JP2001159817A - Photosensitive resin composition, photosensitive element using same, method for producing resist pattern and method for producing printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength and elasticity and a photosensitive element excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, elasticity, work efficiency and productivity. SOLUTION: The photosensitive resin composition contains (A) a binder polymer having 8 dispersity of 1.0-3.0, (B) a photopolymerizable compound including a bisphenol A type (meth)acrylate compound as an essential component and having at least one polymerizable ethylenically unsaturated bond in one molecule and (C) a photopolymerization initiator. The top of a substrate is coated with a layer of the photosensitive resin composition and dried to obtain the objective photosensitive element or the top of a substrate is coated with a layer of the photosensitive resin composition and dried and a protective film is further laminated in such a way that it comes in contact with the layer of the photosensitive resin composition opposite to the substrate to obtain the objective photosensitive element.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board.

[0002]

2. Description of the Related Art Conventionally, in the field of manufacturing printed wiring boards, a photosensitive resin composition and a photosensitive element obtained using a support and a protective film have been widely used as a resist material for etching, plating, and the like. Have been. Printed wiring board, after laminating the photosensitive element on a copper substrate, pattern exposure, remove the unexposed part with a developing solution, subjected to etching or plating,
It is manufactured by a method of peeling and removing a cured portion from a substrate after forming a pattern. As a developing solution for removing the unexposed portion, an alkali developing type using a sodium hydrogen carbonate solution or the like has become mainstream.
Usually, it can be used as long as it has the ability to dissolve the photosensitive resin composition layer to some extent, and at the time of development, the photosensitive resin composition is dissolved or dispersed in a developer.

With the recent increase in the density of printed wiring boards,
Since the contact area between the copper substrate and the patterned photosensitive resin composition layer is reduced, excellent adhesive strength, mechanical strength, chemical resistance, flexibility, etc. are required in the development, etching or plating process steps, and Resolution is required. Among such properties, a method using a photopolymerizable compound having a bisphenol A skeleton to improve chemical resistance is disclosed in Japanese Patent Publication No.
As described in Japanese Patent No. 27205, if the binder polymer has a large degree of dispersion, the adhesion and the resolution tend to be reduced.

[0004]

The invention described in claim 1 provides a photosensitive resin composition having excellent photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength and flexibility. This is useful for increasing the density and resolution of printed wiring. The inventions of claims 2 and 3 provide the effects of the invention of claim 1 and provide a photosensitive resin composition having excellent chemical resistance. The inventions of claims 4, 5 and 6 provide a photosensitive resin composition having further excellent alkali developability in addition to the effects of the inventions of claims 1, 2 and 3.

[0005] The invention according to claims 7 and 8 is based on claim 1,
It is intended to provide a photosensitive resin composition exhibiting the effects of the invention described in 2 or 3, and further having excellent photosensitivity and chemical resistance (plating resistance). The ninth aspect of the present invention provides the first and second aspects.
Another object of the present invention is to provide a photosensitive resin composition exhibiting the effects of the invention described in 3 and further having excellent peeling properties. Claim 10
The invention described in claims 1, 2, 3, 4, 5, 6, 7, 8
Another object of the present invention is to provide a photosensitive resin composition exhibiting the effects of the invention described in 9 and further having excellent adhesion. The invention according to claim 11 is the invention according to claims 1, 2, 3, 4, 5, 6, 7, 8,
It is intended to provide a photosensitive resin composition exhibiting the effects of the invention described in 9 or 10, and further having excellent photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, and flexibility.

The invention according to claims 12 and 13 provides a photosensitive element having excellent light sensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, flexibility, workability and productivity. It is. The invention described in claims 14 and 15 has the effects of the invention described in claim 12 or 13, and provides a photosensitive element having excellent resolution. The invention according to claim 16 is the invention according to claims 12, 13, 1
It is intended to provide a photosensitive element exhibiting the effects of the invention described in 4 or 15 and further having excellent resolution. Claim 1
The inventions described in 7 and 18 provide a photosensitive element having further excellent laminating properties in addition to the effects of the invention described in claim 12 or 13.

The invention according to claim 19 provides a method for producing a resist pattern excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, flexibility, workability and productivity. It is. The invention according to claim 20 provides a method for producing a printed wiring board excellent in light sensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, flexibility, environment, workability, and productivity. Things.

[0008]

According to the present invention, there are provided (A) a binder polymer having a dispersity of 1.0 to 3.0, and (B) a bisphenol A-based (meth) acrylate compound in a molecule containing as essential components. The present invention relates to a photosensitive resin composition comprising a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond and (C) a photopolymerization initiator. The present invention also relates to the photosensitive resin composition wherein (A) the binder polymer contains styrene or a styrene derivative as an essential copolymer component. The present invention also relates to the photosensitive resin composition, wherein (A) the binder polymer contains styrene or a styrene derivative in an amount of 0.1 to 30% by weight based on all copolymerized components.

The present invention also relates to the photosensitive resin composition wherein (A) the binder polymer contains methacrylic acid as an essential copolymer component. The present invention also relates to the photosensitive resin composition, wherein (A) the binder polymer has an acid value of 100 to 500 mgKOH / g. Further, the present invention relates to (A)
The weight average molecular weight of the binder polymer is from 20,000 to
300,000.

Further, the present invention provides a bisphenol A (meth) acrylate compound represented by the general formula (I):

Embedded image (Wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are such that p + q = 4 to 40) Which is a positive integer selected from the following). The present invention also relates to the photosensitive resin composition wherein X and Y are ethylene groups.

The present invention also provides a photopolymerizable compound other than the bisphenol A (meth) acrylate compound,
The present invention relates to the photosensitive resin composition containing a photopolymerizable compound having one polymerizable ethylenically unsaturated bond in a molecule as an essential component. Further, the present invention relates to the photosensitive resin composition wherein (C) the photopolymerization initiator contains 2,4,5-triarylimidazole dimer as an essential component. In the present invention, the component (A), the component (B) and the component (C) are mixed in an amount of 40 to 80 with respect to 100 parts by weight of the total of the component (A) and the component (B). Parts by weight, component (B) is 20
To 60 parts by weight, 0.1 to 20 parts by weight of the component (C), and 3 to 90% by weight of the bisphenol A (meth) acrylate compound in the component (B). .

[0012] The present invention also relates to a photosensitive element obtained by applying a layer of the photosensitive resin composition on a support and drying it. Also, the present invention provides a photosensitive method comprising applying a layer of the photosensitive resin composition on a support, drying the layer, and further laminating a protective film so as to be in contact with the layer of the photosensitive resin composition on the opposite side of the support. Sexual element. The present invention also relates to the photosensitive element, wherein the support has a thickness of 5 to 25 μm. The present invention also relates to the photosensitive element, wherein the support has a haze of 0.001 to 5.0.

[0013] The present invention also relates to the photosensitive element, wherein the layer of the photosensitive resin composition has a transmittance of 5 to 75% with respect to ultraviolet rays having a wavelength of 365 nm. The present invention also relates to the photosensitive element, wherein the protective film has a thickness of 5 to 30 μm. The present invention also relates to the photosensitive element, wherein the tensile strength of the protective film in the longitudinal direction of the film is 13 MPa or more, and the tensile strength in the longitudinal direction of the film is 9 MPa or more.

Further, according to the present invention, the photosensitive element is laminated on a circuit-forming substrate in such a manner that the photosensitive resin composition layer is in close contact with the photosensitive element while removing a protective film which may be present in some cases. The present invention relates to a method for producing a resist pattern, which comprises irradiating an exposed portion, photocuring an exposed portion, and removing an unexposed portion by development. Further, the present invention relates to a method for manufacturing a printed wiring board, wherein a circuit forming substrate on which a resist pattern is manufactured is etched or plated by the method for manufacturing a resist pattern.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto,
(Meth) acrylate means acrylate and its corresponding methacrylate, and (meth) acryloyl group means acryloyl and its corresponding methacryloyl group.

The photosensitive resin composition of the present invention comprises: (A) a binder polymer having a dispersity of from 1.0 to 3.0;
It comprises a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in a molecule containing a bisphenol A-based (meth) acrylate compound as an essential component, and (C) a photopolymerization initiator.

The binder polymer (A) preferably has a degree of dispersion (weight average molecular weight / number average molecular weight) of 1.0 to 3.0, more preferably 1.0 to 2.5. If the degree of dispersion exceeds 3.0, the adhesiveness and resolution tend to decrease. However, the weight average molecular weight and the number average molecular weight in the present invention are values measured by gel permeation chromatography and converted to standard polystyrene.

The weight average molecular weight of the binder polymer (A) is preferably from 20,000 to 300,000, more preferably from 40,000 to 150,000. When the weight average molecular weight is less than 20,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.

The (A) binder polymer includes:
There is no particular limitation as long as the degree of dispersion is 1.0 to 3.0, and examples thereof include an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, and a phenol resin. No. From the viewpoint of alkali developability, an acrylic resin is preferred. These can be used alone or in combination of two or more.

The binder polymer (A) can be produced, for example, by subjecting a polymerizable monomer to radical polymerization. Examples of the polymerizable monomer include, for example, styrene, vinyl toluene, a polymerizable styrene derivative substituted at the α-position or an aromatic ring such as α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, and vinyl. Esters of vinyl alcohol such as -n-butyl ether, alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, ( Meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (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,
Maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like can be mentioned.

Examples of the alkyl (meth) acrylate include those represented by the general formula (II):

Embedded image (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 1 to 12 carbon atoms), and the alkyl group of these compounds includes a hydroxyl group, an epoxy group, a halogen group, and the like. And the like. Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁴ in the general formula (II) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Examples include an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and structural isomers thereof.

Examples of the monomer represented by the general formula (II) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, and (meth) acrylic acid Butyl ester,
Pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Nonyl acrylate, decyl (meth) acrylate, undecyl (meth) acrylate,
And (meth) acrylic acid dodecyl ester. These can be used alone or in combination of two or more.

The binder polymer (A) in the present invention preferably contains a carboxyl group from the viewpoint of alkali developability. For example, a polymerizable monomer having a carboxyl group and another polymerizable monomer may be used. It can be produced by radical polymerization of a monomer. Further, the binder polymer as the component (A) in the present invention preferably contains styrene or a styrene derivative as a polymerizable monomer from the viewpoint of flexibility.

