WO2014167671A1 - Photosensitive resin composition - Google Patents

Abstract

This photosensitive resin composition is characterized in containing: (A) a guanidine compound (however, excluding dicyandiamides, inorganic acids and salts of guanidine, and guanidines of tertiary amine structure); (B) one or more heterocyclic compounds selected from the group consisting of triazoles, tetrazoles, and imidazoles; (C) a surface-active agent; (D) a thermoplastic organic polymer; (E) a photopolymerizable compound having an unsaturated ethylene group; and (F) a photopolymerization initiator.

Description

Photosensitive resin composition

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

The photosensitive resin composition is applied to the copper surface of a printed wiring board substrate (hereinafter simply referred to as “substrate”) as a liquid film containing a solvent, and the solvent is removed by heating and drying. Then, after imagewise exposure to active light, development is made into a photoresist image. However, in recent years, in order to improve various problems such as poor workability; possible air pollution; and poor yield, a film-like support, a dried photosensitive resin composition layer (Hereinafter, simply referred to as “photosensitive layer”), and photosensitive resin composition laminates (hereinafter simply referred to as “photosensitive film”) comprising a protective film layer used as necessary have come to be used. It was. Moreover, as the above-mentioned photosensitive resin composition, both a so-called alkali developing type in which an unexposed portion is developed with an aqueous alkali solution and a so-called solvent developing type in which an unexposed portion is developed with an organic solvent are known. Alkali development type photosensitive resin compositions are widely used.

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, the unexposed portion is developed using a predetermined developer such as an aqueous sodium carbonate solution to form a photoresist image on the substrate. Etching the metal surface of the substrate using the formed photoresist image as a mask, or performing a plating treatment, and then peeling the photoresist image using a predetermined stripping solution such as a sodium hydroxide aqueous solution, Thereby, a printed wiring board or the like can be manufactured.

Further, when developing, the components of the unexposed portion of the photosensitive layer are dissolved and dispersed in the developer. However, when the development is repeated, the components having poor dispersibility increase in the developer and aggregates are generated. This agglomerate also causes adhesion on the substrate and clogging of the developing tank piping.

As the photosensitive resin composition and photosensitive film used as described above, for example, Patent Document 1 discloses a binder polymer having a carboxy group, a photopolymerizable compound, a photopolymerization initiator, a melamine derivative, and dicyandiamides. A photosensitive resin composition containing the above is disclosed. In paragraph [0090] of Patent Document 1, dicyanamide, acryloyl dicyandiamide, methacryloyl dicyandiamide, and organic acid salts thereof are exemplified as dicyandiamides.

Patent Document 2 discloses a photopolymerizable thermosetting resin composition comprising an active energy ray-curable resin, a diluent, a photopolymerization initiator, a curing adhesion imparting agent, and a compound having an epoxy group (Claim 1); Adhesion curing agents are imidazole derivatives, triazole derivatives, tetrazole derivatives, guanamines, polyamines or their organic acid salts or epoxy adducts, tertiary amines, polyphenols, organic phosphines, phosphonium salts, quaternary ammonium salts, many It is disclosed that it is a basic acid anhydride, a photocationic polymerization catalyst, a styrene-maleic acid resin, a silane coupling agent or the like (claim 9). Further, in paragraph [0038] of Patent Document 2, dicyandiamide and its organic acid salt and / or epoxy adduct are exemplified as polyamines, and tetramethylguanidine is exemplified as tertiary amines.

Further, Patent Document 3 contains an oligomer soluble in an alkaline aqueous solution having a carboxyl group and a photoreactive unsaturated group, a specific epoxy compound, a sensitizer, a specific heterocyclic mercaptan compound and a guanidine compound. A photosensitive resin composition is disclosed. [0032] In paragraph [0032] of Patent Document 3, as guanidine compounds, dicyandiamide, guanidine, aminoguanidine, 1,1,3,3-tetramethylguanidine, n-dodecylguanidine, 1,6-diguanidinohexane, Examples include methylolguanidine, biguanide, 1-phenylguanidine, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylguanidine, 1-benzyl-2,3-dimethylguanidine, etc. Yes.

JP 2010-276926 A Japanese Patent Laid-Open No. 10-20493 JP-A-5-346667

However, in the photosensitive resin composition disclosed in Patent Document 1 described above, dicyandiamides are blended in order to increase chemical resistance and plating resistance, and the guanidine skeleton of dicyandiamide is the reason. It is considered that the adhesion between the metal part and the photocured product is improved due to the strong interaction with dicyandiamide, but with dicyandiamide, it is possible to improve the adhesion of the cured film of the photosensitive resin composition to the copper surface. Can not. Furthermore, it was impossible to prevent discoloration of the copper surface or to generate aggregates in the developer after developing the cured film.
Further, Patent Document 2 exemplifies dicyandiamide, tetramethylguanidine, organic acid salts thereof and / or epoxy adducts, etc. as curing adhesion imparting agents for the photopolymerizable thermosetting resin composition. A tertiary amine such as polyamine and tetramethylguanidine cannot improve the adhesion of the cured film of the photosensitive resin composition to the copper surface. Furthermore, it was impossible to prevent discoloration of the copper surface or to generate aggregates in the developer after developing the cured film.
Furthermore, in Patent Document 3, a heterocyclic mercaptan compound and a guanidine compound are used together for the purpose of forming a solder mask excellent in resolution, solder heat resistance, solvent resistance, plating resistance, electrical insulation and thermal stability. Is described. However, in a composition using a heterocyclic mercaptan compound and a guanidine compound in combination, the adhesion of the cured film of the photosensitive resin composition to the copper surface is improved; the discoloration of the copper surface is prevented; It was not possible to satisfy all the problems such as prevention of the formation of aggregates.

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. In addition, there is a problem that the copper surface of the substrate is discolored between lamination and development, and further, there is a problem that aggregates are generated in the developer as described above.

Accordingly, the object of the present invention is to prevent discoloration of the copper surface by forming a very stable resist film that has excellent adhesion to the copper surface and is not affected by changes over time after coating or laminating, and further in which the developer is dispersed. The object is to provide a photosensitive resin composition that is excellent in stability and does not generate aggregates, a photoresist ink using the composition, and a photosensitive film.

That is, the present invention is selected from the group consisting of (A) guanidine compounds (excluding dicyandiamides, guanidine inorganic acid salts and tertiary amine guanidines); (B) triazoles, tetrazoles and imidazoles. (C) a surfactant; (D) a thermoplastic organic polymer; (E) a photopolymerizable compound having an ethylenically unsaturated group and (F) initiation of photopolymerization The present invention relates to a photosensitive resin composition comprising an agent.

The photosensitive resin composition of the present invention is based on (D) a thermoplastic organic polymer; (E) a photopolymerizable compound having an ethylenically unsaturated group, and (F) a total amount of 100 parts by mass of a photopolymerization initiator. (A) The amount of guanidine compound is in the range of 0.0005 to 1 part by mass, (B) the amount of heterocyclic compound is in the range of 0.0005 to 1 part by mass, and (C) The amount of the surfactant is in the range of 0.00001 to 0.1 parts by mass.

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

The photosensitive resin composition of the present invention is based on (D) a thermoplastic organic polymer; (E) a photopolymerizable compound having an ethylenically unsaturated group, and (F) a total amount of 100 parts by mass of a photopolymerization initiator. The amount of the additive is in the range of 0.01 to 20 parts by mass, respectively.

Furthermore, the photosensitive resin composition of the present invention is used for dilution of 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.

In the photosensitive resin composition of the present invention, the blending amount of the organic solvent for dilution is (A) a guanidine compound; (B) a heterocyclic compound; (C) a surfactant; (D) a thermoplastic organic polymer; E) The photopolymerizable compound having an ethylenically unsaturated group, (F) the photopolymerization initiator, the additive, and the organic solvent for dilution are within the range of 5 to 50% by mass.

Furthermore, the present invention relates to a photoresist ink comprising the above photosensitive resin composition.

In addition, the present invention is characterized in that a photosensitive resin composition film obtained by applying the photosensitive resin composition on a film-like support and drying is provided on the film-like support. It relates to a photosensitive film.

When the photosensitive resin composition of the present invention is applied directly to a copper surface as a solution or laminated as a photosensitive film, the adhesive property between the photosensitive resin composition film and the copper surface is excellent, and the copper after lamination Surface discoloration prevention is extremely high and stable, and the cost of the raw materials used is low. Therefore, the photosensitive resin composition of the present invention does not cause the photosensitive resin composition film to be lifted from the copper surface, resulting in chipping of the film edge, or plating peeling due to etching or plating in the next step. If this is used, there is an effect that a good printed wiring board can be efficiently manufactured.

The photosensitive resin composition of the present invention comprises (A) a guanidine compound (excluding dicyandiamides, guanidine inorganic acid salts and tertiary amine structure guanidines); (B) triazoles, tetrazoles and imidazoles. One or more heterocyclic compounds selected from the group consisting of: (C) a surfactant; (D) a thermoplastic organic polymer; (E) a photopolymerizable compound having an ethylenically unsaturated group and (F ) It contains a photopolymerization initiator.

Examples of the (A) guanidine compound that can be used in the photosensitive resin composition of the present invention include biguanide, 1-methylguanidinoacetic acid, p-aminobenzenesulfonylguanidine, N-methyl-N′-nitro-N-nitrosoguanidine, Aminoguanidine, 1-o-tolylbiguanide, 1,3-di-o-tolylguanidine, 1-o-tolylguanidine, triphenylguanidine, 1-phenylbiguanide, 1,3-diphenylguanidine, n-dodecylguanidine, guanidine N- (β-phenethyl) diguanide, guanylurea, guanidoacetic acid, nitroguanidine, 1-phenylguanidine, guanylthiourea, 2-phenyl-1,3-dicyclohexylguanidine, 6-guanidinocaproic acid, 1,1'-iminobis (Octamethylene) Zigua Gin, 1,6-diguanidinohexane, xylyl biguanide, methylolguanidine, dimethylolguanidine, 1-amino-3-salicyloylguanidine and 1- (N-salicyloyl) -amino-3-salicyloylguanidine be able to. These guanidine compounds can be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, guanidine compounds such as dicyandiamides, guanidine inorganic acid salts, and guanidines having a tertiary amine structure are excluded from (A) guanidine compounds. Even if dicyandiamides, guanidine inorganic acid salts, and guanidines having a tertiary amine structure are added to the photosensitive resin composition, the adhesion of the photosensitive resin composition film to the copper surface cannot be improved. Because.
Here, specific examples of dicyandiamides include dicyandiamide, acryloyl dicyandiamide, methacryloyl dicyandiamide, N, N-cyclopenta-4′-oxa-methylene dicyandiamide, N, N′-ethylene-bisdicyandiamide, N-methyldicyandiamide, N-ethyldicyandiamide, N-propyldicyandiamide, N-ethyl-N-methyldicyandiamide, N-β-sulfoethyldicyandiamide, Np-sulfophenyldicyandiamide, N-β-carboxyethyldicyandiamide, Np-oxyphenyldicyandiamide And organic acid salts thereof, epoxy adducts and the like.
Specific examples of inorganic acid salts of guanidine include guanidine hydrochloride, guanidine nitrate, guanidine carbonate, guanidine bicarbonate, guanidine phosphate, guanidine sulfate, and guanidine sulfamate.
Further, as guanidines having a tertiary amine structure, 1,1,3,3-tetramethylguanidine, 1,1,3,3-tetraethylguanidine, 1,1,3,3-tetrapropylguanidine, 1,1 3,3-tetrabutylguanidine and the like.

Next, examples of the (B) heterocyclic compound that can be used in the photosensitive resin composition of the present invention include triazoles, tetrazoles, and imidazoles. These can be used alone or in combination of two or more.

Examples of triazoles include triazole (1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, 4H-1,2,4-triazole), 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, aminobenzotria , Cyclohexano [1,2-d] triazole, 4,5,6,7-tetrahydroxytolyltriazole, 1-hydroxybenzotriazole, ethylbenzotriazole, naphthotriazole, 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] tolyltriazole, 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-bis (1-octyl) amino Methyl] 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) benzo Triazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 1-hydro Xylbenzotriazole-6-carboxylic acid, 1-oleoylbenzotriazole, 1,2,4-triazol-3-ol, 5-amino-3-mercapto-1,2,4-triazole, 5-amino-1, Examples include 2,4-triazole-3-carboxylic acid, 1,2,4-triazole-3-carboxamide, 4-aminourazole, 1,2,4-triazol-5-one, and the like.

Examples of the tetrazole include tetrazole (1H-tetrazole, 2H-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- (2-dimethylaminoethyl) -5-mercapto-1H-tetrazole, 5-phenyl-1H-tetrazole, 5,5 ′ -Bis-1H-tetrazole diammonium salt, 5,5′-azobis-1H-tetrazole and the like.

Examples of imidazoles include 1H-imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 5-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl. -5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl Imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole , 1-shear Ethyl-2-undecylimidazole, 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-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.

Examples of the (C) surfactant that can be used in the photosensitive resin composition of the present invention include nonionic, anionic, cationic, and betaine surfactants. These can be used alone or in combination of two or more.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene 2-ethylhexyl ether, polyoxyethylene isodecyl ether, polyoxyethylene Monolaurate, polyoxyethylene monostearate, polyoxyethylene monostearate, ethylene glycol distearate, polyethylene glycol distearate, polypropylene glycol distearate, glyceryl monoateate, glyceryl monomyristate, polyoxy Ethylene palm fatty acid glyceryl, polyoxyethylene hydrogenated castor oil, polyoxyethylene triisostearic acid, polyglycerin oil Inic acid ester, polyglycerol laurate ester, polyglycerol stearate ester, sorbitan monocaprylate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan Triolate, sorbitan monobehenate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene tetraoleic acid, N-hydroxyethyl lauryl amine, polyoxyethylene lauryl amine , Polyoxyethylene palm alkylamine, polyoxyethylene stearylamine, polyoxyethylene oleyl amine Polyoxyethylene beef tallow alkylamine, polyoxyethylene beef tallow alkylpropylenediamine, coconut fatty acid diethanolamide, tallow fatty acid diethanolamide, lauric acid diethanolamide, oleic acid diethanolamide, coconut fatty acid monoethanolamide, lauric acid isopropanolamide, polyethylene glycol , Polyoxyethylene monomethyl ether, polyoxyethylene dimethyl ether, polyoxyethylene glyceryl ether, polypropylene glycol, polyoxypropylene glyceryl ether, polyoxypropylene diglyceryl ether, polyoxypropylene sorbitol, polybutylene glycol, polyethylene glycol-polypropylene glycol block polymer , Polyoxytetramethyle -Polyoxyethylene glycol, polyoxytetramethylene-polyoxypropylene glycol, polyoxyethylene bisphenol A ether, polyoxypropylene bisphenol A ether, polyoxyethylene polyoxypropylene bisphenol A ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Octyl phenyl ether, polyethylene glycol allyl ether, methoxy polyethylene glycol allyl ether, polyethylene glycol polypropylene glycol allyl ether, polypropylene glycol allyl ether, butoxy polyethylene glycol polypropylene glycol allyl ether, polypropylene glycol diallyl ether, polyethylene glycol diallyl ether, etc. And the like.

Examples of the anionic surfactant include lauryl sulfate sodium salt, polyoxyethylene lauryl ether sulfate sodium salt, lauryl sulfate triethanolamine salt, 2-ethylhexyl sulfate sodium salt, di-2-ethylhexyl sulfosuccinate sodium, alkylbenzene Sulfonic acid, sodium alkylbenzene sulfonate, sodium laurate, potassium laurate, sodium coconut fatty acid, potassium coconut fatty acid, sodium myristate, potassium myristate, sodium palmitate, potassium palmitate, sodium stearate, potassium stearate, oleic acid Sodium, potassium oleate, tallow alkyl methyl taurate sodium, palm oil fatty acid methyl taurate sodium N-decanoyl-N-taurate sodium, coconut oil fatty acid 2-sulfoethyl ester sodium, N-oleyl-N-methylglycine, N-lauroyl-N-methylglycine, high-molecular polycarboxylic acid, high-molecular polycarboxylic acid Acid sodium salt, polymeric polycarboxylic acid ammonium salt and the like.

Cationic surfactants include tetradecylamine acetate, octadecylamine acetate, dodecyltrimethylammonium chloride, cocoalkyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, tallow alkyltrimethylammonium chloride, octadecyltrimethylammonium chloride, behenyltrimethylammonium chloride. Chloride, didecyldimethylammonium chloride, di-cured tallow alkyldimethylammonium chloride, dioleyldimethylammonium chloride, coconut alkyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium chloride, N, N-diacyloxyethyl-N-hydroxyethyl-N -Methylammonium chloride Chloride, 1-methyl-1-hydroxyethyl-2-tallow alkyl imidazolinium chloride, and the like.

Betaine surfactants include: lauryldimethylaminoacetic acid betaine, dodecylbis (aminoethyl) glycine, lauric acid amidopropyldimethylaminoacetic acid betaine, palm kernel fatty acid amidopropyldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl- N-hydroxyethyl imidazolium betaine, monosodium laurylaminodiacetate and the like can be mentioned.

Examples of the (D) thermoplastic organic polymer compound that can be used in the photosensitive resin composition of the present invention include (meth) acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyds. Examples thereof include phenolic resins and phenolic resins. These can be used alone or in combination of two or more. Among these, it is preferable to use a (meth) acrylic resin from the viewpoint of excellent alkali developability.
In the present specification, “(meth) acrylic acid” means acrylic acid and methacrylic acid corresponding thereto, “(meth) acrylate” means acrylate and corresponding methacrylate, and “(meth) The “acryloyl group” means an acryloyl group and a corresponding methacryloyl group.

The (D) 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, and 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 ( Meta Acrylate, pentadecyl (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-hydroxy Butyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate Rate, methoxybenzyl (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, nonylphenoxypolypropylene mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, ethylene glycol Mono (meth) acrylate, glycerol (meth) acrylate, dipentaerythritol mono (meth) acrylate Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-trifluoropropyl (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 , Trimethylolpropane 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 , Α-methylstyrene, β-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-c Styrene derivatives such as styrene, p-bromostyrene, etc. [In these styrene derivatives, the benzene ring is substituted with a functional group such as nitro group, nitrile group, alkoxyl group, acyl group, sulfone group, hydroxyl group, halogen atom, etc. May be. ]; (Meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride , Monomethyl maleate, monoethyl maleate, monoisopropyl maleate, (meth) acrylamide, N-methylol acrylamide, N-hydroxymethyl (meth) acrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl Acrylamide, methylenebisacrylamide, ethylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diacetone acrylamide, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate 2-Methacryloyloxyethyl-2-hydroxypropyl phthalate, divinyl phthalate, divinyl terephthalate, cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, carboxyethyl methyl cellulose, cellulose phthalate, cellulose acetate phthalate, hydroxypropyl Polymethyl alcohol phthalate, hydroxypropyl methylcellulose acetate phthalate Polyvinyl alcohols such as polybutyral resin which is a reaction product of polyvinyl alcohol and butyraldehyde; δ-valerolactone, ε-caprolactone, β-propiolactone, α-methyl-β- Propiolactone, β-methyl-β-propyl Lactones such as piolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, α, α-dimethyl-β-propiolactone, β, β-dimethyl-β-propiolactone Ring-opening polymerized polyesters; one or more diols such as alkylene glycol such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol and the like, maleic acid, fumaric acid , Polyesters obtained by condensation reaction with dicarboxylic acids such as glutaric acid and adipic acid; polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol, bisphenol A, hydroquinone, dihydroxycyclohexane Polycarbonates which are reaction products of diols such as xanthine and carbonyl compounds such as diphenyl carbonate, phosgene and succinic anhydride; (meth) acrylonitrile, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, acetic acid Vinyl, vinyl butyrate, vinyl benzoate, vinyl propionate, 2,2'-bis (4-acryloxydiethoxyphenyl) propane, divinyl succinate, divinyl adipate, divinylbenzene-1,3-disulfonate, isoprene, chloroprene , 3-butadiene, vinyl-n-butyl ether fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, propiolic acid and the like. The polymerizable monomers may be used alone or in combination.

Examples of the (E) photopolymerizable compound having an ethylenically unsaturated group that can be used in the photosensitive resin composition of the present invention include a bisphenol A (meth) acrylate compound; a polyhydric alcohol and an α, β-unsaturated carboxylic acid. Examples include compounds obtained by reacting acids; urethane monomers such as (meth) acrylate compounds having a urethane bond. These can be used alone or in combination of two or more.

Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis [4-{(meth) acryloxydiethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxytriethoxy } 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-{(meta ) Acryloxyoctaethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxynonaethoxy} phenyl] propane, 2, -Bis [4-{(meth) acryloxydecaethoxy} phenyl], 2,2-bis [4-{(meth) acryloxyundecaethoxy} phenyl], 2,2-bis [4-{(meth) Acryloxide decaethoxy} phenyl], 2,2-bis [4-{(meth) acryloxytridecaethoxy} phenyl], 2,2-bis [4-{(meth) acryloxytetradecaethoxy} phenyl], 2,2-bis [4-{(meth) acryloxypentadecaethoxy} phenyl], 2,2-bis [4-{(meth) acryloxyhexadecaethoxy} phenyl], 2,2-bis [4- {(Meth) acryloxydipropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxytripropoxy} phenyl] propane, 2,2-bis [4-{(meth) acrylic Riloxytetrapropoxy} 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], 2,2-bis [4-{(meth) acryloxyundeca Propoxy} phenyl], 2,2-bis [4-{(meth) acryloxide decapropoxy} phenyl], 2,2-bis [4-{( Ta) acryloxytridecapropoxy} phenyl], 2,2-bis [4-{(meth) acryloxytetradecapropoxy} phenyl], 2,2-bis [4-{(meth) acryloxypentadecapropoxy} Phenyl], 2,2-bis [4-{(meth) acryloxyhexadecapropoxy} phenyl], 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-{(meth) acryl Roxyhexaethoxyhexapropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxydiethoxy} fur Nyl] propane, 2,2-bis [4-{(meth) acryloxytriethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxypentaethoxy} phenyl] propane, 2,2- Examples thereof include bis [4-{(meth) acryloxydecaethoxy} phenyl] propane, bisphenol A diglycidyl ether-terdi (meth) acrylate, and the like.

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

In addition, as the bisphenol A-based (meth) acrylate compound, a derivative thereof can also be used, and examples of the derivative include a compound obtained by adding acrylic acid to bisphenol A-diepoxy. For example, it is commercially available as Biscote # 540 (manufactured by Osaka Organic Chemical Industry Co., Ltd., product name).

Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include 1,6-hexanediol di (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, 1,4-tetra Methylene 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, glycerol (meth) acrylate Relate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, trimethylolpropane triglycidyl ether tertri (meth) acrylate, diglycidyl phthalate Ether di (meth) acrylate, glycerin polyglycidyl ether poly (meth) acrylate, phenoxypolyethylene glycol ( ) Acrylate, nonylphenoxypolyethylene 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-normalnonylphenoxyocta Ethylene glycol (meth) acrylate, 4-normal nonyl phe Xyheptaethylene 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, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, polyethylene polytrimethylolpropane di (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol penta (Meth) acrylate, glycerol mono (meth) acrylate glycerol 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 glyco -Mono (meth) acrylate, etc.}, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, hexamethylene diisocyanate, Addition reaction products 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, PO modified urethane di (meth) acrylate and the like can be mentioned.

In this specification, “EO” represents ethylene oxide, and “EO-modified compound” has a block structure of ethyleneoxy group. “PO” represents propylene oxide, and “EO, PO-modified compound” has a block structure of ethyleneoxy group and 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. Examples of EO and PO-modified urethane di (meth) acrylates include the product name UA-13 manufactured by Shin-Nakamura Chemical Co., Ltd.

Other (E) photopolymerizable compounds having an ethylenically unsaturated group include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. 2-phenoxy-2-hydroxypropyl (meth) acrylate, diallyl phthalate, β-hydroxypropyl-β ′-{(meth) acryloyloxy} propyl phthalate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, nonylphenyldioxylene (meth) acrylate, γ-chloro-β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate, β- Hydroxyethyl-β '-( Ta) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate, EO-modified nonylphenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N- (Meth) acrylamides such as methylol (meth) acrylamide; and aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate.

Further, (E) the photopolymerizable compound having an ethylenically unsaturated group may contain (D) a polymerizable monomer exemplified as a polymerizable monomer constituting the thermoplastic organic polymer.

Examples of the photopolymerization initiator (F) that can be 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 derivative, coumarin compound, oxime ester, N-aryl-α-amino acid compound, aliphatic polyfunctional thiol compound, acylphosphine oxide, thioxanthone, tertiary amine compound And the like. These can be used alone or in combination of two or more.

Examples of 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- And morpholino-propanone-1,4,4-dichlorobenzophenone.

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

Examples of quinones include 2-methylanthraquinone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 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 dipropyl 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) dimer, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) dimer 2,2′-bis (o-chlorophenyl) -4,4 ′, , 5′-tetra (p-chloronaphthyl) dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chlorophenyl) dimer, , 2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-chloro-p-methoxyphenyl) dimer, 2,2'-bis (o-chlorophenyl)- 4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o , P-dibromophenyl) dimer, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) dimer, 2, 2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) dimer, etc. .

Examples of acridine derivatives 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, 1,7 Bis (9,9'-acridinyl) heptane, and the like can be mentioned.

Examples of coumarin compounds include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, and 7-ethylamino. -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-ethylaminocoumarin 2,3,6,7,10,11-hexaanhydro-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, and the like.

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

Examples of N-aryl-α-amino acid compounds 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-tolyl) Lysine, 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 trimethylolpropane. Tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhio Examples include propionate, and thioglycolates and thiopropionates of these other polyvalent hydroxy compounds.

Examples of 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, Examples include 4-fluorothioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

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

Other photopolymerization initiators include, for example, ethyl-2,4,6-trimethylbenzoylphenyl phosphinate, ethyl 2,3-dioxo-3-phenylpropiodate-2- (o-benzoylcarbonyl) -oxime, p- Examples thereof include nitrodiphenyl, m-nitroaniline, p-nitroaniline and 2,6-dinitroaniline.

Wherein (A) guanidine compound; (B) heterocyclic compound; (C) surfactant; (D) thermoplastic organic polymer; (E) photopolymerizable compound having an ethylenically unsaturated group and (F) ) The blending ratio of the photopolymerization initiator is as follows.
That is, (D) thermoplastic organic polymer; (E) a photopolymerizable compound having an ethylenically unsaturated group and (F) 100 parts by mass of a photopolymerization initiator; Within the range of 0005 to 1 part by mass, (B) within the range of 0.0005 to 1 part by mass of the heterocyclic compound, and (C) within the range of 0.00001 to 0.1 part by mass of the surfactant.

Here, when the blending amount of the (A) guanidine compound is less than 0.0005 parts by mass with respect to a total of 100 parts by mass of the components (D), (E) and (F), the photosensitive resin composition There is a tendency that the adhesion of the material film to the copper surface tends to be insufficient, and when it exceeds 1 part by mass, various properties as a photosensitive resin composition, such as peelability and sensitivity, tend to be reduced. It is not preferable. The amount of (A) guanidine compound is preferably in the range of 0.001 to 0.5 parts by mass.
Moreover, the photosensitive resin composition in which the compounding quantity of (B) heterocyclic compound is less than 0.0005 mass part with respect to a total of 100 mass parts of (D) component, (E) component, and (F) component. There is a tendency that the adhesion of the physical film to the copper surface and the effect of preventing discoloration of the copper surface cannot be sufficiently imparted, and when it exceeds 1 part by mass, various characteristics as a photosensitive resin composition, such as peelability and sensitivity. Etc. tend to decrease, such being undesirable. The blending amount of (B) the heterocyclic compound is preferably in the range of 0.001 to 0.5 parts by mass.
Furthermore, when the blending amount of (C) the surfactant is less than 0.00001 parts by mass with respect to 100 parts by mass in total of the (D) component, the (E) component, and the (F) component, generation of aggregates is caused. If the amount exceeds 0.1 parts by mass, various characteristics as the photosensitive resin composition, such as peelability and sensitivity, tend to be lowered, which is not preferable. The amount of the (C) surfactant is preferably in the range of 0.0001 to 0.05 parts by mass.

The blending ratio of (D) the thermoplastic organic polymer, (E) the photopolymerizable compound having an ethylenically unsaturated group, and (F) the photopolymerization initiator is (D) 20 to 90 mass of the thermoplastic organic polymer. %, (E) 5 to 70% by mass of the photopolymerizable compound having an ethylenically unsaturated group, and (F) 0.5 to 10% by mass of the photopolymerization initiator.
Here, when the blending ratio of the thermoplastic organic polymer (D) is less than 20% by mass, a cold flow occurs, and the photosensitive resin composition oozes out from the end face of the support when producing a photosensitive film. Moreover, since it exists in the tendency for a sensitivity to run short if it exceeds 90 mass%, it is unpreferable. The blending ratio of the (D) thermoplastic organic polymer is preferably in the range of 40 to 80% by mass.
Moreover, when the blending ratio of the photopolymerizable compound having an ethylenically unsaturated group (E) is less than 5% by mass, the sensitivity tends to be insufficient, and when it exceeds 70% by mass, a cold flow is caused. When producing a photosensitive film, the photosensitive resin composition may ooze out from the end surface of the support, which is not preferable. The blending ratio of the photopolymerizable compound (E) having an ethylenically unsaturated group is preferably in the range of 20 to 60% by mass.
Furthermore, when the blending ratio of (F) the photopolymerization initiator is less than 0.5% by mass, the curing tends to not proceed sufficiently when irradiating the photosensitive layer with an actinic ray and curing, Exceeding 10% by mass is not preferable because the sensitivity of the photosensitive layer to actinic rays becomes too high, and the resolution tends to decrease and the stability tends to decrease. The blending ratio of (F) photopolymerization initiator is preferably in the range of 1.0 to 5.0% by mass.

The photosensitive resin composition of the present invention is composed of the above components (A) to (F), and if necessary, a thermal polymerization inhibitor, a plasticizer, a dye, an antioxidant, a surface tension modifier. Additives such as stabilizers, chain transfer agents, flame retardants, release accelerators, fragrances, imaging agents, thermal cross-linking agents, developability / platability improvers, and the like can be appropriately added. These additives can be used alone or in combination of two or more.

Examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β- Examples thereof include naphthol, 2,6-di-t-butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, and p-toluidine.

Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate; glycol esters such as triethylene glycol diacetate and tetraethylene glycol diacetate; tricresyl phosphate, triphenyl Phosphate esters such as phosphate; Amides such as p-toluenesulfonamide, benzenesulfonamide, Nn-butylacetamide; Aliphatics 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-dicar Fatty acid esters such as phosphate and dioctyl, polyethylene glycol, glycols such as polypropylene glycol, and the like.

As the dye, a pigment, a photochromic agent, or the like can be used. 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, and quinaldine. Red, Rose Bengal, Methanyl Yellow, Thymolsulfophthalein, Xylenol Blue, Methyl Orange, Orange IV, Diphenylthiocarbazone, 2,7-Dichlorofluorescein, Paramethyl Red, Congo Red, Benzopurpurin 4B, α-naphthyl Red, Nile Blue A, Phenacetalin, Methyl Violet, Malachite Green, Parafuchsin, Oil Blue # 603 [manufactured by Orient Chemical Co., Ltd.], Bi Tria 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, o-chloroaniline, leucocrystal violet, and leuco. Examples include malachite green, leucoaniline, and leucomethyl violet.

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, Examples include 2,2-tetrabromoethane, pentabromoethane, tribromoacetophenone, bis- (tribromomethyl) sulfone, tribromomethylphenylsulfone, vinyl chloride, chlorinated olefin.

In addition, the compounding quantity of the said additive is each with respect to (D) thermoplastic organic polymer; (E) photopolymerizable compound which has an ethylenically unsaturated group, and (F) 100 mass parts of total amounts of a photoinitiator. The amount is 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, acetate esters, glycol ethers, glycol ether esters, if necessary for the purpose of viscosity adjustment, An organic solvent for dilution such as petroleum solvent 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, methyl cyclohexanone, methanol, ethanol, propanol, butanol, isopropanol. Butanol, 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, Diethylene glycol Cole 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-methoxype Tyl 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, benzoic acid Methyl, ethyl benzoate, propyl benzoate, butyl benzoate, methyl butyrate, ethyl butyrate, propyl butyrate, N, N-dimethylformamide γ-butyrolactone, N-methyl-pyrrolidone, tetramethylsulfone, chloroform, methylene chloride Examples include 1,1,1-trichloroethane. These may be used alone or in combination of two or more.

Here, the blending amount of the organic solvent for dilution is the above (A) guanidine compound; (B) heterocyclic compound; (C) surfactant; (D) thermoplastic organic polymer; (E) ethylenically unsaturated group. 5 to 50% by weight, preferably 10 to 40% by weight of the total amount of the photopolymerizable compound having (A) and (F) a photopolymerization initiator, and the above-mentioned additive and organic solvent for dilution added as necessary. It is.

The photosensitive resin composition of the present invention is applied as a photoresist ink on a film-like support and dried to obtain a photosensitive film comprising a photosensitive resin composition film on the film-like support. it can. Here, a polyethylene terephthalate film, a polystyrene film, a polypropylene film or the like is used as the film-like support. In addition, you may laminate | stack a protective film on the photosensitive resin composition film | membrane laminated | stacked on the film-form support body as needed. As a protective film, a polyethylene film, a polyvinyl alcohol film, etc. can be used besides the material used as a film-like support.

The photosensitive resin composition of the present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
The basic formulations (1) to (3) comprising (D) a thermoplastic organic polymer; (E) a photopolymerizable compound having an ethylenically unsaturated group and (F) a photopolymerization initiator are shown below:
Basic formulation (1):
Blending amount (% by mass)
(D) Copolymer of methacrylic acid / methyl methacrylate / butyl acrylate (mass ratio 20/70/10) (weight average molecular weight 80000) 64
(E) 2,2-bis (4-methacryloxypentadecaethoxy)
Phenylpropane 23
(E) Polypropylene glycol diacrylate 10
(F) 2- (o-chlorophenyl)
-4,5-diphenylimidazole dimer 2.8
(F) 4,4′-bis (diethylamino) benzophenone 0.2
(D) + (E) + (F) total amount 100
(Photochromic agent) Leuco Crystal Violet (External discount: parts by mass) 0.3
(Organic solvent for dilution) Methyl ethyl ketone (External discount: parts by mass) 80

Basic formulation (2):
Blending amount (% by mass)
(D) Copolymer of methacrylic acid / methyl methacrylate / styrene (mass ratio 25/50/25) (weight average molecular weight 80000) 64
(E) 2,2-bis (4-methacryloxypentaethoxy)
Phenylpropane 33
(F) Benzophenone 2.8
(F) 4,4′-bis (diethylamino) benzophenone 0.1
(F) N-phenylglycine 0.1
(D) + (E) + (F) total amount 100
(Photochromic agent) Leuco Crystal Violet (External discount: parts by mass) 0.2
(Organic solvent for dilution) Methyl ethyl ketone (External discount: parts by mass) 60

Basic formulation (3):
Blending amount (% by mass)
(D) Methacrylic acid / benzyl methacrylate (mass ratio 20/80)
Copolymer (weight average molecular weight 60000) 64
(E) 2,2-bis (4-methacryloxydiethoxy)
Phenylpropane 23
(E) Trimethylolpropane triacrylate 10
(F) 2- (o-chlorophenyl) -4,5-diphenyl imidazole dimer 2.8
(F) Dimethylaminobenzophenone 0.1
(F) 7-diethylamino-4-methylcoumarin 0.1
(D) + (E) + (F) total amount 100
(Photochromic agent) Leuco Crystal Violet (External discount: parts by mass) 0.2
(Organic solvent for dilution) Methyl ethyl ketone (External discount: parts by mass) 60

In the above basic formulations (1) to (3), (A) a guanidine compound, (B) a heterocyclic compound, and (C) a surfactant are added at the mixing ratio shown in the following table, and the product of the present invention and the comparative product A photosensitive resin composition was prepared. The blending amounts of (A) guanidine compound, (B) heterocyclic compound and (C) surfactant in the table are (D) thermoplastic organic polymer, (E) photopolymerization having an ethylenically unsaturated group. It is based on 100 parts by mass of the total amount of the organic compound and (F) photopolymerization initiator.

In the table, in (C) surfactant compound,
The polyoxyethylene lauryl ether has an EO addition number of 20 and a weight average molecular weight of 1000;
The polyoxyethylene oleyl ether has an EO addition number of 15 and a weight average molecular weight of 900;
Polypropylene glycol distearate has a PO addition number of 20 and a weight average molecular weight of 1700;
The weight average molecular weight of the polyglycerol oleate is 700;
The polyoxyethylene sorbitan monolaurate has an EO addition number of 21 and a weight average molecular weight of 1300;
The polyoxyethylene sorbitan monooleate has an EO addition number of 21 and a weight average molecular weight of 1400;
The polyoxyethylene beef tallow alkylpropylamine has an EO addition number of 30 and a weight average molecular weight of 1600;
The polyoxyethylene monomethyl ether has an EO addition number of 22 and a weight average molecular weight of 1000;
The weight average molecular weight of the polyethylene glycol-polypropylene glycol block polymer is 2600;
The polyoxyethylene bisphenol ether has an EO addition number of 5 and a weight average molecular weight of 500;
The weight average molecular weight of polyethylene glycol polypropylene glycol allyl ether is 2000;
The weight average molecular weight of the polymeric carboxylic acid is 5000;

<Creation of photosensitive film>
The obtained solution of the photosensitive resin composition of the present invention and the comparative product was placed on a polyethylene terephthalate film, applied uniformly using an applicator, and dried at 95 ° C. for 5 minutes to obtain a resist film having a thickness of 40 μm. . Next, a polyethylene film was laminated as a protective layer on the surface of the resist film on which the polyethylene terephthalate film was not laminated to obtain a photosensitive film.

<Creation of evaluation board>
Using a laminator on a copper clad laminate for printed circuit boards that was cleaned while peeling off the polyethylene film of the photosensitive film obtained as described above, a roll temperature of 105 ° C., a roll pressure of 0.35 Mpa, and a laminating speed of 1.5 m / min. The board | substrate for evaluation was obtained by laminating | stacking on these conditions.

<Exposure>
A mask aligner (manufactured by Union Optical Co., Ltd., EMA400) was used on the polyethylene terephthalate film of the evaluation substrate, and exposure was performed with an exposure amount of 23 steps from a Stoffer 41-step tablet.

<Development>
After peeling off the polyethylene terephthalate of the exposed evaluation substrate, a 1% by weight sodium carbonate aqueous solution is sprayed at a liquid temperature of 30 ° C. and a spray pressure of 0.1 MPa using an alkali developer (manufactured by Fuji Kiko Co., Ltd., circulation type). The unexposed portion of the resist film was dissolved and removed. At this time, the time required for the unexposed portion of the resist film to completely dissolve was defined as the set development time.

<Adhesion test>
A negative having a pattern with a line width / space width of 4/400 to 40/400 (unit: μm) is placed on the evaluation substrate polyethylene terephthalate film, exposed, and the polyethylene terephthalate film is peeled off. Development using sodium carbonate aqueous solution for development time twice as long as the set development time, washing with water, and the minimum mask width where the cured resist line is normally formed is the adhesion value and the evaluation criteria shown below It was evaluated with. The smaller the value, the better the adhesion.
[Adhesion / Visual]
A: Less than 10 μm B: 10 μm or more and less than 14 μm Δ: 15 μm or more and less than 20 μm x: 20 μm or more

<Discoloration prevention test>
A 41-step tablet made by Stöfer is placed on the evaluation substrate polyethylene terephthalate film, the set exposure is exposed, the polyethylene terephthalate film is peeled off, and then developed with a 1% by weight sodium carbonate aqueous solution for a set development time. , Washed with water. The obtained substrate was held at a temperature of 50 ° C. and a humidity of 95% RH for 48 hours, then immersed in a 3% by weight aqueous sodium hydroxide solution 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]
◎: Less than 10% ○: 10% or more and less than 30% Δ: 30% or more and less than 50% ×: 50% or more

<Aggregate generation prevention test>
Ten unexposed substrates for evaluation cut to an area of 0.1 m ² (10 cm × 10 cm) were prepared, and after polyethylene terephthalate was peeled off, a 1% by weight sodium carbonate aqueous solution (developer) using an alkali developer ) Was sprayed at a liquid temperature of 30 ° C. and a spray pressure of 0.1 MPa to dissolve and remove the resist film, and the same operation was repeated 10 times. Thereafter, the developer was circulated for 1 hour. Thereafter, the mixture was allowed to stand for 24 hours, and the presence or absence of aggregates in the developer was observed.
A: No occurrence of aggregates ○: Floating traces of aggregates are observed in the developer. Δ: Aggregates partially float in the developer. ×: Aggregates float throughout the developer. ing

Claims (8)

(A) Guanidine compound (except dicyandiamides, inorganic acid salts of guanidine, and guanidines having a tertiary amine structure); (B) one or two selected from the group consisting of triazoles, tetrazoles and imidazoles (C) a surfactant; (D) a thermoplastic organic polymer; (E) a photopolymerizable compound having an ethylenically unsaturated group; and (F) a photopolymerization initiator. The photosensitive resin composition characterized by the above-mentioned. (D) Thermoplastic organic polymer; (E) The photopolymerizable compound having an ethylenically unsaturated group and (F) The amount of (A) guanidine compound is 0.0005 with respect to 100 parts by mass of the total amount of the photopolymerization initiator. Is within the range of 1 to 1 part by mass, the blending amount of (B) the heterocyclic compound is within the range of 0.0005 to 1 part by mass, and (C) the blending amount of the surfactant is 0.00001 to 0. The photosensitive resin composition of Claim 1 which exists in the range of 0.1 mass part. In addition, thermal polymerization inhibitors, plasticizers, dyes, antioxidants, surface tension modifiers, stabilizers, chain transfer agents, flame retardants, release accelerators, fragrances, imaging agents, thermal crosslinking agents, and developability / plating properties The photosensitive resin composition of Claim 1 or 2 containing the 1 type (s) or 2 or more types of additive selected from the group which consists of an improver. (D) a thermoplastic organic polymer; (E) a photopolymerizable compound having an ethylenically unsaturated group, and (F) a compounding amount of the additive is 0.01 to 20 with respect to a total amount of 100 parts by mass of the photopolymerization initiator. The photosensitive resin composition of Claim 3 which exists in the range of a mass part. Furthermore, it contains one or more organic solvents for dilution selected from the group consisting of alcohols, ketones, acetate esters, glycol ethers, glycol ether esters and petroleum solvents. 5. The photosensitive resin composition according to any one of 4 above. The blending amount of the organic solvent for dilution is (A) guanidine compound; (B) heterocyclic compound; (C) surfactant; (D) thermoplastic organic polymer; (E) photopolymerizable having an ethylenically unsaturated group. 6. The photosensitive resin composition according to claim 5, which is in the range of 5 to 50% by mass of the total amount of the compound, (F) photopolymerization initiator, additive and organic solvent for dilution. A photoresist ink comprising the photosensitive resin composition according to any one of claims 1 to 6. A photosensitive resin composition film obtained by applying the photosensitive resin composition according to any one of claims 1 to 6 on a film-like support and drying the film is provided on the film-like support. A photosensitive film characterized by comprising: