TW201936772A - Thermosetting composition, cured film, and color filter including a modified polymer (A), a compound (B) having two or more epoxy groups, and a solvent (C) - Google Patents

Abstract

The present invention relates to a thermosetting composition which includes a modified polymer (A), a compound (B) having two or more epoxy groups, and a solvent (C),wherein the modified polymer (A) is formed by using a compound having two or more hydroxyl groups to thermally open the ring of an anhydride portion derived from a monomer (a) of a copolymer of a reaction product of the monomer (a) represented by the following formula (1) and a monomer (b) other than the monomer (a). In formula (1), R1 and R2 each independently represent a hydrogen, an alkyl group having 1-3 carbons or a phenyl group. The cured film formed from the thermosetting composition of the present invention satisfies various characteristics, such as thermal resistance, transparency, flatness, and substrate adhesion, and can be suitably used in electronic parts.

Description

Thermosetting composition, cured film, and color filter

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

The manufacturing steps of elements such as a liquid crystal display element include a step of forming an organic thin film having various functions. For example, a film formation / patterning / heat treatment step for a black matrix resist, a film formation / patterning / heat treatment step for a color filter resist, a film formation / patterning / heat treatment step for a color filter protective film, Indium tin oxide (ITO) conductive film formation step, ITO patterning photoresist film formation / patterning / wet etching / resist stripping step, ITO annealing step, orientation film Film formation / heat treatment / friction (polarized light exposure) steps, etc. In these various steps, the element may be exposed to various chemicals such as organic solvents, acids, and alkali solutions. In addition, when the electrodes are formed by sputtering, the surface may be locally exposed to high temperatures. Therefore, a surface protection 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 characteristics that can withstand various processes in the manufacturing steps as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to a base substrate such as glass, transparency, scratch resistance, coating properties, flatness, and the like are required. Lightfastness etc. In particular, as the required characteristics of the reliability required for a display element have been improved, reduction in heat resistance required for a display element member, specifically, reduction of outgassing during heat treatment has been valued. The reason is that when forming various organic thin films as described above, the cross-linking reaction / densification of the thin film due to heat treatment is always performed, so the element is also subjected to heat many times during the penetration step; therefore, a large amount of escape occurs if used. The protective film of the gas is affected by the escaping gas from the lower layer, and the formation of the upper layer is affected. As a result, the display quality and reliability are lowered.

Hitherto, 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). In addition, a protective film using a siloxane material, which is characterized by high heat resistance and transparency, has also been proposed (Patent Document 2 and Patent Document 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 Literature 4, Patent Literature 5, and Patent Literature 6).

However, in the protective film using polyimide material, in order to prepare a solution of polyimide or a polyimide precursor (polyamic acid), it is necessary to use N-methylpyrrolidone or γ-butyrolactone. The so-called polyfluorene imine solvent has the problem of dissolving the organic thin film of the substrate. Especially when it is used as a protective film for color filters, the said problem becomes a big problem. In addition, in polyfluorene imine, the charge transfer interaction (Charge Transfer (CT) interaction) causes the edge of the light absorption band to extend to the visible light region, so there is a problem of coloring. On the other hand, when a siloxane material (sol-gel material) is used, heat resistance and transparency are sufficient, but since the temperature required for the completion of the silane alcohol group reaction is also 300 ° C or higher, there is also a problem that causes the substrate The problem of deterioration of the organic thin film, or the problem of cracks (cracks) in the film due to the shrinkage during curing during thermal curing. In addition, there is a difficulty that the -Si-O-Si- bond of the siloxane material is easily hydrolyzed by the alkali solution. In addition, when a material of an epoxy resin and a melamine resin is used, although there is no problem in using a solvent or a heat treatment temperature, the heat resistance is insufficient, and a problem of yellowing also occurs. When an acrylic material or a polyester resin is used, the heat resistance of the acrylic site / polyester site as a basic skeleton is insufficient, and a problem of outgassing occurs.

