TW201223982A - Curable resin composition - Google Patents

Abstract

A curable resin composition contains the following (A), (B), (C), (D), and (E), wherein relative to 100 parts by mass of (A), the content of (B) is above 1 part by mass and below 100 parts by mass; (A) is a copolymer containing at least a structure unit selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride and a structure unit derived from the structure for oxidizing unsaturated cycloaliphatic hydrocarbon ring and the monomer of C-C unsaturated double bond, and having the acid value of 30 mg-KOH/g or higher and below 180 mg-KOH/g. (B) is the epoxy resin with the acid value less than 30 mg-KOH/g. (C) is the compound containing at least a group selected from at least two groups consisting of acryl group and methacryl group. (D) is a thermal acid generating agent. (E) is a solvent.

Description

201223982 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a curable resin composition. [Prior Art] In a liquid crystal display or the like, a curable resin composition is used in order to form an overcoat. As such a curable resin composition, for example, a copolymer of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0''6]decyl acrylate and dipentaerythritol hexaacrylate are known. And a curable resin composition of a solvent. Further, it is known that the curable resin composition is applied onto a substrate and baked at 220 ° C for 20 minutes to form a coating film (Patent Document 1). On the other hand, in recent years, in order to realize a lighter and thinner liquid crystal display, development of a plastic liquid crystal display has been expected. However, the heat resistant temperature of a general plastic substrate is only about 100 to 200 ° C. (Non-Patent Document 1). In addition, when the curable resin composition proposed in the prior art is cured at a low temperature of less than 200 ° C to form a coating film, the chemical resistance of the coating film formed may not be sufficient. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. No. 2-9-49854 [Non-Patent Document 1] SHARP Technical Report, No. 85, No. 30-33, April 2003 [Invention] [Invented Problem] -5- 201223982 The present invention provides the following Π]~[6]. [1] A curable resin composition which contains the following (A), (Β), (C), (D), and (Ε), and is contained in an amount of 100 parts by mass relative to (Α), (Β a content of 1 part by mass or more and 1 part by mass or less; (Α) containing at least one structural unit selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and having a structural unit of a epoxidized structure of an unsaturated alicyclic hydrocarbon and a monomer of a carbon-carbon unsaturated double bond, a copolymer having an acid value of 30 mg-KOH/g or more and 180 mg-KOH/g or less (B) An epoxy resin (C) having less than 30 mg-KOH/g (C), a compound (D) having at least one selected from the group consisting of an acryloyl group and a methacryl group, and a thermal acid generator (E) Solvent. [2] The curable resin composition of the above [1], wherein the monomer having a structure for epoxidizing an unsaturated alicyclic hydrocarbon and a carbon-carbon unsaturated double bond is a compound represented by the formula (I) And at least one compound selected from the group consisting of the compounds represented by the formula (Π), [Chemical Formula 1] R1 Ο

I II H2C = C —C—0—X1 f ?

[In the formulae (I) and (II), R1 and R2 are each independently represented by a hydrogen atom or an alkyl group having a carbon number of 1 -6 - 201223982 to 4, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group; X1 and X2 is independently shown as a single bond or an alkanediyl group having a carbon number of 1 to 6, and the -CH2- contained in the alkanediyl group may be substituted by -0, -S- or -NR3-, and R3 is represented by a hydrogen atom or Alkyl group having 1 to 4 carbon atoms]. [3] The curable resin composition according to the above [1] or [2], wherein the compound having at least one selected from the group consisting of a propylene group and a methacryl group is The molecular weight is 150 or more and 3,000 or less. [4] A coating film formed by using the curable resin composition according to any one of the above [1] to [3]. [5] A coating film obtained by applying the curable resin composition according to any one of the above [1] to [3] to a substrate and hardening by heat. [6] A display device comprising the coating film of the above [4] or [5]. [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. The curable resin composition of the present invention contains the following (A), (B), (C), (D) and (E), and the content of (B) is 100 parts by mass based on the content of (A). The curable resin composition 1 (A) in an amount of 1 part by mass or more and 1 part by mass or less contains at least one structural unit selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a copolymer having a structure having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized and a carbon-carbon unsaturated double bond, and having an acid value of 30 mg-KOH/g or more (hereinafter also referred to as "resin (A) )")). 201223982 (B) Epoxy resin having an acid value of less than 30 mg-KOH/g (hereinafter also referred to as "epoxy resin (B)"). (C) A compound having at least one selected from the group consisting of an acryloyl group and a methacryl group (hereinafter also referred to as "polymerizable compound (C)"). (D) Thermal acid generator (E) Solvent 尙 In the present specification, the compounds exemplified as the respective components may be used singly or in combination unless otherwise specified. The curable resin composition of the present invention contains the resin (A). The resin (A) is a structural unit containing at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter also referred to as "(a)") a copolymer with a structural unit derived from a monomer (b) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized and a carbon-carbon unsaturated double bond (hereinafter also referred to as "(b)"), The acid value of the resin (A) is 30 mg-KOH/g or more and 18 mg-KOH/g or less. The resin (A) used in the curable resin composition of the present invention may, for example, be a resin (A2-1): a copolymer obtained by polymerizing (a) and (b), and a resin (A2-2). : (a), (b) and a monomer (c) copolymerizable with (a) and (b) (but not having a structure for epoxidizing an unsaturated alicyclic hydrocarbon) (hereinafter also referred to as In the case of "(c)", the copolymer or the like is polymerized, but the resin (A) is preferably a resin (A2-1). Specific examples of (a) include acrylic acid, methacrylic acid, and crotonic acid-8-'

S 201223982, unsaturated monocarboxylic acids such as 0-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid; maleic acid, fumaric acid, methyl maleic acid , methyl fumaric acid, methylene succinic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrofurfuric acid, 1,2,3,6-four An unsaturated dicarboxylic acid such as hydroquinone, dimethyltetrahydrofurfuric acid or 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxyl Bicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2·2·1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethyl a bicyclic unsaturated compound containing a carboxyl group such as a bicyclo [2.2.1] hept-2-ene; maleic anhydride, methyl maleic anhydride, methylene succinic anhydride, 3-vinyl phthalic anhydride, 4 -vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1 ] Hun-2-ene anhydride (normic anhydride), etc. a carboxylic acid anhydride; a monovalent or higher polyvalent residual acid such as monosuccinic acid [2-(methyl)propenyloxyethyl] succinate or citric acid mono [2-(methyl) propyl decyl oxyethyl] vinegar The unsaturated mono((meth)acryloyloxyalkyl]esters; such as α-(methylidenemethyl)acrylic acid, unsaturated acrylates having a hydroxyl group and a carboxyl group in the same molecule. Among these, acrylic acid, methacrylic acid, and cis-butyl diacid are used: etc., in terms of point of copolymerization reactivity or alkali solubility, it is preferably used -9-201223982, here In the specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The descriptions of "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning. (b), for example, vinylcyclohexene monooxide, epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl group Methacrylate (for example, cyclomer A400; manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, cyclomer M100; manufactured by DAICEL Chemical Industry Co., Ltd.), formula (1) The compound shown, the compound of the formula (II), and the like. [Chemical 2]

In the formulae (I) and (II), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X1 and X2 are each independently shown as a single bond or an alkanediyl group having a carbon number of 1 to 6, and the -CH2- contained in the alkanediyl group may be substituted by -0-, -S- or -NR3-, and R3 is represented by hydrogen. Atom or an alkyl group having 1 to 4 carbon atoms]. Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an η-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. -10-

S 201223982 is a hydroxyalkyl group in which a hydrogen atom may be substituted by a hydroxyl group, and examples thereof include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, and a 3-hydroxypropyl group. 1-hydroxy-1-methylethyl, 2-hydroxy-1.methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. as R1 and R2 is preferably, for example, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group. As the alkanediyl group, for example, methylene, ethyl, propane-1,2-diyl, propane-1,3-diyl, butane-14-diyl, pentane-15-diyl, Alkyl-1,6-diyl and the like. As X1 and X2', for example, a single bond, a methylene group, an exoethyl group, a *-ch2-o- (* is shown as a bond bond with a fluorene bond), and a *_Ch2ch2-o- group is preferable. A single bond, *-CH2CH2-O- group, and more preferably, for example, a single bond, *-CH2CH2-〇- group. The compound represented by the formula (1) is, for example, a compound represented by the formula (1-1) to the formula G-1 5). Preferably, for example, the formula (1-1), the formula (1-3), the formula (1-5), the formula (Bu 7), the formula (1-9), the formula G-ll) to the formula (1-15) . More preferably, for example, the formula (M), the formula (1_7), the formula (1-9), and the formula (I-1 5). -11 - 201223982 [Chem. 3]

H2c=gh -I-

〇 CH3.0 H 20^-0 — '0*"

H2C—G—G*~0 C2H4—s 〇 il H2C =CH *C *0 A C2H4—N H —C2H4—S'

GH3〇 I II O —CH? ch3 o I II H2C =0.—C —〇 —C2H4

CH3〇 I II H2C =ό -—G —O —G2H4 —N H H^C=0———G —〇

H2c ch2oh o T 11 =c-c

(1-12) (1-13) CH3 o I II h2c=g-c-o-g2h4-o

e2H4OH o I 11 H2〇.=—0-C—O

(1-15) The compound represented by the formula (n) is, for example, a compound represented by the formula (II-1) to the formula (11-15). Preferably, for example, the formula (II-1), the formula (II-3), the formula (II-5), the formula (11-7), the formula (11-9), the formula (11-11) to the formula (11- 15). More preferably, it is a formula (II-1), a formula (II-7), a formula (II-9), and a formula (11-15).

