JP4883537B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition, and a photoresist ink and a photosensitive film plate using the composition.

  The photosensitive resin composition is applied to a printed wiring board substrate (hereinafter simply referred to as a substrate) as a liquid film containing a solvent, and is dried by heating to form a dry film. After being exposed imagewise, it is developed to form a photoresist image. However, in recent years, in order to improve its low workability, air pollution, and low yield, it is used as a film-like support, a dried photosensitive resin composition layer (hereinafter simply referred to as a photosensitive layer), and as necessary. A photosensitive resin composition laminate (hereinafter simply referred to as a photosensitive film) composed of a protective film layer has been used. As the photosensitive resin composition, both a so-called alkali developing type in which an unexposed portion is developed with an alkaline aqueous solution and a so-called solvent developing type in which an unexposed portion is developed with an organic solvent are known.

  When using a photosensitive film, if there is a protective film layer from the photosensitive film, it is removed to form a laminate comprising a photosensitive layer and a film-like support, and then heated so that the photosensitive layer is in contact with the substrate. Crimp (laminate). Next, after imagewise exposure using a negative film or the like, a non-exposed portion is developed using a predetermined developer such as sodium carbonate water or 1,1,1-trichloroethane to form a photoresist image on the substrate. To do. The metal surface of the substrate is etched using the formed photoresist image as a mask, or is subjected to plating treatment, and then the photoresist image is stripped using a predetermined stripping solution such as aqueous sodium hydroxide or methylene chloride. Accordingly, a printed wiring board or the like can be manufactured.

  During the above process, the photoresist image must be sufficiently resistant as a mask to etching or plating of the metal surface of the substrate. The etching process is a process of removing metal (usually copper) constituting the surface layer of the substrate using an aqueous solution of ferric chloride, cupric chloride, and ammonium persulfate. There are many kinds of plating solutions used for the plating treatment, such as solder plating, copper sulfate plating, gold plating, nickel plating, and pyrophosphate plating. In any case, the plating process is considerably more severe than the etching process because an electric current is passed in a high concentration chemical solution.

  As the photosensitive resin composition and the photosensitive film used as described above, for example, Patent Document 1 includes (1) a thermoplastic organic polymer binder, and (2) at least one fragrance in the same molecule. A compound having an aromatic ring and having at least two carboxyl groups directly bonded to the same aromatic ring, (3) a specific hexaarylbiimidazole, (4) an oxidizable leucotriarylmethane dye, (5 ) A color-curing photosensitive composition characterized by containing a compound having an addition-polymerizable ethylene group having a boiling point of 50 ° C. or higher at normal pressure.

  Patent Document 2 discloses an epoxy resin composition for semiconductor encapsulation comprising an inorganic filler, an epoxy resin, and a curing agent, and 1,8-diazabicyclo (5,4,0) undecene-7 and trimellitic acid or pyrone. An epoxy resin composition for semiconductor encapsulation is disclosed, wherein a salt with merit acid is added after melt-mixing with a phenol novolac resin in advance.

  Furthermore, Patent Document 3 is characterized by containing a novolak resin, a photosensitizer mainly composed of naphthoquinone diazide sulfonate ester, and an adhesion enhancer composed of a melamine derivative and / or a guanamine derivative. A positive photoresist composition is disclosed.

  Patent Document 4 has a specific repeating unit formed from a polycondensation product of tetracarboxylic acid or its acid anhydride and diamine in the main chain, and photopolymerization is possible at both ends thereof. A photosensitive polyimide precursor having an actinic functional group having a structure modified with an aminobenzene or trimellitic acid derivative having a substituent having a carbon-carbon double bond in its molecule, comprising tetracarboxylic acid or its The acid anhydride contains a rigid structure aromatic tetracarboxylic acid or its acid anhydride in a proportion of 70 to 100 mol%, and the diamine contains a rigid structure aromatic diamine of 70 to 100 mol%. A photosensitive polyimide precursor characterized in that the photosensitive polyimide precursor is contained in the photosensitive polyimide precursor (Claim 1), (A) the photosensitive polyimide precursor, and (B) a photopolymerizable functional group-sensitive A photosensitive polyimide resin composition comprising an auxiliary agent, (C) a photopolymerization initiator, and (D) a solvent (claim 11), and (E) a photosensitive polyimide further comprising 1H-tetrazole. A resin composition (claim 12) is disclosed.

  Furthermore, Patent Document 5 contains (A) a soluble polyimide containing a carboxyl group and / or a hydroxyl group, (B) a (meth) acrylic compound, (C) an epoxy compound, and (D) a latent curing agent. A photosensitive resin composition (Claim 1), wherein the component (D) is a dicyandiamide, phenol norvolak, epoxyphenol, adipic dihydrazide, diallylmelamine, diaminomaleonitrile, hexamethylenetetramine, amine salt, imidazole derivative 3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is at least one compound selected from the group consisting of an amine complex of boron trifluoride, methyltetrahydrophthalic anhydride, and an amine imide compound. Claim 3) is disclosed.

  Patent Document 6 includes (A) a binder polymer containing a (meth) acrylic acid ester having a branched or cyclic saturated hydrocarbon group having 9 or more carbon atoms as a copolymerization component, and (B) ethylenic. A photosensitive resin composition comprising a photopolymerizable compound having an unsaturated bond and (C) a photopolymerization initiator (Claim 1); (B) having an ethylenically unsaturated bond As a photopolymerizable compound, a compound obtained by reacting a polyhydric alcohol with an alpha, beta-unsaturated carboxylic acid, a bisphenol A (meth) acrylate compound, a nonylphenoxypolyethyleneoxy (meth) acrylate compound, and a phthalic acid compound The photosensitive resin composition according to claim 1, which contains at least one selected from the group consisting of: The photosensitive resin composition according to any one of claims 1 to 6, which contains a 2,4,5-triarylimidazole dimer as the photopolymerization initiator (C). (Claim 7) is disclosed.

  Further, in Patent Document 7, (a) liquid epoxy resin, (b) curing agent, (c) curing accelerator, and (d) liquid epoxy resin composition containing an inorganic filler as essential components, 3,4-Dimethyl-6- (2-methyl-1-propenyl) -1,2,3,6-tetrahydrophthalic acid and 1-isopropyl-4-methyl-bicyclo [2,2,2] oct-5 -A liquid epoxy resin composition comprising 5 to 75 parts by weight (parts by mass) of a mixture of ene-2,3-dicarboxylic acid with respect to 100 parts by weight (parts by mass) of the entire curing agent; The composition (claim 3) according to claim 1 or 2, wherein the curing accelerator of the component is an imidazole compound and / or an organic phosphorus compound.

  Patent Document 8 also discloses a polyamic acid which is derived from one or more aromatic dianhydrides and one or more aliphatic diamines and forms a cured polyimide having a modulus of less than 2 GPa when exposed to heat. An ethylenically unsaturated monomer mixture comprising a compound selected from the group consisting of: amine (meth) acrylate, amine methacrylate, and combinations thereof; and an amine-free (meth) acrylate compound; a photoinitiator; The composition according to claim 1, further comprising a tackifier, wherein the composition is a low-temperature curable photosensitive composition characterized in that it can be developed in an aqueous carbonate. (Claim 12); wherein the adhesion promoter is 3-mercapto-1H-1,2,4-triazole, 5-amino-1,3,4-thiadiazole-2-thio And 2-mercaptobenzimidazole, selected from the group consisting of 2- (2′-hydroxy-5-methacrylyloxy-ethylphenyl) -2H-benzotriazole, polybenzimidazole, and combinations thereof. A composition according to claim 12 (claim 13) is disclosed.