According to the situation described above, a material is required in which high heat resistance and various other characteristics, especially adhesion, flatness, and transparency to the base substrate are coexisted. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open Sho 62-163016 [Patent Literature 2] Japanese Patent Laid-Open Sho 62-242918 [Patent Literature 3] Japanese Patent Laid-Open Hei 7-331178 [Patent Literature 4] Japanese Patent Laid-Open Sho 63- 131103 [Patent Document 5] Japanese Patent Laid-Open No. 8-50289 [Patent Document 6] Japanese Patent Laid-Open No. 2013-253263

[Problems to be Solved by the Invention]

A problem of the present invention is to provide a thermosetting composition that provides a cured film that satisfies heat resistance (low outgassing), adhesion, flatness, and transparency, and a cured film formed from the thermosetting composition. Furthermore, an electronic component having the cured film is provided. [Technical means to solve the problem]

The present inventors have made intensive studies in order to solve the problems, and as a result, have completed the present invention by using a thermosetting composition comprising: a monomer having an acid anhydride group; A copolymer obtained by copolymerizing monomers is a copolymer obtained by thermally reacting a compound having at least two or more hydroxyl groups, a compound having at least two or more epoxy groups, and a solvent capable of dissolving these compounds. The present invention includes the following configurations.

[1] A thermosetting composition comprising a modified polymer (A), a compound (B) having two or more epoxy groups, and a solvent (C), wherein the modified polymer (A) is used A compound having two or more hydroxyl groups will be derived from a monomer (as a copolymer derived from a reaction product of a monomer (a) and a monomer (b) other than the monomer (a) represented by the following formula (1): a) The acid anhydride is thermally ring-opened. In Formula (1), R ¹ and R ^{2 are} independently hydrogen, an alkyl group having 1 to 3 carbon atoms, or a phenyl group.

[2] The thermosetting composition according to the 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, an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ³ is a monovalent organic group.

[3] The thermosetting composition according to [1], wherein the compound having two or more hydroxyl groups is a compound selected from the group consisting of the following formulae (3-1) to (3-4) At least one of. 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 an integer of 1 to 20, Further, the hydrogen of the benzene ring may be independently substituted with an alkyl group having 1 to 3 carbon atoms.

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

[5] The thermosetting composition according to the item [1], wherein the compound (B) having two or more epoxy groups includes one selected from the group consisting of the following formulae (4) and (5) At least one of the compounds. In Formula (4), R ⁵ to R ^{8 are} independently hydrogen or an alkyl group 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 a cured film according to [6] as a transparent protective film. [Effect of the invention]

The thermosetting composition according to a preferred embodiment of the present invention is a material having particularly excellent heat resistance, and when used as a color filter protective film for a color liquid crystal display element, display quality can be improved. In particular, it is effectively used as a protective film for a color filter manufactured by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. It can also be used as a protective film and a transparent insulating film for various optical materials.

1. Thermosetting composition of the present invention The thermosetting composition of the present invention contains a modified polymer (A) obtained by thermally reacting a polyfunctional acid anhydride with a compound having two or more hydroxyl groups, The epoxy-based compound (B), and the thermosetting composition is characterized in that the compound (B) having two or more epoxy groups is 10 to 500 parts by weight based on 100 parts by weight of the modified polymer. Parts by weight.

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

Among other monomers (b), when a compound represented by formula (2) and a compound other than indene are used, from the viewpoint of heat resistance, it is preferable to use the entire monomer used in radical polymerization. An addition amount of 0 wt% to 40 wt%, and more preferably 0 wt% to 20 wt% is suitable.

In addition, in the synthesis of the modified polymer (A), at least a solvent is required. The solvent can be left as it is, and it can be made into a liquid or gel-like composition in consideration of handling properties. Alternatively, the solvent can be removed to form a solid composition in consideration of handling properties.

Compounds other than those described above may be included as long as the object of the present invention is not impaired. 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, as a material for obtaining a modified polymer (A), as the monomer (a), a formula (1) is included Compound. The other monomer (b) is preferably one or more compounds selected from the group consisting of a compound represented by formula (2) and indene. 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, and N-cyclohexylmaleimide. Imine, N-phenylmaleimide, N-benzylmaleimide. The compound represented by formula (2) and the monomer (b) other than indene may be included within a range that does not impair the characteristics of the present invention. Specific examples in this case include methacrylic acid, Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, methacrylic acid 2-phenoxyethyl ester, 2-phenylethyl methacrylate, isobornyl methacrylate, dicyclopentyl methacrylate, -2,2,2-trifluoroethyl methacrylate .

