TW201214033A - Photosensitive resin composition - Google Patents

Abstract

A photo-sensitive resin composition, a pattern formed using the same, and a display device including the pattern are provided to include an additional polymeric resin and a polymeric compound. A photo-sensitive resin composition includes a resin, a polymeric compound, a photo-polymerization initiator, a silicon-based surfactant, and a solvent. The resin is an additional polymer containing a structural unit derived from at least one selected from a group including unsaturated carboxylic acid and unsaturated carboxylic acid anhydride and a structural unit derived from a monomer with C2 to C4 cyclic ester and C-C unsaturated double bond. The polymeric compound contains a compound two or more groups represented by chemical formula 1. In the chemical formula, the L1 is ethylene group or propane-1,2-diyl group. The p is the integer of 1 to 20.

Description

201214033 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 the field of liquid crystal display panels and the like, a photosensitive resin composition is used in order to form a photo-sensitive gap material or a protective film. In the photosensitive resin composition as described above, for example, a photosensitive resin composition containing a structural unit derived from an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride and having an epoxy resin is specifically described. A copolymer of a structural unit of a monomer having an alkyl group and a carbon-carbon unsaturated double bond, dipentaerythritol hexaacrylate, a photopolymerization initiator, and a solvent (Patent Document 1) 〇 [Patent Document 1] JP-A-2006- 1 In the photosensitive resin composition proposed in the prior art, the obtained pattern does not necessarily have sufficient flexibility and heat resistance. The present invention provides the following items [1] to [5]. [1] A photosensitive resin composition containing a resin, a polymerizable compound, a photopolymerization initiator, a polyoxynoxy surfactant, and a solvent, and the resin is an addition polymer, and the addition polymer contains a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a cyclic ether derived from carbon atoms 2 to 4 and a carbon-carbon unsaturated double-5-201214033 bond The structural unit of the monomer, the polymerizable compound contains a compound having two or more groups represented by the formula (1), and the content of the compound is 30% by mass or more based on the total amount of the polymerizable compound. Below mass%,

[In the formula (1), L1 represents an ethyl or propane-1,2-diyl group, and p represents an integer of 1 to 20]. [2] The photosensitive resin composition according to [1], wherein the content of the polyfluorene-based surfactant is 0.000% by mass or more and 0.5% by mass or less of the photosensitive resin composition. . [3] The photosensitive resin composition according to [1] or [2], wherein the structural unit derived from a monomer having a cyclic ether having a carbon number of 2 to 4 and a carbon-carbon unsaturated double bond The content is 30 mol% or more and 90 mol% or less with respect to the total amount of the structural unit in the resin. [4] A pattern formed by using the photosensitive resin composition according to any one of [1] to [3]. [5] A display device comprising the pattern as described in [4]. [Embodiment] The photosensitive resin composition of the present invention contains a resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a polyfluorene-based surfactant (D), and a solvent (E). Further, the resin (A) is an addition polymer -6 - 201214033, and the addition polymer contains at least one structural unit selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and The structural unit 'polymerizable compound having a cyclic ether having a carbon number of 2 to 4 and a carbon-carbon unsaturated double bond contains a compound having two or more groups represented by the formula (1), the compound The content is 30% by mass or more and 100% by mass or less based on the total amount of the polymerizable compound (B). Further, in the present specification, the compounds exemplified in the respective components may be used singly or in combination unless otherwise specified.

[In the formula (1), L1 represents an ethyl or propane-1,2-diyl group, and p represents an integer of 1 to 20]. The resin (A) is an addition polymer containing at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter referred to as "(a) The structural unit of the case) and the monomer (b) derived from a cyclic ether having a carbon number of 2 to 4 and a carbon-carbon unsaturated double bond (hereinafter referred to as "(b)") Construction unit. The resin (A) used for the photosensitive resin composition of the present invention is exemplified by a resin (A2-1): a copolymer obtained by polymerizing (〇) and (A2-2): (a) ), (b), monomer (c) copolymerizable with (a) and (b) (but different from (a) and (b), and the following is called "(c)") Copolymers (a) specifically include acrylic acid, methacrylic acid, crotonic acid 201214033, o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid and other unsaturated monocarboxylic acids; maleic acid , fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2 , unsaturated dicarboxylic acids such as 3,6-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]hept-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-vinyl phthalic anhydride, 4·vinyl Phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride' 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-di An anhydride of an unsaturated dicarboxylic acid such as HIMIC Anhydride; succinic acid mono [2-(methyl) propylene oxiranyl], phthalic acid An unsaturated mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid having a divalent or higher monovalent [2-(meth)acryloxyethyl] group; such as α-(hydroxymethyl) Acrylic acid, unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule, etc. From the viewpoint of copolymerization reactivity or alkali solubility, acrylic acid, methacrylic acid, and Malay are suitably used among these. In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acryl-8-201214033 acid and methacrylic acid. "(Meth)acryloyl group" and "( methyl (b) is a cyclic ether having a carbon number of 2 to 4 (selected, for example, from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring). The monomer having at least one of the group consisting of carbon-carbon unsaturated double bonds is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group. The monomer (b 1 ) having an oxirane group and a carbon-carbon unsaturated double bond (hereinafter referred to as "(b 1 )"), having an oxetane group and a carbon- a monomer having a carbon-unsaturated double bond (b2) (hereinafter referred to as "(b2)"), a single-body (b3) having a tetrahydrofuranyl group and a carbon-carbon unsaturated double bond (hereinafter referred to as "( B3)") and so on. (bl) may be a monomer (bl-Ι) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized and a carbon-carbon unsaturated double bond (hereinafter referred to as "(bl-Ι)" In the case of a monomer (bl-2) having a structure in which a cyclic unsaturated aliphatic hydrocarbon is epoxidized and a carbon-carbon unsaturated double bond (hereinafter referred to as "(bl-2)"). (bl) is preferably a monomer (b 1 ) having an oxiranyl group and a (meth) propylene fluorenyloxy group, and having a structure for epoxidizing a cyclic unsaturated aliphatic hydrocarbon with (meth) propylene A methoxy group monomer (bl-2) is preferred. When it is such a monomer, the photosensitive resin composition is excellent in storage stability. Specific examples of (bl-Ι) include glycidyl (meth) acrylate, non-methyl glycidyl (meth) acrylate, non-ethyl glycidyl (meth) acrylate, and glycidol. Vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl decyl glycidyl ether, p-vinyl-9 - 201214033 benzyl glycidyl ether, hydrazine: -methyl-o-vinyl benzyl glycidyl ether , 〇: -methyl-m-vinylbenzyl glycidyl ether, methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-dual ( Glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-gin ( Glycidoxymethyl)styrene, 2,3,5-gin (glycidoxymethyl)styrene, 2,3,6-glucone (glycidoxymethyl)styrene, 3,4, 5- cis (glycidoxymethyl) styrene, 2,4,6-glycol (glycidoxymethyl)styrene, a compound described in JP-A-H07-248625, and the like. (bl-2), vinylcyclohexene monooxide, hydrazine, 2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by DAICEL Chemical Industry Co., Ltd.), methacrylic acid 3, 4 Epoxycyclohexyl ester (for example, CYCLMER A400; manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, 丫(:1^£11^1100 ' DAICEL Chemical Industry Shares 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 independently of each other represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be substituted by a hydroxyl group, and X1 and X2 are independent of each other, and represent a single bond, -r3-, *-r3-o-, irLs-, -10- 201214033 R3 represents an alkanediyl group having 1 to 6 carbon atoms, and * represents a bonding bond with hydrazine. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group. Examples of the hydroxyalkyl group include a methylol 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-methylethyl group. 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like. The R1 and R2 are preferably a hydrogen atom 'methyl group, a methylol group, a 1-hydroxyethyl group or a 2-hydroxyethyl group. Preferred examples thereof include a hydrogen atom and a methyl group. Examples of the alkanediyl group include a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-di group. Base, hexane-1,6-diyl, and the like. Suitable examples of X1 and X2 include a single bond, a methylene group, an ethylidene group, a *-CH2-0- (* represents a bond to a fluorene bond) group, and a *-CH2CH2-0- group. Key, *-CH2CH2-0-based. The compound represented by the formula (I) may, for example, be a compound represented by the formula (1-1) to the formula (1-15). Suitable examples include formula (1-1), formula (1-3), formula (1-5), formula (1-7), formula (1-9), formula (1-11) to formula (I- 15). Preferred examples thereof are the formula (1-1), the formula (1-7), the formula (1-9), and the formula (1-15). -11 - 201214033

ο II i?

