TW201005436A - Radiation sensitive resin composition for forming protective film of touch panel and a method for producing the same - Google Patents

Abstract

The present invention relates to a radiation sensitive resin composition for forming protective film of touch panel, which has high transparency, excellent adhesion with transparent conductive films, high hardness and excellent rubbing resistance to be used as a protective film, and a method for producing the same. A radiation sensitive resin composition for forming protective film of touch panel characterized in comprising (A) an alkali-soluble resin, (B) an ethylenic unsaturated compound having a carboxyl group in a molecule, and (C) a radiation sensitive initiator.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive resin composition which is excellent in formation of a protective film of a transparent conductive film in a touch panel and a method of forming the same. [Prior Art] In terms of touch panels, there are resistive film type, electrostatic capacitance type, ultrasonic type, optical type, electromagnetic induction type, etc.

The A V style is the mainstream. However, there are many disadvantages such as erroneous operation in the resist film type, and there is a tendency for manufacturers using electrostatic capacitance to increase. In the static capacitance type, a transparent conductive film such as an ITO (Indium Tin Oxide) film is formed on a substrate. In order to protect such a transparent conductive film, it is necessary to form a friction-resistant property on the transparent conductive film and to have a good adhesion to the substrate. The protective film of the nature is described (Japanese Laid-Open Patent Publication No. Hei 6-195-174 and Japanese Patent Application Publication No. 2009-69984). In Japanese Laid-Open Patent Publication No. 2009-69984, a ruthenium oxide film is formed as a protective film by a sputtering method or a CVD method. In this case, when the glass substrate is enlarged, a long film formation time is required, and there is a problem that the production efficiency is lowered. In addition, the protective film formed by such a method is extremely poor in adhesion to the substrate or insufficient in hardness, and is likely to be scratched or peeled during transportation or transportation, and has a letter as a touch panel. Degree reduction problem. In view of the above-mentioned situation, it is desired to develop a radiation-sensitive linearity of a protective film for a touch panel, which has high transparency as a protective film, excellent adhesion to a transparent conductive film, high hardness, and excellent abrasion resistance. Resin composition. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. A radiation-sensitive resin composition for forming a protective film for a touch panel which is excellent in transparency and a high hardness and is excellent in abrasion resistance as a protective film. [Means for Solving the Problem] The present invention is achieved by the following: First, a radiation sensitive resin composition for forming a protective film for a touch panel, characterized in that the protective film comprises: (A) an alkali-soluble resin, (B) A compound having a one or more ethylenically unsaturated groups selected from the following formula (1) and the following formula (2); and (C) a radiation-sensitive polymerization initiator. 201005436