JP 62-106450 A Japanese Patent Laid-Open No. 2003-40978 Japanese Patent Laid-Open No. 7-120914 JP 2004-285129 A JP 2004-333672 A Japanese Patent Laid-Open No. 7-120914 JP 2002-97257 A JP 2006-146244 A

  The color curable photosensitive composition described in the above-mentioned Patent Document 1 contains a thermoplastic organic polymer binder, an aromatic carboxylic acid compound and an imidazole dimer. , A component blended as a reaction initiator, and cannot improve the adhesion of the photosensitive composition. Moreover, the epoxy resin composition for semiconductor encapsulation described in Patent Document 2 is intended to improve the adhesion by adding a carboxylic acid such as trimellitic acid to the epoxy resin. Adhesiveness cannot be sufficiently improved only by adding carboxylic acid. Furthermore, the positive photoresist composition described in Patent Document 3 discloses that a novolak resin is used in combination with a heterocyclic compound and a carboxylic acid compound as an adhesion enhancer. The resulting polymer is a novolak resin and cannot be used as a photosensitive resin composition. Further, in the photosensitive polyimide resin composition described in Patent Document 5, it is disclosed that a heterocyclic compound such as 1H-tetrazole is added to the polyimide resin as an additive. Even if only the compound is added, a sufficient adhesion improving effect cannot be obtained. Furthermore, the photosensitive resin composition described in Patent Document 6 includes a binder polymer, a copolymer of (meth) acrylic acid ester, a photopolymerizable compound having an ethylenically unsaturated group, a carboxylic acid compound, and photopolymerization initiation. Heterocyclic compounds are used as agents, but these are compounded as a constituent component of a resin for reacting to form a photosensitive resin, and a resin additive for improving adhesion Is not formulated as In addition, it is thought that the resin additive mix | blended in order to improve adhesiveness does not contribute to reaction with resin used as a base. Further, in the liquid epoxy resin composition described in Patent Document 7, a heterocyclic compound is used as a curing accelerator, but even when only the heterocyclic compound is added, a sufficient adhesion improving effect cannot be obtained. Furthermore, in the photosensitive composition described in Patent Document 8, a heterocyclic compound is used as an adhesion promoter, but even if only the heterocyclic compound is added, a sufficient adhesion improving effect cannot be obtained.

  In addition, due to the recent high integration of semiconductor elements, LSIs have become smaller and higher in performance, and the number of component leads has increased rapidly, and the number of printed wiring boards has been dramatically increased to connect them. In addition, the printed wiring board itself is required to be miniaturized. For this reason, it is necessary to make the wiring of the printed wiring board fine pitch, and for this, it is necessary to improve the adhesion between the photoresist image and the copper foil. At present, sufficient adhesiveness that can cope with the process is not obtained.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition that can form an extremely stable resist film that has excellent adhesion to a copper surface and that is not affected by changes over time after coating or lamination, and a photosensitive property using the same. The object is to provide a film, a photoresist and a printed wiring board.

That is, the photosensitive resin composition of the present invention comprises (A) one or more carboxylic acid compounds selected from the group consisting of fatty acids and aromatic carboxylic acids (excluding carboxybenzotriazole) ; (B) triazole class, one is the group or al selection consisting of tetrazoles and imidazoles or more heterocyclic compounds; photopolymerizable compound having a (D) an ethylenically unsaturated group; (C) a thermoplastic organic polymer ( E) a photopolymerization initiator ; and (F) ammonia, ethylenediamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, diethylenetriamine, diethylamine, dibutylamine, Hexahydroaniline, tetra Ethylenepentamine, pentaethylenehexamine, allylamine, 2-aminopropanol, 3-aminopropanol, 4-aminobutanol, 4-methylaminobutanol, ethylaminoethylamine, 2-ethylhexylamine, di-2-ethylhexylamine, oleylamine, dodecyl It is characterized by containing an amine selected from the group consisting of amine, dicyclohexylamine, octylamine, octadecylamine and hexylamine .

  The photosensitive resin composition of the present invention further comprises a thermal polymerization inhibitor, a plasticizer, a dye (pigment, photochromic agent), an antioxidant, a surface tension modifier, a stabilizer, a chain transfer agent, an antifoaming agent. 1 type, or 2 or more types of additives selected from the group which consists of an agent, a flame retardant, a peeling accelerator, a fragrance | flavor, an imaging agent, a thermal crosslinking agent, and developability and a plating property improvement agent are characterized by the above-mentioned.

  In addition, the photosensitive resin composition of the present invention further includes one or more selected from the group consisting of alcohols, ketones, acetate esters, glycol ethers, glycol ether esters and petroleum solvents. It contains an organic solvent for dilution.

  Furthermore, the photoresist of the present invention is characterized by comprising the above photosensitive resin composition.

  In addition, the photosensitive film of the present invention is characterized in that a photosensitive resin composition layer formed by applying the photosensitive resin composition onto a support and drying it is formed on the support.

  When the photosensitive resin composition of the present invention is applied directly to a copper surface as a solution or laminated as a resist film, the adhesion between the resist film and the copper surface is excellent, and the copper surface after lamination is prevented from being discolored. Is very high and stable, and the cost of the raw materials used is low. Therefore, in the etching or plating process of the next process, the resist film is not lifted off from the copper surface, and the resist end portion is not broken, and the plating is not peeled off. If the photosensitive resin composition of the present invention is used, The advantage is that a good printed wiring board can be efficiently manufactured.

  Examples of the carboxylic acid compound (A) used in the photosensitive resin composition of the present invention include aliphatic carboxylic acids and aromatic carboxylic acids (excluding carboxybenzotriazole). In addition, these can be used individually by 1 type or in combination of 2 or more types.

  Here, the aliphatic carboxylic acid is a compound group having 1 to 30 carbon atoms and having one or more carboxyl groups, and may be structurally saturated, unsaturated, or linear. It may be a branched type and may contain a cyclic structure (alicyclic ring, aromatic ring) in the structure. As a substituent, oxygen (hydroxyl group, carbonyl group, carboxyl group, ether, ester, etc.), nitrogen (amino group, Compounds that can contain an amide group, a nitro group, a cyano group, etc.) are preferred. For example, propionic acid, butyric acid, valeric acid, caproic acid (hexanoic acid), heptanoic acid, caprylic acid (octanoic acid), pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid , Behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, acrylic acid, crotonic acid, cinnamic acid, obtusylic acid, caproleic acid, undecylenic acid, lindenoic acid, tuzuic acid, fizeteric acid, myristoleic acid, palmitolein Acid, elaidic acid, petroceric acid, oleic acid, asclepinic acid, vaccenic acid, gadoleic acid, gondoic acid, cetreic acid, erucic acid, brassic acid, ceracoleic acid, nergonic acid, ximenoic acid, lumenic acid, sorbic acid, linoleic acid, Hiragoic acid, alpha-linolenic acid, Nimmer-linolenic acid, punicic acid, alpha-eleostearic acid, beta-eleostearic acid, moloctic acid, stearidonic acid, arachidonic acid, eicosapentanoic acid, sardine acid, docosahexaenoic acid, nisinic acid, tarililic acid, stearol Acid, crepenic acid, ximenic acid, 2-methylpropanoic acid, 2-methylbutanoic acid, isovaleric acid, neopentanoic acid, 2,3-dimethylpentanoic acid, 4,4-dimethylpentanoic acid, 2-ethylbutyric acid, 2,2 -Dimethylhexanoic acid, 2-ethylhexanoic acid, octanoic acid, isooctanoic acid, isononanoic acid, isodecanoic acid, neodecanoic acid, isotridecanoic acid, isopalmitic acid, isostearic acid, methacrylic acid, senecioic acid, citronellic acid, oxalic acid, malon Acid, succinic acid, glutaric acid, adipic acid, pimelin , Suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, maleic acid, fumaric acid, octenyl succinic acid, dodecenyl succinic acid, Octadecenedioic acid, pentadecenyl succinic acid, tricarballylic acid, glutamic acid, 2,5-dibenzamidopentanoic acid, glycolic acid, lactic acid, alpha-oxybutyric acid, malic acid, tartaric acid, citric acid, gluconic acid, ethylenediaminetetraacetic acid , Hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, dicarboxymethylglutamic acid, hydroxyethyliminodiacetic acid, dihydroxyethylglycine, 1,3-propanediaminetetraacetic acid Examples include acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, dihydroxyethylethylenediaminediacetic acid, and methylglycinediacetic acid. Among these compounds, octanoic acid, isostearic acid, octadecanedioic acid, octenyl succinic acid, ethylenediaminetetraacetic acid, triethylenetetramine hexaacetic acid, tartaric acid and the like are particularly preferable.