In order to improve both adhesion and peeling properties by using the above styrene or styrene derivative as a copolymer component, it is preferable to contain 0.1 to 30% by weight, preferably 1 to 28% by weight.
%, More preferably 1.5 to 27% by weight. If the content is less than 0.1% by weight, the adhesion tends to be poor, and if it exceeds 30% by weight, the peeled pieces tend to be large and the peeling time tends to be long.

These binder polymers are used alone or in combination of two or more. When two or more kinds are used in combination, examples of the binder polymer include two or more kinds of binder polymers composed of different copolymer components, two or more kinds of binder polymers having different weight average molecular weights, and two or more kinds of different dispersion degrees. Binder polymers and the like.

The acid value of the binder polymer (A) is as follows:
It is preferably 100 to 500 mgKOH / g,
More preferably, it is で 300 mgKOH / g. If the acid value is less than 100 mgKOH / g, the developing time tends to be slow, and if it exceeds 500 mgKOH / g, the photocured resist tends to have a reduced resistance to a developing solution.

The bisphenol A-based (meth) acrylate compound (B), which is an essential component as a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule, is not particularly limited. And a compound represented by the general formula (I). In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and is preferably a methyl group. In the general formula (I), X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, preferably an ethylene group or a propylene group, and more preferably an ethylene group.

In the general formula (I), p and q are p + q =
A positive integer chosen to be 4 to 40, 6 to 3
4, preferably from 8 to 30, more preferably from 8 to 28, and preferably from 8 to 20.
Is very preferable, and it is very especially preferable that it is 8-16, and it is very preferable that it is 8-12. When p + q is less than 4, the compatibility with the component (A) decreases, and the photosensitive element tends to peel off when the photosensitive element is laminated on the circuit-forming substrate. When p + q exceeds 40, the hydrophilicity increases, and Sometimes the resist image is easily peeled off,
Plating resistance to solder plating and the like also tends to decrease.

Examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group and a hexylene group. And isopropylene groups are preferred.

The aromatic ring in the general formula (I) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a 3 to 5 carbon atom. 10, a cycloalkyl group, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a nitro group, a cyano group, a carbonyl group, A mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an allyl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms,
Carboxyl group, carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, acyl group having 1 to 10 carbon atoms in the alkyl group, alkoxy group having 1 to 20 carbon atoms, and 1 to 2 carbon atoms
0 alkoxycarbonyl group, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, or a group containing a heterocyclic ring, Aryl group and the like. The above substituents may form a condensed ring. Further, a hydrogen atom in these substituents may be substituted with the above substituent such as a halogen atom. When the number of the substituents is 2 or more, the two or more substituents may be the same or different.

Examples of the compound represented by the general formula (I) include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-(( (Meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) ) Phenyl) propane and other bisphenol A-based (meth) acrylate compounds.

Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include, for example, 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-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonaethoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxydecaethoxy) phenyl), 2,2-bis (4-
((Meth) acryloxyundecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxydodecaethoxy) 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-(( Meta) acryloxyhexadecaethoxy)
Phenyl) and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BP
It is commercially available as E-500 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) is BPE-
It is commercially available as 1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). These are used alone or in combination of two or more.

The 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane includes
For example, 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentapropoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2
-Bis (4-((meth) acryloxyheptapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxynonapropoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxydecapropoxy) phenyl),
2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl), 2,2-bis (4-((meth)
Acryloxide decapropoxy) phenyl), 2,2-
Bis (4-((meth) acryloxytridecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxytetradecapropoxy) phenyl), 2,2-bis (4-((meth) Acryloxypentadecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxyhexadecapropoxy) phenyl) and the like. These are used alone or in combination of two or more.

The 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane includes, for example, 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) Phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane,
2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like. These are used alone or in combination of two or more.

Examples of the photopolymerizable compound other than the bisphenol A (meth) acrylate compound include a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol and an α, β-unsaturated carboxylic acid. Compounds obtained by reacting β-unsaturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond, nonylphenyldioxylene (meth) acrylate, γ-chloro-β-hydroxypropyl-β′-
(Meth) acryloyloxyethyl-o-phthalate,
β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, alkyl (meth) acrylate, EO-modified nonylphenyl Examples thereof include (meth) acrylate, and it is preferable to use a photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule. These are used alone or in combination of two or more.

Compounds obtained by reacting the above polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example,
Polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, 2 to 1 propylene groups
4, polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropanetri (meth) acrylate, trimethylolpropaneethoxytri (meth) acrylate, trimethylolpropanediethoxytri (meth) acrylate, Trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropanepentaethoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate , Polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) Rate, dipentaerythritol hexa (meth) acrylate. Examples of the α, β-unsaturated carboxylic acid include (meth) acrylic acid.

Examples of the glycidyl group-containing compound include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meth) acryloxy-2-hydroxy-propyloxy).
Phenyl etc. are fisted. Examples of the urethane monomer include (meth) acrylic monomers having an OH group at the β-position and diisocyanate compounds such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition product of tris ((meta)
(Acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. EO indicates ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. Also, PO
Represents propylene oxide, and the PO-modified compound has a propylene oxide group block structure. E
Examples of the O-modified urethane di (meth) acrylate include UA-11 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like. Examples of the EO, PO-modified urethane di (meth) acrylate include UA-13 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Is mentioned.

Examples of the photopolymerization initiator (C) in the present invention include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's 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-
Aromatic ketones such as morpholino-propanone-1, 2-
Ethyl anthraquinone, phenanthrenequinone, 2-te
rt-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-
Diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantaraquinone, 2-methyl1,4
Quinones such as naphthoquinone and 2,3-dimethylanthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; and benzyl derivatives such as benzyl dimethyl ketal. 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
2,4,5-triarylimidazole dimer such as -diphenylimidazole dimer, acridine derivative such as 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, coumarin-based compounds and the like can be mentioned.

The substituents of the aryl groups of the two 2,4,5-triarylimidazoles may be the same to give a target compound, or different asymmetric compounds may be given. Further, a thioxanthone-based compound and a tertiary amine compound may be combined like a combination of diethylthioxanthone and dimethylaminobenzoic acid. Also,
From the viewpoints of adhesion and sensitivity, 2,4,5-triarylimidazole dimer is more preferable. These are used alone or in combination of two or more.

The amount of the binder polymer (A) is preferably 40 to 80 parts by weight, and more preferably 45 to 80 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
More preferably, it is 70 parts by weight. This blending amount is 4
If it is less than 0 parts by weight, the photocured product tends to be brittle, and when used as a photosensitive element, the coating properties tend to be poor,
If it exceeds 80 parts by weight, the light sensitivity tends to be insufficient.

The amount of the photopolymerizable compound (B) is as follows:
The total amount of the components (A) and (B) is preferably 20 to 60 parts by weight based on 100 parts by weight, and 30 to 5 parts by weight.
More preferably, it is 5 parts by weight. When the blending amount is 20
If the amount is less than 10 parts by weight, the light sensitivity tends to be insufficient.
If the amount exceeds the weight part, the photocured product tends to become brittle.

The compounding amount of the bisphenol A (meth) acrylate compound, which is an essential component in the photopolymerizable compound (B), is preferably 3 to 90% by weight of the component (B). More preferably, it is 70% by weight. If the amount is less than 3% by weight, the resolution tends to be inferior, and if it exceeds 90% by weight, the resist stripping time tends to be long.

The amount of the photopolymerization initiator (C) is as follows:
It is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B),
More preferably, the amount is from 10 to 10 parts by weight. If the amount is less than 0.1 part by weight, the photosensitivity tends to be insufficient. If the amount is more than 20 parts by weight, absorption on the surface of the composition upon exposure increases, resulting in insufficient photocuring inside. It tends to be.

The photosensitive resin composition of the present invention may contain, if necessary, a dye such as malachite green, a photochromic agent such as tribromophenylsulfone or leucocrystal violet, a thermochromic inhibitor, p-toluenesulfone. Plasticizers such as amides, pigments, fillers, defoamers, flame retardants, stabilizers,
Adhesiveness-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. are each added in an amount of 0.0 to 100 parts by weight of the total of components (A) and (B).
About 1 to 20 parts by weight may be contained. They are,
Used alone or in combination of two or more.

The photosensitive resin composition of the present invention may contain, if necessary, a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether or the like. And a solution having a solid content of about 30 to 60% by weight.

The photosensitive resin composition of the present invention is not particularly limited, but is preferably a metal surface, for example, an iron-based alloy such as copper, copper-based alloy, nickel, chromium, iron, and stainless steel, and preferably copper or a copper-based alloy. Preferably, it is applied as a liquid resist on the surface of the iron-based alloy and dried, and then coated with a protective film if necessary, or used in the form of a photosensitive element.

The thickness of the photosensitive resin composition layer varies depending on the application, but is preferably from 1 to 100 μm, more preferably from 1 to 50 μm, after drying. If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the effect of the present invention is reduced, and the adhesive strength and resolution tend to be reduced.

The transmittance of the photosensitive resin composition layer to ultraviolet rays having a wavelength of 365 nm is preferably 5 to 75%, more preferably 7 to 60%, and more preferably 10 to 40%.
% Is particularly preferred. If the transmittance is less than 5%, the adhesion tends to be poor, and if it exceeds 75%, the resolution tends to be poor. The transmittance can be measured with a UV spectrometer, and examples of the UV spectrometer include a 228A W-beam spectrophotometer manufactured by Hitachi, Ltd.

The support for use as the photosensitive element preferably has a thickness of 5 to 25 μm.
It is more preferably 8 to 20 μm, and 10 to 16 μm.
m is particularly preferred. If the thickness is less than 5 μm, the support tends to be torn at the time of peeling before development.
If it exceeds μm, the resolution tends to decrease.

The haze of the above support is 0.001 to 5.0.
Is preferably, more preferably 0.001 to 2.0, and particularly preferably 0.01 to 1.8. If the haze exceeds 2.0, the resolution tends to decrease. The haze is measured according to JIS K 7105, and is, for example, NDH-100.
It can be measured with a commercially available turbidity meter such as 1DP (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.).

Examples of the support include a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene and polyester.

The protective film used as the photosensitive element preferably has a thickness of 5 to 30 μm, more preferably 10 to 28 μm, and more preferably 15 to 28 μm.
It is particularly preferable that the number is from 25 to 25. If the thickness is less than 5 μm, the protective film tends to be broken during lamination, and if it exceeds 30 μm, the cost tends to be poor.

