WO1993006529A1

WO1993006529A1 - Photosensitive resin composition

Info

Publication number: WO1993006529A1
Application number: PCT/JP1992/001166
Authority: WO
Inventors: Shigeru Hagio; Kazuhiko Kohda; Shinichi Uehara
Original assignee: San Nopco Limited; Ibiden Co., Ltd.
Priority date: 1991-09-14
Filing date: 1992-09-11
Publication date: 1993-04-01
Also published as: DE4293400T1

Abstract

A photosensitive resin composition which is developed by an aqueous alkali solution and has excellent sensitivity, resolution and resistance against electroless plating solution, comprising a graft polymer having, as branch polymers, a polymer of a monomer that has hydrophilic groups, and a binder polymer which is soluble or swellable in an aqueous alkali solution and is capable of forming a film. The composition comprises a graft polymer which has, as branch polymers, a polymer of a monomer that has hydrophilic groups, a binder polymer which is soluble or swellable in an aqueous alkali solution, an ethylenically unsaturated compound, and a photopolymerization initiator.

Description

Specification

Photosensitive resin composition

Technical field

The present invention relates to a photosensitive resin composition. In particular, the present invention relates to a photosensitive resin composition suitable as a register used in manufacturing a printed wiring board.

Background art

2. Description of the Related Art A photosensitive resin composition has been widely used as a register, such as an electroless plating register or a solder register, used in the production of a printed wiring board. This resist is exposed to an electroless copper plating solution at about PH12, 70 for a long time, for example, so that it can withstand highly concentrated aqueous alkali solutions. Although liquid properties are required, conventional registries are only resistant to low concentration or low temperature alkaline. Also, in recent years, circuits have become finer as the density of printed wiring boards has increased, and registers have been required to have excellent sensitivity, resolution, and developability. However, conventional registries do not always satisfy all requirements. On the other hand, an organic solvent is conventionally used as a developer, but the organic solvent poses a risk of air pollution or ignition.

As a conventional photosensitive resin composition for a resist, for example, a carboxyl group and a vinyl group in the same molecule described in JP-A-2-24764 are used. Developable polymers or oligomers, biphenyl-type epoxy compounds, photopolymerizable monomers or oligomers, and photopolymerization initiation A photosensitive resin composition comprising an agent or a sensitizer is known. JP-A-64-36545 discloses a photosensitive resin composition comprising a polymerizable unsaturated oligomer having a carboxy group and a vinyl group, an epoxy compound, and a photopolymerization initiator. Japanese Patent Application Laid-Open No. 1-105240 describes a photosensitive resin composition comprising urethane (meth) acrylate, a linear polymer, and a polymerization initiator.

The photosensitive resin composition described in Japanese Patent Application Laid-Open No. 2-247564 has a pH of 8,70. Although resistant to C plating, it cannot be used with PHI 2, 70 ° C plating. The photosensitive resin composition described in JP-A-64-36545 can sufficiently withstand the electroless copper plating solution at PH12 and PH70, but has a poor resolution of 170 μm and a fine resolution. Cannot be used for circuit processing applications. The photosensitive resin composition described in JP-A No. 11052/40 is resistant to an electroless copper plating solution of pH 12 and 70 and has a good resolution of 70 μηι, There is a drawback that the developer is an organic solvent.

The present invention provides a photosensitive resin composition having developability with an aqueous alkaline solution and having excellent sensitivity, resolution, and electroless plating resistance.

Disclosure of the invention

The above-mentioned problems include (A) a polymer having a carboxyl group, a polymer having an anhydrous carboxyl group, polyvinylphenols, a saponified polyvinyl acetate polymer, a novolak resin, and a hydroxyl resin. A (meth) acrylate copolymer having a group [hereinafter, a (meth) acrylate may be a methacrylate Represents an error rate. A binder-polymer capable of forming a film which is soluble or swellable in at least one kind of aqueous alkaline solution selected from the group consisting of:

(B) an acrylic compound having at least two ethylenically unsaturated bonds and capable of being polymerized

(C) Photopolymerization initiator

and,

(D) (i) A homopolymer of one or more monomers selected from the group consisting of alkyl (meth) acrylate, acrylonitrile, and styrene Alternatively, the copolymer is used as a trunk polymer, and a hydroxy-containing (meta) acrylate, an amino group or an alkylamino group-containing (meta) acrylate is used. Relates, carboxyl group-containing (meta) acrylates, bulesters, bulue

— Tells, N — Vinylpyrrolidone, vinylpyridines, and at least one selected from the group consisting of monomers represented by the following general formula (I): Also, a graft polymer using a homopolymer or a copolymer of a monomer as a branch polymer,

R ¹

I

C H 2 = C (I)

I

_{0 = C - NH - CH 2} - 0 - R 2

(Where R ¹ is hydrogen or an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, and R ² is hydrogen or an alkyl having 1 to 4 carbon atoms. Or alkyl having a hydroxyl group or a hydroxy group having 1 to 4 carbon atoms. Represents an acyl group. A) a thermosetting compound comprising:

(ii) a mixture of (a) the above-mentioned graphite polymer and (b) a block-isolated compound having at least two substituents represented by the following general formula (II): A further thermosetting composition,

-NHC 0 R ³ (Π)

(However, R ³ represents an alkoxy group, an aryloxy group, an alkyl aryloxy group, an alkylidene aminooxy group, an amino group, a lactam group or ] 8 — Represents a dicarbylmethyl group.) Or

(iii) (a) an epoxy compound having at least two epoxy groups and (b) a boron trifluoride amine complex, dicyandiamide, or an organic acid hydridide.ヅ, diaminomaleonritols, melamines, amides represented by the following general formula (ΠΙ), or amides and organic acids or phenols Thermosetting composition comprising at least one epoxy hardening agent selected from salts with knols and ketimine

One +

R ⁴ -C-N-N-CH ₂ CH-R ⁷ (ΠΙ)

0 R ⁵ R ⁶ 0 H

(However, R ⁴ and R ⁷ are aliphatic hydrocarbons having 1 to 6 carbon atoms or aliphatic hydrocarbons having 1 to 6 carbon atoms having an ether bond, and R ⁵ and R ⁶ are carbon atoms. Represents an aliphatic hydrocarbon of the formulas 1 to 6.

This can be achieved by a photosensitive resin composition comprising such a composition. In the photosensitive resin composition of the present invention, a binder polymer capable of forming a film which is soluble or swellable in an aqueous solution of the component (A) is a curing of the photosensitive resin composition. It serves as a binder for the product and gives the photosensitive resin composition developability to an aqueous alkali solution. Examples of such a polymer include a polymer having a carboxyl group, a polymer having an anhydrous carboxyl group, polyvinylphenols, and saponified acetic acid. Examples include a vinyl polymer, a novola, a sock resin, and a (meth) acrylate copolymer having a hydroxyl group.