  Aromatic carboxylic acids (excluding carboxybenzotriazole) have a benzene, naphthalene, or anthracene structure as a skeleton, and have one or two or more carboxyl groups that are directly bonded to them, and have a C1-C12 structure as a substituent. It may be saturated or unsaturated, may be linear or branched, may contain a cyclic structure (alicyclic ring, aromatic ring) in its structure, oxygen (hydroxyl group, carbonyl group, carboxyl group, ether, ester, etc.) ), Nitrogen (amino group, amide group, nitro group, cyano group, etc.), sulfur (thiorule group, sulfide, etc.) and halogen (fluorine, chlorine, bromine, iodine, etc.) are preferable. For example, benzoic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, toluic acid, xylic acid, hemimellitic acid, trimellitic acid, trimesic acid, hemellitic acid, mesitylene acid, utobiic acid, planicylic acid, gamma-isojuric acid , Alpha-isoduric acid, jurylic acid, merophanic acid, planitic acid, pyromellitic acid, meritic acid, diphenic acid, salicylic acid, o-pyrocatechuic acid, beta-resorcylic acid, gentisic acid, gamma-resorcylic acid, protocatechuic acid, thiosalicylic acid , Alpha-resorcylic acid, orceric acid, gallic acid, p-chlorobenzoic acid, anisic acid, creosote acid, o-homosalicylic acid, m-homosalicylic acid, p-homosalicylic acid, vanillic acid, isovanillic acid, syringic acid, veratrum Acid, o-verattle Acid, asarone acid, cumin acid, Meshito acid, m- Hemipin acid, homophthalic acid, Homoisofutaru acid, homo terephthalic acid, Futaron acid, Isofutaron acid and Terefutaron acid. Among these compounds, benzoic acid, naphthoic acid, isophthalic acid, trimellitic acid, pyromellitic acid, toluic acid, salicylic acid, gallic acid, phthalonic acid and the like are particularly preferable.

  (B) As the heterocyclic compound, triazoles, tetrazoles, and imidazoles can be used. These can be used individually by 1 type or in combination of 2 or more types.

  Triazoles include triazole (1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, 4H-1,2,4-triazole) or these Compound group having a benzene ring or naphthalene ring condensed structure; a triazole ring and / or an aromatic ring as a substituent, C1 to C12 may be structurally saturated or unsaturated, linear or branched, The structure may contain a cyclic structure (alicyclic ring, aromatic ring), oxygen (hydroxyl group, carbonyl group, carboxyl group, ether, ester, etc.), nitrogen (amino group, amide group, nitro group, cyano group, etc.), A compound that can contain sulfur (thiol group, sulfide, etc.) and halogen (fluorine, chlorine, bromine, iodine, etc.) is preferable. For example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, 4H— 1,2,4-triazole, benzotriazole, tolyltriazole, carboxybenzotriazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 5-amino-1,2, 4-triazole, 3-mercapto-1,2,4-triazole, chlorobenzotriazole, nitrobenzotriazole, aminobenzotriazole, cyclohexano [1,2-d] triazole, 4,5,6,7-tetrahydroxytolyl Triazole, 1-hydroxybenzotriazole, ethylbenzotriazole, naphtho Azole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] tolyltriazole, 1- [N, N-bis (2 -Ethylhexyl) aminomethyl] carboxybenzotriazole, 1- [N, N-bis (2-hydroxyethyl) -aminomethyl] benzotriazole, 1- [N, N-bis (2-hydroxyethyl) -aminomethyl] tolyl Triazole, 1- [N, N-bis (2-hydroxyethyl) -aminomethyl] carboxybenzotriazole, 1- [N, N-bis (2-hydroxypropyl) aminomethyl] carboxybenzotriazole, 1- [N, N-bis (1-butyl) aminomethyl] carboxybenzotriazole, 1- [N, N- Sus (1-octyl) aminomethyl] carboxybenzotriazole, 1- (2 ′, 3′-di-hydroxypropyl) benzotriazole, 1- (2 ′, 3′-di-carboxyethyl) benzotriazole, 2- ( 2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-amylphenyl) benzotriazole, 2- (2′-hydroxy-4) '-Octoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 1-hydroxybenzotriazole-6-carboxylic acid, 1-oleoylbenzotriazole, 1,2, 4-triazol-3-ol, 5-amino-3-mercapto-1,2,4-triazole, 5 -Amino-1,2,4-triazole-3-carboxylic acid, 1,2,4-triazole-3-carboxamide, 4-aminourazole, 1,2,4-triazol-5-one, etc. . Among these compounds, benzotriazole, tolyltriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] tolyltriazole, 1- [N, N- Bis (2-ethylhexyl) aminomethyl] carboxybenzotriazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 5-amino-1,2,4-triazole, 3 -Mercapto-1,2,4-triazole, cyclohexano [1,2-d] triazole, 1,2,4-triazol-3-ol, 5-amino-3-mercapto-1,2,4-triazole, 5-amino-1,2,4-triazole-3-carboxylic acid, 1,2,4-triazole-3- Rubokishiamido, 4-amino-urazole, 1,2,4-triazole-5-one are particularly preferred.

  As tetrazole, the 1,5-position of tetrazole (1H-tetrazole, 2H-tetrazole) may be structurally saturated or unsaturated of C1 to C12 as hydrogen or a substituent, and may be linear or branched, The structure may contain a cyclic structure (alicyclic ring, aromatic ring), oxygen (hydroxyl group, carbonyl group, carboxyl group, ether, ester, etc.), nitrogen (amino group, amide group, nitro group, cyano group, etc.), Compounds containing sulfur (thiol group, sulfide, etc.) and halogen (fluorine, chlorine, bromine, iodine, etc.) are preferred. For example, 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 1-methyl-5-ethyl-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-phenyl- 5-mercapto-1H-tetrazole, 1- (dimethylaminoethyl) -5-mercapto-1H-tetrazole, 5-phenyl-1H-tetrazole, 5,5′-bis-1H-tetrazole diammonium salt, 5,5 ′ -Azobis-1H-tetrazole etc. are mentioned. Among these compounds, 1H-tetrazole, 5-amino-1H-tetrazole, 5,5'-azobis-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole and the like are particularly preferable.

