JP5065123B2 - Alkali-developable photosensitive resin composition - Google Patents

Description

  The present invention relates to an alkali-developable photosensitive resin composition containing a specific compound imparted with an ethylenically unsaturated bond, and an alkali development obtained by further adding a photopolymerization initiator to the alkali-developable photosensitive resin composition. The present invention relates to a photosensitive photosensitive resin composition.

  Usually, the alkali-developable photosensitive resin composition contains an alkali-developable photosensitive resin composition containing a compound having an ethylenically unsaturated bond and a photopolymerization initiator. Since this alkali-developable photosensitive resin composition can be polymerized and cured by irradiation with ultraviolet rays or electron beams, various photo-curable inks, photosensitive printing plates, printed wiring plates, liquid crystal display color filters, etc. Used in photoresists and the like. In recent years, with the progress of miniaturization and high functionality of electronic devices, an alkali-developable photosensitive resin composition capable of forming a fine pattern with high accuracy is desired.

  In addition, the photopolymerization initiator used in the alkali-developable photosensitive resin composition is expensive, and unreacted components and decomposition products of the photopolymerization initiator remain in the coating film and cause contamination. There has been a demand for an alkali-developable photosensitive resin composition that does not use an initiator or reduces the amount used, is excellent in sensitivity and adhesion, and can form a fine pattern with high accuracy.

  On the other hand, in the following Patent Documents 1 to 4, a photocurable composition in which a reaction product obtained by adding a β-diketone compound to a compound containing an acryloyl group is cured without using a photopolymerization initiator. Although it is described that it can be used as an alkali-developable photosensitive resin composition, no example is described.

Japanese Patent No. 3649331 JP 2005-163041 A JP 2006-241461 A US Pat. No. 5,459,178

  As described above, the problems to be solved are excellent in sensitivity and adhesion, and can obtain an appropriate pattern shape and fine pattern, even though a photopolymerization initiator is not used or a small amount is used. This means that there has never been an alkali-developable photosensitive resin composition.

  Accordingly, an object of the present invention is to provide an alkali-developable photosensitive resin composition that is excellent in sensitivity and adhesion, and can form a fine pattern with high precision, even though a photopolymerization initiator is not used or is used in a small amount. It is to provide.

  In the present invention, a β-diketone compound (B) represented by the following general formula (I) is added to the (meth) acryloyl group of the compound (A) having two or more (meth) acryloyl groups and a hydroxyl group. An alkali-developable photosensitive film comprising a photopolymerizable unsaturated compound (J) having a structure obtained by an esterification reaction between a hydroxyl group of a reaction product obtained and a polybasic acid anhydride (C) The resin composition is provided.

（式中、Ｒ¹は、炭素原子数１〜２０のアルキル基であり、Ｒ²は、Ｒ¹¹、ＯＲ¹¹、ＣＯＲ¹¹、ＳＲ¹¹、ＣＯＮＲ¹²Ｒ¹³又はＣＮを表し、Ｒ¹¹、Ｒ¹²及びＲ¹³は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、アルキル基、アリール基、アリールアルキル基及び複素環基の水素原子は、更にＯＲ²¹、ＣＯＲ²¹、ＳＲ²¹、ＮＲ²²Ｒ²³、ＣＯＮＲ²²Ｒ²³、−ＮＲ²²−ＯＲ²³、−ＮＣＯＲ²²−ＯＣＯＲ²³、−Ｃ（＝Ｎ−ＯＲ²¹）−Ｒ²²、−Ｃ（＝Ｎ−ＯＣＯＲ²¹）−Ｒ²²、ＣＮ、ハロゲン原子、−ＣＲ²¹＝ＣＲ²²Ｒ²³、−ＣＯ−ＣＲ²¹＝ＣＲ²²Ｒ²³、カルボキシル基、エポキシ基で置換されていてもよく、Ｒ²¹、Ｒ²²及びＲ²³は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、上記Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ²¹、Ｒ²²及びＲ²³で表される置換基のアルキレン部分のメチレン基は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、アミド結合又はウレタン結合により１〜５回中断されていてもよく、上記置換基のアルキル部分は分岐側鎖があってもよく、環状アルキルであってもよく、上記置換基のアルキル末端は不飽和結合であってもよく、また、Ｒ¹²とＲ¹³及びＲ²²とＲ²³は、それぞれ一緒になって環を形成していてもよく、Ｒ²は、隣接するベンゼン環と一緒になって環を形成していてもよい。Ｒ³及びＲ⁴は、それぞれ独立に、Ｒ¹¹、ＯＲ¹¹、ＳＲ¹¹、ＣＯＲ¹¹、ＣＯＮＲ¹²Ｒ¹³、ＮＲ¹²ＣＯＲ¹¹、ＯＣＯＲ¹¹、ＣＯＯＲ¹¹、ＳＣＯＲ¹¹、ＯＣＳＲ¹¹、ＣＯＳＲ¹¹、ＣＳＯＲ¹¹、ＣＮ、ハロゲン原子、ニトロ基又は水酸基を表し、ａは０〜３の整数を表し、ｂは０〜４の整数を表し、ａ、ｂが２以上の時はそれぞれの複数の置換基は異なる置換基でもよく、β−ジケトン部分はケト−エノール互変異性体のどちらの構造であってもよい。）

(In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² represents R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² And R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 2 to 20 carbon atoms. Represents a heterocyclic group, and the hydrogen atom of the alkyl group, aryl group, arylalkyl group and heterocyclic group is further OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , —NR ²² —OR ^23. , —NCOR ²² —OCOR ²³ , —C (═N—OR ²¹ ) —R ²² , —C (═N—OCOR ²¹ ) —R ²² , CN, halogen atom, —CR ²¹ ═CR ²² R ²³ , —CO -CR ²¹ = CR ²² R ^23, carboxyl group, substituted by an epoxy group R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl having 7 to 30 carbon atoms. The methylene group of the alkylene part of the substituent which represents an alkyl group or a C2-C20 heterocyclic group, and is represented by said R < ¹¹ >, R < ¹² >, R <^13> , R <^21> , R <^22> and R < ²³ > is unsaturated It may be interrupted 1 to 5 times by a bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, and the alkyl part of the above substituent may have a branched side chain, The alkyl terminal of the substituent may be an unsaturated bond, and R ¹² and R ¹³ and R ²² and R ²³ may be combined to form a ring, R ² is an adjacent benzene ring And R ³ and R ⁴ each independently represent R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , CN, a halogen atom, a nitro group or a hydroxyl group, a represents an integer of 0 to 3, b represents an integer of 0 to 4, a, b When is 2 or more, each of the plurality of substituents may be a different substituent, and the β-diketone moiety may be any structure of a keto-enol tautomer. )

  Further, the present invention provides a structure in which the compound (A) having two or more (meth) acryloyl groups and a hydroxyl group is a reaction product obtained by adding an unsaturated monobasic acid (E) to an epoxy compound (D). In particular, the alkali-developable photosensitive resin composition having the above structure, in particular, the epoxy compound (D) having a structure represented by the following general formula (II) is provided.