CH2—X

C-OH H O X—h^c C CH2~〇—c-W, 0

CHZ-X

CHa-X

CHa-X

x—H2C—C—H2C—O—HSC—C—CHS—X

CHjg- "X

(here, X is an alkyl group selected from a hydrogen atom, a carbon number of 1 to 6, an acryloyl group or a methacryl fluorenyl group, and at least one is an acryloyl group or a methacryl fluorenyl group. W represents a carbon number of 1 An alkyl group of ~6, an alkyl group having 2 to 6 carbon atoms having one unsaturated bond, a phenyl group, a cyclohexyl group. The object of the present invention is to provide a radiation-sensitive resin composition for forming a protective film for a touch panel according to the first aspect of the invention, which is characterized in that (A) an alkali-soluble resin is used. A copolymer formed by copolymerizing (al) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and (a2) a monomer containing an epoxy group-containing unsaturated compound. According to the present invention, the above objects and advantages of the present invention are attained by a radiation sensitive resin composition for forming a protective film of a touch panel, which comprises (D) a polyfunctional cationically polymerizable compound (however, In addition to (A) alkali-soluble resin.). According to the present invention, the fourth object of the present invention is to provide a feeling of forming a protective film for a touch panel as described in claim 3 of the patent application. 201005436 A radiation-linear resin composition is obtained which is characterized by containing (E) a compound which is heated to generate an acid. According to the present invention, the above objects and advantages of the present invention are attained by a protective film for a touch panel formed by the above-described radiation-sensitive resin composition. According to the present invention, the above objects and advantages of the present invention are attained by a method for forming a protective film which is formed by using the above-described radiation sensitive resin composition, followed by irradiation treatment of radiation and heat treatment. In the present invention, the substrate material of the substrate having the transparent conductive film is glass or the like, and the transparent conductive film is an ITO film. Further, a part of such a substrate is sometimes formed of ruthenium dioxide. In the present invention, a protective film is formed on the surface of the transparent conductive film, and a radiation-sensitive resin composition for forming a protective film (hereinafter simply referred to as "the composition for forming a protective film") is applied by exposure, Development and Heating to Form a Protective Film The composition for forming a protective film of the present invention contains a cerium-soluble resin, a carboxy-functional propylene monomer, and a radiation-sensitive polymerization initiator. In the present invention, the alkali-soluble resin (hereinafter, simply referred to as copolymer (A)) is soluble as long as it is used in the development solution used in the development treatment step of the radiation-sensitive resin composition containing the component. However, there is no particular limitation. Further, the alkali-soluble resin in the present invention is more preferably a reactive functional group, and examples of the reactive functional group include an epoxy group and a (methene 201005436-based) acrylonitrile group. When the reactive functional group is an epoxy group, it can be obtained by copolymerizing a radical polymerizable monomer having an epoxy group and other radical polymerizable monomers. When the reactive functional group is a (meth) acrylonitrile group, the radical polymerizable monomer having a hydroxyl group can be copolymerized with another radical polymerizable monomer, and then (meth) propylene hydride can be contained. The isocyanate compound is obtained by reacting a hydroxyl group in the polymer. Examples of the (a 1) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride (hereinafter abbreviated as the compound (al)) include acrylic acid, methacrylic acid, crotonic acid, and 2-acryloxyl succinate. a monocarboxylic acid such as ethyl ester, 2-methylpropenyloxyethyl acetate, 2-propenyloxyethyl hexahydrophthalate or 2-methylpropenyloxyethyl hexahydrophthalate; a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; an acid anhydride of the above dicarboxylic acid; Among these compounds (al), from the viewpoints of copolymerization reactivity, solubility of the obtained polymer and the alkaline developing solution of the copolymer, acrylic acid, methacrylic acid, 2-acryloxyl succinate Ethyl ester, 2-methylpropenyloxyethyl succinate, maleic anhydride or the like is preferred. In the copolymer (A), the compound (al) may be used singly or in combination of two or more. In the copolymer (A), the content of the repeating unit derived from the compound U1) is preferably 5 to 60% by weight, more preferably 7 to 50% by weight, particularly preferably 8 to 40% by weight. When the content of the repeating unit derived from the compound (a1) is 5 to 60 parts by weight, it is possible to obtain a high level of sensitivity such as radiation sensitivity, developability, and storage stability of the radiation sensitive resin composition. A linear resin composition. 201005436 Examples of the epoxy group-containing unsaturated compound (a2) (hereinafter, abbreviated as the compound U2) include glycidyl acrylate, 2-methyl glycidyl acrylate, and 3,4 epoxybutyl acrylate. , an alkyl acrylate alkyl acrylate such as 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl acrylate or 2,3-epoxypropyl acrylate; Glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-methacrylic acid Epoxy cyclohexyl ester, 3,4-epoxycyclohexyl methacrylate, bismuth 2,3-epoxypropyl methacrylate, alkyl methacrylate, α-ethyl methacrylate , α-alkyl acrylate glycidyl ester, n-butyl acrylate glycidyl ester, α-ethyl acrylate 6,7-epoxyheptyl ester, etc. α-alkyl acrylate alkyl acrylate; o-vinyl benzyl glycidol An ether, m-vinylbenzyl glycidyl ether, a glycidyl ether such as ethylene vinyl glycidyl ether or the like. Further, as the other radical polymerizable monomer having an epoxy group, _ can be exemplified by 3-(acryloxymethyl)oxetane and 3-(acryloxymethyl)-3. -ethyloxetane, 3-(acryloxymethyl)-2-methyloxetane, 3-(propyleneoxyethyl)oxetane, 3-(propylene Acrylate having an oxetanyl group, such as a methoxyethyl)_3_ethyloxetane, a 2-ethyl- 3-((acryloyloxyethyl) oxetane, etc.. Further, there may be mentioned 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)-3-ethyloxetane, 3-(( Methacryloxymethyl)-2-methyloxetane, 3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl) a methacrylate having an oxetanyl group, such as a 3-ethyloxetane or a 2-ethyl 201005436 -3-(methacryloxyethyl) oxetane. In the copolymer (A), the compound (a2) may be used singly or in combination of two or more. In the copolymer (A), the content of the repeating unit derived from the compound (a2) is 0. It is preferably 5 to 70% by weight, more preferably 1 to 60% by weight, particularly preferably 3 to 50% by weight. When the content of the repeating unit derived from the compound (a2) is from 〜5 to 70% by weight, the obtained radiation-sensitive resin composition is 'heat resistance having a copolymer, a copolymer, and a radiation-sensitive W linear resin. The storage stability of the composition and the like are high. The compound (hereinafter, simply referred to as the compound (a3)) used in the copolymer (A) is an unsaturated compound having a free radical polymerizable property other than the above compounds (al) and (a2). First, as a specific example of the compound U3), an unsaturated compound containing one or more hydroxyl groups in one molecule can be mentioned. Examples of the unsaturated compound containing one or more hydroxyl groups in one molecule include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 4-hydroxyl acrylate. a hydroxyalkyl acrylate such as benzyl-cyclohexyl methyl ester; 2-ethyl methacrylate 2-ethyl ester 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5·hydroxyamyl methacrylate, 6-hydroxyhexyl methacrylate, hydroxyalkyl methacrylate such as 4-methylcyclohexyl methacrylate or the like. This is equivalent to an unsaturated compound having one or more hydroxyl groups in one molecule, and after the formation of the & copolymer, it can be reacted with an isocyanate compound having a (meth) acrylonitrile group. Polymerization Reactivity and Reactivity between Isocyanate Compounds-10-201005436 From the viewpoint of the unsaturated compound containing one or more hydroxyl groups in one molecule, 2-hydroxyethyl acrylate and methacrylic acid are used. 2-Hydroxyethyl ester or the like is preferred. Examples of the isocyanate compound to be reacted with the unsaturated compound containing the above hydroxyl group include acrylic acid and methacrylic acid derivatives such as 2-propenyloxyethyl isocyanate and 2-methoxyethyl isocyanate. In addition, as a commercial item of 2-propenylmethoxyethyl isocyanate, the product name: karenz AOI (manufactured by Showa Denko Co., Ltd.) can be used as 2-methylpropenyloxyethyl isocyanate. Commercially available products include: karenz MOI (Showa Electric Co., Ltd.). Specific examples of the other compound (a3) include alkyl acrylates such as methyl acrylate and isopropyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and methyl group. Alkyl methacrylate such as butyl acrylate or butyl methacrylate; hexyl acrylate, 2-methylcyclohexyl acrylate, and tricyclohexyl acrylate [5. 