The tensile strength of the protective film in the longitudinal direction of the film is preferably 13 MPa or more, and the tensile strength in the longitudinal direction of the film is preferably 9 MPa or more. The tensile strength in the longitudinal direction of the film is preferably 13 MPa or more, more preferably 13 to 100 MPa, and 14 MPa.
-100 MPa is particularly preferable, and 15-100 M
It is very preferable that the pressure be Pa, and it is extremely preferable that the pressure be 16 to 100 MPa. If the tensile strength is less than 13 MPa, the protective film tends to be broken during lamination. The tensile strength in the film width direction is preferably 9 MPa or more, more preferably 9 to 100 MPa, particularly preferably 10 to 100 MPa.
It is highly preferred that the pressure be 1 to 100 MPa,
It is very preferable that the pressure is 00 MPa. If the tensile strength is less than 9 MPa, the protective film tends to be broken during lamination. The tensile strength is JIS C 2318-1
997 (5.3.3),
For example, it can be measured with a commercially available tensile strength tester such as Tensilon (trade name, manufactured by Toyo Baldwin Co., Ltd.).

Further, these supports and protective films include:
Since it must be removable from the photosensitive resin composition layer later, it must not have been subjected to a surface treatment that makes removal impossible, but there is no particular limitation and treatment is performed as necessary. You may. Further, these supports and protective films may be subjected to antistatic treatment as required.

The photosensitive element composed of two layers, the support and the photosensitive resin composition layer, and the photosensitive element composed of three layers of the support, the photosensitive resin composition layer, and the protective film are obtained as described above. For example, a protective film is further laminated as it is or on the other surface of the photosensitive resin composition layer and stored in a roll shape.

In producing a resist pattern using the photosensitive element, if the above protective film is present, the protective film is removed, and the photosensitive resin composition layer is heated while forming a circuit. For example, a method of laminating by press-bonding to a substrate may be mentioned, and it is preferable to laminate under reduced pressure from the viewpoint of adhesion and followability. The surface to be laminated is usually a metal surface, but is not particularly limited. The heating temperature of the photosensitive resin composition layer is preferably from 70 to 130 ° C., and the pressing pressure is preferably from about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). There are no particular restrictions on the conditions. Further, if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the circuit formation substrate in advance,
In order to further improve the lamination property, a pre-heat treatment of the circuit forming substrate may be performed.

The photosensitive resin composition layer thus completed is irradiated with actinic rays imagewise through a negative or positive mask pattern called an artwork. At this time, when the polymer film present on the photosensitive resin composition layer is transparent, it may be irradiated with actinic light as it is, and when it is opaque, it is necessary to remove it naturally. As a light source of the actinic ray, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet rays is used. In addition, those that effectively emit visible light, such as a flood light bulb for photography and a sun lamp, are also used.

Next, after the exposure, if a support is present on the photosensitive resin composition layer, the support is removed.
Unexposed portions are removed by wet development, dry development, or the like, and developed to produce a resist pattern. In the case of wet development, using a developer corresponding to a photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, for example, developing by a known method such as spraying, rocking immersion, brushing, and scraping. I do. As the developer, a safe and stable one having good operability, such as an alkaline aqueous solution, is used.

Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate, and potassium phosphate. And alkali metal phosphates such as sodium phosphate and potassium pyrophosphate, and the like.
Further, as an alkaline aqueous solution used for development, 0.1
Dilute solution of -5 wt% sodium carbonate, dilute solution of 0.1-5 wt% potassium carbonate, dilute solution of 0.1-5 wt% sodium hydroxide, dilute solution of 0.1-5 wt% sodium tetraborate Solutions and the like are preferred. The pH of the alkaline aqueous solution used for development is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.

The aqueous developer comprises water or an aqueous alkali solution and one or more organic solvents. Here, as the alkaline substance, in addition to the above substances, for example, borax or sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,
3-propanediol, 1,3-diaminopropanol-2, morpholine and the like. The pH of the developing solution is preferably as low as possible within a range where the development of the resist can be sufficiently performed.
More preferably, it is set to 9 to 10.

Examples of the organic solvent include triacetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, and the like.
Examples thereof include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. These are used alone or in combination of two or more. Usually, the concentration of the organic solvent is preferably 2 to 90% by weight,
The temperature can be adjusted according to the developability.
Further, a small amount of a surfactant, an antifoaming agent and the like can be mixed in the aqueous developer.

The organic solvent-based developer used alone includes:
For example, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone and the like can be mentioned. It is preferable to add water to these organic solvents in a range of 1 to 20% by weight to prevent ignition. If necessary, two or more developing methods may be used in combination. Development methods include dip method, battle method,
There are spray method, brushing, slapping, etc.
The high pressure spray method is most suitable for improving the resolution.

As processing after development, if necessary,
The resist pattern may be further cured by heating at about 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² .

For etching the metal surface after development, a cupric chloride solution, a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide-based etching solution can be used. It is desirable to use a ferric solution.

When a printed wiring board is manufactured using the photosensitive element of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching and plating using the developed resist pattern as a mask. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate, solder plating such as high-throw solder plating,
There are nickel plating such as Watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and gold plating such as hard gold plating and soft gold plating.

Next, the resist pattern can be stripped with, for example, a more alkaline aqueous solution than the alkaline aqueous solution used for development. As the strong alkaline aqueous solution, for example, a 1 to 10% by weight aqueous solution of sodium hydroxide, a 1 to 10% by weight aqueous solution of potassium hydroxide or the like is used. Examples of the peeling method include an immersion method and a spray method. The immersion method and the spray method may be used alone or in combination. Further, the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board.

[0068]

The present invention will be described below with reference to examples.

Examples 1 to 4 and Comparative Examples 1 to 5 The materials shown in Table 1 were blended to obtain solutions.

[0070]

[Table 1]

The component (B) shown in Table 2 was dissolved in the obtained solution to obtain a solution of the photosensitive resin composition.

[0072]

[Table 2]

Each component (B) in Table 2 is shown below. * 1: A compound in which R ¹ and R ² are methyl groups, X and Y are ethylene groups, and k + m = 10 (average value) in the above general formula (I), manufactured by Shin-Nakamura Chemical Co., Ltd. * 2: In the general formula (I), a compound in which R ¹ and R ² represent a methyl group, X and Y represent an ethylene group, and k + m = 30 (average value), manufactured by Shin-Nakamura Chemical Co., Ltd. * 3: EO Modified nonylphenyl acrylate (8 repeating units of ethylene glycol chain), manufactured by Kyoeisha Chemical Co., Ltd. * 4: Pentaerythritol triacrylate, Nippon Kayaku
* 5: Polypropylene glycol diacrylate (the repeating unit of the propylene glycol chain is 6 to 7), manufactured by Shin-Nakamura Chemical Co., Ltd.

Then, a solution of the obtained photosensitive resin composition was applied to a 16 μm-thick polyethylene terephthalate film (haze: 1.7%, trade name: GS-16, manufactured by Teijin Limited).
And apply it uniformly on a hot air convection dryer at 100 ° C.
After drying for 10 minutes, a polyethylene protective film (tensile strength in the longitudinal direction of the film: 16 MPa, tensile strength in the width direction of the film: 12 MPa, trade name: NF-15, Tamapoli Co., Ltd.)
To obtain a photosensitive element. The dried film thickness of the photosensitive resin composition layer was 50 μm.

Next, a UV spectrometer (made by Hitachi, Ltd., 22)
The transmittance of the layer of the photosensitive resin composition to ultraviolet rays having a wavelength of 365 nm was measured using an 8A-type W-beam spectrophotometer). The transmittance was measured by first placing a support film and a photosensitive element composed of a layer of the photosensitive resin composition on the measurement side, placing the support film on the reference side, and measuring the transmittance by 70% in T% mode.
It was measured by continuously measuring from 0 to 300 μm and reading the value at 365 nm. Table 3 shows the results.

On the other hand, the copper surface of a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-61), which is a glass epoxy material having a copper foil (thickness: 35 μm) laminated on both sides, is # 6
Polishing using a polishing machine with a brush equivalent to 00 (manufactured by Sankei Co., Ltd.), washing with water, drying with an air stream, heating the obtained copper-clad laminate to 80 ° C. The photosensitive resin composition layer was laminated at a speed of 3 m / min using a heat roll at 120 ° C. while peeling off the protective film.

Next, using an exposure machine (manufactured by Oak Co., Ltd.) HMW-201B having a high-pressure mercury lamp, a 21-step stepper tablet as a negative was placed on the test piece and exposed at 60 mJ / cm ² . did.

Next, the polyethylene terephthalate film was peeled off, a 1% by weight aqueous solution of sodium carbonate was sprayed at 30 ° C. for 60 seconds to remove unexposed portions, and then the steps of the photocured film formed on the copper-clad laminate were carried out. The photosensitivity of the photosensitive resin composition was evaluated by measuring the number of tablets, and the results are shown in Table 3. The light sensitivity is indicated by the number of steps of the step tablet. The higher the number of steps of the step tablet, the higher the light sensitivity.

The resolution was as follows: a photo tool having a 21-step tablet of a stofer and a line width / space width of 10/10 to 50 /
A photo tool having a wiring pattern of 50 (unit: μm) was brought into close contact, and exposure was performed with an energy amount such that the number of remaining steps after development of the 21-step tablet of the stofer was 8.0. Here, the resolution was evaluated based on the smallest value of the space width between the line widths in which the unexposed portions could be clearly removed by the development processing. The smaller the value of the evaluation of the resolution, the better the value. The results are shown in Table 3.

The plating resistance was determined by laminating as described above, exposing with a predetermined amount of exposure, and then developing with the above-mentioned developer, and then immersing in a degreasing bath (PC-455 (manufactured by Meltex Corporation), 25% by weight). It was immersed for 5 minutes and washed with water. Next, a soft etching bath (150 g of ammonium persulfate)
/ Liter) for 2 minutes and washed with water. Then 10
A pretreatment was performed in the order of immersion in a 1% by weight sulfuric acid bath for 1 minute, and a copper sulfate plating bath (copper sulfate 75 g / liter, sulfuric acid 1
90 g / l, chloride ion 50 ppm, Copperglyme PCM (manufactured by Meltex) 5 ml / l), and copper sulfate plating was performed at room temperature at 3 A / dm ² for 40 minutes.

Thereafter, it was washed with water, immersed in 10% by weight of borofluoric acid for 1 minute, and subjected to a solder plating bath (45% by weight of tin borofluoride 64 ml / liter, 45% by weight of lead borofluoride 22 ml / liter, 42% by weight). % Borofluoric acid 200 ml / l, Plutin LA conductivity salt (manufactured by Meltex) 20 g / l, Plutin LA starter (manufactured by Meltex) 41 ml / l), and solder plating was carried out at room temperature. Performed at 5 A / dm ² for 15 minutes.

After washing with water and drying, a 90 ° peel-off test was immediately performed to check the plating resistance. The results are shown in Table 3. The 90 ° peel-off test is to attach a cellophane tape to a plated substrate, adhere it well with a rubber roller, immediately peel it off at a peel angle of 90 ° C, and observe the degree of resist transfer to the cellophane tape. is there. After the peel-off test at 90 ° C., the resist was peeled off, and the presence or absence of solder plating was observed from above using an optical microscope, a projector or the like. The results are shown in Table 3. When the solder plating is buried, solder deposited by solder plating is observed below the transparent resist through the transparent resist.

Further, another test piece was subjected to a cross cut test (JIS-K-5400) after exposure and development with a stofer 21-step tablet at an exposure amount indicating 8 steps, and the results are shown in Table 3. Was. The cross-cut test is to draw 11 perpendicular and 11 parallel lines at 1 mm intervals using a cutter guide at the center of the circuit-forming substrate on which the photosensitive elements are stacked, and 100 lines in 1 cm ² Is to make a grid-like cut so as to form a square, and evaluate the state of the scratch. In addition, the cut was made so that the cutting edge of the cutter knife was maintained at a fixed angle of 35 to 45 degrees with respect to the photosensitive element, and penetrated the photosensitive resin composition layer to reach the circuit forming substrate. The book is drawn at a constant speed over 0.5 seconds. The evaluation of the state of the flaw is as follows.

10 points: Each cut is thin, both sides are smooth, and the intersection of the cut and the square are not peeled at every glance. Eight points: There is slight peeling at the intersection of the cuts, no peeling at a glance, and the area of the defect is within 5% of the area of the entire square. 6 points: Both sides of the cut and the intersection are peeled, and the area of the defective portion is 5 to 15% of the total square area. 4 points: The width of the peeling due to the cut is wide, and the area of the defective portion is 15 to 35% of the total square area. 2 points: The width of the peeling due to the cut is wider than 4 points, and the area of the defective portion is 35 to 65% of the area of the entire square. 0 point: The area of the defective portion is 65% or more of the area of the entire square.

[0085]

[Table 3]

As is clear from Table 3, Examples 1-4
Has excellent resolution and cross-cutting properties and good plating resistance.

[0087]

The photosensitive resin composition according to claim 1 is excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength and flexibility, and has a high density and high printed wiring. Useful for resolution. The photosensitive resin compositions according to claims 2 and 3 exhibit the effects of the invention according to claim 1, and are further excellent in chemical resistance. The photosensitive resin compositions according to the fourth, fifth and sixth aspects have further excellent alkali developability in addition to the effects of the first, second or third aspect of the invention.

The photosensitive resin compositions according to claims 7 and 8 exhibit the effects of the invention according to claim 1, 2 or 3, and are further excellent in photosensitivity and chemical resistance (plating resistance). The photosensitive resin composition according to the ninth aspect has the effects of the invention according to the first, second, or third aspect, and further has excellent peeling properties. Claim 10 is a photosensitive resin composition,
The effects of the invention described in 4, 5, 6, 7, 8 or 9 are exhibited, and the adhesion is further excellent. The photosensitive resin composition according to claim 11 achieves the effects of the invention according to claims 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and further has photosensitivity, resolution,
Excellent chemical resistance (plating resistance), adhesion, mechanical strength and flexibility.

The photosensitive elements according to claims 12 and 13 are excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, flexibility, workability and productivity. The photosensitive element according to claim 14 and claim 15 is the same as claim 1.
The effects of the invention described in 2 or 13 are exhibited, and the resolution is further improved. A photosensitive element according to claim 16 is a photosensitive element according to claim 1.
The effects of the invention described in 2, 13, 14 or 15 are exhibited, and the resolution is further improved. The photosensitive element according to claims 17 and 18 has further excellent laminating properties in addition to the effects of the invention according to claims 12 or 13.

The method for producing a resist pattern according to claim 19 is excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, flexibility, workability and productivity. The method for manufacturing a printed wiring board according to claim 20 is excellent in light sensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, flexibility, environment, workability, and productivity.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 9, 2001 (2001.1.9)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Statement

Patent application title: Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern, and method for producing printed wiring board

[Claims]

3. A bar Indah polymer, photosensitive resin composition according to claim 2 wherein the styrene or styrene derivative as an essential copolymerization component.

4. A bus Indah polymer of styrene or a styrene derivative with respect to the total copolymerizable component, the photosensitive resin composition according to claim 1 or 3, wherein containing 0.1 to 30 wt%.

5. A bar Indah polymer, according to claim 1 for the methacrylic acid as an essential copolymerization component, 3 or 4 photosensitive resin composition.

6. The acid value of the bus Indah polymer is 100 to 5
00mgKOH / g and a claim 1, 2, 3, 4 or 5 the photosensitive resin composition.

7. The method of claim 1 the weight average molecular weight of Ba Indah polymer is 20,000 to 300,000,
7. The photosensitive resin composition according to 3 , 4 , 5, or 6 .

8. A bisphenol A (meth) acrylate compound represented by the general formula (I):

Embedded image (Wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are such that p + q = 4 to 40) The photosensitive resin composition according to claim 1, 2 , 3 , 4 , 5 , 6, or 7 , which is a compound represented by the following formula:

9. The photosensitive resin composition according to claim 8, wherein X and Y are ethylene groups.

10. A photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule as an essential component as a photopolymerizable compound other than the bisphenol A-based (meth) acrylate compound. 3, 4, 5, 6,
The photosensitive resin composition according to 7 , 8 or 9 .

11. The method of claim 1, the photopolymerization initiator is a 2,4,5-triaryl imidazole dimer as an essential component,
The photosensitive resin composition according to 3 , 4, 5, 6, 7, 8 , 9 or 10 .

12. A binder polymer component and photopolymerization.
Amount of compound ingredients and a photopolymerization initiator component, a binder
The binder polymer component is 40 to 80 parts by weight, the photopolymerizable compound component is 20 to 60 parts by weight, and the photopolymerization is based on 100 parts by weight of the total of the polymer component and the photopolymerizable compound component.
The initiator component is 0.1 to 20 parts by weight, and the bisphenol A (meth) acrylate compound is photopolymerizable.
3 to 90% by weight of the compound component.
The photosensitive resin composition according to 4 , 5 , 6 , 7 , 8 , 9 , 10 or 11 .

15. The method of claim 1, 2, 3, 4,
13. A photosensitive element obtained by applying a layer of the photosensitive resin composition according to 8 , 9 , 10 , 11 or 12 on a support and drying.

16. The method of claim 1, 2, 3, 4, 5, 6, 7,
A layer of the photosensitive resin composition according to 8 , 9 , 10 , 11 or 12 is coated on a support and dried, and a protective film is laminated so as to be in contact with the layer of the photosensitive resin composition on the opposite side of the support. Photosensitive element made.

17. The photosensitive element of claim 13, 14, 15 or 16, wherein the thickness of the support is 5 to 25 [mu] m.

The haze of 18. The support is 0.001 to 5.0
18. The photosensitive element according to claim 14, 15, 16 or 17 .

Claims19A wavelength of the photosensitive resin composition layer is 365 nm.
Has a transmittance of 5 to 75% for ultraviolet rays.Item 1
3, 14, 15, 16, 17Or18The photosensitive element described in
Ment.

20. The protective film according to claim 1 4 has a thickness of 5~30μm of, 16, 17, 18 or 19 photosensitive element according.

21. is a longitudinal direction of the film tensile strength of the protective film is 13MPa or more, according to claim 1 6 tensile strength of the film longitudinal direction is not less than 9 MPa, 17, 18, 19
Or the photosensitive element of 20 .

22. The method of claim 1 3,14,15,16,1
7 , the photosensitive element according to 18, 19, 20 or 21 is laminated on a circuit-forming substrate in such a manner that the photosensitive resin composition layer is in close contact with the photosensitive element while peeling off a protective film which may be present in some cases. A method for producing a resist pattern, comprising irradiating an image, curing an exposed portion with light, and removing an unexposed portion by development.

23. A method for manufacturing a printed wiring board, comprising etching or plating a circuit-forming substrate on which a resist pattern has been manufactured by the method for manufacturing a resist pattern according to claim 22 .

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board.

[0002]

2. Description of the Related Art Conventionally, in the field of manufacturing printed wiring boards, a photosensitive resin composition and a photosensitive element obtained using a support and a protective film have been widely used as a resist material for etching, plating, and the like. Have been. Printed wiring board, after laminating the photosensitive element on a copper substrate, pattern exposure, remove the unexposed part with a developing solution, subjected to etching or plating,
It is manufactured by a method of peeling and removing a cured portion from a substrate after forming a pattern. As a developing solution for removing the unexposed portion, an alkali developing type using a sodium hydrogen carbonate solution or the like has become mainstream.
Usually, it can be used as long as it has the ability to dissolve the photosensitive resin composition layer to some extent, and at the time of development, the photosensitive resin composition is dissolved or dispersed in a developer.

With the recent increase in the density of printed wiring boards,
Since the contact area between the copper substrate and the patterned photosensitive resin composition layer is reduced, excellent adhesive strength, mechanical strength, chemical resistance, flexibility, etc. are required in the development, etching or plating process steps, and Resolution is required. Among such properties, a method using a photopolymerizable compound having a bisphenol A skeleton to improve chemical resistance is disclosed in Japanese Patent Publication No.
As described in Japanese Patent No. 27205, if the binder polymer has a large degree of dispersion, the adhesion and the resolution tend to be reduced.

[0004]

The inventions according to claims 1 and 2 provide a photosensitive resin composition which is excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength and flexibility. This is useful for increasing the density and resolution of printed wiring. The inventions of claims 3 and 4 provide the effects of the invention of claim 1 or 2 and provide a photosensitive resin composition having excellent chemical resistance. Claim
The inventions described in 5, 6, and 7 provide a photosensitive resin composition having excellent alkali developability in addition to the effects of the inventions described in claims 1, 2 , 3, and 4 .

[0005] The invention according to claims 8 and 9 is based on claim 1,
The present invention provides a photosensitive resin composition having the effects of the invention described in 2 , 3, 4, 5, 6, or 7 , and further having excellent photosensitivity and chemical resistance (plating resistance). The invention according to claim 10 provides the effects of the invention according to claims 1, 2 , 3, 4, 5, 6 , 7 , 8 or 9 , and provides a photosensitive resin composition having excellent peeling properties. is there. The eleventh aspect of the present invention provides the first , third , fourth , fifth , sixth , seventh , eighth , ninth, or tenth aspects .
It is intended to provide a photosensitive resin composition having the effects of the described invention and further having excellent adhesion. The invention according to claim 12 is the invention according to claims 1, 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 1,
It is intended to provide a photosensitive resin composition which exhibits the effects of the invention described in 0 or 11 , and is excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength and flexibility.

The invention according to claims 13, 15 and 16 is:
An object of the present invention is to provide a photosensitive element having excellent light sensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, flexibility, workability, and productivity. The invention according to claim 14
Means light sensitivity, resolution, chemical resistance (plating resistance), adhesion
Properties, mechanical strength, flexibility, laminating properties, workability and production
It is intended to provide a photosensitive element having excellent properties. The inventions according to claims 17 and 18 are directed to claims 13, 14 , 1
It is intended to provide a photosensitive element exhibiting the effects of the invention described in 5 or 16 and further having excellent resolution. Claim 1
The invention described in Item 9 is Claims 13, 14 , 15, 16, 17
Another object of the present invention is to provide a photosensitive element exhibiting the effects of the invention described in Item 18 , and further having excellent resolution. Claim 20
And 21 are claimed in claims 14, 16, 17, 18
Another object of the present invention is to provide a photosensitive element having excellent laminating properties in addition to the effects of the invention described in Item 19 .

The invention according to claim 22 provides a method for producing a resist pattern excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, flexibility, workability and productivity. It is. The invention according to claim 23 provides a method for manufacturing a printed wiring board excellent in light sensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, flexibility, environment, workability, and productivity. Things.

[0008]

According to the present invention, there is provided an (A ′ ) st
A binder polymer having a dispersity of from 1.0 to 3.0, in which a styrene or styrene derivative is an essential copolymerizable component , (B)
Photosensitive resin composition comprising a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in a molecule containing a bisphenol A (meth) acrylate compound as an essential component, and (C) a photopolymerization initiator About things. Ma
In addition, the present invention provides (A) a bag having a dispersity of 1.0 to 3.0.
Inder polymer, (B) bisphenol A (meta)
At least within the molecule containing an acrylate compound as an essential component
Also has a polymerizable ethylenically unsaturated bond.
Compound and (C ') 2,4,5-triarylimy
Contains photopolymerization initiator containing dazole dimer as an essential component
A photosensitive resin composition comprising: Further, the present invention is Ba <br/> Indah polymer, about the photosensitive resin composition of the styrene or styrene derivative as an essential copolymerization component.
Further, the present invention is Ba Indah polymer of styrene or a styrene derivative with respect to the total copolymerizable component, to the photosensitive resin composition containing 0.1 to 30 wt%.

[0009] In addition, the present invention is, bar Indah polymer,
The present invention relates to the photosensitive resin composition containing methacrylic acid as an essential copolymer component. The present invention also relates to the photosensitive resin composition the acid value of the bus Indah polymer is 100~500mgKOH / g. The present invention also relates to the photosensitive resin composition weight average molecular weight of Ba Indah polymer is 20,000 to 300,000.

Further, the present invention provides a bisphenol A (meth) acrylate compound represented by the general formula (I):

Embedded image (Wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are such that p + q = 4 to 40) Which is a positive integer selected from the following). The present invention also relates to the photosensitive resin composition wherein X and Y are ethylene groups.

The present invention also provides a photopolymerizable compound other than the bisphenol A (meth) acrylate compound,
The present invention relates to the photosensitive resin composition containing a photopolymerizable compound having one polymerizable ethylenically unsaturated bond in a molecule as an essential component. In the present invention , the photopolymerization initiator is 2, 4,
The present invention relates to the photosensitive resin composition containing a 5-triarylimidazole dimer as an essential component. In addition, the present invention is, by
Underpolymer component, photopolymerizable compound component and photopolymerization
The amount of the initiator component depends on the binder polymer component and the light weight.
100 parts by weight of the total amount of the compatible compound components and the binder
40-80 parts by weight of the polymer component, the photopolymerizable compound component is 20 to 60 parts by weight and the photopolymerization initiator component from 0.1 to 2
The present invention relates to the photosensitive resin composition, wherein the photosensitive resin composition is 0 parts by weight and the bisphenol A (meth) acrylate compound accounts for 3 to 90% by weight of the photopolymerizable compound component.

Further , the present invention relates to (A) having a dispersity of 1.0 to 1.0.
3.0 Binder Polymer, (B) Bisphenol
(A) (meth) acrylate compound as an essential component
At least one polymerizable ethylenically unsaturated bond in the
Containing a photopolymerizable compound having a copolymerization and a photopolymerization initiator (C).
The layer of the photosensitive resin composition has a haze of 0.001.
Photosensitivity obtained by coating and drying on a support having a molecular weight of 5.0
Regarding the element. Further, the present invention provides (A) a dispersion degree
A binder polymer having a ratio of 1.0 to 3.0, (B) bis
Phenol A (meth) acrylate compound as an essential component
At least one polymerizable ethylenic in the molecule
Photopolymerizable compound having unsaturated bond and (C) photopolymerization
A layer of a photosensitive resin composition containing an initiator is placed on a support.
Coated and dried, and the photosensitive resin set on the opposite side of the support
The tensile strength in the longitudinal direction of the film is in contact with the product layer.
13MPa or more, tensile strength in film longitudinal direction is 9M
Photosensitive element laminated with a protective film of Pa or more
About the event. The present invention also relates to a photosensitive element obtained by applying a layer of the photosensitive resin composition on a support and drying the layer. Also, the present invention provides a photosensitive method comprising applying a layer of the photosensitive resin composition on a support, drying the layer, and further laminating a protective film so as to be in contact with the layer of the photosensitive resin composition on the opposite side of the support. Sexual element. The present invention also relates to the photosensitive element, wherein the support has a thickness of 5 to 25 μm. The present invention also relates to the photosensitive element, wherein the support has a haze of 0.001 to 5.0.

The present invention also relates to the photosensitive element, wherein the layer of the photosensitive resin composition has a transmittance of 5 to 75% for ultraviolet rays having a wavelength of 365 nm. The present invention also relates to the photosensitive element, wherein the protective film has a thickness of 5 to 30 μm. The present invention also relates to the photosensitive element, wherein the tensile strength of the protective film in the longitudinal direction of the film is 13 MPa or more, and the tensile strength in the longitudinal direction of the film is 9 MPa or more.

Further, according to the present invention, the photosensitive element is laminated on a circuit-forming substrate in such a manner that the photosensitive resin composition layer is in close contact with the photosensitive element while removing a protective film which may be present in some cases. The present invention relates to a method for producing a resist pattern, which comprises irradiating an exposed portion, photocuring an exposed portion, and removing an unexposed portion by development. Further, the present invention relates to a method for manufacturing a printed wiring board, wherein a circuit forming substrate on which a resist pattern is manufactured is etched or plated by the method for manufacturing a resist pattern.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto,
(Meth) acrylate means acrylate and its corresponding methacrylate, and (meth) acryloyl group means acryloyl and its corresponding methacryloyl group.

The photosensitive resin composition of the present invention, (A ') scan
A binder polymer having a dispersity of 1.0 to 3.0, which comprises a styrene or styrene derivative as an essential copolymerizable component;
It comprises (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in a molecule containing a bisphenol A-based (meth) acrylate compound as an essential component, and (C) a photopolymerization initiator. In addition, the sense of the present invention
The light-sensitive resin composition has (A) a degree of dispersion of 1.0 to 3.0.
Binder polymer, (B) bisphenol A
(T) A small amount in the molecule containing an acrylate compound as an essential component.
Having at least one polymerizable ethylenically unsaturated bond
Photopolymerizable compound and (C ′) 2,4,5-triaryl
Including a photopolymerization initiator containing an imidazole dimer as an essential component
Have.

The upper Kiba Indah polymer preferably has a degree of dispersion (weight average molecular weight / number average molecular weight) of 1.0 to 3.0, more preferably 1.0 to 2.5. If the degree of dispersion exceeds 3.0, the adhesiveness and resolution tend to decrease. However, the weight average molecular weight and the number average molecular weight in the present invention are values measured by gel permeation chromatography and converted to standard polystyrene.

[0018] The weight average molecular weight above Fang Indah polymer is preferably 20,000 to 300,000, and more preferably 40,000～150,000. When the weight average molecular weight is less than 20,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.

[0019] As the above Kiba Indah polymer, the degree of dispersion is not particularly limited as long as it is 1.0 to 3.0, for example, acrylic resins, styrene resins, epoxy resins, amide resins, amide-epoxy Resin, alkyd-based resin, phenol-based resin and the like can be mentioned. From the viewpoint of alkali developability, an acrylic resin is preferred. These can be used alone or in combination of two or more.

The upper Kiba Indah polymers, for example, a polymerizable monomer can be produced by radical polymerization. Examples of the polymerizable monomer include, for example, styrene, vinyl toluene, a polymerizable styrene derivative substituted at the α-position or an aromatic ring such as α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, and vinyl. Esters of vinyl alcohol such as -n-butyl ether, alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, ( (Meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acryl Acid, α-chlor ( Data) acrylic acid,
β-furyl (meth) acrylic acid, β-styryl (meth)
Monoesters of maleic acid such as acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiol Acids and the like.

Examples of the alkyl (meth) acrylate include those represented by the general formula (II):

Embedded image (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 1 to 12 carbon atoms), and the alkyl group of these compounds includes a hydroxyl group, an epoxy group, a halogen group, and the like. And the like. Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁴ in the general formula (II) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Examples include an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and structural isomers thereof.

Examples of the monomer represented by the general formula (II) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, and (meth) acrylic acid Butyl ester,
Pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Nonyl acrylate, decyl (meth) acrylate, undecyl (meth) acrylate,
And (meth) acrylic acid dodecyl ester. These can be used alone or in combination of two or more.

Further, resolver Indah polymer put the present invention, the alkali developability of the viewpoint, it is preferable to contain a carboxyl group, for example, polymerizable monomer and other polymerizable monomer having a carboxyl group Can be produced by radical polymerization. Moreover, Luba Indah polymer put the present invention <br/> is preferably from the viewpoint of flexibility is contained styrene or a styrene derivative as a polymerizable monomer.

In order to improve both adhesion and peeling properties by using the above styrene or styrene derivative as a copolymer component, it is preferable to contain 0.1 to 30% by weight, preferably 1 to 28% by weight.
%, More preferably 1.5 to 27% by weight. If the content is less than 0.1% by weight, the adhesion tends to be poor, and if it exceeds 30% by weight, the peeled pieces tend to be large and the peeling time tends to be long.

These binder polymers are used alone or in combination of two or more. When two or more kinds are used in combination, examples of the binder polymer include two or more kinds of binder polymers composed of different copolymer components, two or more kinds of binder polymers having different weight average molecular weights, and two or more kinds of different dispersion degrees. Binder polymers and the like.

[0026] before Kiba Indah acid value of the polymer, 100
~ 500mgKOH / g, preferably 100 ~ 30mgKOH / g.
More preferably, it is 0 mgKOH / g. This acid value is 10
If the amount is less than 0 mgKOH / g, the developing time tends to be slow.
If it exceeds 00 mgKOH / g, the photocured resist tends to have a reduced resistance to developing solution.

The bisphenol A-based (meth) acrylate compound (B), which is an essential component as a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule, is not particularly limited. And a compound represented by the general formula (I). In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and is preferably a methyl group. In the general formula (I), X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, preferably an ethylene group or a propylene group, and more preferably an ethylene group.

In the general formula (I), p and q are p + q =
A positive integer chosen to be 4 to 40, 6 to 3
4, preferably from 8 to 30, more preferably from 8 to 28, and preferably from 8 to 20.
Is very preferable, and it is very especially preferable that it is 8-16, and it is very preferable that it is 8-12. If p + q is less than 4, the compatibility with the binder polymer component is reduced, and the photosensitive element tends to peel off when the photosensitive element is laminated on a circuit-forming substrate.
If it exceeds 0, the hydrophilicity increases, the resist image tends to peel off during development, and the plating resistance to solder plating or the like tends to decrease.

Examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group and a hexylene group. And isopropylene groups are preferred.

The aromatic ring in the general formula (I) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a 3 to 5 carbon atom. 10, a cycloalkyl group, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a nitro group, a cyano group, a carbonyl group, A mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an allyl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms,
Carboxyl group, carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, acyl group having 1 to 10 carbon atoms in the alkyl group, alkoxy group having 1 to 20 carbon atoms, and 1 to 2 carbon atoms
0 alkoxycarbonyl group, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, or a group containing a heterocyclic ring, Aryl group and the like. The above substituents may form a condensed ring. Further, a hydrogen atom in these substituents may be substituted with the above substituent such as a halogen atom. When the number of the substituents is 2 or more, the two or more substituents may be the same or different.

Examples of the compound represented by the general formula (I) include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-(( (Meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) ) Phenyl) propane and other bisphenol A-based (meth) acrylate compounds.

Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include, for example, 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-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonaethoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxydecaethoxy) phenyl), 2,2-bis (4-
((Meth) acryloxyundecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxydodecaethoxy) 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-(( Meta) acryloxyhexadecaethoxy)
Phenyl) and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BP
It is commercially available as E-500 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) is BPE-
It is commercially available as 1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). These are used alone or in combination of two or more.

The 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane includes
For example, 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentapropoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2
-Bis (4-((meth) acryloxyheptapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxynonapropoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxydecapropoxy) phenyl),
2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl), 2,2-bis (4-((meth)
Acryloxide decapropoxy) phenyl), 2,2-
Bis (4-((meth) acryloxytridecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxytetradecapropoxy) phenyl), 2,2-bis (4-((meth) Acryloxypentadecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxyhexadecapropoxy) phenyl) and the like. These are used alone or in combination of two or more.

The 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane includes, for example, 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) Phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane,
2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like. These are used alone or in combination of two or more.

Examples of the photopolymerizable compound other than the bisphenol A (meth) acrylate compound include a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol and an α, β-unsaturated carboxylic acid. Compounds obtained by reacting β-unsaturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond, nonylphenyldioxylene (meth) acrylate, γ-chloro-β-hydroxypropyl-β′-
(Meth) acryloyloxyethyl-o-phthalate,
β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, alkyl (meth) acrylate, EO-modified nonylphenyl Examples thereof include (meth) acrylate, and it is preferable to use a photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule. These are used alone or in combination of two or more.

Compounds obtained by reacting the above polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example,
Polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, 2 to 1 propylene groups
4, polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropanetri (meth) acrylate, trimethylolpropaneethoxytri (meth) acrylate, trimethylolpropanediethoxytri (meth) acrylate, Trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropanepentaethoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate , Polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) Rate, dipentaerythritol hexa (meth) acrylate. Examples of the α, β-unsaturated carboxylic acid include (meth) acrylic acid.

Examples of the glycidyl group-containing compound include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meth) acryloxy-2-hydroxy-propyloxy).
Phenyl etc. are fisted. Examples of the urethane monomer include (meth) acrylic monomers having an OH group at the β-position and diisocyanate compounds such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition product of tris ((meta)
(Acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. EO indicates ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. Also, PO
Represents propylene oxide, and the PO-modified compound has a propylene oxide group block structure. E
Examples of the O-modified urethane di (meth) acrylate include UA-11 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like. Examples of the EO, PO-modified urethane di (meth) acrylate include UA-13 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Is mentioned.

[0039] The photopolymerization initiator that put the present invention, for example, benzophenone, N, N'-tetramethyl-4,
4'-diaminobenzophenone (Michler's ketone),
N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4
-Morpholinophenyl) -butanone-1,2-methyl-
Aromatic ketones such as 1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2
-Benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-
Quinones such as phenantaraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether,
Benzoin ether compounds such as benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, 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
2,4,5-triarylimidazole dimer such as-(p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9,9'-acridinyl) Examples include acridine derivatives such as heptane, N-phenylglycine, N-phenylglycine derivatives, and coumarin-based compounds.

The substituents of the aryl groups of the two 2,4,5-triarylimidazoles may be the same to give a target compound, or different asymmetric compounds may be given. Further, a thioxanthone-based compound and a tertiary amine compound may be combined like a combination of diethylthioxanthone and dimethylaminobenzoic acid. Also,
From the viewpoints of adhesion and sensitivity, 2,4,5-triarylimidazole dimer is more preferable. These are used alone or in combination of two or more.

[0041] The amount of the previous tusks Indah polymer is, by
Total amount of blender polymer component and photopolymerizable compound component 10
The amount is preferably from 40 to 80 parts by weight, more preferably from 45 to 70 parts by weight, based on 0 parts by weight. When the amount is less than 40 parts by weight, the photocured product tends to be brittle, and when used as a photosensitive element, the coating properties tend to be poor. When the amount exceeds 80 parts by weight, the light sensitivity tends to be insufficient. is there.

[0042] The amount of pre-Symbol photopolymerizable compound, a binder
-The amount is preferably 20 to 60 parts by weight, more preferably 30 to 55 parts by weight, based on 100 parts by weight of the total of the polymer component and the photopolymerizable compound component. If the amount is less than 20 parts by weight, the photosensitivity tends to be insufficient, and if it exceeds 60 parts by weight, the photocured product tends to be brittle.

[0043] The amount of the essential components in which the bisphenol A-based (meth) acrylate compound of the photopolymerizable compound is preferably from 3 to 90% by weight in the photopolymerizable compound component, 5-70 % Is more preferable. If the amount is less than 3% by weight, the resolution tends to be inferior, and if it exceeds 90% by weight, the resist stripping time tends to be long.

[0044] The amount of pre-Symbol photoinitiators binder
The amount is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the total amount of the polymer component and the photopolymerizable compound component. If the amount is less than 0.1 part by weight, the photosensitivity tends to be insufficient. If the amount is more than 20 parts by weight, absorption on the surface of the composition upon exposure increases, resulting in insufficient photocuring inside. It tends to be.

The photosensitive resin composition of the present invention may contain, if necessary, a dye such as malachite green, a photochromic agent such as tribromophenylsulfone or leucocrystal violet, a thermochromic inhibitor, p-toluenesulfone. Plasticizers such as amides, pigments, fillers, defoamers, flame retardants, stabilizers,
Adhesion imparting agents, leveling agents, release promoters, antioxidants, fragrances, imaging agent, thermal crosslinking agent or the like Binder
Each of the polymer component and the photopolymerizable compound component can be contained in an amount of about 0.01 to 20 parts by weight based on 100 parts by weight in total. These are used alone or in combination of two or more.

The photosensitive resin composition of the present invention may contain, if necessary, a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether or the like. And a solution having a solid content of about 30 to 60% by weight.

The photosensitive resin composition of the present invention is not particularly limited, but is preferably a metal surface, for example, an iron-based alloy such as copper, copper-based alloy, nickel, chromium, iron, and stainless steel, and preferably copper or a copper-based alloy. Preferably, it is applied as a liquid resist on the surface of the iron-based alloy and dried, and then coated with a protective film if necessary, or used in the form of a photosensitive element.

The thickness of the photosensitive resin composition layer varies depending on the application, but is preferably from 1 to 100 μm, more preferably from 1 to 50 μm, after drying. If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the effect of the present invention is reduced, and the adhesive strength and resolution tend to be reduced.

The transmittance of the photosensitive resin composition layer to ultraviolet rays having a wavelength of 365 nm is preferably 5 to 75%, more preferably 7 to 60%, and more preferably 10 to 40%.
% Is particularly preferred. If the transmittance is less than 5%, the adhesion tends to be poor, and if it exceeds 75%, the resolution tends to be poor. The transmittance can be measured with a UV spectrometer, and examples of the UV spectrometer include a 228A W-beam spectrophotometer manufactured by Hitachi, Ltd.

The support for use as the photosensitive element preferably has a thickness of 5 to 25 μm.
It is more preferably 8 to 20 μm, and 10 to 16 μm.
m is particularly preferred. If the thickness is less than 5 μm, the support tends to be torn at the time of peeling before development.
If it exceeds μm, the resolution tends to decrease.

The haze of the above support is 0.001 to 5.0.
Is preferably, more preferably 0.001 to 2.0, and particularly preferably 0.01 to 1.8. If the haze exceeds 2.0, the resolution tends to decrease. The haze is measured according to JIS K 7105, and is, for example, NDH-100.
It can be measured with a commercially available turbidity meter such as 1DP (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.).

Examples of the support include a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene and polyester.

The protective film used as the photosensitive element preferably has a thickness of 5 to 30 μm, more preferably 10 to 28 μm, and more preferably 15 to 28 μm.
It is particularly preferable that the number is from 25 to 25. If the thickness is less than 5 μm, the protective film tends to be broken during lamination, and if it exceeds 30 μm, the cost tends to be poor.

The tensile strength of the protective film in the longitudinal direction of the film is preferably 13 MPa or more, and the tensile strength in the longitudinal direction of the film is preferably 9 MPa or more. The tensile strength in the longitudinal direction of the film is preferably 13 MPa or more, more preferably 13 to 100 MPa, and 14 MPa.
-100 MPa is particularly preferable, and 15-100 M
It is very preferable that the pressure be Pa, and it is extremely preferable that the pressure be 16 to 100 MPa. If the tensile strength is less than 13 MPa, the protective film tends to be broken during lamination. The tensile strength in the film width direction is preferably 9 MPa or more, more preferably 9 to 100 MPa, particularly preferably 10 to 100 MPa.
It is highly preferred that the pressure be 1 to 100 MPa,
It is very preferable that the pressure is 00 MPa. If the tensile strength is less than 9 MPa, the protective film tends to be broken during lamination. The tensile strength is JIS C 2318-1
997 (5.3.3),
For example, it can be measured with a commercially available tensile strength tester such as Tensilon (trade name, manufactured by Toyo Baldwin Co., Ltd.).

Further, these supports and protective films include:
Since it must be removable from the photosensitive resin composition layer later, it must not have been subjected to a surface treatment that makes removal impossible, but there is no particular limitation and treatment is performed as necessary. You may. Further, these supports and protective films may be subjected to antistatic treatment as required.

The photosensitive element composed of two layers, the support and the photosensitive resin composition layer, and the photosensitive element composed of three layers of the support, the photosensitive resin composition layer, and the protective film are obtained as described above. For example, a protective film is further laminated as it is or on the other surface of the photosensitive resin composition layer and stored in a roll shape.

In producing a resist pattern using the photosensitive element, if the above protective film is present, the protective film is removed, and the photosensitive resin composition layer is heated while forming a circuit. For example, a method of laminating by press-bonding to a substrate may be mentioned, and it is preferable to laminate under reduced pressure from the viewpoint of adhesion and followability. The surface to be laminated is usually a metal surface, but is not particularly limited. The heating temperature of the photosensitive resin composition layer is preferably from 70 to 130 ° C., and the pressing pressure is preferably from about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). There are no particular restrictions on the conditions. Further, if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the circuit formation substrate in advance,
In order to further improve the lamination property, a pre-heat treatment of the circuit forming substrate may be performed.

The photosensitive resin composition layer thus completed is irradiated with actinic rays imagewise through a negative or positive mask pattern called an artwork. At this time, when the polymer film present on the photosensitive resin composition layer is transparent, it may be irradiated with actinic light as it is, and when it is opaque, it is necessary to remove it naturally. As a light source of the actinic ray, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet rays is used. In addition, those that effectively emit visible light, such as a flood light bulb for photography and a sun lamp, are also used.

Next, after the exposure, if a support is present on the photosensitive resin composition layer, the support is removed.
Unexposed portions are removed by wet development, dry development, or the like, and developed to produce a resist pattern. In the case of wet development, using a developer corresponding to a photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, for example, developing by a known method such as spraying, rocking immersion, brushing, and scraping. I do. As the developer, a safe and stable one having good operability, such as an alkaline aqueous solution, is used.

Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate, and potassium phosphate. And alkali metal phosphates such as sodium phosphate and potassium pyrophosphate, and the like.
Further, as an alkaline aqueous solution used for development, 0.1
Dilute solution of -5 wt% sodium carbonate, dilute solution of 0.1-5 wt% potassium carbonate, dilute solution of 0.1-5 wt% sodium hydroxide, dilute solution of 0.1-5 wt% sodium tetraborate Solutions and the like are preferred. The pH of the alkaline aqueous solution used for development is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.

The aqueous developer comprises water or an aqueous alkali solution and one or more organic solvents. Here, as the alkaline substance, in addition to the above substances, for example, borax or sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,
3-propanediol, 1,3-diaminopropanol-2, morpholine and the like. The pH of the developing solution is preferably as low as possible within a range where the development of the resist can be sufficiently performed.
More preferably, it is set to 9 to 10.

Examples of the organic solvent include triacetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, and the like.
Examples thereof include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. These are used alone or in combination of two or more. Usually, the concentration of the organic solvent is preferably 2 to 90% by weight,
The temperature can be adjusted according to the developability.
Further, a small amount of a surfactant, an antifoaming agent and the like can be mixed in the aqueous developer.

The organic solvent-based developer used alone includes:
For example, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone and the like can be mentioned. It is preferable to add water to these organic solvents in a range of 1 to 20% by weight to prevent ignition. If necessary, two or more developing methods may be used in combination. Development methods include dip method, battle method,
There are spray method, brushing, slapping, etc.
The high pressure spray method is most suitable for improving the resolution.

As processing after development, if necessary,
The resist pattern may be further cured by heating at about 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² .

For etching the metal surface after development, a cupric chloride solution, a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide-based etching solution can be used. It is desirable to use a ferric solution.

When a printed wiring board is manufactured using the photosensitive element of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching and plating using the developed resist pattern as a mask. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate, solder plating such as high-throw solder plating,
There are nickel plating such as Watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and gold plating such as hard gold plating and soft gold plating.

Next, the resist pattern can be stripped with, for example, a more alkaline aqueous solution than the alkaline aqueous solution used for development. As the strong alkaline aqueous solution, for example, a 1 to 10% by weight aqueous solution of sodium hydroxide, a 1 to 10% by weight aqueous solution of potassium hydroxide or the like is used. Examples of the peeling method include an immersion method and a spray method. The immersion method and the spray method may be used alone or in combination. Further, the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board.

[0068]

The present invention will be described below with reference to examples.

Examples 1 to 4 and Comparative Examples 1 to 5 The materials shown in Table 1 were blended to obtain solutions.

[0070]

[Table 1]

The resulting solution was mixed with the photopolymerizable compound shown in Table 2.
Dissolving things component to obtain a solution of a photosensitive resin composition.

[0072]

[Table 2]

The components of each photopolymerizable compound in Table 2 are shown below. * 1: A compound in which R ¹ and R ² are methyl groups, X and Y are ethylene groups, and k + m = 10 (average value) in the above general formula (I), manufactured by Shin-Nakamura Chemical Co., Ltd. * 2: In the general formula (I), a compound in which R ¹ and R ² represent a methyl group, X and Y represent an ethylene group, and k + m = 30 (average value), manufactured by Shin-Nakamura Chemical Co., Ltd. * 3: EO Modified nonylphenyl acrylate (8 repeating units of ethylene glycol chain), manufactured by Kyoeisha Chemical Co., Ltd. * 4: Pentaerythritol triacrylate, Nippon Kayaku
* 5: Polypropylene glycol diacrylate (the repeating unit of the propylene glycol chain is 6 to 7), manufactured by Shin-Nakamura Chemical Co., Ltd.

Then, a solution of the obtained photosensitive resin composition was applied to a 16 μm-thick polyethylene terephthalate film (haze: 1.7%, trade name: GS-16, manufactured by Teijin Limited).
And apply it uniformly on a hot air convection dryer at 100 ° C.
After drying for 10 minutes, a polyethylene protective film (tensile strength in the longitudinal direction of the film: 16 MPa, tensile strength in the width direction of the film: 12 MPa, trade name: NF-15, Tamapoli Co., Ltd.)
To obtain a photosensitive element. The dried film thickness of the photosensitive resin composition layer was 50 μm.

Next, a UV spectrometer (made by Hitachi, Ltd., 22)
The transmittance of the layer of the photosensitive resin composition to ultraviolet rays having a wavelength of 365 nm was measured using an 8A-type W-beam spectrophotometer). The transmittance was measured by first placing a support film and a photosensitive element composed of a layer of the photosensitive resin composition on the measurement side, placing the support film on the reference side, and measuring the transmittance by 70% in T% mode.
It was measured by continuously measuring from 0 to 300 μm and reading the value at 365 nm. Table 3 shows the results.

On the other hand, the copper surface of a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-61), which is a glass epoxy material having a copper foil (thickness: 35 μm) laminated on both sides, is # 6
Polishing using a polishing machine with a brush equivalent to 00 (manufactured by Sankei Co., Ltd.), washing with water, drying with an air stream, heating the obtained copper-clad laminate to 80 ° C. The photosensitive resin composition layer was laminated at a speed of 3 m / min using a heat roll at 120 ° C. while peeling off the protective film.

Next, using an exposure machine (manufactured by Oak Co., Ltd.) HMW-201B having a high-pressure mercury lamp, a 21-step stepper tablet as a negative was placed on the test piece and exposed at 60 mJ / cm ² . did.

Next, the polyethylene terephthalate film was peeled off, a 1% by weight aqueous solution of sodium carbonate was sprayed at 30 ° C. for 60 seconds to remove unexposed portions, and then the steps of the photocured film formed on the copper-clad laminate were carried out. The photosensitivity of the photosensitive resin composition was evaluated by measuring the number of tablets, and the results are shown in Table 3. The light sensitivity is indicated by the number of steps of the step tablet. The higher the number of steps of the step tablet, the higher the light sensitivity.

The resolution was as follows: a photo tool having a 21-step tablet of a stofer and a line width / space width of 10/10 to 50 /
A photo tool having a wiring pattern of 50 (unit: μm) was brought into close contact, and exposure was performed with an energy amount such that the number of remaining steps after development of the 21-step tablet of the stofer was 8.0. Here, the resolution was evaluated based on the smallest value of the space width between the line widths in which the unexposed portions could be clearly removed by the development processing. The smaller the value of the evaluation of the resolution, the better the value. The results are shown in Table 3.

The plating resistance was determined by laminating as described above, exposing with a predetermined amount of exposure, and then developing with the above-mentioned developer, and then immersing in a degreasing bath (PC-455 (manufactured by Meltex Corporation), 25% by weight). It was immersed for 5 minutes and washed with water. Next, a soft etching bath (150 g of ammonium persulfate)
/ Liter) for 2 minutes and washed with water. Then 10
A pretreatment was performed in the order of immersion in a 1% by weight sulfuric acid bath for 1 minute, and a copper sulfate plating bath (copper sulfate 75 g / liter, sulfuric acid 1
90 g / l, chloride ion 50 ppm, Copperglyme PCM (manufactured by Meltex) 5 ml / l), and copper sulfate plating was performed at room temperature at 3 A / dm ² for 40 minutes.

Thereafter, it was washed with water, immersed in 10% by weight of borofluoric acid for 1 minute, and subjected to a solder plating bath (45% by weight of tin borofluoride 64 ml / liter, 45% by weight of lead borofluoride 22 ml / liter, 42% by weight). % Borofluoric acid 200 ml / l, Plutin LA conductivity salt (manufactured by Meltex) 20 g / l, Plutin LA starter (manufactured by Meltex) 41 ml / l), and solder plating was carried out at room temperature. Performed at 5 A / dm ² for 15 minutes.

After washing with water and drying, a 90 ° peel-off test was immediately performed to check the plating resistance. The results are shown in Table 3. The 90 ° peel-off test is to attach a cellophane tape to a plated substrate, adhere it well with a rubber roller, immediately peel it off at a peel angle of 90 ° C, and observe the degree of resist transfer to the cellophane tape. is there. After the peel-off test at 90 ° C., the resist was peeled off, and the presence or absence of solder plating was observed from above using an optical microscope, a projector or the like. The results are shown in Table 3. When the solder plating is buried, solder deposited by solder plating is observed below the transparent resist through the transparent resist.

Further, another test piece was subjected to a cross cut test (JIS-K-5400) after exposure and development with a stofer 21-step tablet at an exposure amount indicating 8 steps, and the results are shown in Table 3. Was. The cross-cut test is to draw 11 perpendicular and 11 parallel lines at 1 mm intervals using a cutter guide at the center of the circuit-forming substrate on which the photosensitive elements are stacked, and 100 lines in 1 cm ² Is to make a grid-like cut so as to form a square, and evaluate the state of the scratch. In addition, the cut was made so that the cutting edge of the cutter knife was maintained at a fixed angle of 35 to 45 degrees with respect to the photosensitive element, and penetrated the photosensitive resin composition layer to reach the circuit forming substrate. The book is drawn at a constant speed over 0.5 seconds. The evaluation of the state of the flaw is as follows.

10 points: Each cut is thin, both sides are smooth, and the intersection of the cut and the square are not peeled at every glance. Eight points: There is slight peeling at the intersection of the cuts, no peeling at a glance, and the area of the defect is within 5% of the area of the entire square. 6 points: Both sides of the cut and the intersection are peeled, and the area of the defective portion is 5 to 15% of the total square area. 4 points: The width of the peeling due to the cut is wide, and the area of the defective portion is 15 to 35% of the total square area. 2 points: The width of the peeling due to the cut is wider than 4 points, and the area of the defective portion is 35 to 65% of the area of the entire square. 0 point: The area of the defective portion is 65% or more of the area of the entire square.

[0085]

[Table 3]

As is clear from Table 3, Examples 1-4
Has excellent resolution and cross-cutting properties and good plating resistance.

[0087]

The photosensitive resin compositions according to claims 1 and 2 are excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesiveness, mechanical strength and flexibility, and have high density printed wiring. And is useful for high resolution. The photosensitive resin compositions according to the third and fourth aspects exhibit the effects of the invention according to the first or second aspect , and are further excellent in chemical resistance. The photosensitive resin compositions according to the fifth, sixth and seventh aspects have further excellent alkali developability in addition to the effects of the first, second , third and fourth aspects.

The photosensitive resin compositions according to the eighth and ninth aspects exhibit the effects of the inventions according to the first , second , third, fourth, fifth, sixth and seventh aspects, and further have photosensitivity and chemical resistance (plating resistance). sex)
Is excellent. The photosensitive resin composition according to the tenth aspect has the effects of the invention according to the first , second , third, fourth, fifth, sixth, seventh, eighth, and ninth aspects, and further has excellent peeling properties. The photosensitive resin composition according to claim 11 is a photosensitive resin composition according to claims 1 , 3 , 4, 5, 6,
The effects of the invention described in 7 , 8 , 9 or 10 are exhibited, and the adhesion is further excellent. The photosensitive resin composition according to claim 12 ,
Claims 1, 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10, or
The effects of the invention described in 11 are achieved, and light sensitivity, resolution,
Excellent chemical resistance (plating resistance), adhesion, mechanical strength and flexibility.

The photosensitive elements according to claims 13, 15 and 16 are excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, flexibility, workability and productivity. A photosensitive element according to claim 14, wherein
Degree, resolution, chemical resistance (plating resistance), adhesion, mechanical strength
Excellent degree, flexibility, laminability, workability and productivity
You. The photosensitive element according to the seventeenth and eighteenth aspects has the effects of the invention according to the thirteenth, fourteenth, fifteenth, or sixteenth aspects, and further has excellent resolution. The photosensitive element according to claim 19 is the photosensitive element according to claim 13, 14 , 15, 16, 17, or
The effects of the invention described in Item 18 are exhibited, and the resolution is further improved.
The photosensitive element according to claim 20 and claim 21
In addition to the effects of the invention described in 14, 16, 17, 18 or 19 , the laminating property is further excellent.

The method for producing a resist pattern according to claim 22 is excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, flexibility, workability, and productivity. The method for manufacturing a printed wiring board according to claim 23 is excellent in light sensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, flexibility, environment, workability, and productivity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/028 G03F 7/028 7/033 7/033 H05K 3/00 H05K 3/00 F 3/06 3 / 06 H 3/18 3/18 D (72) Inventor Riki Ishikawa 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Hitachi Chemical Co., Ltd.Yamazaki Office (72) Inventor Akiyo Kimura Higashimachi, Hitachi City, Ibaraki Prefecture 4-3-1, Hitachi Chemical Co., Ltd., Yamazaki Plant (72) Inventor Hitoko Kimura 4-3-1, Higashi-cho, Hitachi, Ibaraki Prefecture Hitachi Chemical Co., Ltd., Yamazaki Plant (72) Inventor Takeshi Ohashi, Ibaraki Hitachi Chemical Industry Co., Ltd., Yamazaki Office, Hitachi City, Hitachi, Ibaraki Pref., Japan (72) Inventor Yudai Fukaya 4-3-1, Higashicho, Hitachi City, Ibaraki Prefecture, Japan

Claims (20)

[Claims] (1) a binder polymer having a dispersity of 1.0 to 3.0, (B) a bisphenol A-based (meth)
A photosensitive resin composition comprising a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in a molecule containing an acrylate compound as an essential component, and (C) a photopolymerization initiator. 2. The method according to claim 1, wherein (A) the binder polymer comprises styrene or a styrene derivative as an essential copolymer component.
The photosensitive resin composition as described in the above. 3. A binder polymer comprising styrene or a styrene derivative in an amount of 0.1 to 3 based on all copolymerized components.
The photosensitive resin composition according to claim 2, which contains 0% by weight. 4. The photosensitive resin composition according to claim 1, wherein (A) the binder polymer contains methacrylic acid as an essential copolymerization component. 5. The method according to claim 1, wherein (A) the binder polymer has an acid value of 10
The photosensitive resin composition according to claim 1, wherein the amount is from 0 to 500 mgKOH / g. 6. The method according to claim 1, wherein the weight average molecular weight of (A) the binder polymer is from 20,000 to 300,000.
6. The photosensitive resin composition according to 2, 3, 4 or 5. 7. A bisphenol A (meth) acrylate compound represented by the general formula (I): (Wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are such that p + q = 4 to 40) The photosensitive resin composition according to claim 1, 2, 3, 4, 5, or 6, which is a compound represented by the following formula: 8. The photosensitive resin composition according to claim 7, wherein X and Y are ethylene groups. 9. A photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule as an essential component as the photopolymerizable compound other than the bisphenol A (meth) acrylate compound. 3,4,5,6,7
Or the photosensitive resin composition according to 8. 10. The method according to claim 1, wherein (C) the photopolymerization initiator comprises a 2,4,5-triarylimidazole dimer as an essential component. Photosensitive resin composition. 11. The compounding amount of the component (A), the component (B) and the component (C) is 100 in total of the component (A) and the component (B).
Component (A) is 40 to 80 parts by weight, and (B)
20 to 60 parts by weight of component and 0.1 to 20 of component (C)
The amount of the bisphenol A (meth) acrylate compound is 3 to 90% by weight in the component (B), and the bisphenol A (meth) acrylate compound is 3 to 90% by weight. Photosensitive resin composition. 12. The method of claim 1, 2, 3, 4, 5, 6, 7,
A photosensitive element obtained by applying a layer of the photosensitive resin composition according to 8, 9, 10 or 11 on a support and drying. 13. The method of claim 1, 2, 3, 4, 5, 6, 7,
A layer of the photosensitive resin composition according to 8, 9, 10 or 11 is coated on a support and dried, and a protective film is further laminated so as to be in contact with the layer of the photosensitive resin composition on the opposite side of the support. Photosensitive element. 14. The photosensitive element according to claim 12, wherein the thickness of the support is 5 to 25 μm. 15. The support has a haze of 0.001 to 5.0.
The photosensitive element according to claim 12, 13 or 14, wherein 16. The wavelength of the layer of the photosensitive resin composition is 365 nm.
2. The ultraviolet ray transmittance of the glass is 5 to 75%.
16. The photosensitive element according to 2, 13, 14 or 15. 17. The photosensitive element according to claim 13, wherein the protective film has a thickness of 5 to 30 μm. 18. The protective film according to claim 13, wherein the tensile strength in the longitudinal direction of the film is 13 MPa or more, and the tensile strength in the longitudinal direction of the film is 9 MPa or more.
Or the photosensitive element of 17; 19. The method of claim 12, 13, 14, 15, 1,
The photosensitive element described in 6, 17 or 18 is laminated on a circuit-forming substrate so that the photosensitive resin composition layer is in close contact with the photosensitive element while peeling off a protective film which may be present in some cases, and irradiating actinic rays imagewise. Light-curing the exposed part,
A method for producing a resist pattern, wherein an unexposed portion is removed by development. 20. A method for manufacturing a printed wiring board, comprising etching or plating a circuit-forming substrate on which a resist pattern has been manufactured by the method for manufacturing a resist pattern according to claim 19.