TWI774872B - Thermosetting composition, cured film and color filter - Google Patents

Abstract

The present invention relates to 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 A monomer derived from a copolymer which is a copolymer derived from a reaction product of a monomer (a) represented by the following formula (1) and a monomer (b) other than the monomer (a) using a compound having two or more hydroxyl groups The acid anhydride site of (a) is thermally ring-opened. The cured film formed from the thermosetting composition of the present invention highly satisfies the properties of heat resistance, transparency, flatness, and substrate adhesion, and can be suitably used for electronic components.

Description

Thermosetting composition, cured film, and color filter

The present invention relates to an insulating material that can be used for forming electronic parts, passivation films, buffer coatings, interlayer insulating films, planarizing films, interlayer insulating films in liquid crystal display elements, and color filters in semiconductor devices. A thermosetting composition such as a protective film for filter), a transparent film formed from the thermosetting composition, and an electronic component having the film.

In the manufacturing process of elements, such as a liquid crystal display element, the process of forming the organic thin film which has various functions is included. For example, the film formation/patterning/heat treatment steps of black matrix resists, the film formation/patterning/heat treatment steps of color filter resists, the film formation/patterning/heat treatment steps of color filter protective films, Film formation steps of indium tin oxide (Indium Tin Oxide, ITO) conductive film, photoresist film formation/patterning/wet etching/resist stripping steps for ITO patterning, ITO annealing step, alignment film Film formation/heat treatment/rubbing (polarized light exposure) steps, etc. In these various steps, the element may be exposed to various chemicals such as organic solvents, acids, and alkaline solutions, and when electrodes are formed by sputtering, the surface may be partially exposed to high temperatures. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and deterioration of the surfaces of various elements. These protective films are required to have various properties capable of withstanding various treatments in the manufacturing steps as described above. Specifically, heat resistance, chemical resistance such as solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to base substrates such as glass, transparency, scratch resistance, coatability, flatness, Lightfastness, etc. In particular, as the required characteristics of the reliability required for the display element increase, the heat resistance required for the display element member, specifically, the reduction of outgassing during heat treatment has been paid attention to. The reason for this is that, when forming various organic thin films as described above, the cross-linking reaction/densification of the thin film caused by the heat treatment is always carried out, so that the penetration step also applies heat to the element many times; For the protective film of the gas, the formation of the thin film of the upper layer is affected by the outgassing gas from the lower layer, and as a result, the display quality and reliability are lowered.

Heretofore, 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). Moreover, the protective film using a siloxane material which is characterized by high heat resistance and transparency is also proposed (patent document 2, patent document 3). Alternatively, protective films using epoxy resins and melamine resins, or protective films using acrylic resins or polyester resins have been proposed (Patent Document 4, Patent Document 5, and Patent Document 6).

However, in the protective film using polyimide material, in order to prepare polyimide or polyimide precursor (polyimide) solution, it is necessary to use N-methylpyrrolidone or γ-butyrolactone with strong The so-called polyimide solvent with high solvency has the problem of dissolving the organic thin film of the substrate. In particular, when it is used as a protective film for a color filter, the above-mentioned problem becomes a big problem. In addition, in polyimide, since the edge of the light absorption band extends to the visible light region by charge transfer interaction (charge transfer (Charge Transfer, CT) interaction), there is also a problem of coloration. 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 reaction of the silanol group is also 300°C or higher, there is also a possibility that the The problem of deterioration of the organic thin film or the problem of cracking (cracking) in the thin film due to curing shrinkage during thermal curing. In addition, there is also a difficulty that the -Si-O-Si- bond of the siloxane material is easily hydrolyzed by an alkaline solution. In addition, in the case of using the materials of epoxy resin and melamine resin, there is no problem in the use of a solvent or heat treatment temperature, but the heat resistance is not sufficient, and the problem of yellowing occurs. When an acrylic material or a polyester resin is used, the heat resistance of the acrylic part/polyester part as the basic skeleton is not sufficient, and the problem of outgassing arises.