（式中、Ｃｙは炭素原子数３〜１０のシクロアルキル基を表し、Ｘは水素原子、フェニル基又は炭素原子数３〜１０のシクロアルキル基を表し、該フェニル基及びシクロアルキル基は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基又はハロゲン原子により置換されても良く、Ｙ及びＺは、それぞれ独立して、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を表し、該アルキル基、アルコキシ基及びアルケニル基は、ハロゲン原子で置換されていてもよく、ｎは０〜１０の数を表し、ｍ及びｒは、それぞれ独立して、０〜４の数を表す。）

(In the formula, Cy represents a cycloalkyl group having 3 to 10 carbon atoms, X represents a hydrogen atom, a phenyl group or a cycloalkyl group having 3 to 10 carbon atoms, and the phenyl group and the cycloalkyl group are carbon atoms. The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms or the halogen atom may be substituted, and Y and Z are each independently an alkyl group having 1 to 10 carbon atoms and the number of carbon atoms. Represents an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, wherein the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and n is a number from 0 to 10 M and r each independently represents a number of 0 to 4.)

  In the present invention, the alkali-developable photosensitive resin composition further containing a photopolymerization initiator (F) and the alkali-developable photosensitive resin composition further contain a color material (G). A colored alkali-developable photosensitive resin composition is provided.

  The alkali-developable photosensitive resin composition of the present invention provides sufficient sensitivity, resolution and adhesion without using a photopolymerization initiator or using a small amount.

  Hereinafter, the alkali-developable photosensitive resin composition of the present invention will be described in detail based on preferred embodiments.

  The alkali-developable photosensitive resin composition of the present invention is represented by the above general formula (I) in the (meth) acryloyl group of the compound (A) having two or more (meth) acryloyl groups and a hydroxyl group. -The photopolymerizable unsaturated compound (J) which has a structure obtained by esterification reaction of the hydroxyl group of the reaction product obtained by adding the diketone compound (B) and the polybasic acid anhydride (C) is contained. .

In the general formula (I), examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ include, for example, methyl, ethyl, Propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, Dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, pentyloxyethyl, octyloxyethyl, methoxyethoxyethyl, ethoxy Ethoxye Examples include til, propoxyethoxyethyl, methoxypropyl, 2-methoxy-1-methylethoxy and the like. Examples of the aryl group having 6 to 30 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, And phenanthrenyl, phenyl, biphenylyl, naphthyl, anthryl, etc. substituted with one or more of the above alkyl groups. Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ include benzyl, chlorobenzyl, α-methylbenzyl, α, α- Examples include dimethylbenzyl, phenylethyl, phenylethenyl and the like. Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ include pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, dimethyl Preferred examples include 5- to 7-membered heterocycles such as dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl, etc. Examples of the heterocyclic alkyl group having 3 to 20 carbon atoms include groups in which an alkyl group such as methyl, ethyl, propyl, butyl or the like is substituted with the substituents exemplified as the heterocyclic group having 2 to 20 carbon atoms. . In addition, a ring that can be formed by combining R ¹² and R ^{13, a} ring that can be formed by combining R ²² and R ²³ , and a ring that can be formed by combining R ² and an adjacent benzene ring Examples of the ring include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring. In addition, halogen atoms that may be substituted for R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ and halogen atoms represented by R ³ and R ⁴ include fluorine, chlorine, bromine and iodine. Can be mentioned.

Among the β-diketone compounds represented by the above general formula (I), those in which R ¹ is a methyl group and a is 0 are preferred because they are advantageous in terms of production, and those in which b is 0, It is more preferable that b is 1 and R ⁴ is an acyl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, because of excellent sensitivity. And a benzoyl group which may be substituted with a halogen atom is more preferable because of excellent sensitivity and production.

  Specific examples of the β-diketone compound having a carbazolyl group represented by the above general formula (I) include the following compound Nos. 1-No. 10 is mentioned.

  The β-diketone compound represented by the general formula (I) is not particularly limited. For example, as shown in the following [Chemical Formula 13], a condensation reaction in the presence of a base catalyst between an acetylcarbazole compound and a carboxylic acid ester. Can be manufactured.

As the carboxylic acid ester, an ester having a corresponding substituent (= R ¹ ) is used, and the ester portion is not particularly limited, but methyl ester, ethyl ester, propyl ester, butyl ester, isoamyl ester, phenyl ester, etc. Preferably used.

  Examples of the base catalyst include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide and sodium hydride; metal alkoxides such as sodium methoxide, sodium ethoxide, lithium diisopropoxide and potassium t-butoxide. Diethylamine, triethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,4,0] -7 -Amines such as undecene; metal amides such as sodium amide and lithium diisopropylamide; ammonium hydroxide salts such as tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide.

  The β-diketone compound used for obtaining the alkali-developable photosensitive resin composition of the present invention is a β-diketone compound represented by the above general formula (I). A compound having a diketone moiety or a compound having a β-ketoester group may be used in combination. Examples of the compound having a β-diketone moiety or the β-ketoester group include 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, 1-methoxy-2,4-pentanedione. 1-phenyl-1,3-butanedione, 1,3-diphenyl-1,3-propanedione, methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, butyl acetoacetate, tert-butyl acetoacetate, acetoacetate- 2-methoxyethyl, acetoacetate-2-ethylhexyl, lauryl acetoacetate, allyl acetoacetate, ethyl propionyl acetate, butyl propionyl acetate, methyl butyryl acetate, methyl benzoyl acetate, ethyl benzoyl acetate, butyl benzoyl acetate, 4,6-dioxo Methyl heptanoate, 5,7-dioxooctanoic acid Chill, 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate, benzyl acetoacetate, 1,4-butanediol diacetoacetate, 1,6-hexanediol diacetoacetate, neopentylglycol diacetoacetate 2-ethyl-2-butyl-1,3-propanediol diacetoacetate, cyclohexanedimethanol diacetoacetate, ethoxylated bisphenol A diacetoacetate, trimethylolpropane triacetoacetate, glycerol triacetoacetate, pentaerythritol tris Acetoacetate, pentaerythritol tetraacetoacetate, ditrimethylolpropane tetraacetoacetate, acetoacetate group-containing oligomer, ethyl acetoacetate Include transesterification reaction and acetoacetic ester group-containing oligomers or polymers obtained by polymerization of methacrylic acid-2-acetoacetoxyethyl the hydroxyl group-containing oligomer or polymer. When the compound having the β-diketone moiety or the compound having a β-ketoester group is used in combination, the total amount used is preferably the amount of the β-diketone compound represented by the general formula (I). 1 mass times or less.

  In the present invention, the ratio of the hydrogen atom of the methylene group sandwiched by the diketone in the β-diketone portion of the compound (B) to one (meth) acryloyl group of the compound (A) is preferably 0. 0.1 to 1.0, more preferably 0.3 to 1.0, and the ratio of the acid anhydride structure of the polybasic acid anhydride (C) to one hydroxyl group of the reaction product is The number is preferably 0.1 to 1.0, and more preferably 0.3 to 0.9.

  In the present invention, the reaction product obtained by the reaction of the compound (A) and the compound (B), and the structure obtained by the esterification reaction of the hydroxyl group of the reaction product and the polybasic acid anhydride (C) The photopolymerizable unsaturated compound (J) may have different isomers depending on the addition type of the substituted acryloyl group, but even a mixture of isomers can be used without any problem.

Compound (A) having two or more (meth) acryloyl groups and hydroxyl groups in the present invention
As a structure which is an esterification reaction product of t-1 hydroxyl groups of a polyol compound having 3 to t hydroxyl groups and an unsaturated monobasic acid (E), III) Esterification of a hydroxy group or an alkylene oxide added to a polyol represented by (III) with a hydroxyl group within t-1 of a derivative having 3 to t hydroxyl groups and an unsaturated monobasic acid (E) Examples thereof include those having a structure which is a reaction product and those having a structure which is a reaction product obtained by adding an unsaturated monobasic acid (E) to an epoxy compound (D).