S -12- 201223982 [化4]

Η2〇2〇Η一C一O—〇2Η4_ ί i? i? Η2〇:ΟΗ—ό 一Ο——Q οη3θ I II h2c=c—c—o gh3 o I II Η2〇=0*—C— O-GH ?H35? Η2〇=τΟ—C~.0—C2H.

H2c=c- (II-2) H2C:CH—C—0—C2H4-S H2C:CH—C—〇—C2H4—N ?H3〇I If H2C=C—c*-o-c2h4-s gh3〇 I II u H2c=c—C—0—C2H4-N _i2Hsf HjjC—ό一〇

CH30 I II HjC—C—G—〇—C2H4—·〇 h2c=

C-ο-τ^Υ 丨〇 II 々 1 (Π, 14) The compound of the formula (1) and the compound of the formula (II) can be used singly. Further, these can be mixed at any ratio. When mixing, the mixing ratio is in molar ratio, and formula (I): formula (II) is preferably 5: 95 to 95: 5, more preferably 10: 90 to 90: 10, and particularly preferably 20: 80~ 80: 20. As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n - butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (Meth)acrylic acid alkyl esters such as (meth) acrylate; cyclohexyl (meth) acrylate, 2 · methylcyclohexyl (meth) acrylate-13 - 201223982 ester, tricyclic [5.2.1.02 '6] decane-8-yl (meth) acrylate (referred to as dicyclopentanyl (meth) acrylate as a conventional name in the art), dicyclopentyloxyethyl ( (meth)acrylic acid cyclic alkyl esters such as methyl acrylate and isodecyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, etc. An aryl or aralkyl acrylate; a dicarboxylic acid diester such as diethyl maleate, diethyl fumarate or diethyl methylene succinate; 2 -hydroxyl a hydroxyalkyl ester such as ethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate; bicyclo [2_2.1] hept-2-ene, 5-methyl bis Ring [2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[22 "heptene·ene, 5-hydroxymethylbicyclo[2.2. 1]hept-2-ene, 5-(2,-hydroxyethyl)bicyclo[221]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo [m] hept-2-ene, 5,6-dihydroxybicyclo[2 2丨]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5 , 6_bis(2'-hydroxyethyl)bicyclo[2 2 hept-2-ene' 5,6-dimethoxybicyclo[22•丨]hept-2-ene, 5,6•diethoxy Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[22丨]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene , 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5461^butoxycarbonylbicyclo[221]hept-2-ene, 5-cyclohexyloxynonylbicyclo, 5_ a phenoxy-suspended bicycloalkenyl, a 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2 2 fluorene]heptan-2-isocyclic bicyclic unsaturated compound,

S 14- 201223982 N - Benikesin is a succinimide, N-cyclohexyl cis-butane diimine, N-benzyl maleimide, N-butaneimine-3 _Synthedimide benzoate benzoate, N-butyl succinimide -4-butylene imidate butyl ester, N-butyl succinimide-6-cis-butyl succinimide Aminohexanoic acid ester, N-butyl succinimide-3 - maleimide propionate, n-(9-acridinyl) maleimide, etc. Derivatives; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride , vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like. As (c), in addition to the foregoing, for example, a monomer having a structure in which a chain olefin is epoxidized and a carbon-carbon unsaturated double bond, having an oxet any 1 and a carbon-carbon unsaturated double a monomer of a bond and a monomer having a tetrahydrofuranyl group and a carbon-carbon unsaturated double bond. As the monomer having a structure in which a chain olefin is epoxidized and a carbon-carbon unsaturated double bond, specifically, for example, glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, fluorene-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, ρ-vinylbenzyl glycidyl ether, α-Methylvinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-P-vinylbenzyl glycidyl ether, 2,3-bis (glycidol) Base oxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis (glycoside 201223982 oil) Base oxymethyl)styrene, 2,3,4-gins (glycidyloxymethyl)styrene, 2,3,5-gin (glycidyloxymethyl)styrene, 2,3,6· Glyceryloxymethyl styrene, 3,4,5-gin (glycidyloxymethyl)styrene, 2,4,6-gin (glycidyloxymethyl)styrene, Tekaiping 7- Compounds and the like described in the publication No. 24 862 5 . As a monomer having an oxetanyl group and a carbon-carbon unsaturated double bond, for example, 3-methyl-3-methylpropenyl methoxymethyl oxetane, 3-methyl- 3-propenyl methoxymethyl oxetane, 3-ethyl-3-methylpropenyl methoxymethyl oxetane, 3-ethyl-3-propenyl methoxymethyl oxalate Huan Dingyuan, 3-methyl-3-methylpropanyloxyethyloxetine, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3 - Methyl propylene decyl oxyethyl oxetane, 3-ethyl-3-propenyl oxy oxy oxetane, and the like. Specific examples of the monomer having a tetrahydrofuranyl group and a carbon-carbon unsaturated double bond include, for example, a tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydroanthracene methacrylate. Vinegar and so on. Among these, 'as (c)' is preferably cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, N-ring Hexyl maleimide and styrene. In the resin (A2-1), the ratio of the structural unit derived from each monomer to the total number of moles of the structural unit constituting the resin (A 2 -1 ) is preferably in the range below. The structural unit derived from (a): 5 to 60 mol% (more preferably 1 〇 to 5 〇 mol%), the structural unit derived from (b): 40 to 95 mol% (more preferably 5 〇) ~9〇mole%). 201223982 If the ratio of the structural unit of the resin (A2-1) is within the above range, the stability, chemical resistance, heat resistance, and mechanical strength tend to be good. As the resin (A2-1) '(b), a resin (A2-1) having a structure epoxidizing a polycyclic unsaturated alicyclic hydrocarbon and a carbon-carbon unsaturated double bond is preferred (b) More preferably, it is a resin (A2-1) of at least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II). For the resin (A2-1), for example, the method described in the document "Experimental method for polymer synthesis" (the issue of the first issue of the 1st edition of the Otsuka Ryokan, Ltd., 1st issue, March 1, 1972) Manufactured from the cited documents described in this document. Specific examples are a method in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and oxygen is substituted with nitrogen to deoxidize, stir, heat, and maintain the temperature. The polymerization initiator, the solvent and the like used herein are not particularly limited, and any of the fields can be used by any user. For example, as a polymerization initiator, for example, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) or the like) or an organic peroxide is mentioned. (Bestylene oxyhydroxide, etc.), as a solvent, as long as it can dissolve each monomer, as a solvent (E) of a curable resin composition, the solvent etc. which are mentioned later can be used. Further, the obtained copolymer may be used as a solid (powder) by directly using the solution after the reaction, or by using a solution which has been concentrated or diluted, or by reprecipitation or the like. In particular, when the polymerization is carried out by using a solvent similar to the solvent (E) to be described later as a solvent, the solution after the reaction can be used as it is, and the production steps can be simplified. -17-201223982 In the resin (A2-2), the ratio of the structural unit derived from each monomer is preferably in the following range with respect to the total number of moles of the total structural unit constituting the resin (A2-2). . From the structure of (a), the number of 2 to 55 mol% (more preferably 5 to 45 mol%), the structural unit derived from (b): 2 to 95 mol% (more preferably 5 to 80 mol) Ear %), the structural unit derived from (c): 1 to 65 mol % (more preferably 1 to 6 〇 Mo Er Ruo resin (A2-2)) The structural unit ratio is in the above range, and the stability is preserved, Solvent resistance, heat resistance, and surface hardness tend to be good. As the resin (A2-2), (b) preferably has a structure for epoxidizing a polycyclic unsaturated alicyclic hydrocarbon and carbon-carbon unsaturated. The double bond monomer resin (A2-2), (b) is more preferably a resin of at least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II) ( A2_2) The resin (A2-2) can be produced by the same method as the resin (A2-1). As a specific example of the resin (A2-1), for example, (meth)acrylic acid / Ο-ΐ) Copolymer, (meth)acrylic acid / copolymer of formula (〗 〖2), (meth)acrylic acid / copolymer of formula (1-3), (meth)acrylic acid / formula (Bu 4) Copolymer, (meth)acrylic acid / (1-5) copolymer, (meth)acrylic acid / copolymer of the formula '(meth)acrylic acid / 〇_7) copolymer, (methyl) acrylic acid / formula (1_ 8) Copolymer, (meth)acrylic acid / copolymer of formula (Bu 9), (meth)propionic acid / copolymer of formula (ι-ίο), (meth)acrylic acid / formula (Ι-ιυ copolymer , (meth)acrylic acid / copolymer of formula (I.12), (meth)acrylic acid / copolymer of formula (1-13), (meth)acrylic acid / copolymer of formula (1-14), (a Acrylic acid / copolymer of formula (1-15), copolymer of (meth)acrylic acid / formula (Π-1), (a)