  Examples of imidazoles include 1H-imidazole or compounds having a ring condensation structure of these and one or two benzene rings as a skeleton; C1 to C12 structurally saturated as substituents on the imidazole ring and / or benzene ring. However, it may be unsaturated, oxygen (hydroxyl group, carbonyl group, carboxyl group, ether, ester, etc.), nitrogen (amino group, amide group, nitro group, cyano group, etc.), sulfur (thiol group, sulfide, etc.), halogen ( Compounds that can contain fluorine, chlorine, bromine, iodine, etc.) are preferred. For example, 1H-imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 5-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl -4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl- 2-Undecyl Midazole, 1-cyanoethyl-2-phenylimidazole, 2-amino-4,5-dicyanoimidazole, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 4-formylimidazole, 1- (2-hydroxyethyl) imidazole 1-vinylimidazole, 1-benzyl-2-formylimidazole, 1-allylimidazole, 2-ethylimidazole, 2-butylimidazole, 2-butylimidazole, 2-butyl-5-formylimidazole, 2-butyl- 5-hydroxymethylimidazole, 2-formylimidazole, 4,5-dihydro-1H-imidazole, 2,5-dihydro-1H-imidazole, 2,3-dihydro-1H-imidazole, tetrahydro-1H-imidazole 2-methyl-4,5-dihydro-1H-imidazole, 2-amino-3- (1H-imidazol-4-yl) propanoyl, 2- (3-aminopropanamido) -3- (1H-imidazole-4- Yl) propanoyl, imidazole-4-ethanamine and the like. Among these compounds, 1H-imidazole, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole are particularly preferable.

  Examples of the (C) thermoplastic organic polymer compound used in the photosensitive resin composition of the present invention include (meth) acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, An alkyd resin etc. can be mentioned. These can be used individually by 1 type or in combination of 2 or more types. Among these resins, it is preferable to use a (meth) acrylic resin from the viewpoint of excellent alkali developability. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and methacrylate corresponding thereto, and (meth) acryloyl group means acryloyl. Means a group and the corresponding methacryloyl group.

  The (C) thermoplastic organic polymer compound can be produced, for example, by radical polymerization of a polymerizable monomer.

  Examples of the polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, butyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl ( (Meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, Tadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, capryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, methoxyethyl (meth) ) Acrylate, butoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, methoxy Benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth) Acrylate, glycidyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, nonylphenoxypopropylene mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, ethylene glycol mono ( (Meth) acrylate, glycerol (meth) acrylate, dipentaerythritol mono (meth) acrylate, dimethylamino ester Chill (meth) acrylate, diethylaminoethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, diethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylo Propane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, pentaerythritol triacrylate, tetraethylene glycol diacrylate, styrene, alpha -Methylstyrene, beta-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-methoxystyrene, m-methoxystyrene, p -Methoxystyrene, o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-chlorostyrene, m-chlorostyrene, p-chloro Styrene derivatives such as styrene and p-bromostyrene, or styrene derivatives in which the benzene ring may be substituted with a functional group such as a nitro group, a nitrile group, an alkoxyl group, an acyl group, a sulfone group, a hydroxyl group, a halogen atom, (Meth) acrylic acid, alpha-bromo (meth) acrylic acid, alpha-chloro (meth) acrylic acid, beta-furyl (meth) acrylic acid, beta-styryl (meth) acrylic acid, maleic acid, maleic anhydride, malein Monomethyl acid, monoethyl maleate, monoisopropyl maleate, (meth) acrylamide, N-methylolacrylamide, N-hydroxymethyl (meth) acrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide, Methylene bisacrylamide, ethylene bisacrylamide, 1,6-hexamethylene bisacrylamide, diacetone acrylamide, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-methacryloyloxyethyl-2 -Hydroxypropyl phthalate, divinyl phthalate, divinyl terephthalate, cellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, carboxyethylcellulose, carboxyethylmethylcellulose, cellulose phthalate, cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate phthalate Polyvinyl alcohols such as polybutyral resin, which is a reaction product of poly (vinyl alcohol) and butyraldehyde, delta-valerolactone, epsilon-caprolactone, beta-propiolactone, alpha-methyl-beta-propiolactone, beta- Methyl-beta-propiolactone, alpha-methyl-beta-propiolactone, beta-methyl-beta-propiolactone, alpha, alpha-dimethyl-beta-propiolactone, beta, beta-dimethyl-beta-propio Polyesters obtained by ring-opening polymerization of lactones such as lactones, alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, and neopentyl glycol Polyesters obtained by condensation reaction of diols alone or two or more diols with dicarboxylic acids such as maleic acid, fumaric acid, glutaric acid and adipic acid, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly Polycarbonates which are reaction products of diols such as pentamethylene glycol, bisphenol A, hydroquinone and dihydroxycyclohexane and carbonyl compounds such as diphenyl carbonate, phosgene and succinic anhydride, (meth) acrylonitrile, o-vinyltoluene, m -Vinyltoluene, p-vinyltoluene, vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl propionate, 2,2'-bis (4-acryloxydiethoxyphenyl) propane, divinyl succinate, divini Ruadipate, divinylbenzene-1,3-disulfonate, isoprene, chloroprene, 3-butadiene, vinyl-n-butyl ether fumaric acid, cinnamic acid, alpha-cyanocinnamic acid, itaconic acid, itaconic anhydride, citraconic acid, citracone An acid anhydride, crotonic acid, propiolic acid, etc. are mentioned. The thermoplastic organic polymer (C) component may be used alone or in combination.

  Examples of the (D) photopolymerizable compound having an ethylenically unsaturated group used in the photosensitive resin composition of the present invention include, for example, bisphenol A (meth) acrylate compounds, polyhydric alcohols, and alpha, beta-unsaturated compounds. Examples include compounds obtained by reacting saturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond, and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis [4-{(meth) acryloxydiethoxy} phenyl] propane and 2,2-bis [4-[{(meth) acryloxy]. Triethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxytetraethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxypentaethoxy} phenyl] propane, 2 , 2-bis [4-{(meth) acryloxyhexaethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxyheptaethoxy} phenyl] propane, 2,2-bis [4- { (Meth) acryloxyoctaethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxynononaethoxy} phenyl] propane 2,2-bis [4-{(meth) acryloxydecaethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxyundecaethoxy} phenyl] propane, 2,2-bis [4 -{(Meth) acryloxide decaethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxytridecaethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxy Tetradecaethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxypentadecaethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxyhexadecaethoxy} phenyl] Propane, 2,2-bis [4-{(meth) acryloxydipropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxytri Ropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxytetrapropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxypentapropoxy} phenyl] propane, 2, 2-bis [4-{(meth) acryloxyhexapropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxyheptapropoxy} phenyl] propane, 2,2-bis [4-{( Meth) acryloxyoctapropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxynonapropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxydecapropoxy} phenyl ] Propane, 2,2-bis [4-{(meth) acryloxyundecapropoxy} phenyl] propane, 2,2-bis [ 4-{(meth) acryloxydodecapropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxytridecapropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryl Roxytetradecapropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxypentadecapropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxyhexadecapropoxy} phenyl ] Propane, 2,2-bis (4-methacryloxypentadecaethoxy) phenylpropane, 2,2-bis [4-{(meth) acryloxydiethoxyoctapropoxy} phenyl] propane, 2,2-bis [4 -{(Meth) acryloxytetraethoxytetrapropoxy} phenyl] propane, 2,2-bis [4-{(meta Acryloxyhexaethoxyhexapropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxydiethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxytriethoxy} phenyl ] Propane, 2,2-bis [4-{(meth) acryloxypentaethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxydecaethoxy} phenyl] propane, bisphenol A diglycidyl ether Examples include di (meth) acrylate.