Z ₁ (OH) _s (—O—CO—L—OH) _t [— (OL) _w —OH] _u (III)
(In the formula, Z ₁ is a polyol residue, s, t, u are a total number of 3 or more, and L represents an alkanediyl group such as methylene, ethylene, propylene, trimethylene, butylene, tetramethylene) , W represents 1-15.)

  Moreover, the ratio of the carboxyl group of the unsaturated monobasic acid (E) to one epoxy group of the epoxy compound (D) is preferably 0.1 to 1.0, more preferably 0.5 to 1.0.

  Specific examples of the compound (A) include pentaerythritol triacrylate, dipentaerythritol pentaacrylate, trimethylolethane diacrylate, trimethylolpropane diacrylate, tetramethylolpropane triacrylate, and 2-hydroxy-3-acryloyl. Roxypropyl acrylate and the following compound No. 11 etc. are mentioned.

  The number of (meth) acryloyl groups in the compound (A) is preferably 2 to 10, more preferably 2 to 6, and the number of hydroxyl groups is preferably 1 to 8, and more preferably 1 to 4. When the number of (meth) acryloyl groups and hydroxyl groups is within these ranges, an alkali-developable photosensitive resin composition having excellent developability and adhesion can be obtained.

  Examples of the epoxy compound (D) include polyfunctional epoxy compounds listed below and those having a structure represented by the general formula (II).

Examples of the polyfunctional epoxy compound include bisphenol type epoxy compounds and glycidyl ethers, and examples of the bisphenol type epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, and bis (hydroxyphenyl) fluorene type epoxies. In addition to alkylidene bisphenol polyglycidyl ether type epoxy resins such as compounds, bisphenol type epoxy compounds such as hydrogenated bisphenol type epoxy compounds may be mentioned.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and 1,8-octanediol diglycidyl ether. 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol di Glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1 Tri (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) methane, and the like.

  Other examples of the polyfunctional epoxy compound include phenol novolac epoxy compounds, (o-, m-, p-) phenylphenol novolac epoxy compounds, (o-, m-, p-) cresol novolac epoxy compounds, o-, m-, p-) novolak type epoxy compounds such as halogenated phenol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds, bisphenol F novolak type epoxy compounds, naphthol novolak type epoxy compounds; A novolak-type epoxy compound formed by condensation polymerization of the epoxy compound and an aromatic hydrocarbon; an addition-reaction type epoxy compound of the epoxy compound and dicyclopentadiene; 3,4-epoxy-6-methylcyclohexylme 3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2,2-bis (3,4-epoxycyclohexyl) Alicyclic epoxy compounds such as propane and 1-epoxyethyl-3,4-epoxycyclohexane; glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate and glycidyl dimer; tetraglycidyl diaminodiphenylmethane, tri Glycidylamines such as glycidyl-p-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as lopentadiene dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds; addition polymers of (o-, m-, p-) hydroxystyrene or (o-, m -, P-) The epoxy compound etc. which are obtained by making the hydroxyl group of the copolymer of hydroxystyrene and ethylene and / or propylene glycidyl ether are mentioned.

  Among these epoxy compounds (D), those having a structure represented by the above general formula (II) are preferable because the properties as an epoxy resin are good.

  In the general formula (II), examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Cy include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. Can be mentioned.

In the general formula (II), examples of the cycloalkyl group having 3 to 10 carbon atoms represented by X include those exemplified as the cycloalkyl group having 3 to 10 carbon atoms represented by Cy. The phenyl group represented by X or the cycloalkyl group having 3 to 10 carbon atoms may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, Examples of the substituent include those exemplified later as those represented by Y and Z, respectively.
Examples of the alkyl group having 1 to 10 carbon atoms represented by Y and Z include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, Examples include heptyl, octyl, isooctyl, t-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl and the like. Examples of the alkoxy group having 1 to 10 carbon atoms represented by Y and Z include, for example, methoxy, ethoxy, propyloxy, butyloxy, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxy Examples include ethyl and methoxypropyl. Examples of the alkenyl group having 2 to 10 carbon atoms represented by Y and Z include vinyl, allyl, butenyl, propenyl, etc. Examples of the halogen atom represented by Y and Z include fluorine, chlorine, bromine and iodine. Is mentioned.
In addition, the phenyl group represented by X and the cycloalkyl group having 3 to 10 carbon atoms may be substituted, and the alkyl group, alkoxy group and alkenyl represented by Y and Z. The group may be substituted with a halogen atom, and examples of the halogen atom include fluorine, chlorine, bromine and iodine. For example, as a C1-C10 alkyl group substituted by the fluorine atom, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl etc. are mentioned, for example.

  As a preferable epoxy compound (D) represented by the general formula (II) in the present invention, for example, the following compound No. 12-No. 20 etc. are mentioned.

（上記化合物Ｎｏ．１３において、Ｈ₃Ｃ−は位置を特定していない事を表す。）

(In the above compound No. 13, H ₃ C- represents that the position is not specified.)

  Among the compounds having the structure represented by the general formula (II) in the epoxy compound (D), it is preferable that Cy is a cyclohexyl group, X is a phenyl group, and m and r are 0. This is because the raw materials are easily available and the productivity is good.

  In the present invention, the production method of the epoxy compound (D) represented by the general formula (II) is not particularly limited. For example, as shown in the following [Chemical Formula 24], a substituted phenylcycloalkyl ketone ( A bisphenol compound (2) is obtained by reacting 1) with a phenol derivative in the presence of an acid catalyst, and is easily produced by reacting this with epichlorohydrin in the presence of an alkali or Lewis acid or a phase transfer catalyst. be able to.

  The said bisphenol compound (2) can be manufactured by conventionally well-known conditions, for example, is obtained by making it react at the temperature of 20-200 degreeC for 1 to 40 hours in presence of an acidic catalyst.

  Examples of the acidic catalyst include methanesulfonic acid, benzenesulfonic acid, m-xylenesulfonic acid, p-toluenesulfonic acid, hydroxymethylsulfonic acid, 2-hydroxyethylsulfonic acid, hydroxypropylsulfonic acid, trifluoromethanesulfonic acid, Sulfonic acids such as sulfosalicylic acid and sulfophthalic acid; sulfuric acid, sulfuric anhydride, fuming sulfuric acid, chlorosulfuric acid, fluorosulfuric acid, hydrochloric acid, hydrogen chloride gas, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid, silicotungstic acid, phosphorus Examples include heteropolyacids such as tungstic acid, strongly acidic ion exchange resins, activated clay, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. The acidic catalyst is preferably used in an amount of 0.1 to 70 parts by mass, more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the substituted phenylcycloalkylketone (1).

  Further, a mercaptan catalyst can be used to promote the reaction. Examples of the mercaptan catalyst include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 1,6-hexanedithiol, and the like. Alkyl mercaptans; aromatic mercaptans such as thiophenol and thiocresol; mercapto organic acids such as mercaptoacetic acid (thioglycolic acid), 3-mercaptopropionic acid, mercaptoundecanoic acid and thiobenzoic acid; 2-mercaptobenzothiazole, etc. And heterocyclic mercaptans.

