JPH0695379A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain developability with an aqueous solution of alkali and to enhance sensitivity, resolution, and resistance to a nonhydrolytic plating solution by forming the photosensitive resin composition comprising a specified binder polymer, a specified epoxy compound, a specified ethylenically unsaturated compound, a specified epoxy hardener, and a specified photopolymerization initiator. CONSTITUTION:The photosensitive resin composition comprises the binder polymer soluble or swellable in aqueous solutions of alkalis and capable of forming a film, the epoxy compound having at least 2 epoxy groups, the ethylenically unsaturated compound having at least 2 ethylenically unsaturated bonds and polymerizable by the photopolymerization initiator, this initiator, and at least one kind of epoxy hardener selected from boron trifluoride amine complex, dicyandiamide, amineimide represented by formula I, and the like. In formula I, each of R<1> and R<4> is a 1-6C aliphatic hydrocarbon group or optionally having an ether bond, and each of R<2> and R<3> is a 1-6C aliphatic hydrocarbon group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photosensitive resin composition. In particular, the present invention relates to a photosensitive resin composition suitable as a resist used when manufacturing a printed wiring board.

[0002]

2. Description of the Related Art Photosensitive resin compositions are widely used as resists such as electroless plating resists and solder resists used in the production of printed wiring boards. Since this resist is exposed to an electroless copper plating solution having a pH of about 12 ° C. and 70 ° C. for a long time, it is required to have resistance to an electroless plating solution that can withstand a high-concentration alkaline aqueous solution. Only resistant to low temperature alkali. Further, in recent years, as the density of printed wiring boards has increased, circuits have become finer, and resists are required to have excellent sensitivity, resolution, and developability, but conventional resists do not necessarily meet all the requirements. Not. On the other hand, as a developing solution, an organic solvent has been conventionally used, but the organic solvent has a risk of air pollution or ignition.

As a conventional photosensitive resin composition for a resist, for example, an alkali developable polymer or oligomer having a carboxy group and a vinyl group in the same molecule as described in JP-A-2-247654, a biphenyl type Epoxy compound, photopolymerizable monomer or oligomer,
Also, a photosensitive resin composition comprising a photopolymerization initiator or a sensitizer is known. Further, JP-A 64-3645 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. Urethane (meth) acrylate [(meth) acrylate represents methacrylate or acrylate. The same applies below. ], A linear polymer, and a photosensitive resin composition comprising a polymerization initiator.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The photosensitive resin composition described in No. 4 is resistant to a plating solution having a pH of 8 and 70 ° C, but cannot be used for a plating solution having a pH of 12 and 70 ° C. The photosensitive resin composition described in JP-A No. 64-3645 can sufficiently withstand an electroless copper plating solution having a pH of 12 and 70 ° C., but has a resolution of 170 μm and cannot be used for fine circuit processing. JP-A-1-105240
Although the photosensitive resin composition described in No. 1 shows resistance to an electroless copper plating solution having a pH of 12 and 70 ° C. and a resolution of 70 μm, it is preferable.
There is a drawback that the developer is an organic solvent. The present invention has developability with an alkaline aqueous solution, and has sensitivity, resolution,
It is intended to provide a photosensitive resin composition having excellent resistance to electroless plating solution.

[0005]

[Means for Solving the Problems] A film-forming binder polymer soluble or swelling in an alkaline aqueous solution, B. An epoxy compound having at least two epoxy groups, C.I. A liquid or solid ethylenically unsaturated compound having at least two ethylenically unsaturated bonds and capable of forming a polymer by a photopolymerization initiator at room temperature; A photopolymerization initiator, and E. Boron trifluoride amine complex, dicyandiamide, organic acid hydrazide, diaminomaleonitriles, melamines, the following general formula 2
It can be achieved by a photosensitive resin composition comprising an amine imide represented by the following formula, a salt of an amine with an organic acid or a phenol, and at least one epoxy curing agent selected from ketimines.

