JP6950573B2 - Thermosetting composition - Google Patents

Description

The present invention can be used to form an insulating material in an electronic component, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a flattening 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 thereof, and an electronic component having the film.

The manufacturing process of an element such as a liquid crystal display element includes a step 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 step, color filter protective film film formation / patterning / heat treatment step, ITO conductive film film formation process, ITO patterning Photoresist film formation / patterning / wet etching / resist peeling step, ITO annealing step, alignment film film formation / heat treatment / rubbing (polarization exposure) step, and the like. In these various steps, the device has an opportunity to come into contact with various chemicals such as organic solvents, acids and alkaline solutions, and the surface is locally exposed to high temperatures when the electrodes are formed by sputtering. In some cases. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and deterioration of the surface of various elements. These protective films are required to have various properties capable of withstanding various treatments during the manufacturing process as described above. Specifically, it has heat resistance, solvent resistance, acid resistance, alkali resistance, and other chemical resistance, water resistance, adhesion to underlying substrates such as glass, transparency, scratch resistance, coatability, flatness, and light resistance. Etc. are required. In particular, as the required characteristics of reliability required for a display element are improved, the heat resistance required for a display element member, specifically, reduction of outgas during heat treatment is regarded as important. This is because when the various organic thin films described above are formed, the thin films are always crosslinked and densified by heat treatment, so that heat is applied to the device many times throughout the process. Therefore, if a protective film that generates a large amount of outgas is used, the thin film formation of the upper layer 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, it has been proposed to use a polyimide material as a protective film (Patent Document 1). Further, 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, or a protective film using an acrylic resin or a polyester resin has been proposed (Patent Documents 4, 5 and 6).

However, in the protective film using a polyimide material, in order to prepare a polyimide or a polyimide precursor (polyamide 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 becomes a big problem especially when it is used as a protective film for a color filter. In addition, polyimide has a problem of being colored because the hem 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, heat resistance and transparency are sufficient, but the temperature required to complete the reaction of silanol groups is as high as 300 ° C or higher, so that the underlying organic thin film There is also a problem of causing deterioration and a problem of cracks in the thin film due to curing shrinkage during thermosetting. In addition, there is a drawback that the −Si—O—Si− bond of the siloxane material is easily hydrolyzed by the alkaline solution. Further, in the case of a material using an epoxy resin and a melamine resin, although there is no problem with 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 was used, the heat resistance of the acrylic part and the polyester part, which are the basic skeletons, was not sufficient, causing a problem of outgassing.

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

Patent Document 1 Japanese Patent Application Laid-Open No. 62-1630116
Patent Document 2 Japanese Patent Application Laid-Open No. 62-242918
Patent Document 3 Japanese Patent Application Laid-Open No. 7-331178
Patent Document 4 Japanese Patent Application Laid-Open No. 63-131103
Patent Document 5 Japanese Patent Application Laid-Open No. 8-50289
Patent Document 6 Japanese Patent Application Laid-Open No. 2013-253263

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

As a result of diligent studies to solve the above problems, the present inventors have at least two or more copolymers obtained by copolymerizing a monomer having an acid anhydride group with another monomer. The present invention is completed by using a thermosetting composition containing a copolymer obtained by thermally reacting a compound having a hydroxyl group of the above, a compound having at least two or more epoxy groups, and a solvent capable of dissolving these. I came to do it. 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] Derived from the monomer (a) of the copolymer which is a reaction product from the monomer (a) represented by the following formula (1) and the monomer (b) other than the (a). Thermosetting containing a modified polymer (A) in which the acid anhydride moiety is thermally ring-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 formula (1), R ¹ and R ² are independently hydrogen, alkyl or phenyl having 1 to 3 carbon atoms.

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 the compound represented by the following formula (2) and indene.

In the formula (2), R ¹ and R ² are independently hydrogen, an alkyl or phenyl having 1 to 3 carbon atoms, 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 the 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 independently 1 It is an integer of ~ 20, and the hydrogen in the benzene ring may be independently substituted with an alkyl having 1-3 carbon atoms.

[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 item [1], wherein the compound (B) having two or more epoxy groups contains at least one selected from the compounds represented by the following formulas (4) and (5). Sex composition.