ο II 9h3o H2C=CH-C—Ο 〇2〇=ΟΗ—CΟ—CH2 H2C=CH _C —O A C2H4 H2C=CH-C—0-C2H4—ο h3o h2c=c—C-0 ch3 o I II h2c=c—c—o—ch2 H2C=C—C—O—〇2 H4

(1-13)

o II η2ο=Π-ο

H2C =CH—C—O—C2H4—S 0 II H2〇=CH—C—O—C2H4—NH CH3o I II Η2〇=0—C—0—C2H4—S CH30 I II H2C =0—C—O a C2H4-NH

(1-10) ch2oh 0 I II h2c=c-c-o

CH3o I II H2〇=C—C*—O—C2H4—o c2h4oh o h2c=c-c—o

(1-15) The compound represented by the formula (π) may, for example, be a compound represented by the formula (II-1) to the formula (11-15). Suitable formulas include formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), and formula (11-11) to formula (11). -15). Preferred examples thereof are the formula (II-1), the formula (II-7), the formula (II-9), and the formula (II-15). -12- 201214033 ?H3〇 H2C:CH—C—Ο ο II H2C:CH—C—O—CH o II h2c:ch-c-o—c2h o II Η2〇:ΟΗ—C—O—CjH Wide. Ch3 o I II h2c=c—c—o ch3 o H2C=C—C—O—CH ch3 o I II h2c=c—C—0—c2h4

/ ?h30 I II H H2C=C—C—O—C2H4—N i? (II-2) H2C:CH—C—O—C2H4—so II u H2C:CH—C—O—C2H4—N CH30 . I 11. h2c=c-c-o-c2h4-s

Η2〇=Π-〇 ch2oh 〇 I II H2〇=C-C-0

H2c=c—c—o—c2h4—〇

C2h4oh ο Η2〇=0-c one o

The compound represented by the formula (a) and the compound represented by the formula (II) may each be used singly. In addition, 'these can be mixed in any ratio. In the case of mixing, the mixing ratio is in a molar ratio, preferably a formula ( 1): Formula (II) = 5: 95 to 95: 5, preferably 1 〇: 90 to 90: 10, particularly suitable for 20: 80 to 80: 20 ° (b2) with oxetane The monomer having a (meth) propylene oxime group is preferred. (b2) may, for example, be 3-methyl-3-methylpropenyloxymethyloxetane or 3-methyl-3- Propylene methoxymethyloxetane, 3-ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane , 3-methylmethyl propyl decyloxy-13- 201214033 ethyl oxetane, 3-methyl-3-propenyloxyethyl oxetane, 3-ethyl-3 - methacryloxyethyl oxetane, 3-ethyl-3-propenyloxyethyl oxetane, etc. (b3) having tetrahydrofuranyl and (meth) acrylonitrile The monomer of the oxy group is preferred. (b3) Specifically, tetrahydrofuran methacrylate (for example, Vi) Scoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuran methyl methacrylate, etc. (c) (meth) acrylates, N-substituted maleimides, unsaturated dicarboxylic acids Acid diesters, alicyclic unsaturated compounds, styrenes, other vinyl compounds, etc. (meth)acrylates include methyl (meth)acrylate and ethyl (meth)acrylate. An alkyl ester such as n-butyl acrylate, a second butyl (meth) acrylate or a third butyl (meth) acrylate; a cyclohexyl (meth) acrylate or a 2-methyl (meth) acrylate Cyclohexyl ester, tricyclo[5.2.1.02·6]decane-8-yl (meth) acrylate (known in the art as dicyclopentyl (meth) acrylate), (methyl) a cycloalkyl ester such as dicyclopentyloxyethyl acrylate or isodecyl (meth)acrylate; a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate Alkyl esters; aryl groups such as phenyl (meth)acrylate and benzyl (meth)acrylate; and arylalkyl esters. Examples of the saturated dicarboxylic acid diester include diethyl maleate, di-14-201214033 ethyl fumarate, diethyl itaconate, etc. N-substituted maleimines may be N-phenyl. Maleidin, N. cyclohexylmaleimide, N-benzyl maleimide, N-succinimide-3-maleimide benzoate, N-amber Imino-4-maleimide butyrate, N-succinimide-6-maleimide caproate, N-ammonium imino-3-maleimide An acid ester, N-(9-acridinyl) maleimide, etc. Examples of the alicyclic unsaturated compound include bicyclo [2.2.1] hept-2-ene and 5-methyl bicyclo [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]heptane- 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-bis(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-di Ethoxy Bicyclo[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- Alkene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxy Carbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1] a bicyclic unsaturated compound such as hept-2-ene or 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene. Examples of the styrenes include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene. Examples of other vinyl compounds include (meth)acrylonitrile, vinyl chloride, -15-201214033 vinylidene chloride, (meth)acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like. From the viewpoints of copolymerization reactivity and alkali solubility, '(c) is styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmalayiya An amine, a bicyclo[2.2.1]hept-2-ene or the like is preferred. Among the resins (A2-1), the ratio of the structural unit derived from each monomer is preferably in the following range with respect to the total number of moles of the structural unit constituting the resin (A2-1): The structural unit of (a): preferably 5 to 60 mol%, preferably 10 to 50 mol%, of the structural unit derived from (b); preferably 40 to 95 mol%, preferably 50 When the ratio of the structural unit of the resin (A2-1) is in the above range, the storage stability and development properties of the photosensitive resin composition and the solvent resistance, heat resistance and mechanical strength of the obtained pattern are 90%. There is a tendency to get better. Resin (A2-1) can be referred to, for example, the "Experimental Method for Polymer Synthesis" (produced by Otsuka, published by: Chemical Co., Ltd., 1st edition, 1st brush, issued March 1, 1927). The method is produced by the method described in the literature. Specifically, a method in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and deoxidation is performed by replacing oxygen with nitrogen, and stirring, heating, Keep warm. Further, the polymerization initiator, solvent and the like used herein are not particularly limited, and any of the substances generally used in the field can be used. For example, the polymerization initiator can be listed as a 16-201214033 azo compound (2,2·-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylhumulonitrile), etc.) In the case of the organic peroxide (such as benzamidine peroxide), the solvent may be one which dissolves each monomer, and the solvent of the photosensitive resin composition may be a solvent or the like described later. Further, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, and a solid (powder) may be taken out by a method such as reprecipitation. In particular, by using the same solvent as the solvent (E) described later in the polymerization, the solution after the reaction can be used as it is, and the production step can be simplified. Among the resins (A2-2), the ratio of the structural unit derived from each monomer is preferably in the following range with respect to the total number of moles of all structural units constituting the resin (A2-2): (a) The structural unit: preferably 2 to 40 mol%, preferably 5 to 35 mol%. The structural unit derived from (c): preferably 1 to 65 mol%, preferably 1 to 60 mol. The ear % is derived from the structural unit of (b): preferably 2 to 95 mol %, preferably 5 to 80 mol %, and the ratio of the structural unit of the resin (A2-2) is in the above range, then the photosensitive resin The storage stability and development properties of the composition and the solvent resistance, heat resistance and mechanical strength of the obtained pattern tend to be improved. The resin (A2-2) is preferably a resin in which (b) is (b1), and (b) is (b1 -1). The resin (A2-2) can be produced by the same method as the resin (A2-1). -17-201214033 Resin (A) is preferably a resin (A2-1), and (b) is a resin of (b 1 ) ( A2-1) is preferable, and (b) is a resin (A2-1) of (bl-2). When it is such a resin, the storage stability and development properties of the photosensitive resin composition and the solvent resistance, heat resistance and mechanical strength of the obtained pattern are excellent. The weight average molecular weight of the resin (A) in terms of polystyrene It is preferably 3,000 to 10,000,000, preferably 5,000 to 50,000, more preferably 5,000 to 25,000, even more preferably 5,000 to 15,000. When the weight average molecular weight of the resin (A) is in the above range, the coating property tends to be excellent, and at the time of development, film loss in the exposed portion is less likely to occur, and it is easy to remove the non-exposed portion by image development. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (?η)] of the resin (A) is preferably from 0.1 to 6.0, preferably from 1.2 to 4.0, more preferably from 1.5 to 3.0, even more preferably from 1.7 to 1.7. 2.7. When the molecular weight distribution is in the above range, the development property tends to be excellent. The acid value of the resin (Α) is usually 20 to 150 mgKOH/g, preferably 40 to 1 35 mgKOH/g, preferably 50 to 135 mg KOH/g. Here, the acid value is determined by measuring the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (A), and it 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, preferably from 20 to 80% by mass, particularly preferably from 40 to 60% by mass based on the total amount of the resin (A) and the polymerizable compound (B). %. Further, in the solid content of the photosensitive resin composition, the cyclic ether equivalent is adjusted so that the resin (A) is from 3 50 to 1 500, and -18 to 201214033 is preferably from 55 to 1200. The amount of the structure and the content of the resin (A) in the photosensitive resin composition are preferably. The cyclic ether equivalent is a mass of a photosensitive resin composition containing lg equivalents of a cyclic ether, and can be obtained, for example, according to the test method specified in JIS K7236. When the content of the resin (A) is in the above range, the developability of the photosensitive resin composition tends to improve the adhesion, solvent resistance and mechanical properties of the obtained pattern. Here, the solid content means the amount by which the solvent (E) is subtracted from the photosensitive resin composition. The polymerizable compound (B) is a compound which can be polymerized by living radicals generated by the polymerization initiator (C). The polymerizable compound (B) contains a compound having two or more groups represented by the formula (1) (hereinafter referred to as "polymerizable compound (B 1 )"), and the content of the compound is relative to the polymerizable compound. The total amount of (B) is 30% by mass or more and 100% by mass or less.

