TW201224653A - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition comprises component (A), component (B), component (C), component (D) and component (E). The photosensitive resin composition can obtain patterns with excellent mechanical properties. The component (A) is a resin. The component (B) is a polymeric compound. The component (C) is a polymerization initiator. The component (D) a compound having at least one function group selected from a group selected from at least the active methylene group and the active methenyl group and a molecular weight less than 3,000. The component (E) is a solvent. In some embodiments, the component (D) is a compound having an acetyl group. In some other embodiments, the component (A) is formed from an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

Description

201224653 VI. Description of the Invention [Technical Field of the Invention] The present invention relates to a photosensitive resin composition. [Prior Art] In recent years, in order to form a spacer or a protective film on a liquid crystal display panel or the like, a photosensitive resin composition is used. Such a photosensitive resin composition is known, for example, from JP-A-2008-181 08, which contains a structural unit derived from an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride and has an epoxy group and an ethyl group. A copolymer of a structural unit of a monomer having an unsaturated double bond, a photosensitive resin composition containing a photopolymerizable compound, a photopolymerization initiator, and a solvent. SUMMARY OF THE INVENTION However, in the case of the photosensitive resin composition proposed in the prior art, the mechanical properties of the obtained pattern may not be sufficient to satisfy the demand. The present invention provides the following [1] to [6]. Π] A photosensitive resin composition containing (A), (B), (C), (D) and (E). (A) Resin (B) Polymerizable compound (C) Polymerization initiator (D) having at least one group selected from the group consisting of active methylene groups and active methine groups and having a molecular weight of less than 3,000 Compound 201224653 (E) Solvent [2] A photosensitive resin composition as described in [1] of at least one group selected from the group consisting of an active methylene group and an active methine group. [3] The resin contains a copolymer of at least one structural unit selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a structural unit derived from an unsaturated compound having a cyclic ether having 2 to 4 carbon atoms. The photosensitive resin composition described in [1] or [2]. [4] The polymerization initiator is a photosensitive resin composition according to any one of [1] to [3], which is a polymerization initiator of the oxime ester compound. [5] A pattern formed by the photosensitive resin composition according to any one of [1] to [4]. [6] Display device containing the pattern described in [5]. According to the photosensitive resin composition of the present invention, a pattern having excellent mechanical properties can be obtained. The photosensitive resin composition of the present invention is a photosensitive resin composition containing (A), (B), (C), (D) and (E). (A) Resin (B) Polymerizable compound (C) Polymerization initiator (D) having at least one group selected from the group consisting of active methylene groups and active methine groups and having a molecular weight of less than 3,000 Compound (E) Solvent. Further, the compounds exemplified as the respective components in the present specification may be used singly or in combination, without particular limitation. -6- 201224653 The photosensitive resin composition of the present invention contains a resin (A). The resin (A) used in the photosensitive resin composition of the present invention is preferably an alkali-soluble resin. The alkali solubility refers to the property of the developer dissolved in the aqueous solution of the alkali compound. The resin having alkali solubility is, for example, a resin (A-1): the polymerization is grouped from an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. And at least one selected from the group consisting of (a) (hereinafter also referred to as "(a)") and an unsaturated compound (b) having a cyclic ether having 2 to 4 carbon atoms (hereinafter also referred to as "(b)") Copolymer, Resin (A-2): a monomer (c) which can be copolymerized with (a) and (b) (however, a cyclic ether having no carbon number of 2 to 4) (hereinafter also referred to as "(c) ))), copolymers (a) and (b), copolymers (a) and (c), and resin (A-4): polymerization (a) The resin obtained by the reaction with (c) and the resin obtained by the reaction of (b), the resin (A-5): a copolymer obtained by polymerizing (b) and (c), and a resin obtained by the reaction of (a). The resin (A) is a copolymer containing a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a structural unit derived from an unsaturated compound having a cyclic ether having 2 to 4 carbon atoms. That is, the resin (A-1) and the resin (A-2) are more preferable as the resin (A-1). (a) specifically, an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, fluorene-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, or the like; 201224653 maleic acid, Fumaric acid, citraconic acid, methyl fumarate, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1 , 2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1, 4-cyclohexene dicarboxylic acid, etc., unsaturated dicarboxylic acids; 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-methyl Bicyclo[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- a carboxyl group-containing bicyclic unsaturated compound such as a olefin or a 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic acid Dicarboxylic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetra Unsaturated dicarboxylic anhydride succinic acid mono [2-(methyl) propylene oxime such as phthalic anhydride, 5,6-dicarboxybicyclo[2.2_1]hept-2-ene anhydrate (nadic anhydride) Unsaturated mono[(meth)acryloxyalkylene group of a polyvalent carboxylic acid having two or more valences such as benzyl ethyl ester and phthalic acid mono [2-(methyl) propylene methoxyethyl] phthalate An ester; an unsaturated acrylate 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. 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. 201224653 (b) is 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)) The ethylenically unsaturatedly bonded monomer is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group. In the aspect (b), for example, a monomer (b1) having an epoxyethyl group and an ethylenically unsaturated bond (hereinafter also referred to as "(bl)"), having an oxetanyl group and an ethylenically unsaturated bond The monomer (b2) (hereinafter also referred to as "(b2)"), a monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter also referred to as "(b3)"), and the like. (b), for example, a monomer having a structure in which an olefin is epoxidized and an ethylenically unsaturated bond (bl-Ι) (hereinafter also referred to as "(bl-1)"), and a cycloolefin ring An oxidized structure and an ethylenically unsaturated bonded monomer (b 1-2) (hereinafter also referred to as "(bl-2)"). (bl) a monomer having an epoxyethyl group and a (meth)acryloxy group as a monomer (bl), having a structure in which a cycloolefin is epoxidized and a (meth)acryloxy group (bl) -2) Better. When it is such a monomer, the photosensitive resin composition is excellent in storage stability. (b 1-1) specifically, for example, epoxypropyl (meth) acrylate, β-methyl propyl propyl (meth) acrylate, β-ethyl propyl propyl (meth) acrylate Ester, epoxypropyl vinyl ether, 〇-vinylbenzyl epoxy propyl ether, m-vinylbenzyl epoxy propyl ether, ρ-vinylbenzyl epoxy propyl ether, α-methyl -〇-vinylbenzylepoxypropyl ether, α-methyl-m-vinylbenzylepoxypropyl ether, α-methyl-ρ-vinylbenzylepoxypropyl ether, 2,3 -bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, -9 - 201224653 2,5-bis(glycidoxymethyl)benzene Ethylene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-glycol (glycidoxymethyl)styrene, 2,3,5-para (glycidoxy) Methyl)styrene, 2,3,6-glycol (glycidoxymethyl)styrene, 3,4,5-glycol (glycidoxymethyl)styrene, 2,4,6 - a compound described in the publication of JP-A No. 7-24 8 625. (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, CYCLMERA400; manufactured by DAIcece Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, CYCLMERM100; manufactured by Daicel Chemical Industry Co., Ltd.) A compound represented by the formula (I), a compound represented by the formula (II), and the like.

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 the alkyl group may be substituted with a hydroxyl group. X1 and X2 are each independently a single bond, -R3-, *-R3-〇-, *-R3-S-, *-R3-NH-. R3 is an alkanediyl group having 1 to 6 carbon atoms. * is the key with the key. -10-201224653 The alkyl group having 1 to 4 carbon atoms may specifically be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an η-butyl group, a sec-butyl group or a tert-butyl group. Examples of the hydroxyalkyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy-1-methyl group. The group '2-carbyl-1-methylethyl, 1-phenylbutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like. R1 and R2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group. The alkanediyl group may, for example, be a methylene group, an ethylene group, a propane-H diyl group, a propane 1,3-diyl group, a butane-1,4-diyl group or a pentane-1,5-diyl group. , hexane-1,6-diyl and the like. X1 and X2 are preferably, for example, a single bond, a methylene group, an ethylene group, a *-ch2-o- (* is a bond bond with a fluorene bond), a *_ch2CH2-0- group, and more preferably a single bond. , *-CH2CH2-0 - base. The compound represented by the formula (I) may, for example, be a compound represented by the formula (1-1) to the formula (1-15). Preferably, for example, the formula (1-1), the formula (1-3), the formula (I-5), the formula (1-7), the formula (1-9), the formula (1-11) to the formula (1) -15). More preferably, it is exemplified by the formula (1-1), the formula (1-7), the formula (1-9), and the formula (1-15). -11 - 201224653

o II

o II H2C=CH-C—Ο H2C=CH-C-〇-CH2 h2c=ch-c—o-c2h4 H2C =CH -C — O -C2 H4—O CH3o II h2c=c—c—o ch3 o I II h2c=c—c—o—ch2 ch3 o I II H2C =C —C —0 —C2H4