2. 1. 02'6] decane-8-yl ester, 2-(tricyclo[5. 2. 1. 02'6] decyl-8-yloxy)ethyl ester, isobornyl acrylate such as alicyclic ester; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, trimethyl methacrylate [5_2. 1. 02 6] decane-8-yl ester, 2-(tricyclo[5. 2. 1. 02'6] decane-8-yloxy)ethyl ester methacrylate alicyclic ester such as isobornyl methacrylate; aryl acrylate such as phenyl acrylate or benzyl acrylate; benzene methacrylate An aryl methacrylate of an ester, benzyl methacrylate or the like; a dicarboxylic acid di-11-201005436 alkyl ester such as diethyl maleate, diethyl fumarate or diethyl itaconate; Tetrahydrofurfuryl methacrylate, tetrahydrofuran methacrylate, tetrahydropyran-2-methyl methacrylate, etc., containing oxygen monoatomic unsaturated hetero and five-membered cyclomethacrylate; 4-propene oxide Methyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propenyloxymethyl-2.methyl-2-isobutyl-1,3-dioxolan Ring, 4-propenyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl-2-ethyl-1,3- Oxygen diatomic unsaturated five-membered ring-shaped ring containing dioxolane, 4-methylpropenyloxymethyl-2-methyl®-2-isobutyl-1,3-dioxolane Acrylate; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxy a vinyl aromatic compound such as styrene or 4-isopropenylphenol; Ν-phenyl maleimide, Ν-cyclohexylmaleimide, Ν-benzyl maleimide, Ν-amber Ν-substituted maleimine, such as imine-3-maleimide benzoate, hydrazine-succinimide-4-maleimine butyrate; In addition to conjugated didiene compounds such as dienes, isoprene and 2,3-dimethyl-1,3-butadiene, acrylonitrile, methacrylonitrile, acrylamide, and methacryl Amines, etc. Among these other radical polymerizable monomers, from the viewpoints of copolymerization reactivity and developability, it is preferred to be as follows: styrene, 4-isopropenylphenol, methacrylic acid tricyclo [5. 2. 1. 02' 6] decane-8-yl ester (tricyclodecyl methacrylate), glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid 3,4-epoxycyclohexane Ester, 2,3-epoxypropyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3-methyl-3-methylpropene-12- 201005436 醯oxymethyl oxetane Alkane, 3-ethyl-3-methylpropenyloxymethyloxetane, methacrylic acid> tetrahydrofurfuryl ester, 1,3-butadiene, 2-hydroxyethyl acrylate, methacrylic acid 2-(6-Hydroxyethylhexyloxy)ethyl ester, 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolan, N-cyclohexane Yttrium imine, N-phenyl maleimide, and the like. In the copolymer (A), the compound (a3) may be used singly or in combination of two or more. In the copolymer (A), the content of the repeating unit derived from the compound (a3) is preferably from 1 to 70% by weight, more preferably from 3 to 60% by weight, more preferably from 5 to 50% by weight, particularly preferably from 5 to 50% by weight. . When the content of the repeating unit derived from the compound (a3) is from 1 to 70% by weight, the heat resistance of the obtained radiation-sensitive resin composition copolymer, the copolymer, and the radiation-sensitive resin composition are stably stored. Sex and other people with high standards. The compound represented by the general formulae (1) and (2) (hereinafter, abbreviated as (B) component) used in the composition for forming a protective film of the touch panel of the present invention has a molecular weight A polyfunctional _(meth) acrylate compound having one or more carboxyl groups can form a protective film having a high level of adhesion to a substrate of a protective film to be formed and a surface hardness of the protective film. The polyfunctional (meth) acrylate compound having one or more carboxyl groups is at least one of a compound having one or more acid anhydride groups in the molecule, and has a hydroxyl group and two or more (meth) propylene groups in the molecule. It is obtained by reacting at least one of a hydroxyl group-containing polyfunctional (meth) acrylate of a mercapto group. Specific examples of-13-201005436 which are compounds having one or more acid anhydride groups in the molecule include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. And other compounds. Among them, succinic anhydride is particularly preferred. Further, specific examples of the polyfunctional (meth) acrylate having a hydroxyl group having a hydroxyl group and two or more (meth) acrylonitrile groups in the molecule include trimethylolpropane diacrylate and trisole. Hydroxymethylpropane dimethacrylate, neopentyl alcohol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and the like. The polyfunctional (meth) acrylate compound having one or more carboxyl groups in the molecule as the component (B) may, for example, be a succinic acid mono-[3-(3-propene) which is a 5-functional acrylate having a carboxyl group. Nonyloxy-2,2-bisacryloxymethyl-propoxy)-2,2-bis-acryloxymethyl-propyl] ester. In the composition for forming a protective film of the touch panel, the amount of the component (B) is preferably 50 to 300 parts by weight, more preferably 60 to 250 parts by weight, per 100 parts by weight of the copolymer (A). When the amount of the component (B) used is 50 to 300 parts by weight, the properties of the radiation-sensitive resin composition obtained are such that the adhesion of the protective film and the high pencil hardness are high. (C) a radiation-sensitive polymerization initiator (C) a radiation-sensitive polymerization initiator (hereinafter, simply referred to as a component (C)) used in the composition for forming a protective film of a touch panel, The component is formed by exposure of radiation such as visible rays, ultraviolet rays, far ultraviolet rays, charged particle rays, and X-rays to generate an active species sufficient to initiate polymerization of the polymerizable unsaturated compound. As such a radiation-sensitive polymerization initiator, for example, a radiation-induced radical polymerization initiator can be cited -14-201005436. The radiation radical polymerization initiator may, for example, be a quinone-based compound, an acetophenone-based compound, a biimidazole-based compound, a serotonin-based compound or a benzophenone-based compound. Specific examples of the above ruthenium-indenyl ruthenium compound include n-octanedione, 1-[4-(phenylthio)-2-(0-benzamide), and ethyl ketone-l- [9-Ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-1-(0-acetamidine), 1-[9-ethyl-6-benzene Mercapto-3-oxa]-octane-1-one oxime-indole-acetic acid, 1-[9-ethyl-6-(2-methylbenzhydryl)-9. H. - oxazol-3-yl]·B. -1-ketooxime-0-benzoate, 1-[9-n-butyl-6-(2-ethylbenzylidene)-9. H. -oxazol-3-yl]-ethane-1-one oxime-0-benzoate, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranbenzoyl) -9. H. -carbazole-3_yl]-1-(0-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzylidene)-9 ·Η·-carbazol-3-yl]-1·(0-acetamidine), ethyl ketone-l-[9-ethyl-6-(2-methyl-5-tetrahydrofuranbenzylidene)- 9_Η·-carbazol-3-yl]- l-(〇-acetamidine), ethyl ketone-1·[ 9-ethyl-6-{2-methyl-4-(2,2-dimethyl -1,3-dioxolanyl)methoxybenzylidene}-9. Η·-carbazol-3-yl]-1-(〇-acetamidine) and the like. Among these, as a suitable 0-fluorenyl hydrazine compound, 1,2-octanedione, 1-[4-(phenylthio)-2-(0-benzamide)] Ethylketone-1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]-1-(0-acetamidine), ethyl ketone-1- [9-Ethyl-6-(2-methyl-4-tetrahydrofuranmethoxybenzylidene)-9. H-carbazol-3-yl]-1-(0-acetamidine) or ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl- 1,3-dioxolanyl)methoxybenzyl sulfonyl b. H. -oxazol-3-yl]-1-(0-acetamidine). These 〇-醯 肟 肟 -15- 201005436, can be used alone or in combination of two or more. The acetophenone compound may, for example, be an α-amine ketone compound or an α-hydroxyketone compound. Specific examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and 2-dimethylamine. 