  Among these, 2,2-bis {4-methacryloxypentaethoxy) phenyl} propane is commercially available as BPE-500 [product name: Shin-Nakamura Chemical Co., Ltd.] 2-bis {4-methacryloxypentadecaethoxy) phenyl} propane is commercially available as BPE-1300 [product name: Shin-Nakamura Chemical Co., Ltd.].

  In addition, as said bisphenol A type (meth) acrylate compound, the derivative | guide_body can also be used and the compound etc. which added acrylic acid to bisphenol A diepoxy etc. are mentioned as this derivative | guide_body. For example, it is commercially available as Biscote # 540 [product name: manufactured by Osaka Organic Chemical Industry Co., Ltd.].

  Examples of the compound obtained by reacting the polyhydric alcohol with an alpha, beta-unsaturated carboxylic acid include 1,6-hexanediol di (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, and 1,4. -Tetramethylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, heptapropylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, glycero (Meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, diglycidyl ether di (meth) acrylate phthalate Glycerin polyglycidyl ether poly (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, Ruphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyalkylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, 4-normal octylphenoxypentapropylene glycol (meth) acrylate, 4-bis {triethylene glycol (meth) Acrylate} nonapropylene glycol, bis {tetraethylene glycol (meth) acrylate} polypropylene glycol, bis {triethylene glycol (meth) acrylate} polypropylene glycol, bis (diethylene glycol acrylate) polypropylene glycol, 4-normalnonylphenoxyoctane ethylene glycol (meta ) Acrylate, 4-normal nonylphenoxyheptane ethylene Glycol dipropylene glycol (meth) acrylate, phenoxytetrapropylene glycol tetraethylene glycol (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate , Trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropanepentaethoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) Acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Lenglycol di (meth) acrylate, pentyl glycol di (meth) acrylate, polyethylene polytrimethylolpropane (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate Glycerin mono (meth) acrylate, glycerin di (meth) acrylate, and the like.

  Examples of urethane monomers such as (meth) acrylate compounds having a urethane bond include compounds having a hydroxyl group and a (meth) acryl group in one molecule [2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, oligoethylene glycol mono (meth) acrylate, oligopropylene glycol Mono (meth) acrylate], isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, hexamethylene diisocyanate, Addition reaction product with diisocyanate compounds such as lylene diisocyanate or 2,2,4-trimethylhexamethylene diisocyanate, tris [(meth) acryloxytetraethylene glycol isocyanate] hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO And PO-modified urethane di (meth) acrylate.

  Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethyleneoxy group. PO represents propylene oxide, and the PO-modified compound has a propyleneoxy group block structure. Examples of the EO-modified urethane di (meth) acrylate include the product name UA-11 manufactured by Shin-Nakamura Chemical Co., Ltd. Examples of EO and PO-modified urethane di (meth) acrylate include Shin-Nakamura Chemical Co., Ltd., product name UA-13, and the like.

  Other compounds include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate , Diallyl phthalate, beta-hydroxypropyl-beta ′-{(meth) acryloyloxy} propyl phthalate, 2- (meth) acryloyl-2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxy Ethyl phthalate, nonylphenyldioxylene (meth) acrylate, gamma-chloro-beta-hydroxypropyl-beta '-(meth) acryloyloxyethyl-o-phthalate, beta-hydroxyethyl-beta'-(meth) a Liloyloxyethyl-o-phthalate, beta-hydroxypropyl-beta '-(meth) acryloyloxyethyl-o-phthalate, EO-modified nonylphenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N-methylol Examples include (meth) acrylamides such as (meth) acrylamide, and aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate.

  Moreover, the monomer illustrated as being possible to mix | blend in the component of (C) thermoplastic organic polymer can also be contained.

  Examples of the (E) photopolymerization initiator used in the photosensitive resin composition of the present invention include aromatic ketones, p-aminophenyl ketones, quinones, benzoin ether compounds, benzoin compounds, benzyl derivatives, 2 , 4,5-triarylimidazole dimer, acridine derivatives, coumarin compounds, oxime esters, N-aryl-alpha-amino acid compounds, aliphatic polyfunctional thiol compounds, acylphosphine oxides, thioxanthones, tertiary amines A compound etc. can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the aromatic ketones include acetophenone, benzophenone, methylbenzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone. 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholino-propane-1,4,4-dichlorobenzophenone and the like can be mentioned.

  Examples of the p-aminophenyl ketones include aminobenzophenone, butylaminoacetophenone, dimethylaminoacetophenone, alpha, alpha-dimethoxy-alpha-morpholino-methylthiophenylacetophenone, dimethylaminobenzophenone, 4,4′-bis (ethylamino). ) Benzophenone, 4,4′-bis (dibutylamino) benzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4,4′-diaminobenzophenone, 2,2-diethoxy-2-phenylacetophenone, and the like.

  Examples of the quinones include 2-methylanthraquinone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, and 2-phenylanthraquinone. 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 3-chloro-2-methylanthraquinone, 9,10-phenantharaquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, 2-methyl Examples include -1,4-naphthoquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone.

  Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin phenyl ether.

  Examples of the benzoin compound include benzoin, methylbenzoin, and ethylbenzoin.

  Examples of the benzyl derivative include benzyl dimethyl ketal, benzyl diethyl ketal, benzyl dipropyne ketal, benzyl diphenyl ketal, and the like.

  Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di ( Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p -Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenylimidazole dimer, 2- (o-bromo) Phenyl) -4,5-diphenylimidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chlorophenyl) imidazole Dimer, 2- (o-chlorophenyl) -4,5-tetra (m-methoxyphenyl) imidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′- Tetra (p-fluorophenyl) imidazole dimer, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-chloro-p-methoxyphenyl) imidazole dimer 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2′-bis (o-chlorophenyl) -4, 4 ', 5,5'-tetra (o, p-dibromophenyl) imidazole dimer, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-chloronaphthyl) ) Imidazole dimer, 2,2'-bi (O, m-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylimidazole dimer, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetra Phenylimidazole dimer, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) imidazole dimer, 2,4-di (p- Methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer 2,2′-bis (p-bromophenyl) -4,4 ′, 5,5′-tetraphenylimidazole dimer, 2,2′-bis (o-bromophenyl) -4,4 ′ , 5,5'-Te Tora (o, p-dichlorophenyl) imidazole dimer, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-iodophenyl) imidazole dimer, 2, 2'-bis (m-bromophenyl) -4,4 ', 5,5'-tetraphenylimidazole dimer, 2,2'-bis (m, p-dibromophenyl) -4,4', 5 5'-tetraphenylimidazole dimer, 2,2'-bis (2,6-dichlorophenyl) -4,5-diphenylimidazole dimer, 2,2'-bis (o-chlorophenyl) -4,4 ' , 5,5′-tetra (p-fluorophenyl) imidazole dimer, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-iodophenyl) imidazole 2-mer, 2,2'-bis (o-c Rophenyl) -4,4 ′, 5,5′-tetra (p-chloronaphthyl) imidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p -Chlorophenyl) imidazole dimer, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-chloro-p-methoxyphenyl) imidazole dimer, 2,2 '-Bis (o-chlorophenyl) -4,4', 5,5'-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2'-bis (o-chlorophenyl) -4,4 ', 5 , 5′-tetra (o, p-dibromophenyl) imidazole dimer, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) imidazole Dimer, 2,2'-bis (o, - dichlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) imidazole dimer, and the like.