1-1-2. Compound having two or more hydroxyl groups In the present invention, as a material for obtaining a modified polymer (A), a compound having two or more hydroxyl groups is used. Preferable examples include: 1,4-bis (hydroxyethoxy) benzene, 1,3-bis (hydroxyethoxy) benzene, 4,4'-isopropylidenebis (2-phenoxyethanol), Bis [4- (2-hydroxyethoxy) phenyl] fluorene, 2,2 '-[(1,1'-biphenyl) -4,4'-diylbis (oxy)] diethanol. Examples of other compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,2-butanediol, and 1,3-butanediol. Diol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-5-pentanetriol, 1,3,5-pentanetriol, 2,3 1,4-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-3-hexanetriol, 1,2-5-hexanetriol 1,2,6-hexanetriol (compound of formula (3-2)), 1,2-heptanediol, 1,7-heptanediol, 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 9,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecane Diol, 1,12-dodecanediol, glycerol, 1,3,6-hexanetriol, trimethylolpropane (compound of formula (3-3)), tris (2-hydroxy isocyanurate) Ethyl) ester, pentaerythritol (compound of formula (3-4)), dipentaerythritol and compound represented by formula (3-1) below. In formula (3-1), R4 is a single bond, -CH2-, -C (CH3) 2-, -SO2-, or -O-, m and n are independently integers of 1 to 20, and the benzene ring Hydrogen may be independently substituted by an alkyl group having 1 to 3 carbon atoms.

The compounds listed here may be used in combination.

1-1-3. Solvents used in the synthesis of the modified polymer (A) As specific examples of solvents used in the synthesis of the modified polymer (A), ethyl acetate and acetic acid may be mentioned. Butyl, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxylate , 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, 2-methoxypropionate Propyl ester, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate , Ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, 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 Alcohol 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 Esters, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. The solvent may be one kind of these solvents or a mixture of two or more kinds of these solvents.

1-1-4. The molecular weight adjuster used in the synthesis of the modified polymer (A) In the synthesis of the modified polymer (A), a molecular weight adjuster may be further included to suppress the molecular weight from increasing and to exhibit Excellent storage stability. Examples of the molecular weight modifier include thiols, xanthonic acids, 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, and 2,5-di-tert-butylhydrogen. Quinone, hydroquinone, methylhydroquinone, tert-butylhydroquinone, methoquinone, p-benzoquinone, methyl-p-benzoquinone, t-butyl-p-benzoquinone, anthraquinone, n-hexyl mercaptan, n- Octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid, dimethyl xanthate sulfide, diisopropyl xanthate disulfide, 2,4-diphenyl 4-methyl-1-pentene and the like.

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

1-1-5. Method for synthesizing modified polymer (A) Regarding the modified polymer (A) used in the present invention, the compound represented by the formula (1) is selected from the group consisting of the compound represented by the formula (2). The represented compound and the monomer in the indene are polymerized in the solvent and in the presence of a thermal radical initiator. In this case, the number of moles of each functional group of the compound represented by the formula (1) and the number of moles of each functional group of the compound having two or more hydroxyl groups need to be set to the following ranges. Here, the functional group means an acid anhydride group in the compound represented by the formula (1), and a compound having two or more hydroxyl groups means a hydroxyl group. 0.5 ≦ X ≦ 5.0, X = (moles of acid anhydride group / moles of hydroxyl group)

Within the above range, the modified polymer (A) has high solubility in a solvent and good heat resistance, flatness, and adhesiveness of the composition, more preferably 0.7 ≦ X ≦ 4.0, and still more preferably 1.0 ≦ X ≦ 3.0.

In the synthesis of the modified polymer (A), the monomers of the formula (1) and the formula (2) are copolymerized in the first-stage radical polymerization, and therefore, the heat of polymerization is large. 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, and 2,4-diphenyl-4-methyl-1-pentene can be suitably used.

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

Regarding the reaction sequence of the raw materials, a polyfunctional acid anhydride copolymer is obtained by radically polymerizing a monomer (a) and other monomers (b) in a solvent in the presence of an azo initiator, and then adding two or more A hydroxy compound is heated.

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

In the modified polymer (A) synthesized as described above, even when a compound having two or more hydroxyl groups has low solubility in a copolymer or a used solvent, it can become uniform after thermal reaction. Transparent liquid to form a defect-free and uniform film. On the other hand, when a radical copolymer is simply polymerized without adding a compound having two or more hydroxyl groups to the system after the polymerization, even if it is a solution that is soluble and transparent to the solvent, After the solvent during film formation evaporates, a compound having two or more hydroxyl groups also precipitates due to poor compatibility, and a uniform film cannot be formed in many cases. Therefore, by deriving into a multi-branched polyester, not only the heat resistance can be improved, but also a defect-free film 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, coating property and flatness will be favorable.

The weight average molecular weight in this specification is a polystyrene conversion value calculated | required by Gel Permeation Chromatography (GPC) (column temperature: 35 degreeC, flow rate: 1 ml / min). Standard polystyrene uses polystyrene with a molecular weight of 645-132,900 (for example, the Agilent Technologies polystyrene calibration kit PL2010-0102), and the column is mixed with a PL gel (PLgel MIXED) -D (Agilent Technologies Co., Ltd.) can be measured using tetrahydrofuran (THF) as a mobile phase. The weight average molecular weight of the commercial item in this specification is a catalogue 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 kind, or two or more kinds.