In view of the above-mentioned circumstances, there has been a demand for a material that has high heat resistance and other properties, in particular, adhesion to a base substrate, flatness, and transparency. [Prior Art Document] [Patent Document]

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

[The problem to be solved by the invention]

An object of the present invention is to provide a thermosetting composition that provides a cured film satisfying heat resistance (low outgassing properties), adhesiveness, flatness, and transparency, and a cured film formed from the thermosetting composition, Furthermore, the electronic component provided with the said cured film is provided. [Technical means to solve the problem]

The inventors of the present invention have made diligent studies in order to solve the above-mentioned problems, and as a result, they have completed the present invention by using a thermosetting composition comprising: a monomer having an acid anhydride group and other A copolymer obtained by copolymerizing a monomer and a compound having at least two or more hydroxyl groups are thermally reacted, a compound having at least two or more epoxy groups, and a solvent capable of dissolving these compounds. The present invention includes the following constitutions.

在式（1）中，R¹ 及R² 獨立地為氫、碳數1～3的烷基或苯基。[1] A thermosetting composition comprising a modified polymer (A), a compound (B) having two or more epoxy groups, and a solvent (C), the modified polymer (A) using The compound having two or more hydroxyl groups will be derived from the monomer ( a) is formed by thermal ring opening of the 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.

在式（2）中，R¹ 及R² 獨立地為氫、碳數1～3的烷基或苯基，R³ 為一價有機基。[2] The thermosetting composition according to the item [1], wherein the monomer (b) is at least one selected from the group consisting of a compound represented by the following formula (2) and an indene.

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

在式（3-1）中，R⁴ 為單鍵、-CH₂ -、-C(CH₃ )₂ -、-SO₂ -或-O-，m及n獨立地為1～20的整數，而且，苯環的氫可獨立地經碳數1～3的烷基取代。[3] The thermosetting composition according to the item [1], wherein the compound having two or more hydroxyl groups is a compound selected from the group consisting of compounds represented by the following formulae (3-1) to (3-4) at least one of them.

In formula (3-1), R ⁴ is a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ - or -O-, m and n are independently an integer of 1 to 20, Also, 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 the item [1], wherein the compound (B) having two or more epoxy groups is a compound having an aromatic ring.

在式（4）中，R⁵ ～R⁸ 獨立地為氫或碳數1～5的烷基。[5] The thermosetting composition according to the item [1], wherein the compound (B) having two or more epoxy groups contains a compound (B) selected from the group consisting of the following formulas (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 the cured film according to the item [6] as a transparent protective film. [Effect of invention]

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

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

1-1. Modified polymer (A) The modified polymer (A) must contain the compound represented by the above-mentioned formula (1) as the monomer (a), and the other monomer (b) selected from the formula ( 2) The compound represented by the compound and the compound in indene is 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. In the compound of formula (1), itaconic anhydride can also be used, and other monomers (b) can also contain compounds other than the above-mentioned compounds.

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

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

Compounds other than those described above may be included within a range that does not impair the purpose of the present invention. As an example of another raw material, a radically polymerizable monomer and a chain transfer agent can be contained.

1-1-1. Monomer (a) and Monomer (b) In the present invention, regarding the material for obtaining the modified polymer (A), as the monomer (a), the material represented by the formula (1) is included. compound. Moreover, as another monomer (b), it is preferable to contain 1 or more types of compounds chosen from the compound represented by Formula (2), and an 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. In addition, the compound represented by the formula (2) and monomers (b) other than indene may be included within a range that does not impair the characteristics of the present invention, and 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 .

在式（3-1）中，R4為單鍵、-CH2-、-C(CH3)2-、-SO2-或-O-，m及n獨立地為1～20的整數，而且，苯環的氫可獨立地經碳數1～3的烷基取代。1-1-2. Compound having two or more hydroxyl groups In the present invention, a compound having two or more hydroxyl groups is used as a material for obtaining the modified polymer (A). Preferably, 1,4-bis(hydroxyethoxy)benzene, 1,3-bis(hydroxyethoxy)benzene, 4,4'-isopropylidenebis(2-phenoxyethanol), Bis[4-(2-hydroxyethoxy)phenyl]diethanol, 2,2'-[(1,1'-biphenyl)-4,4'-diylbis(oxy)]bisethanol. 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 ,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-octanediol, 1,2-nonanediol, 1 ,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecane Diol, 1,12-dodecanediol, glycerin, 1,3,6-hexanetriol, trimethylolpropane (compound of formula (3-3)), tris(2-hydroxyisocyanurate) ethyl) ester, pentaerythritol (compound of formula (3-4)), dipentaerythritol, and a compound represented by the following formula (3-1).