  Examples of the acridine derivative include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (p-ethylphenyl) acridine, 9- (pn-propylphenyl) acridine, 9- (p- iso-propylphenyl) acridine, 9- (pn-butylphenyl) acridine, 9- (p-tert-butylphenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p-ethoxyphenyl) acridine , 9- (p-acetylphenyl) acridine, 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) acridine 9- (m-methylphenyl) acridine, 9- (mn-propylphenyl) ) Acridine, 9- (m-iso-propylphenyl) acridine, 9- (mn-butylphenyl) acridine, 9- (m-tert-butylphenyl) acridine, 9- (m-methoxyphenyl) acridine, 9 -(M-ethoxyphenyl) acridine, 9- (m-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine, 9- (m-diethylaminophenyl) acridine, 9- (m-cyanophenyl) acridine, 9- (m-chlorophenyl) acridine, 9- (m-bromophenyl) acridine, 9-cyanoethylacridine, 9-hydroxyethylacridine, 9-chloroethylacridine, 9-n-propoxyacridine, 9-iso-propoxyacridine, 9-chloroethoxyacridine, 1, - and bis (9,9'-acridinyl) heptane and the like.

  Examples of the coumarin compound include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, and 7-ethyl. Amino-4-methylcoumarin, 7-dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-diethylaminocoumarin, 4,6- Diethyl-7-dimethylaminocoumarin, 4,6-dimethyl-7-ethylamino bear 2,3,6,7,10,11-hexanehydro-1H, 5H-cyclopenta [3,4] [1] benzopyrano [6,7,8-ij] quinolizine 12 (9H) -one, 7- Examples include diethylamino-5 ′, 7′-dimethoxy-3,3′-carbonylbiscoumarin, 3,3′-carbonylbis [7- (diethylamino) coumarin], 7-diethylamino-3-thienoxysilkine.

  Examples of the oxime esters include 1-phenyl-1,2-propanedione-2-o-benzoyloxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, and the like. It is done.

  Examples of the N-aryl-alpha-amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, N- (n-propyl) -N-phenylglycine, N- (n-butyl) -N-phenylglycine, N- (2-methoxyethyl) -N-phenylglycine, N-methyl-N-phenylalanine, N-ethyl-N-phenylalanine, N- (n-propyl) -N-phenylalanine, N- (n-butyl) -N-phenylalanine, N-methyl-N-phenylvaline, N-methyl-N-phenylleucine, N-methyl-N- (p-tolyl) glycine, N- Ethyl-N- (p-tolyl) glycine, N- (n-propyl) -N- (p-tolyl) glycine, N- (n-butyl) -N- (p- Ryl) glycine, N-methyl-N- (p-chlorophenyl) glycine, N-ethyl-N- (p-chlorophenyl) glycine, N- (n-propyl) -N- (p-chlorophenyl) glycine, N-methyl -N- (p-bromophenyl) glycine, N-ethyl-N- (p-bromophenyl) glycine, N- (n-butyl) -N- (p-bromophenyl) glycine, N, N'-diphenylglycine N-methyl-N- (p-iodophenyl) glycine, N- (p-bromophenyl) glycine, N- (p-chlorophenyl) glycine, N- (o-chlorophenyl) glycine, and the like.

  Examples of the aliphatic polyfunctional thiol compound include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and trimethylol. Propane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tris Examples thereof include thiopropionate, thioglycolate of other polyvalent hydroxy compounds, and thiopropionate.

  Examples of the acylphosphine oxides include (2,6-dimethoxybenzoyl) 2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6- And trimethylbenzoyldiphenylphosphine oxide.

  Examples of the thioxanthones include thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-fluorothioxanthone. 4-fluorothioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

  Other photopolymerization initiators include, for example, ethyl-2,4,6-trimethylbenzoylfinyl phosphinate, ethyl 2,3-dioxo-3-phenylpropionate di-2- (o-benzoylcarbonyl) -oxime, Examples include p-nitrodiphenyl, m-nitroaniline, p-nitroaniline, 2,6-dinitroaniline. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid.

  Examples of the tertiary amine compound include dimethylaminobenzoic acid, diethylaminobenzoic acid, diisopropylaminobenzoic acid, and the like.

  Here, (A) carboxylic acid compound, (B) heterocyclic compound, (C) thermoplastic organic polymer, (D) photopolymerizable compound having an ethylenically unsaturated group, and (E) photopolymerization initiator. The blending ratio is as follows. That is, (C) 20 to 90% by mass of a thermoplastic organic polymer, preferably 40 to 80% by mass, (D) 5 to 70% by mass of a photopolymerizable compound having an ethylenically unsaturated group, preferably 20 to 60% by mass. %, (E) 0.5 to 10% by mass, preferably 1.0 to 5.0% by mass of the photopolymerization initiator, and 0.0005 to 1 (A) carboxylic acid compound with respect to 100 parts by mass of the formulation. In the range of mass parts, preferably 0.001 to 0.5 parts by mass, and (B) the heterocyclic compound in the range of 0.0005 to 1 parts by mass, preferably 0.001 to 0.5 parts by mass. is there. In addition, when the blending amount of the thermoplastic organic polymer (C) is less than 20% by mass, a cold flow is caused and the photosensitive resin composition tends to ooze out from the film end surface, and 90% by mass Exceeding this is not preferable because the sensitivity tends to be insufficient. Next, (D) When the blending amount of the photopolymerizable compound having an ethylenically unsaturated group is less than 10% by mass, sensitivity tends to be insufficient, and when it exceeds 70% by mass, a cold flow is caused. , Since the resin tends to ooze out from the end face of the film. In addition, when the blending amount of the (E) photopolymerization initiator is less than 0.5% by mass, the curing tends to not proceed sufficiently when the photosensitive layer is irradiated with an actinic ray and cured. If it exceeds 10% by mass, the sensitivity of the photosensitive layer to actinic rays becomes too high, so that the resolution tends to be lowered and the stability tends to be lowered. Further, the blending amount of the (A) carboxylic acid compound and the (B) heterocyclic compound is less than 0.0005 parts by mass with respect to 100 parts by mass in total of the (C) component, the (D) component, and the (E) component. , The adhesion improving effect tends to be insufficient, and if it exceeds 1 part by mass, other characteristics as the photosensitive resin composition, such as releasability and sensitivity, tend to decrease. It is not preferable.