1-2-1. Compound (B) having two or more epoxy groups Examples of the compound (B) having two or more epoxy groups are bisphenol A type epoxy compounds and bisphenol F type epoxy compounds Glycidyl ether type epoxy compound, glycidyl ester type epoxy compound, bisphenol type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound , Aliphatic polyglycidyl ether compounds, cyclic aliphatic epoxy compounds, polymers of monomers having epoxy groups, copolymers of monomers having epoxy groups and other monomers, and sites having a siloxane bond Epoxy compound. The compound (B) having two or more epoxy groups is preferably a compound having an aromatic ring.

Specific examples of commercially available products of bisphenol A type epoxy compounds are jER 828, jER 1004, and jER 1009 (all are trade names, Mitsubishi Chemical Corporation); specific examples of commercially available products of bisphenol F type epoxy compounds JER 806, jER 4005P (both are trade names, Mitsubishi Chemical Corporation); a specific example of a commercially available product of a glycidyl ether epoxy compound is TECHMORE VG3101L (trade name, Protec) Printec Co., Ltd.), EHPE3150 (trade name, Daicel Co., Ltd.), EPPN-501H, EPPN-502H (both trade names, Nippon Kayaku Co., Ltd.), and jER 1032H60 (trade names, Mitsubishi Chemical Corporation); A specific example of a commercially available product of a glycidyl ester type epoxy compound is Denacol EX-721 (trade name, Nagase chemteX Corporation), and 1 , 2-cyclohexanedicarboxylic acid diglycidyl ester (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.); specific examples of commercially available bisphenol-type epoxy compounds are jER YX4000, jER YX4000H, jER YL6121H (all For business Product name, Mitsubishi Chemical Corporation), and NC-3000, NC-3000-L, NC-3000-H, NC-3100 (both trade names, Nippon Kayaku Co., Ltd.); phenol novolac epoxy compounds Specific examples of commercially available products are EPPN-201 (trade name, Nippon Kayaku Co., Ltd.), jER 152, jER 154 (both trade names, Mitsubishi Chemical Corporation), etc .; cresol novolac epoxy Specific examples of commercially available compounds are EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all are trade names, Nippon Kayaku Co., Ltd.), etc .; bisphenol A novolac epoxy compounds are marketed Specific examples of the products sold are jER 157S65, jER 157S70 (both are trade names, Mitsubishi Chemical Corporation); specific examples of commercially available products of cyclic aliphatic epoxy compounds are Celloxide 2021P, Cello Cell oxide 3000 (both trade names, Daicel Co., Ltd.); specific examples of commercially available epoxy compounds having a siloxane bond site are 1,3-bis [2- ( 3,4-epoxycyclohexyl) ethyl] tetramethyldisilaxane (trade name, Czech Co., Ltd. (Gelest Incorporated), TSL9906 (trade name, Momentive Performance Materials, LLC), COATOSIL MP-200 (trade name, Momentive Performance Materials) Co., Ltd.), Conpoceran SQ506 (trade name, Arakawa Chemical Co., Ltd.), ES-1023 (trade name, Shin-Etsu Chemical Industry Co., Ltd.).

Furthermore, TECHMORE VG3101L (trade name, Printec Co., Ltd.) is 2- [4- (2,3-glycidoxy) phenyl] -2- [4 -[1,1-bis [4- (2,3-glycidoxy) phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3 -Glycidoxy) phenyl] -1- [4- [1- [4- (2,3-glycidoxy) phenyl] -1-methylethyl] phenyl] ethyl] A mixture of phenoxy] -2-propanol; EHPE3150 (trade name, Daicel Co., Ltd.) is a 1,2-epoxy group of 2,2-bis (hydroxymethyl) -1-butanol -4- (2-oxelanyl) cyclohexane adduct; Celloxide 2021P (trade name, Daicel Co., Ltd.) is 3 ', 4'-epoxy ring Hexylmethyl-3,4-epoxycyclohexane carboxylate; Celloxide 3000 (trade name, Daicel Co., Ltd.) is 1-methyl-4- (2-methyl Oxepropyl) -7-oxabicyclo [4.1.0] heptane; COATOSIL MP-200 (trade name, Momentive Performance Materials Co., Ltd.) -Glycidyloxypropyltrimethoxysilane Polymer of ingredients.

1-2-2. Ratio of compound (B) having two or more epoxy groups to modified polymer (A) Compound having two or more epoxy groups in the thermosetting composition of the present invention The ratio of the total amount of (B) to 100 parts by weight of the modified polymer (A) 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 the above 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 a range of 50 parts by weight to 300 parts by weight, but the total amount is determined by adjusting the molar ratio to the multi-branched polyester and epoxy hardener. .

1-3. Other components Various additives can be added to the thermosetting composition of the present invention to improve coating uniformity, adhesiveness, transparency, flatness, and chemical resistance. Examples of additives include epoxy hardeners, solvents, anionic, cationic, non-ionic, fluorine or silicon leveling agents / surfactants, adhesion improvers such as silane coupling agents, hindered phenols, Hindered amine-based, phosphorus-based, sulfur-based compounds and other antioxidants, molecular weight regulators.

1-3-1. Surfactant In the thermosetting composition of the present invention, a surfactant may be added to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 (all are trade names, total Rongshe Chemical Co., Ltd.), Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk- 164, Disperbyk-166, Disperbyk-170, Disperbyk-180, Disperbyk-181, Disperbyk Disperbyk-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (all products) Name, BYK Chemie Japan Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF-50-100CS (the above are all trade names, Shin-Etsu Chemical Industry Co., Ltd.), Surflon S611 (trade name, AGC Seimi Chemical Co., Ltd.), Ftergent 222F, Ftergent 208 G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, FTX-218 (all are Trade name, Neos Co., Ltd.), Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F-477, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac F-558, Megafac F-559, Megafac R-94, Megafac RS-75, Mega Megafac RS-72-K, Megafac RS-76-NS, Megafac DS-21 (both trade names, DIC Corporation), TEGO Twin) 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, Di TEGO Glide 450, TEGO Rad 2200N (both trade names, Evonik Japan Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate , Fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt , Fluoroalkylsulfamates, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene ole alkenyl ether, poly Oxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene lauryl Amine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, poly Oxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl , Alkylbenzene sulfonate, and alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these surfactants.

Among these surfactants, if selected from BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surflon S611, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac F-559, Megafac RS-72-K, Megafac DS-21, TEGO Twin 4000, fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene At least one of an ether, a fluoroalkylsulfonate, a fluoroalkyltrimethylammonium salt, and a fluoroalkylsulfamate is preferred because the uniformity of coating of the thermosetting composition is improved.

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

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

As such a coupling agent, for example, a silane-based, aluminum-based, or titanate-based coupling agent can be used. Specific examples include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxy Silane (for example, trade name, Sila-Ace S510, JNC Corporation), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name Name, Sila-Ace S530, JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane (for example, trade name, Sila-Ace S810, Czech Republic Cosmos (JNC) Co., Ltd., Copolymer of 3-glycidyloxypropyltrimethoxysilane (for example, trade name, CoatOSil MP-200, Momentive Performance Materials Japan ) Co., Ltd.) Silane-based coupling agents, aluminum-based coupling agents such as aluminum alkoxydiisopropoxide, and titanates such as tetraisopropylbis (dioctylphosphite) titanate Coupling agent.

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

In terms of improving the adhesion between the formed cured film and the substrate, the content of the coupling agent is preferably 0.01% by weight or more and 10% by weight or less based on the total amount of the thermosetting composition.

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.

To the thermosetting composition of the present invention, antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added. Among them, from the viewpoint of weather resistance, a hindered phenol type is preferred. Specific examples include: Irganox 1010, Irganox 1010FF, Irganox 1035, Irganox 1035FF, and Yilu Jia Irganox 1076, Irganox 1076FD, Irganox 1098, Irganox 1135, Irganox 1330, Yilujia Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Irganox 245FF, Yilu Irganox 259, Irganox 3114, Irganox 565, Irganox 565DD (all trade names, shares of BASF Japan) Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB (ADK STAB) AO-60, ADK STAB AO-80 (both trade names, ADEKA) Co., Ltd. . Among them, Irganox 1010 and ADK STAB AO-60 are more preferred.

An antioxidant is used in an amount of 0.1 to 10 parts by weight based on the total amount of the thermosetting composition.

1-3-4. Epoxy hardener In order to improve flatness and chemical resistance, the composition of the present invention may further contain an epoxy hardener. As the epoxy hardener, there are heat-sensitive acids such as acid anhydride-based hardeners, amine-based hardeners, phenol-based hardeners, imidazole-based hardeners, catalyst-based hardeners, and sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts. The acid generator and the like are preferably an acid anhydride-based hardener or an imidazole-based hardener or a combination of an acid anhydride-based hardener and an imidazole-based hardener from the viewpoint of avoiding the coloration of the cured film and the heat resistance of the cured film.