In formula (3-1), R4 is a single bond, -CH2-, -C(CH3)2-, -SO2- or -O-, m and n are independently an integer of 1 to 20, and a benzene ring The hydrogen of can be independently substituted with an alkyl group having 1 to 3 carbon atoms.

A plurality of compounds listed here may be used in combination.

1-1-3. Solvent used in the synthesis of the modified polymer (A) Specific examples of the solvent used in the synthesis to obtain the modified polymer (A) include ethyl acetate, acetic acid Butyl, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate , methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethoxypropionate, methyl 2-hydroxypropionate, 2-hydroxypropionate propyl, 2-methoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate, 2-methoxypropionate Propionate, Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Methyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-2-methylpropionate, 2-Methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl, 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate , ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 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, diethyl ether Glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether. The solvent may be one of these solvents, or may be a mixture of two or more of these solvents.

1-1-4. Molecular weight modifier used in the synthesis of the modified polymer (A) During the synthesis of the modified polymer (A), a molecular weight modifier may be further contained in order to suppress the increase of the molecular weight and the appearance of Excellent storage stability. As a molecular weight modifier, thiols, xanthogens, quinones, hydroquinones, 2,4-diphenyl-4-methyl-1-pentene, etc. are mentioned.

Specific examples of molecular weight modifiers include 2-hydroxy-1,4-naphthoquinone, benzoquinone, 1,4-naphthoquinone, 1,4-dihydroxynaphthalene, and 2,5-di-tert-butylhydrogen Quinone, hydroquinone, methylhydroquinone, tert-butyl hydroquinone, methoquinone, p-benzoquinone, methyl-p-benzoquinone, tert-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 base-4-methyl-1-pentene, etc.

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

1-1-5. Synthesis method of modified polymer (A) Regarding the modified polymer (A) used in the present invention, the compound represented by the formula (1) and the compound represented by the formula (2) are combined with each other. The compounds represented and the monomers in the indene are polymerized in the solvent and in the presence of a thermal free radical initiator. In this case, 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 within the following ranges. Here, the functional group refers to an acid anhydride group in the compound represented by the above formula (1), and refers to a hydroxyl group in a compound having two or more hydroxyl groups. 0.5≦X≦5.0, X=(moles of acid anhydride groups/moles of hydroxyl groups)

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

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

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

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

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

In the modified polymer (A) synthesized in the above-described manner, even when the solubility of the compound having two or more hydroxyl groups in the copolymer or in the solvent used is low, after the thermal reaction, it can be homogeneous clear liquid to form a defect-free and uniform film. On the other hand, when the compound having two or more hydroxyl groups is simply added to the system without thermally reacting after the polymerization of the radical copolymer, even if it becomes a solution soluble and transparent to the solvent, the Even after the solvent at the time of thin film formation evaporates, a compound having two or more hydroxyl groups is precipitated due to poor compatibility, and a uniform thin film cannot be formed in many cases. Therefore, by derivatizing into a polybranched polyester, not only 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. Within these ranges, coating properties and flatness are favorable.

The weight average molecular weight in this specification is a polystyrene conversion value calculated|required by gel permeation chromatography (Gel Permeation Chromatography, GPC) (column temperature: 35 degreeC, flow rate: 1 ml/min). The standard polystyrene is polystyrene with molecular weight of 645 to 132,900 (eg, Agilent Technologies Inc. polystyrene calibration kit PL2010-0102), and the column is mixed with PL gel (PLgel MIXED)-D (Agilent Technologies, Inc.), which can be measured using Tetrahydrofuran (THF) as the mobile phase. The weight average molecular weight of a commercial item in this specification is a catalogue description 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) which has two or more epoxy groups may be one type or two or more types.