  The photosensitive resin composition of the present invention may further contain (F) amines for the purpose of enhancing the solubility of the above-mentioned (A) carboxylic acid compound and (B) heterocyclic compound in the resin. it can. Examples of (F) amines include ammonia, ethylenediamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, diethylenetriamine, diethylamine, dibutylamine, hexahydroaniline, Tetraethylenepentamine, pentaethylenehexamine, allylamine, 2-aminopropanol, 3-aminopropanol, 4-aminobutanol, 4-methylaminobutanol, ethylaminoethylamine, 2-ethylhexylamine, di-2-ethylhexylamine, oleylamine, Dodecylamine, dicyclohexylamine, octylamine, octadecylamine, hexylamine, etc. It is possible. These compounds can be used individually by 1 type or in combination of 2 or more types. Of these compounds, monoisopropanolamine, diisopropanolamine, di-2-ethylhexylamine and the like are particularly preferable.

  In addition, the compounding quantity of (F) amines shall be 5 equivalent or less with respect to 1 equivalent of acids used for the said (A) component and (B) component, Preferably it shall be in the range of 0.5-2 equivalent. Is preferred. Here, when the compounding amount of (F) amines exceeds 5 equivalents with respect to 1 equivalent of the acid used for the components (A) and (B), the adhesion improving effect tends to be inhibited. It is not preferable.

  The photosensitive resin composition of the present invention comprises the above components (A) to (E) as essential components, and if necessary, a thermal polymerization inhibitor, a plasticizer, a dye (pigment, photo-coloring). Agents), antioxidants, surface tension modifiers, stabilizers, chain transfer agents, antifoaming agents, flame retardants, release accelerators, fragrances, imaging agents, thermal crosslinking agents, developability / plating property improvers, etc. An agent can be added as appropriate. These additives can be used alone or in combination of two or more.

  Examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, beta -Naphthol, 2,6-di-t-butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, p-toluidine and the like.

  Examples of the plasticizer include phthalates such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate; glycol esters such as triethylene glycol diacetate and tetraethylene glycol diacetate; tricresyl phosphate, tri Phosphate esters such as phenyl phosphate; Amides such as p-toluenesulfonamide, benzenesulfonamide, Nn-butylacetamide; Fats such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dioctyl azelate, dibutyl malate Dibasic acid esters; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dica Fatty acid esters such as carbon dioctyl, polyethylene glycol, or glycols such as polypropylene glycol.

  Examples of the dye include brilliant green, eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, Quinardine Red, Rose Bengal, Methanyl Yellow, Thymolsulfophthalein, Xylenol Blue, Methyl Orange, Orange IV, Diphenylthiocarbazone, 2,7-Dichlorofluorescein, Paramethyl Red, Congo Red, Benzopurpurin 4B, Alpha -Naphthyl Red, Nile Blue A, Phenacetalin, Methyl Violet, Malachite Green, Parafuxin, Oil Blue # 603 [Orient Chemical ) Ltd.], Victoria Pure Blue BOH, Spiron Blue GN [Hodogaya Chemical Co., Ltd.], rhodamine 6G, and the like.

  Examples of the photochromic agent include diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4,4′-biphenyldiamine, and o-chloro in addition to the above-described dye. Examples include aniline, leuco crystal violet, leucomalachite green, leucoaniline, leucomethyl violet, and the like.

  Examples of the developability / plating property improver include carbon tetrachloride, chloroform, bromoform, 1,1,1-trichloroethane, methylene bromide, methylene iodide, methylene chloride, carbon tetrabromide, iodoform, 1,1. 2,2-tetrabromoethane, pentabromoethane, tribromoacetophenone, bis- (tribromomethyl) sulfone, tribromomethylphenylsulfone, vinyl chloride, chlorinated olefin and the like.

  In addition, the compounding quantity of the said additive is with respect to 100 mass parts of total amounts of (C) thermoplastic organic polymer; (D) photopolymerizable compound which has an ethylenically unsaturated group; and (E) photoinitiator. And about 0.01 to 20 parts by mass, preferably about 0.05 to 10 parts by mass.

  In addition to the above components, the photosensitive resin composition of the present invention includes alcohols, ketones, acetates, glycol ethers, glycol ether esters as necessary for the purpose of viscosity adjustment. Organic solvents for dilution such as petroleum solvents can be added as appropriate.

  Examples of the organic solvent for dilution include hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, benzyl alcohol, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, methanol, ethanol, propanol, butanol , Isobutanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethyle Glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3 -Ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3 -Methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxy Pentyl acetate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl propionate, ethyl propionate, methyl benzoate Ethyl benzoate, propyl benzoate, butyl benzoate, methyl butyrate, ethyl butyrate, propyl butyrate, N, N-dimethylformamide gamma-butyrolactone, N-methyl-pyrrolidone, tetramethylsulfone, chloroform, methylene chloride, Examples include 1,1,1-trichloroethane. These solvents can be used alone or in combination of two or more.

  Here, the compounding quantity of a solvent is 5-50 mass% with respect to the photosensitive resin composition, Preferably it exists in the range of 10-40 mass%.

  The photosensitive resin composition of the present invention can be applied as a photoresist ink as described above on a film-like support and dried to form a photosensitive film. As the film-like support, a polyethylene terephthalate film, a polystyrene film, a polypropylene film or the like is used. You may laminate | stack a protective film on the photosensitive resin composition layer laminated | stacked on the film-form support body as needed. As the protective film, a polyethylene film, a polyvinyl alcohol film, or the like is used in addition to the material used as the film-like support.

Examples The photosensitive resin composition of the present invention will be further described with reference to the following examples. However, it should be understood that the present invention is not limited to the following examples.
Example 1
A photosensitive resin composition of the present invention was prepared by adding (A) a carboxylic acid compound and (B) a heterocyclic compound shown in Table 1 below to the following basic formulations (1) to (3).
Basic formulation (1) Compounding amount (g)
(C) Copolymer of methacrylic acid / methyl methacrylate / butyl acrylate (mass ratio = 20/70/10) (mass average molecular weight 80,000) 64
(D) 2,2-bis (4-methacryloxypentadecaethoxyphenyl) propane 23
(D) Polypropylene glycol diacrylate 10
(E) 2- (o-chlorophenyl) -4,5-diphenyl imidazole dimer 2.8
(E) 4,4′-bis (diethylamino) benzophenone 0.2
(F) Diisopropanolamine (A) and / or (B)
1.5 equivalents of 1 equivalent of total acid Leuco Crystal Violet (photochromic agent) 0.2
Methyl ethyl ketone (solvent) 60

Basic formulation (2) Compounding amount (g)
(C) Methacrylic acid / Methyl methacrylate / Styrene

(Mass ratio = 25/50/25) copolymer (mass average molecular weight 80000) 64
(D) 2,2-bis (4-methacryloxypentadecaethoxyphenyl) propane 33
(E) Benzophenone 2.8
(E) 4,4′-bis (diethylamino) benzophenone 0.1
(E) N-phenylglycine 0.1
(F) Diisopropanolamine (A) and / or (B)
1.5 equivalents of 1 equivalent of total acid Leuco Crystal Violet (photochromic agent) 0.2
Methyl ethyl ketone (solvent) 60

Basic formulation (3) Compounding amount (g)
(C) Methacrylic acid / benzyl methacrylate (mass ratio = 20/80)
Copolymer (mass average molecular weight 60000) 64
(D) 2,2-bis (4-methacryloxydiethoxyphenyl) propane 23
(D) Trimethylolpropane triacrylate 10
(E) 2- (o-chlorophenyl) -4,5-diphenyl imidazole dimer 2.8
(E) Dimethylaminobenzophenone 0.1
(E) 7-diethylamino-4-methylcoumarin 0.1
(F) Diisopropanolamine (A) and / or (B)
1.5 equivalents of 1 equivalent of total acid Leuco Crystal Violet (photochromic agent) 0.2
Methyl ethyl ketone (solvent) 60

  In addition, for comparison, the composition of only the basic formulation (1), (2) or (3) [Comparative products (1) -1, (2) -1, (3) -1], the basic formulation ( 1), (2) or (3) a composition in which only (A) a carboxylic acid compound is added as an additive [comparative product (1) -2 to 20, comparative product (2) -2 to 20, comparative product (3) -2 to 20], (B) a composition to which only a heterocyclic compound is added [Comparative product (1) -21 to 41, Comparative product (2) -21 to 41, Comparative product (3) -21 to 41], (F) a composition containing only amines [Comparative product (1) -42, Comparative product (2) -42, Comparative product (3) -42], and (A) Carboxylic acid compound and (B ) A composition in which a heterocyclic compound is added in an addition amount outside the scope of the present invention [Comparative product (1) -43-50, Comparative product (2) -43-50, Comparative product (3)- 3-50] were prepared.

  Furthermore, the obtained composition of the present invention and the comparative product were placed on a support film (material = polyethylene terephthalate), stretched by an applicator, and dried at 80 ° C. for 10 minutes to obtain a resist film having a thickness of 40 μm. Next, the obtained resist film was laminated on a cleaned copper-clad laminate for printed circuit boards using a laminator at a temperature of 80 ° C. to obtain an evaluation substrate (25 × 50 mm).

<Adhesion test>
The substrate for evaluation was irradiated with UV (365 nm) at an exposure dose of 25 mJ / cm ² using a negative having a pattern with a line width / space width of 30/400 to 200/400 (unit: μm). After removing the support film, development was performed for 60 to 70 seconds using an aqueous 1% by weight sodium carbonate solution, followed by washing with water, and the degree of resist peeling was observed. The obtained substrate was lightly rubbed with a plastic eraser to test the degree of resist peeling. Adhesion was evaluated by the value of the line width without any separation. The smaller the value, the better the adhesion:
[Adhesion / Visual]
A: Less than 40 μm B: 40 μm or more and less than 50 μm C: 50 μm or more and less than 60 μm D: 60 μm or more and less than 70 μm E: 70 μm or more

<Discoloration prevention test>
The substrate for evaluation was irradiated with UV (365 nm) at an exposure amount of 25 mJ / cm ² using a step tablet whose brightness changed from transparent to black in 41 steps. After removing the support film, the film was developed with a 1% by weight aqueous sodium carbonate solution for 60 to 70 seconds and washed with water. The obtained substrate was kept at a temperature of 50 ° C. and a humidity of 95% RH for 48 hours, then immersed in 3% by weight caustic soda for 70 seconds, washed with water, and the resist was peeled off. The state of the copper surface after peeling was observed and evaluated according to the following evaluation criteria:
[Discoloration prevention]
a: Less than 10% b: 10% or more and less than 30% c: 30% or more and less than 50% d: 50% or more and less than 80% e: 80% or more

  In the table, BT-LX is 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, and TT-LX is 1- [N, N-bis (2-ethylhexyl) aminomethyl] tolyl. Triazole, CBT-LX represents 1- [N, N-bis (2-ethylhexyl) aminomethyl] carboxybenzotriazole, respectively.

Claims (11)

(A) 1 or more kinds of the carboxylic acid compound is selected from the group consisting of fatty acids and aromatic carboxylic acids (except carboxy benzotriazole); (B) triazoles, group or al consisting of tetrazoles and imidazoles a photopolymerizable compound having a (D) an ethylenically unsaturated group; one or more heterocyclic compounds selected; (C) a thermoplastic organic polymer (E) photopolymerization initiator; and (F ) Ammonia, ethylenediamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, diethylenetriamine, diethylamine, dibutylamine, hexahydroaniline, tetraethylenepentamine, pentaethylene Hexamine, allylamine, 2-aminopropanol, 3-aminopropanol, 4-aminobutanol, 4-methylaminobutanol, ethylaminoethylamine, 2-ethylhexylamine, di-2-ethylhexylamine, oleylamine, dodecylamine, dicyclohexylamine, octyl A photosensitive resin composition comprising an amine selected from the group consisting of amine, octadecylamine and hexylamine . (A) In one or more carboxylic acid compounds selected from the group consisting of fatty acids and aromatic carboxylic acids (excluding carboxybenzotriazole), the fatty acid has 1 to 30 carbon atoms and is a carboxyl group 1 or 2 or more, saturated or unsaturated, may be linear or branched, and may have a cyclic structure in the structure. hydrocarbon group include those having an oxygen-containing groups and / or nitrogen-containing group is also be compound, according to claim 1 photosensitive resin composition. (A) In one or more carboxylic acid compounds selected from the group consisting of fatty acids and aromatic carboxylic acids (excluding carboxybenzotriazole), the aromatic carboxylic acid has a benzene, naphthalene or anthracene structure as a skeleton. , Having 1 or 2 or more carboxyl groups directly bonded to these, having 1 to 12 carbon atoms as a substituent, saturated or unsaturated, straight-chain or branched may even may have a cyclic structure in the structure, oxygen and / or nitrogen may have a group containing a compound according to claim 1 photosensitive resin composition. (C) a thermoplastic organic polymer; (D) a photopolymerizable compound having an ethylenically unsaturated group; and (E) a fatty acid and an aromatic carboxylic acid (carboxy ) relative to 100 parts by mass of the total amount of the photopolymerization initiator. The compounding amount of one or more carboxylic acid compounds selected from the group consisting of (excluding benzotriazole) is in the range of 0.0005 to 1 part by mass, and the compounding amount of (B) the heterocyclic compound is The photosensitive resin composition of any one of Claim 1 thru | or 3 which exists in the range of 0.0005-1 mass part. (F) The compounding amount of amines is (A) one or more carboxylic acid compounds selected from the group consisting of fatty acids and aromatic carboxylic acids (excluding carboxybenzotriazole) and (B) heterocyclic compounds is not more than 5 equivalents of the acid one equivalent is used, claim 1 photosensitive resin composition described (claim 5); Furthermore, thermal polymerization inhibitors, plasticizers, dyes, antioxidants, surface tension modifiers, stabilizers, chain transfer agents, antifoaming agents, flame retardants, release accelerators, fragrances, imaging agents, thermal crosslinking agents and development The photosensitive resin composition of any one of Claim 1 thru | or 5 containing the 1 type (s) or 2 or more types of additive selected from the group which consists of a property improvement / plating property improvement agent. (C) a thermoplastic organic polymer; (D) a photopolymerizable compound having an ethylenically unsaturated group; and (E) a compounding amount of the additive with respect to 100 parts by mass of the total amount of the photopolymerization initiator is 0.01. The photosensitive resin composition of Claim 6 which exists in the range of -20 mass parts. Furthermore, it contains one or more organic solvents for dilution selected from the group consisting of alcohols, ketones, acetates, glycol ethers, glycol ether esters and petroleum solvents. The photosensitive resin composition of any one of thru | or 7 . The photosensitive resin composition according to claim 8 , wherein the amount of the solvent for dilution is in the range of 5 to 50 mass% with respect to the photosensitive resin composition. It claims 1 to photoresist ink, characterized by comprising a photosensitive resin composition according to any one of 9. A photosensitive resin composition layer according to any one of claims 1 to 9 is applied on a support and dried to form a photosensitive resin composition layer on the support. Photosensitive film.