(1-13) i? η2ο=Π-ο

H2C =CH -C —0 — C2H4 -S o II h2c=ch-co-c2h4-n H CH3o I II H2C =C—C —0 A C2H4—s CH3o I II H2C—C—C—O—C2H4 NH

Ch2oh o I II h2c=c-C-0

CH30 I II H2C =0 —C —O—C2H4—o c2h4oh o h2c=c-C-0

(1-15) The compound represented by the formula (n) may, for example, be a compound represented by the formula (II-1) to the formula (II-15). Preferably, for example, the formula (II-1), the formula (II-3), the formula (11-5), the formula (11-7), the formula (11-9), the formula (11-11) to the formula (11) -15). More preferably, for example, the formula (11-1), the formula (II-7), the formula (11-9), and the formula (11-1 5). -12- 201224653 ίί i? H2C:CH—c—ο H2C:CH-C-〇-CH: H2C:CH-C-0-C2H4 h2c=ch—c—0—C2H4-〇ch3o I II H2c=c —C-〇fH3!/ H2C=C-C—O—CH; PH30 h2c=c—C-〇-C2H4_

o

Ch2oh 0 u ^ I 11 H2C=C-c-o ch3 0 I II h2c=c-c—0—C2H4-〇

C2H4OH 0 I II H2C=C-c-o

The compound represented by the formula (I) and the compound represented by the formula (II) may each be used singly. And they can be mixed at any rate. In the case of mixing, the mixing ratio is in terms of 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 80: 20 ο (b 2), preferably a monomer having an oxetanyl group and a (meth) acryloxy group. In the aspect of (b2), for example, 3-methyl-3-(methyl)propenyloxymethyloxetane, 3-ethyl-3-(methyl)propenyloxymethyloxycyclohexane Butane, 3-methyl-3-(methyl)propenyloxyethyloxetane, 3-ethyl-3-(methyl)propenyloxyethyloxetane, and the like. -13- 201224653 (b 3) It is preferred to use a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group. (b 3) 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, (meth) acrylates, N-substituted maleimides, unsaturated dicarboxylic acid diesters, alicyclic unsaturated compounds, styrenes, and other ethylene Base compound, etc. Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, η-butyl (meth) acrylate, and sec-butyl (meth) acrylate. Alkyl esters of esters, tert-butyl (meth) acrylates, etc.; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate vinegar 'tricyclic ring [5_2.1.02, 6] Indole-8-yl (meth) acrylate (in the technical field to which the invention pertains, the conventional name is dicyclopentanyl (meth) acrylate vinegar.), dicyclopentyloxyethyl (meth) acrylate a cycloalkyl ester such as isobornyl (meth) acrylate; a hydroxyalkyl ester such as hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate; benzene An aryl group such as a base (meth) acrylate or a benzyl (meth) acrylate, an aralkyl ester or the like. Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconate. N _ substituted maleimine, for example, N-phenyl malea-14- 201224653 imine, N-cyclohexyl maleimine 'N-benzyl maleimide, N- Amber succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyl ester, N-succinimide-6-maleimide caproic acid Ester, N-succinimide-3-maleimide propionate, N-(9-acridinyl)maleimide, and the like. Examples of the alicyclic unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [2.2.1] hept-2-ene, and 5-ethyl bicyclo [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-dihydroxyl Bicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(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-carbyl-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methyl Bicyclo[2.2.1] hept-2-pyrene, 5-tert-butoxyindolylbicyclo[2.2.1]heptane-2 -diluted,5·cyclohexyloxycarbonylbicyclo[2.2.1]hept-2- Alkene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(with 1^-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6 a bicyclic unsaturated compound such as bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene or the like. Examples of the styrenes include styrene 'α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like. Other vinyl compounds may, for example, be (meth) propylene cyanide, chloroethylene-15-201224653 alkenyl group, vinylidene chloride, (meth) acrylamide, vinyl acetate, hydrazine, 3-butadiene, Isoprene, 2,3-dimethyl-1,3-butadiene, and the like. (c) Aspects of 'styrene, N-phenyl maleimide, ... cyclohexylmaleimide, N-benzyl maleimide, bicyclo [2.2.] g?_2_ From the viewpoint of copolymerization reactivity and alkali solubility, it is preferred. In the resin (A-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-1) is preferably in the following range. The structural unit from (a); 5 to 60 mol% (preferably 1 〇 to 5 〇 Mo Er 0/〇) The structural unit from (b); 40 to 95 mol% (preferably 5 〇 ~ When the ratio of the structural unit of the resin (A-1) is in the above range, the stability, the developability, the solvent resistance, the heat resistance, and the mechanical strength tend to be good. In the case of the resin (A-1), the resin (A1) in which (b) is (bl) is preferable, and the resin (A-1) (b) is (bl-2) is more preferable. The experimental resin (A - 1 ) for polymer synthesis, for example, can be referred to the method described in the literature method (the issued version of the Otsuka Ryokan, Ltd.), which is published in the March 1972 issue. Manufactured by citing literature.