  Moreover, a conventionally well-known solvent can be used for the said reaction, For example, terpene, such as aromatic hydrocarbon type solvents, such as toluene, xylene, cumene; terpine oil, D-limonene, pinene, etc. Hydrocarbon oils; mineral spirits, paraffinic solvents such as Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); alcoholic solvents such as methanol and ethanol; esters such as ethyl acetate Solvents: Halogen solvents such as dichloroethane, carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, chlorobenzene; cyclic ether solvents such as tetrahydrofuran and dioxane; ethers, cellosolve solvents, ketone solvents, aniline, triethylamine, pyridine, dioxane , Acetic acid, acetonitrile , Carbon disulfide, and the like.

The epoxy compound (D) represented by the general formula (II) is a bisphenol compound (2
) And epichlorohydrin can be produced under known conditions.
For example, the reaction is carried out in the range of 20 to 100 ° C., particularly 30 to 80 ° C. in the presence of an alkali or Lewis acid or a phase transfer catalyst. If it is less than 20 ° C., the reaction is delayed and a long reaction time is required.

  Examples of the alkali used in the above reaction include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like, and examples of the Lewis acid include acidic catalysts such as those exemplified above, tin tetrachloride, trifluoride. Boron, titanium tetrachloride, activated clay, aluminum chloride, magnesium chloride, potassium permanganate, potassium chromate and the like can be mentioned. Examples of the phase transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium. Chloride, methyltridecylammonium chloride, benzyltriethylammonium chloride, N, N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N- Benzyl -Methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium bromide, N-butyl-N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N- Methylmorpholinium bromide, N-methyl-N-benzylpiperidinium chloride, N-methyl-N-benzylpiperidinium bromide, N, N-dimethylpiperidinium iodide, N-methyl-N-ethylpiperidi Examples thereof include nium acetate and N-methyl-N-ethylpiperidinium iodide.

  The amount of epichlorohydrin used in this reaction is 1 mole or more, particularly 2 to 10 moles per 1 hydroxyl group of the bisphenol compound (2), and the alkali is 0.1 to 2 mol per hydroxyl group. 0 mol, especially 0.3 to 1.5 mol is used, and the Lewis acid or phase transfer catalyst is 0.01 to 10 mol%, particularly 0.2 to 5 mol, based on one hydroxyl group of the bisphenol compound (2). %used.

  In this reaction, a solvent as exemplified in the column of production of bisphenol compound (2) can be used. Excess epichlorohydrin can also be used as a solvent.

  The unsaturated monobasic acid (E) used in the preparation of the alkali-developable photosensitive resin composition of the present invention is used to improve the sensitivity of the alkali-developable photosensitive resin composition, for example, acrylic acid , Methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, dicyclopentadiene / malate or one carboxyl group and 2 And polyfunctional (meth) acrylates having at least one (meth) acryloyl group.

  The polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups has, for example, one hydroxyl group and two or more (meth) acryloyl groups in one molecule. It can be obtained by reacting a polyfunctional (meth) acrylate with a dibasic acid anhydride or carboxylic acid.

  Examples of the polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups include the following compound Nos. 21-No. 23.

  Examples of the polybasic acid anhydride (C) used for obtaining the alkali-developable photosensitive resin composition of the present invention include succinic anhydride, maleic anhydride, trimellitic anhydride, phthalic anhydride, and methyltetrahydrophthalic anhydride. Monoanhydrides such as acid, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, methyl hymic anhydride 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic anhydride, 3,3′-4,4′-benzophenone tetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrimellitate) 2,2′-3,3′-benzophenonetetracarboxylic anhydride, 3,3 ′, 4,4′- Phenyltetrasulfonic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl- 3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, meso-butane-1,2 , 3,4-tetracarboxylic acid anhydrides and other dianhydrides, glycerol tris (anhydro trimellitate) and other dianhydrides, and dianhydrides and monoanhydrides may be combined. Monoanhydride is particularly preferable.

Reaction product obtained by adding the β-diketone compound (B) represented by the above general formula (I) to the compound (A) having two or more (meth) acryloyl groups and hydroxyl groups in the present invention. In the production of the product, the compound (A) having two or more (meth) acryloyl groups and a hydroxyl group is essential, but the compound (A ′) having a (meth) acryloyl group and not having a hydroxyl group is converted into the present invention. It can also be produced by mixing within the range not impairing the effect (500 parts by mass or less with respect to 100 parts by mass of the compound (A)). The content of the photopolymerizable unsaturated compound (J) having a structure obtained by esterifying the polybasic acid anhydride (C) to the reaction product thus obtained is determined by the alkali development of the present invention. In the photosensitive photosensitive resin composition, it is preferably 1 to 70% by mass, more preferably 20 to 60% by mass, and the acid value of the solid content is preferably 20 to 100 mg · KOH / g, more preferably 50 to 100 mg · KOH. / G.
Examples of the compound (A ′) having a (meth) acryloyl group and not having a hydroxyl group include pentaerythritol tetraacrylate, trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and ditrimethylol. Examples include propane tetraacrylate, isocyanuric acid EO-modified triacrylate, bisphenol AEO-modified diacrylate, bisphenol FEO-modified diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, and trimethylolpropane PO-modified triacrylate.

  The alkali-developable photosensitive resin composition of the present invention may contain a solvent in addition to the photopolymerizable unsaturated compound (J), for example, the photopolymerizable unsaturated compound (J). When the amount is within the above preferred range, a solvent can be used for the remainder other than the photopolymerizable unsaturated compound (J). Specific examples of the solvent include those exemplified as the solvent described later. Moreover, without removing the solvent used when synthesizing the photopolymerizable unsaturated compound (J) from the components (A) to (E), it is contained in the alkali-developable photosensitive resin composition of the present invention as it is. Also good. Moreover, (A)-(E) each component can be used by 1 type or in mixture of 2 or more types.

  The alkali-developable photosensitive resin composition of the present invention can be used as an alkali-developable photosensitive resin composition without adding a photopolymerization initiator (F), but in order to obtain a more sensitive resin composition. Further, it may be mixed with a photopolymerization initiator (F) and a solvent to form an alkali-developable photosensitive resin composition.

  In the alkali-developable photosensitive resin composition of the present invention, when the photopolymerization initiator (F) is used, the content of the photopolymerizable unsaturated compound (J) is from the alkali-developable photosensitive resin composition to the solvent. It is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, based on the total mass of all solids excluding.

  As the photopolymerization initiator (F), conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl- 1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl Anthraquinone, 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4-butyl Benzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s -Triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine, Camphorquinone, N-1414, N-1717, N-1919, PZ-408 (manufactured by ADEKA), IRGACU E369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by Ciba Specialty Chemicals), benzoyl peroxide, compounds represented by the following general formulas (IV) to (VI), and the like. A photoinitiator can be used 1 type or in combination of 2 or more types. When using these other photopolymerization initiators, the amount used is preferably 1 mass times or less the amount of the β-diketone compound of the present invention.

（式中、Ｒ⁵¹、Ｒ⁵²及びＲ⁵³は、それぞれ独立に、上記一般式（Ｉ）におけるＲ²と同じであり、Ｙ²は、ハロゲン原子又はアルキル基を表し、ｇは０〜５の整数である。）

Wherein R ⁵¹ , R ⁵² and R ⁵³ are each independently the same as R ² in the general formula (I), Y ² represents a halogen atom or an alkyl group, and g is 0-5. (It is an integer.)