[In the formula (1), L1 represents an ethyl or propane-1,2-diyl group, and p represents an integer of 1 to 20]. In the photosensitive resin composition of the present invention, a polymerizable compound (B1) is contained, and a pattern excellent in flexibility can be obtained. The softness of the pattern can be determined by the total amount of displacement measured by a micro hardness tester. When the liquid crystal display device is placed in a low temperature environment, the internal pressure of the liquid crystal cell decreases as the volume of the liquid crystal layer shrinks, and a problem such as generation of bubbles in the liquid crystal cell occurs. When a pattern having excellent flexibility is used as the photosensitive gap material, the pattern -19-201214033 is deformed in accordance with the volume shrinkage of the liquid crystal layer, so that the decrease in the internal pressure of the liquid crystal cell can be suppressed, and the generation of bubbles can be suppressed. In the group represented by the formula (1), p is from 1 to 20, preferably from 1 to 18, preferably from 1 to 15. The number of the group represented by the formula (1) which the polymerizable compound (B 1 ) has is 2 or more, and more preferably 3 or more. The total of the structures represented by the formula (1) and represented by -0-L1 is the sum of p contained in the group represented by each formula (1) of the polymerizable compound (B1). In the polymerizable compound (B 1 ), 2 to 40 is preferred, and 6 to 20 is preferred. The polymerizable compound (B 1 ) may be a polyol compound which is subjected to ethylene oxide denaturation (hereinafter referred to as "EO denaturation") or propylene oxide denaturation (hereinafter referred to as "PO denaturation") ( Methyl) acrylates. Ethylene oxide denaturation means that -(CH2CH20)p-H is added to a hydroxyl group, and a structure represented by -〇-(CH2CH20)p-H is imparted. The propylene oxide variability is the same as described above, and means a structure represented by -0-(CH2CH(CH3)0)p-H or -0-(CH(CH3)CH20)p-H. Examples of the above polyol compound include butanediol, neopentyl glycol, tricyclodecane dimethanol, bisphenol A, bis(2-hydroxyethyl)isocyanurate, trimethylolpropane, pentaerythritol, and dipentaerythritol. , three pentaerythritol, and the like. Examples of the polymerizable compound (B 1 ) include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, EO-denatured butanediol di(meth)acrylate, and EO-denatured neopenta-2. Di(meth)acrylate of alcohol, bis(meth)acrylate of EO-denatured tricyclodecane dimethanol, bis(meth)acrylate of EO-denatured bisphenol A, EO denaturing ginseng (2- -20- 201214033 Tris(meth)acrylate of hydroxyethyl)isocyanurate, tri(meth)acrylate of EO-denatured trimethylolpropane, tri(meth)acrylate of EO-denatured pentaerythritol, EO-denatured pentaerythritol Tetra (meth) acrylate ' EO denatured dipentaerythritol hexa (meth) acrylate, EO denatured pentaerythritol seven (meth) acrylate, PO modified butane diol di (meth) acrylate, PO Di(meth) acrylate of denatured neopentyl glycol, di(meth) acrylate of PO modified tricyclodecane dimethanol, di(meth) acrylate of PO denatured bisphenol A, PO denatured ginseng ( 2 -hydroxyethyl)isocyanurate tris(meth)acrylate PO modified trimethylolpropane tris(meth)acrylate, EO modified pentaerythritol tri(meth)acrylate, PO modified pentaerythritol tetrakis(meth)acrylate, PO denatured dipentaerythritol hexa(methyl) Acrylate, EO modified heptaerythritol, hepta(meth)acrylate, and the like. KAYARAD DPEA-12C Nippon Kayaku Co., Ltd. can also be used; SR415, SR454, SR492, SR492, SR499, CD501 'SR502, SR9020, CD9021, SR9035, SR480, CD540, SR9036 (above is Sartomer), EBECRYL11 (manufactured by DAICEL CYTEC Co., Ltd.); Light Acrylate 9EG-A and commercially available products such as 4E9-A and TMP-6EO-3 A (manufactured by Kyoeisha Chemical Co., Ltd.) of the same product type. The polymerizable compound (B) may also contain a polymerizable compound different from the polymerizable compound (B 1 ) (hereinafter referred to as "polymerizable compound (B2)"). The polymerizable compound (B2) may, for example, be a compound having a polymerizable carbon-carbon unsaturated bond, and is preferably a (meth)acrylate compound-21 - 201214033. The polymerizable compound (B2) having one polymerizable carbon-carbon unsaturated bond may, for example, be a compound exemplified in the above (a), (b) and (c), and among them, a (meth) acrylate is preferred. Examples of the polymerizable compound (β2 ) having two polymerizable carbon-carbon unsaturated bonds include 1,3-butylene glycol di(meth)acrylate and 1,3-butylene glycol (meth)acrylate. , 6-hexanediol di(meth)acrylate, bisphenol A bis(acryloxyethyl)ether, ethoxylated bisphenol A di(meth)acrylate, 3-methylpentyl Glycol di(meth)acrylate or the like. The polymerizable compound (B2) having three or more polymerizable carbon-carbon unsaturated bonds may be exemplified by trimethyl methacrylate tris(meth) acrylate vinegar or pentaerythritol tris(meth) acrylate ginseng (2 - Hydroxyethyl)isocyanurate tris(meth)acrylate, propoxylated trimethylolpropane tris(meth)acrylate 'pentaerythritol tetra(meth)acrylate, dipentaerythritol five (a) Acrylate, dipentaerythritol hexa(meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (methyl) propionate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol Reaction product of (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol di(meth) acrylate vinegar with an acid anhydride, dipentaerythritol penta (methyl) propylene vinegar and an acid anhydride Reaction product of tripentaerythritol hepta (meth) acrylate with an acid anhydride, caprolactone denatured trimethyl methacrylate tri(meth) acrylate, caprolactone denatured pentaerythritol tri (meth) acrylate, caprolactone denaturation (2-hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone denatured pentaerythritol tetrakis(methyl)propane vinegar-22- 201214033, caprolactone denatured dipentaerythritol penta (methyl) Acrylate, caprolactone denatured dipentaerythritol hexa(meth) acrylate, caprolactone denatured tripentaerythritol tetra (meth) acrylate, caprolactone denatured tripentaerythritol penta (meth) acrylate, caprolactone denature Pentaerythritol hexa(meth) acrylate, caprolactone denatured tripentaerythritol hepta (meth) acrylate, caprolactone denatured tripentaerythritol octa (meth) acrylate, caprolactone denatured pentaerythritol tri(meth) acrylate and The reaction product of an acid anhydride, a reaction product of caprolactone-denatured dipentaerythritol penta (meth) acrylate and an acid anhydride, caprolactone-denatured tripentaerythritol hepta (meth) acrylate, an acid anhydride, and the like. Among them, monomers having more than 3 functions are preferred, and dipentaerythritol hexa(meth)acrylate is preferred. The content of the polymerizable compound (B 1 ) is 30% by mass or more and 100% by mass or less based on the total amount of the polymerizable compound (B), and is preferably 50% by mass or more and 100% by mass or less, and preferably 75% by mass or more. 100% by mass or less. When the content of the polymerizable compound (B1) is within the above range, the flexibility of the obtained pattern tends to be high. The content of the polymerizable compound (B) is preferably from 5 to 95% by mass, preferably from 20 to 80% by mass, based on the total amount of the resin (A) and the polymerizable compound (B). Further, in the solid content of the photosensitive resin composition, the content of the polymerizable compound (B) is preferably adjusted so that the polymerizable carbon-carbon unsaturated bond equivalent is 300 to 1,000, and preferably 350 to 7 50. . The polymerizable carbon-carbon unsaturated bond equivalent represents the mass of the solid component of the photosensitive resin composition containing lg equivalent of a carbon-carbon unsaturated bond. The polymerizable carbon-carbon unsaturated bond equivalent can be obtained by measuring, for example, an infrared absorption spectrum, an absorption peak derived from a carbon-carbon unsaturated bond contained in the solid content of the photosensitive resin composition of -23 to 201214033 (for example, an acrylic group) The number of carbon-carbon unsaturated bonds obtained by the strength of 8 1 OcnT1) and the mass of the solid content of the photosensitive resin composition were calculated. When the content of the polymerizable compound (B) is in the above range, the sensitivity, the smoothness, and the reliability of the obtained pattern tend to be improved. The photosensitive resin composition of the present invention preferably contains a polymerization initiator (C). The polymerization initiator (C) is not particularly limited as long as it is a compound which can initiate polymerization by the action of light or heat, and a known polymerization initiator can be used. The polymerization initiator (C) may, for example, be an acetophenone compound, a biimidazole compound, a triazine compound, a mercaptophosphine oxide compound or an anthracene compound. Further, a photo-and/or thermal cationic polymerization initiator (for example, an anion derived from a key cation and an anion derived from Lewis acid) described in JP-A-2008-181087 can be used. Among them, at least one selected from the group consisting of a biimidazole compound, an acetophenone compound and an anthracene compound is preferred, and an acetophenone compound is particularly preferred. If these polymerization initiators are used, they tend to have high sensitivity, and are suitable. The acetophenone compound may, for example, be diethoxyacetophenone, 2-hydroxy-2-methyl-1_phenylpropan-1-one, benzyldimethylketal, 2-hydroxyl-[[ 2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 2-hydroxy-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]-phenyl 2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone '2-morpholinyl-1-(4-methylsulfonylphenyl)-2-methylpropan-1-one, 2·Benzyl-2-dimethylamino-1-(4-?-24- 201214033 phenylphenyl)butan-1-one, 2-dimethylamino-2-(2-methyl Benzyl)-1-(4-morpholinylphenyl)butan-1-one, 2-dimethylamino-2-(3-methylbenzyl)-1-(4-morpholinylbenzene Butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)butan-1-one, 2-dimethyl Amino-2-(2-ethylbenzyl)-1-(4-morpholinylphenyl)butane-1-anthracene, 2-dimethylamino-2-(2-propylbenzyl) )-1-(4-morpholinylphenyl)butan-1-one, 2-dimethylamino-2-(2-butylbenzyl)-1-(4-morpholinylphenyl) Butan-1-one, 2-dimethylamino-2-(2,3-dimethylbenzyl)-(4-morpholinylphenyl) 1-ketone, 2-dimethylamino-2-(2,4-dimethylbenzyl)-1-(4-morpholinylphenyl)butan-1-one, 2-dimethyl Amino-2-(2-indolyl)-1-(4-mercapto-based) butyl-1-pyrene, 2-dimethylamino-2-(2-bromobenzyl)-1- (4-morpholinylphenyl)butan-1-one, 2-dimethylamino-2-(3-chloroindolyl)-1-(4-morpholinylphenyl)butane-butanone 2-Dimethylamino-2-(4-chlorobenzyl)-1-(4-morpholinylphenyl)butan-1-one, 2-dimethylamino-2-(3- Bromobenzyl)-1-(4-morpholinylphenyl)butan-1-one, 2-dimethylamino-2-(4-bromobenzyl)-1-(4-morpholinylbenzene Butane-1-one, 2-dimethylamino-2-(2-methoxybenzyl)-1-(4-morpholinylphenyl)butan-1-one, 2-di Methylamino-2-(3-methoxybenzyl)-1-(4-morpholinylphenyl)butan-1-one, 2-dimethylamino-2-(4-methoxy Benzyl)-1-(4-morpholinylphenyl)butan-1-one, 2-dimethylamino-2-(2-methyl-4-methoxybenzyl)-1- (4-morpholinylphenyl)butan-1-one, 2-dimethylamino-2-(2-methyl-4-bromobenzyl)-1-(4-morpholinylphenyl) Butane-buxoton, 2-dimethylamino-2- (2-bromo-4-methoxybenzyl)-1-(4-morpholinylphenyl)butan-1-one, -25- 201214033 2-yl-2-methyl-丨-[4_ (丨-methylvinyl) phenyl]propane-fluorenone ketone oligomer or the like. The biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4,5,5-tetraphenylbiimidazole, 2,2,_bis(2 3 ·dichlorophenyl) _ 4,4,5,5-tetraphenyl bismuth (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2, bis(2-chlorophenyl)-4 '4',5,5·-tetraphenylbiimidazole, 2,2,-bis(2·chlorophenyl)_tetrakis(alkoxyphenyl)biimidazole, 22,_bis(2chlorophenyl) -4,4',5,5|-tetrakis(dialkoxyphenyl)biimidazole, 2,2,_bis(2-chlorophenyl)-4,4',5,5,-tetrakis Oxyphenyl)biimidazole (see, for example, Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204, etc.), alkoxycarbonyl group at the 4, 4, 5, 5-position of a phenyl group A substituted imidazole compound (see, for example, Japanese Patent Laid-Open Publication No. Hei 7-10913). Suitable examples are 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 triazine compound may, for example, be 2,4·bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloromethyl). -6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6_(4-methoxystyryl)-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]-nt triazine, -26- 201214033 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-trimethylbenzoguanidinium diphenylphosphine oxide. The above hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylsulfonylphenyl)butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenyl Propane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfonylphenyl)octane-1-one-2-imine, N-ethoxycarbonyl- L-[9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine, N-ethyloxyl-l-[9- Ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolanylmethoxy)benzylidenyl}-9H-indazol-3-yl ] Ethyl-1-imine and the like. Commercial products such as IRGACURE OXE-01, OXE-02 (above, Chiba Japan) and N-1919 (made by ADEKA) can also be used. Further, the polymerization initiator (C) may, for example, be a benzoin compound such as benzoin, benzoin methyl ether, benzoin acetic acid, benzoin isopropyl ether or benzoin isobutyl ether; diphenyl ketone, methyl phthalate benzoate, 4-phenyldiphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3,,4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone a diphenyl ketone compound such as 2,4',6-trimethyldiphenyl ketone; an oxime compound such as 9,10-phenanthrenequinone or 2-ethylhydrazine, '10-butyl-2-chloroindole丫D ketone, sulfhydryl, phenylacetate methyl vinegar, titanocene compound, and the like. These are preferably used in combination with a polymerization initiation aid (C丨) described later. Further, as the polymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-A-2002-44205 can also be used. -27- 201214033 The above-mentioned polymerization initiator having a group capable of causing chain transfer, for example, a compound of the following formulas (a) to (f): [Chemical 7] c〇〇^_S such as a female soil G〇(8) C4H9 —S—CH2 —C—Ο '—Lh.