Examples of the polymer having a carboxyl group include monomers having a carboxyl group and (meth) acrylic acid esters, styrenes, and acrylic polymers. Examples include copolymers with vinyl monomers such as nitriles. The weight average molecular weight is preferably from 500 to 200,000.

Specific examples of the monomer having a carboxyl group include (meth) acrylic acid, itaconic acid, crotonic acid, sorbic acid, fumaric acid, and promal acid. Piolic acid, maleic acid, cinnamic acid, and the like.

Specific examples of (meth) acrylyl esters include methyl (meth) acrylate, ethyl (meta) acrylate, and isobutyl (meta) acrylate. Alkyl (meta) acrylate, alkyl (meta) acrylate, pentyl (meta) acrylate having 1 to 4 carbon atoms in the alkyl group, such as relay, t-butyl (meta) acrylate, etc. Octyl (meta) acrylate, heptyl (meta) acrylate, octyl (meta) acrylate, isooctyl (meta) ) Acrylate, 2-ethylhexyl (meta) acrylate, nonyl (meta) acrylate, decyl (meta) acrylate, isodecyl (meth) T) acrylate, undecyl (meth) acrylate, raurinore (meta) acrylate, myristyl (meta) acrylate, cetyl (meth) Meta-acrylate, stearyl (meta) acrylic, orail (meta) acrylic, cyclohexyl (meta) acrylic, Cyclopentyl (meta) acrylate, phenyl (meta) acrylate, benzil (meta) acrylate, naphthyl (meta) acrylate Alkyl or aryl (meta) acrylic, such as rate, Methoxylate (meta) acrylate, methoxydiethylene glycol (meta) acrylate, methoxyethylene glycol (meta) acrylate Relate, meth- oxylate recall (meta) acrylate, meth- oxypropyl recall (meta) acrylate, ethoxychetyl (Meta) acrylate, butyl acrylate (meta) acrylate, phenoxyshetyl (meta) acrylate, phenoxydiethylene glycol (meta) Meta-relate, phenoxy-jetoxy (meta) -relate, phenoxylate-radiation re-co-sol (meta) -relate, phenoxy-relate Hexaethylene long-call Meta-relate, methoxypolyethylene glycol (meta) acrylate, ethoxypolyethylene glycol (meta) acrylate , Nonylphenolic ethylene glycol (meta) acrylate, nonylphenolic propylene glycol Polyether diol mono-e.g. (Meta) acrylate, etc.-Tenoré (meta) acrylate, 2-Chlorocinole (meta) acrylate, 2-Cloth Isopropyl (meta) acrylate, 2-bromoethyl (meta) acrylate, 2,3-dibromopropyl (meta) acrylate, tribromo Phenyl (meta) acrylate, trifluoroethyl (meta) acrylate, tetrafluoropropyl (meta) acrylate, octa Fluoropentyl (meta) acrylate, heptadecafluorodecyl (meta) acrylate, and rogenchialkyl (meta) acrylate, 2 — Hidlo Ki Shechill

(Meta) acrylate, 2-hydroxypropyl (meta) acrylate, 3-hydroxypropyl (meta) acrylate, 4-hydroxy Xyl butyl (meta) acrylate, 5—hydroxypentyl (meta) acrylate, 6—hydroxy hexyl (meta) acrylate, 2 — Hydroxy 3 — Fenoxypropyl (meta) acrylate, 3 — Chloro 2 — Hydroxypropyl (meta) acrylate, 3 — Black mouth 2 — Hydroxybutyl (meta) acrylate, etc. Meta) acrylate, 2-cyanoethyl acrylate, tetrahydrol Ruffled (meta) clear rate.

Specific examples of styrenes include styrene, α-methylstyrene, ρ-isopropenylstyrene, vinyltoluene, and the like. Specific examples of acrylonitriles include acrylonitrile and α-methylacrylonitrile.

In addition to the above vinyl monomers, vinyl formate, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl laurate, vinyl benzoate, vinyl benzenesulfonate, vinyl isopropyl ether, vinyl pyrrolidone, Use chloride bur etc.

Examples of the polymer having an anhydrous carboxyl group include a monomer having an anhydrous hydroxyl group and a (meth) acrylic acid ester, styrene, acrylonitrile, and the like. And a copolymer of a vinyl monomer and. The weight-average molecular weight is preferably from 2000 to 1.00;

Specific examples of the monomer having a carboxyl anhydride group include 2,3—dichloromaleic anhydride, 2—cyclomouth maleic anhydride, citrate anhydride, and citrate anhydride. Dodecenyl succinic acid, anhydrous nonenyl succinic acid, bromomaleic anhydride, maleic anhydride and the like.

Polyvinylphenols include homopolymers of vinylphenol, or vinylphenol and (meth) acrylic acid esters, styrenes, and Copolymers with vinyl monomers such as acrylonitriles, monomers having a carboxyl group, and monomers having an anhydrous carboxyl group are exemplified. Specifically, Maruzen Resin II, Maruzen Resin MB, Resin CMM, Resin CHM, Resin MAA, Resin MS-2, Resin MS-3 (Maruzen Petrochemical Co., Ltd.) And so on. The weight average molecular weight of the polyvinyl phenols is preferably from 2000 to 500,000.

Examples of the saponified vinyl acetate polymer include a completely saponified vinyl acetate polymer, a partially saponified vinyl acetate polymer having a saponification degree of 88 to 99 mol%, and the like. The weight average molecular weight of the saponified vinyl acetate polymer is preferably from 500 to 500,000.

Examples of the novolac resin include a phenol novolac resin and a cresol novolac resin which are swollen or soluble in an aqueous alkali solution. The weight average molecular weight of the nopolak resin is preferably from 500 to 500.

As the (meth) acrylate copolymer having a hydroxy group, a mono (meth) acrylate having a hydroxy group and a (meth) acrylate copolymer having a hydroxy group can be used. (Meta) Acrylic acid esters, styrenes, acrylonitriles, monomers having a carboxyl group, monomers having a carboxyl anhydride group And a copolymer with a vinyl monomer. The weight average molecular weight of the copolymer is 50,000 to: L 0000 is preferred.

As specific examples of the mono (meth) acrylate of the hydroxy compound, those mentioned in the specific examples of the (meth) acrylic ester described above are used. be able to .