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

[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 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 when used as a color filter protective film of a color liquid crystal display element, display quality can be improved. In particular, it is useful as a protective film for color filters manufactured by a dyeing method, a pigment dispersion method, an electrodeposition method and a printing method. It can also be used as a protective film and a transparent insulating film for various optical materials.

1. 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 with a compound having two or more hydroxyl groups, and two or more epoxy groups. The thermosetting composition containing the compound (B) having two or more epoxy groups is 10 to 500 parts by weight with respect to 100 parts by weight of the modified polymer. It is a thermosetting composition.

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

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

In addition, at least a solvent is required for the synthesis of the modified polymer (A). The solvent may be left as it is to form a liquid or gel-like composition in consideration of handleability and the like, or the solvent may be removed to form a solid composition in consideration of transportability and the like.

Other compounds other than the above may be contained as long as the object of the present invention is not impaired. Examples of other raw materials may include radically polymerizable monomers and chain transfer agents.

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). Further, as the other monomer (b), preferably, one or more compounds selected from the compound represented by the formula (2) and the indene are contained. Specific examples of the 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. Further, a compound represented by the formula (2) and a monomer (b) other than inden may be contained as long as the characteristics of the present invention are not impaired, and specific examples thereof include methacrylic acid and 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 Compounds 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, triolethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2. -Pentandiol, 1,5-Pentanediol, 2,4-Pentandiol, 1,2,5-Pentantriol, 1,3,5-Pentantriol, 2,3,4-Pentantriol, 1,2-hexane Of diol, 1,6-hexanediol, 2,5-hexanediol, 1,2,3-hexanetriol, 1,2,5-hexanetriol, 1,2,6-hexanetriol (formula (3-2)) Compounds), 1,2-heptanediol, 1,7-heptanediol, 1,2,5-heptantriol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3 , 6-octanediol, 1,2,8-octanetriol, 1,2-nonandiol, 1,9-nonanediol, 1,2,9-nonantriol, 1,2-decanediol, 1,10-decane Diol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, 1,3,6-hexanetriol, trimethylpropane (compound of formula (3-3)), Examples thereof include tris isocyanurate (2-hydroxyethyl), pentaerythritol (compound of formula (3-4)), dipentaerythritol, and compounds 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 independently 1 It is an integer of ~ 20, and the hydrogen in the benzene ring may be independently substituted with an alkyl having 1-3 carbon atoms.

A plurality of the compounds listed here can be used in combination.

1-1-3. Solvent used for synthesis of modified polymer (A) Specific examples of the solvent used for synthesis to obtain modified polymer (A) include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, and 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- Ethyl ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyruvin Methyl acetate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, Propropylene 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 them.

1-1-4. Molecular Weight Adjusting Agent Used for Synthesis of Modified Polymer (A) Even if a molecular weight adjusting agent is further contained in order to suppress an increase in molecular weight and exhibit excellent storage stability during the synthesis of the modified polymer (A). good. Examples of the molecular weight adjusting agent include mercaptans, xanthogens, quinones, hydroquinones, 2,4-diphenyl-4-methyl-1-pentene and the like.

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, and methylhydroquinone. t-butylhydroquinone, methquinone, p-benzoquinone, methyl-p-benzoquinone, t-butyl-p-benzoquinone, anthraquinone, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid , Dimethylxanthogen sulfide, diisopropylxanthogen disulfide, 2,4-diphenyl-4-methyl-1-pentene and the like.

The molecular weight adjusting agent may be used alone or in combination of two or more.

1-1-5. Method for Synthesizing Modified Polymer (A) The modified polymer (A) used in the present invention includes a compound represented by the above 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 above 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 modified polymer (A) has high solubility in a solvent, and the heat resistance, flatness, and adhesion of the composition are good, but more preferably 0.7 ≦ X ≦ 4.0. Yes, more preferably 1.0 ≦ X ≦ 3.0.

In the synthesis of the modified polymer (A), in the radical polymerization of the first stage, the polymerization heat is large because the monomers of the formulas (1) and (2) are copolymerized. When it is difficult to control the polymerization due to the heat of polymerization, 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.

It is preferable to use 80 parts by weight or more of the reaction solvent with respect to 100 parts by weight of the solute because the reaction proceeds smoothly. The reaction is carried out at 40 ° C. to 200 ° C. for 0.2 to 20 hours.