—CH2—S

Φ) C4H9—S—(ΙΉ2 (c)

The above polymerization initiator having a group capable of causing chain transfer can also be used as the component (c) constituting the resin (A). Among the photosensitive resin compositions of the present invention, a polymerization initiation aid (C1) can be used together with the above polymerization initiator (C). The polymerization initiation aid (C 1 ) is preferably formed by using the compound represented by the formula (III) 201214033.

(m) R4 [In the formula (III), the dotted line indicated by W1 represents an aromatic ring having a carbon number of 6 to 12 which may be substituted by a halogen atom; Y1 represents -0- or -S-; and R4 represents a carbon number of 1 to 6 A monovalent saturated hydrocarbon group; R5 represents a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a halogen atom or an aromatic group j having a carbon number of 6 to 12 which may be substituted by a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. 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. Cyclo, hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dioxin ring, phenylbenzene ring, chlorophenyl benzene ring, bromophenyl benzene ring, naphthalene ring, chlorine Naphthalene ring, bromine ring, and the like. Examples of the i-valent saturated nicotyl group having 1 to 6 carbon atoms include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-methylpropyl, 2-methylpropyl, and t-butyl groups. , n-pentyl, i•methylbutyl, 2-methylbutyl, 3-methylbutyl, ^-dimethylpropyl, dimethylpropyl, 2,2•dimethylpropyl, Is n-hexyl, cyclohexyl and the like. a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a halogen atom, and -29 to 201214033, for example, a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms as described above, in addition to a heptyl group, an octyl group, a decyl group or a fluorenyl group. , undecyl, dodecyl, 1-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 phenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, chlorobromophenyl, biphenyl or chlorobiphenyl. , dichlorobiphenyl, bromophenyl, dibromophenyl, naphthyl, chloronaphthyl, dichloronaphthyl, bromonaphthyl, dibromonaphthyl and the like. Specific examples of the compound represented by the formula (ΙΠ) include: 2-[2-oxo-2-(2-phenyl)ethylidene]-3-methylnaphtho[2,1-<1] Thiazoline, 2-[2-oxo-2-(2-phenyl)ethylidene]-3-methylnaphtho[1,2-(1]thiazoline, 2-[2-oxo-2 -(2-phenyl)ethylidene]-3-methylnaphtho[2,3-d]thiazoline, 2-[2-oxo-2-(2-naphthyl)ethylene]-3 -methylbenzothiazoline, 2-[2-oxo-2-(1-naphthyl)ethylidene]-3-methylbenzothiazoline, 2-[2-oxo-2-( 2 -naphthyl)ethylidene]-3-methyl-5-phenylbenzothiazoline, 2-[2-oxo-2-(1-naphthyl)ethylidene]-3-methyl-5 -Phenylbenzothiazoline, 2-[2-oxo-2-(2-naphthyl)ethylidene]-3-methyl-5-fluorobenzothiazoline, 2-[2-oxo- 2-(1-Naphthyl)ethylidene]-3-methyl-5-fluorobenzothiaporphyrin, 2-[2-oxo-2·(2-naphthyl)ethylene]-3- Methyl-5-chlorobenzothiazoline, 2-[2-oxo-2-(1-naphthyl)ethylidene]-3-methyl-5-chlorobenzothiazoline, 2-[2- Oxo-2-(2-naphthyl)ethylidene]-3-methyl-5-bromobenzothiazoline, 2-[2-oxo-2-(1-naphthyl)ethylene]- 3-methyl-5-bromobenzothiazoline, 2-[2-oxygen -2- (4-phenylphenyl)ethylidene 3-methylbenzothiazoline, 2-[2-oxo-2-(4-phenylphenyl)ethylidene 3-methyl -5-phenylbenzothiazoline, 2-[2-oxo-2-(2-naphthyl) -30-201214033 ethyl]-3-methylnaphtho[2, ld]thiazoline, 2 -[2-oxo-2-(2-naphthyl)ethylidene]-3-methylnaphtho[l,2-d]thiazoline, 2-[2-oxo-2-(4-benzene Phenyl)ethylidene]-3-methylnaphtho[2,1-d]thiazoline, 2-[2-oxo-2-(4-phenylphenyl)ethylidene-3- Methylnaphtho[l,2-d]thiazoline, 2-[2-oxo-2-(4-fluorophenyl)ethylidene]-3-methylnaphtho[2,1-d]thiazole Porphyrin, 2_[2-oxo-2-(4-fluorophenyl)ethylidene]-3-methylnaphtho[I,2-d]thiazoline, 2-[2-oxo-2-( 2-phenyl)ethylidene]-3-methylnaphtho[2,1-d]oxazoline, 2-[2-oxo-2-(2-phenyl)ethylidene-3- Methylnaphtho[1,2-«1]oxazoline, 2-[2-oxo-2-(2-phenyl)ethylidene]-3-methylnaphtho[2,3-d] Spirooxazoline, 2-[2-oxo-2-(2-naphthyl)ethylidene]-3-methylbenzoxazoline, 2-[2-oxo-2-(1-naphthyl) Ethylene]-3-methylbenzooxazolin, 2-[2-oxo-2-(2-naphthyl)ethylene ]-3-methyl-5-phenylbenzoxazole, 2-[2-oxo-2-(1-naphthyl)ethylidene]-3-methyl-5-phenylbenzoquinone Oxazoline, 2-[2-oxo-2-(2-naphthyl)ethylene]-3_methyl_5-fluorobenzoxazoline, 2-[2_oxo_2_ ( 1- Naphthyl)ethylidene 3-methylfluorobenzoxazoline, 2-[2.oxo-2-(2-naphthyl)ethylidene]-3-methyl-5-gas benzoxanthene Porphyrin, 2_[2_oxo-2_(1-naphthyl)ethylidene]methyl-5-chlorobenzoxazoline, 2-[2-oxo-2-(2-naphthyl)-ethylidene ]]-3-methyl-5-bromobenzooxorphyrin, 2_[2-oxo-2_(1-naphthyl)ethylene b 3_methyl·5-bromobenzoxazoline, 2- [2-oxo-2-(4-phenylphenyl)ethylidene]_3_methylbenzoxazoline, 2-[2-oxo-2-(4-phenylphenyl)-ethylene 3-methyl-5-phenylbenzoxazoline, 2_[2_oxo-2-(1-naphthyl)ethylidene]-3-methylnaphtho[2,1-d] Oxazoline, 2-[2-oxo-2-(1-naphthyl)ethylidene]-3-methylnaphtho[l,2_d]oxazoline, 2-[2-oxo-2- (4-Benzene-31 - 201214033 phenyl)ethylene]-3-methylnaphtho[2,ld]oxazoline, 2-[2-oxo-2-(4-phenylphenyl) Ethylene]_3-methylnaphtho[l,2-d] Oxazoline, 2-[2-oxo-2-(4-fluorophenyl)ethylidene]-3-methylnaphtho[2, Ι-d]oxazoline, 2-[2-oxo- 2-(4-fluorophenyl)ethylidene]-3-methylnaphtho[1,2-(1]oxazoline, etc. In addition, the polymerization initiation aid (C1) can also be of the formula (IV) Or a compound represented by the formula (V). 【化9】