Preferred as the non-polar polymer are polyvinylphenols and a (meth) acrylate copolymer having a hydroxyl group. In addition, two or more binder polymers can be used in combination. The content of the binder polymer in the photosensitive resin composition is preferably from 20 to 80% by weight. No. When the amount is less than 20% by weight, the developing property is deteriorated, and when the amount exceeds 80% by weight, the electroless plating resistance is deteriorated.

Next, an acrylic compound having at least two ethylenically unsaturated bonds as the component (B) constituting the photosensitive resin composition of the present invention and capable of being polymerized has an activity of It has the property of being hardened by energies, and gives the composition of the present invention excellent sensitivity to active energy rays. For this reason, the photosensitive resin composition of the present invention exhibits excellent resolution. As the acrylic compound, a known monomer which is preferably cured by irradiation with an active energy ray having a boiling point of 100 or more at atmospheric pressure, can be used.

Specific examples of such a monomer include, for example, 1) Ethylene glycol (meta) acrylate, propane diol (meta) acrylate Butanediol di (meta) acrylate, pentanedioldi (meta) acrylate, hexanedioldi (meta) acrylate, neopentyl glycol (meta) ) Clearate, hydroxypivalate neopentyl glycolate (meta) clearate, polyethylene glycolate (meta) clearate, vol. Principal recollection (meta) cryate, porphyra transcript Refrigerant collage (meta) acrylate, trimethyl propane Re (meta) Multi-valued alcohol, such as penta-erythritol, penta-erythritol, pentaerythritol, and terephthalate (meta) acrylic (Meth) acrylic acid esters; 2) Trade name ARONIX M-1 100, Aronix M — 120 0, Aronix M — 6

100, Aronix M—6 200, Aronix M—6

250, Aronix M—6 300, Aronix M—6

4 0 0, Aronix M — 7 1 0 0, Aronix M — 8

0 3 0, Aronix M — 8 0 6 0, Aronix M — 8

100 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), trade name: Calad DPCA—120, Charad DPCA—20, Power Chard DPCA—30, Car Lad DPCA — 60, Charad R — 526, Charad R — 629, Charad R-644 (all manufactured by Nippon Kayaku Co., Ltd.) ) And other poly (meth) acrylates: 3) 1,6—Hexane diol diglycidyl ether di (meth) acrylate, trimethylolpropane Triglycidyl ether tri (meta) acrylate, glycerin triglycidyl ether tri (meta) acrylate, isocyanate Triglycidyl ether (meta) acrylate, novolac epoxy resin (meta) acrylic acid (Meta) of compounds having two or more epoxy groups in one molecule such as (meth) acrylic acid ester of ester and bisphenol A type epoxy resin Acrylates; 4) isophorone diiso cyanate, diphenyl methane diisocyanate, trimethyl hexyl methyl isocyanate, tri A reaction product of a range isocyanate, a hexamethylene range isocyanate and a hydroxyl group-containing (methyl) acrylate, and a mixture of these polystyrenes. The terminal is made up of an isolanet and a polyol. A reaction product of a polymer and a (meta) acrylate containing a hydroxy group is exemplified. For example, the trade names Sumijur N (a biuret derivative of hexamethylene diisocyanate), Sumijur L (the trimethyl tertiary mouth of the trimethylisocyanate) (Modified with propanol) [The above is a product of Sumitomo Bayer Urethane Co., Ltd.], etc., and a hydroxy group-containing (meta) acrylate is added to a polyisocyanate compound known as such. The used reactants can be used. Here, the hydroxy group-containing (meta) crelet includes a branch polymer of a graph polymer (D-i) described later. .

In addition to the above-mentioned acrylic compounds, the monomers that constitute the (D-i) graphite polymer can also be used. Furthermore, mixtures of the above-mentioned acrylic compounds can also be used.

The content of the acrylic compound in the photosensitive resin composition is preferably from 20 to 80% by weight. When the content is less than 20% by weight, the sensitivity is lowered and the resolution is deteriorated. When the content is more than 80% by weight, the adhesion is deteriorated.

Specific examples of the photopolymerization initiator of the component (C) in the photosensitive resin composition of the present invention include: 11- (41-isopropylpropyl) 12-hydroxy2-medium Chilpro non-one

1-Hydroxycyclohexylphenyl ketone, 2,2-Jetoxysethenon, 2,2—Dimethoxyxy 2—Phenylacetophenone, 2—Hydroxyxy 2-Methyl-one propane-one-one, 2-methylone-one (4-one

(Methylthio) phenyl) 1 2 — morpho rhino propane 1 , 4-Fenoxy Chloroacetophenone, 4- (2-Hydroxy Toxi) 1-Fhenyl (2 -Hydroxy 2 -Pup pill) ) Ketone, p-t-Butyldichloroacetophenone, P-t-butylinchlorotriacetone, p-Dimethylaminoacetopheno Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether And benzoins such as benzyldimethyl ketal; benzophenone, benzophenone methyl ether, benzoyl benzoic acid, methyl benzoyl benzoate, hydroxy. Siben Phenonone, 41-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 3,3'-bis (N, N-diethylamino) benzopheno , 4,4'-bis (N, N-Jetylamino) Benzofuenonon, 4 ', 4 "-Jet-Louisofta mouth phenon, 3,3', 4,4'1- Benzofu, such as tetra (t-butyl peroxycarbonyl) benzophenone, 41-benzoyl 4'-methinoresifeninoresulfide, acriluhibenzofufenon, etc. Nonones: thioxanthone, 2—methylthioxanthone, isopropylthioxanthone, 2,4—dimethinolethioxanthone, 2,4—getinolexanthonthone, 2 , 4 — diisopropirchioxanthon Xanthones such as chloroxanthontone and 2,4-dichlorothioxanthon; diketones such as diacetyl and benzyl; 2—ethylethyl Trakinon, 2—t Thizolean trakinonone, 2, 3 — diphenyl anthraquinone, 1, 2 — benzanthrakinonone, octamethylan anthraquinone, camphorquino Quinones such as benzophenone, dibenzosuberone, 9,10-phenanthrene quinone, and the like. The content of the photopolymerization initiator in the photosensitive resin composition is 0.01 to 0.1%. 30% by weight is preferred.

The graphitic polymer (D-i), which is one of the components (D) of the photosensitive resin composition of the present invention, has a relatively rigid structure which is suitable as a structural material. The monomer constituting the trunk polymer of the graphite polymer in the present invention, comprising the polymer and the hydrophilic branched polymer exhibiting excellent adhesion to the support, is Such as methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, etc. The alkyl (meta) acrylate, acrylonitrile, and styrene having 1 to 4 carbon atoms in the phenol group.

