 and 2 could not satisfy all the characteristics.

  The cured film obtained from the thermosetting composition of the present invention has good heat resistance, flatness, and underlying adhesion, and is a protective film for various optical materials such as color filters, LED light emitting elements, and light receiving elements. In addition to the insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film, it can be used as a passivation film, a buffer coat film, and a planarizing film.

Claims (7)

Monomer (a) -derived acid anhydride of the copolymer, which is a reaction product from the monomer (a) and the monomer (b) other than (a) represented by the following formula (1) A thermosetting composition comprising a modified polymer (A) in which a site is thermally opened with a compound having two or more hydroxyl groups, a compound (B) having two or more epoxy groups, and a solvent (C).

In the formula (1), R ¹ and R ² are independently hydrogen, alkyl having 1 to 3 carbon atoms, or phenyl. The thermosetting composition according to claim 1, wherein the monomer (b) is at least one selected from a compound represented by the following formula (2) and indene.

In Formula (2), R ¹ and R ² are independently hydrogen, alkyl having 1 to 3 carbons or phenyl, and R ³ is a monovalent organic group. The thermosetting composition according to claim 1, wherein the compound having two or more hydroxyl groups is at least one selected from compounds represented by the following formulas (3-1) to (3-4).

In Formula (3-1), R ⁴ is a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, or —O—, and m and n are each independently 1 It is an integer of -20, and hydrogen of a benzene ring may be independently substituted by C1-C3 alkyl.   The thermosetting composition according to claim 1, wherein the compound (B) having two or more epoxy groups is a compound having an aromatic ring. The thermosetting composition according to claim 1, wherein the compound (B) having two or more epoxy groups contains at least one selected from compounds represented by the following formulas (4) and (5).

In the formula (4), R ^{5 to} R ⁸ are independently hydrogen or alkyl having 1 to 5 carbons.   The cured film formed from the thermosetting composition of any one of Claims 1-5.   A color filter having the cured film according to claim 6 as a transparent protective film.