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

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

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. The amount added when the epoxy hardener is an acid anhydride-based hardener, more specifically, it is preferred that the carboxylic acid anhydride group or carboxyl group in the epoxy hardener is 0.1 to 1.5 times equivalent to the epoxy group. Way to add. At this time, the carboxylic acid anhydride group is calculated as a divalent. When a carboxylic anhydride group or a carboxyl group is added so that it may become 0.15-times equivalent to 0.8-times equivalent, since chemical resistance will improve further, it is more preferable.

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

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

0.01 to 10 parts by weight of an ultraviolet absorber is added to the total amount of the thermosetting composition and used.

1-3-6. Anti-agglomerating agent The composition of the present invention may contain an anti-agglomerating agent from the viewpoint of preventing the solid component from being fused with the solvent and preventing aggregation.

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

0.01 to 10 parts by weight of an anti-agglomerating agent is added to the total amount of the thermosetting composition and used.

1-3-7. Thermal crosslinking agent From the viewpoint of further improving heat resistance, chemical resistance, in-plane uniformity, flexibility, flexibility, and elasticity, the composition of the present invention may contain thermal crosslinking Agent.

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

0.1 to 10 parts by weight of a thermal crosslinking agent is added to the total amount of the composition and used.

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 are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, and ethyl acetate. Methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxybutyl acetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy- Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate Ester, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, 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 ethyl Ester, 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 kind of these solvents or a mixture of two or more kinds of these solvents.

1-5. Storage of thermosetting composition When the thermosetting composition of the present invention is stored in a range of -30 ° C to 25 ° C, the stability of the composition over time is improved. When the storage temperature is -20 ° C to 10 ° C, the precipitates are not present, which is more preferable.

2. A cured film formed from a thermosetting composition The thermosetting composition of the present invention is obtained by mixing a modified polymer (A) and a compound (B) having two or more epoxy groups in accordance with a target. Characteristics, and optionally add epoxy hardener, solvent, surfactant, adhesion improver, antioxidant and other additives.

A coating film can be formed by applying the thermosetting composition prepared in the above manner (in the case of a solvent-free solid state, after dissolving in a solvent) to the surface of a substrate and removing the solvent by, for example, heating. . The coating of the thermosetting composition on the substrate surface can be formed by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, and a slit coating method. Then, the coating film is temporarily fired using a hot plate, an oven, or the like. The temporary scorching conditions vary depending on the type of each component and the blending ratio. Generally, it is 5 minutes to 15 minutes when using an oven at 70 ° C to 150 ° C, and 1 minute to 5 minutes if using a hot plate. Thereafter, in order to harden the coating film, it was formally fired. The actual firing conditions vary depending on the type and blending ratio of each component, usually at 180 ° C to 250 ° C, preferably 200 ° C to 250 ° C, 30 minutes to 90 minutes if using an oven, and 5 minutes if using a hot plate. From minutes to 30 minutes, a cured film can be obtained by performing a heat treatment.

When the hardened film obtained in the above manner is heated, 1) the modified polymer (A) reacts with the compound (B) having two or more epoxy groups to form a three-dimensional network, so it is very tough, transparent, Excellent heat resistance, chemical resistance, flatness, and adhesion. In addition, for the same reason, excellent light resistance, sputtering resistance, scratch resistance, and coating properties are also expected. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and the color filter can be used to produce a liquid crystal display element or a solid-state imaging element. In addition, in addition to the protective film for a color filter, if the cured film of the present invention is used as a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode, or a transparent insulating film formed between a transparent electrode and an alignment film, A transparent insulating film is also effective. Furthermore, the cured film of the present invention is effective even when used as a protective film for a light emitting diode (Light Emitting Diode, LED) light emitting body. [Example]

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

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

[Synthesis Example 1] Synthesis of a modified polymer (A1) solution In a four-necked flask equipped with a stirrer, methyl 3-methoxypropionate (MMP) and N-cyclohexyl maleamidine were charged at the following weights. Imine, maleic anhydride, free radical initiator V-65 (manufactured by Wako Pure Chemical Industries), α-methylstyrene dimer, heated and stirred at 80 ° C for 2 hours under a dry nitrogen stream to obtain free radicals Copolymer (first stage of synthesis). MMP 23.333 g N-cyclohexylmaleimide 6.464 g maleic anhydride 3.537 g V-65 0.100 g 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 (second stage of synthesis).

The solution was cooled to room temperature to obtain a 30% by weight solution of the light 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 weight-average molecular weight Mw of the obtained modified polymer (A1) was 14,000, and the polydispersity Mw / Mn was 3.8.

[Synthesis Example 2 to Synthesis Example 10] Synthesis of the solution of the modified polymer (A2) to the modified polymer (A10) According to the method of Synthesis Example 1, the temperature, time, and ratio (unit: g) shown in Table 1 were used. ) The components are reacted to obtain a solution of the modified polymer (A2) to the modified polymer (A10).

[Comparative Synthesis Example 1 to Comparative Synthesis Example 2] The solution of polyester (R1) and polyester (R2) was synthesized at a temperature, time, and ratio shown in Table 1 so that it had no branch structure and did not have the content contained in this technical solution. By reacting the usual linear polyester with a specific structure, a solution of polyester (R1) and polyester (R2) is obtained. The reaction temperature was 150 ° C. for 3 hours.

Table 1 Unit of loading: grams

The compounds used in the synthesis examples and comparative synthesis examples described in Table 1 by abbreviations are as follows. CHMI: N-cyclohexyl maleimide NPM: N-phenyl maleimide 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, BPE-60, BPE-100: Newpol BPE-40, Newpol BPE-60, Newpol BPE-100; manufactured by Sanyo Chemical Industry Co., Ltd .; It is a diol having the following structure and a compound having a hydroxyl value of 276, 228, and 167, respectively

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, and a difunctional ring were used in the proportions (parts by weight) shown in Table 2. YX4000H for oxygen compounds, trimellitic anhydride (TMA) as hardener, S510 as silane coupling agent, ADK STAB AO-60 as antioxidant, F-556 as surfactant and as dilution The solvent, propylene glycol monomethyl ether acetate (PGMEA), was mixed and dissolved, and filtered through a membrane filter (pore size 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, the components were mixed and dissolved in the proportions (parts by weight) shown in Table 2 to obtain a thermosetting composition.

Table 2 Unit: parts by weight (except surfactants)

Each of the obtained thermosetting compositions was used to evaluate heat resistance, flatness ratio, and substrate adhesion by the methods described below. The evaluation results of the cured films of Examples 1 to 13 are summarized in Table 3. In addition, regarding Comparative Example 1 and Comparative Example 2, the heat resistance, flattening rate, and substrate adhesion of a cured film formed using a conventional thermosetting composition containing a linear polyester having no branched structure were evaluated. The evaluation results are collectively 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. Next, post-bake (Post Bake, PB) at 230 ° C. for 30 minutes in an oven to obtain a glass substrate with a cured film (this film thickness is set to PB). 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 set It is the initial film thickness. Thereafter, the glass substrate with a cured film was post-baked at 230 ° C. for 60 minutes in an oven, and the film thickness was measured in the same manner (this is set to the film thickness after EB1). In addition, the glass substrate with a cured film after PB was separately post-baked at 250 ° C. for 60 minutes, and the film thickness was similarly measured (this is set to the film thickness after EB2). Residual film rate 1 and residual film rate 2 were calculated using the following equations. Those with a residual film rate between PB-EB1 of 99% or more were set to ○, those with less than 99% to 98% were set to △, and less than 98%. Or x. In addition, those having a residual film rate between PB-EB2 of 99% or more were designated as ○, those with less than 99% to 98% were designated as Δ, and those with less than 98% were designated as ×. Residual film rate 1 (%) = (film thickness after EB1 / film thickness after PB) x 100 Residual film rate 2 (%) = (film thickness after EB2 / film thickness after PB) x 100

[Evaluation method of flatness] A step including surface resist was measured using a step / surface roughness / fine shape measuring device (trade name, P-17, KLA TENCOR Co., Ltd.) in advance. The obtained thermosetting composition was spin-coated on a patterned uneven substrate (pattern substrate with a line of 100 μm, a space of 50 μm, and a film thickness of 1 μm) at 650 rpm for 10 seconds, and pre-baked on a hot plate at 80 ° C. 2 minutes. Then, it baked at 230 degreeC in the oven for 30 minutes, and obtained the color filter substrate with a cured film with an average film thickness of a protective film of 1.5 micrometers. Then, the obtained color filter substrate with a cured film was measured for a surface level difference. The flattening ratio is calculated from the maximum value of the surface step difference (hereinafter abbreviated as "maximum step difference") of the color filter substrate without a cured film and the color filter substrate with a cured film using the following calculation formula. The results are shown in Table 3. As for the results of flatness, 100% to 80% were evaluated as ◎, 79% to 60% were evaluated as ○, and less than 60% were evaluated as ×. Flattening rate (%) = ((maximum step of uneven substrate-maximum step of uneven substrate with cured film) / maximum step of uneven substrate) × 100