[0006]

[Chemical 2]

(However, R ¹ and R ⁴ have 1 to 6 carbon atoms.
Aliphatic hydrocarbons having 1 to 6 carbon atoms having an ether bond or R ² and R ^{3 each} having 1 carbon atom
Represents an aliphatic hydrocarbon of ~ 6. )

A. The film-forming binder polymer which is soluble or swellable in the alkaline aqueous solution serves as a binder for the cured product of the photosensitive resin composition and imparts developability to the alkaline aqueous solution to the photosensitive resin composition. Examples of such polymers include polymers having a carboxy group, polymers having an anhydrous carboxy group, polyvinylphenols, polyvinyl alcohols, novolac resins, and hydroxy group-containing (meth) acrylate copolymers.

As the polymer having a carboxy group,
A monomer having a carboxy group and a (meth) acrylic acid ester [(meth) acrylic acid represents acrylic acid or methacrylic acid. The same applies below. ], And copolymers with vinyl monomers such as styrenes and acrylonitriles. The weight average molecular weight is preferably 5,000 to 200,000.

Specific examples of the monomer having a carboxy group include (meth) acrylic acid, itaconic acid, crotonic acid, sorbic acid, fumaric acid, propiolic acid, maleic acid and cinnamic acid.

Specific examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate and isobutyl. (Meth) acrylate, sec
-Butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth ) Acrylate, nonyl (meth) acrylate, decyl (meth)
Acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate,
Oleyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate and other alkyl or aryl (meth) acrylates, methoxyethyl ( (Meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) Acrylate, phenoxyethyl (meth) acrylate,
Phenoxydiethylene glycol (meth) acrylate, phenoxydiethoxy (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth)
Polyether diol monoether (meth) acrylate such as acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-chloroisopropyl (meth) acrylate, 2- Bromoethyl (meta)
Acrylate, 2,3-dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate,
Halogenated alkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-
Hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2
In addition to hydroxy group-containing (meth) acrylates such as -hydroxypropyl (meth) acrylate and 3-chloro-2-hydroxybutyl (meth) acrylate,
Examples thereof include glycidyl (meth) acrylate, 2-cyanoethyl acrylate, and tetrahydrofurfuryl (meth) acrylate.

Specific examples of styrenes include styrene,
Examples include α-methylstyrene, p-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, vinylpyrrolidone, vinyl chloride and the like can be mentioned.

Examples of the polymer having an anhydrous carboxy group include a copolymer of a monomer having an anhydrous carboxy group and a vinyl monomer such as (meth) acrylic acid ester, styrenes and acrylonitriles. The weight average molecular weight is preferably 2000 to 100000.

Specific examples of the monomer having a carboxy anhydride group include 2,3-dichloromaleic anhydride and 2 anhydride.
-Chloromaleic acid, citraconic anhydride, dodecenylsuccinic anhydride, nonenylsuccinic anhydride, bromomaleic anhydride, maleic anhydride and the like can be mentioned.

The polyvinylphenols include homopolymers of vinylphenol or vinyl monomers such as vinylphenol and (meth) acrylic acid ester, styrenes, acrylonitriles, monomers having a carboxy group, and monomers having an anhydrous carboxy group. Copolymers of Specifically, Marzen Resin M,
Maruzen resin MB, resin CMM, resin CHM, resin MAA, resin MS-2, resin MS-3 [above,
Maruzen Petrochemical Co., Ltd.] and the like. The weight average molecular weight of polyvinylphenols is 2,000 to 50,000.
Is preferred.

Examples of polyvinyl alcohols include fully saponified vinyl acetate polymers and partially saponified vinyl acetate polymers. The weight average molecular weight of polyvinyl alcohol is preferably 5,000 to 50,000.

Examples of the novolac resin include phenol novolac resin and cresol novolac resin which are swellable or soluble in an alkaline aqueous solution. The weight average molecular weight of the novolac resin is preferably 500 to 5000.

