WO2008015754A1 - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition characterized by containing: (A) a carboxylic acid compound; (B) one or more heterocyclic compounds selected from the group consisting of triazoles, tetrazoles and imidazoles; (C) a thermoplastic organic polymer; (D) a photopolymerizable compound having an ethylenically unsaturated group; and (E) a photopolymerization initiator.

Description

 Specification

 Photosensitive resin composition

 Technical field

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

 Background art

 [0002] A 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. Then, after being imagewise exposed to actinic light and developed, a photoresist image is obtained. However, in recent years, in order to improve the low workability, air pollution, and low yield, a film-like support, a dried photosensitive resin composition layer (hereinafter simply referred to as a photosensitive layer), and necessary Accordingly, a photosensitive resin composition laminate (hereinafter simply referred to as a photosensitive film) comprising a protective film layer used accordingly has come to be used. As the photosensitive resin composition, both so-called alkali developing type in which an unexposed portion is developed with an aqueous alkali solution and so-called solvent developing type in which an unexposed portion is developed with an organic solvent are known.

 [0003] As for the method of using the 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 the photosensitive layer is in contact with the substrate. Heat-press (laminate) as follows. Next, after imagewise exposure using a negative film or the like, a predetermined developer such as sodium carbonate water or 1, 1, 1 trichloroethane is used V to develop the unexposed portion, and a photo is formed on the substrate. A resist image is formed. Using this formed photoresist image as a mask, the metal surface of the substrate is etched or subjected to a squeezing process, and then the photoresist image is subjected to a predetermined stripping solution such as sodium hydroxide aqueous solution or methylene chloride. The printed wiring board and the like can be manufactured by using this.

[0004] During the above process, the photoresist image must have sufficient resistance as a mask against etching or plating of the metal surface of the substrate. The etching process is performed on the surface layer of the substrate using an aqueous solution of ferric chloride, cupric chloride, and ammonium persulfate. This is a step of removing the metal (usually copper) that constitutes it. In addition, there are many types of plating solutions used in the plating process, such as soldering, copper sulfate plating, gold plating, nickel plating, and pyrophosphoric acid plating. In any case, the plating process is considerably stricter than the etching process because an electric current flows in a high concentration chemical solution.

 [0005] 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, (2) at least in the same molecule. A compound having one aromatic ring and having at least two carboxyl groups directly bonded to the same aromatic ring, (3) a specific hexaarylbiimidazole, (4) an oxidizable leukotri A color curable photosensitive composition comprising an arylmethane dye and (5) a compound having an addition-polymerizable ethylene group having a boiling point of 50 ° C. or higher at normal pressure is disclosed.

[0006] Patent Document 2 discloses an epoxy resin composition for semiconductor encapsulation comprising an inorganic filler, an epoxy resin, and a curing agent, in which 1, 8 diazabicyclo (5, 4, 0) undecene 7 and trimellit are used. An epoxy resin composition for semiconductor encapsulation is disclosed, which is prepared by adding an acid or a salt with pyromellitic acid in advance after being melt-mixed with a phenol novolac resin.

 [0007] Further, Patent Document 3 contains novolak rosin, a photosensitizer mainly composed of naphthoquinone diazide sulfonate, and an adhesion enhancer composed of a melamine derivative and Z or guanamine derivative. A positive photoresist composition characterized by the following is disclosed.

[0008] In addition, 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, A photopolymerizable polyimide precursor having an actinic functional group having a structure terminal-modified with an aminobenzene or trimellitic acid derivative having a substituent having a carbon-carbon double bond in its molecule. The carboxylic acid or its anhydride contains a rigid structure aromatic tetracarboxylic acid or its anhydride in a ratio of 70 to LOO mol%, and the diamine contains a rigid structure of an aromatic diamine. 70-: A photosensitive polyimide precursor characterized in that it is contained in a proportion of LOO mol% (Claim 1), (A) the photosensitive polyimide precursor, and (B) a photopolymerizable functional group. Photosensitive aid, (C) a photopolymerization initiator, and (D) a photosensitive polyimide resin composition containing a solvent (Claim 11), and (E) a photosensitive polyimide resin composition according to Claim 11 further containing 1H-tetrazole (Claim 12). It is disclosed.

 [0009] Further, Patent Document 5 includes (A) a soluble polyimide containing a carboxyl group and Z or a hydroxyl group, (B) a (meth) acrylic compound, (C) an epoxy compound, and (D) a latent hard A photosensitive resin composition containing a sensitizing agent (Claim 1), wherein the component (D) is dicyandiamide, phenol norpolac, epoxy phenol, adipic acid dihirazide, diarylmelamine, diaminomaleo-tolyl, hexamethylenetetramine, amine 3. The compound according to claim 1, wherein the compound is at least one compound selected from the group consisting of a salt, a derivative of imidazole, an amine complex of boron trifluoride, methyltetrahydrophthalic anhydride, and an amine amine compound. A photosensitive resin composition (Claim 3) is disclosed.

 [0010] Further, 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) A photosensitive resin composition comprising: a photopolymerizable compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator. (Claim 1); (B) ethylenically unsaturated As a photopolymerizable compound having a bond, a compound obtained by reacting a polyhydric alcohol with alpha, beta unsaturated power rubonic acid, a bisphenol A (meth) attareito toy compound, nourphenoxy The photosensitive resin according to any one of claims 1 to 4, comprising at least one selected from the group consisting of a polyethyleneoxy (meth) acrylate compound and a phthalic compound. Composition (Claim 5); (C) Light The photosensitive resin composition according to any one of claims 1 to 6, characterized in that it contains 2, 4, 5 triarylimidazole dimer as a co-initiator (Claim 7). Is disclosed.

[0011] Further, Patent Document 7 discloses a liquid epoxy resin composition containing (a) liquid epoxy resin, (b) curing agent, (c) curing accelerator, and (d) inorganic filler as essential components. 3, 4 Dimethyl-6- (2-Methyl-1-probe) 1, 2, 3, 6-Tetrahydride Phthalic acid and 1-isopropyl mono 4-methyl mono bicyclo [2, 2 , 2] Octoxy 5 ene 2,3-dicarboxylic acid liquid epoxy resin containing 5 to 75 parts by weight (parts by weight) of 100 parts by weight (parts by weight) of the entire curing agent Composition; (c) Component curing acceleration The composition of claim 1 or 2 which is an imidazole compound and Z or an organophosphorus compound (Claim 3) is disclosed.

 [0012] In addition, Patent Document 8 discloses a cured polyimide having a modulus of less than 2 GPa induced by one or more aromatic dianhydrides and one or more aliphatic diamine forces and exposed to heat. A polyamic acid that forms bismuth, an amine (meth) atalylate, an amine metaacrylamide, and their combined strength. A low-temperature curable photosensitive composition comprising a saturated monomer mixture, a photoinitiator, and a sensitizer and capable of being developed in an aqueous carbonate (Claim 1); further comprising an adhesion promoter The composition according to claim 1, wherein the adhesion promoter is 3-mercapto-1H- 1, 2, 4 triazole, 5-amino-1, 3, 4-thiadiazole. 2 thiols, 2 mercaptobenses 13. The group selected from the group consisting of midazole 2- (2, -hydroxy-5-metatalyloxyethyl phenyl) 2H benzotriazole, polybenzimidazole, and combinations thereof. A composition of claim 13 (claim 13) is disclosed.

 Patent Document 1: Japanese Patent Laid-Open No. 62-106450

 Patent Document 2: Japanese Patent Laid-Open No. 2003-40978

 Patent Document 3: Japanese Patent Laid-Open No. 7-120914

 Patent Document 4: Japanese Patent Laid-Open No. 2004-285129

 Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-333672

 Patent Document 6: JP-A-7-120914

 Patent Document 7: Japanese Unexamined Patent Publication No. 2002-97257

 Patent Document 8: Japanese Unexamined Patent Publication No. 2006-146244

 Disclosure of the invention

 Problems to be solved by the invention

[0014] A color curable photosensitive composition described in the above-mentioned Patent Document 1 comprises a thermoplastic organic polymer binder, an aromatic carboxylic acid compound, and an imidazole dimer. However, the imidazole dimer is a component blended as a reaction initiator and cannot improve the adhesion of the photosensitive composition. In addition, the semiconductor described in Patent Document 2 The epoxy resin composition for body sealing is designed to improve the adhesion by adding a carboxylic acid such as trimellitic acid to Epoxy resin. Cannot be improved sufficiently. Further, 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. In the composition, the base polymer is novolac resin and cannot be used as a photosensitive resin composition. In addition, 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 a heterocyclic compound is added to the above, sufficient adhesion improving effect cannot be obtained. Furthermore, the photosensitive resin composition described in Patent Document 6 is used as a binder polymer, as a copolymer of (meth) acrylic acid ester, as a photopolymerizable compound having an ethylenically unsaturated group, as a carboxylic acid salt. As a compound and a photopolymerization initiator, a heterocyclic compound is used for each V, but these are compounded as a constituent component of a resin for reacting to form a photosensitive resin, It is not formulated as a resin additive for improving adhesion. In addition, it is thought that the resin additive blended for the purpose of improving the adhesion does not contribute to the reaction with the base resin. Further, in the liquid epoxy resin composition described in Patent Document 7, a sufficient force-improving effect can be obtained even if only a heterocyclic compound is added. Absent. Furthermore, the adhesive composition described in Patent Document 8 cannot achieve a sufficient adhesion improving effect even if only a heterocyclic compound in which a heterocyclic compound is used as an adhesion promoter is added.