（式中、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³及びＹ²は上記一般式（IV）と同じであり、Ｒ’⁵¹、Ｒ’⁵²及びＲ’⁵³は、Ｒ⁵¹と同じであり、Ｙ’²はＹ²と同じであり、Ｒ⁵⁴はジオール残基又はジチオール残基を表し、Ｚ²は酸素原子又は硫黄原子を表し、ｅ及びｆは、それぞれ独立に、０〜４の整数である。）

(In the formula, R ⁵¹ , R ⁵² , R ⁵³ and Y ² are the same as those in the general formula (IV), R ′ ⁵¹ , R ′ ⁵² and R ′ ⁵³ are the same as R ⁵¹ , and Y ′ ² Is the same as Y ² , R ⁵⁴ represents a diol residue or a dithiol residue, Z ² represents an oxygen atom or a sulfur atom, and e and f are each independently an integer of 0 to 4.)

（式中、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³及びＹ²は上記一般式（IV）と同じであり、Ｚ³は酸素原子、硫黄原子又はセレン原子を表し、Ａは複素環基を表し、ｇは０〜４の整数であり、ｐは０〜５の整数であり、ｑは０又は１である。）

(In the formula, R ⁵¹ , R ⁵² , R ⁵³ and Y ² are the same as those in the general formula (IV), Z ³ represents an oxygen atom, a sulfur atom or a selenium atom, A represents a heterocyclic group, g Is an integer from 0 to 4, p is an integer from 0 to 5, and q is 0 or 1.)

  In the alkali-developable photosensitive resin composition of the present invention, the content of the photopolymerization initiator (F) is preferably a proportion of the total mass of the total solid content excluding the solvent from the alkali-developable photosensitive resin composition. It is 0.01-20 mass%, More preferably, it is 0.05-20 mass%. Moreover, the said photoinitiator (F) can be used by 1 type or in mixture of 2 or more types.

The solvent contained in the alkali-developable photosensitive resin composition of the present invention is not particularly limited as long as it is a solvent that can dissolve or disperse the above-mentioned components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone Ketones such as acetone, methyl isopropyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; acetic acid Ester solvents such as methyl, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate Cellsolve solvents of: alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; BTX solvents such as benzene, toluene, xylene; hexane, heptane, octane, cyclohexane, etc. Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.), etc. Paraffinic solvents; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid , Acetonitrile, disulfur Carbon, N, N- dimethylformamide, N- methylpyrrolidone, and among these, ketones or cellosolve solvent. These solvents can be used alone or in combination of two or more.
In the alkali-developable photosensitive resin composition of the present invention, the content of the solvent is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total solid content in the alkali-developable photosensitive resin composition. It is good to adjust it to be%.

  The colored alkali-developable photosensitive resin composition of the present invention is obtained by adding the coloring material (G) to the alkali-developable photosensitive resin composition.

As the pigment used as the coloring material in the colored alkali-developable photosensitive resin composition of the present invention, any of the known pigments used in the production of conventional color filters can be used. Specific examples of organic pigments are shown by color index (CI) numbers below. In the list below, “x” represents C.I. I. It is an integer that can be arbitrarily selected from the numbers.
・ PigmentBlue:
<C. I> 1, 1: 2, 1: x, 9: x, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 24, 24: x, 56, 60, 61, 62
・ PigmentGreen:
<C. I> 1,1: x, 2,2: x, 4,7,10,36
・ Pigment Orange
<C. I> 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 59, 60, 61, 62, 64
・ PigmentRed
<C. I> 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 3, 81: x, 83, 88, 90, 112, 119, 122, 123, 144, 146, 149, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 224, 226
・ PigmentViolet:
<C. I> 1, 1: x, 3, 3: 3, 3: x, 5: 1, 19, 23, 27, 32, 42
・ Pigment Yellow
<C. I> 1, 3, 12, 13, 14, 16, 17, 24, 55, 60, 65, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,156,175

  Further, as black pigments, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # manufactured by Mitsubishi Chemical Corporation 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, diamond black LI, diamond black LH, diamond black N339, diamond Rack SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LR, Can Curve Inc. Carbon Black Thermax N990, N991, N907, N908, N990, N991, N908 manufactured by Asahi Carbon Co., Ltd. Carbon Black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa carbon black ColorBlackFw200, ColorBlackFw2, ColorBlackFw2V, ColorBlackFw1, ColorBlack Fw18, ColorBlackS170, ColorBlackS160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, SpecialBlack350, PrintexU, PrintexV, Printex140U, Printex140V (both trade names), and the like.

  Other pigments include miloli blue, iron oxide, titanium oxide, calcium carbonate, magnesium carbonate, silica, alumina, cobalt, manganese, talc, chromate, ferrocyanide, various metal sulfates, sulfides, selenides, Inorganic pigments such as phosphate ultramarine blue, bitumen, cobalt blue, cerulean blue, pyridiane, emerald green, and cobalt green can also be used. These pigments can be used alone or in combination of two or more.

  The dyes that can be used as the colorant (G) include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes. Examples thereof include dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, and the like. These may be used alone or in combination of two or more.

  In the colored alkali-developable photosensitive resin composition of the present invention, the content of the colorant (G) is preferably a ratio of the total solid content excluding the solvent from the colored alkali-developable photosensitive resin composition. It is 0.5 to 70%, more preferably 5 to 60% by mass.

  In the alkali-developable photosensitive resin composition and colored alkali-developable photosensitive resin composition of the present invention, a monomer having an unsaturated bond, a chain transfer agent, a surfactant and the like can be used in combination.

Examples of the monomer having an unsaturated bond include: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, acrylic Methoxyethyl acid, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Acid-t-butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythris Tall tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate and the like.
In the alkali-developable photosensitive resin composition of the present invention, the content of the monomer having an unsaturated bond is preferably 0 in terms of the total mass of the total solid content excluding the solvent from the alkali-developable photosensitive resin composition. 0.01 to 50% by mass, more preferably 10 to 40% by mass. These may be used alone or in combination of two or more.

  Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3 -Mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto- 2-butanol, mercapto Enol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro Mercapto compounds such as pionate), disulfide compounds obtained by oxidizing the mercapto compound, iodinated alkyls such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Compounds. These may be used alone or in combination of two or more.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these can be used alone or in combination of two or more.

  The properties of the cured product can be improved by further using a thermoplastic organic polymer in the alkali-developable photosensitive resin composition and the colored alkali-developable photosensitive resin composition of the present invention. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester. These may be used alone or in combination of two or more.

  In addition, for the alkali-developable photosensitive resin composition and the colored alkali-developable photosensitive resin composition, if necessary, a thermal polymerization inhibitor such as anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; Conventional additives such as adhesion promoters, fillers, defoamers, dispersants, leveling agents, silanes and pulling agents, flame retardants, and the like can be added. These may be used alone or in combination of two or more.

  The alkali-developable photosensitive resin composition and the colored alkali-developable photosensitive resin composition of the present invention are prepared by known means such as spin coater, bar coater, roll coater, curtain coater, various screen printing, ink jet printing, and immersion. It is applied on a supporting substrate such as metal, paper, plastic, and glass. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  The (colored) alkali-developable photosensitive resin composition of the present invention is mainly used as a (colored) alkali-developable photosensitive resin composition, mixed with the solvent, the photopolymerization initiator, and a coloring material. The (colored) alkali-developable photosensitive resin composition is not particularly limited in its use, and is a photocurable paint, a photocurable adhesive, a printing plate, a printed wiring board photoresist, a plasma display, an electroluminescence panel, It can be used for various applications such as formation of a pixel portion of a color filter used for a video camera or a liquid crystal display, or a liquid crystal split orientation control protrusion.