2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butane-1·one, 2-methyl-1-(4-methylthiophenyl) -2-morpholinol-1-one, etc. As a specific example of the α-hydroxyketone compound, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4) -isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one' 1-hydroxy Cyclohexyl ketone and the like. Among these acetophenone compounds, an α-aminoketone compound is preferred, and 2-benzyl 2-dimethylamino-indolyl-4-morpholinylphenyl)-butan-1-one, 2-di Methylamino 2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, 2-methyl-1-(4-methylsulfide Phenyl)-2-morpholinpropan-1-one is particularly preferred. Specific examples of the biimidazole compound include 2,2·-bis(2-chlorophenyl)-4,4′,5,5·-fluorene (4-ethoxycarbonylphenyl)-1. , 2·-biimidazole, 2,2·-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl 1,2'-biimidazole, 2,2'-bis (2 ,4-dichlorophenyl)-4,4',5,5--tetraphenyl-1,2·-biimidazole, 2,2··bis(2,4,6-trichlorophenyl)- 4,4\5,5, tetraphenyl-1,2'-biimidazole, and the like. In the radiation sensitive resin composition of the present invention, when a biimidazole compound is used as the (C) radiation sensitive polymerization initiator, an aliphatic or aromatic group having a dialkylamine group may be added for sensitization thereof. Compound (hereinafter, simply referred to as "amine sensitizer"). -16-201005436 Examples of the amine-based sensitizer include 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamine)benzophenone. . Among these amine sensitizers, 4,4·-bis(diethylamine)benzophenone is particularly preferred. Further, in the case where the imiprazole compound and the amine-based sensitizer are used in the radiation-sensitive resin composition of the present invention, a thiol compound can be added as a hydrogen radical supply agent. Although the biimidazole compound is sensitized, cracked, and produces an imidazole radical by an amine-based sensitizer, it does not exhibit a high polymerization initiation energy in this state, and the upper portion of the pattern of the obtained protective film becomes large, and the pattern ® The case where the lower part becomes a bad shape. However, in the system in which the biimidazole compound and the amine-based sensitizer coexist, by adding a thiol compound, a hydrogen radical can be supplied from the thiol compound in the imidazole radical. As a result, the imidazole free radical is converted into a neutral imidazole, and a component having a sulfur radical having a high polymerization initiation energy is produced, whereby the shape of the protective film can be formed into a better shape. Examples of the thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazolyl, 2-mercaptobenzimidazolyl, 2-indolyl-5-methyl oxybenzene An aromatic thiol compound such as thiazole; an aliphatic monothiol compound such as 3-mercaptopropionate or methyl 3-mercaptopropionate; neopentyltetrakis(mercaptoacetate), neopentyl An aliphatic thiol compound having two or more functional groups such as tetraol tetrakis(3-mercaptopropionate). Among these thiol compounds, 'particularly 2-mercaptobenzothiazole is preferred." When a biimidazole compound and an amine sensitizer are used, the amount of the amine sensitizer added is relative to the biimidazole compound. 1 〇〇 by weight.  It is preferably 1 to 50 parts by weight, more preferably 1 to 20 parts by weight. When the amine sensitizer is added in an amount of 0. When it is 1 to 50 parts by weight, the shape of the obtained protective film is good. -17- 201005436 Further, when the biimidazole compound and the amine-based sensitizer and the thiol compound are used, the amount of the thiol compound added is 0% by weight based on 100 parts by weight of the biimidazole compound. It is preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. When the amount of thiol compound added is 〇. When it is 1 to 30 parts by weight, the shape and adhesion of the protective film are the best. The ratio of the total use of the component (C) is 0. 100 parts by weight relative to the copolymer (a). It is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight. When the amount of (C) radiation-sensitive polymerization initiator is 〇. When the amount is 1 to 50 parts by weight, the radiation-sensitive resin composition of the present invention can form a protective film having high hardness and adhesion even at a low exposure amount. The (D) polyfunctional cationically polymerizable compound (hereinafter abbreviated as (D) component) may, for example, be the following (except for (A) an alkali-soluble resin). Examples of the compound having two or more epoxy groups in the molecule include bisphenol A diglycidyl ether 'bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and hydrogenated bisphenol A condensed water. Diglycidyl ether of bisphenol compound such as glyceryl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether; 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether Polyglycidyl ether of a polyhydric alcohol such as trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; by aliphatic group such as ethylene glycol, propylene glycol or glycerin Polyglycidyl ether of polyether polyol obtained by adding one or more alkylene oxides to a polyol; Phenol NOVOLAC Epoxy Resin; cresol novolac epoxy resin; polyphenol epoxy Resin; aliphatic long-chain dibasic acid-18-201005436 bis glycidyl ester; glycidyl ester of higher fatty acid; epoxidized soybean oil, epoxidized linseed oil, and the like. As a commercially available product having two or more epoxy groups in the molecule, for example, as the bisphenol A type epoxy resin, EPIKOTE 1001, the same 1002, the same 1003, and the same 1004 (above, Japan Epoxy) Examples of the bisphenol F-type epoxy resin include EPIKOTE 807 (manufactured by Japan Epoxy Resins Co., Ltd.); and the phenolic epoxy resin: EPIKOTE 152 and 154 1st, 57S65 (above; Iapan Epoxy Resins Co., Ltd.), EPPN 201, 202 (above, Nippon Chemical Co., Ltd.), etc.; as a cresol novolac epoxy resin, EOCN 102, The same as 103S (above, Nippon Kayaku Co., Ltd.), EPIKOTE 180S75 (made by Japan Epoxy Resins Co., Ltd.), etc.; as the polyphenol type epoxy resin, EPIKOTE 1032H60, the same XY-4000 (above, Japan) Epoxy Resins (manufactured by Epoxy Resins), etc.: as a cyclic aliphatic epoxy resin, CY-175, 177, 179, araldite CY-182, 192, 184 (above, Ciba Specialty Chemicals) System) and so on. Examples of the compound containing two or more 3,4-epoxycyclohexyl groups in the molecule include 3,4·epoxycyclohexylmethyl-3',4·-epoxycyclohexaneformate. , bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6 -Methylcyclohexyl-3_,4'-epoxy-6'-methylcyclohexanecarboxylate, methylene biguanide, 4-epoxycyclohexane). Among these epoxy compounds, a phenolic epoxy resin and a polyphenol epoxy resin are preferred. -19- 201005436 (E) A compound which generates an acid by heating (hereinafter, simply referred to as a thermosensitive acid generator and (E) component), examples thereof include a benzyl sulfonium salt and a benzothiazolium salt. , money salt, scale salts, etc. Among these, the protective film of the benzyl sulfonium salt is suitably used because of its high surface hardness. Specific examples of the onium salt include 4-ethyl phenyl phenyl hexafluoroantimonate, 4-ethyl methoxy phenyl dimethyl hexafluoro arsenate, and dimethyl carbonate. 4--4-benzyloxyoxyphenyl hexafluoroantimonate, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzene An alkyl sulfonium salt such as methyl methoxy)phenyl hydrazine hexafluoro arsenate or dimethyl-3-chloro-4-ethoxy phenyl hexafluoroantimonate; benzyl-4-hydroxyphenyl Methyl hydrazine hexafluoroantimonate, benzyl-4-hydroxyphenylmethyl sulfonium hexafluorophosphate, 4-acetoxyphenylbenzyl methyl hexafluoroantimonate, benzyl-4-methyl Oxyphenylmethyl hydrazine hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethyl hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethyl hydrazine A benzyl sulfonium salt such as hexafluoroarsenate or the like. Among these, 4-ethyl phenyl phenyl hexafluoroantimonate, benzyl-4 hydroxyphenyl methyl hexafluorophosphate, benzyl-2-methyl-4-hydroxyphenyl Methyl hydrazine hexafluoroantimonate or the like is suitably used. As a commercial product of an acid generator which is suitably used as a heat-sensitive acid generator, the alkyl sulfonium salt may be exemplified by Asahi Kasei Co., Ltd. Product name: ADEKAOPUTON CP-66, CP-77. In addition, as the benzamidine salt, the trade name of Sanshin Chemical Industry Co., Ltd.: SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI - 100L, SI-1 10L. -20- 201005436 The proportion of the component (E) is 0. 100 parts by weight relative to the copolymer (A). 1 to 10 parts by weight is preferred, with 0. 