[In the formulae (IV) and (V), the ring W2, the ring W3 and the ring W4 are independent of each other' represents an aromatic ring having 6 to 12 carbon atoms or a heterocyclic ring having 2 to 10 carbon atoms which may be substituted by a halogen atom; Y2~ Y5 is independent of each other, and represents -〇- or _3-; r6~r9 represents a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic group having 6 to 12 carbon atoms, and the saturated hydrocarbon group and the hydrogen atom contained in the aromatic group may be The aromatic ring having a carbon atom of 6 to 12 may be substituted by a halogen atom, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms. The same aromatic ring of the formula (ΙΠ) may be used as the hydrogen atom contained in the aromatic ring. Examples of the heterocyclic ring having 2 to 10 carbon atoms which may be optionally substituted by a halogen atom as described above and which may be substituted by a halogen atom include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a pyran ring and the like. The saturated hydrocarbon group substituted with a monovalent hydroxy group may, for example, be a hydroxymethyl group, a hydroxyethyl group, a -32-201214033 hydroxypropyl group or a hydroxybutyl group. Examples of the aryl group substituted with a hydroxy group include a hydroxyphenyl group, a hydroxynaphthyl group and the like. The monovalent alkoxy-substituted saturated hydrocarbon group may, for example, be a methoxymethyl 'methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a butoxymethyl group, an ethoxyethyl group or an ethoxy group. Examples of the aryl group substituted by an alkoxy group such as a propyl group or a propoxy butyl group include a methoxyphenyl group and 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. Alkoxynaphthalenes; 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10- Diethoxy ruthenium, dipropoxy ruthenium, diisopropoxy ruthenium, dibutoxy ruthenium, dipentyl oxime, dihexyloxy ruthenium, methoxy ethoxy ruthenium, methoxy propylene oxide Base, methoxyisopropoxy oxime, methoxybutoxy oxime, ethoxy propoxy oxime, ethoxyisopropoxy oxime, ethoxybutoxy oxime, propoxy isopropyl a dialkoxy oxime such as oxindole, propoxy oxybutoxy fluorene or isopropoxy butyl hydrazine; dimethoxytetracene, diethoxytetracene, dipropoxy and tetra Further, a dialkoxytetracene group such as benzene, diisopropoxytetracene or dibutoxytetracene may be used, and a thioxanthone compound may also be used as the polymerization initiator (C1). The thioxanthone compound may, for example, be 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone and the like. Further, the polymerization initiation aid (c 1 ) may, for example, be an amine compound or a carboxylic acid compound. Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-di Methylamino benzoic acid isoamyl ester, 4-dimethylamino benzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)diphenyl ketone (commonly known as micbutone), 4,4'-bis(diethylamino)diphenyl ketone-like aromatic amine compound. The carboxylic acid compound may, for example, be benzosulfonyl acetic acid, methyl benzene sulfonyl acetic acid, ethyl benzene sulfonyl acetic acid, methyl ethyl benzene sulfonyl acetic acid, dimethyl benzene sulfonyl acetic acid or methoxy benzene sulfonate. Acetic acid, dimethoxybenzenesulfonyl acetic acid, chlorobenzenesulfonyl acetic acid, dichlorobenzenesulfonyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthyl An aromatic hetero atom such as aminic acid or naphthyloxyacetic acid. A suitable combination of the polymerization initiator (C) and the polymerization initiation aid (C 1 ) is exemplified by an acetophenone compound, a thioxanthone compound, an acetophenone compound, and an aromatic amine compound. Specifically, is it 2-? Lolinyl-1-(4-methylsulfonylphenyl)-2-methylpropan-1-one and 2,4-diethylthioxanthone, 2-dimethylamino-2-benzyl 1-(4-morpholinylphenyl)butan-1-one with 2,4-diethylthioxanthone, 2-dimethylamino-2-(4-methylbenzyl)-1 -(4-morpholinylphenyl)butan-1-one with 2,4-diethylthioxanthone, 2-morpholinyl-1-(4-methylsulfonylphenyl)-2- Methylpropane-1·one and 2-isopropylthioxanthone with 4-isopropylthioxanthone, 2-morpholinyl-1-(4-methylsulfonylphenyl-34-201214033)- 2-methylpropan-1-one with 4,4'-bis(diethylamino)diphenyl ketone, 2-dimethylamino-2-benzyl-1-(4-morpholinylbenzene Butane-1-one and 4,4'-bis(diethylamino)diphenyl ketone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4) -morpholinylphenyl)butan-1-one and 4,4'-bis(diethylamino)diphenyl ketone. The combination of the polymerization initiator (C) and the polymerization initiation aid (C 1 ) is preferably a combination of an acetophenone compound and a thioxanthone compound, 2-morpholinyl·1-4-methylsulfonate. Phenyl)-2-methylpropan-1-one with 2,4-diethylthioxanthone, 2-morpholinyl-1-(4-methylsulfonylphenyl)-2-methyl Propane-1-one and 2-isopropylthioxanthone and 4-isopropylthioxanthone are preferred. According to these combinations, a pattern having high sensitivity and high visible light transmittance can be obtained. The content of the polymerization initiator (C) is preferably from 0.5 to 30% by mass, preferably from 1 to 20% by mass, more preferably from 1 to 20% by mass based on the total amount of the resin (A) and the polymerizable compound (B). 10% by 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 polymerization initiator (C1) to be used is preferably 0.1 to 10% by mass, and more preferably 0.3 to 7% by mass based on the total amount of the resin (A) and the polymerizable compound (B). When the amount of the polymerization initiation aid (C1) is within the above range, the pattern can be obtained with high sensitivity, and the obtained pattern shape is good. The photosensitive resin composition of the present invention contains a polyfluorene-based surfactant (D). The polyoxo-based surfactant may be an interface active agent having a siloxane coupling. Specifically, TORAY SILICONE DC3PA and the same -35-201214033 product type SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA; polyether modified eucalyptus SH8400 (trade name: Toray Dow Corning Co., Ltd.), KP321, KP322 , KP323 'KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF43 00, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.) The fluorene-based surfactant (D) is 0.0001% by mass or more and 0.05% by mass or less based on the photosensitive resin composition, and is preferably 0.0005 mass% or more and 0.04 mass% or less, more preferably 0.001 mass% or more and 0.03 mass%. %the following. By containing the surfactant in this range, it is possible to suppress unevenness during coating and unevenness during development, and to improve the flatness of the coating film. When the flatness of the coating film is good, when a plurality of patterns are formed on the same substrate, the variation in height between the patterns can be reduced. The photosensitive resin composition of the present invention contains a solvent (E). The solvent which can be used in the present invention may be, for example, an ester solvent (a solvent containing _C Ο Ο -), an ether solvent other than an ester solvent (a solvent containing - 〇-), an ether ester solvent (including -C Ο Ο - and - a solvent of hydrazine - a ketone solvent (solvent containing -C 0 -) other than an ester solvent, an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine, etc. are selected and used. Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acid ester, isoamyl acetate, and propionic acid. Butyl ester, isopropyl butyrate, ethyl butyrate-36- 201214033, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexanol acetate , 7-Ding, etc. Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol ether, and diethylene glycol monobutyl ether. , propylene glycol monomethyl ether, propylene glycol monoethyl ether glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-yl-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether ethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether , anisole, etc. Examples of the ether ester solvent include methyl methoxyacetate, butyl methoxyacetate acetate, methyl ethoxyacetate, methyl ethoxyacetate methoxypropionate, and 3-methoxy group. Ethyl propionate, 3-ethoxypropionic acid, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxyethyl ester, propyl 2-methoxypropionate , 2-ethoxypropionic acid methyl ester, 2-ethylpropionic acid ethyl ester, 2-methoxy-2-methylpropionic acid methyl ester, 2-ethoxy-2-propionic acid ethyl ester, 3-methyl Oxybutyl butyl acetate, 3-methyl-3-methoxybutyrate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, alcohol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, Ethylene glycol monoacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether ketone ketone solvent can be cited as 4-hydroxy-4-methyl-2-pentanone, acetone, Ια 2-g Ketone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone 'ethyl lactone diol monoethyl'-propylmethoxyethyl methyl ester, '3-methyl ester propionic acid Butanone such as oxymethyl acetoacetate, cyclo-37-201214033 hexanone, isophorone, and the like. Examples of the alcohol solvent include methanol, ethanol, propanol, alcohol, ethylene glycol, propylene glycol, and glycerin. Examples of the aromatic hydrocarbon solvent include benzene, toluene and a dimethylamine solvent, and examples thereof include N,N-dimethylformamide and N-methylpyrrolidone. These solvents may be used singly or in the form of coating properties and drying properties, and the boiling point of the above lamat is 120 ° C or more and 180 ° C or less, wherein propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate B An ester, diethylene glycol methyl ethyl ether, 3-methoxymethoxy-1-butanol or the like is preferred. In the solvent (E) resin composition, the solvent (E) resin composition in the flat photosensitive resin composition of the coating film is preferably 60 to 95% by mass, %. In other words, the solid content % of the photosensitive resin composition is preferably from 1 〇 to 30% by mass. The solvent (E) is a film coated with a photosensitive resin composition. Further, the photosensitive resin composition of the present invention is a functional thiol compound (T). A compound having two or more sulfonyl groups in a polyfunctional thiol group. In particular, the sensitivity of the photosensitive resin composition of the present invention derived from a carbon atom bonded to an aliphatic hydrocarbon group is a polyfunctional thiol compound (T), specifically, butanol, hexanol, cyclohexane toluene, trimethylbenzene or the like. Amine, hydrazine, hydrazine-dimethyl ethane are used in combination. Among the solvents mentioned above, an organic solvent is preferred. The acid ester, 3-ethoxypropyl butyl acetate, and the like are excellent in suppressing the solubility. The content is preferably from 70 to 90% by mass based on the photosensitive material. The content of the component is preferably from 5 to 40%, and the flatness is high in the above-mentioned range. Further, it is also possible to further contain a poly-t-compound (Τ), which means that if a compound having two sulfonyl groups is used, it tends to become high. Examples thereof include hexanedithiol-38-201214033, decanedithiol, 1,4-bis(methylsulfonyl)benzene, butanediol bis(3_sulfonylpropionate), butanediol (3-sulfonyl acetate), ethylene glycol bis(3-sulfonyl acetate), trimethylolpropane ginseng (3-propionic acid acetate), butanediol bis(3-sulfonyl) Propionate), trimethylolpropane ginseng (3-sulfonylpropionate), trimethylolpropane ginseng (3-sulfonylacetate), pentaerythritol bismuth (3-sulfonylpropionate) , pentaerythritol bismuth (3. sulfonyl acetate), hydroxyethyl ginseng (3-sulfonylpropionate), pentaerythritol bismuth (3-sulfonylbutyrate), 1,4-bis(3- The content of the sulfonylbutoxy)butane polyfunctional thiol compound (T) is preferably from 0.1 to 10% by mass, preferably from 0.5 to 7% by mass, based on the polymerization initiator (C). When the content of the polyfunctional thiol compound (Τ) is in the above range, the photosensitive resin composition tends to have high sensitivity and high developability, and therefore it is suitable for the photosensitive resin composition of the present invention. Various additives such as a chelating agent, other polymer compound, adhesion promoter, antioxidant, ultraviolet absorber, light stabilizer, and chain transfer agent may be used as necessary. The photosensitive resin composition of the present invention does not substantially contain a coloring agent such as a pigment or a dye. In the photosensitive resin composition of the present invention, the content of the colorant relative to the entire composition is preferably less than 1% by mass', preferably less than 0.5% by mass. In the case where the photosensitive resin composition of the present invention is charged to a quartz cell having an optical path length of 1 cm and a transmittance is measured using a spectrophotometer at a measurement wavelength of 400 to 700 nm, the average transmittance is preferably 70%. The above is preferably 80% or more. -39- 201214033 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, and further 95%. The above is preferred. The average transmittance is a coating film having a thickness of 3 μm after being subjected to heat curing (for example, curing at a temperature of 100 to 250 ° C for 5 minutes to 3 hours) using a spectrophotometer at a measurement wavelength of 400 〜 The average enthalpy obtained in the case of measurement under conditions of 700 nm. Thereby, a coating film excellent in transparency in the visible light region can be provided. The photosensitive resin composition of the present invention can be applied to, for example, a substrate, a color filter such as glass, metal, or plastic, or a substrate on which various insulating or conductive films, drive circuits, or the like are formed, as will be described later. A coating film is formed. The coating film is preferably dried and hardened. Further, the obtained coating film can be patterned into a desired shape and used as a pattern. Further, these coating films or patterns may be used to form a part of components such as a display device. First, the photosensitive resin composition of the present invention is applied onto a substrate. As described above, it can be applied by various coating apparatuses such as a spin coater, a slit and a rotary coater, a slit coater, an inkjet, a roll coater, and a dip coater. Next, drying or pre-baking is preferably carried out to remove volatile components such as a solvent. Thereby, a smooth unhardened coating film can be obtained. In this case, the film thickness of the coating film is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and may be exemplified by, for example, 1 to 6 μηι 〇 • Step-by-Step For the obtained uncured coating film, Light rays such as ultraviolet rays generated by mercury lamps and light-emitting diodes are irradiated through a reticle for forming a target-40-201214033 pattern. The shape of the reticle is not particularly limited at this time, and the shape or size may be selected in accordance with the use of the pattern. Recently, the exposure machine uses a filter that cuts light of less than 350 nm to cut off this wavelength region, and a band pass filter that can take out light near 436 nm, near 408 nm, and around 365 nm to take the wavelengths. The area is selectively taken out, and the entire surface of the exposure surface can be uniformly irradiated with parallel rays. At this time, in order to accurately position the mask and the substrate, a mask aligner, a stepper, or the like can be used. By bringing the exposed coating film into contact with the developing solution, a predetermined portion, for example, a non-exposed portion, is dissolved and developed to obtain a target pattern shape. The development method may be any of a liquid coating method, a dipping method, a spray method, and the like. It is even possible to tilt the substrate at any angle during development. The developing solution used for development is preferably an aqueous solution of a basic compound. The basic compound is either an inorganic or an organic basic compound. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, Sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like. Examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine 'dimethylamine, trimethylamine, monoethylamine, diethylamine, and triethylamine. , monoisopropylamine, diisopropylamine, ethanolamine, and the like. The concentration of the inorganic and organic basic compounds in the aqueous solution is preferably from -41 to 201214033 0.01 to 10% by mass, preferably from 0.03 to 5% by mass. The aforementioned developing solution may also contain a surfactant. The surfactant may be any of a nonionic surfactant, an anionic interface active agent or a cationic surfactant. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aromatic ether, polyoxyethylene alkyl aromatic ether, other polyoxyethylene derivatives, and polyoxyethylene/polyoxypropylene block copolymers. , sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like. Examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate or sodium oleyl sulfate; alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate; and dodecylbenzene; An alkyl aryl sulfonate such as sodium sulfonate or sodium dodecyl naphthalene sulfonate, etc. The cationic surfactant may, for example, be an amine such as stearylamine hydrochloride or lauryl trimethyl ammonium chloride. Salt or quaternary ammonium salt, etc. The concentration of the surfactant in the alkali developing solution is preferably 0.01 to 1 〇 by mass. /. It is preferably 0.05 to 8 mass%, preferably 0.1 to 5 mass%. The pattern is obtained by washing with water after development. It can be further post-baked as necessary. The post-baking is preferably carried out at a temperature ranging from 150 to 24 (TC: 10 to 180 minutes. When the uncured coating film is exposed, the mask formed with the pattern is not used, and the entire illumination and/or illumination is omitted. According to the present invention, it is possible to obtain a pattern which is excellent in both flexibility and heat resistance. In this manner, it is obtained from the photosensitive resin composition of the present invention. The pattern can be used effectively as, for example, a photosensitive spacer material constituting a part of the color filter substrate and/or the array substrate, a patternable protective film, an interlayer insulating film, a protrusion for controlling liquid crystal alignment, and a micro A lens, a coating for adjusting a film thickness, a member for a touch panel, and a coating film having no pattern obtained as described above can be effectively used as a part of a color filter substrate and/or an array substrate. The color filter substrate and the array substrate are preferably used in a liquid crystal display device, an organic EL display device, etc. [Embodiment] Hereinafter, the present invention will be described in detail by way of examples. %) and "parts" are mass% and parts by mass unless otherwise specified. Synthesis Example 1 In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was passed at 0.0 2 L/min to make a nitrogen atmosphere. 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added, and the mixture was heated while stirring to 70 ° C. Next, 55 parts by mass of methacrylic acid was obtained, 3 4-epoxytricyclo[5.2.1.06 6]decyl acrylate (compound represented by formula (1-1) and compound represented by formula (II-1) in a molar ratio of 50:50) 175 The mass fraction and 70 parts by mass of N-cyclohexylmaleimide are dissolved in 140 parts by mass of 3-methoxybutyl acetate, and the solution is prepared -43-201214033, and the solution is dripped using a drip pump for 4 hours. Into the flask at 70 ° C. On the other hand, using another drip pump, it takes 5 hours to make the polymerization initiator 2,2'-azobis(2,4-dimethylhumulonitrile) 3 parts by mass of a solution of 22 parts by mass of 3-methoxybutyl acetate dissolved in the flask. After the completion of the dropwise addition of the polymerization initiator solution, it was kept at 70 ° C. After 4 hours, it was cooled to room temperature to obtain a copolymer (resin Aa) solution having a solid content of 3.6% by mass and an acid value of the solution of 34.3 mg.KOH/g. The weight average molecular weight (Mw) of the obtained resin Aa. It was 13,600, and the number average molecular weight (?n) was 5,400, and the molecular weight distribution was 2.5.