Mixing, heating, and heat preservation methods. When it is substituted, it is deoxidized and stirred. The polymerization initiator and the solvent used herein are not particularly limited, and are generally used by users in the field. Examples of the polymerization initiator include azo compounds (2, 2 azobisisobutyronitrile, 2, 2' azobis (2,4-dimethylvaleronitrile), etc.) or organic peroxidation. The solvent (such as benzamidine peroxide) may be dissolved in the solvent, and the solvent of the photosensitive resin composition may be a solvent or the like described later. Further, as the obtained copolymer, the solution after the reaction can be used as it is, or it can be used as a solid (powder) by using a concentrated or diluted solution or by reprecipitation or the like. In particular, in the case of this polymerization, a solution obtained by reacting with the same solvent as the solvent (D) described later can be used as a solvent, and the production steps can be simplified. In the resin (A-2), the ratio of the structural unit derived from each monomer to the total number of moles of the entire structural unit constituting the resin (A-2) is preferably in the following range. The structural unit derived from (a); 2 to 40 mol% (preferably 5 to 35 mol%) of the structural unit derived from (c); 1 to 65 mol% (preferably 1 to 60 mol%) The structural unit derived from (b); 2 to 95 mol% (preferably 5 to 80 mol%). The ratio of the structural unit of the resin (A-2) is in the above range, and the stability, developability, and solvent resistance are preserved. The properties, heat resistance and mechanical strength tend to be good. In the case of the resin (A-2), the resin (A-2) wherein (b) is (bl) is preferable, and the resin (A-2) of (b) is (bl-2) is more preferable. -17- 201224653 Resin (A-2) can be produced by the same method as the resin (Al). In the resin (A-3), the ratio of the structural unit derived from each monomer is relative to the entire constituent resin (A-3). In terms of the total number of moles of the structural unit, the following range is preferred. The structural unit from (a): 2 to 40 mol% (preferably 5 to 35 mol. /.) The structural unit from (c); 60 to 98 mol% (preferably 65 to 95 m) %) When the ratio of the structural unit of the resin (A-3) is in the above range, the stability, developability, and solvent resistance tend to be good. The resin (A-3) can be produced in the same manner as the resin (A-1). The resin (A-4) is a copolymer of (a) and (c) and a resin (A-4) obtained by reacting with (b), for example, can be produced in a two-stage process. In this case, you can refer to the above-mentioned document "Experimental method for polymer synthesis" (Dazu Takashi, Ltd., the first issue of the Chemicals, the first edition of the first brush, issued on March 1, 1972). It is produced by the method and the like described in the publication No. 89533. First, in the first stage, a copolymer of (a) and (c) is obtained in the same manner as in the above-described method for producing the resin (A_1). In this case, as in the above, the obtained copolymer may be used as it is, or may be used as a solid (powder) by using a concentrated or diluted solution or by re-sinking. Further, the weight average molecular weight and molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (?η)] in terms of polystyrene in the same manner as above are preferable. However, 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 constituting the entire structural unit of the above-mentioned 201224653 copolymer. The structural unit from (a); 5 to 50 mol% (preferably 1 〇 to 45 mol%) of the structural unit derived from (c); 50 to 95 mol% (preferably 55 to 9 m) %) 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 the above (b). Since the reactivity of the cyclic ether is high and the unreacted (b) is not easily retained, (b) used in the resin (A-4) is preferably (bl) or (b2), more preferably (bl-Ι). Specifically, 'the environment inside the flask is replaced by nitrogen to air, so that relative to the mole number of (a), 5 to 80 mol% of the reaction catalyst of (b), carboxyl group and cyclic ether (for example) The total amount of (a), (b), and (c) is 0.001 to 5% by mass, and the polymerization inhibitor (for example, hydroquinone, etc.) is relatively (a). The total amount of (b) and (c) is 0.001 to 5% by mass in a flask, and the reaction is carried out at 60 to 13 Torr for 1 to 10 hours to obtain a resin (A-4). Further, similarly to the polymerization conditions, the calorific value due to the production equipment or the polymerization or the like can be considered, and the feeding method or the reaction temperature can be appropriately adjusted. Further, the number of moles of (b) at this time is preferably from 10 to 75 mol%, more preferably from 15 to 70 mol%, based on the number of moles of (a). In this range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to be good. In the first stage of the resin (A-5), a copolymer of (b) and (c) is obtained in the same manner as in the production method of the above-mentioned resin (A-1). In the above contract, the obtained copolymer ' can be used as it is, or can be used as a solid (powder) by using a concentrated or diluted solution, or using a method of reprecipitation, etc., -19-201224653. 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. The structural unit derived from (b); 5 to 95 mol% (preferably 1 〇 to 90 mol%). The structural unit derived from (c): 5 to 95 mol% (preferably 丨〇~90 mol) %) Further, similarly to the method for producing the resin (A-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) It is obtained by reacting an acid anhydride. The hydroxyl group produced by the reaction of a 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 reactivity of the cyclic ether is high, and the unreacted (b) is not easily retained, and (b) is preferably (bl), particularly preferably (bl-Ι). The polystyrene-equivalent weight average molecular weight of the resin (A) is preferably 3,000 to 10,000,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A) is in the above range, the coating property tends to be excellent, and the film is less likely to be formed in the exposed portion during development, and the non-exposed portion is easily removed by development. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (?η)] of the resin (A) 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 (Α) is 20 to 150 mgKOH/g, preferably 40 to 135 mgKOH/g, more preferably 50 to 135 mgKOH/g. Here, the acid value is determined by measuring the amount (mg) of potassium hydroxide necessary for neutralizing the resin (A) lg, and can be determined by titration with an aqueous potassium hydroxide solution. The content of the resin (A) is preferably from 5 to 95% by mass, more preferably from 20 to 80% by mass, based on the total of the resin (A) and the polymerizable compound (B) -20 to 201224653. ~60% by mass. When the content of the resin (A) is in the above range, the developability of the photosensitive resin composition, the adhesion of the obtained pattern, the solvent resistance, and the mechanical properties tend to be good. Here, the solid fraction refers to the amount of the solvent (E) removed from the photosensitive resin composition. The photosensitive resin composition of the present invention contains a polymerizable compound (B). The polymerizable compound (B) is a compound which can be polymerized by a living radical generated by the polymerization initiator (C), for example, a compound having a polymerizable ethylenically unsaturated bond, etc., preferably a (meth) acrylate. Compound. The aspect of the polymerizable compound (B) having one ethylenically unsaturated bond can be, for example, the same as the compound exemplified as the above (a), (b) and (c), wherein (meth) acrylate is used. The class is better. The polymerizable compound (B) having two ethylenically unsaturated bonds may, for example, be 1,3-butanediol di(meth)acrylate or 1,3-butanediol (meth)acrylate. 1,6-hexanediol di(meth)acrylate' ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A bis(acryloxyethyl)ether, ethoxylate Bisphenol A di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3-methylpentane Glycol di(meth)acrylate or the like. The polymerizable compound (B) having three or more ethylenically unsaturated bonds can be exemplified by, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra-21 - 201224653 alcohol tri(meth)acrylate , ginseng (2-hydroxyethyl) isocyanurate tri(meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethyl ketone (Methyl) acrylic acid vinegar, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol Reaction of penta (meth) acrylate, tripentaerythritol hexa(meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri(meth) acrylate and anhydride , a reaction of dipentaerythritol penta (meth) acrylate with an acid anhydride, tripentaerythritol hepta (meth) acrylate and anhydride caprolactone modified trishydroxypropyl propyl tris(meth) acrylate, Modified pentaerythritol tri(meth)acrylate, caprolactone modified ginseng (2-hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate , caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified tripellitate tetrakis (meth) acrylate, Ester-modified tripentaerythritol penta (meth) acrylate, caprolactone modified tripellitate hexa(meth) acrylate, caprolactone modified tripellitate pentoxide (meth) acrylate, caprolactone modified tripentaerythritol Reaction of octa (meth) acrylate, caprolactone-modified pentaerythritol tri(meth) acrylate with an acid anhydride, reaction of caprolactone-modified dipentaerythritol penta (meth) acrylate with an acid anhydride, caprolactone Modified tripentaerythritol hepta (meth) acrylate, acid anhydride, and the like. Among them, a photopolymerizable compound (B) having 3 or more functional groups is preferred, and dipentaerythritol hexa(meth)acrylate is more preferred. The content of the polymerizable compound (B) is preferably from 5 to 95% by mass, more preferably from 2 to 80% by mass, based on the total amount of the resin (A) and the polymerizable compound -22-201224653 (B). When the content of the polymerizable compound (B) is in the above range, the sensitivity, the smoothness, and the letterability of the obtained pattern tend to be good. The photosensitive resin composition of the present invention preferably contains a polymerization initiator (C). In the case of the polymerization initiator (C), a compound which can be polymerized by the action of light or heat is not particularly limited, and a conventional polymerization initiator can be used. The polymerization initiator (C) may, for example, be an alkylphenone compound, a biimidazole compound, a triazine compound, a fluorenyl ortho-oxide compound or an anthracene compound. Further, it is also possible to use an optical and/or thermal cationic polymerization initiator (for example, an iron cation and an anion derived from Lewis acid) described in JP-A-2008-1081. Among them, at least one selected from the group consisting of a biimidazole compound, an alkylphenone compound and an oxime ester compound is preferred, and an oxime ester compound is preferred. In the case of a polymerization initiator containing such a compound, it is particularly preferable to have a high sensitivity. The above-mentioned alkyl phenone compound may, for example, be diethoxyacetophenone, 2-hydroxy-2-methyl-2-indole-phenylpropanone, benzyldimethylketal, or 2-hydroxy-1. -[4-(2-Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 2-hydroxy-l-{4-[4-(2-hydroxy-2-methyl-propionium) -benzyl]-phenyl}-2-methyl-propan-1·one, 1-hydroxycyclohexyl phenyl ketone, 2-morpholino-1-(4-methylsulfonylphenyl) -2_methylpropan-1-one, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2 -(2-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(3-methylbenzyl)-1-(4) -W-phenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-cyanophenyl)butan-1-one, 2 _Dimethylamino 2_(2_ethylbenzyl-23- 201224653 Ma Daishen; Λ) Butan-1-one, 2-dimethylamino 2-_2 (2-propylmorpholine benzene) Base) τ , — (d) fluorenyl)·1-(4. 1-keto, 2-monomethylamino 2-(2·butyl-chiral morpholino ( Γδ^*)-1-(4-) Benzo)-ketone, 2-dimethylamino 2-_2 (2,3-dimethyl-K (4-morpholinobenzene, -to Butyl)-butanone, 2·-methylamino-2-(2,4-dimethylsuccinylphenyl)butanone, 2•dimethylamino 2_( 2 -Dimethylamino-2-(2-bromobenzyl 2 dimethylamino-2-(3- gas phenyl 2-dimethylamino-2-(4- benzylbenzyl 2-dimethylamino) -2-(3-bromo-2)dimethylamino-2-(4_漠!! dimethylamino-2·(2-methoxy, 2-dimethylamino·2_( 3_Methoxy)_1-(4-morpholinophenyl)butan-1-one)-(4.morpholinophenyl)butan-1-one)-1 -(4-morpholino Phenyl) butyl ketone ketone) -1 - (4-morpholinophenyl) butyl ketone ketone) 1' (4-morpholinophenyl) butyl-1-keto)-1 _ (4 · morpholinophenyl) butyl-1-ketone, porphyrin phenyl) butyl hydrazine, 2 dimethylamino group · 2 · 卞 ) ^ ) small (4, Lin Dai phenyl) butyl small Ketone, 2·dimethylamino 2·(4•methoxyindolyl)-1_(4′ phenylphenyl)butanone, 2 dimethylamino 2·^yl 4-methoxy Alkyl) 4-(4-morpholinophenyl)butanone, h-amino-2-(2-Tianqi/|, white#·^,,~~methyl (2 methyl-4) -bromomethyl)-1-(4-indolyldimethylamino-2.(2-bromo-4-yloxy) ) Butan-1-one, 2_ ! β ^Norgan)·Κ(4_?琳琳phenyl) Butane b嗣, 2-hydroxy_2_methyl_丨_[ 4_(1_yl) Ding· 1. Oligomers, etc. "Ethyl" phenyl] propyl _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ , 2,-bis(2,3-dichlorophenyl)-'4',5,5'-tetraphenylbiimene (for example, special opening $ Μ" bulletin, special Kaiping 6-7 5 3 73 No. K. et al., U, bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2,_bis(2虮phenylη〆," ,四-24- 201224653 (alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)_4,4,5,5,-tetrakis(dialkyloxyphenyl)biimidazole 2,2'-bis(2-chlorophenyl)_4,4,5,5,_tetra(trisyloxyphenyl)-linked oxime (for example, Japanese Patent Publication No. 48-38403, JP-A-62) -1, 74,204, and the like. Reference is made to the imidazole compound in which the phenyl group at the 4,4'5,5,-position is substituted with a carbonyl alkoxy group (for example, JP-A-71-1942, etc.). Preferred is 2,2'-bis(2-chlorophenylbu-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 aforementioned three-exposure compound can be, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5- Triazine, 2,4-bis(trichloromethyl)_6·(4-methoxynaphthyl)-1,3,5-triazine, 2,4·bis(trichloromethyl)_6_piperidinyl - H5·Triazine, 2,4-bis(trichloromethyl)·6-(4-methoxysupoyl)-^^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 The above-mentioned fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. The oxime ester compound may, for example, be N-benzylideneoxy- 1-(4-phenylsulfonylphenyl)butan-1-one-2-imine, N-ethoxycarbonyloxy-i-phenylpropan-1-one-2-imine, N- Benzamethyleneoxy-1-(4-phenylsulfonate) Phenyl)octane-1-one-2-imine, N-acetoxy-l-[9-ethyl-6-(2-methylbenzimidyl)-9H-indazole-3- Ethyl-1-imine, N-acetoxy-l-[9-ethyl-6--25- 201224653 {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, Ciba Japan), and N-1919 (made by Adeka) can also be used. Further, examples of the polymerization initiator (C) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone and anthracene-benzene. Methyl carbaryl benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra (tert-butyl) a benzophenone-based compound such as oxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone, etc. Lanthanide compound; 10-butyl-2-chloroacridone, benzyl ester, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with a polymerization initiation aid (C 1 ) to be described later. Further, as a polymerization initiator having a group capable of generating chain transfer, a photopolymerization initiator described in JP-A-2002-544205 can be used. The polymerization initiator having a group capable of causing chain transfer may, for example, be a compound of the following formulas (a) to (f). -26- 201224653 η)! Liu ~ 〇 ~ "Εν〇.