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 epoxy compounds, glycidyl ester epoxy compounds, bisphenol epoxy compounds, phenol novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds , Aliphatic polyglycidyl ether compounds, cycloaliphatic epoxy compounds, polymers of monomers with epoxy groups, copolymers of monomers with epoxy groups and other monomers, and siloxane bond sites of epoxy compounds. The compound (B) having two or more epoxy groups is preferably a compound having an aromatic ring.

Specific examples of commercially available bisphenol A epoxy compounds are jER 828, jER 1004, and jER 1009 (all are trade names, Mitsubishi Chemical Corporation); specific examples of commercially available bisphenol F epoxy compounds It is jER 806 and jER 4005P (both trade names, Mitsubishi Chemical Corporation); a specific example of a commercially available glycidyl ether type epoxy compound is TECHMORE VG3101L (trade name, Plintech ( Printec Co., Ltd.), EHPE3150 (trade name, Daicel Co., Ltd.), EPPN-501H, EPPN-502H (all trade names, 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, Nagase chemteX Co., Ltd.), 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 are trade names, Mitsubishi Chemical Co., Ltd.), and NC-3000, NC-3000-L, NC-3000-H, NC-3100 (all trade names, Nippon Kayaku Co., Ltd.); phenol novolac-type ring Specific examples of commercially available oxygen compounds are EPPN-201 (trade name, Nippon Kayaku Co., Ltd.), jER 152, jER 154 (all trade names, Mitsubishi Chemical Corporation), etc.; cresol novolak type Specific examples of commercially available epoxy compounds are EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all trade names, Nippon Kayaku Co., Ltd.), etc.; bisphenol A novolak type epoxy compounds Specific examples of commercially available products are jER 157S65 and jER 157S70 (both are trade names, Mitsubishi Chemical Corporation); specific examples of commercially available cycloaliphatic epoxy compounds are Celloxide 2021P, Celloxide 3000 (all are trade names, Daicel Co., Ltd.); a specific example of a commercially available epoxy compound having a siloxane bond site is 1,3-bis[2 -(3,4-Epoxycyclohexyl)ethyl]tetramethyldisiloxane (trade name, 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 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-propanols; EHPE3150 (trade name, Daicel Co., Ltd.) is the 1,2-epoxy group of 2,2-bis(hydroxymethyl)-1-butanol -4-(2-oxacyclopropyl)cyclohexane adduct; Celloxide 2021P (trade name, Daicel Co., Ltd.) is a 3',4'-epoxy ring Hexylmethyl-3,4-epoxycyclohexanecarboxylate; Celloxide 3000 (trade name, Daicel Co., Ltd.) is 1-methyl-4-(2-methyl) oxacyclopropyl)-7-oxabicyclo[4.1.0]heptane; COATOSIL MP-200 (trade name, Momentive Performance Materials Co., Ltd.) is based on 3 -Glycidyloxypropyltrimethoxysilane as a raw material polymer.

1-2-2. The ratio of the compound (B) having two or more epoxy groups to the modified polymer (A) The 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 parts by weight to 500 parts by weight. When the ratio of the total amount of the compound (B) having two or more epoxy groups is in the above range, the balance of flatness, heat resistance, chemical resistance, and substrate adhesion is favorable. The total amount of the compound (B) having two or more epoxy groups is preferably in the range of 50 parts by weight to 300 parts by weight, but the total amount is determined by adjusting the molar ratio to the multibranched polyester and the epoxy hardener .

1-3. Other Components In the thermosetting composition of the present invention, various additives may be added to improve coating uniformity, adhesiveness, transparency, flatness, and chemical resistance. Additives mainly include: epoxy hardener, solvent, anionic, cationic, nonionic, fluorine-based or silicon-based leveling agent/surfactant, silane coupling agent and other adhesion improvers, hindered phenol-based, Antioxidants such as hindered amine-based, phosphorus-based, sulfur-based compounds, and molecular weight modifiers.