5 to 5 parts by weight is more preferred. When the amount of (E) component is 0. When the amount is 1 to 10 parts by weight, the radiation sensitive resin composition of the present invention can form a protective film having a high pencil hardness and abrasion resistance. (Optional Additive) In the radiation-sensitive resin composition of the present invention, it is necessary to be blended with the above components (F) having two or more ethylenic unsaturations within a range not detracting from the desired effect. An additive such as a polyfunctional propylene monomer bonded to a urethane bond, (G) an adhesion aid, (H) an acid anhydride for improving heat resistance, and (I) a surfactant. (F) a polyfunctional propylene monomer having two or more ethylenically unsaturated groups and a urethane bond (hereinafter, simply referred to as a polyfunctional urethane acrylate and a component (F)), (α) a polyfunctional isocyanate compound, a (meth) acrylate compound having one hydroxyl group in the molecule, and a compound which is required to react with the (r) polyol. Examples of the (α) polyfunctional isocyanate compound which is a constituent of the above polyfunctional urethane acrylate include 2,3-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,2-ethylene 2 Isocyanate, 1,3-propylidene diisocyanate, 1,4-butylene diisocyanate, 1,5·pentyl diisocyanate, 1,6-extended hexyl diisocyanate, diphenylmethane diisocyanate , hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, i, 2 · phenyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, xylene diisocyanate , cyclohexane diisocyanate, and the like. Among these (α) polyfunctional isocyanate compounds, 2,3-toluene is used from the viewpoint of the compatibility of the obtained radiation-sensitive linear resin composition of the urethane-methacrylate acrylate. Diisocyanate, isophorone diisocyanate, 1,6-extended hexyl diisocyanate, 1,3-phenylene diisocyanate or the like is preferred. These can be used alone or in combination. Further, (5) a (meth) acrylate compound containing one hydroxyl group in the molecule may, for example, be 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or 3-hydroxypropyl acrylate. 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, caprolactone modified 2-hydroxyethyl acrylate, ® polyethylene glycol monoacrylate, polypropylene glycol monoacrylic acid Ester and the like. Among these (3) (meth) acrylate compounds having one hydroxyl group in the molecule, 2-hydroxy acrylate is used from the viewpoint of polymerizability and solubility of the obtained polyfunctional compound ethyl acrylate acrylate. Ethyl ester, 3-hydroxypropyl acrylate, neopentyl alcohol triacrylate, dipentaerythritol pentaacrylate, etc. are preferred. These can be used alone or in combination. Further, examples of the (r) polyalcohol which can be reacted as required include polyglycol polyalcohol, polyester polyol, polycarbonate polyalcohol, polycaprolactone polyalcohol and the like. Among these polyether polyols, polyethylene glycol, polypropylene glycol or the like having a weight average molecular weight of 10,000 or less is preferred. The above-mentioned polyfunctional urethane acrylate is synthesized by a known method, and is obtained by a predetermined amount of (α) polyfunctional isocyanate compound and () having one or more hydroxyl groups in the molecule ( The methyl acrylate compound and the (r) polyol to be added are charged at 60 ° C to 10 (TC is warmed and stirred until the free isocyanate group disappears. The reaction time is usually about 60 to 240 minutes. -22 - 201005436 In addition, a catalyst such as hydroquinone monomethyl ether or dibutyltin dilaurate (IV) may be added during the reaction, and hydroquinone to prevent gelation due to dark reaction in storage may be added. , p-benzoquinone, tert-butyl catechol, etc. As a commercial product of the above polyfunctional urethane acrylate, KAYARAD DPHA-40H, UX-2021, UX-230 1, UX — 3204, same as UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937 (above, Nippon Chemical Co., Ltd.), ART - RESINUN - 9000PEP, with UN - 9200A, with UN — ® 3 320HS (above, root industrial (share) system) The amount of the component (F) to be used is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the copolymer (A). When the amount of the compound (F) is 1 to 1 When the amount is 50 parts by weight, a radiation-sensitive resin composition which is balanced at a high level of the properties such as the adhesion of the obtained protective film and the high pencil hardness can be obtained. Next, as a (G) adhesion aid (hereinafter, For example, the component (G) may be used. For example, a functional decane coupling agent having a reactive substituent may be used. Examples of the reactive substituent include a carboxyl group, a methacryl fluorenyl group, an isocyanate group, and an epoxy group. Specific examples include, for example, benzoic acid trimethoxy decyl ester, r-methyl propylene oxypropyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane. , r-isocyanate propyl triethoxy decane, r-glycidoxypropyl trimethoxy decane, r-glycidoxypropyl triethoxy decane, yS - (3,4 · epoxycyclohexyl Ethyltrimethoxydecane, etc. -23- 201005436 This kind of (G) Preferably, it is preferably from 1 to 40 parts by weight, more preferably from 1 to 40 parts by weight, per 100 parts by weight of the copolymer (A). When the amount of the (G) adhesion aid is from 1 to 50 parts by weight, In the resin composition of the present invention, in order to enhance the heat resistance of the formed protective film, (H) an acid anhydride for the purpose of improving heat resistance (hereinafter, simply referred to as (H) may be added. The component.) may, for example, beaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, trimesic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, or lower An aliphatic dicarboxylic anhydride such as HIMIC Anhydride; an alicyclic polyvalent carboxylic acid dianhydride such as 1,2,3,4-butyric acid dianhydride or cyclopentanetetracarboxylic dianhydride; An aromatic polyvalent carboxylic anhydride such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, etc.; ethylene glycol trimellitic anhydride, glycerol, and benzene An acid anhydride-containing acid anhydride such as an acid anhydride. Among these, from the viewpoint of obtaining a cured film having high heat resistance, an aromatic polyvalent carboxylic acid anhydride, particularly trimellitic anhydride is preferable. The (H) component is 0. by weight relative to 100 parts by weight of the copolymer (A). It is preferably 1 to 50 parts by weight, more preferably 1 to 40 parts by weight. When the amount of the component (H) is from 1 to 50 parts by weight, the heat resistance of the obtained protective film is optimum. The resin composition of the present invention may further contain (I) a surfactant (hereinafter, simply referred to as (I) component) in order to improve coating properties. Examples of such a component (I) include a fluorine-based surfactant and an anthraquinone surfactant. As the fluorine-based surfactant, for example, BM CHEMIE company trade name: BM-1, bm-1100, Dainippon Ink Chemical Industry Co., Ltd. -24-201005436 Product name: MEGAFACEF14 2D, same as F172, Same as F173, F183, NEOS (stock) product name: TTX-218 and other commercial products. Examples of the above-mentioned oxime-based surfactants include: Toray Dow Corning Organic 矽 (s), trade names: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57'DC — 190. Shin-Etsu Chemical Co., Ltd. Product name: Commercial product such as KP341. The component (I) is 0. by weight relative to 100 parts by weight of the copolymer (A). 01~10 parts by weight is better, and more is 0. 05 to 5 parts by weight is preferred. When the amount of the (I) component is 0. When it is 01 to 10 parts by weight, it is possible to suppress the coarsening of the film which is formed when the coating film is formed on the substrate. The composition for forming a protective film of a touch panel used in the present invention is formed by mixing and dissolving a copolymer (A), a component (B), and a component (C). Among the above-mentioned solvents, from the viewpoints of solubility of each component, reactivity of each component, and easiness of formation of a coating film, for example, an alcohol, a glycol ether, an ethylene glycol alkyl ether acetate, or the like is preferably used. Ester and diethylene glycol. Among these, 'such as benzyl alcohol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl ether, diethylene glycol two Methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethyl ethoxypropionate, and -3-methoxybutyl acetate may be particularly suitably used. Together with the above solvent, in order to further improve the in-plane uniformity of the film thickness, a high boiling point solvent can be used in combination. Examples of the high-boiling point solvent which can be used include N-methyl lysine, ethyl acetoate, isophorone, 1-octanol, 1-nonanol, benzyl acetate, and ethyl benzoate. , diethyl oxalate, maleic acid-25- 201005436 ethyl ester, r-butyrolactone, ethylene carbonate, propylene carbonate and the like. Among them, N-methylpyrrolidone and r-butyrolactone are preferred. (a) Step 1 When a film is formed by a coating method, the radiation-sensitive resin composition solution of the present invention is applied onto the transparent conductive film, and then the coated surface is heated (prebaked) to form Membrane. The solid content concentration of the composition solution used in the coating method is preferably 5 to 50% by weight, Ο