The reaction sequence of the raw materials is as follows: 2 after obtaining a polyfunctional acid anhydride copolymer by radical polymerization of the monomer (a) and the other monomer (b) in the presence of a solvent and an azo initiator. A compound having one or more radicals is added and heated.

In the case of the radical polymerization, the reaction temperature of 40 ° C. to 120 ° C. is preferable, and the 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 the mixture is reacted at 100 to 200 ° C. for 0.1 to 6 hours.

In the modified polymer (A) synthesized in this way, even if 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 and is defective. It is possible to form a uniform thin film without a solvent. On the other hand, when a compound having two or more hydroxyl groups is simply added to the system after polymerization of the radical copolymer without thermal reaction, even if the solution is soluble in a solvent and becomes a transparent solution, a thin film is formed. In many cases, after the solvent evaporates, a compound having two or more radicals is precipitated due to poor compatibility, and a uniform thin film cannot be formed. Therefore, by inducing the polybranched polyester, it is possible not only to improve the heat resistance but also to form a defect-free thin film.

The weight average molecular weight of the obtained modified polymer is preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000. Within these ranges, the coatability and flatness are good.

The weight average molecular weight in the present specification is a polystyrene-equivalent value obtained by the GPC method (column temperature: 35 ° C., flow rate: 1 ml / min). Polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 of Agilent Technologies, Ltd.) was used as the standard polystyrene, and PLgel MIXED-D (Agilent Technologies, Ltd.) was used for the column. It can be measured using THF as the mobile phase. The weight average molecular weight of the commercially available product in the present specification is a value listed in the catalog.

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 kind or two or more kinds.

1-2-1 Compound having two or more epoxy groups (B)
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, and phenol novolac type epoxy compound. , Cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound, aliphatic polyglycidyl ether compound, cyclic aliphatic epoxy compound, polymer of monomer having epoxy group, common weight of monomer having epoxy group and other monomer It is an epoxy compound having a coalescence and a siloxane binding site. The compound (B) having two or more epoxy groups is preferably a compound having an aromatic ring.

Specific examples of commercially available bisphenol A type epoxy compounds are jER 828, 1004, 1009 (all trade names, Mitsubishi Chemical Co., Ltd.); specific examples of commercially available bisphenol F type epoxy compounds are jER 806, 4005P. (All are trade names, Mitsubishi Chemical Co., Ltd.); Specific examples of commercially available glycidyl ether type epoxy compounds are TECHMORE VG3101L (trade name, Printec Co., Ltd.), EHPE3150 (trade name, Daicel Co., Ltd.), EPPN. -501H, 502H (trade name, Nippon Kayaku Co., Ltd.), and jER 1032H60 (trade name, Mitsubishi Chemical Co., Ltd.); specific examples of commercially available glycidyl ester type epoxy compounds are Denacol EX-721 (trade name). (Product name, Nagase Chemtex Co., Ltd.), and diglycidyl 1,2-cyclohexanedicarboxylate (trade name, manufactured by Tokyo Kasei Kogyo Co., Ltd.); Specific examples of commercially available biphenyl type epoxy compounds are jER YX4000, YX4000H, YL6121H (trade name, Mitsubishi Chemical Co., Ltd.) and NC-3000, NC-3000-L, NC-3000-H, NC-3100 (trade name, Nippon Kayaku Co., Ltd.); Specific examples of commercially available type epoxy compounds are EPPN-201 (trade name, Nippon Kayaku Co., Ltd.), jER 152, 154 (both trade names, Mitsubishi Chemical Co., Ltd.) and the like; cresol novolac type epoxy compounds. Specific examples of commercially available products of EOCN-102S, 103S, 104S, 1020 (all trade names, Nippon Kayaku Co., Ltd.) and the like; specific examples of commercially available products of bisphenol A novolak type epoxy compounds are jER 157S65, 157S70 (both trade names, Mitsubishi Chemical Co., Ltd.); specific examples of commercially available cyclic aliphatic epoxy compounds are seroxide 2021P, 3000 (both trade names, Daicel Co., Ltd.); Specific examples of commercially available epoxy compounds having 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane (trade name, Jerest Incorporated), TSL9906 (trade name, Momentive. Performance Materials LLC), COATOSIL MP-200 (trade name, Momentive Performance Materials LLC), Con Poselan SQ506 (trade name, Arakawa Chemical Co., Ltd.), ES-1023 (trade name, Shin-Etsu Chemical Co., Ltd.).