1-3-1. Surfactant In the thermosetting composition of the present invention, a surfactant may be added to improve coating uniformity. Specific examples of surfactants include Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 (all are trade names, totaling Rongshe Chemical Co., Ltd.), Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk- 164, Disperbyk-166, Disperbyk-170, Disperbyk-180, Disperbyk-181, Disperbyk Gram (Disperbyk)-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (all are commodities 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 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, FTX-218 (all trade names, 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 Megafac F-558, Megafac F-559, Megafac R-94, Megafac RS-75, Megafac RS-72-K, Megafac afac) RS-76-NS, Megafac DS-21 (all trade names, DIC), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (all trade names, Evonik, Japan) (Evonik Japan Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylates, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonic acid salt, diglycerol tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl sulfamate, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, Polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene Laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitol Anhydride oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oil acid esters, polyoxyethylene naphthyl ethers, alkyl benzene sulfonates and alkyl diphenyl ether disulfonates. 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, fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene At least one of ether, fluoroalkyl sulfonate, fluoroalkyl trimethylammonium salt, and fluoroalkyl sulfamate is preferred since the coating uniformity of the thermosetting composition becomes high.

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

1-3-2. Coupling Agent The thermosetting composition of the present invention may further contain a coupling agent from the viewpoint of further improving the adhesiveness of 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-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, Silane (for example, trade name, Sila-Ace S510, JNC Co., Ltd.), 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, JNC) JNC Co., Ltd.), a copolymer of 3-glycidyloxypropyltrimethoxysilane (eg, trade name, CoatOSil MP-200, Momentive Performance Materials Japan ) Co., Ltd.) and other silane-based coupling agents, aluminum-based coupling agents such as aluminum acetoxydiisopropoxide, and titanate-based coupling agents such as tetraisopropylbis(dioctylphosphite) titanate coupling agent.

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

It is preferable that content of a coupling agent is 0.01 weight% or more and 10 weight% or less with respect to the total amount of thermosetting composition from the point which the adhesiveness of the formed cured film and a board|substrate improves.

1-3-3. Antioxidant From the viewpoint of improving transparency and preventing yellowing of the cured film when exposed to high temperature, the thermosetting composition of the present invention may further contain an antioxidant.

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

0.1 weight part - 10 weight part of antioxidants are added and used with respect to the total amount of 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 epoxy hardeners, there are acid anhydride-based hardeners, amine-based hardeners, phenol-based hardeners, imidazole-based hardeners, catalyst-type hardeners, and sensitized heat such as perylene salts, benzothiazolium salts, ammonium salts, and phosphonium salts. From the viewpoint of avoiding coloration of the cured film and heat resistance of the cured film, etc., an acid anhydride-based curing agent, an imidazole-based curing agent, or a combined use of an acid anhydride-based curing agent and an imidazole-based curing agent is preferable.

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

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 curing agents, 2-undecylimidazole having a good balance between curing properties and solubility in solvents is preferred.

In the case of using an epoxy curing agent, the ratio of the epoxy curing agent to 100 parts by weight of the compound (B) having two or more epoxy groups is 0.1 parts by weight to 60 parts by weight. When the epoxy curing agent is an acid anhydride-based curing agent, the amount added is preferably 0.1 to 1.5 times the equivalent of the carboxylic acid anhydride group or carboxyl group in the epoxy curing agent in more detail with respect to the epoxy group. way to add. At this time, the carboxylic acid anhydride group is calculated as divalent. If the carboxylic acid anhydride group or the carboxyl group is added so as to be 0.15 times the equivalent to 0.8 times the equivalent, the chemical resistance is further improved, which is more preferable.

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

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

0.01 weight part - 10 weight part of ultraviolet absorbers are added and used with respect to the total amount of the thermosetting composition.

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

Specific examples of the anti-agglomeration agent 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, Disperbyk Disperbyk-2015 (all 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 trade names, Gongrongshe Chemical Co., Ltd.).

0.01 weight part - 10 weight part of anti-agglomeration agents are added and used with respect to the total amount of the thermosetting composition.