Synthesis Example 2 In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was passed through at 0.02 L/min to make a nitrogen atmosphere, and 3 to methoxy-1-butanol was added in an amount of 200 parts by mass and 3- 5 parts by mass of methoxybutyl acetate was heated and heated to 70 ° C while stirring. Next, 60 parts by mass of methacrylic acid and 3,4-epoxytricyclo[5.2.1 ·02 6]decyl acrylate (represented by the compound represented by the formula (^) and the formula (π -1 )) The compound was dissolved in a molar ratio of 5 〇:50 by 240 parts by mass of 14 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was dropped into the heat for 4 hours using a dropping funnel. In a flask at 7 ° C. On the other hand, using another dropping funnel, it takes 4 hours to dissolve 30 parts by mass of the polymerization initiator 2,2'-azobis(2,4-dimethylhumulonitrile) in 3-methoxy A solution of 225 parts by mass of butyl acetate was dropped into the flask. After the completion of the dropwise addition of the polymerization initiator solution, -44 - 201214033 was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solid content of 32.6% by mass and an acid value of ll 〇 mg-KOH / g (solid content) Conversion) copolymer (resin Ab) solution. The obtained resin Aa had a weight average molecular weight Mw of 13,400 and a molecular weight distribution of 2.50. Synthesis Example 3 In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was passed through at 0.0 2 L/min to make a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethyl methyl ether was added thereto, and the mixture was heated while stirring. 7 0 °C. 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. a mixture of the compounds, molar ratio = 50: 50) 340 parts by mass of dicyclopentenyl acrylate (compound represented by the following formula (xl)) 20 parts by mass dissolved in diethylene glycol ethyl group The solvent was prepared by preparing 190 parts by mass of a base ether. (χΐ) Using a drip pump, it took 4 hours to drop the obtained solution into a flask kept at 70 °C. On the other hand, another use of a drip pump takes 5 hours to dissolve 30 parts by mass of the polymerization initiator 2,2·-azobis(2,4-dimethylhumulonitrile) in diethylene glycol B. A solution of 240 parts by mass of methyl ether was dropped into the flask. After the completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 7 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer (tree -45 - 201214033, fat 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 a solid component. Synthesis Example 4 In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was passed through at 0. 02 L/min to make a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethyl methyl ether was added thereto, followed by heating while stirring. Up to 70 °C. 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 (Π- l) a mixture of the compounds represented by the molar ratio = 50: 50) 320 parts by mass of dicyclopentyl acrylate (compound represented by the following formula (x2)) 40 parts by mass dissolved in diethylene glycol ethyl The solution was prepared by preparing 190 parts by mass of methyl ether. (X2) Using a drip pump, it took 4 hours to drop the obtained solution into a flask kept at 7 CTC. On the other hand, using another drip pump, it takes 5 hours to dissolve the polymerization initiator 2,2·-azobis(2,4-dimethylhum), 30 parts by mass in diethylene glycol B. A solution of 240 parts by mass of methyl ether was dropped into the flask. After the completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Ad) solution having a solid content of 41.81 %. The weight average molecular weight of the obtained resin Ad ( -46 - 201214033

Mw) is 7·9χ103, the molecular weight distribution (Mw/Mn) is 1.82, and the acid value in terms of solid content is 60 mg-KOH/g" Synthesis Example 5 In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, 0.0 2 L/min of nitrogen gas was passed to make a nitrogen atmosphere, 60 parts by mass of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 90 t while stirring. Next, 13 parts by weight of methyl methacrylate, 7 parts by weight of methacrylic acid, 14 parts by weight of n-butyl methacrylate, 6 parts by weight of 2-ethylhexyl acrylate, and azobisindole were continuously added dropwise over 3 hours. 0.4 parts by weight of oxalic acid and 0.8 parts by weight of n-dodecyl mercaptan. Then, after maintaining at 90 ° C for 30 minutes, the temperature was raised to 1 〇 51 and held for 3 hours, and then cooled to room temperature to obtain a copolymer (resin Ae ) solution having a solid content of 40.1%. The obtained resin Ae had a weight average molecular weight (Mw) of 1.6 x 10 4 and a molecular weight distribution (Mw / Mn) of 2.02. The measurement of the weight average molecular weight (Mw) and the number average molecular weight (?n) of the obtained resins Aa to Ae was carried out by the following conditions using the GPC method. Device: Κ2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M Column temperature: 40 ° C Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL/min. Detector: RI - 47 - 201214033 The ratio of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was defined as a molecular weight distribution (Mw/Mn). EXAMPLES AND COMPARATIVE EXAMPLES <Preparation of photosensitive resin composition> The components of Table 1 were mixed to obtain photosensitive resin compositions 1 to 8. [Table 1] Photosensitive resin composition 1 2 3 4 5 60 6 7 8 Resin (VIII) (parts) Aa 60 60 Ab 50 60 Ac 60 Ad 60 Ae 40 Polymerizable compound (B1) (part) B1a 40 40 50 20 40 40 B1b 20 Blc 40 Polymerizable compound (B2) (part) B2a 40 B2b 20 Polymerization initiator (C) (part) Ca 6 3 3 3 6 3 3 Cb 6 Polymerization start aid (C1) (part) C1a 6 6 6 6 Polyfunctional thiol (T1) (parts) 1 1 1 Thermal crosslinker Ha 3.2 Polyoxo-based surfactant (D) 0.03 0.03 0.03 0.03 0.03 0.03 Solvent (E) (parts) Ea 20 20 20 20 20 20 20 Eb 18 18 18 18 18 18 18 Ec 20 20 20 20 20 20 20 Ed 42 42 42 42 42 42 42 Ee 100 Solid content (%) 33 33 33 33 33 33 33 33 Average transmittance of the composition (%) 90% 90% 92% 92% 91% 91% 90% 89% Membrane (3"m) Average Transmittance (%) 98% 99% 98% 98% 98% 98% 99% 97% Acrylic Equivalent (g/eq) 490 504 403 698 278 504 504 521 Epoxy equivalent (g/eq) 652 500 600 500 652 469 500 0 The ingredients in Table 1 are as follows. In Table 1, the parts of the resin (A) represent parts by mass in terms of solid content. Resin (A); Aa: Resin Aa-48-201214033 Resin (A) obtained in Synthesis Example 1; Ab: Resin resin (A) obtained in Synthesis Example 2; A c : Resin resin obtained in Synthesis Example 3 ( A); A d : resin resin (A) obtained in Synthesis Example 4; A e : resin polymerizable compound (B 1 ) obtained in Synthesis Example 5; B 1 a : ethylene oxide-alcohol hexaacrylate ( Compound DPEA12 represented by the following formula; manufactured by Nippon Kayaku Co., Ltd.) ch2o-a° ch2o-a° a0och2-c-ch2 ο ch2-c ch2o a0 ch2o-a° ch2o-a° , x 〇〇A° = —ch2ch2o 4— c — ch=ch2 or —c-ch:ch2 Polymerizable compound (Bl) ; Bib: polyethylene glycol II EBECRYL1 1 ; DAICEL CYTEC Co., Ltd. contains 2 propylene decyloxy groups, 1 1 - 〇CH2CH2-) polymerizable compound (B 1 ) ; B 1 c : tetradecyl glycol (Light Acrylate 14EG-A: manufactured by Kyoritsu Chemical Co., Ltd.; in the presence of 2 propylene decyloxy groups, 14 -OCH2CH2 -) Polymerizable compound (B2); B2a: dipentaerythritol (KAYARADDPHA; polymerizable compound (B2) manufactured by Nippon Kayaku Co., Ltd.; B2b: trimethylol propyl ester (NK ester A-TMPT; Shin-Nakamura Chemical Industries, Ltd.) polymerization initiator (C); Ca: 2- morpholin-1- (4-phenyl) -2-methyl-propan-1-one (IRGACURE 907; manufactured)