In addition, 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 Co., Ltd.) is 2,2-bis (hydroxymethyl) -1. It is a 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of −butanol; seroxide 2021P (trade name, Daicel Co., Ltd.) is 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxy. Rate; Celoxide 3000 (trade name, Daicel Co., Ltd.) is 1-methyl-4- (2-methyloxylanyl) -7-oxabicyclo [4.1.0] heptan; COATOSIL MP-200 (COATOSIL MP-200). (Product 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 of the epoxy 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 substrate 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 with the multi-branched polyester and the epoxy curing agent.

1-3. Other Ingredients Various additives can be added to the thermosetting composition of the present invention in order to improve coating uniformity, adhesiveness, transparency, flatness, and chemical resistance. Additives include epoxy hardeners, solvents, anionic, cationic, nonionic, fluorine-based or silicon-based leveling agents / surfactants, adhesion improvers such as silane coupling agents, hindered phenols, and hindered amines. Antioxidants such as system, phosphorus and sulfur compounds, molecular weight modifiers, and epoxy curing agents are mainly mentioned.

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 (trade name, Kyoeisha Chemical Co., Ltd.), Disperbak-161, Disperbake-162, Disperbake-163, Disperbake-164, Disperbake-166, Disperbake-170, Disperbake-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 product names, Big Chemie Japan Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF-50-100CS (All product names, Shin-Etsu Chemical Industry Co., Ltd.), Surflon-S611 (Products) Name, AGC Seimi Chemical Co., Ltd.), Futagent 222F, Futagent 208G, Futagent 251 and Futagent 710FL, Futagent 710FM, Futagent 710FS, Futagent 601AD, Futagent 650A, FTX-218, (all product names) , Neos Co., Ltd.), 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, Mega Fuck F-554, Mega Fuck F-555, Mega Fuck F-556, Mega Fuck F-558, Mega Fuck F-559, Mega Fuck R-94, Mega Fuck RS-75, Mega Fuck RS- 72-K, Megafuck RS-76-NS, Megafuck DS-21 (all trade names, DIC Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (trade name, Ebonic Japan Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylsulfonate, diglycerin Tetrax (fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfon Acidate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxy Ethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxy Examples thereof include ethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonates, and alkyldiphenyl ether disulfonates. It is preferable to use at least one selected from these.

Among these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surfron-S611, Footergent 710FL, Footergent 710FM, Footergent 710FS, Footergent 601AD, Footergent 650A, Megafuck F-477, Megafuck F-556, Megafuck F-559, Megafuck RS-72-K, Megafuck DS-21, TEGO Twin 4000, Fluoroalkylbenzene Sulfonate, Fluoroalkyl Carboxate, At least one selected from fluoroalkylpolyoxyethylene ether, fluoroalkylsulfonate, fluoroalkyltrimethylammonium salt, and fluoroalkylaminosulfonate enhances the coating uniformity of the thermosetting composition. Therefore, it is preferable.

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

1-3-2. 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 cured film to be formed 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, Sila Ace S510, JNC Co., Ltd.), 2- (3). , 4-Epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name, Silaace S530, JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane (for example, trade name, Silaace S810, JNC Co., Ltd.), 3-glycidyloxypropyl Silane-based coupling agents such as a copolymer of trimethoxysilane (for example, trade name, CoatOSil MP200, Momentive Performance Materials Japan LLC), aluminum-based coupling agents such as acetalkoxyaluminum diisopropylate, and aluminum-based coupling agents. Examples thereof include titanate-based coupling agents such as tetraisopropylbis (dioctylphosphite) titanate.

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

When 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 a high temperature.

Antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added to the thermosetting composition of the present invention. Of these, the hindered phenol type is preferable 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 trade names, ADEKA Corporation). Of these, Irganox 1010 and ADK STAB AO-60 are more preferable.

The antioxidant is used by adding 0.1 to 10 parts by weight based on 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. Examples of the epoxy curing agent include acid anhydride-based curing agents, amine-based curing agents, phenol-based curing agents, imidazole-based curing agents, catalytic curing agents, and sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts. Although there are heat-sensitive acid generators and the like, an acid anhydride-based curing agent, an imidazole-based curing agent, or a combination thereof is preferable from the viewpoint of avoiding coloring of the cured film and heat resistance of the cured film.

Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimeric acid anhydride; Aromatic polyvalent carboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride, and styrene-maleic anhydride copolymers. Among these, trimellitic acid anhydride and hexahydrotrimellitic acid anhydride, which have a good balance between heat resistance and solubility in a solvent, are preferable.

Specific examples of the imidazole-based 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 trimeritate. Among these, 2-undecylimidazole, which has a good balance between curability and solubility in a solvent, is preferable.

When an epoxy curing agent is used, 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. Regarding the amount added when the epoxy curing agent is an acid anhydride-based curing agent, more specifically, the carboxylic acid anhydride group or the carboxyl group in the epoxy curing agent is 0.1 to 1.5 with respect to the epoxy group. It is preferable to add in a double equivalent amount. At this time, the carboxylic acid anhydride group is calculated as divalent. It is more preferable to add the carboxylic acid anhydride group or the carboxyl group in an equivalent amount of 0.15 to 0.8 times because the chemical resistance is further improved.

1-3-5. Ultraviolet absorber The thermosetting composition of the present invention may contain an ultraviolet absorber from the viewpoint of further improving the ability to prevent deterioration 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, 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-aggregation agent The composition of the present invention may contain an anti-aggregation agent from the viewpoint of blending the solid content with the solvent to prevent aggregation.

Specific examples of the anti-aggregation agent are Disperbak-145, Disperbake-161, Disperbake-162, Disperbake-163, Disperbake-164, Disperbake-182, Disperbake-184, Disperbake-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, Futergent 710FM, Futergent 710FS (trade name, Neos Co., Ltd.), Floren G-600, Floren G-700 (trade name, Kyoeisha Chemical Co., Ltd.).

The anti-aggregation agent 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 cross-linking agent The composition of the present invention may contain a thermal cross-linking agent from the viewpoint of further improving heat resistance, chemical resistance, in-plane uniformity, flexibility, flexibility, and elasticity.

Specific examples of the thermal cross-linking agent include Nicarac MW-30HM, Nicarac MW-100LM, Nicarac MX-270, Nicarac MX-280, Nicarac MX-290, Nicarac MW-390, and Nicarac MW-750LM. Sanwa Chemical Co., Ltd.).

The thermal cross-linking agent is used by adding 0.1 to 10 parts by weight based on 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, methyl 2-hydroxy-2-methylpropionate , 2-Hydroxy-2-methylpropionate ethyl, 2-methoxy-2-methylpropionate methyl, 2-ethoxy-2-methylpropionate ethyl, pyruvate methyl, pyruvate ethyl, pyruvate propyl, methyl acetoacetate, Ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, 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 them.

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

2. Cured film formed from a 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 desired properties, depending on the desired properties. Further, an epoxy curing agent, a solvent, a surfactant, an adhesion improver, an antioxidant, and other additives can be selectively added as necessary.

When the thermosetting composition prepared as described above (after being dissolved 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, for example, heating, a coating film is formed. Can be formed. The thermosetting composition can be applied to the surface of the substrate by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, or a slit coating method. Next, this coating film is tentatively fired on a hot plate, an oven, or the like. The pre-baking conditions vary depending on the type and blending 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, the main firing is performed to cure the coating film. The main firing conditions vary depending on the type and blending ratio of each component, but are usually 180 to 250 ° C., preferably 200 to 250 ° C., 30 to 90 minutes for an oven, and 5 to 30 minutes for a hot plate, and heat treatment is performed. As a result, a cured film can be obtained.

The cured film thus obtained is very difficult to form a three-dimensional network because 1) the modified polymer (A) reacts with the compound (B) having two or more epoxy groups when heated. It is tough and has excellent transparency, heat resistance, chemical resistance, flatness, and adhesion. Further, the light resistance, the spatter resistance, the scratch resistance, and the coating property are also 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 image sensor can be manufactured using this color filter. Further, the cured film of the present invention is effective when used as a transparent insulating film formed between the TFT and the transparent electrode or as a transparent insulating film formed between the transparent electrode and the alignment film, in addition to the protective film for the color filter. Is. Further, the cured film of the present invention is also effective when used as a protective film for an LED light emitter.

Next, the present invention will be specifically described with reference to Synthetic Examples, Examples and Comparative Examples, but the present invention is not limited to 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 with a stirrer, methyl 3-methoxypropionate (MMP), N-cyclohexylmaleimide, maleic anhydride, radical initiator V-65 (Wako Pure Chemical Industries, Ltd.) (Industrial), α-methylstyrene dimer was charged under the following weight 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 6.464g
Maleic anhydride 3.537g
V-65 0.100g
α-Methylstyrene dimer 0.050g

Then, the reaction solution was cooled to 25 ° C., 5.669 g of 4,4'-isopropyridenebis (2-phenoxyethanol) was added, and the mixture was stirred at 150 ° C. for 3 hours (second stage of synthesis).

The solution was cooled to room temperature to give a 30 wt% solution of the pale yellow clear 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 weight average molecular weight Mw of the obtained modified polymer (A1) was 14,000, and the polydispersity Mw / Mn was 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 is reacted at the temperature, time, and ratio (unit: g) shown in Table 1. Then, a solution of the modified polymers (A2) to (A10) was obtained.

[Comparative Synthesis Examples 1 and 2] Synthesis of Solutions of Polyesters (R1) and (R2) A general linear polyester having no branched structure and having no specific structure included in this claim is provided at the temperature shown in Table 1. The reaction was carried out over time and at a rate to obtain a solution of polyester (R1) and (R2). However, the reaction temperature was 150 ° C. for 3 hours.

The compounds used in the synthetic example and the comparative synthetic example, which are abbreviated in Table 1, are as follows.
CHMI: N-Cyclohexylmaleimide NPM: N-Phenylmaleimide IN: Inden MAH: Maleic anhydride ODPA: 4,4'-Oxydiphthalic anhydride BPDA: 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride V-65: 2,2'-azobis (2,4-dimethylvaleronitrile); manufactured by Wako Pure Chemical Industries, Ltd. αMSD: α-methylstyrene dimer bisA-2EOH: 4,4'-isopropyridenebis (2- Phenoxyethanol)

BPE-40, 60, 100: Nieuport BPE-40, Nieuport BPE-60, Nieuport BPE-100; manufactured by Sanyo Chemical Industries, Ltd .; diols having the following structures with hydroxyl values of 276, 228 and 167, respectively. Compound

HT: 1,2,6-Hexanetriol TMP: Trimethylolpropane PE: Pentaerythritol BD: 1,4-Butanediol MMP: Methyl 3-methoxypropionate

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

Using each of the obtained thermosetting compositions, the heat resistance, flattening rate, and substrate adhesion were evaluated by the methods described below. The evaluation results of the cured films of Examples 1 to 13 are summarized in Table 3. Further, as Comparative Examples 1 and 2, the heat resistance, flattening ratio, and substrate adhesion of the cured film formed by using the thermosetting composition containing a linear polyester having no branch 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 a hot plate at 80 ° C. for 2 minutes. Subsequently, post-baking (PB) was performed in an oven at 230 ° C. for 30 minutes to obtain a glass substrate with a cured film (this is referred to as the post-PB film thickness). The film thickness of the obtained glass substrate with a cured film was measured using a step / surface roughness / fine shape measuring device (trade name, P-17, KLA TENCOR Co., Ltd.) and used as the initial film thickness. Then, 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 is referred to as the EB1 post-film thickness). Further, a 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 EB2 post-film thickness). The residual film ratios 1 and 2 are calculated using the following formulas, and those with a residual film ratio of 99% or more between PB and EB1 are ○, those with a residual film ratio of less than 99% to 98% are Δ, and those with a residual film ratio of less than 98% are ×. And said. Further, those having a residual film ratio of 99% or more between PB and EB2 were evaluated as ◯, those having a residual film ratio of less than 99% to 98% were evaluated as Δ, and those having a residual film ratio of less than 98% were evaluated as x.

Remaining film ratio 1 (%) = (EB1 post-film thickness / PB post-thickness) × 100
Remaining film ratio 2 (%) = (EB2 post-film thickness / PB post-thickness) × 100

[Evaluation method of flatness]
Concavo-convex substrate (line 100 μm, space 50 μm, film thickness 1 μm) including a resist pattern whose surface step is measured in advance using a step / surface roughness / fine shape measuring device (trade name, P-17, KLA TENCOR Co., Ltd.) The resulting thermocurable composition was spin-coated on a substrate) at 650 rpm for 10 seconds and prebaked on a hot plate at 80 ° C. for 2 minutes. Subsequently, it was post-baked in an oven at 230 ° C. for 30 minutes to obtain a color filter substrate with a cured film having an average film thickness of 1.5 μm. Then, the surface step was measured with respect to the obtained color filter substrate with a cured film. From the maximum value of the surface step of the color filter substrate without the cured film and the color filter substrate with the cured film (hereinafter abbreviated as "maximum step"), the flattening rate was calculated using the following formula, and the results are shown in Table 3. rice field. As for the flatness result, 100 to 80% was evaluated as ⊚, 79 to 60% was evaluated as ◯, and less than 60% was evaluated as x.

Flattening rate (%) = ((maximum step of uneven substrate-maximum step of concave-convex 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 a hot plate at 80 ° C. for 2 minutes. Subsequently, it was post-baked in an oven at 230 ° C. for 30 minutes to obtain a glass substrate with a cured film. A cross-cut test (JIS K 5400, using 3M No. 361) was performed on both the obtained uneven substrate with a cured film and the glass substrate with a cured film produced in the same manner, and the following classifications 0 to 5 were performed. Classifications 0 to 1 were evaluated as ◯, categories 2 to 3 were evaluated as Δ, and categories 4 to 5 were evaluated as ×. The adhesion evaluation on the concave-convex substrate with the cured film was designated as "adhesion evaluation 1", and the adhesion evaluation on the glass substrate with the cured film was designated as "adhesion evaluation 2".

<Category 0> ... The edges of the cut are completely smooth, and there is no peeling in the eyes of any grid.
<Category 1> ... Small peeling of the coating film at the intersection of cuts. The cross-cut area is clearly not affected by more than 5%.
<Category 2> ... The coating film is peeled off along the edge of the cut and / or at the intersection. The cross-cut area is clearly affected by more than 5%, but not more than 15%.
<Category 3> ... The coating film has partially or completely peeled off along the edge of the cut, and / or various parts of the eyes have partially or completely peeled off. The cross-cut area is clearly affected by more than 15%, but not more than 35%.
<Category 4> ... The coating film has partially or completely peeled off along the edge of the cut, and / or some eyes have 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 a hot plate at 80 ° C. for 2 minutes. Subsequently, heat treatment was performed in an oven at 230 ° C. for 30 minutes to obtain a glass substrate with a cured film having a film thickness of 1.5 μm. In the obtained glass substrate with a cured film, the light transmittance of the cured film at 400 nm was measured with an ultraviolet-visible near-infrared spectrophotometer (trade name, V-670, JASCO Corporation). In this case, using only the glass substrate as a reference, the light transmittance of the cured film alone was calculated (in this case, interference due to multiple reflections is not considered). When the light transmittance was 98% or more, the transparency was evaluated as ◯, when the transmittance was less than 95%, the transparency was evaluated as ×, and the interval 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, in Comparative Examples 1 and 2, not all the characteristics could be satisfied.

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

Claims (6)

An acid anhydride derived from the monomer (a) of the copolymer which is a reaction product from the monomer (a) represented by the following formula (1) and the monomer (b) other than the (a). site, thermally ring-opened modified polymer with a compound having two or more hydroxyl groups (a), a compound having two or more epoxy groups (B) and a thermosetting composition containing a solvent (C) A thermosetting composition in which the compound having two or more hydroxyl groups is at least one selected from the compounds represented by the following formula (3-1) .

In the formula (1), hydrogen ^{R 1} and ^{R 2} are independently Ri alkyl or phenyl der 1 to 3 carbon atoms,
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 independently 1 It is an integer of ~ 20, and the hydrogen in the benzene ring may be independently substituted with an alkyl having 1-3 carbon atoms. The thermosetting composition according to claim 1, wherein the monomer (b) is at least one selected from the compound represented by the following formula (2) and indene.

In the formula (2), R ¹ and R ² are independently hydrogen, an alkyl or phenyl having 1 to 3 carbon atoms, and R ³ is a monovalent organic group. 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 the compounds represented by the following formulas (4) and (5).

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