Hydroxy group-containing (meth) acrylate copolymers include hydroxy group-containing mono (meth) acrylate and (meth) acrylic acid ester, styrenes, acrylonitriles, monomers having a carboxy group, monomers having an anhydrous carboxy group. And a copolymer with a vinyl monomer. The weight average molecular weight of the copolymer is preferably 5,000 to 100,000.

As specific examples of the hydroxy group-containing mono (meth) acrylate, those mentioned above in the specific examples of the (meth) acrylic acid ester can be used.

The content of the binder polymer in the photosensitive resin composition is preferably 20 to 80% by weight. 20% by weight
If it is less than the range, developability is deteriorated and the cured product becomes hard and brittle. In addition, the viscosity decreases, and there is a risk of edge fusion when the photosensitive resin composition is laminated. If it exceeds 80% by weight, the photosensitive resin composition is easily dissolved in the developing solution, the adhesion is lowered and the resolution is deteriorated. Two or more binder polymers may be used in combination.

B. The epoxy compound having at least two epoxy groups undergoes a crosslinking reaction by heating after irradiation with active energy rays to form a strong bond, thereby improving the adhesiveness of the resist and the resistance of the electroless plating solution. Therefore, the pattern formed using the photosensitive resin composition of the present invention has excellent resolution. Specific examples of such epoxy compounds include 1) DER331J, DER
337J, DER661J, DER664J, DER6
67J [above, Dow Chemical Co.], Epicron 800
[Dainippon Ink and Chemicals, Inc.], Epicoat 100
1, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 100
9, Epicoat 1055, Epicoat 801, Epicoat 807, Epicoat 808, Epicoat 815, Epicoat 816, Epicoat 819, Epicoat 827,
Epicoat 828, Epicoat 834, Epicoat 87
1 [above, Yuka Shell Epoxy Co., Ltd.] Bisphenol A type epoxy resin; 2) DER431, DER
438, DER439 (above, Dow Chemical Co., Ltd.), Araldite EPN1138 (Ciba Geigy Co., Ltd.), Epicoat 152, Epicoat 154, Epicoat 172.
[Above, novolak type epoxy resin such as manufactured by Yuka Shell Epoxy Co., Ltd.]; 3) Syracure 6100, Syracure 6110, Syracure 6200, ERL225
6, ERL4090, ERL4617, ERL5411
(Above, Union Carbide), Araldite CY
-175, Araldite CY-176, Araldite C
Y-179, Araldite CY-182, Araldite CY-184, Araldite CY-192 (above, manufactured by Ciba Geigy), Chisso Knox 090, Chisso Knox 091, Chisso Knox 092, Chisso Knox 30.
1, Chisso Knox 313 [above, Chisso Co., Ltd.],
Alicyclic epoxy resins such as alicyclic diepoxy adipate, alicyclic diepoxy acetal, alicyclic diepoxy carboxylate, and vinylcyclohexenedioxide; 4) 1,6-hexanediol diglycidyl ether, 2,2- Dibromoneopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane diglycidyl ether, neopentyl glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Tellurium, polyglycerides of aliphatic polyhydric alcohols such as diglycidyl ether of hydrogenated bisphenol A Ethers; 5) Bisphenol A
Aromatic polyhydric alcohol derivatives such as alkylene oxide adduct diglycidyl ether, bisphenol F alkylene oxide adduct diglycidyl ether, and bisphenol S alkylene oxide adduct diglycidyl ether; 6) diglycidyl p-oxybenzoic acid, dimer Glycidyl esters such as acid glycidyl ester, tetrahydrophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, and hexahydrophthalic acid diglycidyl ester; 7) N, N-diglycidylaniline, tetraglycidyldiaminodiphenylmethane, triglycidyl p-aminophenol Such as glycidyl amine; 8) Heterocyclic epoxy resins such as triglycidyl isocyanurate, hydantoin type epoxy resin; 9) 3-penta Sill phenyl glycidyl ether, n- butylphenol glycidyl ether, ter
glycidyl ester of t-carboxylic acid, α-pinene oxide, acrylic glycidyl ether, octylene oxide, cyclohexane vinyl monooxide, styrene oxide, phenyl glycidyl ether, butyl glycidyl ether, glycidyl (meth) acrylate,
Examples include monoepoxy compounds such as epichlorohydrin.