The polymerization initiator having a group capable of causing chain transfer can also be used as a component constituting a resin (〇). In the photosensitive resin composition of the present invention, the above polymerization initiator (C) can be used as a polymerization polymerization. Start aid (C1). The polymerization start aid (C1) can be used in combination with the polymerization initiator (C) to use for polymerization of a poly-27-201224653-compatible compound which starts polymerization by a polymerization initiator. In the case of the polymerization initiation aid (C1), for example, a compound represented by the following formulas (III) to (V), a thioxanthone compound, an amine compound, a carboxylic acid compound, and the like can be given.

W1

N I Ο , 11 5C=CH-C-R5 (m) I R4 [In the formula (III), the dotted line represented by W1 is an aromatic ring having a carbon number of 6 to 12 which may be substituted by a halogen atom. Y1 is -0- or -S-. R4 is a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms. R5 is a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a halogen atom or an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom or an odor. Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring and a naphthalene ring. The aromatic ring having 6 to 12 carbon atoms which may be substituted by a halogen atom may, for example, be a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring or a pentylbenzene. Ring, hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chlorine Naphthalene ring, bromine ring, and the like. Examples of the monovalent saturated hydrocarbon group having 1 to 6 carbon atoms include methyl ethyl group, η-propyl group, isopropyl group, η-butyl group, 1-methylpropyl group, and 2-methylpropyl-28-201224653. Base, tert-butyl, η-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl' 1,2-dimethyl Propyl, 2,2-dimethylpropyl, η-hexyl, cyclohexyl and the like. The monovalent saturated hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a halogen atom may be, for example, a heptyl group, an octyl group, an anthryl group or an anthracenyl group, in addition to the above-mentioned monovalent saturated hydrocarbon group having 1 to 6 carbon atoms. Eleven base, dodecyl, h chlorobutyl, 2-chlorobutyl, 3-chlorobutyl, and the like. The aryl group having 6 to 12 carbon atoms which may be substituted by a halogen atom may, for example, be a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a biphenyl group or a chloro group. Phenyl, dichlorobiphenyl, bromophenyl, dibromophenyl, naphthyl, chloronaphthyl, dichloronaphthyl, bromonaphthyl, dibromonaphthyl and the like. Specific examples of the compound represented by the formula (III) include 2-[2-o-oxo-2-(2-phenyl)ethylidene]_3-methylnaphtho[2,ld]thioxaline, 2-[2-o-oxo-2-(2-phenyl)ethylidene]·3-methylnaphtho[i,2-d]thiaporphyrin, 2-[2-oxo-o- 2- (2 -phenyl)ethylidene]_3_methylnaphtho[2,3-d]thiaporphyrin, 2-[2-oxo-oxo-2-(2-naphthyl)ethylidene]_3-methylbenzene And thiazide, 2-[2_sideoxy-2-(1-naphthyl)ethylidene]-3-methylbenzothiazoline, 2-[2-oxo-2-(2-naphthyl) Ethylene]-3-methyl-5-phenylbenzothiaporphyrin, 2-[2-o-oxo-2-(1-naphthyl)ethylene]-3-methyl-5-benzene Benzothiazoline, 2-[2-oxo-2-(2-naphthyl)ethylene]-3-methyl-5-fluorobenzothiaporphyrin, 2-[2-anoxo- 2-(1-naphthyl)ethylidene]-3-methyl-5-fluorobenzothiazepine, 2-[2-oxo-oxy-2-(2-naphthyl)ethylene]-3 Methyl-5-chlorobenzothiazoline, 2-[2-oxo-oxy-2-(p-naphthyl)ethylidene-3-methyl-5-chlorobenzothiazoline, 2-[2-anoxo- 2-(2-naphthyl)ethylidene]-3-methyl-5-bromobenzothiaporphyrin' 2-[2- side -29- 201224653 oxy-2-(1-naphthyl)ethylene ]-3-methyl-5-bromo And thiazoline, 2-[2-oxo-2-(4-phenylphenyl)ethylidene]-3-methylbenzothiazoline, 2-[2-oxo-2-(4-benzene) Phenylphenyl)ethylidene]-3-methyl-5-phenylbenzothiazoline, 2-[2-oxo-2-(2-naphthyl)ethylidene]-3-methylnaphtho [2, l_d] thiazoline, 2-[2-oxo-2-(2-naphthyl)ethylidene]-3-methylnaphtho[l,2-d]thiazoline, 2-[2- Side oxy-2_(4-phenylphenyl)ethylidene]-3-methylnaphtho[2,1-d]thiazoline, 2-[2-oxo-2-(4-phenylphenyl) Ethylene]-3-methylnaphtho[l,2-d]thiazoline, 2-[2-oxo-2-(4-fluorophenyl)ethylidene]-3-methylnaphtho [2,1-d]thiazoline, 2-[2-oxo-2-(4-fluorophenyl)ethylidene]-3-methylnaphtho[l,2-d]thiazoline, 2- [2-Sideoxy-2-(2-phenyl)ethylidene]-3-methylnaphtho[2,ld]oxazoline, 2-[2-oxo-2-(2-phenyl) Ethylene]-3-methylnaphtho[l,2-d]oxazoline, 2-[2-oxo-2-(2-phenyl)ethylidene]-3-methylnaphtho[ 2,3-d]oxazoline, 2-[2-oxo-2-(2-naphthyl)ethylidene]-3-methylbenzoxazoline, 2-[2- sideoxy-2_ (1-naphthyl)ethylidene]-3-methylbenzoxazoline, 2-[2-oxo-2-(2-naphthyl)ethylene]-3 -methyl-5-phenylbenzoxazoline, 2-[2-oxo-2-(1-naphthyl)ethylidene]-3-methyl-5-phenylbenzoxazoline, 2-[2-Sideoxy-2-(2-naphthyl)ethylidene]_3_methyl-5-fluorobenzoxazoline, 2-[2-Sideoxy-2-(1-naphthyl) Ethylene]-3-methyl-5-fluorobenzoxazoline, 2_[2-oxo-2-(2-naphthyl)ethylidene]-3-methyl-5-chlorobenzoxan Oxazoline, 2-[2-oxo-2-(1-naphthyl)ethylidene]-3-methyl-5-chlorobenzoxazoline, 2-[2-oxo-2-(2) -naphthyl)ethylidene]-3-methyl-5-bromobenzoxazoline, 2-[2-xyloxy-2-(1-naphthyl)ethylidene]-3-methyl-5 -bromobenzoxazoline, 2-[2-oxo-2-(4-phenylphenyl)ethylidene]-3-methylbenzoxazoline, 2-[2- side oxygen_2_ (4-phenylphenyl)ethylidene]-3-methyl-5-phenylbenzo-30-201224653 Oxazoline, 2-[2-xyloxy-2-(1-naphthyl)-ethylidene 3-methylnaphtho[2,ld]oxazoline, 2-[2-oxo-2-(1-naphthyl)ethylidene]-3-methylnaphtho[1,2- d] oxazoline, 2-[2-oxo-2-(4-phenylphenyl)ethylidene]-3-methylnaphtho[2,ld]oxazoline, 2-[2- side Oxy-2-(4-phenylphenyl)ethylidene]-3-methylnaphtho[l,2-d]oxazoline, 2-[ 2-oxo-2-(4-fluorophenyl)ethylidene]-3-methylnaphtho[2,ld]oxazoline, 2-[2-oxo-2-(4-fluorophenyl) Ethylene]-3-methylnaphtho[l,2-d]B.