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

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

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

1-4. Solvent (C) The thermosetting composition of the present invention contains a solvent (C). The solvent (C) used in the composition of the present invention is preferably a solvent in which the modified polymer (A) and the compound (B) having two or more epoxy groups can be dissolved. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl acetate. Methyl oxyacetate, 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-methoxypropionate 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-Oxobutyrate, Ethyl 2-Oxobutyrate, 4-Hydroxybutyrate -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 solvents, or may be a mixture of two or more of these solvents.

1-5. Storage of thermosetting composition When the thermosetting composition of the present invention is stored in the range of -30°C to 25°C, the temporal stability of the composition becomes favorable. When the storage temperature is -20°C to 10°C, the precipitates do not exist, which is more preferable.

2. Cured film formed from thermosetting composition With regard to the thermosetting composition of the present invention, the modified polymer (A) and the compound (B) having two or more epoxy groups are mixed and adjusted according to the purpose According to the characteristics, epoxy hardeners, solvents, surfactants, adhesion improvers, antioxidants and other additives can be added as needed.

When the thermosetting composition prepared as described above (in the case of a solvent-free solid state, after being dissolved in a solvent) is coated on the surface of a substrate, and the solvent is removed by heating, for example, a coating film can be formed . The coating film of the thermosetting composition on the surface of the substrate can be formed by conventionally known methods such as spin coating, roll coating, dipping, and slit coating. Next, the coating film is temporarily calcined with a hot plate, an oven, or the like. The temporary sintering conditions vary depending on the type of each component and the mixing ratio, but it is usually 70°C to 150°C, 5 minutes to 15 minutes when an oven is used, and 1 minute to 5 minutes when a hot plate is used. Then, in order to harden a coating film, main sintering is performed. The main sintering conditions vary depending on the type of each component and the mixing ratio, but it is usually 180°C to 250°C, preferably 200°C to 250°C, 30 minutes to 90 minutes when an oven is used, and 5 minutes when a hot plate is used. A cured film can be obtained by performing a heat treatment for 30 minutes to 30 minutes.

The cured film obtained in the above-mentioned manner is very strong and tough because 1) the modified polymer (A) reacts with the compound (B) having two or more epoxy groups to form a three-dimensional network when heated. Excellent heat resistance, chemical resistance, flatness, and adhesion. Also, for the same reason, it is expected to be excellent in light resistance, sputtering resistance, scratch resistance, and coatability. Therefore, when the cured film of this invention is used as a protective film for color filters, it is effective, and a liquid crystal display element or a solid-state imaging element can be manufactured using the said color filter. In addition to the protective film for color filters, if the cured film of the present invention is used as a transparent insulating film formed between a thin film transistor (Thin Film Transistor, TFT) and a transparent electrode, or a film formed between a transparent electrode and an orientation film A transparent insulating film is also effective. Furthermore, the cured film of this invention is effective even if it is used as a protective film of 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 modified polymer (A1) solution In a four-necked flask with a stirrer, methyl 3-methoxypropionate (MMP) and N-cyclohexylmalein were charged with the following weights Imine, maleic anhydride, radical initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.), α-methylstyrene dimer, heated and stirred at 80°C for 2 hours under dry nitrogen flow to obtain 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

Then, the reaction liquid was cooled to 25 degreeC, 5.669 g of 4,4'-isopropylidenebis(2-phenoxyethanol) were injected|thrown-in, and it stirred at 150 degreeC for 3 hours (synthesis second stage).

The solution was cooled to room temperature to obtain a 30% by weight solution of a light yellow transparent modified polymer (A1). A part of the solution was sampled, and the weight average molecular weight was determined 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] The solution of modified polymer (A2) to modified polymer (A10) was synthesized according to the method of Synthesis Example 1, and the temperature, time and ratio (unit: g) described in Table 1 were used. ) reacts the components to obtain a solution of the modified polymer (A2) to the modified polymer (A10).

[Comparative Synthesis Example 1 to Comparative Synthesis Example 2] Synthesis of solutions of polyester (R1) and polyester (R2) at the temperature, time, and ratio described in Table 1 without a branched structure and without a branched structure contained in this technical solution The general linear polyester of the specific structure is reacted to obtain a solution of polyester (R1) and polyester (R2). However, the reaction temperature was set to 150° C. for 3 hours.