Ab Ac Ad Ae dipentaquat, KAYARAD acrylate (containing hexaacrylate in the compound diacrylate compound) alkane triacrylate _methylsulfonyl BASF Japan -49- 201214033 polymerization initiator (C); Cb: 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one (IRGACURE 369; manufactured by BASF Japan) polymerization starting aid (Cl); CU : 2,4-Diethylthioxanthone (DETX-S; manufactured by Nippon Kayaku Co., Ltd.) Thermal crosslinking agent; Ha: Isocyanate compound (Duranate E-402-B8 0T: manufactured by Asahi Kasei Chemicals Co., Ltd.) (T1): pentaerythritol oxime (3-sulfonylpropionate) (PEMP; SC Organic Chemical Co., Ltd.) polyfluorene surfactant (D); SH8400: Toray Dow Corning 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-methoxy Ethyl butyl acetate solvent (E); Ee: Diethylene glycol dimethyl ether solvent (E) is a method in which the solid content of the photosensitive resin composition is mixed as "solid content (%)" in Table 1. The solvent component (Ea) to (Ee) in the solvent (E) represents the mass ratio in the solvent (E). <Average transmittance of the composition> The ultraviolet/visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation, quartz channel, optical path length) was used for each of the obtained photosensitive resin compositions 1 to 8'. :1cm), measured at -400-201214033, average transmittance at 400 to 700 nm, % of the film, showing the average transmittance of the film, using the obtained photosensitive resin compositions 1 to 7, and using the following Under the conditions, a film was formed so that the film thickness after hardening became 3 μm. A square glass substrate (# 1 73 7 ; manufactured by Corning Co., Ltd.) having a side length of 2 inches was washed with a neutral detergent, water, and alcohol, followed by drying. The photosensitive resin composition was spin-coated on the glass substrate in such a manner that the film thickness after the post-baking was 3·0 μm, and then pre-baked at 90 ° C for 1 minute in a dust-free oven. After cooling, the distance between the substrate coated with the photosensitive resin composition and the mask made of quartz glass was set to ΙΟΟμηη, and an exposure machine (TME-150RSK; Topcon Corporation, light source: ultrahigh pressure mercury lamp) was used in the atmosphere. In the environment, the light is irradiated with an exposure amount of l〇〇mJ/cm2 (based on 3 65 nm). Further, the irradiation of the photosensitive resin composition at this time was carried out by passing the light emitted from the ultrahigh pressure mercury lamp through an optical filter (UV-3 5; manufactured by Asahi Co., Ltd.). After illuminating, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C, and was visualized by shaking for 60 seconds, and then at 150 ° C. The film was heated by heating for 180 minutes. The average transmittance (%) of 400 to 700 nm was measured for the obtained film using a microscopic spectrophotometer (OSP-SP200; manufactured by OLYMPUS Co., Ltd.). A higher transmittance means that the absorption becomes smaller. The results are disclosed in Table 1 ° -51 - 201214033 <Form Formation> A square glass substrate (#1737; manufactured by Corning Co., Ltd.) having a side length of 2 inches was washed with a neutral detergent, water, and alcohol, and then Dry. The photosensitive resin composition was spin-coated on the glass substrate so that the film thickness after post-baking became 4.5 μm. Next, pre-bake at 90 °C for 1 在 minutes in a clean oven. After cooling, the distance between the substrate coated with the photosensitive resin composition and the quartz glass mask was set to ΙΟΟμηι, and an exposure machine (TME-150RSK; Topcon Corporation, light source: ultrahigh pressure mercury lamp) was used in the atmosphere. The light was irradiated with an exposure amount of 100 mJ/cm 2 (based on 365 nm). Further, at this time, the irradiation of the photosensitive resin composition was carried out by passing the light emitted from the ultrahigh pressure mercury lamp through an optical filter (UV-35; manufactured by Asahi Co., Ltd.). In addition, the reticle adopts a pattern (a square light-transmitting portion having a side length of 10 μm, and the interval of the square is 1 ΟΟμιη) (that is, a light-transmitting portion) is formed on the same plane as a reticle after illumination at 23 ° C. The coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, and shaken for 60 seconds to develop a image, and after washing with water, at 150 ° C in an oven. After drying for 180 minutes, the pattern was obtained. <Measurement of the pattern line width> The line width of the obtained pattern was measured by a three-dimensional non-contact surface shape measuring system (Micromap MM527N-PS-M100; manufactured by Ryoden System Co., Ltd.). Between the surface of the substrate and the height of the pattern -52- 201214033 5 ° /. The height of the pattern is measured at the height of the line. The results are disclosed in Table 4. <Mechanical characteristics (total displacement amount and recovery rate)> Using a dynamic ultra-micro hardness tester (DUH-W201: manufactured by Shimadzu Corporation), the total amount of displacement (μηι) was measured for the obtained pattern and The elastic displacement amount (μιη ) was calculated and the recovery rate (%) was calculated. It can be judged that the larger the total amount of displacement, the higher the softness. The results are disclosed in Table 4. - Measurement conditions - Test mode: Load-de-load test Test force: 20mN Load speed: 4.41mN/sec Hold time: 5sec Indenter: Cone head (diameter 50μιη)

Recovery rate (%): (elastic displacement amount (μιη) / total displacement amount (μιη)) xlOO <coat film formation> sequentially washed with neutral detergent, water and propan-2-ol A 2-inch square glass substrate (#1 73 7, manufactured by Corning) was then dried. The photosensitive resin composition was spin-coated on the glass substrate so that the film thickness after post-baking was 3 μm. Next, pre-bake at l〇〇°C for 3 minutes in a dust-free oven. After cooling, an exposure machine (TME-150RSK; Topcon Corporation, light source: ultrahigh pressure mercury lamp) was used, and the light was irradiated with an exposure amount of 100 mJ/cm2 (based on 3 65 nm) in a gas atmosphere of -53-201214033. Further, at this time, the light emitted from the ultrahigh pressure mercury lamp was irradiated onto the photosensitive resin composition through an optical filter (UV-3 5; manufactured by Asahi Co., Ltd.). In addition, no reticle is used. After illuminating, the coating film was immersed in a water-based developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 t, and shaken for 60 seconds to visualize it, after washing with water, in an oven. The pattern was obtained by post-baking at 220 ° C for 20 minutes. <Heat resistance evaluation> The obtained coating film was heated at 240 ° C for 1 hour in a dust-free oven, and the film thickness was measured. The change rate was obtained from the film thickness before and after heating according to the following formula. Film thickness change rate (%): film thickness after heating (μm) / film thickness before heating (μηι) If the heat resistance of the coating film is good, heat resistance of the pattern formed using the same photosensitive resin composition Sex is also good. The results are disclosed in Table 2. [Table 2] mm Comparative Example 1 2 3 4 5 6 1 2 Photosensitive resin composition 1 2 3 4 6 7 5 8 Pattern line width (10)] 19.5 20.1 23.2 23.5 20.3 21.0 21.2 25.0 Mechanical property total displacement amount [/ /m] 1.56 1.35 1.42 1.7 1.40 1.52 0.71 1.62 Recovery rate ra 30« 32% 35% 28% 33% 35« 80% 29% Heat resistance film thickness change rate [%] 92% 93% 93% 90% 92% 93 % 96% 83% It was confirmed that the pattern obtained by the photosensitive resin composition of the present invention is excellent in flexibility. Further, it was confirmed that the coating film obtained by the photosensitive resin composition of the present invention -54 - 201214033 has excellent heat resistance. By using such a photosensitive resin composition to form a coating film or pattern ', and applying these as a photosensitive gap material to a liquid crystal display device', it is possible to suppress liquid crystal layer foaming which occurs in a low-temperature environment, and to improve liquid crystal display. The durability of the device. Industrial Applicability The photosensitive resin composition of the present invention can provide a pattern excellent in both flexibility and heat resistance. The pattern obtained by the photosensitive resin composition of the present invention can be effectively used as, for example, a photosensitive gap member constituting a color filter substrate and/or an array substrate, a pattern protective film, and an interlayer insulating film. For the control of the liquid crystal alignment, the microlens, the coating for adjusting the film thickness, etc., the member for the touch panel, the coating film having the pattern obtained as described above can be effectively used as the color filter. A protective film on a portion of the substrate and/or the array substrate. The color filter substrate and the array substrate are suitably used for a liquid crystal display device, an organic EL display device, or the like. -55-

Claims (1)

201214033 VII. Patent application scope: 1. A photosensitive resin composition containing a resin, a polymerizable compound, a photopolymerization initiator, a polyoxymethylene surfactant, and a solvent, and the resin is an addition polymer. The addition polymer contains: 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 cyclic ether having a carbon number of 2 to 4 and carbon-carbon The structural unit of the monomer having a saturated double bond, and the polymerizable compound contains a compound having two or more groups represented by the formula (1), and the content of the compound is 30% by mass or more based on the total amount of the polymerizable compound. 100% by mass or less, ' /py (1) [In the formula (1), L1 represents an ethyl group or a propane-oxime, a diamino group, and p represents an integer of 1 to 20]. (2) The photosensitive resin composition of the first aspect of the invention, wherein the content of the polyfluorene-based surfactant is 0.000 1% by mass or more and 0.05% by mass or less based on the photosensitive resin composition. 3. The photosensitive resin composition of claim 1, wherein the content of the structural unit derived from the monomer having a cyclic ether having 2 to 4 carbon atoms and a carbon-carbon unsaturated double bond is relative to the resin The total amount of structural units is 3 〇 mol% or more and 90 mol% or less. 4. A pattern formed by using a photosensitive resin composition as in the first aspect of the patent application. -56- 201214033 5 · A display device containing the pattern of item 4 of the scope of the patent application. -57- 201214033 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201214033 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention. :no