[In the formulae (IV) and (V), the ring w2, W3 and the ring W4 are each independently, and are an aromatic ring having 6 to 12 carbon atoms or a hetero ring having 2 to 10 carbon atoms, and the aromatic ring and the heterocyclic ring are contained therein. The hydrogen atom may be substituted with a halogen atom. Y2 to Y5 are each independently, and -0- or -S^R6 to R9 are a monovalent saturated hydrocarbon group having a carbon number of 1 to 12 or an aryl group having a carbon number of 6 to 12, and the saturated hydrocarbon group and a hydrogen atom contained in the aryl group It may be substituted by a halogen atom, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms. The aromatic ring having the carbon number of 6 to 12 may, for example, be an aromatic ring similar to those exemplified in the formula (III), and the hydrogen atom contained in the aromatic ring may be optionally substituted with the halogen atom exemplified above. The heterocyclic ring having 2 to 10 carbon atoms which may be substituted by a halogen atom may, for example, be a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring or a pyran ring. Further, the monovalent hydroxy-substituted saturated hydrocarbon group may, for example, be a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group or a hydroxybutyl group. The hydroxy-substituted aryl group may, for example, be a hydroxyphenyl group or a hydroxynaphthyl group. Examples of the monovalent alkoxy-substituted saturated hydrocarbon group include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a butoxymethyl group, and an ethoxyethyl group. Ethoxypropyl, propoxybutyl and the like. The alkoxy-substituted aryl group may, for example, be a methoxyphenyl group or an ethoxynaphthyl group. Specific examples of the compound represented by the formula (IV) and the formula (V) include dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene, dibutoxynaphthalene, and the like. Di-alkoxy naphthalenes; 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9, 10-Diethoxy oxime, dipropoxy ruthenium, diisopropoxy ruthenium, dibutoxy ruthenium, dipentyl fluorene, dihexyloxy ruthenium, methoxy ethoxy ruthenium, methoxy Propyloxy oxime, methoxyisopropoxy oxime, methoxybutoxy oxime, ethoxy propoxy oxime, ethoxyisopropoxy oxime, ethoxybutoxy fluorene, propoxy Ethyl isopropoxide, propoxy oxybutoxy fluorene, isopropoxy butyl hydrazine, etc.; dimethoxy butyl, diethoxy butyl hydride Province, diisopropoxy butyl, dibutoxy butyl and other di-alkoxydin provinces; The thioxanthone compound may, for example, be 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-ethylthioxanthone, 2,4-dichlorosultone or 1-chloro -4-propoxypyranone and the like. -32- 201224653 The amine compound may, for example, be an aliphatic amine compound such as triethanolamine, methyldiethanolamine or triisopropanolamine, methyl 4-dimethylaminobenzoate or 4-dimethylaminobenzoin. Ethyl acetate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-di Methyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (general name; Michler's ketone), 4,4'-bis(diethylamino)benzophenone Aromatic amine compound. Examples of the carboxylic acid compound include phenylsulfonyl acetic acid, methylphenylsulfonyl acetic acid, ethylphenylsulfonyl acetic acid, methylethylphenylsulfonyl acetic acid, and dimethylphenylsulfonate. Acetic acid, methoxyphenylsulfonyl acetic acid, dimethoxyphenylsulfonyl acetic acid, chlorophenylsulfonyl acetic acid, dichlorophenylsulfonyl acetic acid, N-phenylglycine, benzene An aromatic heteroacetic acid such as oxyacetic acid, naphthylthioacetic acid or N-naphthylglycine acid 'naphthyloxyacetic acid. The combination of the polymerization initiator (C) and the polymerization initiation aid (c丨) may, for example, be an acetophenone compound and a thioxanthone compound, an acetophenone compound or a fragrant amine compound, and specifically, for example, Such as 2_ 呷 疏 疏 壤 壤 壤 、. . Methyl ketone exposure ketone 'brew base>-2-methyl propyl 1- copper and 2,4-diethylamino 2 -benzyl-morpholinophenyl) butyl- , ketone with a t-dimethyl ketone, 2-dimethylamino 2-_2 (4-methylbenzyl, ~ethyl succinyl-1-ketone and 2,4 _diethyl thioxanthone, 2 _ Morpholinophenyl) _ _ \ ·1 '(4-methylphenyl)·2-methylpropane 丨 ketone with isopropyl thioxanthone and sulfonyl ketone, 2-morpholino Methylsulfonylphenyl bromide 2,4'-bis(diethylamino)benzophenone, decane, ~'methylamino 1--4-morpholino Phenyl) butyl-indole ketone oxime 4 4, _ bis (~7, 2' benzyl- ', arylamino) bis-methyl-33- 201224653 ketone, 2-dimethylamino 2-- (4 -Methyl group)-1-(4-morphinylphenyl) ketone and 4,4'-bis(diethylamino)benzophenone. Among them, a combination of an acetophenone compound and a thioxanthone compound is preferred, 2-morpholino-1-(4-methylsulfonylphenyl)-2-methylpropanone and 2,4-diethylthiophene. Toxyl ketone, 2-morpholino-1-(4-methylsulfonylphenyl)_2-methyl two-infant-1-pyrene and 2-isopropylthioshenone with 4-isopropylthiaspin Better. In the combination of these, a pattern having high sensitivity and high visible light transmittance can be obtained. The content of the polymerization initiator (C) is preferably from 5% to 30% by mass, more preferably from 1 to 2% by mass, based on the total amount of the resin (A) and the polymerizable compound (b). Good for 1~1 〇 mass%. When the content of the polymerization initiator (C) is within the above range, the pattern can be obtained with high sensitivity. The amount of the photopolymerization initiation aid (C1) to be used is preferably from 0.1 to 10% by mass, more preferably from 3% to 7% by mass, based on the total amount of the resin (A) and the polymerizable compound (B). When the amount of the polymerization starting aid (C 1 ) is in the above range, the shell|j can obtain a pattern with high sensitivity and the obtained pattern shape is good. The photosensitive resin composition of the present invention contains a compound having at least one group selected from the group consisting of an active methylene group and an active methine group and having a molecular weight of less than 300 Å (hereinafter also referred to as "compound (D)). ".). The active methylene group refers to a methylene group which is reactive with a nucleophilic reagent, and the active methine group refers to a methine group which is reactive with a nucleophilic reagent. It is preferred that at least one group selected from the group consisting of an active methylene group and an active methine group is a group represented by the formula (VI). -X8 -CHRk -Rm (VI) [In equation (VI), 3 is -(:〇-, -SO- or -so2-. -34- 201224653 11"1 is -00-1111, -C0-0 -Rn, -C〇-NRp-Rn, -SO-Rn, -S02-Rn, cyano or nitro.

Rk, Rn and Rp are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Rk and Rm may be bonded to each other to form a ring. The base represented by the formula (VI) may, for example, be a group represented by the formula (VI_i) to the formula (VI-9). Recognize h3 0 0 Everyone 〇c6h13 From·3 λ 0 (VI-1) (VI-2) (VI-3) (VI-4) fYH3 oo 0 0 II II oo -^N〇2 o —Bu c ( VI-5) (VI-6) (VI-7) (VI-8) (VI-9) For the compound (D), for example, Trimethylpropane tris (acetoacetate) ", pentaerythritol oxime (acetamidine acetate) "pentaerythritol tetrakis (acetoacetate)", 2-{[2,2-bis(hydroxymethyl)-3-hydroxypropoxy]methyl}-2-( Hydroxymethyl)propanoid-1,3-diol (ethyl acetate) "2-{[2,2-bis(hydroxymethyl)-3-hydroxypΓopoχy]methyl}-2-(hydroxymethyl)propane- l, 3-diol hexakis (acetoacetate) " acetonitrile acetate of a polyol having a molecular weight of less than 3,000. Further, as the compound (D), for example, the compound (D-1) to the compound (D-12) can be mentioned. Further, the compound (D-1) is a compound represented by the following formula (D-1). -35- 201224653