裝入量的單位：克Table 1

Loading unit: grams

The compounds used in the synthesis examples and comparative synthesis examples described by the abbreviations in Table 1 are as follows, respectively. CHMI: N-cyclohexylmaleimide NPM: N-phenylmaleimide IN: Indene MAH: Maleic anhydride ODPA: 4,4'-oxydiphthalic anhydride BPDA: 3,3 ',4,4'-Biphenyltetracarboxylic dianhydride V-65: 2,2'-azobis(2,4-dimethylvaleronitrile); manufactured by Wako Pure Chemical Industries, Ltd. αMSD: α- Methylstyrene dimer bisA-2EOH: 4,4'-isopropylidene bis(2-phenoxyethanol)

BPE-40, BPE-60, BPE-100: Newpol BPE-40, Newpol BPE-60, Newpol BPE-100; manufactured by Sanyo Chemical Industry Co., Ltd.; are diols with the following structures, and are compounds with hydroxyl valences 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 bifunctional ring in the proportions (parts by weight) described in Table 2 YX4000H as oxygen compound, trimellitic anhydride (TMA) as hardener, S510 as silane coupling agent, ADK STAB AO-60 as antioxidant, F-556 as surfactant and dilution Propylene glycol monomethyl ether acetate (PGMEA) as a solvent was mixed and dissolved, and was filtered with a membrane filter (pore size: 0.2 μm) to obtain a thermosetting composition.

[Examples 2 to 13 and Comparative Example 1 and Comparative Example 2] According to the method of Example 1, the respective components were mixed and dissolved at the ratio (parts by weight) described in Table 2 to obtain a thermosetting composition.

單位：重量份（表面活性劑除外）Table 2

Unit: parts by weight (except for surfactants)

Using each of the obtained thermosetting compositions, heat resistance, planarization rate, and substrate adhesion were evaluated by the methods described below. The evaluation results of the cured films of Examples 1 to 13 are collectively described in Table 3. Moreover, about the comparative example 1 and the comparative example 2, the heat resistance, planarization rate, and base adhesion of the cured film formed using the thermosetting composition containing the linear polyester of a normal non-branched structure were evaluated. The evaluation results are collectively described 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. Then, it was post-baking (Post Bake, PB) for 30 minutes at 230 degreeC in an oven, and the glass substrate with a cured film was obtained (it was made into the film thickness after PB). For the obtained glass substrate with a cured film, the film thickness was measured using a level difference/surface roughness/fine shape measuring apparatus (trade name, P-17, KLA TENCOR Co., Ltd.), and set is the initial film thickness. After that, the glass substrate with a cured film was post-baked at 230° C. in an oven for 60 minutes, and the film thickness was measured in the same manner (it was assumed to be the film thickness after EB1). Moreover, the glass substrate with a cured film after PB was post-baked at 250 degreeC for 60 minutes separately, and the film thickness was measured similarly (it was made into EB2 post-film thickness). The residual film ratio 1 and the residual film ratio 2 were calculated using the following formulas, and the residual film ratio between PB-EB1 was set to be 99% or more as ○, less than 99% to 98% as △, and less than 98%. set as ×. In addition, the remaining film ratio between PB-EB2 was set to 99% or more as ○, less than 99% to 98% as Δ, and less than 98% as ×. Residual film rate 1 (%) = (film thickness after EB1 / film thickness after PB) × 100 Residual film rate 2 (%) = (film thickness after EB2 / film thickness after PB) × 100

[Evaluation method of flatness] A resist containing a surface level difference was measured in advance using a level difference/surface roughness/fine shape measuring device (trade name, P-17, KLA TENCOR Co., Ltd.). The obtained thermosetting composition was spin-coated at 650 rpm for 10 seconds on a patterned uneven substrate (a patterned substrate with lines of 100 μm, spaces of 50 μm, and film thickness of 1 μm), and pre-baked on a hot plate at 80°C 2 minutes. Then, it post-baked at 230 degreeC in an oven for 30 minutes, and obtained the color filter board|substrate with a cured film whose average film thickness of a protective film is 1.5 micrometers. Then, the surface level difference was measured about the obtained color filter board|substrate with a cured film. From the maximum value of the surface level difference (hereinafter abbreviated as "maximum level difference") of the color filter substrate without a cured film and the color filter substrate with a cured film, the planarization rate was calculated using the following calculation formula , the results are shown in Table 3. Regarding 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 level difference of uneven substrate - Maximum level difference of uneven substrate with cured film)/Maximum level difference of uneven substrate) × 100