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 5% by weight, sufficient adhesion,
Resistance to electroless plating solution cannot be obtained, and if it exceeds 50% by weight, developability deteriorates.

C. The ethylenically unsaturated compound which has at least two ethylenically unsaturated bonds and is liquid or solid at room temperature and capable of forming a polymer by a photopolymerization initiator has a property of being hardened by active energy rays. The composition of the present invention has excellent sensitivity to active energy rays. Therefore, the photosensitive resin composition of the present invention exhibits excellent resolution. As the ethylenically unsaturated compound, a known monomer that can be cured by irradiation with active energy rays having a boiling point of 100 ° C. or higher under atmospheric pressure can be preferably used.

Specific examples of such a monomer include 1) ethylene glycol di (meth) acrylate,
Propanediol di (meth) acrylate, butanediol di (meth) acrylate, pentanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetrahydrofuran glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) (Meth) acrylic acid esters of polyhydric alcohols such as acrylates; 2) Trade name Aronix M-110
0, Aronix M-1200, Aronix M-61
00, Aronix M-6200, Aronix M-6
250, Aronix M-6300, Aronix M-
6400, Aronix M-7100, Aronix M
-8030, Aronix M-8060, Aronix M-8100 [above, Toa Gosei Chemical Industry Co., Ltd.], trade name Kayarad DPCA-120, Kayarad DPCA
-20, Kayarad DPCA-30, Kayarad DPC
A-60, Kayarad R-526, Kayarad R-62
9, Kayarad R-644 [above, Nippon Kayaku Co., Ltd.]
(Meth) acrylic acid esters of polyester such as;
3) 1,6-hexanediol diglycidyl ether di (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, glycerin triglycidyl ether tri (meth) acrylate,
Isocyanuric acid triglycidyl ether tri (meth)
(Meth) acrylic acid esters of compounds having two or more epoxy groups in one molecule, such as acrylate, (meth) acrylic acid ester of novolac type epoxy resin, and (meth) acrylic acid ester of bisphenol A type epoxy resin; 4) Isophorone diisocyanate, diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, tolylene diisocyanate, a reaction product of hexamethylene diisocyanate and a hydroxy group-containing (meth) acrylate, and a terminal isocyanate prepolymer composed of these polyisocyanates and polyols and a hydroxy group. Reaction products with contained (meth) acrylates are mentioned. For example, the product name Sumijour N
(Buret derivative of hexamethylene diisocyanate), Sumidule L (trimethylolpropane modified form of tolylene diisocyanate) [above, Sumitomo Bayer Urethane Co., Ltd.] The added reaction product can be used. As the hydroxy group-containing (meth) acrylate referred to here, those mentioned in the above specific examples of the (meth) acrylic acid ester can be used.

In addition to the above ethylenically unsaturated compounds, A.
The monomer having an ethylenically unsaturated bond, which constitutes the film-forming binder polymer soluble or swellable in the alkaline aqueous solution, can be used. Furthermore, a mixture of the above-mentioned ethylenically unsaturated compounds can be mentioned.

The content of the ethylenically unsaturated compound in the photosensitive resin composition is preferably 20 to 80% by weight. If it is less than 20% by weight, the sensitivity is lowered and the resolution is deteriorated.
If the content exceeds 10% by weight, the adhesion will be poor.