  In addition, as an active light source used for curing the alkali-developable photosensitive resin composition and the colored alkali-developable photosensitive resin composition of the present invention, a light source that emits light having a wavelength of 300 to 450 nm is used. For example, ultrahigh pressure mercury, mercury vapor arc, carbon arc, xenon arc, or the like can be used.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further in detail, this invention is not limited to these Examples etc. In the following examples and the like, “%” means mass%.
In Examples 1-1 to 1-4, an alkali-developable photosensitive resin composition containing a photopolymerizable unsaturated compound (J) was produced. In Examples 2-1 to 2-4, the alkali-developable photosensitive resin composition produced in Examples 1-1 to 1-4 was mixed with a monomer having an unsaturated bond and a solvent to obtain the present invention. An alkali-developable photosensitive resin composition was prepared. Moreover, in Examples 3-1 to 3-4, a coloring material (G), a monomer having an unsaturated bond, and a solvent are added to the alkali-developable photosensitive resin composition produced in Examples 1-1 to 1-4. By mixing, a colored alkali-developable photosensitive resin composition of the present invention was prepared. In Examples 4-1 to 4-4, the photopolymerization initiator (F), the colorant (G), the non-photosensitive initiator (F) were added to the alkali-developable photosensitive resin compositions produced in Examples 1-1 to 1-4. A monomer having a saturated bond and a solvent were mixed to prepare a colored alkali-developable photosensitive resin composition of the present invention.

[Example 1-1] Alkali-developable photosensitive resin composition No. <Step 1> Production of bis (4-hydroxyphenyl) -4-biphenylyl (cyclohexyl) methane 70.5 g of biphenylyl cyclohexyl ketone, 200.7 g of phenol and 10.15 g of thioacetic acid were charged, and trifluoromethanesulfonic acid 40 0.0 g was added dropwise at 18 ° C. over 20 minutes. After reacting at 17 to 19 ° C. for 18 hours, 500 g of water was added to stop the reaction, 500 g of toluene was added, and the organic phase was washed with water until the pH became 3 to 4, and the organic phase was separated. Toluene, water and excess phenol were distilled off. Toluene was added to the residue and the precipitated solid was filtered off and dispersed and washed with toluene to obtain 59.2 g of light yellow crystals (yield 51%). The melting point of the pale yellow crystals was 239.5 ° C., and it was confirmed that the pale yellow crystals were the target product.

<Step 2> Production of bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane Bis (4-hydroxyphenyl) -4-biphenylyl (cyclohexyl) methane 57 obtained in Step 1 0.5 g and epichlorohydrin 195.8 g were added, 0.602 g of benzyltriethylammonium chloride was added, and the mixture was stirred at 64 ° C. for 18 hours. Subsequently, the temperature was lowered to 54 ° C., and 43.0 g of a 24% by weight aqueous sodium hydroxide solution was added dropwise and stirred for 30 minutes. Epichlorohydrin and water were distilled off, 216 g of methyl isobutyl ketone was added and washed with water, and 2.2 g of 24 wt% sodium hydroxide was added dropwise. After stirring at 80 ° C. for 2 hours, the mixture was cooled to room temperature, neutralized with a 3 wt% aqueous sodium monophosphate solution, and washed with water. The solvent was distilled off to obtain 57 g of light yellow solid (yield 79%). (Melting point 64.2 ° C., epoxy equivalent 282, n = 0.04). The pale yellow solid was confirmed to be the target product.

<Step 3> Production of Epoxy Acrylate Solution A-BC Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane obtained in Step 2 (hereinafter also referred to as compound d-1) 842.7 g, acrylic acid (hereinafter also referred to as compound e-1) 220.5 g, 2,6-di-tert-butyl-p-cresol 4.29 g, benzyltriethylammonium chloride 5.42 g and propylene glycol-1- 708.8 g of monomethyl ether-2-acetate was added and stirred at 120 ° C. for 14 hours. What cooled this to room temperature was used as the epoxy acrylate solution A-BC.

<Step 4> Alkali-developable photosensitive resin composition No. Preparation of 1 Epoxy acrylate solution A-BC obtained in Step 3 19.00 g, 1- [9-ethyl-6- (4-fluoro-2-methylbenzoyl) -9H-carbazol-3-yl] -butane-1 , 3-dione (hereinafter also referred to as compound b-1) 3.32 g, 1,8-diazabicyclo [5,4,0] -7-undecene 0.24 g, propylene glycol-1-monomethyl ether-2-acetate 0 .64 g was charged and stirred at 120 ° C. for 12 hours. To this was added 6.73 g of propylene glycol-1-monomethyl ether-2-acetate and cooled to room temperature. After cooling, 2.9 g of succinic anhydride (hereinafter also referred to as compound c-1) and 6.9 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, the alkali-developable photosensitive resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was used. 1 was obtained (Mw = 4430, Mn = 2110, acid value 96.5 mgKOH / g).
The alkali-developable photosensitive resin composition No. 1 is a photopolymerizable unsaturated compound (J) containing 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-1 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of 1 to 2 is sandwiched between diketones in the β-diketone portion of the compound b-1 that is the component (B) Michael addition polymerization of 0.5 methylene group hydrogen atoms, and the addition of 0.9 moles of acid anhydride structure of compound (C) as component (C) to one hydroxyl group It was obtained.

[Example 1-2] Alkali-developable photosensitive resin composition No. <Step 1> Preparation of epoxy acrylate solution 2,2-bis [4- (2,3-epoxypropoxy) phenyl] propane (hereinafter also referred to as compound d-2) 185 g, acrylic acid (compound e-1 ) 73.5 g, 2,6-di-tert-butyl-p-cresol 0.7 g, benzyltriethylammonium chloride 1.7 g and propylene glycol-1-monomethyl ether-2-acetate 174.0 g were charged at 120 ° C. The mixture was stirred for 16 hours and cooled to room temperature to obtain an epoxy acrylate solution.

<Step 2> Alkali-developable photosensitive resin composition No. 2. Preparation of 13.93 g of the epoxy acrylate solution obtained in Step 1, 1- [9-ethyl-6- (4-fluoro-2-methylbenzoyl) -9H-carbazol-3-yl] -butane-1,3 -Charging a dione (compound b-1) 3.32g, 1,8-diazabicyclo [5,4,0] -7-undecene 0.24g, propylene glycol-1-monomethyl ether-2-acetate 0.64g, Stir at 8 ° C. for 8 hours. To this was added 5.73 g of propylene glycol-1-monomethyl ether-2-acetate and cooled to room temperature. After cooling, 2.9 g of succinic anhydride (compound c-1), propylene glycol-1-monomethyl ether-2- Acetate 5.8g was added and it stirred at 100 degreeC for 5 hours. After cooling to room temperature, the alkali-developable photosensitive resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was used. 2 was obtained (Mw = 4300, Mn = 2140, acid value 114.5 mgKOH / g).
The alkali-developable photosensitive resin composition No. The photopolymerizable unsaturated compound (J) 2 contains 1.0 of the carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-2 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of 1 to 2 is sandwiched between diketones in the β-diketone portion of the compound b-1 that is the component (B) Michael addition polymerization of 0.5 methylene group hydrogen atoms, and the addition of 0.9 moles of acid anhydride structure of compound (C) as component (C) to one hydroxyl group It was obtained.

[Example 1-3] Alkali-developable photosensitive resin composition No. Production of 3 Epoxy acrylate solution A-BC 53.5 g, 1- (9-propyl-9H-carbazol-3-yl) -butane-1,3-dione (hereinafter also referred to as compound b-2) 8.8 g, , 8-diazabicyclo [5,4,0] -7-undecene (0.8 g) and propylene glycol-1-monomethyl ether-2-acetate (20.3 g) were charged and stirred at 120 ° C. for 13 hours. This was cooled to room temperature, 6.8 g of tetrahydrophthalic anhydride (hereinafter also referred to as compound c-2) and 17.62 g of propylene glycol-1-monomethyl ether-2-acetate were added, and the mixture was stirred at 100 ° C. for 5 hours. After cooling to room temperature, the alkali-developable photosensitive resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was used. 3 was obtained (Mw = 4440, Mn = 2290, acid value 55.8 mgKOH / g).
The alkali-developable photosensitive resin composition No. 3 includes a photopolymerizable unsaturated compound (J) containing 1.0 carboxyl group of the compound e-1 as the component (E) for one epoxy group of the compound d-1 as the component (D). One acrylate group of the epoxy adduct as the component (A) having a structure added at a ratio of the number is sandwiched between diketones in the β-diketone portion of the compound b-2 as the component (B) The hydrogen atom of the methylene group is Michael addition polymerized at a ratio of 0.67, and further, the acid anhydride structure of compound (C) component c-2 is added at a ratio of 0.5 to one hydroxyl group. It was obtained.

[Example 1-4] Alkali-developable photosensitive resin composition No. 4 Preparation of epoxy acrylate solution A-BC 35.6 g, 1- [9-ethyl-6- (4-fluoro-2-methylbenzoyl) -9H-carbazol-3-yl] -butane-1,3-dione (compound b-1) Charged 8.31 g, 0.5 g of 1,8-diazabicyclo [5,4,0] -7-undecene, and 16.0 g of propylene glycol-1-monomethyl ether-2-acetate at 120 ° C. for 10 hours. Stir. To this cooled to room temperature, 6.4 g of tetrahydrophthalic anhydride (compound c-2) and 14.5 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, the alkali-developable photosensitive resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was used. 4 was obtained (Mw = 4810, Mn = 2190, acid value 65.9 mgKOH / g).
The alkali-developable photosensitive resin composition No. 4 includes a photopolymerizable unsaturated compound (J) having 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-1 as the component (D). One acrylate group of the epoxy adduct as the component (A) having a structure added at a ratio of the number is sandwiched between diketones in the β-diketone portion of the compound b-1 as the component (B). Michael addition polymerization is performed at a ratio of 0.67 hydrogen atoms in the methylene group, and the acid anhydride structure of compound (c), component (C), is added at a ratio of 0.7 to one hydroxyl group. It was obtained.

[Comparative Example 1-1] Comparative resin composition No. Preparation of 1 Epoxy acrylate solution A-BC 53.5 g, 1- (2-naphthyl) butane-1,3-dione (hereinafter also referred to as compound b′-1) as a β-diketone compound having a structure different from that of component (B) 6.4 g, 0.88 g of 1,8-diazabicyclo [5,4,0] -7-undecene, and 17.9 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 4 hours. To this was cooled to room temperature, 6.8 g of tetrahydrophthalic anhydride (compound c-2) and 6.8 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, a comparative resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution. 1 was obtained (Mw = 5200, Mn = 2320, acid value 57.0 mgKOH / g).
The comparative resin composition No. 1 is a photopolymerizable unsaturated compound (J) containing 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-1 as the component (D). Hydrogen of methylene group sandwiched by diketone in β-diketone part of compound b′-1 for one acrylate group of epoxy adduct as component (A) having a structure added at a ratio of It was obtained by Michael addition polymerization at a ratio of 0.67 atoms, and further by adding an acid anhydride structure of compound c-2 as component (C) at a ratio of 0.5 to one hydroxyl group. Is.

[Comparative Example 1-2] Comparative resin composition No. Production of 2 154 g of 2,2-bis [4- (2,3-epoxypropoxy) phenyl] propane, 59.0 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol, tetra-n -0.11 g of butylammonium bromide and 23.0 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 16 hours. Cooled to room temperature, charged with 36.0 g of propylene glycol-1-monomethyl ether-2-acetate, 67.0 biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide, 120 ° C. for 4 hours, 100 ° C. For 3 hours, at 80 ° C. for 4 hours, at 60 ° C. for 6 hours, and at 40 ° C. for 11 hours. After cooling to room temperature, 90.0 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain a target propylene glycol-1-monomethyl ether-2-acetate solution as a comparative resin composition No. 2 was obtained (Mw = 7500, Mn = 2100, acid value (solid content) 91 mgKOH / g).

[Examples 2-1 to 2-4 and Comparative Examples 2-1 and 2-2] Alkali-developable photosensitive resin composition No. 5-No. 8 and comparative resin composition No. 3, no. 4 Preparation of the alkali-developable photosensitive resin composition No. obtained in Examples 1-1 to 1-4. 1-No. 4 and Comparative Examples 1-1 and 1-2, Comparative Resin Composition Nos. 1-No. Then, 7.0 g of trimethylolpropane triacrylate (compound a′-1) as a monomer having an unsaturated bond and 78 g of propylene glycol-1-monomethyl ether-2-acetate as a solvent were added to 17 g of 2 and stirred well. , Alkali-developable photosensitive resin composition No. 5-No. 8 and comparative resin composition No. 3, no. 4 was obtained.

The alkali-developable photosensitive resin composition No. prepared in Examples 2-1 to 2-4 and Comparative Examples 2-1 and 2-2. 5-No. 8 and comparative resin composition No. 3, no. Evaluation of 4 was performed as follows.
That is, the alkali-developable photosensitive resin composition was spin-coated (700 rpm) for 5 seconds on a glass substrate, air-dried for 15 minutes, and then pre-baked on a 90 ° C. hot plate for 90 seconds. Using a mask having a mask opening of 30 μm, exposure was performed at 100 mJ / cm ² with a high-pressure mercury lamp. Then, it was developed by being immersed in a 2.5% by mass sodium carbonate solution at 25 ° C. for 60 seconds, and washed thoroughly with water. At this time, the case where the pattern was formed was indicated by ◯, and the case where the pattern was not formed was indicated by ×. The results are shown in Table 1.

  The alkali-developable photosensitive resin compositions of Examples 2-1 to 2-4 were cured by exposure without an initiator and formed a pattern by alkali development. On the other hand, the comparative resin compositions of Comparative Examples 2-1 and 2-2 were not cured even when exposed without an initiator, and a pattern could not be formed by alkali development.

[Examples 3-1 to 3-4 and Comparative examples 3-1 and 3-2] Colored alkali-developable photosensitive resin composition No. 1-No. 4 and comparative colored resin composition no. 1, no. 2 Preparation of alkali-developable photosensitive resin composition No. obtained in Examples 1-1 to 1-4. 1-No. 4 and Comparative Examples 1-1 and 1-2, Comparative Resin Composition Nos. 1-No. 2 to 70 g of trimethylolpropane triacrylate (compound a′-1) as a monomer having an unsaturated bond, carbon black (“MA100” manufactured by Mitsubishi Chemical Corporation) 30 g as a coloring material (G), and a solvent Add 75 g of propylene glycol-1-monomethyl ether-2-acetate and stir well. Then, the colored alkali-developable photosensitive resin composition No. 1-No. 4 and comparative colored resin composition no. 1, no. 2 was obtained.