In addition, due to the recent high integration of semiconductor elements, LSIs have become smaller and higher performance, and the number of component leads has increased rapidly, and the number of printed circuit boards has been dramatically increased to connect them. Further, there is a demand for downsizing the printed wiring board itself. 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, but the conventional photosensitive resin composition has recently been improved. At present, sufficient adhesiveness that can cope with fine pitches is obtained. Accordingly, an object of the present invention is to provide a photosensitive resin composition that can form a very stable resist film that has excellent adhesion to a copper surface, and whose strength is not affected by changes over time after coating or lamination, and It is intended to provide a photosensitive film, a photoresist, and a printed wiring board using the above.

 Means for solving the problem

 That is, the photosensitive resin composition of the present invention comprises: (A) a carboxylic acid compound; (B) one or two kinds selected from the group power of triazoles, tetrazoles and imidazoles. (C) a thermoplastic organic polymer; (D) a photopolymerizable compound having an ethylenically unsaturated group; and (E) a photopolymerization initiator. .

 [0018] The photosensitive resin composition of the present invention is further characterized by containing (F) an amine.

 [0019] 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. 1 type or 2 or more types of additives selected from the group consisting of an agent, an antifoaming agent, a flame retardant, a release accelerator, a fragrance, an imaging agent, a thermal cross-linking agent, and a developability 'plating property improver It is characterized by.

 [0020] Further, the photosensitive resin composition of the present invention is further selected from the group consisting of alcohols, ketones, acetic acid esters, glycol ethers, glycol ether esters and petroleum solvents. It contains seeds or two or more organic solvents for dilution.

 [0021] Further, the photoresist of the present invention is characterized in that it comprises the above photosensitive resin composition.

[0022] Further, the photosensitive film of the present invention is obtained by coating the above-mentioned photosensitive resin composition on a support and forming a dried photosensitive resin composition layer on the support. Features. The invention's effect

[0023] The photosensitive resin composition of the present invention has excellent adhesion between the resist film and the copper surface when directly applied as a solution on the copper surface or laminated as a resist film, and the copper surface after lamination The anti-discoloring property is extremely high and stable, and the cost of raw materials used is low. Therefore, the resist film is used in the next process, such as etching and mating. As a result, there is no lift of the copper surface force, no chipping of the resist end, and no plating peeling, and the photosensitive resin composition of the present invention can be used to efficiently produce a good printed wiring board. If you can, it will have a positive effect.

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0024] Examples of the (A) carboxylic acid compound used in the photosensitive resin composition of the present invention include aliphatic carboxylic acids and aromatic carboxylic acids (excluding carboxybenzotriazole). These can be used alone or in combination of two or more.

[0025] Here, the aliphatic carboxylic acid is a group of compounds having 1 to 30 carbon atoms and having one or more carboxyl groups, and may be structurally saturated or unsaturated. As a substituent that may contain a cyclic structure (alicyclic ring, aromatic ring) in a structure that is good in both a chain type and a branched type, oxygen (hydroxyl group, carboxylic group, carboxyl group, ether, ester, etc.), Compounds that can contain nitrogen (amino groups, amide groups, nitro groups, cyanos groups, etc.) are preferred. For example, propionic acid, butyric acid, valeric acid, caproic acid (hexanoic acid), heptanoic acid, strength prillic acid (octanoic acid), pelargonic acid, strength purine acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearin Acid, araquinic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melissic acid, acrylic acid, crotonic acid, cinnamate, obusilic acid, proproleic acid, undecylenic acid, lindenic acid, zudetic acid, fizeteric acid , Myristoleic acid, palmitoleic acid, elaidic acid, petrothelic acid, oleic acid, asclepic acid, baccenoic acid, gadoleic acid, gondoic acid, cetreic acid, erucic acid, brassic acid, cerakoleic acid, nergonic acid, ximenoic acid, Lumequenic acid, sorbic acid, linoleic acid, hiragoic acid, alpha linolenic , Gamma--linolenic acid, pucric acid, alpha-eleostearic acid, beta-eleostearic acid, moloctic acid, stearidonic acid, arachidonic acid, eicosapentanoic acid, succinic acid, docosahexaenoic acid, -cinnic acid, Talylic acid, stearolic acid, crepenic acid, ximenic acid, 2-methylpropanoic acid, 2-methylbutanoic acid, isovaleric acid, neopentanoic acid, 2,3 dimethylpentanoic acid, 4,4 dimethylpentanoic acid, 2 ethyl Butyric acid, 2,2-Dimethylhexanoic acid, 2-Ethylhexanoic acid, Octanoic acid, Isooctanoic acid, Isononanoic acid, Isodecanoic acid, Neodecanoic acid, Isotridecanoic acid, Isopalmitic acid, Isos Theatric acid, methacrylic acid, senesic acid, citronellic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undehydronic acid, dodecanedioic acid, tridecanediic acid Acid, Tetradecanedioic acid, Pentadecanedioic acid, Hexadecanedioic acid, Octadecanedioic acid, Maleic acid, Fumaric acid, Otaturucuccinic acid, Dodece-succinic acid, Octadecenedioic acid, Pentadec-lucuccinic acid, Tripotentylvalic acid, Glutamine Acid, 2, 5 dibenzamidopentanoic acid, glycolic acid, lactic acid, alpha-butyric acid, malic acid, tartaric acid, citrate, darconic acid, ethylenediamine amine acetic acid, hydroxyethylene ethyleneamine triacetic acid, ditrimethyl triacetic acid, diethylenetriamine Pentaacetic acid, triethylene tetramine hexaacetic acid, dica Boxymethylglutamic acid, hydroxyethyliminodiacetic acid, dihydroxyethylglycine, 1,3 propanediaminetetraacetic acid, 1,3 diamino1-2 hydroxypropanetetraacetic acid, dihydroxyethylethylenediamine diacetic acid, methylglycine diacetic acid Etc. Among these compounds, octanoic acid, isostearic acid, octadecanedioic acid, octaturic succinic acid, ethylenediammine tetraacetic 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 more carboxy groups that are directly bonded to them. 12 structurally saturated or unsaturated is acceptable. Either a linear or branched structure may contain a cyclic structure (alicyclic ring, aromatic ring). Oxygen (hydroxyl group, carbocyclic group, carboxyl group) Group, ether, ester, etc.), nitrogen (amino group, amide group, nitro group, cyan group, etc.), sulfur (thiol group, sulfide, etc.), nitrogen, rogen (fluorine, chlorine, bromine, iodine, etc.) Preferred compounds are

. For example, benzoic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, toluic acid, xylyl acid, hemmellitic acid, trimellitic acid, trimesic acid, hemellitic acid, mesitylene acid, utobiic acid, pre-cylic acid, Gamma Isoduric acid, alpha-isoduric acid, diuric acid, merophanic acid, plate acid, pyromellitic acid, meritic acid, diphenic acid, salicylic acid, o pyropyrotechnic acid, beta-resorcylic acid, gentisic acid, normal — Resorcylic acid, protocatechuic acid, thiosalicylic acid, alpha-resorcylic acid, olseric acid, gallic acid, p-cyclobenzoic acid, annisic acid, creosote acid, o homosalicylic acid, m-homosalicy Luric acid, p-homosalicylic acid, vanillic acid, isovanillic acid, syringic acid, veratromic acid, O monobellatrumic acid, asaronic acid, cumic acid, mesitic acid, m-hemipic acid, homophthalic acid, homoisophthalic acid, homoterephthalic acid Acid, phthalonic acid, isophthalonic acid, terephthalonic acid and the like. Of 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.

 [0027] As the (B) heterocyclic compound, triazoles, tetrazoles, and imidazoles can be used. These can be used alone or in combination of two or more.