D. Specific examples of the photopolymerization initiator of
-(4-Isopropylphenyl) -2-hydroxy-2
-Methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one , 2-methyl-1- [4- (methylthio)
Phenyl] -2-morpholinopropane-1,4-phenoxydichloroacetophenone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl)
Ketone, pt-butyldichloroacetophenone, p-
Acetophenones such as t-butyltrichloroacetophenone and p-dimethylaminoacetophenone; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n
Benzoins such as butyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal; benzophenone, benzophenone methyl ether, benzoylbenzoic acid, benzoylbenzoate methyl, hydroxybenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 3,3'-bis (N, N-diethylamino) benzophenone, 4,4 '
-Bis (N, N-diethylamino) benzophenone,
4 ', 4 "-diethylisophthalophenone, 3,3',
4,4'-Tetra (t-butylperoxycarbonyl)
Benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide and acrylated benzophenone; thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,
Xanthones such as 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and 2,4-dichlorothioxanthone; diketones such as diacetyl and benzyl; 2-ethylanthraquinone, 2-t-butylanthraquinone, 2,3-diphenylanthraquinone, 1,2
-Benzanthraquinone, Octamethylanthraquinone, Camphorquinone, Dibenzosuberone, 9,10-
Examples thereof include quinones such as phenanthrenequinone.

The content of the photopolymerization initiator in the photosensitive resin composition is preferably 0.01 to 30% by weight.

E. The epoxy curing agent of (1) reacts with the epoxy compound by heating after irradiation with active energy rays to initiate a crosslinking reaction. Examples of such an epoxy curing agent include boron trifluoride n-hexylamine complex, boron trifluoride monoethylamine complex, boron trifluoride benzamine complex, boron trifluoride diethylamine complex, boron trifluoride piperidine complex, and trifluoride. Boron trifluoride amine complex such as boron triethylamine complex and boron trifluoride aniline complex; dicyandiamide; succinic acid hydrazide, adipic acid hydrazide, isophthalic acid hydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, etc. Organic acid hydrazide of N-benzylaminomaleonitrile, amino-N-isobutylamino, amino-N-benzylideneaminomaleonitrile, amino-N
-Butylidene aminomaleonitrile, amino-n-propylidene aminomaleonitrile, diaminomaleonitriles such as diaminomaleonitrile; melamines such as melamine and diallylmelamine; amine imides represented by the following general formula 3;

[0032]

[Chemical 3]

(However, R ¹ and R ⁴ have 1 to 6 carbon atoms.
Aliphatic hydrocarbons having 1 to 6 carbon atoms having an ether bond or R ² and R ^{3 each} having 1 carbon atom
Represents an aliphatic hydrocarbon of ~ 6. ) Ethylenediamine, hexamethylenediamine, a salt of piperidine with a dicarboxylic acid having 3 to 8 carbon atoms, 2,4,4-trimethyl-2,4,
7-trihydroxyflavan and N, N'-dimethyl 1,
Salt with 3-propanediamine, salt with phenylenediamine and phenylphosphonic acid, salt with aniline and phenylphosphonic acid, salt with p, p′-diaminodiphenylmethane and phenylphosphonic acid, with benzylamine and phenylphosphonic acid Salts, salts of phenylenediamine and phenylphosphoric acid, salts of aniline and phenylphosphoric acid, salts of benzylamine and phenylphosphoric acid, etc. Salts of amines and organic acids or phenols; diethylenetriamine, triethylenetetramine, etc. Ketimines produced by reacting polyamines with ketones such as methyl ethyl ketone and isobutyl methyl ketone are mentioned.

The content of the epoxy curing agent in the photosensitive resin is preferably 0.1 to 10% by weight. If it 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 is deteriorated.

The photosensitive resin composition of the present invention may optionally contain a crosslinking catalyst, a thermal polymerization inhibitor, a filler, a dye, a pigment, a heat stabilizer, an adhesion promoter, a plasticizer, a defoaming agent, a leveling agent,
An anti-sagging agent, a flame retardant and the like 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 resist. When it is used as a liquid resist, it can be directly applied on a support by a method such as a dipping method, a spray method, a flow coating method or a screen printing method to form a photosensitive layer having a thickness of 10 to 150 μm. The solvent used at this time may be a solvent that dissolves the photosensitive resin composition, and examples thereof include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, propylene glycol methyl ether, propylene glycol. Glycol ethers such as ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate, glycol esters such as propylene glycol ethyl ether acetate, alcohols such as methanol and ethanol, dichloromethane, 1,1,1-trichloroethane Examples include chlorine-containing aliphatic solvents such as, and aromatic hydrocarbon solvents such as toluene and xylene.
These solvents may be used alone or as a mixture.

The photosensitive resin composition of the present invention can be used as a dry film. As the supporting film when used as a dry film, for example, a film made of polyethylene terephthalate, polypropylene, polyethylene or the like is used, and a polyethylene terephthalate film is particularly preferable. The thickness of the film is preferably 5 to 100 μm. Further, one of these films may be used as a protective film for the photosensitive layer. The solvent described above can be used as a solvent for making the photosensitive resin composition into a liquid state when producing a dry film. A liquid photosensitive resin composition is uniformly applied on a support film, and the solvent is removed by heat drying or hot air drying to form a photosensitive layer. The thickness of the photosensitive layer is preferably 10 to 100 μm. Next, the dry film in which the photosensitive layer is formed on the support film is kept as it is, or a protective film is laminated on the photosensitive layer and wound up in a roll shape for storage.

Next, a method of using the photosensitive resin composition of the present invention will be described. 1) by applying a liquid resist on a substrate by the above-mentioned method and removing the solvent by heat drying or hot air drying, or 2) laminating a photosensitive layer on the substrate by a dry film by a usual laminating method. Then, a photosensitive layer of the photosensitive resin composition of the present invention is formed on a substrate. After that, the photosensitive layer is irradiated with an active energy ray through a negative mask or a positive mask. Examples of active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps,
Ultraviolet light using a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a tungsten lamp, etc. as a light source, an argon laser, a helium cadmium laser, a krypton laser, etc. are used.

Next, the unexposed portion of the photosensitive layer is removed by a method such as spraying, dipping, or brushing using a developing solution. The developer is, for example, lithium hydroxide,
Sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, sodium silicate, silica Potassium acid, sodium metasilicate, potassium metasilicate, ammonia,
An aqueous solution of monoethanolamine, diethanolamine, triethanolamine, monomethylamine, dimethylamine, triethylamine or the like is used. Further, an antifoaming agent, an organic solvent, etc. may be added to the developing solution.

After development, the developing solution is removed by washing with water, irradiation with active energy rays and heat treatment at 100 to 200 ° C. are carried out. The pattern-formed cured product thus obtained has excellent electroless plating solution resistance.

[0041]

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

Examples 1 to 4 and Comparative Examples 1 to 2 Photosensitive resin compositions having the compositions shown in Table 1 were prepared. In addition,
The compounding ratio described below is% by weight.

[0043]

[Table 1]

* 1: Methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate / n-butyl acrylate copolymer (weight ratio = 25/40/20/15) * 2: Methyl methacrylate / methacrylic acid / acrylic N-Butyl acid copolymer (weight ratio = 50/25/25) * 3: manufactured by Yuka Shell Epoxy Co., Ltd.

This photosensitive resin composition was coated on a polyethylene terephthalate film having a thickness of 25 μm and the temperature was 80 ° C.
The film was heated and dried for 10 minutes with a normal air dryer to obtain a photosensitive layer having a thickness of 40 μm. The photosensitive layer was covered with a polyethylene film having a thickness of 20 μm to prepare 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 device while peeling off the polyethylene film.

Next, through a negative mask, 250 mJ / cm ² exposure was performed using a high pressure mercury lamp. After the exposure, the film was left at room temperature for 30 minutes, and then spray developed with a 1% sodium carbonate aqueous solution at 20 ° C. for 100 seconds. After the development, the developer remaining on the substrate was removed by washing with water, air-dried, and then exposed with a high pressure mercury lamp at 5 J / cm ² . Then, heat treatment was performed at 150 ° C. for 60 minutes to perform heat curing.

The performance of the resist thus obtained on the substrate was evaluated by the following method. The results are shown in Table 2. Sensitivity A step wedge with an optical density difference of 0.15 was used as a negative mask, and the number of steps of the negative image remaining after development was taken as the sensitivity. Developability The portion from which the photosensitive resin composition was removed after development was observed with a magnifying glass and evaluated according to the following criteria. ◯: No residue X: Residue resolution The minimum width (μm) of the line / space (= 1/1) formed after development was defined as the resolution. Adhesiveness Adhesiveness is defined as the minimum width (μm) at which one independent pattern is formed without breaking or meandering when the interval between two adjacent patterns is 400 μm. Resistance to Electroless Plating Solution The resist after heat curing was immersed in an electroless copper plating solution having a pH of 12 and 70 ° C. for 15 hours, and the appearance was observed.

[0048]

[Table 2]

○: No change ×: Swelling

[0050]

The present invention has the following effects. (1) Excellent resistance to electroless plating solution. Since a resist using a conventional photosensitive resin composition is inferior in adhesiveness to a substrate surface, when it is immersed in an electroless copper plating solution having a pH of 12 at 70 ° C., phenomena such as peeling and swelling from the substrate surface appear. The photosensitive resin composition of the present invention can provide a resist having excellent electroless plating solution resistance by forming a strong bond by thermal crosslinking to improve the adhesion to the substrate surface.

(2) It has excellent sensitivity and resolution. A resist using a conventional photosensitive resin composition cannot be used for fine processing having a line width of 100 μm or less because of poor 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 by using a binder polymer having excellent developability, it has excellent sensitivity and resolution. A resist can be provided.

(3) The developability with an alkaline aqueous solution is excellent. A resist using a conventional photosensitive resin composition, which has the above-mentioned two effects, uses an organic solvent as a developing solution. Since the photosensitive resin composition of the present invention uses a binder polymer having excellent developability with respect to an alkaline aqueous solution, the alkaline aqueous solution can be used as a developer and there is no concern about air pollution.

Since the photosensitive resin composition of the present invention exerts the above effects, in addition to a solder resist used in the production of a printed wiring board, a plating resist in the full additive method, an etching resist, an interlayer insulating material, etc.,
It is suitable for applications such as fine processing of metals, PS plates, photosensitive liquids for screen printing and resist inks.

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[Procedure amendment]

[Submission date] November 8, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] (However, R ¹ and R ⁴ are aliphatic hydrocarbons having 1 to 6 carbon atoms or aliphatic hydrocarbons having 1 to 6 carbon atoms having an ether bond, and R ² and R ³ are those having 1 to 6 carbon atoms. Represents an aliphatic hydrocarbon.)

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[0006]

[Chemical 2]