Table 1 Compound A1 A2 A3 X)-A1 八^O-A2 Ό-Α3 D-1 (VI-1) (VI-1) (VI-1) D-2 (VI-2) (VI-2) ( VI-2) D-3 (VI-4) (VI-4) (VI-4) D-4 (VI-1) (VI-1) (VI-2) Table 2 Compound A1 A2 A3 A4 JChk5 a8- o'^"^o-a6 Ό-Α7 D-5 (VI-1) (VI-1) (VI-1) (VI-1) D-6 (VI-2) (VI-2) (VI -2) (VI-2) D-7 (VI-4) (VI-4) (VI-4) (VI-4) D-8 H (VI-1) (VI-1) (VI-1) -36- 201224653 Table 3 Compound A1 A2 A3 A4 A5 A6 α10-ο Corpse-A11 D-9 (VI-1) (VI-1) (VI-1) (VI-1) (VI-1) (VI- 1) ΑΛ / D-10 (VI-2) (VI-2) (VI-2) (VI-2) (VI-2) (VI-2) α12·〇/ > α13-ο Va14 D-ll (VI-4) (VI-4) (VI-4) (VI-4) (VI-4) (VI-4) D-12 H (VI-1) (VI-1) (VI-1) ( (VI-1) The content of the compound (D) is preferably from 0.1 to 50% by mass, more preferably from 1 to 30% by mass, based on the total amount of the resin (A) and the polymerizable compound (B). . When the content of the compound (D) is in the above range, the pattern is excellent in the formation of the pattern, and the obtained pattern tends to have excellent mechanical properties. The photosensitive resin composition of the present invention contains a solvent (E). The solvent usable in the present invention may be, for example, an ester solvent (a solvent containing -COO-), an ether solvent other than an ester solvent (a solvent containing -〇-), an ether ester solvent (a solvent containing -COO- and -0-) And a ketone solvent (solvent containing -CO-) other than an ester solvent, an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine, etc. are used, and an ester solvent is mentioned, for example. Ester, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, butyric acid Isopropyl ester, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexanol acetate, γ-butane Ester and the like. Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl-37-201224653-ether ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl group. Ether, diethylene 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 glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, methyl anisole and the like. Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate 'methoxyacetate' vinegar, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropene. Methyl ester 'ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropane Ethyl acetate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, 2 Ethyl ethoxy-2-methylpropionate, 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 Ester, diethylene glycol monobutyl ether acetate, and the like. The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 4-methyl-2- Pentanone, cyclopentanone 'cyclohexanone, isophorone and the like. Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of the aromatic hydrocarbon solvent include benzene, toluene, toluene, and trimethyl- 38- 201224653 Benzene, etc. Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like. 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 120 ° C or more and 180 ° C or less is preferred from the viewpoint of coatability and drying property. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3- Methoxy-1-butanol or the like is preferred. When the solvent (E) is used as the solvent, the unevenness in coating can be suppressed and the flatness of the coating film can be improved. The content of the solvent (E) in the photosensitive resin composition is preferably from 60 to 95% by mass, more preferably from 70 to 90% by mass, based on the photosensitive resin composition. In other words, the solid content of the photosensitive resin 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 within the above range, the flatness of the film to which the photosensitive resin composition is applied tends to be high. Further, the photosensitive resin composition of the present invention may further contain a polyfunctional thiol compound (T). The polyfunctional thiol compound (T) refers to a compound having two or more sulfonyl groups in the molecule. Particularly, a compound having two or more sulfonyl groups bonded to a carbon atom derived from an aliphatic hydrocarbon group is used, and the photosensitive resin composition of the present invention tends to have an increased sensitivity. Specific examples of the polyfunctional thiol compound (T) include hexanedithiol, decanedithiol, 1,4-bis(methylsulfonyl)benzene, and butanediol bis(3-sulfonylpropylpropane). Acid ester), butanediol bis(3-sulfonyl acetate), ethylene glycol bis(3-sulfonyl-39-201224653-based acetate), trimethylolpropane ginseng (3-sulfonyl) Acetate), butanediol bis(3-sulfonylpropionate), trimethylolpropane ginseng (3-sulfonylpropionate), trimethylolpropane ginseng (3-sulfonylpropyl) Acid ester), pentaerythritol oxime (3-sulfonylpropionate), pentaerythritol oxime (3-sulfonyl acetate), hydroxyethyl ginseng (3-sulfonylpropionate), pentaerythritol bismuth (3) - sulfobutyl butyl ester), 1,4-bis(3-sulfonylbutoxy)butane, and the like. The content of the polyfunctional thiol compound (T) is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass based on the polymerization initiator (C). When the content of the polyfunctional thiol compound (T) is in the above range, the photosensitive resin composition tends to have high sensitivity and good developability. The photosensitive resin composition of the present invention may contain a surfactant (F). Examples of the surfactant include an anthrone-based surfactant, a fluorine-based surfactant, and an anthrone-based surfactant having a fluorine atom. The anthrone-based surfactant may, for example, be a surfactant having a siloxane coupling. Specifically, for example, toray siliconeDC3PA, with SH7PA, with DC11PA, with SH21PA, with SH28PA, with SH29PA, with SH30PA, polyether modified fluorenone oil SH8400 (trade name: Dow Corning Toray), KP321, KP3 22 , KP3 23, KP324, KP3 26, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, 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 interfacial activity having a fluorocarbon chain -40 to 201224653. Specifically, such as Fluorinert (registered trademark) FC430, with FC431 (Sumitomo 3M (share) system), MEGAFACE (registered trademark) F142D, with F171, with F172, with F173, with F177, with F183, with R30 (DIC (share) )), EFTOP (registered trademark) EF301, EF303, EF351, EF3 52 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, same as S382, same as SC101, same as SC105 (Asahi Glass) )), E5844 (made by Daikin Precision Chemical Research Institute). Examples of the fluorenone-based surfactant having a fluorine atom include a surfactant having a siloxane coupling and a fluorocarbon chain. Specifically, for example, MEGAFACE (registered trademark) R08, BL20, F475, and F477, Same as F443 (DIC system). It is preferably MEGAFACE (registered trademark) F 4 7 5. The surfactant (F) is 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more, based on the photosensitive resin composition. /. The following, more preferably 〇.〇1% by mass or more 〇.〇5 mass. /. the following. By allowing the surfactant to be contained in this range, the flatness of the coating film can be made good. The photosensitive resin composition of the present invention may contain various additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, an ultraviolet absorber, a photostabilizer, and a chain transfer agent as necessary. The photosensitive resin composition of the present invention contains substantially no coloring agent such as a pigment or a dye. In the photosensitive resin composition of the present invention, the colorant content of the entire composition is, for example, preferably less than 1% by mass, more preferably -41 to 201224653 is less than 0.5% by mass. The photosensitive resin composition of the present invention is filled in a quartz liquid bath having an optical path length of 1 cm, and the average transmittance in the case of measuring the transmittance at a measurement wavelength of 400 to 700 nm by using a spectrophotometer is preferably 70% or more. More preferably 80% or more. When the photosensitive resin composition of the present invention is formed into a coating film, the average transmittance of the coating film is preferably 90% or more, more preferably 95% or more. The average transmittance is a film having a thickness of 3 μm after heat-hardening (for example, hardening at 1 〇〇 to 250 ° C for 5 minutes to 3 hours) using a spectrophotometer, and measuring a wavelength of 400 to 70 nm. The average enthalpy of the measurement is measured. Thereby, a coating film excellent in transparency in the visible light region can be provided. The photosensitive resin composition of the present invention is coated on a substrate such as a substrate, a substrate such as glass, metal, or plastic, or a substrate on which a color filter, various insulating or conductive films, a driver circuit, or the like is formed, as will be described later. A coating film can be formed. The coating film is preferably dried and hardened. Further, the obtained coating film is patterned into a desired shape, and can also be used as a pattern. Further, these coating films or patterns may be used as part of the constituent parts of the display device or the like. First, the photosensitive resin composition of the present invention is applied onto a substrate. The coating can be carried out by various coating apparatuses such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater, and a dip coater as described above. Next, it is preferred to remove the volatile component such as a solvent by drying or prebaking. Thereby, a smooth unhardened coating film can be obtained. -42- 201224653 The film thickness of the coating film in this case is not particularly limited, and may be appropriately adjusted depending on the material to be used, for example, about 1 to 6 μm. Further, the obtained uncured coating film is passed through a target mask to be irradiated with light such as a mercury lamp or a light-emitting diode. The shape of the mask at this time is not particularly limited, and the shape or size may be selected depending on the application. In recent years, the exposure machine can be shielded by using a furnace light sheet that covers a wavelength range of less than 3 50 nm, and is taken out by using a band pass filter that takes out light near 436 nm, near, and near 365 nm, and the like. Uniform parallel rays are uniformly illuminated on the entire exposed surface. If the cover is aligned with an apparatus such as an exposure machine or a stepper, the correct position of the substrate and the substrate can be performed. The coating film after exposure is brought into contact with the developing solution to dissolve and develop the specific portion and the exposed portion, whereby the desired pattern shape can be obtained. The developing method may be a liquid immersion method, a dipping method, a spray method or the like. Further, the substrate can be tilted at an arbitrary angle during development. The developing solution used for development is an aqueous solution of a basic compound. The basic compound may be an inorganic or organic basic compound. Specific examples of the inorganic basic compound may, for example, be sodium, potassium hydroxide or hydrogen phosphate. Sodium, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, potassium carbonate, sodium bicarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonium organic alkaline The compound may, for example, be tetramethylammonium hydroxide, a UV-pattern light for use, or a 4 〇 8 nm selective use of a photo-mask, for example, any of the di-ammonium hydroxide, sodium, Carbon, etc. , 2-43-201224653 hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, single Isopropylamine, diisopropylamine, ethanolamine, etc. The concentration in the aqueous solution of the inorganic and organic basic compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The aforementioned developer may contain a surfactant. The surfactant may be any of a nonionic surfactant, an anionic interface active agent or a cationic surfactant. Nonionic surfactants, such as polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, ethylene oxide/propylene oxide block copolymers, 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, or the like. Examples of the anionic surfactant include, for example, sodium lauryl sulfate or sodium oleyl sulfate, higher alcohol sulfate salts, sodium lauryl sulfate or ammonium lauryl sulfate, and dodecylbenzene. Sodium sulfonate or sodium aryl sulfonate such as sodium dodecyl sulfonate. The cationic surfactant may, for example, be a stearylamine hydrochloride or a lauryl trimethylammonium chloride-like amine salt or a fourth-order ammonium salt. The concentration of the surfactant in the alkali developing solution is preferably in the range of 0.01 to 1% by mass, more preferably 0.05 to 8% by mass, still more preferably 0.1 to 5% by mass. After development, it can be washed with water to obtain a pattern. Then, if necessary, post-baking can also be carried out on -44 - 201224653. Post-baking, for example, at a temperature range of 150 to 240 ° C, preferably 1 〇 to 180 minutes. When the uncured film is exposed, the mask is formed without using a pattern. Light irradiation and/or omitting development can provide a coating film having no pattern. The pattern obtained by the photosensitive resin composition of the present invention can be used as, for example, a spacer constituting a part of a color filter substrate and/or an array substrate, a patternable protective film, and an interlayer insulating film. a liquid crystal alignment control protrusion, a microlens, a film thickness adjustment coating, or the like, and a member for a touch panel, and the coating film having the pattern obtained as described above can be used as one of the color filter substrate and/or the array substrate. Part of the protective film. The color filter substrate and the array substrate can be used for a liquid crystal display device, an organic EL display device, or the like. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples. In the examples, "%" and "parts" are not specifically described as mass % and mass parts. (Synthesis Example 1) In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was introduced into a nitrogen atmosphere at 0.02 L/min, and 200 parts by mass of 3-methoxy-1-butanol and 3-methyl group were added. 105 parts by mass of oxybutyl acetate was heated to 70 ° C with stirring. Next, 60 parts by mass of methacrylic acid, 3,4_cyclo-45-201224653 oxytricyclo[5.2.1.02.6]decyl acrylate (the compound represented by formula (11) and formula (II-1) The compound represented by the mixture is mixed with a molar ratio of 5 〇: 50.) 240 parts by mass and 14 parts by mass of 3-methoxybutyl acetate to prepare a solution, which is dripped in a dropping funnel for 4 hours. To a flask of 70 〇c. On the other hand, 30 parts by mass of a polymerization initiator 2,2,-azobis(2,4-dimethylvaleronitrile) is dissolved in a solution of 225 parts by mass of 3-methoxybutyl acetate, and another The dropping funnel took 4 hours to drip into the flask. After the completion of the dropwise addition of the polymerization initiator solution, 70 was maintained for 4 hours. (:, and then cooled to room temperature' to obtain a solution of a copolymer (resin Aa) having a solid content of 32.6 mass% and an acid value of i10 mg_KOH/g (solid content conversion). The obtained resin Aa had a weight average molecular weight Mw of 13,400 and a molecular weight. The distribution is 2.50.