S -18- 201223982 based on acrylic acid / copolymer of formula (II-2), (meth)acrylic acid / copolymer of formula (π_3), copolymer of (meth)acrylic acid / formula (Π-4), a copolymer of methyl)acrylic acid/formula (ΙΙ-5), a copolymer of (meth)acrylic acid/formula (ΙΙ-6), a copolymer of (meth)acrylic acid/formula (ΙΙ-7), (meth)acrylic acid / copolymer of formula (Π-S), copolymer of (meth)acrylic acid / formula (Π-9), copolymer of (meth)acrylic acid / formula (π_ 10), (methyl) Acrylic / copolymer of 式-ll, (meth)acrylic acid / copolymer of formula (11-12), copolymer of (meth)acrylic acid / formula (Π-13), (meth)acrylic acid / a copolymer of the formula (Π-14), a copolymer of (meth)acrylic acid/formula (11-15), a copolymer of (meth)acrylic acid/formula (1-1)/formula (ΙΙ-1), (methyl) Acrylic acid / copolymer of formula (1-2) / formula (ΙΙ-2), (meth)acrylic acid / copolymer of formula (1-3) / formula (ΙΙ-3), (meth)acrylic acid / Copolymer of (1-4) / formula (ΙΙ-4), copolymerization of (meth)acrylic acid / formula (1-5) / formula (1b 5) , (meth)acrylic acid / copolymer of formula (1-6) / formula (11_6), (meth)acrylic acid / copolymer of formula (I-7) / formula (ΙΙ-7), (methyl) Acrylic acid / copolymer of formula (1-8) / formula (ΙΙ-8), (meth)acrylic acid / copolymer of formula (1-9) / formula (ΙΙ-9), (meth)acrylic acid / formula ( 1-10) / copolymer of formula (Π-10), (meth)acrylic acid / copolymer of formula (1-11) / formula (Π-ll), (meth)acrylic acid / formula (1-12) / copolymer of the formula (11-12), (meth)acrylic acid / copolymer of the formula (1-13) / formula (11-13), (meth)acrylic acid / formula (1-14) / formula (Π -14) copolymer, (meth)acrylic acid / copolymer of formula (I-15) / formula (11-15), (meth)acrylic acid / formula (1-1) / formula (1-7) Copolymer, (meth)acrylic acid / copolymer of formula (1-1) / formula (Η-7), copolymer of crotonic acid / formula (1-1), copolymerization of crotonic acid / formula (1-2) , crotonic acid / copolymer of formula (I-3), crotonic acid / copolymer of formula (1-4), crotonic acid / copolymer of formula (1-5), crotonic acid / formula (1-6) Copolymer, crotonic acid / copolymerization of formula (1-7)-19- 201223982 Copolymer of crotonic acid/formula (Ι·8), copolymer of arsenic acid 7 (1-9), copolymer of crotonic acid/type (ι-ίο), copolymer of succinic acid/formula (1-11) Copolymer of soybean acid/formula (M2), copolymer of crotonic acid/formula (丨_13), copolymer of acid/formula (I-1 4), copolymer of crotonic acid/formula (1-1 5) Bar> copolymer of formula (11-丨), copolymer of crotonic acid/formula (11-2), copolymer of barley acid/formula (11_3), copolymer of crotonic acid/formula (Π·4) a copolymer of barley acid/formula (Π5), a copolymer of crotonic acid/formula (ΙΙ-6), a copolymer of barley acid/formula (Π7), and a crotonic acid/formula (ΙΙ-8) Copolymer, crotonic acid / copolymer of formula (Π·9), copolymer of crotonic acid / formula (π-10), copolymer of crotonic acid / formula (11-11), crotonic acid / formula (Π-12) Copolymer, crotonic acid / copolymer of formula (Π_13), copolymer of crotonic acid / formula (Π-14), copolymer of crotonic acid / formula (11_15), maleic acid / formula (1.1) a copolymer, a copolymer of maleic acid / formula (Ι 2), a copolymer of maleic acid / hydrazine / 3), a copolymer of maleic acid / formula (1-4) , maleic acid / copolymer of formula (Bu 5), copolymer of maleic acid / formula (1-6), copolymer of maleic acid / formula (1-7), maleic acid Acid / copolymer of formula (1-8), copolymer of maleic acid / formula (1-9), copolymer of maleic acid / formula (1-10), maleic acid / a copolymer of the formula (1-1 1}, a copolymer of maleic acid/formula (1 -1 2 ), a copolymer of cis-butylic acid/formula (1-1 3), maleic acid / copolymer of formula (I.14), cis-succinic acid / copolymer of formula (1-1 5), copolymer of maleic acid / formula (H·1), maleic acid / Copolymer of formula (Π-2), copolymer of maleic acid/formula (Π_3), copolymer of maleic acid/formula (11·4), cis-butanedioic acid/form (11 _ 5) copolymer, maleic acid / copolymer of formula (11-6), copolymer of maleic acid / formula (ΙΙ-7), maleic acid / formula (Π-8) Copolymer, butadiene

-20- S 201223982 Copolymer of diacid / formula (Π-9), copolymer of maleic acid / formula (Π-10), copolymer of maleic acid / formula (II·11), Copolymer of maleic acid / formula (Π_12) 'maleic acid / copolymer of formula (II-13), copolymer of maleic acid / formula (11-14), maleic acid Copolymer of formula /(ΙΙ-15), (meth)acrylic acid/maleic anhydride/copolymer of formula (1-1), (meth)acrylic acid/maleic anhydride/formula (1- 2) a copolymer, (meth)acrylic acid/maleic anhydride/copolymer of the formula (1-3), (meth)acrylic acid/maleic anhydride/copolymer of the formula (1-4), (meth)acrylic acid/maleic anhydride/copolymer of formula (1-5), (meth)acrylic acid/maleic anhydride/copolymer of formula (1-6), (meth)acrylic acid/ Maleic anhydride/copolymer of formula (1-7), (meth)acrylic acid/maleic anhydride/copolymer of formula (1-8), (meth)acrylic acid/maleic anhydride/ Copolymer of formula (1-9), (meth)acrylic acid/maleic anhydride/copolymer of formula (1-10), (meth) propylene /maleic anhydride / copolymer of formula (1-1 1), (meth)acrylic acid / maleic anhydride / copolymer of formula (1-12), (meth)acrylic acid / maleicene Anhydride/copolymer of formula (1-13), (meth)acrylic acid/maleic anhydride/copolymer of formula (1-14), (meth)acrylic acid/maleic anhydride/formula (1- 15) copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1), (meth)acrylic acid/maleic anhydride/copolymer of formula (ΙΙ-2) (Meth)acrylic acid/maleic anhydride/copolymer of the formula (ΙΙ-3), (meth)acrylic acid/maleic anhydride/copolymer of the formula (ΙΙ-4), (meth)acrylic acid/ Maleic anhydride/copolymer of formula (II-5), (meth)acrylic acid/maleic anhydride/copolymer of formula (ΙΙ-6), (meth)acrylic acid/maleic anhydride/ Copolymer of the formula (ΙΙ-7), (meth)acrylic acid/maleic anhydride/copolymer of the formula (ΙΙ-8), (meth)acrylic acid/maleic anhydride/formula (ΙΙ-9) Copolymer, ( -21 - 201223982 methyl) acrylic acid / maleic anhydride / formula ( Copolymer of II_10), copolymer of (meth)acrylic acid/maleic anhydride/copolymer of formula (11-11), copolymerization of (meth)acrylic acid/maleic anhydride/formula (Π-12) , (meth)acrylic acid/succinic acid anhydride/copolymer of formula (11 -1 3 ), (meth)acrylic acid/succinic dianhydride / copolymer of formula (II-14) , (meth)acrylic acid/succinic acid anhydride/copolymer of formula (Π_15), and the like. Specific examples of the resin (A 2 - 2 ) are, for example, (meth)acrylic acid/copolymer of the formula (1 _ 1)/methyl (meth) acrylate, (meth)acrylic acid / formula (1-2) ) / copolymer of methyl (meth) acrylate, copolymer of (meth) acrylate / formula G-3) / methyl (meth) acrylate, (meth) acrylate / formula (a) · 4) / Copolymer of methyl (meth) acrylate, copolymer of (meth) acrylate / U. 5) / methyl (meth) acrylate, (meth) acrylic / formula (T_6) / methyl ( Copolymer of methyl) acrylate, copolymer of (meth)acrylic acid / formula (1-7) / methyl (meth) acrylate, (meth) acrylic acid / formula (1-8) / methyl ( Copolymer of methyl) acrylate, copolymer of (meth)acrylic acid / formula (1-9) / methyl (meth) acrylate, (meth) acrylic acid / formula (1-10) / methyl ( Copolymer of methyl acrylate, (meth)acrylic acid / copolymer of formula (1-11) / methyl (meth) acrylate, (meth) acrylate / formula (1-12) / methyl ( Copolymer of methyl acrylate, (a Acrylic/copolymer of formula (1-13)/methyl (meth) acrylate, copolymer of (meth)acrylic acid / formula (1-1 4) / methyl (meth) acrylate, (A) Acrylic acid / copolymer of formula (1-15) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate, (a Acrylic acid / copolymer of formula (II-2) / methyl (meth) acrylate, copolymer of (meth) acrylate / formula (11_3) / methyl (meth) acrylate, (methyl )Acrylic/Formula (11-4)/

S -22- 201223982 Copolymer of methyl (meth) acrylate, copolymer of (meth) acrylate / formula (II-5) / methyl (meth) acrylate, (meth) acrylate / formula ( Π-6)/Methyl (meth) acrylate copolymer, (meth) acrylate / copolymer of formula (Π-7) / methyl (meth) acrylate, (meth) acrylate / formula ( Copolymer of Π_8)/methyl(meth)acrylate, copolymer of (meth)acrylic acid/formula (ΙΙ-9)/methyl(meth)acrylate, (meth)acrylic acid/formula (11 -10)/Methyl (meth) acrylate copolymer, (meth) acrylate / copolymer of formula (Π-11) / methyl (meth) acrylate, (meth) acrylate / formula (Π -12)/Methyl (meth) acrylate copolymer, (meth) acrylate / copolymer of formula (Π-13) / methyl (meth) acrylate, (meth) acrylate / formula (II -14)/Methyl (meth) acrylate copolymer, (meth) acrylate / copolymer of formula (Π-15) / methyl (meth) acrylate, (meth) acrylate / formula (1 -1)/dicyclopentanyl Copolymer of methyl acrylate, copolymer of (meth)acrylic acid / hydrazine (Π-1) / dicyclopentanyl (meth) acrylate, (meth)acrylic acid / formula (1-1) / Copolymer of the formula (Π-1)/dicyclopentanyl (meth) acrylate, crotonic acid / copolymer of the formula (1-1) / dicyclopentanyl (meth) acrylate, butylene Diacid / copolymer of formula (1-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula (1-1) / dicyclopentanyl ( Copolymer of methyl acrylate, (meth) acrylate / copolymer of formula (I-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate, crotonic acid / formula a copolymer of (ΙΙ-1)/dicyclopentanyl (meth) acrylate, a copolymer of maleic acid/formula (ΙΙ-Ι)/dicyclopentanyl (meth) acrylate, ( Methyl)acrylic acid/maleic anhydride/copolymer of formula (II-1)/dicyclopentanyl (meth) acrylate, (meth)acrylic acid/formula (ΙΙ-1)/methyl (a) Copolymerization of acrylate/dicyclopentanyl (meth) acrylate , (meth)propane-23- 201223982 olefinic acid / copolymer of formula (I-1) / phenyl (meth) acrylate, (meth) acrylate / formula (II-1) / phenyl (methyl Copolymer of acrylate, (meth)acrylic acid / copolymer of formula (1-1) / formula (II-1) / phenyl (meth) acrylate, crotonic acid / formula (1-1) / benzene Copolymer of (meth) acrylate, copolymer of maleic acid / formula (1-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula ( 1-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / copolymer of formula (1-1) / methyl (meth) acrylate / phenyl (meth) acrylate , crotonic acid / copolymer of formula (II-1) / phenyl (meth) acrylate, copolymer of maleic acid / formula (Π-1) / phenyl (meth) acrylate, (a Acrylic acid/maleic anhydride/copolymer of formula (II-1)/phenyl (meth) acrylate, (meth)acrylic acid / formula (II-1) / methyl (meth) acrylate /Phenyl (meth) acrylate copolymer, (meth) acrylate / formula (1-1) / Copolymer of diethyl phthalate, (meth)acrylic acid / copolymer of formula (II-1) / diethyl maleate, (meth)acrylic acid / formula (1-1) / formula (II-1)/copolymer of diethyl maleate, crotonic acid/copolymer of formula (1-1)/diethyl maleate, maleic acid/formula (1- 1) / copolymer of diethyl maleate, (meth)acrylic acid / maleic anhydride / copolymer of formula (1-1) / diethyl maleate, (methyl) Acrylic acid / copolymer of formula (1-1) / methyl (meth) acrylate / diethyl maleate, copolymerization of crotonic acid / formula (II-1) / diethyl maleate , maleic acid / copolymer of formula (II-1) / diethyl maleate, (meth)acrylic acid / maleic anhydride / formula (II-1) / cis-butene Copolymer of diethyl acid, (meth)acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate / diethyl maleate, (meth) acrylic acid / hydroxyl group Copolymer of ethyl (meth) acrylate, (meth) acrylate / formula (11-1)/2-

S -24- 201223982 Copolymer of hydroxyethyl (meth) acrylate, (meth)acrylic acid / formula (1-1) / formula (11-1)/2 -hydroxyethyl (meth) acrylate Copolymer, crotonic acid / copolymer of formula (1-1)/2-hydroxyethyl (meth) acrylate, maleic acid / formula (1-1)/2-hydroxyethyl (methyl) Copolymer of acrylate, (meth)acrylic acid/maleic anhydride/copolymer of formula (1-1)/2-hydroxyethyl (meth) acrylate, (meth)acrylic acid/form (1- 1) copolymer of methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, copolymerization of crotonic acid / formula (11-1) / 2-hydroxyethyl (meth) acrylate , maleic acid / copolymer of formula (11-1)/2-hydroxyethyl (meth) acrylate, (meth)acrylic acid / maleic anhydride / formula (II-1)/2 a copolymer of -hydroxyethyl (meth) acrylate, a copolymer of (meth)acrylic acid / ((-1) / methyl (meth) acrylate / 2 - hydroxyethyl (meth) acrylate) , (meth)acrylic acid / copolymer of formula (1-1) / bicyclo [2.2.1] hept-2-ene , (meth)acrylic acid / copolymer of formula (II-1) / bicyclo [2.2.1] hept-2-ene, (meth)acrylic acid / formula (1-1) / formula (II-1) / double ring [2.2.1] Copolymer of hept-2-ene, crotonic acid / copolymer of formula (1-1) / bicyclo [2.2.1] hept-2-ene, maleic acid / formula (1-1) /bicyclo[2.2.1] copolymer of hept-2-ene, (meth)acrylic acid/maleic anhydride/copolymer of formula (1-1)/bicyclo[2.2.1]hept-2-ene, (Meth)acrylic acid / copolymer of formula (1-1) / methyl (meth) acrylate / bicyclo [2.2.1] hept-2-ene, crotonic acid / formula (11-1) / bicyclo [2_2 .1] copolymer of hept-2-ene, copolymer of maleic acid / formula (Π-1) / bicyclo [2.2.1] hept-2-ene, (meth)acrylic acid / maleicene Anhydride / copolymer of formula (II-1) / bicyclo [2.2.1] hept-2-ene, (meth)acrylic acid / formula (II-1) / methyl (meth) acrylate / bicyclo [2.2. 1] copolymer of hept-2-ene, copolymer of (meth)acrylic acid/(1_1)/N-cyclohexylmethyleneimine, '(meth)acrylic acid/form-25-201223982 ( II-1) / N-cyclohexyl maleimide copolymer, (meth)acrylic acid / formula (1-1) / Copolymer of formula (Π-1)/Ν-cyclohexylmethyleneimine, copolymer of crotonic acid / formula (I - 1 ) / fluorene - cyclohexyl maleimide, butene Diacid / copolymer of formula (Il) / N-cyclohexyl maleimide, (meth)acrylic acid / maleic anhydride / formula (I-1) / fluorene-cyclohexyl cis-butene Copolymer of quinone imine, (meth)acrylic acid / copolymer of formula (1-1) / methyl (meth) acrylate / hydrazine - cyclohexyl maleimide, croton acid / formula (II a copolymer of -1)/Ν-cyclohexylmethyleneimine, a copolymer of maleic acid/(II-1)/fluorene-cyclohexylmethyleneimine, (methyl Acrylic acid/maleic anhydride/copolymer of formula (II-1)/fluorene-cyclohexylmethyleneimine, (meth)acrylic acid / formula (II-1)/methyl (methyl) Copolymer of acrylate/fluorene-cyclohexylmethyleneimine, copolymer of (meth)acrylic acid/formula (1-1)/styrene, (meth)acrylic acid/formula (ΙΙ-1)/ Copolymer of styrene, (meth)acrylic acid / copolymer of formula (1-1) / formula (ΙΙ-1) / styrene, crotonic acid / formula (1-1) / benzene a copolymer of ethylene, a copolymer of maleic acid/formula (1-1)/styrene, a copolymer of (meth)acrylic acid/maleic anhydride/formula (1-1)/styrene, ( Methyl)acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / styrene, crotonic acid / copolymer of formula (II-1) / styrene, maleic acid / formula (ΙΙ-1)/copolymer of styrene, (meth)acrylic acid/maleic anhydride/copolymer of formula (ΙΙ-1)/styrene, (meth)acrylic acid/formula (ΙΙ-1)/ Copolymer of methyl (meth) acrylate / styrene, (meth) acrylate / copolymer of formula (1-1 ) / fluorene - cyclohexyl maleimide / styrene, (methyl) Acrylic acid / formula (ΙΙ-1) / Ν - cyclohexyl maleimide / styrene copolymer, (meth) acrylic acid / formula (1_1) / formula (11-1) / Ν · cyclohexyl cis Copolymer of enediamine/styrene, crotonic acid/form

S -26- 201223982 (I-1) / N-cyclohexyl maleimide / styrene copolymer, maleic acid / formula (1-1) / N-cyclohexyl-butene Copolymer of quinoneimine/styrene, (meth)acrylic acid/maleic anhydride/copolymer of formula (1-1)/N-cyclohexylmethyleneimine/styrene, (methyl Acrylic acid / (1_1) / methyl (meth) acrylate / N - cyclohexyl maleimide / styrene copolymer, crotonic acid / formula (II-1) / N-cyclohexyl cis Copolymer of butylenediimide/styrene, copolymer of maleic acid/(II-1)/N-cyclohexylmethyleneimine/styrene, (meth)acrylic acid/ Maleic anhydride / copolymer of formula (II-1) / N-cyclohexyl maleimide / styrene, (meth) acrylic acid / formula (II-1) / methyl (methyl) Acrylate / N-cyclohexyl maleimide / styrene copolymer and the like. The polystyrene-equivalent weight average molecular weight of the resin (A) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 6,000 to 15,000. When the weight average molecular weight of the resin (A) is in the above range, the coatability tends to be good, and film reduction is less likely to occur during development, and the release of the non-pixel portion during development is re-escaped. Good tendency. The molecular weight distribution of the resin (A) [weight average molecular weight (Mw) / number average molecular weight (?n)], preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0, still more preferably from 1.5 to 3.0, still more preferably 1.8. ~2.8. When the molecular weight distribution is in the above range, the developability tends to be excellent. The acid value of the resin (Α) is 30 mg-KOH/g or more and 180 mg-KOH/g or less, more preferably 40 mg-KOH/g or more, 150 mg-KOH/g or less, and still more preferably 50 mg-KOH/g or more. 135 mg-KOH/g or less. Here, the acid -27-201223982 valence measured by the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (A) can be determined by titration with an aqueous potassium hydroxide solution. Got it. When the acid value of the resin (A) is in the above range, it tends to be excellent in chemical resistance. The content of the resin (A) is preferably 40 to 90% by mass, more preferably 4 to 80% by mass, particularly preferably 40 to 70%, based on the total amount of the resin (A) and the polymerizable compound (c). quality%. When the content of the resin (A) is in the above range, the chemical resistance tends to be good. The curable resin composition of the present invention contains an epoxy resin (B) having an acid value of less than 30 mg-ΚΟΗ/g. The acid value of the epoxy resin (B) is preferably 20 mg-KOH/g or less, more preferably 10 mg-KOH/g or less. Here, the term "epoxy resin" means a compound having two or more oxirane groups, or a mixture thereof, and is not limited to a polymer compound. The epoxy group (B) has an oxirane group, preferably an epoxidized structure of the chain olefin as the epoxy resin (B), for example, a bisphenol A type epoxy resin or a bisphenol F type epoxy resin. Resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, and the like. Commercial products of these types can also be used. As a commercially available bisphenol A type epoxy resin, for example, Epikote 828, the same 1001, the same 1002, the same 1003, the same 1004, the same 1〇〇7, the same 1009, the same 1010 (above, Mitsubishi Chemical Corporation) )Wait. Examples of the commercially available bisphenol F-type epoxy resin include Epikote 80 7 and the same 384 (manufactured by Mitsubishi Chemical Corporation). As a commercially available phenol novolak type epoxy resin, for example, Epikote 152, 154, 157H65 (above, Mitsubishi Chemical Corporation), EPPN201, and 202 (above, Japan)

S • 28- 201223982 chemical (stock) system, etc. As a commercially available cresol novolac type epoxy resin, for example, Sumi-epoxy ESCN-195XL-80 (manufactured by Sumitomo Chemical Co., Ltd.), EOCN-102 > EOCN-103S, EOCN-104S, EOCN-1 020, EOCN-1025, EOCN- 1 027 (above, Nippon Kayaku Co., Ltd.), Epikote 180S75 (Mitsubishi Chemical Co., Ltd.), etc. Further, as the epoxy resin which is commercially available, for example, CY 175, CY177, CY179 (above, manufactured by ASAHI KASEI E-materials), ERL-4234, ERL-4299, ERL-422 1, ERL- 4206 (above, UCC company), show 丨 bow (transliteration) 509 (Showa Denko (share) system), Araldite CY-182 ' with CY-192, with CY-1 84 (above, ASAHI KASEI E-materials system ), Epiclon 200, cycloaliphatic epoxy resin such as 400 (above, DIC (share)), Epikote 871, 872, EP1032H60 (above, Mitsubishi Chemical Co., Ltd.); Epikote 190P, same 191P ( The above-mentioned, Mitsubishi Chemical Co., Ltd. is an aliphatic polyglycidyl ether such as Epolite 100MF (manufactured by Kyoei Chemical Co., Ltd.) or EPIOL TMP (manufactured by Sakamoto Oil Co., Ltd.). Among them, as the epoxy resin (B), a bisphenol A type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolac type epoxy resin are preferable. The content of the epoxy resin (B) is 1 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the resin (A), preferably 5 parts by mass or more and 70 parts by mass or less. It is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 25 parts by mass or less, and particularly preferably 5 parts by mass or more and 10 parts by mass or less. When the content of the epoxy resin (B) is within the above range, the obtained coating film tends to have excellent flatness. -29-201223982 The curable resin composition of the present invention contains a polymerizable compound (C) having at least one selected from the group consisting of a propylene group and a methacryl group. The molecular weight of the polymerizable compound (C) is preferably 150 or more and 3,000 or less, more preferably 200 or more and 1,500 or less. When two or more polymerizable compounds (C) are contained, the weight average molecular weight of the mixture is preferably in the above range. Examples of the compound having at least one selected from the group consisting of an acryl fluorenyl group and a methacryl fluorenyl group include 1,6-hexanediol di(meth)acrylate and ethylene glycol. Di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bisphenol A bis(acryloxyethyl)ether, 3-methyl Pentyl diol di(meth) acrylate or the like. Examples of the compound having at least one selected from the group consisting of a propylene group and a methacryl group include, for example, trimethylolpropane tri(meth)acrylate, neopentyl alcohol (Meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl alcohol Reaction of (meth) acrylate with an acid anhydride, reaction of dipentaerythritol penta (meth) acrylate with an acid anhydride, caprolactone denatured pentaerythritol tetra (meth) acrylate, caprolactone denaturation Dipentaerythritol penta (meth) acrylate, caprolactone denatured dipentaerythritol hexa(meth) acrylate, ethylene oxide denatured pentaerythritol tetra (meth) acrylate, ethylene oxide denature Pentaerythritol penta (meth) acrylate, ethylene oxide-denatured neopentyltetraol hexa(meth) acrylate, propylene oxide-denatured neopentyltetrakis (meth) acrylate, propylene oxide-denatured dipentaerythritol Fives(

S -30- 201223982 Methyl) acrylate, propylene oxide, dipentaerythritol hexa(meth) acrylate, etc. Among them, the polymerizable compound (C)' is preferably a compound having at least one selected from the group consisting of a propylene group and a methacryl group, and more preferably a trimethylolpropane. Tris(meth)acrylate and dipentaerythritol hexa(meth)acrylate. When the polymerizable compound (C) is a compound such as these, the obtained coating film tends to be excellent in chemical resistance. To the extent that the effects of the present invention are not impaired, a compound having at least one selected from the group consisting of an acryloyl group and a methacryl group can be used. As such a compound, for example, (a), (b), (c) 'nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl group constituting the monomer of the resin (A) Acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like. The content of the polymerizable compound (C) is preferably 10 to 60% by mass, more preferably 20 to 60% by mass, particularly preferably 3, based on the total amount of the resin (A) and the polymerizable compound (C). 0 to 6 0% by mass. When the content of the polymerizable compound (C) is within the above range, the coating film tends to be excellent in strength, smoothness, and letterability. The curable resin composition of the present invention contains a thermal acid generator (D). The thermal acid generator is a compound which generates an acid by the action of heat. It is preferably a compound capable of generating an acid below the post-baking temperature which will be described later. The thermal acid generator (D) is, for example, a key salt of a benzothiazolium salt, an ammonium salt or a phosphonium salt. 31 - 201223982 As the above sulfonium salt, for example, (4-hydroxyphenyl) dimethyl bis(trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl) (2.methylbenzyl) A Bis(bis(trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl)benzylmethylindole bis(trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl) (4- Methylbenzyl)methyl bis(trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl)(1-naphthylmethyl)methyl bis(trifluoromethanesulfonyl) fluorene Amine, (4-methoxycarbonyloxyphenyl) dimethylhydrazine bis(trifluoromethanesulfonyl) quinone imine, (4-methoxycarbonyloxyphenyl)benzylmethylindole bis (trifluoro Methanesulfonyl) quinone imine, (4-methoxycarbonyloxyphenyl) (2-methylbenzyl)methyl bis(trifluoromethanesulfonyl) ruthenium, (4-methoxy) Carbonyloxyphenyl)(4-methylbenzyl)methylindole bis(trifluoromethane extended) quinone imine, (4-ethoxymethoxyphenyl) benzylidene bis(trifluoromethanesulfonate) Indenylamine, (4-ethyloxyphenyl)(4-methylbenzyl) A Bis(trifluoromethanesulfonyl) quinone imine, (4_acetoxyphenyl) (2-methylbenzyl)methyl bis(trifluoromethanesulfonyl) quinone imine, (4 _ ethoxylated phenyl) dimethyl bis(trifluoromethanesulfonyl) quinone imine, (4-ethoxymethoxyphenyl) (1-naphthylmethyl)methyl hydrazine bis (trifluoro Methanesulfonyl) quinone imine; (4-hydroxyphenyl) dimethyl sulfonium hexafluorophosphate, (4-hydroxyphenyl) (2-methylbenzyl) methyl sulfonium hexafluorophosphate, (4 -hydroxyphenyl)benzylmethylphosphonium hexafluorophosphate, (4-hydroxyphenyl)(4-methylbenzyl)methylphosphonium hexafluorophosphate, (4-hydroxyphenyl) (1-naphthyl) Methyl)methylphosphonium hexafluorophosphate, (4-ethoxyphenyl) dimethylphosphonium hexafluorophosphate, (4-ethoxymethoxyphenyl)benzylmethylphosphonium hexafluorophosphate, (4-Ethyloxyphenyl)(2-methylbenzyl)methyl hexafluorophosphate, (4-ethoxymethoxyphenyl)(4-methylbenzyl)methylphosphonium hexafluorophosphate Salt, (4-ethoxymethoxyphenyl)(1-naphthylmethyl)methylphosphonium hexafluorophosphate

S-32- 201223982 salt; (4-hydroxyphenyl) dimethyl sulfonium trifluoromethanesulfonate, (4-hydroxyphenyl) (2-methylbenzyl) methyl fluorene trifluoromethanesulfonate, 4-hydroxyphenyl)benzylmethylindole trifluoromethanesulfonate '(4-hydroxyphenyl)(4-methylbenzyl)methylindole trifluoromethanesulfonate, (4-hydroxyphenyl) (1-Naphthylmethyl)methylindole trifluoromethanesulfonate, (4-acetoxyphenyl)dimethyltrifluoromethanesulfonate, (4-acetoxyphenyl)benzyl Methyl fluorene trifluoromethane sulfonate, (4-acetoxyphenyl) (2-methylbenzyl) methyl fluorene trifluoromethane sulfonate, (4-ethyl methoxy phenyl) 4-methylbenzyl)methylindole trifluoromethanesulfonate, (4-acetoxyphenyl)(1-naphthylmethyl)methylsulfonium trifluoromethanesulfonate; (4-acetonitrile) (phenyl) dimethyl hexafluoroantimonate, (4-benzyloxycarbonyloxyphenyl) dimethyl hexafluoroantimonate, (4-benzylidene oxyphenyl) dimethyl hydrazine Hexafluoroantimonate, (3-chloro-4-acetoxyphenyl)dimethylhydrazine hexafluoroantimonate, (4-hydroxyphenyl)benzylmethylphosphonium hexafluorophosphate Citrate, (4-acetoxyphenyl) benzylmethyl hexafluoroantimonate, (4-methoxyphenyl)benzylmethyl hexafluoroantimonate, (4-hydroxy- 2-methylphenyl)benzylmethylphosphonium hexafluoroantimonate, (4-hydroxyphenyl)bisbenzylphosphonium hexafluoroantimonate, (4-acetoxyphenyl)bisbenzylphosphonium Fluoride, (4-methoxyphenyl) bisbenzyl hexafluoroantimonate, (4-hydroxy-3-tert-butyl-5-methylphenyl) bisbenzyl hexafluoroantimony Acid salt, (4-hydroxyphenyl)(4-chlorobenzyl)methylphosphonium hexafluoroantimonate, (4-hydroxyphenyl)(4-nitrobenzyl)methylphosphonium hexafluoroantimonate, (4-hydroxy-3-methylphenyl)(4-nitrobenzyl)methylindole hexafluoroantimonate, (4-hydroxyphenyl)(3,5-dichlorobenzyl)methyl 6 Gas-recording acid salt, (4-carbazhen-3-ylphenyl)(2-chloroindenyl)methyl mirror hexafluoroantimonate; -33- 201223982 (4-acetoxyphenyl) dimethyl Hexafluoroarsenate, (4-benzylideneoxyphenyl)dimethylhydrazine hexafluoroarsenate, (3-chloro-4-hydroxyphenyl)benzylmethylphosphonium hexafluoroarsenate, (3-chloro-4-hydroxyphenyl) dibenzyl Base hexafluoroarsenate; (4-hydroxyphenyl)benzylmethylphosphonium hexafluorophosphate, (4-hydroxyphenyl)(4-methoxybenzyl)methylphosphonium hexafluorophosphate, 4-hydroxyphenyl)bisbenzylphosphonium hexafluorophosphate, (4-hydroxyphenyl)(4-methoxybenzyl)benzylphosphonium hexafluorophosphate, (4-hydroxyphenyl) (4-chloro Benzyl)methylphosphonium hexafluorophosphate or the like. As the aforementioned benzothiazole salt, for example, 3-benzylbenzothiazolium hexafluoroantimonate, 3-(4-methoxybenzyl)benzothiazole hexafluoroantimonate, 2-methylsulfonate Mercapto-3-benzylbenzothiazole hexafluoroantimonate, 5-chloro-3-benzylbenzothiazole hexafluoroantimonate; 3-benzylbenzothiazole hexafluorophosphate; 3- Benzylbenzothiazole key tetrafluoroborate and the like. Among them, as the thermal acid generator <(D), a phosphonium salt and a benzothiazole key salt are preferred, and a sulfonium salt is more preferred, and (4-hydroxyphenyl)benzylmethyl fluorene is more preferred. (Trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl) (2-methylbenzyl)methyl bis(trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl) (4-methylbenzyl)methylindole bis(trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl)(1-naphthylmethyl)methylhydrazine bis(trifluoromethanesulfonyl)醯imine, (4-acetoxyphenyl) dimethyl bis(trifluoromethanesulfonyl) quinone imine, (4-hydroxyphenyl) benzylmethyl bis (trifluoromethane sulfonate) Indenylamine, (4-acetoxyphenyl)(2-methylbenzyl)methylindole bis(trifluoromethanesulfonyl) quinone imine, (4-acetoxyphenyl) (4-methylbenzyl)methylindole bis(trifluoromethanesulfonyl) quinone imine, (4-acetoxyphenyl) (fluorenyl-naphthylmethyl)methylhydrazine bis(trifluoro Methanesulfonyl) imine;

S-34- 201223982 (4-hydroxyphenyl)benzylmethylphosphonium hexafluorophosphate, (4-hydroxyphenyl)(2-methylbenzyl)methylphosphonium hexafluorophosphate, (4-hydroxybenzene) (4-methylbenzyl)methylphosphonium hexafluorophosphate, (4-hydroxyphenyl)(1-naphthylmethyl)methylphosphonium hexafluorophosphate, (4-ethyloxyphenyl) Dimethyl sulfonium trifluoromethanesulfonate, (4-acetoxyphenyl)benzylmethylphosphonium hexafluorophosphate, (4-ethyloxyphenyl) (2-methylbenzyl) Methyl hydrazine hexafluorophosphate, (4-acetoxyphenyl) (4-methylbenzyl) methyl sulfonium hexafluorophosphate, (4-ethyl methoxy phenyl) (1-naphthyl group) Methyl hexafluorophosphate; (4-hydroxyphenyl) dimethyl fluorene trifluoromethane sulfonate, (4-hydroxyphenyl) benzyl methyl fluorene trifluoromethane sulfonate, (4- (hydroxybenzyl) (2-methylbenzyl)methyl fluorene trifluoromethanesulfonate, (4-hydroxyphenyl) (4-methylbenzyl) methyl fluorene trifluoromethanesulfonate, (4 -hydroxyphenyl)(1-naphthylmethyl)methylindole trifluoromethanesulfonate, (4-acetoxyphenyl)benzylmethylguanidine trifluoromethyl Sulfonic acid salt, (4-acetoxyphenyl) (2-methylbenzyl)methyl fluorene trifluoromethanesulfonate, (4-ethyloxyphenyl) (4-methylbenzyl) Methyl fluorene trifluoromethane sulfonate, (4-ethoxymethoxyphenyl) (1-naphthylmethyl)methyl fluorene trifluoromethanesulfonate; (4-hydroxyphenyl)benzylmethyl hydrazine Hexafluoroantimonate, (4-hydroxyphenyl) bisbenzyl hexafluoroantimonate, (4-acetoxyphenyl)benzylmethyl hexafluoroantimonate and (4-acetoxy) At least one selected from the group consisting of phenyl) bisbenzylphosphonium hexafluoroantimonate. As the thermal acid generator (D), it is also possible to use san-aid SI-250, the same SI-L85 > the same SI-L110, the same SI-L145, the same SI-L150, the same SI-L160 (Sanxin Chemical Industry ( Commercial products such as shares). -35-201223982 The content of the thermal acid generator (D) is preferably 0.1 part by mass or more, and the mass part or less, based on 100 parts by mass of the total of the resin (A) and the polymerizable compound (C). It is preferably 0.1 part by mass or more and 5 parts by mass or less. When the content of the thermal acid generator (D) is in the above range, the visible light transmittance of the coating film tends to be high. The curable resin composition of the present invention contains a solvent (E). The solvent (E)' is not particularly limited as long as it can dissolve the respective components contained in the curable resin composition of the present invention. For example, an ester solvent (a solvent containing -C Ο Ο -), an ether solvent other than an ester solvent (a solvent containing -〇-), an ether ester solvent (a solvent containing -C Ο 0 - and -Ο -), an ester solvent The ketone solvent (solvent containing -C Ο -), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine or the like is optionally used. As the ester solvent, for example, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, η-butyl acetate, isobutyl acetate, amyl acid, isoamyl acetate Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoxyacetate, ethyl acetate Ester, cyclohexanol acetate, γ•butyrolactone, and the like. As the ether solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether: diethylene glycol Alcohol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol

S -36- 201223982 Diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether, methyl anisole Wait. As the ether ester solvent, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate and the like. As the ketone solvent, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentyl Ketone, cyclopentanone, cyclohexanone, isophorone, and the like. The alcohol solvent is, for example, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin or the like. As the aromatic hydrocarbon solvent, for example, benzene, toluene, xylene, and genus m rtir can be used as a guanamine solvent, for example, hydrazine, dimethyl-dimethylformamide, hydrazine, hydrazine-dimethylacetamide. , Ν-methylpyrrolidone and the like. These solvents may be used singly or in combination of two or more. Among the above solvents, in terms of applicability 'dryness, it is preferably -37 to 201223982. The boiling point of lamat is l〇 (TC or more, 20 (the organic solvent below TC is more preferably contained by propylene glycol) Methyl ether, propylene glycol monomethyl ether acetate vinegar, diethylene glycol methyl ethyl ether, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate and 3-methoxy-1 a solvent selected from at least one selected from the group consisting of butanol, more preferably a solvent selected from at least one selected from the group, and a solvent (E) of the curable resin composition of the present invention. The content 'is preferably 30 to 95% by mass with respect to the total amount of the curable resin composition', more preferably 50 to 90% by mass, still more preferably 55 to 85% by mass. In other words, 'curable resin composition The solid content is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, still more preferably 15 to 45% by mass. Here, the solid content means a composition consisting of a curable resin. The amount of the solvent (E) after removal. When the content of the solvent (E) is within the above range, a spin coater, a slit & spin coater, When coating with a coating machine such as a slit coater (also referred to as a die coater or a curtain flow coater), an injection, or a roll coater, the coating property is excellent. The curable resin composition of the present invention The material may further contain an additive such as a chelating agent, other polymer compound, adhesion promoter, thermal radical generator, ultraviolet absorber, chain lock transfer agent, etc. as a chelating agent, for example, glass. As the other polymer compound, for example, a thermosetting resin such as a maleimide resin, a polyvinyl alcohol, a polyacrylic acid, a polyethylene glycol monoalkyl ether, or a polyfluorene. A thermoplastic resin such as an alkyl acrylate, a polyester or a polyurethane.

S-38-201223982 As a adhesion promoter, for example, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-amino group) Ethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxylate Decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane' 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-sulfonylpropyltrimethoxydecane, etc. . Specific examples of the thermal radical generating agent include 2,2'-azobis(2-methylvaleronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile). Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxydiphenylketone. Further, as the coagulant, for example, sodium polyacrylate or the like is specifically mentioned. Specific examples of the chain transfer agent include dodecanethiol, 2,4-diphenyl-4-methyl-1-pentene, and the like. The curable resin composition of the present invention preferably contains a surfactant (F) as a surfactant, and for example, a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based interfacial activity having a fluorine atom. Agents, etc. As the polyoxymethylene surfactant, for example, an interface having a siloxane coupling. Specifically, for example, Ding Oray Silicone DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the polyether modified polyoxyxene oil SH8400 (trade name: Dow Corning Toray -39-201223982 (stock)) , KP321, KP3 22, KP3 23, KP3 24, KP3 2 6, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive) Performance Materials Japan Co., Ltd.). The fluorine-based surfactant is, for example, a surfactant having a fluorocarbon chain. Specifically, for example, Fluorinert (registered trademark) FC43 0, FC431 (Sumitomo 3M (share) system), MEGAFACE (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same R3 0 (DIC ( ())), F-Top (registered trademark) EF301, EF303, EF351' with EF352 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, same as S382, with SC101, with SC105 (Asahi Glass) (share) system, E5844 ((share) daikinfinechemical research institute) and so on. The polyfluorene-based surfactant having a fluorine atom is, for example, a surfactant having a siloxane chain and a fluorocarbon chain. Specifically, for example, megaface (registered trademark) R08, same as BL20, the same F475, the same F477, and the same F443 (DIC system). For example, MEGAFACE (registered trademark) F475 is preferred. The content of the surfactant (F) is 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 〇·〇1 by mass, based on the curable resin composition. % or more, 〇·〇5 mass% or less. The flatness of the coating film can be improved by including the surfactant in the above range. The curable resin composition of the present invention is substantially a coloring agent which does not contain a pigment and dyes -40 - 201223982. That is, in the curable resin composition of the present invention, the content of the coloring agent with respect to the entire composition is, for example, preferably less than 1% by mass, more preferably less than 5% by mass. The curable resin composition of the present invention is filled in a quartz cell having an optical path length of 1 cm, and the average transmittance is preferably 70% when the transmittance is measured using a spectrophotometer at a measurement wavelength of 400 to 70 Onm. More preferably, it is 80% or more. In the curable resin composition of the present invention, when the coating film is formed, the average transmittance of the coating film is preferably 90% or more, and more preferably 95% or more. The average transmittance is a coating film having a thickness of 2 μm after heat hardening (for example, 1 2 0 to 240 ° C, 1 Torr to 120 minutes), and a spectrophotometer is used to measure a wavelength of 400 to 700 nm. The average enthalpy when measuring. Thereby, a coating film excellent in transparency in the visible light region can be provided. The coating film of the present invention can be obtained by applying the curable resin composition of the present invention to a substrate and hardening it by heat. Examples of the substrate include glass, metal, plastic, etc., and a color filter, various insulating films, conductive films, drive circuits, and the like may be formed on the substrate. Since the curable resin composition of the present invention can be cured at a temperature of 200 ° C or lower, a coating film can be formed on a substrate having a low heat resistance as a plastic. The application of the curable resin composition of the present invention to a substrate can be carried out by using a spin coater, a slit & spin coater, a slit coater, an injection, a roll coater, a dip coater, or the like. Various coating devices are used. After coating, vacuum drying or prebaking, it is preferred to remove the volatile component of -41 - 201223982, such as a solvent. The coating film can be formed by baking the volatile film with the coating film which has been removed at 120 to 24 ° C for 10 to 1 20 minutes. The film thickness □ of the coating film formed by the curable resin composition of the present invention is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like. For example, 0. 1~1 0 μιη. According to the present invention, even when the curing temperature is less than 200 °C, a coating film excellent in chemical resistance can be formed. The coating film thus obtained is useful as an overcoat used for, for example, a liquid crystal display device or an electronic paper. Further, it can also be used for a display device such as a touch panel. Therefore, a display device having a high-quality coating film can be manufactured at a high yield. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples. In the examples, "%" and "parts" are % by mass and part by mass without special notice. (Synthesis Example 1) In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was passed at 0.02 L/min to prepare a nitrogen atmosphere, and 140 parts of diethylene glycol ethyl methyl ether was placed and stirred. Heat to 70 °C. Next, 40 parts of methacrylic acid, and a mixture of monomer (1-1) and monomer (Π-1) {monomer (1-1): monomer (Π-1) in the mixture Ratio = 5 0: 5 0 } 3 60 parts, dissolved

S-42-201223982 A solution was prepared in 1 part of diethylene glycol ethyl methyl ether, and the solution was drained for 4 hours using a dropping pump, and dropped into a flask maintained at a temperature of 70 °C.

On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 240 parts of diethylene glycol ethyl methyl ether, and this solution was used for another. The drip pump took 5 hours to drip into the flask. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin A a ) having a solid content of 4 2 · 3 %. The obtained resin Aa had a weight average molecular weight (Mw) of 8,000 'molecular weight distribution (Mw/Mn) of 1.91 and an acid value of 60 mg-KOH/g. (Synthesis Example 2) In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was passed at 0.02 L/min to produce a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol was placed and 3 105 parts by mass of -methoxybutyl acetate was heated to 70 ° C while stirring. Then '60 parts of methacrylic acid, and a mixture of monomer (I-1) and monomer (11-1) {monomer ratio of monomer (1 -1): monomer (II-1) in the mixture = 5〇: 50} 24 parts 'dissolved in 3_methoxybutyl acetate. 1 40 parts to prepare a solution, this solution took 4 hours using a drop pump, and dropped into a flask maintained at 70 ° C Inside. -43- 201223982 On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of 3-methoxybutyl acetate. This solution was dropped into the flask over 4 hours using another drop pump. After the completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin Ab) having a solid content of 32.6%. The obtained resin Ab had a weight average molecular weight (Mw) of 1,3,400, a molecular weight distribution (Mw/Mn) of 2 to 50, and an acid value of 113 to 9 mg-KOH/g. The measurement of the weight average molecular weight (Mw) and the number average molecular weight (?n) of the obtained resin Aa and resin Ab was measured by the following conditions using the GPC method. Device: Κ2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M Column temperature: 40 ° C Solvent: THF (tetrahydrofuran) Flow rate: l. 〇 mL / min Detector: Ri The weight average molecular weight in terms of the polystyrene obtained above And the ratio of the number average molecular weight (Mw / Mn) as a molecular weight distribution. [Example 1] The polymerizable compound (c): trimethylolpropane triacrylate (A-TMPT: Shin-Nakamura) was mixed with 1 42 parts of the solution of the resin Aa obtained in Synthesis Example 1 (60 parts in terms of solid content). Chemical (stock) system, molecular weight: 296) 4 parts, resin (B): o-cresol novolac type epoxy resin (Sumi_ep〇xy ESCN-195XL-

S -44 - 201223982 80 ; Sumitomo Chemical Co., Ltd., acid value: 〇.lmg-KOH/g) 10 parts, thermal acid generator (D): (4-hydroxyphenyl) (2-methylbenzyl) ) methyl bis(trifluoromethanesulfonyl) quinone imine (SI-250; manufactured by Sanxin Chemical Co., Ltd.) 0.5 parts, 1,3,5-para (4-hydroxy-3,5-di- Tert-butylbenzyl)-1,3,5-triterpene-2,4,6(1H,3H,5H)-trione (IRGANOX 3114; manufactured by Ciba Japan Co., Ltd.) 1.0 part and solvent (E) A curable resin composition 1 was obtained. The solvent has a mass ratio of propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, and diethylene glycol ethyl methyl ether of 2 0 : 2 0 : 60, and is hardenable. The solid content of the resin composition 1 was mixed as in 17.7%. [Example 2] Except that dinonoltetraol hexaacrylate (KAYARAD DPHA; manufactured by Sakamoto Chemical Co., Ltd., molecular weight: 578) was substituted for trimethylolpropane triacrylate, and 1,3,5 was not used. - ginseng (4-hydroxy-3,5-di-16 1 -butylbenzyl)-1,3,5-triterpene-2,4,6(111,311,511)-trione Example 1 was carried out in the same manner to obtain a curable resin composition 2. [Example 3] Operation was carried out in the same manner as in Example 1 except that trimethylolpropane triacrylate was replaced with neopentyl alcohol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Chemical Co., Ltd.). Resin composition 3 ^ [Comparative Example 1] Dipentaerythritol hexaacrylate was mixed with 1 8 4 parts of the resin solution containing the resin A b obtained in Synthesis Example 2 (60 parts by weight - 45 - 201223982). KAYARAD DPHA; manufactured by Nippon Chemical Co., Ltd., 1,3,5-gin (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2, 0.8 parts of 4,6 (1H,3H,5H)-trione (IRGANOX 31 14; manufactured by Ciba Japan; / Co., Ltd.) and a solvent gave a curable resin composition 4. The solvent has a mass ratio of propylene glycol monomethyl ether acetate, 3-ethoxyethyl propionate, 3-methoxy-1-butanol, and 3-methoxybutyl acetate. 4 : 2 0 : 3 3 : 3 3 , and the solid content of the curable resin composition 4 was 17.7 ° /. Mix as usual. <Average transmittance of the composition> For the obtained curable resin composition, an ultraviolet visible near-infrared spectrophotometer (V-65 0; manufactured by JASCO Corporation) (quartz cell, optical path length) was used. : lcm), the average transmittance (%) at 400 to 700 nm was measured. The results are shown in Table 1. <Production of Coating Film> A 2-square glass substrate (Eagle 2 000; manufactured by Corning Co., Ltd.) was washed with a neutral detergent, water, and 2-propanol, followed by drying. The curable resin composition was spin-coated on the glass substrate, preliminarily baked at 1 °C for 3 minutes, and then baked at 150 °C for 60 minutes. After the film was allowed to stand for cooling, the film thickness of the film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and the result was 2. Ομηι. <Transmission rate measurement>

S-46-201223982 The obtained coating film was measured for transmittance (%) at 400 nm and average transmittance (%) at 400 to 700 nm using a microscopic spectrophotometer (OSP-SP200; manufactured by OLYMPUS). The results are shown in Table 1. <Chemical resistance> The obtained coating film was immersed in N-methylpyrrolidone at 30 ° C for 30 minutes, and the film thickness and transmittance before and after immersion were measured, and the film thickness was changed according to the following formula ( %) and transmittance change (%). Both are the same, and the closer to 1%, the smaller the change before and after the immersion. When the film thickness change (%) is closer to 1% by weight, it is preferable because the film is dissolved or swollen. When the transmittance change (%) is closer to 100%, the color or discoloration of the coating film is small, so it is preferable. Film thickness change (%): (film thickness after immersion (μπι) / film thickness before immersion (μιη)) > 100 transmittance change (%): (transmission rate after immersion (%) / before immersion Transmittance (%)) Further, the adhesion test was performed on the film after immersion. Using a blade and a super tool guide (made by Taisho Machinery Co., Ltd.), a cut mark was placed on the coated film at intervals of 1 mm to make 100 squares of 1 mm x 1 mm. Next, a scotch tape (registered trademark) of 24 mm width (manufactured by Nichiban Co., Ltd.) was attached to the cut square of the coating film, and rubbed with an eraser from above the scotch tape to adhere the scotch tape to the coating film. After that, the end portion of the transparent adhesive tape was held after 2 minutes, and the film was peeled off in one go while maintaining a right angle with the coating film surface. Thereafter, the coating film was visually counted as the number of squares remaining on the substrate without being peeled off. The more the number of squares remaining on the substrate, the better the adhesion. -47-201223982 [Table i] Example 1 Example 2 Example 3 Comparative Example 1 Transmittance (%) of the curable resin composition 98.8 98.8 98.8 99.2 Transmittance (%) of the coating film (average of 400 to 700 nm) 99.8 99.8 99.7 99.8 Transmittance of coating film (%) (400 nm) 99.7 99.7 99.5 99.7 Resistance to film thickness (%) 98 101 79 0 Change in transmittance (%) 100 100 100 *) Adhesion 100 100 100 * "The coating film was completely dissolved in N-methylpyrrolidone by immersion, and therefore it was impossible to measure. From the results of Table 1, it was confirmed that the curable resin composition of the present invention was hardened at 150 ° C. In addition, the coating film formed is excellent in chemical resistance, and the curable resin composition of the present invention can form a coating film excellent in chemical resistance even when the curing temperature is less than 200 ° C. It is also useful as a member of a display device using a plastic substrate.

S -48-

Claims (1)

201223982 VII. Patent application scope: 1. A curable resin composition containing the following (A) ' (B), (C), (D) and (E), relative to the content of (A) 1 The content of (B) is 1 part by mass or more and 100 parts by mass or less; (A) containing at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride; a structural unit and a structural unit derived from a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized and a carbon-carbon unsaturated double bond, and an acid value of 30 mg-KOH/g or more and 180 mg-KOH/g or less (B) an epoxy resin having an acid value of less than 30 mg-KOH/g (C) a compound having at least one selected from the group consisting of a propylene fluorenyl group and a methacryl fluorenyl group ( D) Thermal acid generator (E) Solvent. 2. The curable resin composition of claim 1, wherein the monomer having a structure for epoxidizing an unsaturated alicyclic hydrocarbon and a carbon-carbon unsaturated double bond is represented by the formula (I) a compound selected from the group consisting of a compound of the formula (II) and at least one selected from the group consisting of -49- 201223982 [In the formula (I) and the formula (π), R1 and R2 are each independently represented by a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group; X1 and X2 is independently shown as a single bond or an alkanediyl group having a carbon number of 1 to 6, and the -CH2-' contained in the diradical of the house may be substituted by -〇-, -S- or -NR3-, and R3 is not a hydrogen atom or Alkyl group having 1 to 4 carbon atoms]. 3. The curable resin composition of claim 1, wherein the molecular weight of the compound having at least one selected from the group consisting of two groups consisting of an acryloyl group and a methacryl group is 150 Above, below 3,000. A coating film formed by using a curable resin composition as in the first aspect of the patent application. A coating film obtained by applying a curable resin composition according to claim 1 of the patent application to a substrate and hardening by heat. A display device comprising a coating film as in item 4 of the patent application. -50- 201223982 Four designated representatives: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No 201223982 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention: no