[0028] The 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 condensed ring structure of benzene ring or naphthalene ring; C1 to C12 structurally saturated or unsaturated as a substituent on triazole ring and Z or aromatic ring, linear or branched Oxygen (hydroxyl group, carbol group, carboxyl group, ether, ester, etc.), nitrogen (amino group, amide group, nitro group, cyano) which may contain cyclic structure (alicyclic ring, aromatic ring) in the structure. Group), sulfur (thiol group, sulfide, etc.), and halogen (fluorine, chlorine, bromine, iodine, etc.) are preferable. For example, 2— (2, monohydroxy-1,5 monomethylphenol) benzotriazole, 1H—1, 2, 3 —triazole, 2H-1, 2,3 triazole, 1H-1, 2,4 triazole, 4H— 1, 2, 4 Triazole, Benzotriazole, Tolyltriazole, Carboxybenzotriazo Monore, 3 Amino 1, 2, 4 Tria: / Nore, 4 Amino-1, 2, 4 Tria: / Monole, 5 Ami No 1, 2, 4 triazole, 3-mercapto 1, 2, 4 triazole, black mouth benzotriazole, nitrobenzo triazole, amino benzotriazole, cyclohexano [1, 2-d] tria, nonor, 4, 5, 6, 7-Tetrahydroxytrinorretria, Norole, 1-Hydroxyben, Notriazole, Ethylbenzotriazole, Naphthotriazole, 1- [N, N-Bis (2-ethylhexyl) aminomethyl] ben Zotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] tolyltriazole, 1- [N, N bis (2-ethylhexyl) aminomethyl] carboxybenzotriazole, 1- [ N, N Bis (2-hydroxyethyl) monoamino Til] benzotriazole, 1- [N, N bis (2-hydroxyethyl) -aminomethyl] tolyltriazole, 1- [N, N bis (2-hydroxyethyl) monoaminomethyl] carboxy benzotriazole, 1— [N, N bis (2-hydroxypropyl) aminomethyl] carboxbenzotriazole, 1— [N, N bis (1-butyl) aminomethyl] carboxybenzotriazole, 1— [N, N bis (1 —Octyl) aminomethyl] carboxybenzotriazole, 1— (2,3, -di-hydroxypropyl) benzotriazole, 1— (2,3, —di-carboxyethyl) benzotriazole, 2— (2′—Hydroxy—3 ′, 5, —Di-tert-butylphenol) benzotriazole, 2 -— (2, —hydroxy-3,5, —amylphenol) benzotriazole, 2— (2'-hydroxy 4'-Otoxyphenyl) benzotriazole, 2- (2, -hydroxy-5, -tert-butylphenol) benzotriazole, 1-hydroxybenzotriazole-6-force rubonic acid, 1-oleoylbenzotriazole, 1, 2, 4 —Triazole—3-ol, 5 amino 3-mercapto— 1, 2, 4 triazole, 5 —amino 1, 2, 4 triazole 1 3-carboxylic acid, 1, 2, 4 triazole 1— Examples thereof include carboxamide, 4-aminourazole, 1,2,4 triazol-5-one, and the like. Among these compounds, benzotriazole, tolyltriazole, carboxy benzotriazole, 1-hydroxybenzotriazole, 1- [N, N bis (2-ethylhexyl) aminomethyl] tolyltriazole, 1 — [N, N Bis (2-ethylhexyl) aminomethinore] force Norevoxiben: / Triazo, Inore, 3 Amino 1, 2, 4-Tria: / Inore, 4-Amino 1, 2, 4 Tria: / 1 Norre, 5 amino-1, 2, 4 Tria: 1 Monore, 3-Menolecapto 1, 2, 4 Triazole, Cyclohexano [1, 2— d] Triazole, 1, 2, 4 Triazole— 3 years old Monore, 5 amino-3-Menolecapto 1,2,4 Tria: / Monole, 5-amino-1, 2,4 Triazole 3-Strong rubonic acid, 1, 2,4 Triazole-3 Carboxamide, 4 Aminourazole, 1 , 2, 4 Triazol 5 Etc. are particularly preferred.

As tetrazole, tetrazole (1H-tetrazole, 2H-tetrazole) can be either linear or branched at positions 1 and 5 of C1 to C12 as hydrogen or substituents. Oxygen (hydroxyl group, carbonyl group, carboxyl group, ether, ester, etc.), nitrogen (amino group, amide group, nitro group, cyano group, etc.) that may contain a cyclic structure (alicyclic ring, aromatic ring) in the structure ), Sulfur (thiol group, sulfide, etc.), halogen Compounds containing fluorine (fluorine, chlorine, bromine, iodine, etc.) are preferred. For example, 1H-tetrazole, 5 amino-1H-tetrazole, 5-methyl-1H-tetrazole, 1-methyl-5ethyl 1H tetrazole, 1methyl-5 mercapto-1H-tetrazole, 1-fe-luo 5-mercapto-1H- Tetrazole, 1 (dimethylaminoethyl) 5 mercapto 1H-tetrazole, 5 phenyl 1H-tetrazole, 5,5'-bis 1H-tetrazole 2 ammo-um salt, 5, 5, -azobis 1H-tetrazole, etc. It is done. 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-condensed structure of 1 to 2 benzene rings and 1 to 2 benzene rings; structures of C1 to C12 as substituents on the imidazole ring and Z or benzene ring. Saturated or unsaturated oxygen (hydroxyl group, carboxyl group, carboxyl group, ether, ester, etc.), nitrogen (amino group, amide group, nitro group, cyano group, etc.), sulfur (thiol group, sulfide) Etc.) and halogen (fluorine, chlorine, fluorine, iodine, etc.) are preferred. For example, 1H-imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 5-methylimidazole, 2 phenol 4,5 dihydroxymethylimidazole, 2 phenol 4-methyl-5 hydroxymethylimidazole , 2, 3 Dihydro- 1H Pillow mouth [1, 2-a] benzimidazole, 2-Undecylimidazole, 2-Heptadecylimidazole, 2 Ethyl-4-methylimidazole, 2 Phenylimidazole, 2 —Fe-Lu 4-methylimidazole, 1 benzyl-2-methylimidazole, 1 benzyl 2-phenylimidazole, 1-cyanoethyl—2-methylimidazole, 1-cyanoethyl—2-ethyl 4-methylimidazole, 1 cyanoethyl Ndecylimidazole, 1-cyanethyl 1-2 phenolimidazole, 2 amino-4 5 Dicanoimidazole, 2 Mercaptobenzimidazole, 2 Mercaptomethylbenzimidazole, 4 Formylimidazole, 1- (2-Hydroxyethyl) imidazole, 1-Bureumidazole, 1 Benzyl-2— Formylimidazole, 1-arylimidazole, 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-imidazole-4-yl) propanoyl, 2 -— (3 aminopropanamide) -3- (1H-imidazole-4-yl) propanoyl, Examples include imidazole-4 ethamamine. Of these compounds, 1H-imidazole, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, and 2-phenolimidazole are particularly preferable.

[0031] Examples of the (C) thermoplastic organic polymer compound used in the photosensitive resin composition of the present invention include (meth) acrylic resin, styrene resin, epoxy resin, and amide resin. Examples thereof include cocoa resin, amide epoxy resin, and alkyd resin. These can be used singly or in combination of two or more. Among these resins, it is preferable to use (meth) acrylic resin from the viewpoint of excellent alkali developability. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding to the acrylic acid, and (meth) acrylate refers to acrylate and the corresponding metatalylate. Means an allyloyl group and a corresponding methacryloyl group.

 [0032] The (C) thermoplastic organic polymer compound can be produced, for example, by radical polymerization of a polymerizable monomer.

[0033] 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, cyclo Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nor (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meta ) Atarylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) atta Rate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, force prill (meth) acrylate, 2-ethyl hexyl (meth) acrylate, 3-ethyl hexyl (meth) acrylate, isobornyl (Meta) Atalylate, methoxyethyl (meth) acrylate, butoxychetyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydride

Sibutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3 1-hydroxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, benzyl benzyl (Meth) Atarylate, Furfuryl (Meth) Atarylate, Tetra

) Atarylate, cresyl (meth) acrylate, naphthyl (meth) acrylate, glycidyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nourphenoxypolyethylene glycol mono (meth) acrylate, no Urphenoxypopropylene mono (meth) atalylate, 2-hydroxy-3 phenoxypropyl acrylate, ethylene glycol mono (meth) acrylate, glycerol (meth) acrylate, dipentaerythritol mono (meth) acrylate, dimethylamino Ethyl (meth) acrylate, Jetylaminoethyl (meth) akujire, 2, 2, 2 HJ Funore Petinore (meth) akujire, 2, 2, 3, 3—Terafunore P propyl ( (Meth) acrylate, diethylene glycol di (meth) atta Relate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylo

Propanediol di (meth) acrylate, 1, 3 butanediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hex (meth) acrylate Rate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tritalylate, ethylene glycol ditalylate, diethylene glycol ditalylate, pentaerythritol Triatalylate, tetraethylene glycol ditalylate, styrene, alpha-methyl styrene, beta-methyl styrene, o-methylol styrene, m-methyl styrene, p-methyl styrene , O ethenorestyrene, m-ethynole styrene, p ethyl styrene, o-methoxy styrene, m-methoxy styrene, ρ-methoxy styrene, o ethoxy styrene, m-ethoxy styrene, ρ ethoxy styrene, o chloro styrene, m-chloro styrene , P chlorostyrene, p bromos Styrene derivatives such as tylene, or styrene derivatives in which the benzene ring may be substituted with a functional group such as -tro group, nitrile group, alkoxyl group, acyl group, sulfone group, hydroxyl group, halogen atom, (meth) acrylic Acid, alpha-bromo (meth) acrylic acid, alpha-cyclo (meth) acrylic acid, beta-furyl (meth) acrylic acid, beta-styryl (meth) acrylic acid, maleic acid, maleic anhydride, maleic acid Monomethyl, Monoethyl maleate, Monoisopropyl maleate, (Meth) acrylamide, N-methylolacrylamide, N Hydroxymethyl (meth) acrylamide, N-methoxymethylacrylamide, N Ethoxymethylacrylamide, N-butoxymethylacrylamide, Methylenebis Acrylamide Ethylene bis acrylamide, 1, 6 hexamethylene bis acrylamide, diacetone acrylamide, 2-atallyloyllochetyl phthalate, 2-atallyloyllochechetyl 2-hydroxychetyl phthalate, 2-methacryloyl oral chichechinoley 2-hydroxypropyl phthalate Rate, divinyl phthalate, divinino terephthalate, cellulose, hydroxy methenores cerealose, hydroxy ethino ceno relose, hydroxy propino leseno relose, canoleboxi methino seleno relose, canole boxi chineno leseno relose, canole box chineno les Methinorescenellose, Cellulose phthalate, Cenorelose acetate phthalate, Hydroxypropyl methylcellulose phthalate, Hydroxypropinoremethinolecellulose Polyvinyl alcohols such as polybutyral rosin, which is a reaction product of tate phthalate polyvinylinol alcohol and butyraldehyde, delta-valerolatataton, epsilon brilliant prolatatanes, beta-propiolatatanes, alpha-methyl-beta-propiolatatanes, beta-methyl Rotatones such as roux terpropionatatone, alpha-methyl-beta-propiolatatatone, beta-methy loubeta-propiolatatane, alpha, alpha-dimethyl-beta-propiolatatatone, beta, beta-dimethyl-beta-propiolatatatone, etc. Polymerized polyesters, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycolate, etc. Polyesters obtained by condensation reaction of alkylene glycol 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 , Polypentamethylene glycol, bisphenol A, hydroquinone, dihydroxycyclohexa Polycarbonates, which are the reaction products of diols such as diphenyl carbonate, carbogene compounds such as diphenyl carbonate, phosgene, and succinic anhydride, (meth) acrylonitrile, o vinyl toluene, m butyl toluene, p Butyltoluene, Butyl acetate Butyl butyrate, Benzo benzoate, Bull propionate, 2, 2, One bis (4-Atari-oxydiethoxyphenol) Propane, Dibutyl succinate, Dibutyl adipate, Dibutene benzene 1,3 disulfonate, isoprene, black mouthprene, 3-butadiene, butyl _n -butyl ether fumaric acid, cai cinnamate, alpha cyanocin cinnamate, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, Examples include crotonic acid and propiolic acid. The thermoplastic organic polymer (C) component may be used alone or in combination.

 [0034] Examples of the photopolymerizable compound (D) having an ethylenically unsaturated group used in the photosensitive resin composition of the present invention include, for example, a bisphenol A-based (meth) atalytoi compound, Examples thereof include a compound obtained by reacting a polyvalent alcohol with an alpha or beta unsaturated carboxylic acid, a urethane monomer such as a (meth) atalytoi compound having a urethane bond. These can be used alone or in combination of two or more.

[0035] Examples of the bisphenol A-based (meth) attareito toy compound include 2, 2 bis [4-

{(Meth) Atarioxydiethoxy} Phenol] propane, 2, 2 bis [4— [{(Meth) Ataryloxytriethoxy} Phenol] propane, 2, 2 bis [4— {(Meth) Ataridioxy Tetraethoxy} phenol] propane, 2, 2 bis [4— {((Meth) Atalyloxypentaethoxy} phenol] bread, 2, 2 bis [4— {((Meth) attaoxyhexahexoxy} [Phenol] propane, 2, 2 —bis [4— {(Meth) Atalyloxyheptaethoxy} phenyl] propane, 2, 2 bis [4— {(Meth) Attaroxyxoxyethoxy) ] Propane, 2, 2 Bis [4— {(Meth) Atari mouth Xinonathoxy} Fuel] Propane, 2, 2 Bis [4— {(Meth) Atalyloxydeca Toxi} Phenyl] propane, 2, 2 Bis [4 {(Meth) Atyloxydecaethoxy} Fuel] propane, 2, 2 Bis [4— {(Meth) Ataridioxy Dodecatoxy} phenol] propane, 2, 2 bis [4— {(meth) ataryloxytridecateoxy} propane], 2, 2 bis [4— {(meth) atarioxytetradecaethoxy } Phenol] propane, 2, 2 bis [4— {(Meth) Atalyloxypentadecaethoxy} Phenol] propane, 2, 2 bis [4— {(Meth) Atari mouth Oxyhexadedeoxy ethoxy} phenol] propane, 2, 2 bis [4 {((meth) attaryloxy dip) propane} propane, 2, 2 bis [4— {(meth) attaryloxytripropoxy} phe- Propane], 2, 2 bis [4 {((meth) attaxytetrapropoxy} phenol) propan, 2, 2 bis [4— {(meth) attaryloxy pentapropoxy} phenol] propane, 2 , 2 —Bis [4— {((Meth) Atalyloxyhexapropoxy} phenol] propane, 2, 2 bis [4-{(Meth) Atalyloxyheptapropoxy} phenol] propane, 2, 2 bis [4 — {(Meth) Atari-xoxypropoxy} phenol] propane, 2, 2 bis [4— {(Meth) Ataryloxynonapropoxy} phenol] propane, 2, 2 bis [4— {(Metal ) Atari mouth oxidizer force} Fuel] propane, 2, 2 bis [4— {(meth) atari mouth Xyldecapropoxy} fehr] propane, 2, 2 bis [4 {(meth) atalyloxide decapropoxy} fehl] puff pan, 2, 2 bis [4— {(meth) atalyloxytri Decapropoxy} phenyl] propane, 2,2bis [4 — {(meth) atoxytetradecapropoxy} phenol] propane, 2,2bis [4 — {(meth) atalyloxypentadecapropoxy } Phenol] propane, 2, 2 bis [4 — {(Meth) atoxy hexade propoxy} Phenol] propane, 2, 2 bis (4-methacryloxypentadecaethoxy) phenol propane, 2, 2 Bis [4— {(Meth) Atalyloxydiethoxyoctapropoxy} phenol] propane, 2, 2 Bis [4 {(Meth) Atalyloxy tetraethoxytetrapropoxy} phenol] propane, 2, 2 Bis [4— {(Meth) Atalyloxyhexaethoxyhexyl Propoxy} phenyl] propane, 2,2bis [4 — {(meth) acryloxydiethoxy} phenol] propane, 2,2bis [4 — {(meth) atari-mouth oxytriethoxy}- Propane], 2, 2 bis [4— {(Meth) Atalyloxypentaethoxy} phenol] propane, 2, 2 bis [4— {(Meth) Atari oxydeoxy ethoxy} phenol] propane, bis Examples include phenol A diglycidyl ether di (meth) acrylate.

 [0036] Among these, 2, 2 bis {4-methacryloxypentaethoxy) phenol} propane is commercially available as BPE-500 [Product name: Shin-Nakamura Igaku Kogyo Co., Ltd.] 2,2-bis {4metatalyloxypentadecaethoxy) phenol} propane is commercially available as BPE-1300 [product name: Shin-Nakamura Chemical Co., Ltd.].

[0037] As the above bisphenol A-based (meth) atalytotoy compound, a derivative thereof can also be used. As a powerful derivative, acrylic acid is added to bisphenol A-diepoxy. And the like. 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 or beta unsaturated carboxylic acid include 1, 6 hexanediol di (meth) acrylate, phenoxy tetraethylene dallicol (meth) acrylate, 1,4-tetramethylene glycol di (meth) atalylate, 1,4-cyclohexanediol di (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycoldi (Meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenol) propane di (meth) acrylate, heptapropylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, Glycerol (meta) atta Rate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropantri (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, phthalic acid Diglycidyl ether di (meth) acrylate, glycerin polyglycidyl ether poly (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nourphenoxy Lithylene glycol (meth) acrylate, Nourphenoxy polyalkylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, 4 normaloctylphenoxypentapropylene glycol (meth) acrylate, 4-bis { Triethylene glycol (meth) acrylate relay treapropylene glycol, bis {tetraethylene glycol (meth) acrylate} Polypropylene glycol, bis {Triethylene glycol (meth) acrylate} Polypropylene glycol, bis (diethylene glycol glycolate) Rate) Polypropylene glycol, 4-nonolemarnonylphenoxyoctane ethylene glycol (meth) acrylate, 4 normal-norphenoxyheptane ethylene glycol dipropylene Glycol (meth) Atari rate, phenoxyethanol tetra propylene glycol tetraethylene glycol (meth) Atari rate, trimethylolpropane di (meth) Atari rate, trimethylolpropane jet carboxymethyl tri (meth) Atari rate, Torimechiro Propane ethoxytri (meth) acrylate, trimethylol propane triethoxy tri (meth) acrylate, trimethylol propane tetraethoxy tri (meth) acrylate, trimethylol propane pentaethoxy tri (meth) acrylate, tetramethylol methane tri (Meth) acrylate, tetramethylol methane tetra (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meta) ) Atalylate, polyethylene polytrimethylolpropane (meth) atarylate, tetramethylolpropanetetra (meth) atarylate, pentaerythritol tri (meth) atarylate, pentaerythris Penta (meth) Atari, glycerin mono (meth) Atari rate, glycerin di (meth) Atari rate and the like.

 [0039] Examples of urethane monomers such as the above (meth) ataretoy compound having a urethane bond include compounds having a hydroxyl group and a (meth) acryl group in one molecule [2-hydroxypropyl (meth) atari , 2 hydroxyethyl (meth) acrylate, 3 1-hydroxy 2-hydroxypropyl (meth) acrylate, oligoethylene glycol mono (meth) acrylate, oligopropylene glycol mono (meth) acrylate] And isophorone diisocyanate, 2, 6 toluene diisocyanate, 2, 4 toluene diisocyanate, 1, 6 hexamethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate Or diisocyanate compounds such as 2,2,4 trimethylhexamethylene diisocyanate Addition reaction products, tris [(meth) acrylate polytetraethylene glycol isocyanate] hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, etc. It is done.

 [0040] EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethyleneoxy group. Ρο represents propylene oxide, and the PO-modified compound has a block structure of propyleneoxy group. Examples of the EO-modified urethane di (meth) acrylate include the product name UA-11 manufactured by Shin-Nakamura Chemical Co., Ltd. In addition, examples of EO and PO-modified urethane di (meth) acrylates include the product name UA-13 manufactured by Shin-Nakamura Chemical Co., Ltd.

[0041] Other compounds include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) Atalylate, butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, 2-phenyloxy 2-hydroxypropyl (meth) acrylate, diallyl phthalate, beta-hydroxypropyl-beta, {(Meth) attalyloyloxy} propyl phthalate, 2- (meth) chlorooxyl 2-hydroxypropyl phthalate, 2- (meth) acryloxychethyl 2- hydroxy ethyl phthalate, norphenyl-xylene (meth) Atalylate, Gamma ^ —— Black mouth 1 beta 1 Hydroxypropyl 1 beta, (Meth) Atalyloxy Schietil o phthalate, Beta Hydroxyethyl beta, (Meth) Atalyloxy Shetil o o Phthalate, Beta 1 Hydroxypropyl 1 Beta , (Meta) Atari Royl Okishe Luo phthalate, EO-modified norfanol (meth) acrylate, N, N dimethyl (meth) acrylamide, (meth) acrylamides such as N-methylol (meth) acrylamide, N, N dimethylaminoethyl Examples include aminoalkyl (meth) acrylates such as (meth) acrylate.

 [0042] Further, (C) the monomer exemplified as being able to be blended in the component of the thermoplastic organic polymer is included.

 [0043] Examples of the (E) photopolymerization initiator used in the photosensitive resin composition of the present invention include aromatic ketones, p-aminophenol ketones, quinones, benzoin ether compounds, and benzoin compounds. , Benzyl derivatives, 2, 4, 5 triarylimidazole dimers, atalidine derivatives, coumarin compounds, oxime esters, N-aryl alpha amino acid compounds, aliphatic polyfunctional thiol compounds, acyl phosphine oxides And thixanthones and tertiary amine compounds. These can be used alone or in combination of two or more.

 [0044] Examples of the aromatic ketones include, for example, acetophenone, benzophenone, methylbenzophenone, N, N, monotetramethyl-1,4'-diaminobenzophenone (Michler ketone), N, N, -tetraethinole 4, 4'-Diaminobenzophenone, 4-methoxy 4 'Dimethinoreaminobenzophenone, 2-Benzyl-2-dimethylamino-1- 1- (4-Morpholinol) Butanone 1, 2-Methyl-1 [4 (Methylthio) phenol] 2 Morpholino- Examples include propan-1, 4, 4-dichroic benzofenone.

[0045] Examples of the p aminophenol ketones include aminoaminobenzophenone and butylamino. Acetophenone, dimethylaminoacetophenone, alpha, alpha 1 dimethoxy 1 alpha morpholino methylthiophene phenophenone, dimethylamino benzophenone, 4, 4, 1 bis (ethylamino) benzophenone, 4, 4, 1 bis (dibutylamino) benzophenone, Examples include 2,2 dimethoxy 1-2 phenylacetophenone, 4,4,1 diaminobenzophenone, 2, 2-jetoxy 2-phenylacetophenone, and the like.

[0046] Examples of the quinones include 2-methylanthraquinone, 2-ethyl anthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, otamethyl anthraquinone, 1, 2 benzanthraquinone, 2, 3 vens. Anthraquinone, 2 Phenylolanthraquinone, 2, 3 Diphenylanthraquinone, 1 Black mouth anthraquinone, 2 Black mouth anthraquinone, 3 Chloro-2-methylanthraquinone, 9, 10 Phanthanthraquinone, 1, 2 Naphthoquinone, 1, 4 Naphthoquinone, Examples include 2-methyl-1,4 naphthoquinone, 1,4 dimethylanthraquinone, 2,3 dimethylanthraquinone, 2 amylanthraquinone, and 2 aminoanthraquinone.

 [0047] Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethinoreethenore, benzoinpropinoreethenore, benzoinphenol-noreethenore and the like.

[0048] Examples of the benzoin compound include benzoin, methylbenzoin, ethyl benzoin, and the like.

 [0049] Examples of the benzyl derivative include benzyl dimethyl ketal, benzyl jet ketal, benzyl dipropyne ketal, benzyl diphenol ketal and the like.

[0050] Examples of the 2,4,5 triarylimidazole dimer include, for example, 2- (o black-mouthed phenol) 4,5 diphenyl-loumidazol monomer, 2- (o black-mouthed phenol) ) — 4,5 Di (methoxyphenol) imidazole dimer, 2— (o Fluorophenol) —4,5 Diphenyl-Limidazolurnimer, 2— (o-methoxyphenol) — 4,5 Diphenyl -Ruimidazole dimer, 2— (p-methoxyphenol) — 4, 5 Diphenol-Limidazolurnimer, 2, 2, — Bis (o-mouthed phenol) 1, 4, 5, 4, 5, 1-tetrafluoro-lumidazolurnimer, 2— (o bromophenol) — 4, 5 Diphenyl-Louidazolurnimer, 2, 2, —bis (o black) Mouth ferrule) —4, 4, 4, 5, 5, tetra- (p-phole) imidazole dimer, 2— (o —clo-faule) 1,4,5-tetra (m—) Methoxyphenol) imidazole dimer, 2, 2, —bis (o black mouth) 1, 4, 4, 5, 5, 1 tetra (p fluorophenol) imidazole dimer 2, 2, One bis (o bromophenol) 1,4,4,5,5, one tetra (p chlorophenol p-methoxyphenol) imidazole dimer, 2,2,1 bis (o chlorophenol) 1, 4, 4, 5, 5, 5-tetra (o, p diclonal phenol) imidazole dimer, 2, 2, 1 bis (o diphenyl)-4, 4, 5, 5, 5, —Tetra (o, p dibromophenol) imidazole dimer, 2, 2, 1bis (o black mouth phenol) 1, 4, 4, 5, 5, 5, 1 tetra (p black mouth naphthyl) imidazole 2,2,1bis (o, m-dichlorophenol-nore) 4, 4 ,, 5, 5, 1 tetraphenyl imidazole dimer, 2, 2, 1 bis (o, p dichlorophenol) 1, 4, 4, 5, 5, 1, tetratetraimidazole 2,2,1bis (o, pdichlorophenol) 1,4,4,5,5,1 tetra (m-methoxyphenol) imidazole dimer, 2,4 di (p-methoxyphenol) 5) Hue-Louimidazolurnimer, 2— (2,4 Dimethoxyphenol) — 4, 5 Diphlo-Louimidazolurnimer, 2— (p-Methylmercaptophenol) — 4,5 Diph -Loimidazole dimer, 2, 2, —bis (p bromophenol) — 4, 4 ,, 5, 5, —tetraphenyl-midazolurnimer, 2, 2, —bis (o bromophenol) ) — 4, 4 ,, 5, 5, —tetra (o, p-dichlorophenol) imidazole dimer, 2, 2, —bis (o bromophenol) —4, 4, 4, 5, 5, — Tetra (p Yodoferu) Imida Zornimer, 2, 2, —bis (m-bromophenol) 4, 4 ,, 5, 5, —Tetraphenol-Limidazolene dimer, 2, 2, —bis (m, p dibromophenol) — 4, 4 ,, 5, 5, —tetraphenyl-lumidazolunimer, 2, 2, —bis (2,6 dichlorophenol) 1, 4,5 diphenyl-lumidazolurnimer, 2, 2, 1 Bis (o-black mouth) 1, 4, 4, 5, 5, 1 tetra (p fluorophenol) imidazole dimer, 2, 2, 1 bis (o bromophenol) 1, 4, 4, , 5, 5, 1-tetra (p-phenylphenol) imidazole dimer, 2, 2, 1-bis (o-cyclohexane) 1, 4, 4, 5, 5, 5, 1-tetra (p-chloronaphthyl) ) Imidazole dimer, 2, 2, -bis (o black mouth file)-4, 4, 5, 5, 5,-Tetra (p black mouth file) imidazole dimer, 2, 2, —Bis (o bromophenol) — 4, 4, 5, 5, 5, tetra (p B port one p- Metokishifue - Le) imidazole dimer, 2, 2, velvetleaf scan (o Black port Hue - Le) one 4, 4 ,, 5, 5, one tetra (o, p Jikurorofue - Le) imidazole Dimer, 2, 2, 1 Bis (o black) 1, 4, 4, 5, 5, 1, Tetra (o, p dibromophenol) imidazole dimer, 2, 2, Bis (O bromophenol) —4, 4, 4, 5, 5, —tetra (o, p dichlorophenol) imidazole dimer, 2, 2, monobis (o, p dichlorophenol) 4, 4, , 5, 5, -tetra (o, p diclonal phenol) imidazole dimer.

 [0051] Examples of the above-mentioned atalidine derivatives include 9 phenylacridine, 9- (p-methylphenyl) atridine, 9- (pethylphenyl) atrazine, 9- (p-n-propylphenol) atridine. , 9— (p—isopropylphenyl) ataridin, 9— (p—n—butylphenol) atridine, 9— (p—tert butylphenol) atalysine, 9— (p—methoxyphenyl) atharidin, 9 — (P ethoxyphenyl) atridine, 9— (p acetylphenyl) acrylidine, 9— (p dimethylaminophenol) atridine, 9— (p cyanophenol) atalidine, 9— (p black mouth) (Phenol) Atalidine, 9— (p-bromophenol) Atalidine, 9— (m—Methylphenol) Atridine, 9— (m—n—Propylphenol) Atridine, 9— (m —isopropyl) Atalidine, 9— (m—n—butylphenol 9- (m-methoxyphenyl) atridine, 9- (m-ethoxyphenyl) atridine, 9- (m-acetylphenyl) atridine 9- (m-dimethylaminophenol) atridine, 9- (m-jetylaminophenol) atalidine, 9- (m-cyanphenol) atalidine, 9- (m E) Atharidin, 9- (m-bromophenyl) atalidine, 9-Cyanoethylataridin, 9-Hydroxyethylatridine, 9-cloethylethylatridine, 9 n-propoxytalidine, 9-isopropoxyatalysin, 9-clomouth Examples include ethoxyataridin, 1,7 bis (9,9, mono-atarizyl) heptane, and the like.

[0052] Examples of the coumarin compounds include 7 amino-4 methylcoumarin, 7 dimethylamino4 methylcoumarin, 7-jetylamino-4 methylcoumarin, 7-methylamino4 methylcoumarin, 7-ethylamino-4 methylcoumarin, and 7-dimethyl. Aminocycline Penta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-jetylaminocyclopenta [c] coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4, 6-jetyl 7-ethylaminocoumarin, 4, 6-dimethyl 7-jetylaminocoumarin, 4, 6-dimethyl-7 -Dimethylaminocoumarin, 4, 6-Jetyloo 7-Jetylaminocoumarin, 4, 6-Jetinoreol 7 Dimethinoreaminocoumarin, 4, 6 Dimethinoremino 7 Ethinoreaminocoumarin, 2, 3,

6, 7, 10, 11 1-hexane hydro- 1H, 5H cyclopenta [3, 4] [1] benzopyrano [6,

7, 8—ij] quinolizine 12 (9H) —one, 7 getinoreamino-1,5,7,1 dimethoxy-1,3,3, -carbolbiscoumarin, 3,3, -carbonylbis [7- (jetylamino) coumarin] 7 Jetylamino 3-Cenoki silk marine and the like.

 [0053] Examples of the oxime esters include 1-phenyl-1, 2-propanedione 2-obenzoyloxime, 1-phenol-1, 2-propanedione 1-2- (o ethoxycarbonyl). ) Oxime and the like.

 [0054] Examples of the N-aryl alpha amino acid compound include N-phenyldaricin, 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 ethinole 1 N—phenylenolanine, N— (n-propyl) N-phenolaranine, N- (n-butyl) N-phenylalanine, N-methyl N phenylvaline, N-methyl leucine, N-methyl N- (p tolyl) glycine, N ethyl N— (p-tolyl) glycine, N— (n-propyl) N— (p-tolyl) glycine, N— (n-butyl) N— (ρ tolyl) glycine, N—methyl N— (p black mouth phenol) Glycine, N— Ethyl N— (p -L) glycine, N— (n-propyl) N— (p-phloro-phenyl) glycine, N—methyl N— (p bromophenol) glycine, N ethyl N— (p — bromophenol) glycine, N— (n-butyl) N— (p bromophenol) glycine, N, N, monodiphenyl glycine, N— methyl N— (p tert-phenyl) glycine, N— (p — bromophenol) glycine, N— (p black mouth file) glycine, N— (o black mouth file) glycine and the like can be mentioned.

[0055] Examples of the aliphatic polyfunctional thiol compound include hexanedithiol, decanedithiol, 1,4 dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, and ethylene glycol bisthioglycolate. , Trimethylolpropane tristiglycolate, butanediol bisthiopropionate , Trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tripropionate, and other polyvalent Hydroxy compounds such as thioglycolate and thiopropionate can be mentioned.

 [0056] Examples of the above acylphosphine oxides include (2, 6 dimethoxybenzoyl) 2, 4, 4 pentylphosphine oxide, bis (2, 4, 6 trimethylbenzoyl) phenol-phosphine oxide, 2, 4, 6 Trimethylbenzoyl diphosphine phosphine oxide and the like.

 [0057] Examples of the thixanthones include thixanthone, 2,4-jetinorexanthone, 2-clothioxanthone, 2,4 dimethylthioxanthone, 2 isopropyl thixanthone, 4 isopropyl thixanthone, 2,4 diisopropylthione. Xanthone, 2-fluorothixanthone, 4-fluorothixanthone, 2-chlorothixanthone, 4-chlorothixanthone, 1-chloro-4-propoxythixanthone, and the like.

 [0058] Examples of other photopolymerization initiators include, for example, ethyl 2,4,6 trimethylbenzoyl phosphinate, 2,3 dixo 3 phenylpropionate diethyl 2- (o benzoylcarbonyl) monooxime, and p-nitrodiphenyl, m-nitrotrolin, p-tro-phosphorus, 2,6-di-tro-phosphorus and the like. Further, a thixanthone compound and a tertiary amine compound may be combined, such as a combination of jetylthioxanthone and dimethylaminobenzoic acid.

 [0059] Examples of the tertiary amine compound include dimethylaminobenzoic acid, jetylaminobenzoic acid, diisopropylaminobenzoic acid, and the like.

[0060] Here, (A) a carboxylic acid compound, (B) a heterocyclic compound, (C) a thermoplastic organic polymer, (D) a photopolymerizable compound having an ethylenically unsaturated group, and (E) The blending ratio of the photopolymerization initiator is as follows. That is, (C) thermoplastic organic polymer 20 to 90% by mass, preferably 40 to 80% by mass, (D) photopolymerizable compound having an ethylenically unsaturated group 5 to 70% by mass, preferably 20 to 60% by mass, (E) a photopolymerization initiator 0.5 to 10% by mass, preferably 1.0 to 5.0% by mass with respect to 100 parts by mass of (A) carboxylic acid compound In the range of 0.005 to 1 part by weight, preferably 0.001 to 0.5 part by weight, and (B) heterocyclic compound The product is in the range of 0.0005 to 1 part by weight, preferably 0.001 to 0.5 part by weight. In addition, if the blending amount of the thermoplastic organic polymer (C) is less than 20% by mass, there is a tendency for a cold flow to occur and the photosensitive resin composition to ooze out the film end face force, and 90% by mass. Exceeding this is not preferable because the sensitivity tends to be insufficient. Next, if the blending amount of (D) the photopolymerizable compound having an ethylenically unsaturated group is less than 10% by mass, the sensitivity tends to be insufficient, and if it exceeds 70% by mass, cold flow is reduced. This is not preferred because the tendency is to cause edging and exudation of the film edge force. In addition, when the blending amount of the (E) photopolymerization initiator is less than 0.5% by mass, the curing tends not to proceed sufficiently when the photosensitive layer is irradiated with an actinic ray and cured. Exceeding 10% by mass is not preferable because the sensitivity of the photosensitive layer to the active light beam becomes too high, and the resolution tends to decrease and the stability tends to decrease. Further, the blending amount of (A) carboxylic acid compound and (B) heterocyclic compound is less than 0.0005 parts by mass with respect to 100 parts by mass in total of (C) component, (D) component and (E) component If it is, the adhesion improving effect tends to be insufficient, and if it exceeds 1 part by mass, other characteristics as a photosensitive resin composition, such as peelability and sensitivity, are reduced. Favorable because of the trend.

The photosensitive resin composition of the present invention contains (F) amines for the purpose of increasing the solubility of the above-mentioned (A) carboxylic acid compound and (B) heterocyclic compound in the resin. It can be further blended. Examples of (F) amines include ammonia, ethylenediamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, diethylenetriamine, jetylamine, 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 and the like. wear. These compounds can be used alone or in combination of two or more. Of these compounds, monoisopropanolamine, diisopropanolamine, di-2-ethylhexylamine and the like are particularly preferred! [0062] The amount of the (F) amine is 5 equivalents or less, preferably 0.5 to 2 equivalents, per 1 equivalent of the acid used in the components (A) and (B). It is preferable that Here, if the compounding amount of (F) amines exceeds 5 equivalents with respect to 1 equivalent of the acid used in the above components (A) and (B), the adhesion improving effect tends to be inhibited. It is not preferable.

 [0063] The photosensitive resin composition of the present invention comprises the above components (A) to (E) as essential components. If necessary, a thermal polymerization inhibitor, a plasticizer, a dye ( Dyes, photochromic agents), antioxidants, surface tension modifiers, stabilizers, chain transfer agents, antifoaming agents, flame retardants, release accelerators, fragrances, imaging agents, thermal crosslinking agents, developability 'plating properties Additives such as improvers can be added as appropriate. These additives can be used alone or in combination of two or more.

 [0064] Examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, tert-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chlorael, naphthylamine, Examples include beta naphthol, 2,6-di-tert-butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, and p-toluidine.

 [0065] Examples of the plasticizer include phthalic esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diaryl phthalate; glycol esters such as triethylene glycol diacetate and tetraethylene glycol diacetate; Phosphate esters such as tricresyl phosphate, triphenyl phosphate; p Amides such as toluenesulfonamide, benzenesulfonamide, N-n-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, diester Aliphatic dibasic acid esters such as octylazelate and dibutylmaleate; triethyl taenoate, tryptyl citrate, glycerin triacetyl ester, butyl laurate, 4, 5-diepoxycyclohexane 1, 2— Zikal Fatty acid esters such as phosphate Jiokuchiru, polyethylene glycol, and the like or glycols such as polypropylene glycol.

[0066] Examples of the dye include brilliant green, eosin, ethyl violet, ellis mouth cin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3 diphenyltriazine, alizarin red S, thymol. Phthalein, methyl Niolet 2B, Kinano Resin Red, Rose Benganore, Methaninore Yellow, Ziminolesnore Hofarein, Xylenol Blue, Methyl Orange, Orange IV, Diphenylthiocarcinone, 2, 7-Dichlorofluorescein, Paramethyl Red, Congo Red, Benzopurpurin 4B, Alpha 1 naphthyl red, Nile blue A, Phenacetalin, Methyl violet, Malachite green, Parafuchsin, Oil blue # 603 [Orient Chemical Co., Ltd.], Victoria Pure Blue BOH, Spiron Blue GN [Hodogaya匕 匕 学 工業 株式会社], Rhodamine 6G and the like.

[0067] Examples of the photochromic agent include diphenylamine, dibenzylaniline, triphenylamine, jetylaniline, diphenyl-1-p-diylenediamine, p-toluidine, 4, 4, 2-biphenyl in addition to the above-mentioned dyes. Examples include lujamine, o-chloroaniline, leuco crystal violet, leucomalachite green, leuco-phosphorus, and leucomethyl violet.

 [0068] Examples of the developability / plating property improver include carbon tetrachloride, black mouth form, bromoform, 1,1,1-trichloroethane, methylene bromide, methylene iodide, methylene chloride, tetraodor. Carbon, odoform, 1, 1, 2, 2-tetrabromoethane, pentabromoethane, tribromoacetophenone, bis (tribromomethyl) sulfone, tribromomethylphenolsulfone, vinyl chloride, chlorinated olefins Etc.

 [0069] The amount of the additive is as follows: (C) thermoplastic organic polymer; (D) a photopolymerizable compound having an ethylenically unsaturated group; and (E) a total amount of photopolymerization initiator of 100 mass. It is about 0.01 to 20 parts by mass, preferably about 0.05 to 10 parts by mass, respectively.

 [0070] In addition to the above components, the photosensitive resin composition of the present invention includes alcohols, ketones, acetates, glycol ethers as necessary for the purpose of viscosity adjustment and the like. Organic solvents for dilution such as alcohols, glycol ether esters and petroleum solvents can be appropriately prepared.

[0071] Examples of the organic solvent for dilution include hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, benzyl alcohol, methyl ethyl ketone, Ryoseton, methyl isobutyl ketone, cyclohexanone, Methylcyclohexanone, methanol, ethanol, propanol, butanol, isobutanol, hexanol, cyclohexane Nonole, Ethylene glycol monole, Diethylene glycol, Glycerin, Ethylene glycol monomethenoate ethere, Ethylene glycol monoethanolinoatere, Ethyleneglycol monobutenoleatenore, Propylene glycol monomethyl ether, Propylene glycol monoethylenate Tenoré, Diethyleneglycol-monomethinoreateolate, Diethyleneglycololemonoetinoreatenore, Diethyleneglycololemonobutinoleatenore, Diethyleneglycolanol dimethylether, Diethyleneglycoljetylether, 2-methoxybutylacetate, 3- Methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , 3-Ethyl 3-Methoxybutynoacetate, 2-Ethoxybutinoleacetate, 4-Ethoxybutinoleacetate, 4-Propoxybutinoleacetate, 2-Methoxypentinoleacetate, 3-Methoxypentylacetate, 4-Methoxypentylacetate Acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4 methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, methyl acetate, ethyl acetate, methyl acetate, ethyl acetate, propyl acetate , Butyl acetate, Amyl acetate, Propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, Methylenopropionate, Ethyl Lopionate, methyl benzoate, ethyl benzoate, propyl benzoate, butinole benzoate, methinolevylate, ethinolevbutyrate, propinolevbutyrate, N, N dimethylformamide gamma-one butyroratatone, N-methyl-pilipidone , Tetramethylsulfone, black mouth form, methylene chloride, 1,1,1-trichloro mouth ethane, and the like. These solvents can be used alone or in combination of two or more.

 [0072] Here, the blending amount of the solvent is 5 to 50% by mass, preferably 10 to 40% by mass with respect to the photosensitive resin composition.

[0073] The photosensitive resin composition of the present invention can be applied as a photoresist ink as described above onto 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. If necessary, a protective film may be laminated on the photosensitive resin composition layer laminated on the film-like support. As a protective film, the above film In addition to the materials used as the support, a polyethylene film, polybulal alcohol film, or the like is used. Example

 The photosensitive resin composition of the present invention will be further described with reference to the following examples, but it was understood that the present invention is not limited to the following examples.

 Example 1

 (A) Carboxylic acid compound and (B) heterocyclic compound shown in Table 1 below were added to the following basic formulations (1) to (3) to prepare a photosensitive resin composition of the present invention.

Basic formulation (1) Compounding amount (g)

(C) Methacrylic acid Z Methyl methacrylate

 (Mass ratio = 20/70/10) copolymer (mass average molecule

 80000) 64

 (D) 2, 2-bis (4-methacryloxypentadecaethoxy

 (Fuenore) Propane 23

 (D) Polypropylene glycol ditalylate 10

 (E) 2- (o—Black-headed Fuinole) -4, 5—Difeninore

 Imidazole dimer 2.8

(E) 4, 4, mono-bis (jetylamino) benzophenone 0.2

(F) Diisopropanolamine (A) and Z or (B) Total acid 1 equivalent 1.5 equivalents Leuco Crystal Violet (photochromic agent) 0.2 Methylethylketone (solvent) 60 Basic formulation (2 ) Blending amount (g)

(C) Methacrylic acid Z Methyl metatalylate Z Styrene

Copolymer (mass ratio = 25/50/25) (mass average molecular weight

 80000) 64

(D) 2, 2-bis (4-methacryloxypentadecaethoxy (Fuel) Propane 33

 (E) Benzophenone 2.8

(E) 4, 4, 1-bis (Jetylamino) benzophenone 0.1

(E) N ferulglycin 0.1

(F) Diisopropanolamine (A) and Z or (B) Total acid 1 equivalent 1.5 equivalents Leuco Crystal Violet (photochromic agent) 0.2 Methyl ethyl ketone (solvent) 60

Basic formulation (3) Compounding amount (g)

(C) Methacrylic acid / benzyl metatalylate (mass ratio = 20/80)

 Copolymer (mass average molecular weight 60000) 64

 (D) 2, 2 Bis (4-methacryloxydiethoxy

 (Fuenore) Propane 23

 (D) Trimethylolpropane triatrate 10

 (E) 2- (o Black-headed Fuinole) 4, 5—Difeninore

 Imidazole dimer 2.8

 (E) Dimethylaminobenzofenone 0.1

 (E) 7 Jetylamino 1-Methylcoumarin 0.1

 (F) Diisopropanolamine (A) and Z or (B) Total acid 1 equivalent 1.5 equivalents Leuco Crystal Violet (photochromic agent) 0.2 Methyl ethyl ketone (solvent) 60

In addition, for comparison, a composition comprising only the basic composition (1), (2) or (3) [Comparative product (1) 1, (2)-1, (3) -1], the above basic composition (1 ), (2) or (3) with only (A) a carboxylic acid compound added as an additive [Comparative product (1) 2-20, Comparative product (2) -2- 20, Comparative product (3) —2 to 20], (B) Composition containing only heterocyclic compounds [Comparative product (1) 21 to 41, Comparative product (2) —21 to 41, Comparative product (3) —21 to 41], (F) Compositions containing only amines [Comparative product (1) 42, Comparative product (2) —42, Comparative product (3) —42], and (A) Carvone A composition comprising an acid compound and (B) a heterocyclic compound added in an amount outside the scope of the present invention [Comparative product (1) 43-50, comparative product (2) -43-50, comparative product (3) -43 ~ 50] were prepared.

 [0078] Further, the obtained composition of the present invention and the comparative product were placed on a support film (material = polyethylene terephthalate), stretched with an applicator, and dried at 80 ° C for 10 minutes to form a resist film having a thickness of 40 m. Got. Next, the obtained resist film was laminated on a cleaned copper-clad laminate for printed circuit boards at a temperature of 80 ° C. using a laminator to obtain a substrate for evaluation (25 × 50 mm).

 [0079] <Adhesion test>

The substrate for evaluation was irradiated with UV (365 nm) at an exposure dose of 25 mjZcm ² using a negative having a pattern with a line width Z space width of 30 Z400 to 200 Z400 (unit: m). After the support film was removed, the film was developed for 60 to 70 seconds using a 1% strength by weight aqueous sodium carbonate solution, washed 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 line width value without any separation. The adhesion is small, the better the value:

 [Adhesion Z visual inspection]

 Α: Less than 40 πι

 Β: 40 μm or more and less than 50 μm

 Ο: 50 μm or more and less than 60 μm

 Ό: 60 μm or more and less than 70 μm

 Ε: 70 / ζ πι or more

 [0080] <Discoloration prevention test>

The substrate for evaluation was irradiated with UV (365 nm) with an exposure dose of 25 mjZcm ² using a step tablet whose brightness changed from transparent to black in 41 steps. After removing the support film, it was developed with a 1% strength 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 but less than 30% c: 30% or more but less than 50% d: 50% or more but less than 80% e: 80% or more

[table 1]

Addition amount of (A) carboxylic acid compound and (B) heterocyclic compound when the total amount of components (C), (D) and (E) in basic composition (1) is 100 parts by mass (parts by mass)

BT—LX is 1 1 [N, N-bis (2-ethylhexyl) aminomethyl] benzotri Azole, TT-LX is 1- [N, N-bis (2-ethylhexyl) aminomethyl] tolyltriazole, CBT-LX is 1- [N, N-bis (2-ethylhexyl) Aminomethyl] carboxybenzotriazole is shown respectively.

[Table 2]

 Table 2 When the total amount of components (C), (D) and (E) in the basic composition (1) is 100 parts by mass,

Addition amount of (A) carboxylic acid compound and (B) heterocyclic compound (parts by mass)

[Table 3]

Table 3 When the total amount of components (C), (D) and (E) in the basic composition (1) is 100 parts by mass,

Addition amount of (A) carboxylic acid compound and (B) heterocyclic compound (parts by mass)

Four] Addition amount of (A) carboxylic acid compound and (B) heterocyclic compound when the total amount of components (C), (D) and (E) in basic blend (2) is 100 parts by mass (mass parts) )

Five] Addition amount of (A) carboxylic acid compound and (B) heterocyclic compound when the total amount of components (C), (D) and (E) in basic composition (2) is 100 parts by mass (parts by mass)

6]

Table 6 When the total amount of components (C), (D) and (E) in the basic composition (2) is 100 parts by mass,

Addition amount of (A) carboxylic acid compound and (B) heterocyclic compound (parts by mass)

7] Table 7 When the total amount of components (C), (D) and (E) in the basic composition (3) is 100 parts by mass,

Addition amount of (A) carboxylic acid compound and (B) heterocyclic compound (parts by mass)

8] Table 8 When the total amount of components (C), (D) and (E) in the basic composition (3) is 100 parts by mass,

Addition amount of (A) carboxylic acid compound and (B) heterocyclic compound (parts by mass)

9]

Table 9 When the total amount of components (C), (D) and (E) in the basic composition (3) is 100 parts by mass,

Claims

The scope of the claims

 [1] (A) Carboxylic acid compound; (B) One or more heterocyclic compounds selected from the group power consisting of triazoles, tetrazoles and imidazoles; (C) Thermoplastic organic A photosensitive resin composition comprising: a polymer; (D) a photopolymerizable compound having an ethylenically unsaturated group; and (E) a photopolymerization initiator.

 [2] The compound (A) according to claim 1, wherein the (A) carboxylic acid compound is selected from the group consisting of fatty acids and aromatic carboxylic acids (excluding carboxybenzotriazole) and one or more selected. Photosensitive resin composition.

 [3] The fatty acid has 1 to 30 carbon atoms, has one or more carboxyl groups, is saturated or unsaturated, and may be linear or branched. Even if it has a cyclic structure in its structure, it may have a hydrocarbon group, an oxygen-containing group, and Z or a nitrogen-containing group as substituents. Item 3. The photosensitive resin composition according to Item 2.

 [4] The aromatic carboxylic acid has a benzene, naphthalene or anthracene structure as a skeleton, has one or two or more carboxyl groups directly bonded thereto, and has a carbon atom power of ~ 12 as a substituent. Saturated or unsaturated, having a group containing oxygen and Z or nitrogen, whether linear or branched, or having a cyclic structure in the structure However, the photosensitive resin composition according to claim 2, which is a composite.

 [5] (C) a thermoplastic organic polymer; (D) a photopolymerizable compound having an ethylenically unsaturated group; and (E) (A) a carboxylic acid salt with respect to 100 parts by mass of the total amount of the photopolymerization initiator. The blending amount of the compound is in the range of 0.0005 to 1 part by mass, and the blending amount of the (B) heterocyclic compound is in the range of 0.005 to 1 part by mass. Anyway, the photosensitive resin composition according to item 1.

 6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising (F) an amine.

 [7] The photosensitive resin according to claim 6, wherein the amount of the (F) ammine is 5 equivalents or less based on 1 equivalent of the acid used in (i) the carboxylic acid compound and (ii) the heterocyclic compound. Fat composition.

[8] Furthermore, thermal polymerization inhibitors, plasticizers, dyes, antioxidants, surface tension modifiers, stabilizers, chain transfer agents, antifoaming agents, flame retardants, release accelerators, fragrances, imaging agents, heat Crosslinker and present The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition contains at least one additive selected from one or more selected additives. .

 [9] (C) thermoplastic organic polymer; (D) a photopolymerizable compound having an ethylenically unsaturated group; and (E) a total amount of the photopolymerization initiator. The photosensitive resin composition according to claim 8, wherein each is in the range of 0.01 to 20 parts by mass.

 [10] Furthermore, 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 according to any one of claims 1 to 9, which comprises

 [11] The photosensitive resin composition according to claim 10, wherein the amount of the solvent for dilution is in the range of 5 to 50% by mass relative to the photosensitive resin composition.

[12] A photoresist ink characterized in that the photosensitive resin composition according to any one of claims 1 to 11 is also obtained.

[13] A photosensitive resin composition according to any one of claims 1 and 11 is applied on a support and dried to form a photosensitive resin composition layer on the support. A photosensitive film characterized by being formed.