It is preferably 10 to 40% by weight, more preferably 15 to 35% by weight. The coating method of the composition solution is not particularly limited, and for example, a suitable method such as a spray coating method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method, or a rod coating method can be employed, and in particular, a spin coating method or The slit die coating method is preferred. In particular, the radiation sensitive resin composition of the present invention is particularly suitable for use in a slit die coating method, and even when the moving speed of the slit die is set to 150 mm/sec, coating unevenness does not occur. The film thus formed is preferably subjected to prebaking. The pre-baking conditions vary depending on the type of each component, the blending ratio, etc., and it is preferably carried out at 70 to 120 ° C for about 1 to 10 minutes. The film thickness after prebaking of the film is preferably 0.5 to 10.0/zm, preferably about 1.0 to 5.0. Step (1) Step 1 Next, at least a portion of the formed film is exposed. In this case, when a part of the film is exposed, it is usually performed by interposing a photomask having a prescribed pattern for exposure. As the radiation used in the exposure, for example, visible rays, -26-201005436 ultraviolet rays, far ultraviolet rays, electron beams, rifling wires, and the like can be used, but radiation having a wavelength in the range of 19 〇 to 45 〇 nm is preferable, particularly containing 3 Radiation of 65 nm ultraviolet light is preferred. The amount of exposure is such that the intensity of the wavelength of the exposed radiation of 3 65 nm is measured by an illuminance meter (manufactured by OAI model 356 OAI Optical Associates Inc.), preferably 100 to 1 〇, 〇〇〇 J/m 2 , It is preferable to use 500 to 3, 〇〇〇j/m2. (C) Step 1 Next, by developing the film after exposure, unnecessary portions are removed to form a prescribed pattern. The developing solution used for development is preferably an alkaline developing solution, and examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium methyl citrate, and ammonia water: An aqueous solution of a basic compound such as a new ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. Further, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be appropriately added to the aqueous solution of the basic compound. As the developing method, any one of a puddle method, a dipping method, and a shower method can be used, and the development time is preferably from 10 to 180 seconds. After the development, for example, after rinsing in running water for 30 to 90 seconds, a desired pattern/embodiment is formed by performing air drying operation using, for example, compressed air or compressed nitrogen, and a synthesis example and an embodiment are disclosed. The present invention is described, -27- 201005436, but the present invention is not limited to the following embodiments. (Production of Polymer) Synthesis Example 1 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2·-azobis(2,4-dimethylvaleronitrile) and diethylene glycol were charged first. 200 parts by weight of methyl ethyl ether. Next, 40 parts by weight of glycidyl methacrylate, 18 parts by weight of styrene, 20 parts by weight of methacrylic acid, and 22 parts by weight of N-cyclohexylmaleimine were added, followed by nitrogen substitution, and then slowly stirring was started. . The temperature of the solution was raised to 70 ° C, and the temperature was maintained for five hours to obtain a polymer solution containing the copolymer (A-1). The solid content concentration of the obtained polymer solution was 33.1% by weight. The number average molecular weight of the obtained polymer was 7,00 (the number average molecular weight was a polystyrene-equivalent molecular weight measured by GPC (gel permeation chromatography) HLC-8020 (manufactured by TOS®H). Further, the molecular weight distribution (Mw/Mn) was 2. Synthesis Example 2 ^ In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2 azobisisobutyronitrile and 200 parts by weight of diethylene glycol methyl ethyl ether were placed in advance. Next, 40 parts by weight of glycidyl methacrylate, 35 parts by weight of tricyclo [5.2.1.0 '6] decane-8-yl methacrylate, 20 parts by weight of methacrylic acid, and 1,3 - butyl are charged. After 5 parts by weight of the alkene and further nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 80 ° C. The temperature was maintained for five hours to obtain a polymer solution containing the copolymer (A-2). The solid content concentration of the obtained polymer solution was 33.3 wt%. The number average molecular weight of the obtained polymer was 6,500. Further, the molecular weight distribution (Mw/Mn) was -28-201005436. Synthesis Example 3 In the flask equipped with a cooling tube and a mixer, '2,2'·azobis(2,4-dimethylvaleronitrile was first charged) 5 parts by weight and diethylene glycol monoacetic acid 200 parts by weight. Next, 40 parts by weight of 3-(methacryloyloxyethyl)oxetane (Oxethane), 1 part by weight of styrene, 3 parts by weight of methacrylic acid, and cyclohexylmaleimide 20 were charged. After the weight portion was replaced with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C ' to maintain the temperature for five hours to obtain a polymer solution containing the copolymer (A - 3). The solid content concentration of the obtained polymer solution was 33.1% by weight. The number average molecular weight of the obtained polymer was 7,300. Further, the molecular weight distribution (Mw/Mn) was 2. Synthesis Example 4 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of diethylene glycol methyl ethyl ether were placed in advance. Next, 50 parts by weight of glycidyl methacrylate and 50 parts by weight of styrene were placed, and after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 80 ° C, and the temperature was maintained for five hours to obtain a polymer solution containing the copolymer (A-4). The solid content concentration of the obtained polymer solution was 32.8% by weight. The number average molecular weight of the obtained polymer was 7, 〇〇〇. Further, the molecular weight distribution (Mw/Mn) was 2. Synthesis Example 5 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2·-azobis(2,4-dimethylvaleronitrile) and propylene glycol monomethyl ether acetate were placed in advance. -29- 201005436 Parts by weight. Next, 30 parts by weight of benzyl methacrylate, 10 parts by weight of styrene, 30 parts by weight of phenyl maleimide, and 20 parts by weight of 2-hydroxyethyl methacrylate, and 1 part by weight of methacrylic acid were charged. After the nitrogen substitution, 'start slowly stirring. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for five hours to obtain a polymer solution containing the copolymer (A-5). The solid content concentration of the obtained polymer solution was 33.1% by weight. The obtained polymer had a number average molecular weight of 7,000. Further, the molecular weight distribution (Mw/Mn) was 2. ❹ Synthesis Example 6 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobisisobutyronitrile and 250 parts by weight of 3-methoxybutyl acetate were charged, followed by loading of methacrylic acid. 18 parts by weight, 25 parts by weight of tricyclo [5.2.1.0''6] decane-8-yl methacrylate, 5 parts by weight of styrene, 30 parts by weight of 2-hydroxyethyl methacrylate, and benzyl methacrylate 22 parts by weight, after the nitrogen substitution, the solution was slowly stirred while the temperature of the solution was raised to 280 ° C, and the temperature was maintained for five hours to carry out polymerization, thereby obtaining a copolymer having a solid concentration of 28.8% by weight. (A-6) solution. The obtained copolymer (A-6) had a number average molecular weight of 7,000. Further, the molecular weight distribution (Mw/Mn) was 2. Next, in the copolymer (A-6) solution, 14 parts of 2-methylpropenyloxyethyl isocyanate (trade name: Karenz MOI, manufactured by Showa Denko Co., Ltd.) and 0.1 parts by weight of 4-methoxyphenol were added. Thereafter, the mixture was stirred at 40 ° C for one hour, and further stirred at 60 ° C for two hours to cause a reaction. The isocyanate group derived from 2-methylpropenyloxyethyl isocyanate and the copolymer (A-6) -30-201005436 The hydroxyl group is reacted by IR (infrared absorption polymer solution (A-6), The solution after reacting at 40 ° C for one hour and two hours, respectively, was reduced by IR light in the vicinity of the isocyanate of 2-methylpropenyloxyethyl isocyanate. (Α-6) polymer solution. Synthesis Example 7 A flask equipped with a cooling tube and a stirrer, charged with 5 parts by weight of dimethyl valeronitrile, and with ethylene glycol diethyl ether, charged with methacrylic acid 2 , 3-glycidyl ester 25 parts by weight of quinone imine 10 parts by weight, p-isopropene phenol 10 parts by weight of tetrahydrofurfuryl ester, 20 parts by weight of 3-ethyl-3-methylpropene butane, methyl group 15 parts by weight of acrylic acid, and then slowly stirring was started. The solution temperature was maintained at this temperature for five hours to obtain a copolymer (Α φ liquid. The solid content concentration of the obtained polymer solution was such that the number average molecular weight of the polymer was 8,000. The other (Mw/Mn) was 2. Synthesis Example 1 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of di-(2,4-dimethylvaleronitrile) and diethylene glycol were added. Then, 60 parts by weight of methyl methacrylate was charged. After 30 parts by weight of N-cyclohexylmaleimide, slow stirring was started, and the solution temperature was confirmed by the spectrum. By writing and adding at 60 ° C, it was confirmed that the concentration of 2270 cm·1 derived from the ester group was 30.0 % 2,2_-azobis (2,4-200 parts by weight. Part, N-cyclohexyl) The horse parts and the methacryloyloxymethyloxane were raised to 70 ° C by nitrogen substitution, and the polymer of the dimension 7-3 was dissolved in 3.2% by weight. In addition, the molecular weight distribution line was charged with 2,2·-azoethyl ether 200 weight & benzene and benzene, 1 〇 and then nitrogen substitution was carried out to 70 ° C, maintaining -31-.201005436 the temperature for five hours A polymer solution containing the copolymer (a-1) was obtained. The solid content concentration of the obtained polymer solution was 32.6% by weight. The number average molecular weight of the obtained polymer was 6,400. Further, the molecular weight distribution (Mw/Mn) was 2. Preparation and Evaluation of Resin Composition Example 1 A solution (corresponding to 100 parts by weight of the copolymer (A-1) (solid content)) containing the copolymer (A-1) obtained in the above Synthesis Example 1 was added, and (B-1) ® Succinic acid mono-[3-(3-propenyloxy-2,2·bis-acrylomethoxymethyl-propoxy)-2,2-bis-acrylomethoxymethyl-propyl 200 parts by weight of an ester, and (C-1)2-methyl1-4-methylphenylthio)-2-morpholinilpropan-1-one (trade name: IRGACURE 907, manufactured by Ciba Specialty Chemicals Co., Ltd.) 10 (D - 1) furfural type epoxy resin (trade name: EPIKOTE 1 52, manufactured by Japan Epoxy Resins Co., Ltd.) 30 parts by weight, (G - l)r-glycidoxypropyltrimethoxy group 30 parts by weight of decane and FTX-218 (manufactured by NEOS) as 0.2 parts by weight of (I-1) 1 _ surfactant, and further added solvent (S-1) diethylene glycol methyl ethyl ether to make the solid content concentration 22% by weight. Then, the resin composition was prepared by filtration using a micropore filter having a pore size of 0.5 /zm. Evaluation of Protective Film (1) Evaluation of Transparency The above composition was applied onto a Si〇2 dip-coated glass substrate using a spinner, and then prebaked on a hot plate at 80 ° C for two minutes to form a coating film. The film is exposed to 1 000 〗/m2. Thereafter, after developing with a potassium hydroxide 0.05% by weight aqueous solution at 25 ° C, it was washed with pure water for one minute, and then heated in an oven of -32-.201005436 23 0 ° C for 30 minutes, thereby forming a film thickness. It is a 2.0/m protective film. For the substrate having the protective film formed as described above, a transmittance of 400 to 800 nm was measured using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)). The minimum 透过 of 400 to 800 nm transmittance is shown in Tables 1 and 2. When the yttrium is more than 95%, the transparency of the protective film can be said to be good. (2) Pencil hardness evaluation ® A protective film was formed in the same manner as in the evaluation of transparency, and the surface hardness of the protective film was measured by the 8.4.1 pencil scratch test of JIS K-5400 - 1 990. This is disclosed in Tables 1 and 2. When the temperature is above 4H, it can be said that the surface hardness is good. (3) Evaluation of the micro hardness The protective film was formed by the same method as the transparency evaluation, and a Vickers indenter was used using a micro compression tester (trade name: FISCHERSCOPE HC-110, manufactured by Fischer Instruments). The load speed and the de-loading speed were both set to 5 mN/sec, and the load up to 50 mN was maintained for 10 seconds, and then the Martens hardness was measured by removing the load. This is disclosed in Tables 1 and 2. If the 値 is 650 N/mm2 or more, the film hardness can be said to be good. (4) The abrasion resistance test was carried out by the same method as the transparency evaluation, and a Gakushin-Type abrasion tester was used, and a load of 200 g was applied to the steel wool #〇〇〇〇 and reciprocated 1〇. Times. The condition of the abrasion was evaluated by the naked eye according to the following criteria -33- .201005436 . This is disclosed in Tables 1 and 2. Judgment standard ◎: No scratches at all: 11 to 3 scratches △ : 4 to 10 scratches X: If the scratches of 10 or more are ◎, 〇, △, it can be said to be good Friction resistance. (5) Adhesion test (substrate on the glass substrate and filmed with ITO® film on the surface) After washing and drying 4 吋 glass wafers with pure water, the composition was applied to each substrate using a spinner. Thereafter, prebaking was performed at 80 ° C for two minutes on a hot plate to form a coating film, and 1 000 Å/m 2 was exposed on the obtained film. Thereafter, it was washed with pure water by a 0.05% by weight aqueous solution of potassium hydroxide at 25 ° (after development for one minute, and then heated in an oven at 230 ° C for 30 minutes, thereby forming a film thickness of 2.0 #m. Protective film.