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B. Has at least two epoxy groups of
The epoxy compound is heated after irradiation with active energy rays.
This causes a cross-linking reaction to form a strong bond.
To improve resist adhesion and resistance to electroless plating solution.
It Therefore, it is formed using the photosensitive resin composition of the present invention.
The pattern is excellent in resolution. Such an epoxy
Specific examples of the compound include 1) DER331J and DER
337J, DER661J, DER664J, DER6
67J [above, Dow Chemical Co.], Epicron 800
[Manufactured by Dainippon Ink and Chemicals, Inc.], Epicoat 100
1, Epicoat 1002, Epicoat 1003, Epico
1004, Epicoat 1007, Epicoat 100
9, Epicoat 1055, Epicoat 801, Epicor
807, Epicote 808, Epicote 815, Epi
Coat 816, epicoat 819, epicoat 827,
Epicoat 828, Epicoat 834, Epicoat 87
1 [above, Yuka Shell Epoxy Co., Ltd.]
Enol A type epoxy resin; 2) DER431, DER
438, DER439 (above, Dow Chemical Co., Ltd.),
Lardite EPN1138 (Ciba-Geigy), Epi
Coat 152, epicoat 154, epicoat 172
Novolac such as [above, Yuka Shell Epoxy Co., Ltd.]
Type epoxy resin; 3) Syracure 6100, Siraki
Viewer 6110, Syracure 6200, ERL225
6, ERL4090, ERL4617, ERL5411
(Above, Union Carbide), Araldite CY
-175, Araldite CY-176, Araldite C
Y-179, Araldite CY-182, Araldite
CY-184, Araldite CY-192 (above, Ciba
Geigy), Chisso Knox 090, Chisso Knock
SU 091, Chisso Knox 092, Chisso Knox 30
1, Chisso Knox 313 [above, Chisso Co., Ltd.],
Alicyclic Diepoxy Adipate, Alicycl
Epoxy acetal, Alicyclic Diepoki
Cicarboxylate, vinyl cyclohexene dioxane
Cycloaliphatic epoxy resin such as dode; 4) 1,6-hexanediene
All diglycidyl ether, 2,2-dibromoneope
Ethyl glycol diglycidyl ether, ethylene glycol
Cole diglycidyl ether, glycerin diglycidyl
Ether, trimethylolpropane diglycidyl ete
Le, neopentyl glycol diglycidyl ether,
Ropylene glycol diglycidyl ether, polyethylene
Glycol diglycidyl ether, polypropylene
Recall diglycidyl ether, hydrogenated bispheno
Aliphatic polyhydric alcohols such as diglycidyl ether of le A
Polyhydric glycidyl ether; 5) Bisphenol A
Alkylene oxide adduct Diglycidyl ether, bis
Phenol F alkylene oxide adduct diglycidyl ester
Ether, bisphenol S alkylene oxide adduct di
Aromatic polyhydric alcohol derivatives such as glycidyl ether
Polyvalent glycidyl ether; 6) diglycidyl p-oxy
Benzoic acid, dimer acid glycidyl ester, tetrahydride
Lophthalic acid diglycidyl ester, phthalic acid diglycidyl
Ester, diglycidyl hexahydrophthalate ester
Glycidyl esters such as ruthenium; 7) N, N-diglycidyl
Luaniline, tetraglycidyl diaminodiphenyl meta
Glycine such as triglycidyl p-aminophenol
Diamine; 8) triglycidyl isocyanurate, hi
Heterocyclic epoxy resin such as danthin type epoxy resin
And so on.

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[0032]

[Chemical 3]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location G03F 7/032 501 7/033 7/038 505 H01L 21/027 H05K 3/00 F 6921-4E 3 / 18 D 7511-4E 3/28 D 7511-4E

Claims (1)

[Claims] 1. A. A film-forming binder polymer soluble or swelling in an alkaline aqueous solution, B. An epoxy compound having at least two epoxy groups, C.I. A liquid or solid ethylenically unsaturated compound having at least two ethylenically unsaturated bonds and capable of forming a polymer by a photopolymerization initiator at room temperature, D. A photopolymerization initiator, and E. At least one selected from boron trifluoride amine complex, dicyandiamide, organic acid hydrazide, diaminomaleonitriles, melamines, amine imides represented by the following general formula 1, salts of amines with organic acids or phenols, and ketimines. A photosensitive resin composition comprising one type of epoxy curing agent. [Chemical 1] (However, R ¹ and R ⁴ are aliphatic hydrocarbons having 1 to 6 carbon atoms or aliphatic hydrocarbons having 1 to 6 carbon atoms and having an ether bond, and R ² and R ³ are those having 1 to 6 carbon atoms. Represents an aliphatic hydrocarbon.)