(Synthesis Example 2) In a 1-liter flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was introduced into a nitrogen atmosphere at a volume of 〇2 L /min, and 200 parts by mass of 3-methoxy-1-butanol was added thereto. And 5 parts by mass of 3-methoxybutyl acetate, and heated to 70 ° C while stirring. Next, '55 parts by mass of methacrylic acid, 3,4-epoxytricyclo[5.2.1· 02·6]decyl acrylate (the compound represented by the formula (1_1) and the formula (Π-1)) The compound is a mixture of molar ratios of 50:50.) 175 parts by mass and 70 parts by mass of N-cyclohexylmaleimide are dissolved in 3-methoxybutyl acetate M0 parts by mass to prepare a solution. This solution was dropped into a flask kept at 70 ° C for 4 hours by dropping the pump. On the other side, 201224653, 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 225 parts by mass of 3-methoxybutyl acetate. The additional drip pump took 5 hours to drip into the flask. After the completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer having a solid content of 33.6 mg-KOH/g of a solid content of 32.6% by mass. Solution. The obtained resin Ac had a weight average molecular weight (Mw) of 1,3,600, a number average molecular weight (??) of 5,400, and a molecular weight distribution of 2.5. (Synthesis Example 3) In a 1-liter flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was introduced into a nitrogen atmosphere at 〇_02 L/min, and 140 parts by mass of diethylene glycol ethyl methyl ether was added thereto. Heat to 7 ° C with stirring. Next, 40 parts by mass of methacrylic acid and 3,4-epoxytricyclo[5.2.1.02·6]decyl acrylate (the compound represented by the formula (1-1) and the formula (II-1) are represented. Mixture of the compound, molar ratio = 50: 50) 340 parts by mass, dicyclopentenyl acrylate (compound represented by the following formula (xl)) 20 parts by mass dissolved in diethylene glycol ethyl methyl ether 190 Parts by mass to prepare a solution.

The obtained solution was dropped for 4 hours using a dropping solution, and dropped into a flask maintained at 70 °C. On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in a solution of 240 parts by mass of diethylene glycol ethyl methyl ether-47- 201224653 It took 5 hours to drip into the flask with another dripping pump. After completion of the dropwise addition of the polymerization initiator solution, it was maintained at 7 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin Ac) having a solid content of 41.8%. The obtained resin Ac had a weight average molecular weight (Mw) of 9.6 x 10, a molecular weight distribution (Mw/Mn) of 2.02, and an acid value of 60 mg-KOH/g in terms of solid content. The weight average molecular weight (Mw) and the number average molecular weight (?n) of the obtained resin Aa were measured by the following conditions using the GPC method. Device; Κ2479 (manufactured by Shimadzu Corporation) pipe column; SHIMADZU Shim-pack GPC-80M column temperature; 40 ° C solvent; THF (tetrahydrofuran)

Flow rate; 1.0 mL/min detector; RI The molecular weight distribution of the weight average molecular weight and the number average molecular weight (Mw/Mn) in terms of polystyrene obtained above. (Examples 1, 2 and Comparative Example 1) <Adjustment of photosensitive resin composition> The components of Table 4 were mixed to obtain photosensitive resin compositions 1 to 3. -48- 201224653 Table 4 Photosensitive resin composition 1 2 3 4 5 6 Resin (eight) (parts) A a 60 60 60 45 Ab 60 Ac 60 Polymerizable hetero (8) (parts) 40 40 40 55 40 40 ; Agent (C) (part) 2 2 2 2 2 2 Chemical decoration (D) (part) 5 10 5 5 5 Additive (F) (part) 0.1 0.1 0.1 0.1 0.1 0.1 Solvent (E) (%) E a 26 26 26 26 26 E b 20 20 20 20 20 E c 17 17 17 17 17 25 Ed 37 37 37 37 37 25 E f 50 Solid content (%) 33 33 33 33 33 33 Average transmittance of the composition (%) 91 90 91 90 91 91 Average transmittance of film (%) 99 99 99 99 99 99 The components in Table 4 are as follows. Resin (A); Aa: Resin Aa obtained in Synthesis Example 1 The parts in Table 1 are parts by mass in terms of solid content. Polymerizable compound (B); dipentaerythritol hexaacrylic acid vinegar (KAYARAD DPHA; manufactured by Sakamoto Chemical Co., Ltd.) Compound (D); Trimethylolpropane ginseng (acetamidine acetate) (Compound (D-1)) (molecular weight; 386) (manufactured by Nippon Synthetic Chemical Co., Ltd.) Polymerization initiator (C); N-acetoxyl-l-[9-ethyl-6-(2-methylbenzhydryl)- 9H-carbazol-3-yl]ethane-oxime-imine (IRGACUREOXE02; -49- 201224653 BASF Japan) Surfactant (F); Polyether modified fluorenone oil (toray silicone SH8400; Dow Corning Toray (solvent) solvent (E); Ea; propylene glycol monomethyl ether acetate solvent (E); Eb; 3-ethoxypropionate ethyl ester solvent (E); Ec; 3-methoxy- 1-butanol solvent (E); Ed; 3-methoxybutyl acetate solvent (E); Ee; diethylene glycol methyl ethyl ether solvent (E) as a solid component of the photosensitive resin composition The solvent component (Ea) to (Ee) in the solvent (E) was mixed in the solvent (E) in a mass ratio of the solid content (%) of Table 1. <Average transmittance of the composition> Each of the obtained photosensitive resin compositions 1 to 3 was subjected to an ultraviolet-visible near-infrared spectrophotometer (V-6 50; manufactured by JASCO Corporation) (quartz liquid bath, optical path) Length; lcm), the average transmittance (%) of 400 to 700 nm was measured. The results are shown in Table 4. <Average Permeation of Films> Each of the obtained photosensitive resin compositions 1 to 3 was formed into a film under the following conditions so that the film thickness after curing was 3 μm. A 2-inch square glass substrate (EAGLEXG; manufactured by Corning Co., Ltd.) was sequentially washed with a neutral detergent, water and alcohol, and then dried. On the glass substrate, the film thickness of the photosensitive resin composition after baking was 3.0 μm, and the coating was performed by a vacuum drying machine (manufactured by Microtek Co., Ltd.) to reduce the degree of pressure. After drying under reduced pressure at 66 kPa, the mixture was pre-baked at 80 ° C for 2 minutes on a hot plate to dry. After cooling, an exposure machine (TME-150RSK; TOPCON (light source), light source; ultra-high pressure mercury lamp) was used, and the exposure light amount was 60 mJ/cm2 (365 nm reference) in an atmosphere. Further, at this time, the irradiation of the photosensitive resin composition is carried out by passing the emitted light from the ultrahigh pressure mercury lamp through an optical filter (UV-33; manufactured by Asahi Co., Ltd.). After the light irradiation, the coating film was immersed and shaken at 23 ° C for 60 seconds in an aqueous developing solution containing a nonionic surfactant of 0.12% and potassium hydroxide of 0.04%, and then developed in an oven. The film was heated at 25 ° C for 15 minutes to obtain a film. The obtained film was subjected to a microscopic spectrophotometer (OSP-SP200; manufactured by OLYMPUS Co., Ltd.) to measure an average transmittance (%) of 400 to 700 nm. A higher transmittance means that the absorption becomes smaller. The results are shown in Table 4. <Form Formation> A 2-inch square glass substrate (EAGLEXG; manufactured by Corning Co., Ltd.) was sequentially washed with a neutral detergent, water, and alcohol, followed by drying. On the glass substrate, the photosensitive resin composition was subjected to spin coating so that the film thickness after baking was 3.5 μm, and the pressure reduction was reduced to 66 kPa by a vacuum dryer (manufactured by Microtek Co., Ltd.). After pressure drying, it was pre-baked at 80 ° C for 2 minutes on a hot plate to dry. After cooling, the distance between the substrate on which the photosensitive resin composition is applied and the mask made of quartz glass is ΙΟμηη, and an exposure machine (TME-15 0RSK; TOPCON, light source; ultrahigh pressure mercury lamp) is used, in an atmospheric environment. Light with an exposure dose of 60 m]/cm2 (365 nm reference). -51 - 201224653 In this case, the irradiation of the photosensitive resin composition is carried out by passing the emitted light from the ultrahigh pressure mercury lamp through an optical filter (UV-33; manufactured by Asahi Co., Ltd.). Further, as the mask, a pattern (a light-shielding portion having a square of 13 μm on one side and a square interval of ΙΟΟμπΟ (that is, a light-transmitting portion)) is formed on the same plane. The water-based developer having a nonionic surfactant of 0.12% and potassium hydroxide of 0.04% was subjected to immersion and shaking at 25 ° C for 100 seconds, and then developed, and after washing with water, 2 3 5 ° was carried out in an oven. C, 1 and 5 minutes after baking to obtain a pattern. <Measurement of pattern width> The width of the obtained pattern is measured by a three-dimensional non-contact surface shape measuring system (Micromap MM527N-PS-M100; Measurement by the system company. The height of the pattern is measured at a height of 5% higher than the substrate surface. The results are shown in Table 5. <Mechanical characteristics (total displacement amount and recovery rate)> Use of the obtained pattern The dynamic ultra-micro hardness tester (DU Η - W 2 0 1 ; (share) manufactured by Shimadzu Corporation) measures the total displacement amount (μηι) and the elastic displacement amount (μηι), and calculates the recovery rate (%). High, the more excellent the liquid crystal panel can be manufactured. The results are shown in Table 5. - Measurement conditions -

Test mode; load-de-load test test force; 5〇mN -52- 201224653 load speed: 4.41mN/sec hold time; 5sec pressure: truncated cone pressure (diameter 50μιη) recovery rate (%); (elastic displacement Amount (μπι) / total amount of displacement (μιη)) χ 100 <sensitivity> A 2-square glass substrate (EAGLEXG; manufactured by Corning Co., Ltd.) was washed with a neutral detergent, water and alcohol in order, and then dried. On the glass substrate, the photosensitive resin composition was subjected to spin coating so that the film thickness after baking was 3.5 μm, and the pressure reduction was reduced to 66 kPa by a vacuum dryer (manufactured by Microtek Co., Ltd.). After pressure drying, it was pre-baked at 80 ° C for 2 minutes on a hot plate to dry. After cooling, the distance between the substrate on which the photosensitive resin composition was applied and the mask made of quartz glass was 1 μm, and the exposure machine was used (Ding 14£-1501131<:;1'〇?(:(^(股)) System, light source; ultra-high pressure mercury lamp), in the atmosphere, the exposure of the exposure is 200mJ/cm2 (3 65nm reference). In addition, the exposure of the photosensitive resin composition is such that the radiation from the ultra-high pressure mercury lamp passes. An optical filter (UV-33; manufactured by Asahi Separation Co., Ltd.) is used. As a mask, a pattern (a square light-transmitting portion having a side of 13 μm and a square interval of ΙΟΟμιη) is used (ie, Light-transmitting portion) A photomask formed on the same plane. After light irradiation, the coating film is at 25 ° C, 100 in an aqueous developing solution containing a nonionic surfactant 〇·12% and potassium hydroxide 0.04%. After dipping for a second, shaking for development, washing with water, baking in a microwave at 23 5 ° C for 15 minutes, and obtaining a pattern. -53- 201224653 In addition to changing the exposure amount to 100, 50, 25 mJ/cm2 ( 3 6 5 nm standard) other than the above method, respectively, get the pattern. Also, made The spin coating in the case of the pattern was carried out in the same manner as in the case of patterning at an exposure amount of 200 mJ/cm 2 . The film thickness of the obtained pattern was measured by a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The residual film ratio was calculated by the following formula. The higher the residual film rate, the higher the residual film rate, the higher the sensitivity. The results are shown in Table 5. (Exposure D0 mj/cm2 height) Residual film rate (%) =--- X 1 0 0 (the height of the exposure amount of 200 mJ / cm 2 ) [wherein, the exposure amount D is 1 〇〇, 50 or 25.] Table 5 Example 1 Example 2 Comparative Example 1 Example 3 Example 4 Example 5 Photosensitive resin composition 1 2 3 4 5 6 Mechanical properties. Total amount of displacement [〆®] 0.51 0. 55 0. 65 0.48 0.52 0.58 Recovery rate [%] 80 75 68 83 80 75 Residual film rate D° ; 100raJ/cra2 99 100 99 100 99 100 (%) D0; 50mJ/cra2 95 96 94 97 95 97 D 0 ; 25mJ/cm2 91 92 90 93 92 93 Type 3 width _] 17.9 .18.3 17.4 17.5 19.4 18.3 From Table 5 As a result of the example shown, it is understood that the photosensitive resin composition containing the compound (D) can be obtained in a pattern in which the sensitivity is not lowered and the mechanical properties are excellent. -54 - 201224653 The use of the photosensitive resin composition of the present invention, excellent mechanical properties can be obtained in different patterns. -55-

Claims (1)

201224653 VII. Patent application scope 1. A photosensitive resin composition characterized by (A), (B), (C), (D) and (E): (A) Resin (B) Polymerizable compound (C) Polymerization initiator (D) A compound (E) having at least one group selected from the group consisting of an active methylene group and an active methine group and having a molecular weight of less than 30,000. 2. The photosensitive resin composition according to claim 1, wherein at least one selected from the group consisting of an active methylene group and an active methine group is an ethyl acetonitrile group. 3. The photosensitive resin composition according to claim 1 or 2, wherein the resin contains at least one structural unit selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and has a carbon number of 2 a copolymer of structural units of an unsaturated compound of a cyclic ether of ~4. 4. The photosensitive resin composition according to claim 1, wherein the polymerization initiator is a polymerization initiator containing an oxime ester compound. And a pattern formed by the photosensitive resin composition as recited in any one of claims 1 to 4. 6. A display device' is characterized by the type described in claim 5. -56- 201224653 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201224653 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention. :no