Φ For the substrate having the protective film formed as described above, the adhesion of the protective film was evaluated by the 8.5.3 adhesion checkerboard tape method of JIS K-5400-1990. In a hundred checkerboards, the number of remaining checkerboards is displayed. The same evaluation as in the case of a 4 Å glass wafer was carried out except that a glass substrate on which an ITO film was formed on the surface was used instead of the 4 Å glass wafer, and the adhesion to the ITO film was evaluated. This is disclosed in Tables 1 and 2. Examples 2 to 20 and Comparative Examples 1 to 3 The types and amounts of the respective components of the composition are as shown in Tables 1 and 2, and are shown in Tables 1 and 2, except that the solvent is used to adjust to Tables 1 and 2. A resin composition was prepared in the same manner as in Example 1 except for the solid content concentration described. Using the resin composition for forming a protective film prepared as described above, a protective film was formed as in Example 1 and evaluated. The above evaluation results are disclosed in Tables 1 and 2. The protective film was formed and evaluated in the same manner as in Example 1 using a resin composition prepared by forming a protective film as described above. The above evaluation results are disclosed in Tables 1 and 2.

【Table 1】

Window Example 1 2 3 4 5 6 7 8 • 9 10 11 12 A-1 100 100 100 100 100 100 100 100 100 100 100 100 A-2 A-3 (A) Component A-4 A-5 A-6 A-7 (B) Ingredient B-1 200 200 200 200 200 200 200 200 150 50 2D0 200 C-1 10 10 5 5 10 10 10 10 10 10 10 10 C-2 - 5 5 5 (9) Composition D-1 30 30 30 30 50 10 - - 10 - 30 30 D-2 30 E-1 1 - Old component E-2 - - - 2 - - - - - - - 1 E-3 <F) component FT - - - 20 - - - - 10 - - - (G) Ingredient G-1 30 30 30 30 30 30 30 30 30 30 30 30 (H>Component H-1 (1> Ingredient 1-1 0JZ 0.2 0.2 05 0_2 02 0.2 02 0.2 0_2 0.2 Comparative ruling example — β-1 DPHA b-1 Solvent S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S- 1 Solid content temperature 22 22 22 22 22 22 22 22 22 22 22 22 Transparency (%) 99 98 99 Suppressed »9 9δ 9S 99 99 S9 99 99 曲•砚度5Η 5Η SH 6H 6M 6Η 5Η 7Η 6Η 4Η 6Η 微小 Tiny β (N/mm1) 740 720 740 760 7βΟ 750 7 30 780 750 690 760 760 Resistant to rubbing 0 Ο Ο Ο Φ Ο Δ Ο Ο Adhesion evaluation on glass 100 100 100 100 100 80 100 80 100 100 100 100 ΠΌ 100 100 100 100 100 100 100 100 100 100 100 100 -35- 201005436 [Table 2] Ο mm Comparative Example 13 14 15 16 17 18 IS 20 1 2 3 <A> Component A-1 100 A 100 - - A-2 A-3 A-4 A -5 - A-6 A — — — — 100 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — Component C-1 10 10 10 10 10 10 10 5 10 10 10 C-2 • - - - - - - - 5 - - - (D) Component D-^-1 30 30 30 30 30 30 30 30 - 30 30 D -2 - (E) component E-1 *- E-2 E-3 1 (F) component F-1 10 <G) component G-1 30 30 30 - 30 30 30 30 30 30 30 (H) component H —1 « (D component 1-1 0.2 0.2 OJZ 02 - 0.2 0.2 02 〇·2 0·2 0.2 Comparative synthesis example 1 a-1 - 100 — DPHA b-1 - one-one — one--» 30 200 200 media S-1 22 22 22 22 22 22 22 22 22 22 22 Transparency (%) 99 99 99 99 99 99 Crowd 99 99 99 99 Ship pen hardness. 6H 5H 5H 5H 4H 5H 5H 5Η 3Η 3Η 6Η Tiny ΒΚΝ/关 1 750 730 740 720 690 740 750 740 620 640 720 Scratch resistance Ο Ο Δ 0 Ο Ο XX 密 Adhesive ms Coffee 100 100 100 TOO too 100 100 too 80 60 0 ΓΤΟ上100 too 100 100 100 100 100 100 80 70 0 In addition, in Tables 1 and 2, (Β) a polyfunctional acrylate, (C) a radiation-sensitive polymerization initiator, (D) a polyfunctional cationic polymerizable compound, (E) a thermosensitive acid generator, (F) Polyfunctional urethane acrylate, (G) adhesion aid, (H) acid anhydride, (I) surfactant, and (S) solvent are abbreviated as follows. B - 1: succinic acid mono-[3-(3-propenyloxy-2,2-bis-acrylomethoxymethyl-propoxy)-2,2-bis-acryloyloxymethyl-propyl ] ester C - 1: 2-methyl-1-(4-methylphenylthio)-2-morpholinepropane-buxone (trade name: IRGACURE 907, manufactured by Oil?a Specialty Chemicals Co., Ltd.) C-2: B Keto-1-[9-ethyl_6-(2-methylbenzhydryl)-9H-oxazolyl-3-yl]-l-(〇-acetamidine) (trade name iRGACURE 〇χ〇2) , ciba -36- 201005436

Specialty Chemicals Co., Ltd.) D — 1 : Furfural type epoxy resin (trade name: EPIK0TE1 5 2, manufactured by Japan Epoxy Resins) D — 2: Double 酣A酣 type epoxy resin (Japan Epoxy Resins) Product Name: EPIKOTE 157S65) E - 1: Benzyl-2-methyl-4-hydroxyphenylmethyl hexafluoroantimonate (SI-80, manufactured by Sanshin Chemical Industry Co., Ltd.) E - 2: Benzyl -4-hydroxyphenylmethyl sulfonium hexafluorophosphate (SI-110, manufactured by Sanshin Chemical Industry Co., Ltd.) E- 3 : 4-acetic acid phenyl dimethyl hexafluoroantimonate (Sanshin Chemical Co., Ltd.) Industrial (stock) SI — 150) F-1: Polyfunctional urethane acrylate (UN- 3 320HS manufactured by K.K.) G - 1: 7-glycidoxypropyltrimethoxy矽 Η Η - 1 : trimellitic anhydride 1-1: fluorosurfactant (trade name: FTX - © 218) S-1: diethylene glycol methyl ether S-2: propylene glycol monomethyl ether acetate b —l: Dipentaerythritol hexaacrylate (product name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) [Simple description] None. [Main component symbol description] No 0 -37-

Claims (1)

201005436, f VII. Patent application scope: 1. A radiation sensitive resin composition for forming a protective film of a touch panel, comprising: (A) an alkali-soluble resin; (B) having a formula selected from the following formula (1) And a compound having one or more ethylenically unsaturated groups of the following formula (2); (C) a radiation-sensitive polymerization initiator; (wherein X is an alkyl group selected from a hydrogen atom, a carbon number of 1 to 6, an alkylene group or a methacryl fluorenyl group, and at least one is an acryloyl group or a methacryl fluorenyl group; and W is a carbon An alkylene group having 1 to 6 alkyl groups, an alkyl group having 2 to 6 carbon atoms having one unsaturated bond, a phenyl group, and a cyclohexyl group. [2] The radiation sensitive resin composition for forming a protective film of a touch panel according to the first aspect of the invention, wherein the (A) alkali-soluble resin is an (al) unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride. And (a2) a copolymer formed by copolymerization of a monomer containing an epoxy group-containing unsaturated compound. 3. The radiation sensitive resin composition for forming a protective film for a touch panel of the first or second aspect of the patent application, which comprises (D) a polyfunctional cationically polymerizable compound (however, in addition to (A) an alkali soluble resin other than). In the radiation-sensitive resin composition for forming a protective film of the touch panel of the third aspect of the invention, (E) a compound which generates an acid by heating. A protective film for a touch panel, which is formed by a radiation sensitive resin composition as in the first aspect of the patent application. A method for forming a protective film, which comprises forming a film on a substrate of a touch panel by using a radiation-sensitive resin composition as in the first aspect of the patent application, followed by irradiation treatment of radiation and heat treatment. 〇 -39- 201005436 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Λ 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: