TW201234103A - Colored photosensitive composition - Google Patents

Abstract

A colored photo-sensitive composition and a color filter based on the composition are provided to include a halogenated copper phthalocyanine pigment, halogenated zinc phthalocyanine pigment, and quinophthalone pigment containing coloring agent. A colored photo-sensitive composition includes a coloring agent, polymeric compound, polymerization initiator, and solvent. The coloring agent includes halogenated copper phthalocyanine pigment, halogenated zinc phthalocyanine pigment, and quinophthalone pigment. The halogenated copper phthalocyanine pigment is C.I pigment green 7. The quinophthalone pigment is C.I pigment yellow 138.

Description

201234103 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a color-sensitive photosensitive composition suitable for forming a color image of a color filter used in a liquid crystal display element or a solid-state image sensor. [Prior Art] A color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel is manufactured by using a coloring photosensitive composition. It is known that such a coloring photosensitive composition contains a coloring agent, a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the coloring agent is c. I. Pigment Green 3 6 and C. I. Pigment Yellow 1 5 Composition of 0 (Patent Document 1). [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2005- 1 573 1 1 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The coloring photosensitive composition is used. The green filter formed can not fully satisfy the color separation ability with the red filter. ε: <8^ -5-201234103 [Means for Solving the Problem] The present invention provides the following [1] to [8], [1] containing a coloring agent, a polymerizable compound, a polymerization initiator, and a solvent, and coloring The agent contains a coloring photosensitive composition of a copper halide titanium phthalocyanine pigment, a zinc halide titanium cyanine pigment, and a coloring agent for a quinophthalone pigment. [2] The coloring photosensitive composition of the above [1], which is contained in an amount of 20 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the content of the zinc halide titanium phthalocyanine pigment. [3] The coloring photosensitive composition of the above [1] is contained in an amount of 50 parts by mass or more and 200 parts by mass or less based on the content of the quinone quinone pigment. [4] The content of the copper oxytetraphthalocyanine pigment is 20 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the zinc halide titanium cyanine pigment, and the content of the quinacridone pigment is relative to the zinc halide titanium phthalocyanine pigment. The coloring photosensitive composition of the above [1] is 50 parts by mass or more and 200 parts by mass or less. [5] The colored photosensitive composition according to any one of the above [1] to [4], which is a C.I. Pigment Green. [6] The quinacone pigment is a colored photosensitive resin composition according to any one of the above [1] to [3]. [7] The colored photosensitive composition according to any one of the above [1] to [6], which contains a coloring agent, a polymerizable compound, a polymerization initiator, a solvent, and a resin. [8] A color filter light sheet formed of the colored photosensitive composition according to any one of the above [1] to [7].

[Effect of the Invention] According to the colored photosensitive composition of the present invention, a green filter excellent in color separation ability from a red filter can be obtained. BEST MODE FOR CARRYING OUT THE INVENTION The coloring photosensitive composition of the present invention contains a coloring agent (A), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), and the coloring agent contains copper halide titanium halide. A pigmented photosensitive composition of a phthalocyanine pigment, a zinc halide phthalocyanine pigment, and a quinacridone pigment. The colored photosensitive composition of the present invention is preferably a resin (B). Further, the compounds exemplified as the respective components in the present specification can be used singly or in combination, without particular limitation. The coloring agent (A) used in the coloring photosensitive composition of the present invention contains a copper halide titanium phthalocyanine pigment, a zinc halide titanium phthalocyanine pigment, and a quinophthalone pigment hydrazine as a copper oxytitanium phthalocyanine pigment as copper oxychloride. The cyanine pigment is better, and the CI pigment green 7 is better. When the copper halide phthalocyanine pigment is the above pigment, the transmittance in the vicinity of 600 nrn can be lowered, and the color separation ability with the red filter is excellent. As the zinc halide titanium cyanine pigment, C.L pigment green 58 is preferred. The content of the copper oxyhalide pigment is preferably 20 parts by mass or more and 150 parts by mass or less, more preferably 80 parts by mass or more and 120 parts by mass or less, based on 1 part by mass of the zinc halide phthalocyanine pigment. When the content of the copper oxyhalide pigment is in the above range, the high transmittance at 520 nm can be maintained at 201234103, the transmittance at around 60 Onm can be lowered, and the color separation ability with the red filter is excellent, and a high-definition green filter can be obtained. Light film. When such a green filter is used as a filter for a green pixel provided in a display device such as a liquid crystal display device, the color reproducibility of the display device can be improved. The colorant (A) further contains a quinophthalone pigment. The content of the quinacridone pigment is preferably 50 parts by mass or more and 200 parts by mass or less, more preferably 12 parts by mass or more and 200 parts by mass or less, based on 100 parts by mass of the phthalocyanine pigment. The quinacridone pigment is preferably C · I · Pigment Astragalus. By containing the above-described quinacridone pigment, the color separation ability with the blue filter tends to be excellent. The pigment may be subjected to a rosin treatment, a surface treatment such as a pigment derivative or a pigment dispersant introduced with an acidic group or a basic group, a graft treatment of a pigment surface with a polymer compound or the like, a sulfuric acid micronization method, or the like. The micronization treatment, the removal treatment of an organic solvent or water to remove impurities, the removal treatment of an ionic impurity by an ion exchange method, or the like. Further, the pigment is preferably uniform in particle size. By dispersing the pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained. As the pigment dispersant, a commercially available surfactant can be used. Examples of the surfactant include 'an oxime-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, amphoteric, polyester-based, polyamine-based, propylene-based, and urethane-based interface. Active agent. In addition to the above-mentioned surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amines Examples of the polyaminourethanes and polyethyleneimines include, for example, commercial products.

S 201234103 kp (Shin-Etsu Chemical Co., Ltd.), Fu Ruolin (Kongrong Chemical Co., Ltd.), SOLSPERSE (Zeneca), EFKA (made by CIBA), AJISPER (Ajinomoto Fine-Techno 〇 0., 111 (;.), 〇丨5戸61^>^(8丫〖3卩&11 company), etc. These may be used alone or in combination of two or more. In the case of the total mass of the pigment, it is preferably 100% by mass or less, more preferably 5 to 50% by mass. If the amount of the pigment dispersant used is within the above range, a uniform dispersion state can be obtained. The content of the coloring agent (A) is preferably from 5 to 60% by mass, more preferably from 5 to 45% by mass, based on the solid content of the coloring photosensitive composition. The desired spectral or color concentration. The solid component refers to the total amount of solvent removed by the colored photosensitive composition. The colored photosensitive composition of the present invention preferably contains the resin (B). The coloring photosensitive composition of the present invention The resin (B) used in the substance has alkali solubility The term "alkali solubility" refers to the property of a developer which is dissolved in an aqueous solution of an alkali compound. The above-mentioned resin having alkali solubility can be exemplified by a resin (B-1): from an unsaturated carboxylic acid and not At least one selected from the group consisting of saturated carboxylic anhydrides (a) (hereinafter also referred to as "(a)") and a compound having a cyclic ether having a carbon number of 2 to 4 (b) (hereinafter also referred to as "(b)" a copolymer obtained by polymerization, a resin (B-2): a monomer (c) copolymerizable with (a) and (b) (however, a cyclic ether having no carbon number of 2 to 4) (hereinafter also "(c)") -9- 201234103, a copolymer obtained by polymerizing (a) and (b), and a resin (B-3): a copolymer (a copolymer of cerium and (c), a resin (B) -4): a copolymer obtained by polymerizing (a) and (c) and a resin resin (B-5) obtained by the reaction of (b): a copolymer obtained by polymerizing (b) and (c) and (a) The resin or the like obtained by the reaction. (a) Specifically, an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, anthracene-vinylbenzoic acid, m-vinylbenzoic acid or P-vinylbenzoic acid may be mentioned. Acids; maleic acid, fumaric acid, lemon Kang acid, methyl fumarate, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3, Unsaturated dicarboxylic acids such as 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1, 4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3- Dicarboxylic acid, 5-carboxybicyclo[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]heptane-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxyl a carboxyl group-containing bicyclic unsaturated compound such as -6-ethylbicyclo[2.2.1]hept-2-ene: maleic anhydride, citraconic anhydride, itaconic anhydride, 3·vinylphthalic anhydride, 4 -vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic acid An unsaturated dicarboxylic anhydride such as an acid anhydride or a 5,6-dicarboxybicyclo[2.2.1]heptane-2-ene anhydrate (nadic anhydride);

S -10- 201234103 succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester, etc. An unsaturated mono((meth)acryloxyalkylene) ester of a polyvalent carboxylic acid; an unsaturated acrylic vinegar having a hydroxyl group and a carboxyl group in the same molecule as α-(hydroxymethyl)acrylic acid. Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferably used from the viewpoint of copolymerization reactivity or alkali solubility. Here, in the present specification, "(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) polymerization of a cyclic ether having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (dioxolane ring)) Sex compounds. (b) a monomer having a cyclic ether having 2 to 4 carbon atoms and an ethylenically unsaturated bond, preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group Better. In the case of (b), for example, a monomer having an epoxy group (bl) (hereinafter also referred to as "(bl)") or a monomer having an oxetanyl group (b2) (hereinafter also referred to as "(b2)" "), and a monomer having a tetrahydrofuranyl group (b3) (hereinafter also referred to as "(b3)"). The epoxy group is a single body, and the body (bl) means a polymerizable compound having an epoxy group. (b), for example, a monomer having a structure in which a chain olefin is epoxidized and an ethylenically unsaturated bond (b 1 _ 1 ) (hereinafter also referred to as "(bl-1)"), and a ring having a ring The epoxidized structure of the olefin and the ethylenically unsaturated bonded monomer (bl-2) (hereinafter also referred to as "(bl-2)"). -11 - 201234103 为 , 体 简 简 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体It is more preferable to have (meth) propylene methoxy group (bl-2). Specific examples of (bl-Ι) include epoxypropyl (meth) acrylate, cold methyl epoxy propyl (meth) acrylate, ethyl epoxy propyl (meth) acrylate, and a ring. Oxypropyl vinyl ether, 〇-vinylbenzyl epoxy propyl ether, m-vinyl decyl epoxypropyl ether, p-vinylbenzyl epoxy propyl ether, α-methyl-hydrazine- Vinylbenzyl epoxypropyl ether, α-methyl-m-vinylbenzyl epoxypropyl ether, α-methyl-P-vinylbenzyl epoxypropyl ether, 2,3-dual ( Glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2.6-bis ( Glycidoxymethyl)styrene, 2,3,4-cis (glycidoxymethyl)styrene, 2,3,5-glycol (glycidoxymethyl)styrene, 2.3 .6- ginseng (glycidoxymethyl)styrene, 3,4,5-glycol (glycidoxymethyl)styrene, 2,4,6-paran (glycidoxymethyl) A compound or the like described in JP-A-H07-248625. (bl-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4- Epoxycyclohexyl methacrylate (for example, CYCLMERA 400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, CYCLMERM100; manufactured by Daicel Chemical Industry Co., Ltd.), I) the compound represented by the formula, the compound represented by the formula (II), and the like.

S -12- 201234103 【化1】

[In the formula (I) and the formula (π), R1 and R2 each independently represent an alkyl group having a hydrogen number of 1 to 4, and the hydrogen atom contained in the alkyl group may be a hydroxy group; X1 and X2 are each independently a single bond, -R3 -, * -R3-0·, , wood-r3-nh-. R3 is an alkanediyl group having 1 to 6 carbon atoms. * is the key with the key. Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, a propyl group, an isopropyl group, an η-butyl group, a sec-butyl group, a tert-butyl group, etc. (hydroxyalkyl group, for example, a hydroxyl group) Base, 1-hydroxyethylethyl II, 1-hydroxypropyl '2-hydroxypropyl, 3-hydroxypropyl, methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-, 3-hydroxybutyl '4-hydroxybutyl, etc. R1 and R2 are preferably a hydrogen atom, a methyl group, a hydroxyhydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group. Examples of the alkanediyl group include a methylene group, an ethylene group, a diyl group, a propane, a 3-diyl group, a butane-1,4-diyl group, a pentane-1, and a hexane-1,6-diyl group. Preferably, X1 and X2 are, for example, a single bond, a methylene group, an anthracene CH2-0-(* is a bond bond with a fluorene bond), and: (:-CH2CH2- is preferably a single bond, *-ch2ch2- The compound represented by the formula (I) may, for example, be a formula (I.1 atom or a substituted group; wood R 3 - S _ ethyl, η- > ' 2-hydroxy 1-hydroxy-1 - hydroxybutylmethyl, 1-propane-1,2-5-diyl, L-group, * 0 · group * more) ~ (-13- 201234103 I - 1 5 ) Preferably, for example, the formula (I-1), the formula (1-3), the formula (1-5), the formula (1-7), the formula (Ι·9), and the formula (1-11) are exemplified. The formula (1-15) is more preferably as the formula (1-1), the formula (1-7), the formula (1-9), and the formula (1-15). [Chemical 2 H2C=CH-C-〇

H2C =CH—C—Ο—C2H4 Ο Η 2〇s=CH—C ch3o I II H2〇"C;—C一ο ch3o HjC^C—*C—O—CH CH3〇I II H^C= C - one 0 - C ^ H 4

Η20=Π

H2C=CH-e-0-C2H4-S o II H2C=CH-C—0 —C2H4-N H ch3〇 H2C=C—C—0—C2H4-S

Ch3o H2C=C—C—O—〇2h4-N h2c—

a*i2) c2h4oh o h2c=c-c-o ch3 ο 1 It H2G—C —C—O—C2H4 · (W3)

(1-14) (1-15) The compound represented by the formula (11) may, for example, be a compound represented by the formula (11-1) to the formula (11-1). Preferably, for example, the formula (11-1), the formula (II-3), the formula (Π-5), the formula (II-7), the formula (Π-9), and the formula (Π-ll) to the formula (11) -15). More preferably (ΙΙ·1), formula (ΙΙ-7), formula (ΙΙ-9), formula (-14-

S 201234103 11-15) 【化3】 Η2〇:ΟΗ—

CH3 ο I II μι H2e=C—C—O—C2H4-N CH3〇H2C=C—c—〇H2O—〇—ci~j· ch3 o I II H2C==C—c—0—c2h4 〒H3 o HjjC:. C-Q-c2H4-〇(Π-2) HsCjCH-C-〇-C2H4-S o II H Η2〇ί〇ΗTM0_0_C2H4—Νί· 9Η3ό ^ ^ I η H2C=G——c —o—c2h4-s

(Π-8) ?2HS?

Ch^OH ο H2C—c~ c h2c==c a c—ο

(Π-15) C2H40HO Η2〇=0" c~~o

(11-14) The compound represented by the formula (1) and the compound represented by the formula (II) can be used singly. Also, they can be mixed at any ratio. In the case of mixing, the mixing ratio is in molar ratio, preferably Formula (I): Formula (II) is 5: 95 to 95: 5, more preferably 10: 90 to 90: 10, and particularly preferably 20: 80 to 8 0 : 20 The monomer (b2) having an oxetanyl group refers to a polymerizable compound having an oxetanyl group. (b2) It is preferred to have an oxetanyl group and an ethylenically unsaturated bond t monomer, and it is more preferable to use a -15-201234103 body having an oxetanyl group and a (meth) acryloxy group. (b2) Aspects may, for example, be 3-methyl-3-(methyl)propenyloxymethyloxetane, 3-ethyl-3-(methyl)propenyloxymethyloxalate Cyclobutane, 3-methyl-3-(methyl)propenyloxyethyloxetane, and 3-ethyl-3-(methyl)propenyloxyethyloxetane . The monomer (b3) having a tetrahydrofuran group means a polymerizable compound having a tetrahydrofuran group. (b 3 ) A monomer having a tetrahydrofuranyl group and an ethylenically unsaturated double bond is preferred, and a monomer having a tetrahydrofuranyl group and a (meth) propyl storage group is more preferable. (b3) Specific examples thereof include tetrahydrofurfuryl acrylate (e.g., Bisko V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like. (C), for example, methyl (meth) acrylate, ethyl (meth) acrylate, η butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- (meth)acrylic acid alkyl esters such as butyl (meth) acrylate; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02'6癸-8-yl (meth) acrylate (a customary name in the technical field to which the invention pertains is dicyclopentanyl (meth) acrylate.), dicyclopentanyloxyethyl (methyl) (meth)acrylic acid cyclic alkyl esters such as acrylate and isobornyl (meth) acrylate; (meth)acrylic acid such as phenyl (meth) acrylate or benzyl (meth) acrylate Aryl or aralkyl esters;

S -16- 201234103 Dicarboxylic acid diester of diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl a hydroxyalkyl ester of (meth) acrylate or the like; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo[2.2. 1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl) Bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6- Dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo [2.2.1] Hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene , 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-A Bicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]heptane-2, stimulating, 5-cyclohexyloxy Ring [2.2.1] hept-2-thene, 5-phenoxy mineral bicyclo [2.2.1] hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1] a bicyclic unsaturated compound of hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N·cyclo Hexylmalanimine, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide Butyl ester, N. amber imine-6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9-acridinyl) Malay Dicarbonyl quinone imine derivatives such as quinone imine; -17- 201234103 Styrene, hydrazine: -methyl styrene, m-methyl styrene, ρ·methyl styrene, vinyl toluene, ρ-甲Oxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2, 3-dimethyl-1,3-butadiene. Among these, 'styrene, fluorene-phenyl maleimide, fluorene-cyclohexylmaleimide, fluorene-benzyl maleimide, bicyclo[2.2.1]hept-2-ene, etc. From the viewpoint of copolymerization reactivity and alkali solubility, it is preferred. In the resin (Β-1), the ratio of the structural unit derived from each monomer to the total number of structural units constituting the resin (Β-1) is preferably in the following range. The structural unit from (a); 5 to 60 mol% (preferably 1 〇 to 50 mol%) of the structural unit derived from (b); 40 to 95 mol% (preferably 50 to 9 0 mol) %) When the ratio of the structure of the resin (B-1) is in the above range, the stability, developability, solvent resistance, heat resistance, and mechanical strength tend to be good. The resin (B-1) is preferably a resin in which (b) is (b 1 ), and (b) is (bl-2). For the resin (B-1), for example, the method described in the document "Experimental method for polymer synthesis" (Otsuka Ryokan, Ltd., 1st edition, 1st edition, 1st, 1st, 1st, 1st, 1970) Manufactured in the literature cited in the literature.

S -18- 201234103 Specifically, for example, a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are added to a reaction vessel, and oxygen is substituted by oxygen to deoxidize, and stirred, heated, and kept warm. The method. Further, the polymerization initiator, solvent and the like used herein are not particularly limited and can be generally used by users in the field. a polymerization initiator such as an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and an organic peroxide (benzene) In the case where the solvent is a solvent, the solvent can be used as the solvent for coloring the photosensitive composition, and a solvent or the like described later can be used. Further, the obtained copolymer may be used as a solid (powder) by directly using the solution after the reaction, using a concentrated or diluted solution, or by reprecipitation or the like. In particular, as a solvent in the polymerization, a solution which is reacted with the same solvent as the solvent (E) described later can be used as it is, and the production steps can be simplified. In the resin (B-2), the ratio of the structural unit derived from each monomer to the total number of moles of the total structural unit constituting the resin (B-2) is preferably in the following range. Structural unit derived from (a); 2 to 40 mol% (preferably 5 to 35 mol%); structural unit derived from (b); 2 to 95 mol% (preferably 5 to 8 mol%) ) The structural unit derived from (c); 1 to 65 mol% (preferably 1 to 6 mol%) The ratio of the structural unit of the resin (B-2) is in the above range, and the stability and developability are preserved. Solvent resistance, heat resistance and mechanical strength have become good. 19- 201234103 Good tendency. The resin (B-2) is preferably a resin of (b) (bl) and a resin of (b) horse (bl-2). The resin (B-2) can be produced by the same method as the resin (B-1). In the resin (B-3), the ratio of the structural unit derived from each monomer to the total number of moles of the entire structural unit constituting the resin (B-3) is preferably in the following range. The structural unit derived from (a); 2 to 40 mol% (preferably 5 to 35 mol%) from the structure of (c); 60 to 98 mol% (preferably 65 to 95 mol%) When the ratio of the structural unit of the resin (B-3) is in the above range, the stability, developability, and solvent resistance are improved. @^ Resin (B-3) can be used with the resin (B- Manufactured in the same manner. The resin (B-4) and the resin (B-5) can be produced, for example, in a two-stage process. In this case, reference may also be made to the above-mentioned document "Experimental method for polymer synthesis" (Otsuno, the issuing house) (manufactured by the Chemicals, the first edition, the first edition, the first brush, issued on March 1, 1972), and the method described in JP-A-2001-89533, etc. Resin (B-4), first, first In the same manner, in the same manner as the above-mentioned method for producing the resin (B-1), a copolymer of (a) and (c) is obtained. In this case, the copolymer obtained in the same manner as above can be used as it is, and the solution after the reaction can be used as it is. Concentrated or diluted solution can be used, or used for reprecipitation, etc.

The method of S-20-201234103 is taken out as a solid (powder). The ratio of the structural units derived from (a) and (c) is preferably in the following range with respect to the total number of moles of the entire structural unit constituting the above-mentioned copolymer. The structural unit derived from (a); 5 to 50 mol% (preferably 10 to 4 5 mol%) of the structural unit derived from (c); 50 to 95 mol% (preferably 55 to 90 mol%) Next, in the second stage, a part of the carboxylic acid and the carboxylic anhydride of (a) from the obtained copolymer is reacted with the cyclic ether of (b). Since the reactivity of the cyclic ether is high and the unreacted (b) is not easily retained, it is more preferable that (b) is (bl) and further (bl-Ι). Specifically, 'the environment inside the flask is replaced by nitrogen instead of air. For the number of moles of (a), 5 to 80 mol% of (b), relative (a), (b) and (c) A total of 0.001 to 5% by mass of a reaction catalyst of a carboxyl group and a cyclic ether (for example, dimethylaminomethyl phenol), and a total of (a), (b), and (c) A polymerization inhibiting agent (for example, hydroquinone) of 0.001 to 5% by mass is placed in a flask at 60 to 130. (:, the resin (A - 4 ) is obtained by performing the reaction for 1 to 10 hours. Further, similarly to the polymerization conditions, the amount of heat generated by the production equipment or the polymerization can be appropriately determined, and the feeding method or the reaction temperature can be appropriately adjusted. In this case, the number of moles of (b) is preferably from 10 to 75 mol%, preferably from 15 to 70 mol%, relative to the number of moles of (a). (q) In this range, the balance between storage stability, solvent resistance, and heat resistance is improved. The specificity of the resin (B-4) is, for example, (meth)acrylic acid/dicyclopentanyl group (A). Copolymer of acrylate copolymer with epoxypropyl (meth) acrylate, copolymer of (meth)acrylic acid / benzyl (meth) acrylate and epoxy propyl (meth) acrylate Reactive resin, copolymer of (meth)acrylic acid/cyclohexyl (meth) acrylate copolymer with epoxypropyl (meth) acrylate, copolymer of (meth)acrylic acid/styrene and epoxy Propyl (meth) acrylate-reacted resin, (meth) acrylate / (meth) acrylate Copolymer of a copolymer of a copolymer with a glycidyl (meth)acrylate, a copolymer of (meth)acrylic acid/N-cyclohexylmaleimide and a resin reactive with a propylenepropyl (meth)acrylate , (meth)acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer and epoxy propyl (meth) acrylate resin, (meth) acrylate /Dicyclopentane (meth) acrylate / cyclohexyl (meth) acrylate copolymer and epoxy propyl (meth) acrylate resin, (meth) acrylate / dicyclopentanyl (Meth)acrylate/styrene copolymer with epoxypropyl (meth) acrylate resin, (meth)acrylic acid / dicyclopentanyl (meth) acrylate / (meth) acrylate Copolymer of methyl copolymer and epoxypropyl (meth) acrylate, copolymer of (meth)acrylic acid / dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide Resin reactive with epoxypropyl (meth) acrylate, crotonic acid / dicyclopentane a resin in which a copolymer of a base (meth) acrylate is reacted with a glycidyl (meth) acrylate;

S -22- 201234103 Copolymer of crotonic acid / benzyl (meth) acrylate copolymer with epoxy propyl (meth) acrylate, copolymer of crotonic acid / cyclohexyl (meth) acrylate and ring Oxypropyl (meth) acrylate-reacted resin, crotonic acid/styrene copolymer, epoxy propyl (meth) acrylate-reacted resin, crotonic acid/crotonate methyl copolymer and epoxy a propyl (meth) acrylate-reacted resin, a copolymer of crotonic acid/N-cyclohexylmaleimide, a resin reactive with a glycidyl (meth) acrylate, a crotonic acid/dicyclopentanyl group Copolymer of (meth) acrylate / benzyl (meth) acrylate copolymer with epoxy propyl (meth) acrylate, crotonic acid / dicyclopentanyl (meth) acrylate / cyclohexyl Copolymer of (meth) acrylate copolymer with epoxypropyl (meth) acrylate, copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / styrene and epoxy propyl ( Methyl) acrylate-reacted resin, crotonic acid/dicyclopentanyl (methyl) Copolymer of acrylate/crotonate methyl group reacted with epoxy propyl (meth) acrylate, crotonic acid / dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide a resin in which a copolymer is reacted with a glycidyl (meth) acrylate; a resin in which a copolymer of maleic acid/dicyclopentanyl (meth) acrylate is reacted with a glycidyl (meth) acrylate, Copolymer of maleic acid/benzyl (meth) acrylate copolymer with epoxypropyl (meth) acrylate, copolymer of maleic acid / cyclohexyl (methyl) propylene vinegar and epoxy a propyl (meth) acrylate-reacted resin, a copolymer of maleic acid/styrene, a resin reactive with a glycidyl (meth) acrylate, a copolymer of maleic acid/maleic acid methyl and a ring Oxypropyl (meth) acrylate reaction -23- 201234103 resin, maleic acid / N-cyclohexyl maleimide copolymer and epoxy propyl (meth) acrylate resin, Malay Copolymer of acid/dicyclopentanyl (meth) acrylate/benzyl (meth) acrylate with epoxy Copolymer of a (meth) acrylate-reactive resin, a copolymer of maleic acid/dicyclopentanyl (meth) acrylate/cyclohexyl (meth) acrylate, and a reaction of a glycidyl (meth) acrylate Resin, maleic acid/dicyclopentanyl (meth) acrylate/styrene copolymer with epoxy propyl (meth) acrylate resin, maleic acid / dicyclopentanyl (A a copolymer of acrylate/maleic acid methyl ester and epoxypropyl (meth) acrylate, maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmalay Resin copolymerized with propylene propylene (meth) acrylate; copolymer of (meth) acrylate / maleic anhydride / dicyclopentanyl (meth) acrylate with epoxy propyl (Meth)acrylate-reacted resin '(meth)acrylic acid/maleic anhydride/benzyl (meth)acrylate copolymer and epoxypropyl (meth)acrylate-reacted resin, (methyl) Acrylic acid/maleic anhydride/cyclohexyl (meth) acrylate copolymer with epoxy propyl (methyl) propyl Resin-reacted resin, (meth)acrylic acid/maleic anhydride/styrene copolymer and epoxypropyl (meth)acrylate vinegar resin, (meth)acrylic acid/maleic anhydride/(methyl) Copolymer of methyl acrylate copolymer with epoxypropyl (meth) acrylate, copolymer of (meth)acrylic acid/maleic anhydride/N-cyclohexylmaleimide and epoxypropyl group Acrylate-reactive resin, (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth) acrylate/benzyl (methyl) propyl-24-

S 201234103 Resin copolymer copolymer with epoxypropyl (meth) acrylate, (meth)acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / cyclohexyl (methyl Copolymer of acrylate copolymer and epoxypropyl (meth) acrylate resin (meth)acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / styrene copolymer and ring Oxypropyl (meth) acrylate-reacted resin, (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth) acrylate/(meth)acrylic acid methyl copolymer and epoxypropyl (Meth)acrylate-reacted resin, copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth)acrylate/N-cyclohexylmaleimide and epoxypropyl ( a resin reactive with methyl acrylate; a resin reacted with a copolymer of (meth)acrylic acid/dicyclopentanyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate, (a) Copolymer of acrylic acid/mercapto (meth) acrylate with 3,4-epoxycyclohexylmethyl Acrylate-reacted resin, copolymer of (meth)acrylic acid/cyclohexyl (meth)acrylate and 3,4-epoxycyclohexylmethyl methacrylate-reacted resin, (meth)acrylic acid/styrene Resin copolymerized with 3,4-epoxycyclohexylmethyl methacrylate, copolymer of (meth)acrylic acid/(meth)acrylic acid methyl group and 3,4-epoxycyclohexylmethyl group Acrylate-reactive resin, copolymer of (meth)acrylic acid/N-cyclohexylmaleimide and 3,4-epoxycyclohexylmethyl methacrylate-reacted resin, (meth)acrylic acid/ a resin in which a copolymer of dicyclopentanyl (meth) acrylate/benzyl (meth) acrylate is reacted with 3,4-epoxycyclohexylmethyl methacrylate, (meth) propylene-25- 201234103 Resin, (meth)acrylic acid, copolymer of acid/dicyclopentanyl (meth) acrylate/cyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate /Dicyclopentyl (meth) acrylate / styrene copolymer with 3,4-epoxycyclohexylmethylmethyl Oleate-reactive resin, (meth)acrylic acid/dicyclopentanyl (meth)acrylate/(meth)acrylic acid methyl copolymer and 3,4-epoxycyclohexylmethyl methacrylate Reaction of the reacted resin, copolymer of (meth)acrylic acid/dicyclopentanyl (meth) acrylate/N-cyclohexylmaleimide with 3,4-epoxycyclohexylmethyl methacrylate Resin: a resin of crotonic acid/dicyclopentanyl (meth) acrylate copolymer with 3,4·epoxycyclohexylmethyl methacrylate, crotonic acid/benzyl (meth) acrylate Resin copolymerized with 3,4-epoxycyclohexylmethyl methacrylate, copolymer of crotonic acid/cyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate Ester-reacted resin, copolymer of crotonic acid/styrene and 3,4-epoxycyclohexylmethyl methacrylate-reacted resin, crotonic acid/crotonate methyl copolymer and 3,4-epoxy ring Hexylmethyl methacrylate-reacted resin, copolymer of crotonic acid/N-cyclohexylmaleimide and 3,4-epoxy ring Hexylmethyl methacrylate-reacted resin, copolymer of crotonic acid/dicyclopentanyl (meth) acrylate/benzyl (meth) acrylate and 3,4-epoxycyclohexylmethylmethyl Acrylate-reactive resin, resin of crotonic acid/dicyclopentanyl (meth) acrylate/cyclohexyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate , a copolymer of crotonic acid/dicyclopentanyl (meth) acrylate/styrene and 3,4-epoxycyclohexyl

-26- S 201234103 methacrylate-reactive resin, copolymer of crotonic acid/dicyclopentanyl (meth) acrylate/crotonate methyl and 3,4-epoxycyclohexylmethyl methacrylate Resin-reacted resin, resin of crotonic acid/dicyclopentanyl (meth) acrylate/N-cyclohexylmaleimide and 3,4-epoxycyclohexylmethyl methacrylate a copolymer of maleic acid/dicyclopentanyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, maleic acid/benzyl (meth) acrylate Resin copolymerized with 3,4·epoxycyclohexylmethyl methacrylate, copolymer of maleic acid/cyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethylmethyl Acrylate-reacted resin, maleic acid/styrene copolymer, 3,4-epoxycyclohexylmethyl methacrylate-reacted resin, maleic acid/maleic acid methyl copolymer and 3,4 - epoxycyclohexylmethyl methacrylate-reacted resin, copolymer of maleic acid/N-cyclohexylmaleimide and 3,4-epoxycyclohexylmethylmethyl Resin-reactive resin, copolymer of maleic acid/dicyclopentanyl (meth) acrylate/benzyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate Resin, maleic acid/dicyclopentanyl (meth) acrylate/cyclohexyl (meth) acrylate copolymer and 3,4-epoxycyclohexylmethyl methacrylate resin, horse Resin copolymerized with 3,4-epoxycyclohexylmethyl methacrylate with acid/dicyclopentanyl (meth) acrylate/styrene copolymer, maleic acid/dicyclopentanyl (A) Resin copolymerized with 3,4-epoxycyclohexylmethyl methacrylate, maleic acid / dicyclopentylene (meth) acrylate / N- a resin in which a copolymer of cyclohexylmaleimide is reacted with 3,4-epoxycyclohexyl-27-201234103-based methyl methacrylate; (meth)acrylic acid/maleic anhydride/dicyclopentanyl ( Resin copolymerized with 3,4-epoxycyclohexylmethyl methacrylate, (meth)acrylic acid/maleic anhydride/benzyl (methyl) Resin copolymerized with 3,4·epoxycyclohexylmethyl methacrylate, copolymer of (meth)acrylic acid/maleic anhydride/cyclohexyl (meth)acrylate and 3,4- An epoxycyclohexylmethyl methacrylate-reacted resin, a copolymer of (meth)acrylic acid/maleic anhydride/styrene, and a resin reacted with 3,4-epoxycyclohexylmethylmethyl acrylate, (meth)acrylic acid/maleic anhydride/N- copolymer of methyl/acrylic acid/maleic anhydride/methyl (meth)acrylic acid methyl ester and 3,4-epoxycyclohexylmethyl methacrylate Resin of cyclohexylmaleimine co-polymer with 3,4·epoxycyclohexylmethyl methacrylate, (meth)acrylic acid/maleic anhydride/dicyclopentanyl (methyl) Resin copolymerized with acrylate/benzyl (meth) acrylate and 3,4·epoxycyclohexylmethyl methacrylate, (meth)acrylic acid/maleic anhydride/dicyclopentanyl group Copolymer of acrylate/cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate a resin, a copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth)acrylate/styrene and a resin reacted with 3,4-epoxycyclohexylmethyl methacrylate, a resin which reacts with a copolymer of methyl methacrylate/maleic anhydride/dicyclopentanyl (meth) acrylate/methyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate, Copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth) acrylate/N-cyclohexylmaleimide with 3,4-epoxycyclohexyl

-28- S 201234103 A methacrylate-reactive resin. In the first stage of the resin (B-5), a copolymer of (b) and (c) is obtained in the same manner as in the above-described method for producing the resin (B-1). In this case, as described above, the copolymer obtained can be used as it is, or can be used as a solid (powder) by using a solution which is concentrated or diluted, or by a method such as reprecipitation. The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of the entire structural unit constituting the above-mentioned copolymer. Constructing unit from (b); 5 to 95 mol% (preferably 1 〇 to 90 mol%) of structural unit derived from (c); 5 to 95 mol% (preferably 1 〇 to 90 mol) Further, in the same manner as the method for producing the resin (B-4), the cyclic ether derived from (b) and the carboxylic acid or carboxyl group (a) which may be contained in the copolymer of (b) and (c) Anhydride is obtained by reaction. The hydroxyl group produced by the reaction of the cyclic ether with a carboxylic acid or a carboxylic anhydride can be further reacted with a carboxylic anhydride. The amount of (a) to be reacted in the above copolymer is preferably from 5 to 80 mol% based on the number of moles of (b). The cyclic ether is highly reactive and unreacted (b) is not easily retained, and (b) is preferably (bl) and further preferably (b 1 -1 ). Specific examples of the resin (B-5) include a resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate/epoxypropyl (meth) acrylate with (meth)acrylic acid, and a benzyl group. (Meth)acrylate/epoxypropane-29- 201234103 Copolymer of (meth) acrylate copolymer with (meth)acrylic acid, cyclohexyl (meth) acrylate / epoxy propyl (methyl a copolymer of a copolymer of acrylic acid and vinegar with (meth)acrylic acid, a copolymer of styrene/epoxypropyl (meth)acrylate, a resin reacted with (meth)acrylic acid, or a (meth)acrylic acid Copolymer of ester/epoxypropyl (meth) acrylate copolymer with (Shenyl) acrylic acid, copolymer of N-cyclohexylmaleimide/epoxypropyl (meth) acrylate ( a copolymer of a methyl methacrylate reaction, a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / epoxy propyl (meth) acrylate and (meth) acrylic acid Resin, dicyclopentanyl (meth) acrylate / cyclohexyl (methyl) propyl Copolymer of a acrylate/epoxypropyl (meth) acrylate copolymer with (meth)acrylic acid, dicyclopentanyl (meth) acrylate / styrene / epoxy propyl (methyl) Copolymer of acrylate copolymer with (meth)acrylic acid, copolymer of (dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / epoxy propyl (meth) acrylate (Meth)acrylic acid-reactive resin, copolymer of dicyclopentanyl (meth) acrylate/N-cyclohexylmaleimide/epoxypropyl (meth) acrylate and (meth)acrylic acid Reaction resin; resin of dicyclopentanyl (meth) acrylate/epoxypropyl (meth) acrylate copolymer with crotonic acid, benzyl (meth) acrylate / epoxy propyl ( a copolymer of a methyl acrylate copolymer reacted with crotonic acid, a copolymer of cyclohexyl (meth) acrylate/epoxypropyl (meth) acrylate, a resin reactive with crotonic acid, a styrene/epoxy propylene a copolymer of a base (meth) propionate and a croton acid, a croton

S -30- 201234103 Copolymerization of a copolymer of methyl ester/epoxypropyl (meth) acrylate with crotonic acid and copolymerization of N-cyclohexylmaleimide/epoxypropyl (meth) acrylate a resin which reacts with crotonic acid, a copolymer of dicyclopentanyl (meth) acrylate/benzyl (meth) acrylate/epoxypropyl (meth) acrylate, and a resin which reacts with crotonic acid, Copolymer of cyclopentyl (meth) acrylate / cyclohexyl (meth) acrylate / epoxy propyl (meth) acrylate copolymer with crotonic acid, dicyclopentanyl (meth) acrylate Resin/styrene/epoxypropyl (meth) acrylate copolymer reactive with crotonic acid, dicyclopentanyl (meth) acrylate / methyl crotonate / epoxy propyl (methyl) Copolymer of acrylate copolymer with crotonic acid, copolymer of dicyclopentanyl (meth) acrylate/N-cyclohexylmaleimide/epoxypropyl (meth) acrylate and crotonic acid Reactive resin: dicyclopentanyl (meth) acrylate / epoxy propyl (meth) propylene Copolymer of copolymer of maleic acid with maleic acid, copolymer of benzyl (meth) acrylate/epoxypropyl (meth) acrylate, resin reacted with maleic acid, cyclohexyl (meth) acrylate /Polypropylpropyl (meth) acrylate copolymer with maleic acid resin, styrene / epoxy propyl (meth) acrylate copolymer with maleic acid resin, maleic acid Copolymer of ester/epoxypropyl (meth) acrylate copolymer with maleic acid, copolymer of N-cyclohexylmaleimide/epoxypropyl (meth) acrylate and maleic acid Reaction resin, resin of dicyclopentanyl (meth) acrylate/mercapto (meth) acrylate/epoxypropyl (meth) acrylate copolymer with maleic acid, dicyclopentane a copolymer of a (meth)propene-31 - 201234103 enoate/cyclohexyl (meth) acrylate/epoxypropyl (meth) acrylate copolymer with maleic acid, dicyclopentanyl ( Copolymer of methyl acrylate/styrene/epoxypropyl (meth) acrylate reacted with maleic acid Resin, dicyclopentanyl (meth) acrylate / methyl maleate / epoxy propyl (meth) acrylate copolymer with maleic acid resin, dicyclopentanyl (methyl a resin in which a copolymer of acrylate/N·cyclohexylmaleimide/epoxypropyl (meth)acrylate is reacted with maleic acid; dicyclopentyl (meth) acrylate/glycidyl Copolymer of a (meth) acrylate copolymer with (meth)acrylic acid and maleic anhydride, a copolymer of benzyl (meth) acrylate/epoxypropyl (meth) acrylate and (methyl) Acrylic acid and maleic anhydride-reactive resin, copolymer of cyclohexyl (meth) acrylate/epoxypropyl (meth) acrylate, resin reacted with (meth)acrylic acid and maleic anhydride, styrene/ring Copolymer of oxypropyl (meth) acrylate copolymer with (meth)acrylic acid and maleic anhydride, copolymer of methyl (meth) acrylate / epoxy propyl (meth) acrylate Acrylic acid and maleic anhydride reactive resin, (N-cyclohexylmaleimide / Copolymer of a copolymer of glycidyl (meth) acrylate with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / epoxy Copolymer of propyl (meth) acrylate copolymer with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / epoxy propyl a copolymer of (meth) acrylate copolymer with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (

S-32- 201234103 A copolymer of methyl acrylate/styrene/epoxypropyl (meth) acrylate with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (methyl) Copolymer of acrylate/methyl (meth) acrylate/epoxypropyl (meth) acrylate copolymer with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / Copolymer of N-cyclohexylmaleimide/epoxypropyl (meth) acrylate copolymer with (meth)acrylic acid and maleic anhydride; dicyclopentanyl (meth) acrylate / 3 a copolymer of 4-epoxycyclohexylmethyl methacrylate with (meth)acrylic acid, benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Resin copolymerized with (meth)acrylic acid, copolymer of cyclohexyl (meth) acrylate/3,4-epoxycyclohexylmethyl methacrylate, resin reacted with (meth)acrylic acid, styrene Copolymer of /3,4-epoxycyclohexylmethyl methacrylate and (meth)acrylic acid a resin, a copolymer of (meth) methacrylate/3,4-epoxycyclohexylmethyl methacrylate, a resin reactive with (meth)acrylic acid, N-cyclohexylmaleimide/3, Copolymer of 4-epoxycyclohexylmethyl methacrylate with (meth)acrylic acid, dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3, 4 · Copolymer of epoxycyclohexylmethyl methacrylate reacted with (meth)acrylic acid, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3, 4-epoxy Copolymer of cyclohexylmethyl methacrylate reacted with (meth)acrylic acid, dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate Resin copolymerized with (meth)acrylic acid, dicyclopentanyl-33- 201234103 (meth) acrylate / methyl (meth) acrylate / 3, 4 · epoxy cyclohexyl methyl methacrylate Resin copolymer copolymer with (meth)acrylic acid, dicyclopentanyl (meth) acrylate / N-cyclohexylmalay a copolymer of a quinone imine/3,4-epoxycyclohexylmethyl methacrylate copolymer with (meth)acrylic acid; a dicyclopentanyl (meth) acrylate / 3,4·epoxy ring a resin in which a copolymer of hexylmethyl methacrylate is reacted with crotonic acid, a copolymer of benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, and a resin reacted with crotonic acid, Copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer with crotonic acid, styrene / 3,4-epoxycyclohexylmethyl methacrylate Resin copolymerized with crotonic acid, a copolymer of methyl crotonate/3,4-epoxycyclohexylmethylmethyl acrylate, and a resin reacted with crotonic acid, N-cyclohexylmaleimide /3,4-epoxycyclohexylmethyl methacrylate copolymer and crotonic acid resin, dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3, 4 _ Resin copolymerized with cyclohexylmethyl methacrylate and crotonic acid, dicyclopentyl (meth) acrylate / cyclohexyl a resin of (meth) acrylate/3,4-epoxycyclohexylmethyl methacrylate copolymerized with crotonic acid, dicyclopentanyl (methyl) propylene vinegar/styrene/3, Resin of 4-epoxycyclohexylmethyl methacrylate copolymer with crotonic acid, dicyclopentanyl (meth) acrylate / methyl crotonate / 3,4-epoxycyclohexylmethyl A resin of a acrylate copolymer reacted with crotonic acid, dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate Resin copolymerized with crotonic acid-34-201234103: a copolymer of dicyclopentanyl (meth) acrylate/3,4-epoxycyclohexylmethyl methacrylate copolymerized with maleic acid, Copolymer of benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymerized with maleic acid, cyclohexyl (meth) acrylate / 3, 4-epoxy ring Copolymer of hexylmethyl methacrylate copolymer with maleic acid, copolymer of styrene/3,4-epoxycyclohexylmethyl methacrylate Resin reacting resin, methyl maleate/3,4-epoxycyclohexylmethyl methacrylate copolymer with maleic acid, N-cyclohexylmaleimide/3,4_ Resin copolymerized with cyclohexylmethyl methacrylate and maleic acid, dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexyl Resin copolymerized with methyl methacrylate and maleic acid, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethylmethyl Copolymer of acrylate copolymer with maleic acid, copolymer of dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate reacted with maleic acid Resin, dicyclopentanyl (meth) acrylate / methyl maleate / 3,4-epoxycyclohexylmethyl methacrylate copolymer with maleic acid resin, dicyclopentane a resin in which a copolymer of a base (meth) acrylate/N-cyclohexylmaleimide/3,4-epoxycyclohexylmethyl methacrylate is reacted with maleic acid; Copolymer of dicyclopentanyl (meth) acrylate/3,4-epoxycyclohexylmethyl methacrylate with (meth)acrylic acid and maleic anhydride, benzyl (meth)acrylic acid Ester/3,4-epoxycyclohexylmethylmethylpropane-35- 201234103 Copolymer of enoate reacts with (meth)acrylic acid and maleic anhydride. The purpose of the product is 'cyclohexyl (meth) acrylate / Copolymer of 3,4-epoxycyclohexylmethylmethylpropane acrylate with resin (meth)acrylic acid and maleic anhydride, styrene/3,4-epoxycyclohexylmethyl methacrylate Resin copolymerized with (meth)acrylic acid and maleic anhydride, copolymer of methyl (meth)acrylate/3,4-epoxycyclohexylmethyl methacrylate with (meth)acrylic acid and horse Resin for the reaction of anhydride, resin of N-cyclohexylmaleimide/3,4-epoxycyclohexylmethyl methacrylate, resin reacted with (meth)acrylic acid and maleic anhydride, dicyclopentane Copolymerization of alkyl (meth) acrylate / benzyl (meth) acrylate / 3, 4 - epoxy cyclohexyl methyl methacrylate Resin reacting with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Copolymer of (meth)acrylic acid and maleic anhydride, copolymer of dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate Copolymer of (meth)acrylic acid and maleic anhydride-reactive resin, dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Resin reacting with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate The copolymer is copolymerized with (meth)acrylic acid and maleic anhydride, and the like. The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100, more preferably from 5,000 to 50,000. When the weight average molecular weight of the resin (B) is in the above range, the coating property tends to be good. -36-

In S 201234103, film formation is less likely to occur during development, and the non-exposed portion has a good tendency to be removed during development. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (?n)) of the resin (B) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is in the above range, the developability tends to be excellent. The acid value of the resin (Β) is preferably from 20 to 150 mg/g-KOH, more preferably from 50 to 1 35 mg/g-KOH, still more preferably from 70 to 135 mg/g-KOH. Here, the acid value is determined by measuring the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution. When the coloring photosensitive composition of the present invention contains the resin (B), the total amount of the resin (B) relative to the resin (B) and the polymerizable compound (C) is usually 5 to 95% by mass, preferably 20%. 80% by mass, more preferably 40 to 60% by mass. When the content of the resin (B) is in the above range, the developability 'adhesion, solvent resistance and mechanical properties of the cured pattern tend to be good. The colored photosensitive composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) may be a compound which is polymerized by an active radical, an acid or the like generated by the polymerization initiator (D), and may, for example, be a compound having a polymerizable ethylenically unsaturated bond, preferably (A) Base) acrylate compound. The polymerizable compound (C) having one polymerizable ethylenically unsaturated bond may, for example, be the same as those exemplified as the above (a), (b) and (c), wherein (meth) acrylate The class is better. Polymerizable compound having two polymerizable ethylenically unsaturated bonds

-37- 201234103 (C), for example, 1,3-butanediol di(meth)acrylate, L3-butanediol (meth)acrylate, 1,6·hexanediol di(meth)acrylic acid Ester, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate vinegar, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, four Ethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A bis(acryloxyethyl)ether, ethoxylated bisphenol A di(meth)acrylate, C Oxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate, etc. The polymerizable ethylenically unsaturated bonded polymerizable compound (C) may, for example, be trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate or ginseng (2-hydroxyethyl). Isocyanurate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane III Methyl) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol 5 (a) Reaction of acrylate, tripentaerythritol hexa(meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri(meth) acrylate and anhydride, Reaction of pentaerythritol penta(meth) acrylate with anhydride, trimellititol hepta (meth) acrylate and anhydride caprolactone modified trimethylolpropane tris(meth)acrylate vinegar, caprolactone modification Pentaerythritol tri(meth) acrylate, caprolactone modified ginseng (2-hydroxyethyl) isocyanurate tri(meth) acrylate, caprolactone

S -38- 201234103 Modified pentaerythritol tetra(meth)acrylate, caprolactone modified diquaternary pentoxide (meth) acrylate, caprolactone modified dipentaerythritol hexa() acrylate, caprolactone modified Pentaerythritol tetra(meth) propylene, caprolactone modified tripentaerythritol penta (meth) acrylate, caprolyl tripentaerythritol hexa(meth) acrylate, caprolactone modified triquatern pentoxide (meth) acrylate Reaction of caprolactone-modified tripentaerythritol octa acrylate, caprolactone-modified pentaerythritol tris(meth)acrylic anhydride, reaction of caprolactone-modified dipentaerythritol penta(methyl)propyl ester and anhydride Caprolactone-modified trimellititol seven (methenoate and anhydride, etc. Among them, a monomer having 3 or more functional groups is preferred, and dipentaerythritol hexa() acrylate is more preferable. The content of the polymerizable compound (C) is relative to the resin. The total amount of (B) and the poly-compound (C) is preferably from 5 to 95% by mass, more preferably from 80 to 80% by mass. The content of the polymerizable compound (C) is in the above-described range sensitivity or the obtained pattern. Smoothness, reliability, machine The coloring photosensitive composition of the present invention contains a polymerization initiator (D) as a polymerization initiator (D), which is a compound which can initiate polymerization by generating an active group, an acid or the like by light action. The polymerization initiator (D) is preferably a biimidazole compound, an alkylphenone, a triammine compound, a mercaptophosphine oxide compound or a ocular compound, and may be used. In the case of the photocationic pentylene methyl ester ester described in JP-A-2008-1081, 087, the pentylene methyl ester and the enoic acid) propylmethyl group I 20 are used, and the compound is used freely. Further polymerization -39- 201234103 Starting agent (for example consisting of a ruthenium cation and an anion derived from Lewis acid). The biimidazole compound may, for example, be 2,2'-bis(2.chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di Chlorophenyl)-4,4 ',5,5 '-tetraphenylbiimidazole (for example, Japanese Laid-Open Patent Publication No. Hei No. Hei 6-75-73, No. Hei 6-75373, No. 6-75373), 2, 2' - bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2,-bis(2-chlorophenyl)_ 4,4',5,5' - Tetrakis (oxyphenyl) miloxime, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(di-phenyloxyphenyl)-biphenyl 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, Japanese Patent Publication No. 48-38403 and JP-A-62- Japanese Patent Laid-Open No. 174204. The base of the 4, 4, 5, 5-position is substituted with a thiol compound (for example, JP-A-7-109 1 3). . Preferably, for example, 2,2'-bis(2-chlorophenyl)-4,4,5,5,-tetraphenylbiimidazole '2,2,_bis (2,3-dichlorophenyl) -4,4',5,5'-tetraphenylbiimidazole, 2,2,_bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole . The above alkyl phenone compound may, for example, be diethoxyphenyl hydrazine, 2-methyl-2-morpholino-1-(4-methylsulfonylphenyl)propane oxime ketone, 2 Dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-indolone, 2•-methylamino-1-(morpholinophenyl)-2- (4 Methylphenylmethyl) butyl-1-ketone, 2-hydroxy-2-methyl-1-phenylpropane-fluorenone-ketone, benzyldimethyl-copper 2-hydroxy-2-methyl- 1-[4-(2-Hydroxyethoxy)phenyl]propanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-oxime-(4 lib 1 4-isopropenylphenyl) An oligomer of propan-1-one, etc., preferably 2_methyl_2_?

S -40- 201234103 (4-Methylsulfonylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2·benzylbutene-1- Ketones, etc. Commercial products such as IRGACURE 369 and 907 (above, manufactured by BASF Japan) can also be used. The aforementioned triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloromethane). 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxysulphate)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2- (5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like. The above-mentioned mercaptophosphine oxide compound may, for example, be 2,4,6-trimethylbendenyldiphenylphosphine oxide. Commercial products such as IRGACURE 819 (manufactured by BASF Japan) can also be used. The above hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylsulfonylphenyl)butan-1-one-2-imine or N-benzylideneoxy-1-( 4-phenylsulfonylphenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)- 9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1·[9-ethyl-6- { 2-methyl-4-( 3,3-dimethyl -2,4-dioxolylmethoxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine and the like. Commercial products such as IRGACUREOXE-01, OXE-02 (above, BASF Japan), N-1919 (made by ADEKA), and the like -41 - 201234103 can also be used. Further, the polymerization initiator (D) may, for example, be a benzoin compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether; benzophenone or anthracene-benzylidene group. Methyl benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(1^butylbutyloxycarbonyl) a benzophenone compound such as benzophenone or 2,4,6-trimethylbenzophenone; a quinone compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone; Butyl-2-chloroacridone, benzyl ester, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with a polymerization starting aid (D 1 ) (particularly an amine compound described later) which will be described later. The colored photosensitive composition of the present invention may contain a polymerization initiation aid (D1). The polymerization initiation aid (D1) can be used in combination with the polymerization initiator (D) to promote the polymerization of the polymerizable compound which starts polymerization by the polymerization initiator, or a sensitizer. The polymerization starting aid (D 1 ) may, for example, be an amine compound, a thiazoline compound, a compound oxime compound, a thioxanthone compound or a carboxylic acid compound. The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethylamine. Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-toluidine, 4,4 '-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzol Ketones and the like, among which 4,4'-bis(diethylamino)benzophenone is preferred. EAB-F (Batu Tugu Chemical Industry Co., Ltd.) can also be used.

Commercial products of S-42- 201234103. The thiazoline compound may, for example, be a compound represented by the formula (Ill-I) to the formula (III-3). 【化4】

(_ alkoxy oxime compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl a thioxanthone compound such as -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene or 2-ethyl-9,10-dibutoxyfluorene, and examples thereof include 2-isopropyl group. Thioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc. The compound may, for example, be phenylsulfonyl acetic acid, methylphenylsulfonyl acetic acid, ethylphenylsulfonyl acetic acid, methyl ethylphenylsulfonyl acetic acid or dimethylphenylsulfonyl acetic acid. Methoxyphenylsulfonyl acetic acid, dimethoxyphenylsulfonyl acetic acid, chlorophenylsulfonyl acetic acid, dichlorophenylsulfonyl acetic acid, N-phenylglycine, phenoxy Acetic acid, naphthalene sulfuric acid, N-naphthalene-43-201234103-glycine, naphthyloxyacetic acid, etc. The content of the polymerization initiator (D) is relatively the total amount of the resin (b) and the polymerizable compound (C).佳为〇·ι~4〇% by mass, more preferably ～300% by mass. The total amount of polymerization initiator (D) is In the case where the coloring photosensitive composition is highly sensitive, the chemical resistance, mechanical strength, and surface smoothness of the obtained pattern tend to be good. When the polymerization starting aid (D1) is used, the amount is used. The total amount of the resin (Β) and the polymerizable compound (C) is preferably 〇1 to 50% by mass, more preferably 0. 1 to 40% by mass. Further, each polymerization initiator (D) 1 molar amount is preferably 0.01 to 10 moles, more preferably 〇·〇ι~5 molar polymerization initiator (D 1 ) is in this range, and the obtained colored photosensitive composition is The sensitivity is higher and the productivity of the obtained pattern is improved. Further, the colored photosensitive composition of the present invention may further contain a polyfunctional thiol compound (Τ). The polyfunctional thiol compound (Τ) is A compound having two or more sulfonyl groups in the molecule. When a compound having two or more sulfonyl groups adjacent to an aliphatic hydrocarbon group is used, the sensitivity of the coloring photosensitive composition of the present invention is high, which is preferable. The thiol compound (Τ) may, for example, be hexanedithiol or decanedithiol, , 4-bis(methylsulfonyl)benzene, butanediol bis(3-sulfonylpropionate), butanediol bis(3-sulfonylacetate), ethylene glycol double (3- Sulfhydryl acetate), trimethylolpropane ginseng (3-sulfonyl acetate)

S -44- 201234103 'Butanediol bis(3-sulfonylpropionate), trimethylolpropane ginseng (3_sulfonylpropionic acid vinegar)' Trimethylolpropane ginseng (3-sulfonyl) Acetate), pentaerythritol bismuth (3-sulfonyl propionate), pentaerythritol 3 (3_), hydroxyethyl ginseng (3-sulfonyl propionic acid), Pentaerythritol oxime (3-expansion butyl vinegar), 1,4-bis(3-propenyl butyloxy) butyl or the like. The content of the polyfunctional thiol compound (T) is preferably from 0.5 to 20% by mass, more preferably from 1 to 1% by mass, based on the polymerization initiator (D). When the content of the polyfunctional thiol compound (T) is in this range, the sensitivity tends to be high and the developability tends to be good. The colored photosensitive composition of the present invention contains a solvent (E). The solvent (E) is not particularly limited, and a solvent which is usually used in the field can be used. (For example, it can be used in an acetal solvent (a solvent containing -COO-, a solvent not containing -〇-), and an ether other than a vinegar solvent. Solvent (molecular-containing 〇-, non-COO-containing solvent), ether vinegar solvent (molecular-containing -COO- and -0-solvent), ketone solvent other than ester solvent (molecular inclusion - CO-, It is selected from the group consisting of an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, and a dimethyl hydrazine. The ester solvent may, for example, be methyl lactate, ethyl lactate or butyl lactate. Methyl 2-hydroxyisobutanoate, ethyl acetate, η-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyrate Ester, methyl pyruvate 'ethyl pyruvate, propyl pyruvate 'methyl acetate methyl acetate, ethyl acetate ethyl acetate, cyclohexanol acetate, r-butyrolactone, etc.. Ether solvent, for example, B Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether -45- 201234103, two Glycol 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 diethyl ether, diethylene Alcohol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, methyl anisole, etc. Ether ester solvent, for example, methoxyacetic acid Methyl ester, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate , 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester, 2-methoxy-2-methylpropionic acid methyl ester, 2-ethoxy-2-methylpropionic acid ethyl ester , 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl 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, etc. The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone or 3-heptanone. , 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, etc. Alcohol solvent, for example, methanol 'ethanol, propanol, butanol, hexanol, ring Hexanol, ethylene glycol, propylene glycol, glycerin, etc. The aromatic hydrocarbon solvent may, for example, be benzene, toluene, toluene, trimethylbenzene or the like -46 -

S 201234103 The guanamine solvent may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone. These solvents may be used singly or in combination of two or more kinds. Among the above solvents, an organic solvent having a boiling point of 1 atm of from 1 2 0 ° C to 1 80 ° C is preferred from the viewpoint of coatability and dryness. Among them, propylene glycol monomethyl ether 'propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, etc. good. The content of the solvent (E) in the coloring photosensitive composition is preferably from 60 to 95% by mass, more preferably from 70 to 90% by mass, based on the coloring photosensitive composition. In other words, the solid content of the colored photosensitive composition is preferably from 5 to 40% by mass, more preferably from 1 to 30% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating tends to be good. The coloring photosensitive composition of the present invention preferably contains a surfactant (F). The surfactant may, for example, be an anthrone-based surfactant, a fluorine-based surfactant, or an anthrone-based surfactant having a fluorine atom. By containing a surfactant, the flatness at the time of coating tends to be good. The anthrone-based surfactant may, for example, be a surfactant having a siloxane coupling. Specifically, for example, toray si 1 icοneDC3 PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, a polyether modified fluorenone oil SΗ8400 (trade name: Dow Corning Toray) , KP 3 21, KP 3 2 2, KP323 'KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, -47- 201234103 TSF4440, TSF4445, TSF-4446, TSF4452 , TSF4460 (Momentive Performance Materials . Japan contract company system) and so on. The fluorine-based surfactant may, for example, be an interface active agent having a fluorocarbon chain. Specifically, for example, Fluorinert (registered trademark) FC430, FC431 (Sumitomo 3M (share) system), MEGAFACE (registered trademark) F142D, same F171, same F172, same F173, same F177 'same F183, same R30 (DIC (share) system, EFTOP (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass) (share) system, E5844 ((share) Daikin Precision Chemical Research Institute). The ketone-based surfactant having a fluorine atom may, for example, be a surfactant having a siloxane chain and a fluorocarbon chain. Specifically, for example, MEGAFACE (registered trademark) R08, the same BL20, the same F475, the same F4 77, and the same F443 (DIC system) can be mentioned. It is preferably MEGAFACE (registered trademark) F475. The surfactant (F) is 0.001% by mass or more and 22% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more, based on the coloring photosensitive composition. %the following. When the surfactant is contained in this range, the flatness of the coating film can be improved. The colored photosensitive composition of the present invention may contain a sputum agent as necessary

S-48- 201234103, various other polymer compounds, adhesion promoters, antioxidants, UV absorbers, light stabilizers, chain transfer agents and other additives. The colored photosensitive composition of the present invention can be prepared as follows. First, the pigment of the coloring agent (A) is mixed with the solvent (E), and the average particle diameter of the pigment is about 〇·2 μm or less, and is dispersed by using a bead mill or the like. At this time, some or all of the pigment dispersant and resin (Β) may be used as needed. In the obtained pigment dispersion liquid, a polymerizable compound (C), a polymerization initiator (D), a residual resin (Β), other components, and, if necessary, a solvent (Ε) added thereto are added thereto. At a specific concentration, a desired color-sensitive photosensitive composition can be obtained. The colored photosensitive composition of the present invention is processed by a filter, for example, by the steps shown in the following (1) to (4). (1) The step of obtaining a coating film by applying the colored photosensitive composition of the present invention to a substrate (2) The step (3) of applying a film after exposure by a coating film through a mask to obtain an exposure film After the exposure, the coating film is developed with an alkali developing solution to obtain a pattern (4). The method of obtaining a pattern by baking the pattern to obtain a hardened pattern may be, for example, a photolithography method. Inkjet method, printing method, and the like. Among them, the light lithography method is preferred. The photolithography method is a method in which the coloring photosensitive composition is applied onto a substrate, dried, exposed to a photomask, and developed to obtain a pattern. The substrate may be, for example, glass, metal or plastic, and may be in the form of a plate -49-201234103 or a film. Examples of the plastic material include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers, polyvinyl alcohol, polyethylene terephthalate, polyethylene naphthalate, and poly(methyl). Acrylates, cellulose esters, polycarbonates, polymills, polyether oximes, polyether ketones, polyphenylene sulfides, and polyphenylene ethers. Here, (meth)acrylic acid means at least one selected from the group consisting of acrylic acid and methacrylic acid. A structure such as a color filter, various insulating or conductive films, and a driving circuit can be formed on the substrate. According to the colored photosensitive composition of the present invention, a hardened pattern can be formed at a lower temperature, especially when the pattern is formed on a plastic substrate. Examples of the method of applying the substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Further, a dip coater, a roll coater, a bar coater, a spin coater, a slit & spin coater, and a slit coater (also referred to as a die coater or a curtain coater) can be used. A coating device such as a non-rotating coater or an inkjet is applied. Among them, it is preferred to use a slit coater, a spin coater, a roll coater or the like. The method of drying the substrate coating film may, for example, be a method such as heat drying, natural drying, air drying, or reduced pressure drying. The plural methods can also be combined. The drying temperature is preferably 10 to 120 t, more preferably 25 to 100 ° C. And the heating time is preferably 10 seconds to 60 minutes, 30 seconds to 30 minutes is better -50-

S 201234103 Drying under reduced pressure is preferably carried out at a temperature of 20 to 25 ° C under a pressure of 50 to 150 Pa. The film thickness of the coating film after drying is not particularly limited and may be appropriately adjusted depending on the material to be used, the purpose of use, etc., and is usually 0.1 to 20 μm, preferably 1 to 6 μm. The dried coating film is exposed through a photomask for forming a desired pattern. The shape of the pattern on the reticle at this time is not particularly limited, and a pattern shape for the intended use can be used. The light source used for the exposure is preferably a light source that generates light of a wavelength of 250 to 45 nm. For example, it is possible to use a band filter having a wavelength of less than 3 50 nm and a filter in the wavelength range for masking, and a band pass filter for extracting light in the vicinity of 436 nm, near 408 nm, and around 3 65 nm in the wavelength range. . Specifically, for example, a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, or the like can be given. It is preferable to uniformly illuminate the entire exposed surface with the parallel light to perform the correct alignment of the mask with the substrate, and it is preferable to use a mask to align the exposure machine, the stepper, and the like. After the exposure, the contact developing solution is allowed to dissolve and develop a specific portion, for example, an unexposed portion, to obtain a pattern. The developer may be an organic solvent. However, since the exposed portion of the coating film is less likely to be dissolved or swollen by the developer, a good shape pattern can be obtained, and an aqueous solution of a basic compound is preferred. The developing method may be any one of a stirring paddle method, a dipping method, a spray method, and the like. Further, the substrate can be tilted at an arbitrary angle during development. It is preferred to carry out water washing after development. Examples of the basic compound include sodium hydroxide, potassium hydroxide, phosphorus-51 - 201234103 disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, Inorganic basic compound of potassium citrate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonium, etc.: tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydrogen Organic bases such as oxides, monomethylamine 'dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, etc. Sex compounds. The concentration of the aqueous solution of the inorganic and organic basic compounds such as potassium hydroxide, sodium hydrogencarbonate and tetramethylammonium hydroxide is preferably 0.01 to 10% by mass, more preferably 〇.〇. 3 to 5 mass%. The aqueous solution of the aforementioned basic compound may contain a surfactant. Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, ethylene oxide/propylene oxide block copolymers, and the like. A sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a glycerin fatty acid ester, a polyoxyethylene fatty acid ester, a polyoxyethylene alkylamine, etc. Ionic surfactant; anionic interfacial activity of sodium lauryl sulfate, sodium oleyl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate, etc. A cationic surfactant such as stearylamine hydrochloride or lauryl trimethylammonium chloride. The concentration of the surfactant in the aqueous solution of the basic compound is preferably 0.01' 10% by mass, more preferably 0.05 to 8% by mass, and particularly preferably 0.1 to 5

S -52- 201234103% by mass. Further, post-baking can be performed as necessary. Post-baking is preferably carried out, for example, at a temperature of from 50 to 230 ° C for 2 to 240 minutes. The colored photosensitive composition of the present invention can obtain good patterns and color filters of color density, brightness, contrast, sensitivity, resolution, heat resistance, etc., and can also use such color filters or patterns. The conventional aspect is used in a display device which is a part of the component, such as a conventional liquid crystal display device, an organic EL device, a solid-state imaging device, an electronic paper, or the like. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail by way of examples. In the example, "%" and "part" are not specifically described, and are % by mass and parts by mass. Synthesis Example 1 182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was changed from nitrogen to nitrogen, and then the temperature was raised to 1 Torr. After 〇c, 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, and tricyclodecane skeleton monomethacrylate (FA, manufactured by Hitachi Chemical Co., Ltd.) -513M) A solution of 3.6 g of azobisisobutyronitrile added to a mixture of 22.0 g (〇.i〇mole) and propylene glycol monomethyl vinegar acetate 136g was dropped from the dropping funnel to the flask for 2 hours, and further At 100 00 it -53- 201234103, stirring was continued for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and epoxy propyl methacrylate was 35.5 g [0.25 mol, (50 mol% relative to the carboxyl group of methacrylic acid used in the reaction)] 9 g of benzylaminophenol phenolphthalein and 0.145 g of hydroquinone were placed in a flask, and the mixture was reacted at 110 ° C for 6 hours to obtain a resin solution B1 having a solid content of 79 mg KOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 13,000 and the molecular weight distribution (Mw/Mn) was 2.1. Synthesis Example 2 250 parts of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a gas introduction tube. Thereafter, a nitrogen gas was introduced into the flask through a gas introduction tube, and the atmosphere inside the flask was replaced with a nitrogen gas. Thereafter, after raising the temperature of the solution in the flask to 100 ° C, 152.6 parts of benzyl methacrylate, 41.7 parts of methacrylic acid, 1.5 parts of azobisisobutyronitrile, and 150 parts of propylene glycol monomethyl ether acetate were added. The resulting mixture was dropped into the flask using a dropping funnel for 2 hours, and after completion of the dropwise addition, the mixture was further stirred at 100 ° C for 2.5 hours to obtain a weight average molecular weight Mw of 2 - 3 x 10 4 , a solid content of 34 % by mass, and a solution acid value of 47 mg - KOH / g. Resin solution B2. The weight average molecular weight (Mw) and the number average molecular weight (??) of the resin obtained in the synthesis example were measured by the following conditions using the Gpc method. Device; Κ2479 (made by Shimadzu Corporation)

Pipe string; SHIMADZU Shim-pack GPC-80M

S -54- 201234103 Column temperature; 40 ° C solvent; THF (tetrahydrofuran)

Flow rate; 1.0 mL/min detector; RI The ratio of the weight average molecular weight and the number average molecular weight (Mw/Mn) in terms of polystyrene obtained above was taken as the molecular weight distribution. Example 1 [Preparation of coloring photosensitive composition] Pigment: CI Pigment Green 58 51 parts of propylene-based pigment dispersant 1 〇 part of resin solution B2 (solid content conversion) 20 parts of propylene glycol monomethyl ether acetate 267 parts mixed Pigment dispersion liquid A which is sufficiently dispersed by a bead mill using a bead mill, pigment: CI pigment yellow 1 3 8 8 1 part propylene-based pigment dispersant 12 parts resin solution B2 (solid content conversion) 28 parts of propylene glycol monomethyl ether acetate A pigment dispersion liquid in which 402 parts of the ester are mixed and the pigment is sufficiently dispersed using a bead mill. Pigment: CI Pigment Green 7 29 parts of propylene-based pigment dispersant 5.7 parts of resin solution B2 (solid content conversion) 11 parts of propylene glycol monomethyl ether B Acid ester 173 parts • 55- 201234103 A pigment dispersion liquid c and a resin which are mixed and fully dispersed by a bead mill, and resin: resin solution B 1 (solid content conversion) 66 parts, polymerizable compound: dipentaerythritol hexaacrylate (曰Chemicals (manufactured by the company) 57 parts, polymerization initiator: 2 · dimethylamino-1- (4-morpholinophenyl)-2-benzylbutan-1-one (IRGACURE3 69; BASFJapan Company system) 15 parts, polymerization start help Agent: 4,4'-bis(diethylamino)benzophenone (EAB-F; manufactured by Baotu Valley Chemical Industry Co., Ltd.) 4.9 parts, solvent: 450 parts of propylene glycol monomethyl ether acetate, and Additive: Sumi-Epoxy ESCN-195XL (manufactured by Sumitomo Chemical Co., Ltd.) 6.1 parts were mixed to obtain a coloring photosensitive composition. Comparative Example [Preparation of coloring photosensitive composition] Pigment: CI Pigment Green 36 5.5 parts Pigment: CI Pigment Yellow 1 50 2.4 parts of polyester pigment dispersant 1.2 parts of propylene glycol monomethyl ether acetate 38 parts of pigment dispersion mixed with a bead mill to fully disperse the pigment, mixed -56-

S 201234103 Resin: Resin solution B1 (solid content conversion) 6.6 parts Polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Sakamoto Chemical Co., Ltd.) 5.7 parts Polymerization initiator: 2-dimethylamino group-1 - (4-morpholinophenyl)-2-mercaptobutan-1-one (IRGACURE 369; manufactured by BASF Japan) 1.5 parts of polymerization starting aid: 4,4'-bis(diethylamino)diphenyl Methyl ketone (EAB-F Baotu Valley Chemical Industry Co., Ltd.) 0.4 9 parts Additive: Sumi-Epoxy ESCN-195XL (Sumitomo Chemical Co., Ltd.) 〇· 6 1 part solvent: propylene glycol monomethyl ether acetate 38 A coloring photosensitive composition was obtained in portions. <Formation of Drawings> A PET film (Toray Road Milla 75-T60) was bonded to a square glass plate to prepare a substrate. The colored photosensitive composition was applied by a spin coating method on the PET film side of the substrate, and prebaked on a hot plate at 8 (TC for 2 minutes. After cooling, the substrate coated with the colored photosensitive composition was applied. The distance from the quartz glass mask was set to ΙΟμιη, and the exposure was performed using an exposure machine (TME-150RSK; TOPCON) to expose the light to an exposure amount of 200 mJ/cm 2 (3 5 5 nm) in the atmosphere. At this time, the irradiation of the coloring photosensitive composition is performed by passing the light from the ultrahigh pressure mercury lamp to the optical filter (UV-35; Asahi Separation Co., Ltd.). The reticle is used to form 1 〇~ 1 〇〇μιη line and interval pattern. After light irradiation, immersed in tetramethylammonium hydrazine. 1% aqueous solution at 23 ° C for 80 seconds for development, and washed with pure water to form a graph. The film thickness of the obtained pattern was measured to be 2 μm using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The pattern formed in the same manner as above was further heated at 50 ° C for 5 minutes. (post-baking), obtaining a hardened pattern. Again, it will The pattern formed in the same manner was further heated (post-baking) at 1 〇〇t for 5 minutes to obtain a cured pattern. The film thickness of the obtained cured pattern was measured in the same manner as above. 2 μηη. <Color Performance Evaluation> The spectral spectrum of the obtained pattern was measured by a microscopic spectrometer (osp-SP200 OLYMPUS) to measure a transmittance (?1) at 600 nm and a transmittance (T2) at 520 nm. The smaller the T1 ratio (T1/T2) of T2 is, the better the color separation ability with the red filter is. The results are shown in Table 1. [Table 1] The ratio of T1 to T1 _ No post-baking and baking 50 ° C post-baking __100 ° c Example 0.23 0.23 ___0.23 Comparative Example 0.49 0.49 - ^ 0.49 < Solvent resistance evaluation > -58-

S 201234103 1 ml of propylene glycol monomethyl ether acetate was dropped on the pattern formed on the substrate, and after 30 seconds, it was rotated for 10 seconds using a spin coater at a rotation number of 100 rpm for 10 seconds. Figure on propylene glycol monomethyl ether acetate. The film thickness was measured from the film thickness measured before and after the contact with propylene glycol monomethyl ether acetate, and the film thickness retention was calculated by the following formula. The higher the film thickness retention, the better the curing property, and when the coloring photosensitive composition other than green is repeatedly applied, the dissolution of the solvent contained in the coloring photosensitive composition is suppressed, and mixing can be prevented when the color filter is produced. ). The results are shown in Table 2. (film thickness retention ratio) (%) = (film thickness after contact) / (film thickness before contact) <resolution evaluation> The obtained pattern was subjected to a laser microscope (Axio Imager MAT Carl Zeiss) Observe to make the resolution the minimum size as the resolution. The higher the resolution, the higher the fine color filter can be produced. The results are shown in Table 2. [Table 2] Decompression degree (μιη) Film thickness retention rate (%) No post-baking, baking, 50°C, post-baking, 100°C, no post-baking, baking, 50°C, post-baking, loot: Example 20 20 20 90 92 92 Comparative Example 40 40 40 88 91 90 [Industrial Applicability] According to the colored photosensitive composition of the present invention, green color excellent in color separation ability with red filter-59-201234103 sheet can be obtained. Filter. -60- έ>

Claims (1)

201234103 VII. Patent application scope: 1. A color-sensitive photosensitive composition characterized by containing a coloring compound, a polymerization initiator and a solvent, and the coloring agent contains a halocyanine pigment, a zinc halide phthalocyanine pigment, and The colored photosensitive composition according to claim 1, wherein the content of the copper oxytitanium pigment is 20 parts by mass or more and 150 parts by mass relative to the content of the zinc halide phthalocyanine pigment. the following. 3. The coloring photosensitive composition as described in claim 1 wherein the content of the ketone pigment is 100 parts by mass or more and 200 parts by mass or less based on 100 parts by mass of the zinc halide titanium cyanine pigment. 4. The colored photosensitive composition according to claim 1, wherein the content of the copper oxytitanium pigment is 20 parts by mass or more and 150 parts by mass or less based on the content of the zinc halide phthalocyanine pigment. The content of the zinc halide titanium cyanine pigment is 100 parts by mass or more and 200 parts by mass or less. 5. The colored photosensitive composition according to claim 1, wherein the copper oxytitanium pigment is C.I. Pigment Green 7. 6. The colored photosensitive resin composition as described in claim 1 wherein the quinophthalone pigment is C.I. Pigment Yellow 138. The coloring photosensitive composition as described in claim 1, wherein the coloring agent, the polymerizable compound, the polymerization initiator, the solvent, and the resin are used. 8. A color filter 'characteristics of the coloring composition described in the item 1 of the characteristic item 1, a copper-titanium coloring material, a halogenated one-piece, a quinone amount, and a halogenated one. For the quinophthalone fraction, the halogenation contains the representative map of the request -61 - 201234103: (1) The representative representative of the case is: no (2) The symbol of the representative figure is simple: no 201234103 V. If there is a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: no S -4 -