In addition, the stem polymer is derived from only the above-mentioned monomer. For example, 2-merethylhexyl (meth) acrylate, glycidyl (meta) ac Polymers using a copolymer such as lilate or vinyl acetate in the range of 0 to about 50% by weight may be used.

Specific examples of the monomer constituting the branch polymer of the graphite polymer in the present invention include a hydroxy group-containing (meta). Examples of acrylates are 2-hydroxyethyl (meta) acrylate, 2-hydroxypropyl (meta) acrylate, and 3-chlorolate. -2-Hydroxybutyl (meta) acrylate, 4-Hydroxybutyl (meta) acrylate, 3-Hydroxybutyl (meta) acrylate Rate, 5—Hydroxy Pencil (meta) acrylate, 6—Hydroxyhexyl (meta) acrylate, or 1, 4 -Monoesters of cyclohexane dimethanol and (meth) acrylic acid, etc., trade name ARONIX M5700 [manufactured by Toa Gosei Chemical Industry Co., Ltd. ], TONEM 100 [Power product creator, manufactured by Union Carbide Co., Ltd.] Ester H0-mpp [manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.], Light Ester M-60 OA [2—Hydroxy 3—Phenoxypropiryl Cleitol And divalent alcohols, for example, 1,10-decanediol, neopentylglycol, bis (2-hydrogen). (Meth) acrylic acid, such as addition reaction product of telephthalate, bisphenol A and ethylene oxide or propylene oxide Monoesters with acids can be used.

Examples of the (meth) acrylate containing an amino group or an alkylamino group include (meth) acrylamide, Ν, Ν-dimethinoleaminoethyl (meta). ) Acrynoreamid, Ν, Ν — dimethyl (meta) acrylamide, Ν, チル — dimethylaminop pill (meta) acrylamide, Ν, Ν — Di-t-butyl Aminoethyl (meta) acrylamide. As the (meth) acrylate containing a carboxy group, (meta)

) Acrylic acid, fumaric acid, itaconic acid or Toagosei Chemical Industry Co., Ltd. product name Aronix M-5400, Aronix M-5500 Some are known.

Examples of vinyl esters include vinyl formate, vinyl acetate, butyl butyrate, vinyl propionate, vinyl laurate, vinyl benzoate, vinyl benzenesulfonate, and the like.

Examples of vinyl ethers include vinyl isopropyl ether and vinyl isopropyl ether.

Examples of vinyl pyridines include 2-vinyl pyridine, 4-vinyl pyridine, 2-vinyl-6-methyl pyridine, 4-1 vinyl-1 meth-iso-le- pyridine, and 2-vinyl-5-ethyl pyridine. Examples include lysine and (4-pidinolinoethyl) pyridine.

Each of the above monomers has a hydrophilic property, and in particular, a homopolymer or a copolymer of these monomers is used as a branch polymer of a graphite polymer. It is effective at times. That is, the graphite polymer imparts strong adhesion when the composition of the present invention is adhered to a support such as glass, ceramics, or plastic. In addition, a random polymer of these monomers or a photosensitive resin composition using a block polymer cannot exhibit sufficient adhesion. — As the acrylamide derivatives represented by the general formula (I), N—methylol (meth) acrylamide, N—proboximetyl (meta) ac Lilamid, N — n — Butoxy cinnole (meta) acrizorea mid, / 3 — Hydroxy citine methyl ('meta) acrylamid, N — Ethoxymethyl (meth) acrylamide, N—Methoxymethyl (meth) acrylamide, α—Hydroxymethyl N—Methylol Lil Amid, α — Hydroxyl Ν Ν — Butoxyl Cryuramide, α — Hydroxyl Propyl Ν Ν — Proboxyxyl Chrylamide, α — Ethyl Ν — Methyl phenol clear amide, α — Propyl New - Ru methylotrophic Rua click Li Norea mi de of any hydrophilic a and mono- mers that having a thermally crosslinkable can be cited. These monomers have a hydrophilic property and a condensation cross-linking property, in which water or alcohol is eliminated by heating. Graphite polymers, in which the copolymer is a branched polymer, are generally crosslinked at a temperature of 100 ° C or higher to form a polymer network structure, and the electroless polymerized cured product is obtained. The present invention can further improve the fluidity and make the present invention more effective.

Among the hydrophilic monomers, preferred are a hydroxy group-containing (meth) acrylate and an acrylamide derivative represented by the general formula (I). The branched polymer is not only derived from the hydrophilic monomer as described above, but also includes various hydrophobic monomers that exert various other functions, such as 0 to 100. Up to about 25% by weight may be used as a component for copolymerization. A specific example of the hydrophobic monomer is the stem polymer described above. Monomers to be formed can be mentioned.

Since the graphite polymer used in the present invention has excellent adhesiveness and electroless plating resistance, a pattern formed using the composition of the present invention has excellent resolution. .

Examples of the method for producing a graphite polymer include a chain transfer method, an oxidized graph polymerization method, an ion-graft polymerization method, a radiation-graft polymerization method, and a macromolecular method. The macromer method is preferred in terms of design.

The weight average molecular weight of the trunk polymer is preferably from 500 to 500,000, and the weight average molecular weight of the branch polymer is preferably from 500 to 100,000. In addition, the molar ratio of the stem polymer to the branch polymer is preferably stem polymer branch polymer = 95Z5 to 50/50. The weight average molecular weight of the graphite polymer is preferably from 500 to 500,000. The content of the graphite polymer in the photosensitive resin composition is preferably from 10 to 60% by weight. If the content is less than 10% by weight, the adhesion to the substrate surface is reduced, and the resolution and the electroless plating resistance are deteriorated. If it exceeds 60% by weight, the imageability deteriorates.

The compound having at least two substituents represented by the general formula (Π) in (D-ii), which is one of the components (D) of the photosensitive resin composition of the present invention, is a resin composition of the present invention. Heating the active energy after irradiation with active energy generates an isocyanate group, which reacts with the carboxy group or Z in the polymer and the anhydrous lipoxy group to form an amide bond or a nitro or imine. Bond to improve the adhesion of the registry and the resistance to electroless plating. Improve . Specific examples of such compounds include tolene isocyanate, xylene isocyanate, hexamethylene diisocyanate, and diphenylmethyl isocyanate. Tungsten isolation, 1, 5 — naphthalene isolation, isophorone isolation, triphenylmethanthry A multifunctional isocyanate such as a reaction product of a polypropylene glycol having a netol or isocyanate group at the end thereof with a toluenediisocyanate; Alcohols such as methanol, ethanol, etc., phenols such as phenol, methylphenol, methylethyl ketone, dimethyl alcohol, etc. Oxims, such as oxosim, getylamine, triglyceride Examples thereof include compounds having a 13-dicarbonylmethyl group, such as ethylamine, aniline, and other amides, cabrolactam, ethyl malonate, and ethyl acetate ethyl acetate. In addition, Desmodur AP Stable, Desmodur CT Stable [manufactured by Sumitomo Bayer Urethane Co., Ltd.], NO-KNOCK D—500 [Dainippon Ink Chemical Industry Manufactured by Nippon Polyurethane Industrial Co., Ltd.], Adiron VXL 8 1 (made by Hext).

The content of the pro-isocarbonate compound having at least two substituents represented by the general formula (II) in the photosensitive resin composition is preferably 5 to 50% by weight. Yes. If the amount is less than 5% by weight, sufficient adhesion and electroless plating resistance cannot be obtained, and if the amount exceeds 50% by weight, developability deteriorates. Further, the epoxy compound having at least two epoxy groups in (D-iii-la) as the component (D) of the photosensitive resin composition of the present invention is a component of the present invention. By heating the object after irradiating it with an active energy ray, a cross-linking reaction is caused to form a strong bond, thereby improving the adhesiveness of the resist and the resistance to electroless plating. Therefore, the pattern formed using the photosensitive resin composition of the present invention has excellent resolution. Specific examples of such epoxy compounds include: 1) DER3311J, DER337J, DER6661J, DER6664J, DER6667J Chemical Co., Ltd.], Epicron 800 [Dai Nippon Ink Chemical Industry Co., Ltd.], Epicourt 1001, Epicolate 1002, Co. Picocoat 103, epic 104, epic 107, epic 109, epic 105, cop Picote 801, epic 807, epic 808, epic 815, epic 816, epic 8 19, Epikoto 827, Epikoto 828, Epikoto 834, Epikoto 871 [or more, manufactured by Yuka Chemical Epoxy Co., Ltd.] Bisphenol A type epoxy resin; 2) DER431, DER438, DER439 (all manufactured by Dow Chemical Company), Rudite EPN 1 1 3 8 (Chipagagi Co., Ltd.), Epicoat 152, Epico1 154, Epico1 172 [above, Yuka Shell Epoxy Co., Ltd.] 3) Shirakawa-610, Shirakawa-610, Shirakawa-620, ERL 225 ^^ ERL 4 0 9 0, ERL 4 6 1 7, ERL 5 4 1 1 (all manufactured by Union Carbide Co., Ltd.), ARALD CY-175 ARANO RED CY — 176, ARA DY CY — 179 ARA NO RED CY — 18 2, Araldite C Υ-18 4 Araldite CY — 1992 (all manufactured by Ciba-GaiGi Co., Ltd.) Chisso Knox 0900, Chisonox 091, Gas Knox 092, Gas Knock 310, Gas Knox 313 [More than Chisso Corporation], Ali Cyclic dipoxy adipate, alicyclic diepoxy acetal, alicyclic liquid eoxypoxy, ruby oxylate, bursekiro hexenixide Alicyclic epoxy resins such as 4) 1, 6-hexanediol diglycidyl ether, 2, 2—dibromomoneopentyl Glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, trimethylolpronon diglycidyl ether, neopentyl glycol Callig ligidyl ether, propylene glycol digidyl ether, Polyethylene glycol digidyl ether, Polypropylene glycol digidyl ether Aliphatic polyhydric alcohols, such as ethers, hydrogenated bisphenols, etc., polyhydric alcohols, etc .: 5) Bisphenols A Lenoxide adduct diglycidyl ether, bisphenol F Alkylenoxide adduct diglycidyl ether, bisphenol S Al Les emission O sulfoxide adduct jig Li Shi Gilles ether of any aromatic polycarboxylic alcohol derivative polyhydric grayed Li Shi Jill ether: 6) Jig Li Shi Jil P-oxybenzoic acid, glycidyl dimer acid ester, diglycidyl tetrahydrophthalate, diglycidyl phthalate, hexyl hydrophthalic acid diglycidyl ester Glycidyl ester; 7) N, N-diglycidylalanine, tetraglycidyldiaminodiphenenyl methane, triglycidyl p—aminofenolate Glycidylamine; 8) Heterocyclic epoxy resin such as triglycidyl isocyanurate, hydantoline type epoxy resin; 9) 3—Pentadecylphenylglycidyl ether, n-butylphenyl Enol glycidyl ether, glycidyl ester of tert-monocarboxylic acid, α-pinene oxide, acrylglycidyl ether, o Tylene oxide, cyclohexane vinyl monooxide, styrene oxide, phenylglycidyl ether, butylglycidyl ether, glycidinole (meta) acrylate, epichlorohydrin And monoepoxy compounds.

The content of the epoxy compound having at least two epoxy groups in the photosensitive resin composition is preferably 5 to 50% by weight. If it is less than 50% by weight, sufficient adhesion and electroless plating resistance cannot be obtained, and if it exceeds 50% by weight, the developability deteriorates.

The epoxy curing agent (D-iii-i b) in the present invention reacts with the epoxy compound by heating the photosensitive resin composition of the present invention after irradiation with active energy, and initiates a crosslinking reaction. Let Examples of such an epoxy curing agent include boron trifluoride n-hexylamine complex and trifluoroboron monoethyl. Amine complex, boron trifluoride benzylamine complex, boron trifluoride getylamine complex, trifluoride, boron sulfide piperidine complex, trifluoride Boron trifluoride amine complexes such as borophosphoric triethylamine complex, trifluoride, sophiboron aniline complex, etc .; disocyanamide; konoxy acid Hydrazide, adipic acid hydrazide, isophthalic acid hydrazide, P-oxybenzoic acid hydrazide, salicylic acid Organic acids such as hydrazide, phenylamine hydrid, hydronic acid hydridide, etc .; N—Penzinole Aminomale , Amino N-Isobutino Reamino, Amino N-Benzylidenamiminorionuriru, Amino N — Butylide Naminole Reno Retorn, Amino n — Propilide Naminole Onion Reil, Jiaminomare Nion Rare diaminomale nitriles: melamine, diaramylamine, and other melamines; represented by the following general formula (（) Min imid;

R ⁴ -C-N-N-CH z CH-R ⁷ (ΙΠ)

II / \ I

0 R ⁵ R ⁶ 0 H

(However, R ⁴ and R ⁷ are aliphatic hydrocarbons having 1 to 6 carbon atoms or aliphatic hydrocarbons having 1 to 6 carbon atoms having an ether bond, and R ⁵ and R ⁶ are Represents an aliphatic hydrocarbon having 1 to 6 carbon atoms.)

Ethylenediamine, hexamethylenediamine, salt of pyridin with dicarboxylic acid having 3 to 8 carbon atoms, 2,4,4 trimethyltinー 2, 4, 7 — Trihydroxyfurano X and N, N ' -Dimethizole 1,3—Salts with propanediamine, salts of phenylenediamine with phenylphosphonic acid, salts of aniline with phenylphosphonic acid, Salts of P, P'-diaminodiphenylmethane and phenylphosphonic acid, salts of benzylamine and phenylphosphonic acid, phenylenediamine and phenylphosphonic acid Organic acids or phenols, such as salts with phosphoric acid, salts of aniline with phenylphosphoric acid, salts of benzylamine and phenylphosphoric acid And a salt thereof; produced by reacting a polyamine such as diethyltriamine, triethylenetetramine and a ketone such as methylethylketone or isobutylmethylketone. Ketimin to be used.

The content of the epoxy curing agent in the photosensitive resin is preferably 0.1 to 10% by weight. If the amount is less than 0.1% by weight, the curing of the epoxy compound does not proceed sufficiently, and if it exceeds 10% by weight, the developability deteriorates.

As described above, the photosensitive resin composition of the present invention essentially contains the components (A), (B), (C) and (D), and furthermore, the photosensitive resin composition of the present invention If necessary, a condensation-crosslinking catalyst, a thermal polymerization inhibitor, a filler, a colorant such as a dye or pigment, a heat stabilizer, an adhesion promoter, a plasticizer, a pigment such as silica or talc, A leveling agent or the like which provides workability may be added in the range of 0.1 to 50% by weight.

The photosensitive resin composition of the present invention can be dissolved in a solvent and used as a liquid registry. When used as a liquid registry, dipping method, spray method, flow coating method, screen method A photosensitive layer having a thickness of 10 to 15 μm can be formed by directly applying the composition on a substrate by a method such as lean printing. The solvent used at this time may be any solvent that dissolves the photosensitive resin composition, for example, ketones such as acetone, methylethylketone, methylisobutylketone, and the like. Glycol ethers such as methylcellosolve, ethyl cellulose solvent, propylene glycol methyl ether, propylene glycol ethyl ether, methyl ethyl solvent solve acetate, ethyl acetate Glycol esters such as rosacea acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, methanol, ethanol, etc. Alcohols such as alcohol, dichloromethane, 1,1,1,1-trichloroethane and other chlorine-containing aliphatic solvents, toluene, There are aromatic hydrocarbon solvents such as styrene. These solvents are used alone or as a mixture.

Further, the photosensitive resin composition of the present invention can be used as a dry film resist. Examples of supporting films when used as a dry-soles-registry are, for example, polyethylene terephthalate, polypropylene, and polypropylene. Films consisting of polyethylene etc. are used, and particularly preferred are polyethylene phthalates. The thickness of the film is preferably 5 to 100 μm. Also, one of these phenols may be used as a protective film for the photosensitive layer. As the solvent used for converting the photosensitive resin composition into a liquid when producing the dry film resist, those described above can be used. Liquid The photosensitive resin composition is uniformly coated on a supporting film, and the solvent is removed by heating or hot-air drying to form a photosensitive layer. The thickness of the photosensitive layer is preferably from 100 to 100 / m. Next, the dry film resist having the photosensitive layer formed on the support film is left as it is or a protective film is laminated on the photosensitive layer and rolled up. Will be saved.

Next, a method for using the photosensitive resin composition of the present invention will be described. 1) Applying the liquid resist on the substrate by the above-mentioned method, and removing the solvent by heating drying or hot air drying; or 2) Dry film The photosensitive layer of the photosensitive resin composition of the present invention is formed on a substrate by laminating a photosensitive layer on the substrate by a conventional laminating method. After that, the photosensitive layer is irradiated with active energy rays through a negative mask or a posimask. The active energy rays include, for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, tungsten lamps, etc. UV lasers, argon lasers, helium cadmium lasers, Krypton lasers, etc. are used.

Next, the unexposed portion of the photosensitive layer is removed by a method such as spraying, dipping, or brushing using a developer. Developers include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, carbonated lithium, hydrogencarbonate. Um, sodium bicarbonate, sodium hydrogen carbonate, sodium phosphate, potassium phosphate, pyrrolium Sodium phosphate, potassium pyrophosphate, sodium silicate, potassium silicate, sodium metasilicate, lithium metasilicate, Ammonia, monoethanolamine, diethanolamine, triethanolamine, monomethylamine, dimethylamine, triethylamine For example, an aqueous solution is used. Further, an antifoaming agent, an organic solvent, and the like may be added to the developer.

After the development, the developer is removed by washing with water, and irradiation with activated energy is performed and heat treatment is performed at 100 to 200. The cured product formed with the pattern obtained in this way has excellent electroless plating liquid resistance.

BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

Synthesis example 1

2 — Hydroxyl methyl acrylate 50 parts by weight, N — 50 parts by weight of methyl acrylamide, thioglycolic acid used as chain transfer agent, azobisui Radical chain transfer polymerization was carried out using soptiron nitrile as a polymerization initiator to obtain an oligomer having a carboxyl group at a molecular chain terminal.

By reacting the oligomer with glycidyl (meth) acrylate, it has a (meth) acrylyl group at one end of the molecular chain. A macro monomer was obtained.

20 parts by weight of this macromonomer and 80 parts by weight of methyl methacrylate are subjected to solution polymerization in a solvent solution of methyl chloride. Raft Polymer 1 was obtained.

Synthesis example 2

20 parts by weight of the macromonomer of Synthesis Example 1 and 5 parts by weight of methyl methacrylate and 5 parts by weight of butyl acrylate were subjected to solution polymerization in a solvent solution of methyl chloride and a graphite polymer. I got 2.