The colored alkali-developable photosensitive resin composition No. prepared in Examples 3-1 to 3-4 and Comparative Examples 3-1 and 3-2. 1-No. 4 and comparative colored resin composition no. 1, no. Evaluation of 2 was performed as follows.
That is, the alkali-developable photosensitive resin composition was spin-coated (700 rpm) for 5 seconds on a glass substrate, air-dried for 15 minutes, and then pre-baked on a 90 ° C. hot plate for 90 seconds. Using a mask with a mask opening of 30 μm, exposure was performed with a high-pressure mercury lamp at 200 mJ / cm ² . Then, it was developed by being immersed in a 2.5% by mass sodium carbonate solution at 25 ° C. for 40 seconds, and thoroughly washed with water.
At this time, the case where the pattern was formed was indicated by ◯, and the case where the pattern was not formed was indicated by ×. The results are shown in Table 2.

  The colored alkali-developable photosensitive resin compositions of Examples 3-1 to 3-4 were cured by exposure without an initiator, and a pattern was formed by alkali development. On the other hand, the comparative colored resin compositions of Comparative Examples 3-1 and 3-2 were not cured even when exposed without an initiator, and a pattern could not be formed by alkali development.

[Examples 4-1 to 4-4 and Comparative Examples 4-1 and 4-2] Colored alkali-developable photosensitive resin composition No. 5-No. 8 and comparative colored resin composition No. 3, no. 4 Preparation of the alkali-developable photosensitive resin composition No. obtained in Examples 1-1 to 1-4. 1-No. 4 and Comparative Examples 1-1 and 1-2, Comparative Resin Composition Nos. 1-No. 2 to 70 g of trimethylolpropane triacrylate (compound a′-1) as a monomer having an unsaturated bond, IRGACURE OXE 02 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator (F) 3 g) and 30 g of carbon black (“MA100” manufactured by Mitsubishi Chemical Co., Ltd.) as a coloring material (G) and 75 g of propylene glycol-1-monomethyl ether-2-acetate as a solvent were added and stirred well. Resin composition No. 5-No. 8 and comparative colored resin composition No. 3, no. 4 was obtained.

The colored alkali-developable photosensitive resin composition No. prepared in Examples 4-1 to 4-4 and Comparative Examples 4-1 and 4-2. 5-No. 8 and comparative colored resin composition No. 3, no. Evaluation of 4 was performed as follows.
That is, the alkali-developable photosensitive resin composition was spin-coated (700 rpm) for 5 seconds on a glass substrate, air-dried for 15 minutes, and then pre-baked on a 90 ° C. hot plate for 90 seconds. After exposure with a high-pressure mercury lamp as a light source using a predetermined mask, the film was immersed in a 2.5% by mass sodium carbonate solution for 40 seconds at 25 ° C., and then thoroughly washed with water. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour.
The following evaluation was performed about the obtained pattern. The results are shown in Table 3.

<Sensitivity>
At the time of exposure, the exposure amount of 50 mJ / cm ² is sufficient for a, 50 mJ / cm ² is insufficient, b is 100 mJ / cm ² for exposure, 100 mJ / cm ² is insufficient, 200 mJ / cm ^The one exposed in ² was designated as c.
<Resolution>
At the time of exposure and development, A is good pattern formation even if the line width is 10 μm or less, B is good pattern formation if the line width is 20 μm, and good pattern formation is not possible unless the line width is 30 μm or more. What was also evaluated as C.
<Adhesion>
The pattern obtained by development was observed for peeling. The pattern in which no peeling was observed was marked with ◯, and the pattern in which peeling was observed was marked with x.

  The colored alkali-developable photosensitive resin compositions of Examples 4-1 to 4-4 were high in sensitivity and excellent in resolution. Moreover, it was excellent in adhesiveness with the substrate and had little pattern peeling. On the other hand, the comparative colored resin compositions of Comparative Examples 4-1 and 4-2 were low in sensitivity, and had low resolution and adhesion to the substrate.

Claims (8)

A hydroxyl group of a reaction product obtained by adding a β-diketone compound represented by the following general formula (I) to a (meth) acryloyl group of a compound having two or more (meth) acryloyl groups and a hydroxyl group; An alkali-developable photosensitive resin composition comprising a photopolymerizable unsaturated compound having a structure obtained by an esterification reaction with a polybasic acid anhydride.

(In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² represents R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² And R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 2 to 20 carbon atoms. Represents a heterocyclic group, and the hydrogen atom of the alkyl group, aryl group, arylalkyl group and heterocyclic group is further OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , —NR ²² —OR ^23. , —NCOR ²² —OCOR ²³ , —C (═N—OR ²¹ ) —R ²² , —C (═N—OCOR ²¹ ) —R ²² , CN, halogen atom, —CR ²¹ ═CR ²² R ²³ , —CO -CR ²¹ = CR ²² R ^23, carboxyl group, substituted by an epoxy group R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl having 7 to 30 carbon atoms. The methylene group of the alkylene part of the substituent which represents an alkyl group or a C2-C20 heterocyclic group, and is represented by said R < ¹¹ >, R < ¹² >, R <^13> , R <^21> , R <^22> and R < ²³ > is unsaturated It may be interrupted 1 to 5 times by a bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, and the alkyl part of the above substituent may have a branched side chain, The alkyl terminal of the substituent may be an unsaturated bond, and R ¹² and R ¹³ and R ²² and R ²³ may be combined to form a ring, R ² is an adjacent benzene ring And R ³ and R ⁴ each independently represent R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , CN, a halogen atom, a nitro group or a hydroxyl group, a represents an integer of 0 to 3, b represents an integer of 0 to 4, a, b When is 2 or more, each of the plurality of substituents may be a different substituent, and the β-diketone moiety may be any structure of a keto-enol tautomer. ) The alkali-developable photosensitive resin composition according to claim 1, wherein the β-diketone compound is a compound in which R ¹ is a methyl group and a is 0 in the general formula (I). In the general formula (I), the β-diketone compound is R ¹ is a methyl group, R ⁴ is an acyl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, and a is 0. The alkali-developable photosensitive resin composition according to claim 1, wherein b is 0 or 1.   The alkali development according to any one of claims 1 to 3, wherein the compound having two or more (meth) acryloyl groups and a hydroxyl group has a structure which is a reaction product obtained by adding an unsaturated monobasic acid to an epoxy compound. Photosensitive resin composition. The alkali-developable photosensitive resin composition according to claim 4, wherein the epoxy compound has a structure represented by the following general formula (II).

(In the formula, Cy represents a cycloalkyl group having 3 to 10 carbon atoms, X represents a hydrogen atom, a phenyl group or a cycloalkyl group having 3 to 10 carbon atoms, and the phenyl group and the cycloalkyl group are carbon atoms. The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms or the halogen atom may be substituted, and Y and Z are each independently an alkyl group having 1 to 10 carbon atoms and the number of carbon atoms. Represents an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, wherein the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and n is a number from 0 to 10 M and r each independently represents a number of 0 to 4.)   6. The alkali-developable photosensitive resin composition according to claim 5, wherein, in the general formula (II), Cy is a cyclohexyl group, X is a phenyl group, and m and r are 0.   Furthermore, the photopolymerization initiator is contained, The alkali developable photosensitive resin composition in any one of Claims 1-6.   A colored alkali-developable photosensitive resin composition obtained by further adding a colorant to the alkali-developable photosensitive resin composition according to claim 1.