[Evaluation method of adhesiveness] The obtained thermosetting composition was spin-coated on a concavo-convex substrate (line: 100 μm, space: 50 μm, film thickness: 1 μm) at 650 rpm for 10 seconds, and was heated at 80° C. Pre-bake on hotplate for 2 minutes. Then, it post-baked at 230 degreeC in an oven for 30 minutes, and obtained the uneven|corrugated board|substrate with a cured film. The cross-cut test (Japanese Industrial Standards (JIS) K 5400) was performed on both the obtained uneven substrate with a cured film and the similarly produced glass substrate with a cured film, and the tape was peeled off: Using 3M product No. 361), evaluation was performed according to the following classifications 0 to 5, and classification 0 to classification 1 were set to ○, classification 2 to classification 3 were set to △, and classification 4 to classification 5 were set to ×. Let the adhesiveness evaluation of the uneven|corrugated board|substrate with a cured film be "adhesion evaluation 1", and let the adhesiveness evaluation of the glass substrate with a cured film be "adhesion evaluation 2". <Category 0> The edge of the ¼ cut is completely smooth, and there is no flaking in the mesh of any of the lattices. <Classification 1> Small peeling of the coating film at the intersection of the ¼ cut. In the cross-cut section, the affected section will not clearly exceed 5%. <Classification 2> ¼ of the coating film peeled off along the edge of the cut and/or at the intersection. In the cross-cut section, the affected section clearly exceeds 5% but does not exceed 15%. <Classification 3> ¼ of the coating film was partially or entirely peeled off along the cut edge, and/or many parts of the mesh were partially or entirely peeled off. In the cross-cut section, the affected section clearly exceeds 15% but does not exceed 35%. <Classification 4> ¼ of the coating film was partially or entirely peeled off along the cut edge, and/or the meshes at multiple locations were partially or entirely peeled off. In the cross-cut section, the affected section does not clearly exceed 35%. <Classification 5> ¼ of any degree of peeling that cannot be classified even if it is classified as 4.

[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 for 30 minutes at 230 degreeC in an oven, and obtained the glass substrate with a cured film whose film thickness is 1.5 micrometers. About the obtained glass substrate with a cured film, the light transmittance in 400 nm of a cured film was measured using an ultraviolet-visible-near-infrared spectrophotometer (trade name: V-670, JASCO Corporation). In this case, only the glass substrate is used as a reference, and the light transmittance of the cured film alone is calculated (in this case, interference due to multiple reflection is not considered). When the light transmittance was 98% or more, it was evaluated as transparency ○, when the light transmittance was less than 95%, it was evaluated as transparency x, and the difference was evaluated as Δ.

[產業上的可利用性]As is clear from the results shown in Table 3, 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 the characteristics could not be 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, etc. The insulating film between the TFT and the transparent electrode and between the transparent electrode and the orientation film, as well as the passivation film, the buffer coating film and the planarization film.

none

none.

none.

Claims (6)

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 A compound derived from a copolymer which is a reaction product derived from a monomer (a) represented by the following formula (1) and a monomer (b) other than the monomer (a) using a compound having two or more hydroxyl groups The acid anhydride site of the monomer (a) is thermally ring-opened, and the compound having two or more hydroxyl groups is at least one selected from the compounds represented by the following formula (3-1);

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

In formula (3-1), R ⁴ is a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ - or -O-, m and n are independently an integer of 1 to 20, Also, 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 claim 1, wherein the monomer (b) is at least one selected from the group consisting of compounds 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 (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 group consisting of compounds represented by the following formulas (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 4. A color filter characterized in that it has the cured film described in claim 5 as a transparent protective film.