[Evaluation method of adhesion] The obtained thermosetting composition was spin-coated on an uneven substrate (line: 100 μm, space: 50 μm, film thickness: 1 μm) at 650 rpm for 10 seconds, at 80 ° C. Pre-bake on hot plate for 2 minutes. Then, it baked at 230 degreeC in the oven for 30 minutes, and obtained the uneven | corrugated board | substrate with a cured film. A cross-cut test (Japanese Industrial Standards (JIS) K 5400 was performed on both the obtained uneven substrate with a cured film and a glass substrate with a cured film produced in the same manner, and a peeling tape was used: 3M Manufacturing No. 361) was evaluated based on the following classifications 0 to 5, classifications 0 to 1 were ○, classifications 2 to 3 were △, and classifications 4 to 5 were ×. The adhesiveness evaluation of the uneven | corrugated substrate with a cured film was made into "adhesiveness evaluation 1", and the adhesiveness evaluation of the glass substrate with a cured film was made into "adhesiveness evaluation 2". <Class 0> ¼ The cut edges are completely smooth, and there is no flaking in the grid of any grid. <Class 1> Small peeling of the coating film at the intersection of ¼ cutting. In the cross-cut section, the affected section does not clearly exceed 5%. <Class 2> ¼ The coating film peels off along the edges of the cut and / or at the intersection. In the cross-cut section, the affected section clearly exceeds 5% but does not exceed 15%. <Class 3> ¼ The coating film has large or partial peeling along the edge of the cut, and / or many parts of the grid have peeled off partially or entirely. In the cross-cut section, the affected section clearly exceeds 15% but does not exceed 35%. <Class 4> ¼ The coating film has large or partial peeling along the edge of the cut, and / or multiple or multiple grids have peeled off partially or entirely. In the cross-cut section, the affected section does not clearly exceed 35%. <Class 5> Even if it is a class 4, it is not possible to classify any of the degrees of peeling.

[Evaluation method of transparency] 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. Then, it heat-processed in the oven at 230 degreeC for 30 minutes, and obtained the glass substrate with a cured film with a film thickness of 1.5 micrometers. With respect to the obtained glass substrate with a cured film, an ultraviolet-visible near-infrared spectrophotometer (trade name: V-670, Japan Spectroscopy Corporation) was used to measure the transmittance of the cured film at 400 nm. In this case, only the glass substrate is used as a reference, and the light transmittance of the cured film monomer is calculated (in this case, interference caused by multiple reflections is not considered). A case where the light transmittance was 98% or more was evaluated as transparency ○, and a case where the light transmittance was less than 95% was evaluated as transparency ×, and the interval was evaluated as Δ.

It is clear from the results shown in Table 3 that the thermosetting compositions of Examples 1 to 13 satisfy heat resistance, flatness, and adhesion. On the other hand, in Comparative Example 1 and Comparative Example 2, all characteristics were not satisfied. table 3 [Industrial availability]

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

no

no.

Claims (7)

A thermosetting composition comprising a modified polymer (A), a compound (B) having two or more epoxy groups, and a solvent (C), wherein the modified polymer (A) is The use of a compound having two or more hydroxyl groups will be derived from a copolymer derived from a monomer (a) represented by the following formula (1) and a reaction product of a monomer (b) other than the monomer (a). The monomer (a) is formed by thermally ring-opening an acid anhydride site; In Formula (1), R ¹ and R ^{2 are} independently hydrogen, an alkyl group having 1 to 3 carbon atoms, or a phenyl group. The thermosetting composition according to item 1 of the scope of patent application, 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, an alkyl group having 1 to 3 carbon atoms or a phenyl group, 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 selected from the compounds represented by the following formulae (3-1) to (3-4) At least one of: 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 an integer of 1 to 20, Further, the hydrogen of the benzene ring may be independently substituted with an alkyl group having 1 to 3 carbon atoms. The thermosetting composition according to item 1 of the scope of patent application, 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 includes a compound selected from the following formulae (4) and (5) At least one of: In Formula (4), R ⁵ to R ^{8 are} independently hydrogen or an alkyl group having 1 to 5 carbon atoms. A cured film formed from the thermosetting composition according to any one of claims 1 to 5 in the scope of patent application. A color filter, characterized in that it has a hardened film as described in item 6 of the patent application scope as a transparent protective film.