Examples 1-4, Comparative Examples 1-2

Photosensitive resin compositions having the compounding ratios shown in Table 1 were prepared. This photosensitive resin composition solution was applied on a 25 m thick polyethylene terephthalate film, and was heated and dried for 10 minutes with a normal air dryer at 80 to obtain a thickness of 4 mm. A photosensitive layer of 0 / m was obtained. This photosensitive layer was coated with a 20-m-thick polyethylene film to form a dry film. Next, the photosensitive layer was laminated on a glass epoxy resin substrate provided with an electroless copper plating catalyst by a laminating apparatus while peeling off the polyethylene film, and then using a high-pressure mercury lamp through a negative mask. Exposure at mJ / cm2 was performed. After exposure, it was left at room temperature for 30 minutes, and then 20% with 1% aqueous sodium carbonate solution. Spray development was performed for 100 seconds at C. After the development, the developing solution remaining on the substrate was removed by washing with water, and after drying with air, exposure was performed at 10 JZ cm 2 using a high-pressure mercury lamp. Next, heat treatment was performed at 150 ° C. for 60 minutes to perform heat curing. table 1

* 1: Styrene maleic anhydride copolymer (AMA Co., Ltd., SMA resin 100)

* 2: Polyvinylphenol (Maruzen Petrochemical Co., Ltd., resin MS-3)

* 3: Methyl methacrylate butyl acrylate acrylate copolymer (weight ratio = 80 Z 18/2)

* 4: Yuka Sherae Poxy Co., Ltd. The performance of the resist on the substrate thus obtained was evaluated by the following method. Table 2 shows the results.

Table 2

① Sensitivity

As a negative mask, a step page having an optical density step of 0.15 was used, and the number of steps of the negative image remaining after the development was regarded as the sensitivity.

②Developability

After development, the portion from which the photosensitive resin composition had been removed was observed with a magnifying glass and evaluated according to the following criteria.

〇: No residue

X: Residual

③ Resolution

The minimum width (μm) of the line-to-space (= 1/1) formed after development was resolved. ④Adhesiveness

When the distance between two adjacent patterns is 400 m, the minimum width (μm) that can be formed without breaking or meandering one independent pattern is Adhesion was adopted.

液 Electroless resistance

The heat-cured resist was immersed in an electroless copper plating solution at 70 ° C for 15 hours at PH12, and the appearance was observed.

〇: No change

X: Full

Synthesis example 3

2 — Hydroxyl methyl methacrylate 50 parts by weight, N — methylol acrylamide 50 parts by weight, thioglycolic acid used as chain transfer agent, azobis Using isopyronitrile as a polymerization initiator, radical chain transfer polymerization was carried out to obtain an oligomer having a carboxyl group at a molecular chain terminal.

By reacting the oligomer with glycidylmethacrylate, a macromonomer having a methacrylyl group at one end of the molecular chain can be obtained. Obtained.

20 parts by weight of this macromonomer and 80 parts by weight of methyl methacrylate were subjected to solution polymerization in a solvent solution of methyl chloride to obtain a graphite polymer 1.

Examples 5 to 7

Solution 1 was prepared by uniformly dissolving the following compounds.

Graphite polymer 130 parts by weight One Termere 5

Acid

30 parts by weight Merak 4 d

Etil

\ Rubium thioate Π 20 parts by weight

Le \ ruen o 10 parts by weight

Benzov Enon Heavy tall 1 5 parts by weight

No, hydroquinone monomethyl ether 0.1 parts by weight

Methizoresero Solve Lulu 3 3 100 Weight parts Ruzyri 2

Methyl ethyl ketone amount 50% by weight Specific ratio

To this solution 1, the following compounds were added, respectively.

A resin composition was prepared. \ Rele 2

1) Reacted product of toluene thiocyanate and t-butanol

15 parts by weight

2) Reacted product of hexamethylene diisocyanate isocyanurate with methylethylketoxime

15 parts by weight

3) Reaction product of diphenyl methane diisocyanate and methyl phenol

15 parts by weight Examples 8 to; L 0

Solution 2 was prepared by uniformly dissolving the following compounds.

Graphite polymer 120 parts by weight Ratio 20 20 parts by weight

Stycle 5-lino maleic anhydride copolymer (

A R C

Chemical resin, S MA resin

\ Acid

1 0 0 0) acid n2 20 parts by weight

Trimethylol \ Tibro non triacrylic

1 2 2 parts by weight

\ Le 5

Tetray ethylene co-mail

1 10 parts by weight

Benzov enon body 5 parts by weight

Les

No., Idloquinone monomethyl ether acid 0.Methylsesolve 100 parts by weight Methylethyl ketone 50 parts by weight To this solution 2, the same compounds as in Examples 5 to 7 were added. Then, a photosensitive resin composition was prepared and evaluated in the same manner as in Example 1.

Comparative Examples 4 to 5

The following compounds were added to the solution 1 prepared in Examples 5 to 7, respectively, to prepare a photosensitive fat composition, which was evaluated in the same manner as in Example 1.

. 7) Epic Coat 8 2 8 (Yuka Kazushi Epoxy Co., Ltd.)

1 5 parts by weight

8) None Comparative Examples 6-7 The same compounds as in Comparative Examples 4 to 5 were added to Solution 2 prepared in Examples 8 to 10, respectively, to prepare photosensitive resin compositions, which were evaluated in the same manner as in Example 1.

Table 3 shows the results.

Table 3

Example 11: L4, Comparative Examples 8 to 9

A photosensitive resin composition having the composition shown in Table 4 was prepared. The mixing ratio described below is% by weight. Table 4

* 1: Methacrylic acid methyl methacrylate 2-ethylhexyl hexyl ^ acrylic acid η-butyl copolymer (weight ratio = 25 to 40 2 0 no 1 5)

* 2: methacrylic acid methylsmethacrylic acid noacrylic acid η-butyl copolymer (weight ratio = 50/25)

* 3: Yuka Shell Epoxy Co., Ltd. The results are shown in Table 5

Five

The invention's effect

The present invention has the following effects.

(1) Excellent electroless plating resistance.

A resist using a conventional photosensitive resin composition has poor adhesion to the substrate surface, and is therefore 70%. When immersed in the electroless copper plating solution of C and PH12, phenomena such as peeling and swelling from the substrate surface appear. The photosensitive resin composition of the present invention provides a resist having excellent electroless plating resistance by forming a strong bond by thermal crosslinking and improving the adhesion to the substrate surface. can do .

(2) Excellent sensitivity and resolution. A resist using a conventional photosensitive resin composition could not be used for fine processing with a line width of 100 μm or less due to inferior sensitivity and resolution. The photosensitive resin composition of the present invention forms a strong bond by thermal crosslinking to improve the adhesion to the substrate surface, and also has a binder polymer excellent in developability. By using, a register with excellent sensitivity and resolution can be provided.

(3) Excellent developability with aqueous alkali solution.

A conventional resist using a photosensitive resin composition, which has the above two effects, uses an organic solvent as a developer. Since the photosensitive resin composition of the present invention uses a binder polymer having excellent image resilience to an aqueous solution of an alkaline solution, it is possible to use an aqueous solution of an aqueous solution for the developing solution. No worries about air pollution.

Because of the above-mentioned effects, the photosensitive resin composition of the present invention can be used in a solder register or a full-additive method used in the production of a printed wiring board. Suitable for applications such as resists, etching resists, and interlayer insulating materials, as well as fine processing of metal, PS plates, photosensitive liquids for screen printing, and resist inks. It is.

Claims

The scope of the claims

1. (A) Polymer having a carboxyl group, polymer having an anhydrous carboxyl group, polyvinyl phenols, saponified polyvinyl acetate polymer, novolak resin, and A film that is soluble or swellable in at least one kind of aqueous solution selected from the group consisting of (meta) acrylate copolymers having a hydroxyl group Binder polymer that can be formed

(C) Pre-polymerization initiator

and,

(D) (1) Homopolymer of one or more monomers selected from the group consisting of alkynole (meta) acrylate, acrylonitrile and styrene Alternatively, the copolymer is used as a trunk polymer, and a hydroxy-containing (meta) acrylate, an amino group or an alkylamino group (meta) group is contained. Acrylates, carboxyl-containing (meta) acrylates, vinyl esters, vinyl ethers, N-vinylpyrrolidone, vinyl pyridines and represented by the following general formula (I) A thermosetting compound composed of at least one monomer selected from the group consisting of monomers, and a graft polymer having a homopolymer or copolymer of the monomers as a branch polymer. R ¹

I

CH ₂ = C (I)

I

_{0 = C - NH - CH 2} - 0 - R 2

(Where R ¹ is hydrogen or an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, and R ² is hydrogen or an alkyl having 1 to 4 carbon atoms. Or an alkyl group having a hydroxy group having 1 to 4 carbon atoms, or an alkyl group having a hydroxy group having 1 to 4 carbon atoms.)

(ii) (a) a combination of the above-mentioned graphite polymer and (b) a block dissociate compound having at least two substituents represented by the following general formula (II): Thermosetting composition consisting of a mixture

-HC 0 R ³ (II)

(However, R ³ is an alkoxy group, an aryloxy group, an alkyl aryloxy group, an alkylidene aminooxy group, an amino group, a force pro- gram. Residue or | 3 — represents a dicarbylmethyl group.) Or

(iii) (a) an epoxy compound having at least two epoxy groups and (b) a trifluorothiamine compound, a dithiamide, an organic compound, Acid hydrazides, diamminomalleonitriles, melamines, amides represented by the following general formula (ΠΙ), or amides Thermosetting composition comprising at least one epoxy hardening agent selected from salts with organic acids or phenols and ketimine R ⁴ -C-N-N-CH a CH-R ⁷ (HI)

0 R ⁵ R ⁶ OH

(However, R ⁴ and R ⁷ are an aliphatic hydrocarbon having 1 to 6 carbon atoms or an aliphatic hydrocarbon having 1 to 6 carbon atoms having an ether bond, and R ⁵ and R ⁶ are carbon atoms. Represents an aliphatic hydrocarbon of the formulas 1 to 6.

A photosensitive resin composition comprising the same.

2. The polymer having a carboxyl group can be obtained from the monomer having a carboxyl group and the (meth) acrylic acid ester, styrenes and acrylonitriles. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a copolymer having a weight average molecular weight of 5,000 to 20,000 with a vinyl monomer.

3. The polymer having an anhydrous carboxyl group is composed of a monomer having an anhydrous sulfoxyl group and an ester of (meth) acrylic acid, styrenes and acrylonitrile. 2. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a copolymer having a weight-average molecular weight of 2000 to 1000 with a vinyl monomer selected from the group consisting of:

4. Polyvinyl phenol is (a) a homopolymer of vinyl phenol: or (b) vinyl phenol and (meth) acrylic acid ester, styrene, With vinyl monomer selected from acrylonitrile, vinyl monomer having carboxyl group and vinyl monomer having anhydrous carboxyl group 2. The photosensitive resin composition according to claim 1, which is a copolymer having a weight average molecular weight of 2000 to 5000.

5. The feeling according to claim 1, wherein the saponified vinyl acetate polymer is a completely saponified vinyl acetate polymer having a weight average molecular weight of 500 to 500, or a partially saponified vinyl acetate polymer. Light resin composition.

6. Claim that the novolac resin is a phenolic novolac resin having a weight-average molecular weight of 500 to 500, or a cresol novolac resin. 3. The photosensitive resin composition according to item 1.

7. Hydroxy group-containing (meta) acrylate copolymer (hydroxy) -containing mono (meta) acrylate and (meta) acrylate From the group consisting of acrylates, styrene, acrylonitrile, vinyl monomers having a carboxyl group, and vinyl monomers having an anhydrous norboxyl group 2. The photosensitive resin composition according to claim 1, which is a copolymer having a weight average molecular weight of 5,000 to 100,000 with a selected vinyl monomer.

8. The weight average molecular weight of the trunk polymer of the graphite polymer is 50,000 to 500,000, and the weight average molecular weight of the branch polymer is 500,000 to 100,000. The photosensitive resin composition according to claim 1.

9. The photosensitive material according to claim 1, wherein the molar ratio between the stem polymer and the branch polymer of the graft polymer is 955 to 50/50, that is, the trunk polymer is a branch polymer. Resin composition.

10. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the graphite polymer is from 500 to 500,000.

11. The photosensitive resin composition according to claim 1, wherein the content of the binder polymer (A) is 20 to 80% by weight based on the composition.

12. The photosensitive resin composition according to claim 1, wherein the content of the acrylic compound (B) is from 20 to 80% by weight based on the composition.

13. The photosensitive resin composition according to claim 1, wherein the content of the photopolymerization initiator (C) is from 0.01 to 30% by weight based on the composition.

14. The photosensitive resin composition according to claim 1, wherein the content of the graphite polymer (D-i) is from 10 to 60% by weight based on the composition.

15. The photosensitive resin composition according to claim 1, wherein the content of the block-isolated (D-ii-lb) is 5 to 50% by weight based on the composition.

16. The photosensitive resin composition according to claim 1, wherein the content of the epoxy compound (D-iiii-a) is 5 to 50% by weight based on the composition.

17. The photosensitive resin composition according to claim 1, wherein the content of the epoxy curing agent (D-iiii-b) is 0.1 to 10% by weight based on the composition.

18. The photosensitive resin composition according to claim 1, which is used for an alkaline development type resist.

19. The photosensitive resin composition according to claim 1, which is used for a solder resist, a plating resist, and an interlayer insulating material.

20. A dry film register or a liquid register formed from the composition of claim 1.

21. A circuit substrate formed from a conductive substrate treated with the composition of claim 1.

22. A laminated substrate comprising a dry film register or a liquid register according to claim 20 and a fiber-filled resin substrate.

23. A circuit board formed from the board of claim 22.