JP2002156756A - Photosensitive resin composition, photosensitive element using the 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 having very superior sensitivity, adhesion, chemical resistance, flexibility and contamination property with respect to a plating bath, and to provide a method for producing a printed wiring board using the composition. SOLUTION: The photosensitive resin composition contains (A) a binder polymer, (B) a photopolymerizable compound, having at least one polymerizable ethylenically unsaturated group in one molecule and (C1) a coumarin derivative of formula (I) and (C2) a boron salt compound of formula (II) as (C) a photopolymerization initiator system. The photosensitive resin composition is applied and dried on a base and a protective film is optionally disposed, to obtain the objective photosensitive element. The photosensitive element is sued in the method for producing a printed wiring board.

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 by using a support and a protective film thereon are widely used as resist materials used for etching, plating and the like. ing. Printed wiring board, the photosensitive element is laminated on a copper substrate, after pattern exposure, the cured portion is removed with a developer, subjected to etching or plating,
It is manufactured by a method in which a cured portion is peeled off from a substrate after a pattern is formed. 2. Description of the Related Art With the recent increase in the density of printed wiring boards, demands for high-resolution and high-adhesiveness of photosensitive elements have been increasing as compared with conventional photosensitive elements.

[0003] On the other hand, a photosensitive resin composition having high sensitivity and low plating bath contamination is desired from the viewpoint of improving workability, and these characteristics depend on the type of photopolymerization initiator used. And the amount. Examples of highly sensitive photopolymerization initiators include, for example, German Patent No. 2,027,46.
7, European Patent Publication No. 11,786, European Patent Publication No. 220, European Patent Publication No. 589, JP-A-6-69631 and the like. Has the disadvantage of having plating bath contamination.

[0004] In addition, a photosensitive resin composition which has a high sensitivity by combining a dimer of 2,4,5-triphenylimidazole which is a photopolymerization initiator and a hydrogen-donating compound with low plating bath contamination has been proposed. In US Pat. No. 3,479,185, when the amount of 2,4,5-triphenylimidazole dimer used is increased in order to adjust the sensitivity to the required sensitivity, the resist pattern can be reduced. There is a disadvantage that the line width is large, and when the amount of the hydrogen-donating compound used is increased, the adhesion to copper and the storage stability are poor. Further, it is conceivable to use a compound having a highly reactive ethylenically unsaturated group such as 2,4,5-triphenylimidazole dimer and polyethylene glycol dimethacrylate. There is a disadvantage that the chemical resistance is extremely poor.

[0005]

The inventions according to claims 1, 6, 7 and 8 provide a photosensitive resin composition having extremely excellent sensitivity, adhesion, chemical resistance, flexibility and plating bath contamination. Things. The invention of claim 2 provides the effect of the invention of claim 1 and provides a photosensitive resin composition having extremely excellent sensitivity and adhesion. Claim 3
The invention described provides the effect of the invention described in claim 1 or 2, and further provides a photosensitive resin composition having extremely excellent resolution and adhesion. The invention according to claim 4 is
Another object of the present invention is to provide a photosensitive resin composition having extremely excellent release characteristics in addition to the effects of the invention described in the first, second or third aspect. The invention described in claim 5 provides a photosensitive resin composition having extremely excellent alkali developability in addition to the effects of the invention described in claim 1, 2, 3 or 4.

The ninth aspect of the present invention is to provide a photosensitive element having extremely excellent sensitivity, adhesion, chemical resistance, flexibility, plating bath contamination and workability. Claim 1
The invention described in No. 0 is a process for producing a resist pattern having extremely excellent sensitivity, adhesion, chemical resistance, flexibility, plating bath contamination and workability, which is extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards. It provides the law. The invention according to claim 11 is a resist pattern excellent in sensitivity, adhesion, chemical resistance, flexibility, plating bath contamination and workability, which is extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards. And a method for producing a printed wiring board having the following.

[0007]

The present invention provides (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in a molecule, and (C) a photopolymerization initiator. The system (C1) has the general formula (I)

Embedded image (Wherein, Z ¹ and Z ² each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amino group, -10 alkylamino group, C2-C20 dialkylamino group, mercapto group, C1-C10 alkylmercapto group, allyl group, C1-C20 hydroxyalkyl group, carboxyl group, carbon of alkyl group A carboxyalkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or a group containing a heterocyclic group; Further, Z ¹ and Z ² may form a ring, a plurality of Z ¹ or a plurality of Z ² may be bonded to form a ring, and m is an integer of 0 to 2. Yes, n is 0
A coumarin derivative represented by the formula (II):

Embedded image (Wherein, Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ and Z ¹⁰
Each independently has the same meaning as Z ¹ in the general formula (I)) relates to a photosensitive resin composition containing a boron salt compound represented by the formula:

In the present invention, the component (C1) may have the general formula (III)

Embedded image (Wherein, Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ each independently have the same meaning as Z ¹ in formula (I) above, and p is 0 to 2)
And g is an integer of 0 to 3), and a general formula (I
V)

Embedded image (Wherein, Z ¹⁵ , Z ¹⁶ , Z ¹⁷ and Z ¹⁸ each independently have the same meaning as Z ¹ in the general formula (I), and i is 0 to 8)
And h is an integer of 0 to 3) or a general formula (V)

Embedded image (Wherein, Z ¹⁹ , Z ²⁰ , Z ²¹ and Z ²² each independently have the same meaning as Z1 in the above general formula (I), and a is 0 to 6)
B is an integer of 0 to 6, c is an integer of 0 to 2, and d is an integer of 0 to 1). .

The present invention also relates to the photosensitive resin composition, which further comprises (C3) a 2,4,5-triarylimidazole dimer as a photopolymerization initiator system (C). The present invention also relates to the photosensitive resin composition, wherein the component (A) is a carboxyl group-containing binder polymer containing styrene or a styrene derivative as a copolymer component. In the present invention, the component (A) has an acid value of 30 to 200.
mgKOH / g, weight average molecular weight 20,000-30
It is related with the said photosensitive resin composition which is 000.

The present invention also relates to (A ') a binder polymer containing styrene or a styrene derivative as a copolymerization component, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and The present invention relates to a photosensitive resin composition containing (C2 ′) onium salt compound. Further, the present invention provides (A) a binder polymer,
(B ′) a bisphenol A-based acrylate compound having at least one polymerizable ethylenically unsaturated group in the molecule or a methacrylate compound corresponding thereto, and (C ′)
2 ') A photosensitive resin composition containing an onium salt compound. Further, the present invention provides (A) a binder polymer, (B ″) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in a molecule and having a urethane bond, and (C2 ′) onium salt. The present invention relates to a photosensitive resin composition containing a compound.

[0011] The present invention also relates to a photosensitive element obtained by applying the photosensitive resin composition on a support and drying the composition. Further, the present invention, the photosensitive element, while peeling the protective film in some cases, laminated on a circuit-forming substrate so that the photosensitive resin composition layer is in close contact, irradiating actinic rays imagewise, The exposed part is light cured,
The present invention relates to a method for producing a resist pattern, wherein an unexposed portion is removed 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.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The photosensitive resin composition of the present invention has four features. 1 of the photosensitive resin composition of the present invention
One feature is (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in a molecule, and (C) a photopolymerization initiator system comprising (C1) It contains a coumarin derivative represented by I) and (C2) a boron salt compound represented by the general formula (II). Another feature of the photosensitive resin composition of the present invention is that (A ′) a binder polymer containing styrene or a styrene derivative as a copolymer component, and (B) at least one polymerizable ethylenic polymer in a molecule. It contains a photopolymerizable compound having a saturated group and a (C2 ') onium salt compound.

Further, another one of the photosensitive resin compositions of the present invention is also provided.
One feature is (A) a binder polymer, (B ') a bisphenol A-based acrylate compound having at least one polymerizable ethylenically unsaturated group in a molecule or a corresponding methacrylate compound and (C2') onium salt compound Is contained. Another feature of the photosensitive resin composition of the present invention is (A) a binder polymer, (B ″) having at least one polymerizable ethylenically unsaturated group in a molecule, and having a urethane bond. And (C2 ') onium salt compound.

Examples of the binder polymer as the component (A) in the present invention include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins and the like. Can be 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) in the present invention 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 acrylate, alkyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate,
Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2 , 2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, acrylic acid, methacrylic acid, α
-Bromoacrylic acid, α-chloroacrylic acid, β-furylacrylic acid, β-styrylacrylic acid, maleic acid,
Maleic anhydride such as maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate and the like, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like can be mentioned.

The above-mentioned alkyl acrylate or alkyl methacrylate includes, for example, compounds of the general formula (VI)

Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² 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 ² in the general formula (VI) 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 (VI) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, and hexyl acrylate. , Heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, methacryl Propyl acrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, methacrylate Acrylic acid 2-ethylhexyl ester, methacrylic acid nonyl ester, decyl methacrylate esters, methacrylic acid undecyl ester, and methacrylic acid dodecyl ester. These can be used alone or in combination of two or more.

The binder polymer as the component (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. The styrene or styrene derivative as a copolymer component, in order to improve both adhesion and release characteristics,
It is preferably contained in an amount of 0.1 to 30% by weight, more preferably 1 to 28% by weight, and particularly preferably 1.5 to 27% by weight. If the content is less than 0.1% by weight, the adhesion tends to be inferior. If the content exceeds 30% by weight,
The peeled pieces tend to be large and the peeling time tends to be long.

Examples of the styrene derivative include α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene, p-ethoxystyrene,
-Chlorostyrene, p-bromostyrene and the like,
In these styrene derivatives, the benzene ring may be substituted with a functional group such as a nitro group, a nitrile group, an alkoxyl group, an acyl group, a sulfone group, a hydroxyl group, a halogen atom, and a methyl group, a tert-butyl group. Is preferably substituted with a single alkyl group such as From the viewpoint of adhesion, styrene or p-methylstyrene is preferred. These styrenes or styrene derivatives are used alone or in combination of two or more.

These binder polymers are used alone or in combination of two or more.

When the binder polymer of the component (A) in the present invention has a carboxyl group, it preferably has an acid value of 30 to 200 mgKOH / g.
More preferably, it is １００100 mgKOH / g. When the acid value is less than 30 mgKOH / g, the developing time tends to be long, and when it exceeds 200 mgKOH / g, the developing solution resistance of the photocured resist tends to decrease. Further, the weight average molecular weight of the binder polymer as the component (A) in the present invention 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
If the ratio exceeds, the development time tends to be long. In addition, the weight average molecular weight in the present invention is measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene.

Examples of the photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule of the component (B) in the present invention include polyhydric alcohols and polyhydric alcohols having α, β-unsaturation. Compounds obtained by reacting carboxylic acids, 2,2-bis (4- (acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-
(Methacryloxypolyethoxy) phenyl) propane,
2,2-bis (4- (acryloxypolypropoxy) phenyl) propane, 2,2-bis (4- (methacryloxypolypropoxy) phenyl) propane, 2,2-bis (4- (acryloxypolyethoxypoly) Bisphenol A-based acrylate compounds such as propoxy) phenyl) propane and 2,2-bis (4- (methacryloxypolyethoxypolypropoxy) phenyl) propane and glycidyl group-containing compounds are reacted with α, β-unsaturated carboxylic acid. The resulting compound, a urethane monomer having a urethane bond in the molecule, nonylphenyldioxylene acrylate, nonylphenyldioxylene methacrylate, γ-
Chloro-β-hydroxypropyl-β′-acryloyloxyethyl-o-phthalate, γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-
o-phthalate, β-hydroxyethyl-β′-acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β′-methacryloyloxyethyl-o-phthalate, alkyl acrylate, alkyl methacrylate and the like.

Examples of the polyhydric alcohol include polyethylene glycol diacrylate having 2 to 14 ethylene groups, polyethylene glycol dimethacrylate having 2 to 14 ethylene groups, and 2 to 14 propylene groups. Is a polypropylene glycol diacrylate, polypropylene glycol dimethacrylate having 2 to 14 propylene groups, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate,
The number of trimethylolpropane trimethacrylate, trimethylolpropaneethoxytriacrylate, trimethylolpropaneethoxytrimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethanetrimethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, the number of propylene groups is 2 Polypropylene glycol diacrylate, the number of propylene groups is 2
And polypropylene glycol dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

The α, β-unsaturated carboxylic acid includes
For example, acrylic acid and methacrylic acid are used. Examples of the 2,2-bis (4- (acryloxypolyethoxy) phenyl) propane include, for example, 2,2-bis (4
-(Acryloxydiethoxy) phenyl) propane,
2,2-bis (4- (acryloxytriethoxy) phenyl) propane, 2,2-bis (4- (acryloxypentaethoxy) phenyl) propane, 2,2-bis (4
-(Acryloxydecaethoxy) phenyl) and the like. Examples of the 2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane include, for example, 2,2
-Bis (4- (methacryloxydiethoxy) phenyl)
Propane, 2,2-bis (4- (methacryloxytriethoxy) phenyl) propane, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane,
2,2-bis (4- (methacryloxydecaethoxy) phenyl) propane and the like, and 2,2-bis (4-
(Methacryloxypentaethoxy) phenyl) propane is BPE-500 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
It is commercially available as

Examples of the 2,2-bis (4- (acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4- (acryloxydiethoxyoctapropoxy) phenyl) propane, 2-
Bis (4- (acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4- (acryloxyhexaethoxyhexapropoxy) phenyl)
And propane and methacrylate corresponding thereto.

The glycidyl group-containing compound includes, for example, trimethylolpropane triglycidyl ether triacrylate, trimethylolpropane triglycidyl ether trimethacrylate, 2,2-bis (4-
Acryloxy-2-hydroxy-propyloxy) phenyl, 2,2-bis (4-methacryloxy-2-hydroxy-propyloxy) phenyl and the like can be used. Examples of the urethane monomer include addition of an acrylic monomer having an OH group at the β-position or a methacrylic monomer corresponding thereto, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Reactant, tris (methacryloxytetraethylene glycol isocyanate hexamethylene isocyanurate, E
O-modified urethane dimethacrylate, EO, PO-modified urethane dimethacrylate 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.

Examples of the above-mentioned alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. These can be used alone or 2
Used in combination of more than one type.

In the coumarin derivative represented by the general formula (I), which is the component (C1) in the present invention, Z ¹ and Z ² in the formula each independently represent a halogen atom, a carbon number of 1 to 20. An alkyl group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amino group, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a mercapto group, An alkyl mercapto group having 1 to 10 carbon atoms, an allyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, and an acyl having 1 to 10 carbon atoms in the alkyl group. A group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms or a group containing a heterocyclic ring. Further, Z ¹ and Z ² may form a ring, and a plurality of Z ¹ or a plurality of Z ² may combine to form a ring. Further, a hydrogen atom in these substituents may be substituted with the above substituent such as a halogen atom. When m and n are each 2 or more, 2
The above Z ¹ and two or more Z ² may be the same or different. m is an integer of 0 to 2, and n is an integer of 0 to 4.

Examples of the halogen atom include fluorine, chlorine, bromine, iodine, and astatine.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, sec-butyl group, tert-
Butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Examples include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, and structural isomers thereof. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group and a phenanthryl group. ,
It may be substituted with a cyano group, a mercapto group, an allyl group, an alkyl group having 1 to 20 carbon atoms, or the like. The above carbon number 1
Examples of the alkylamino group 10 include a methylamino group, an ethylamino group, a propylamino group, and an isopropylamino group. As the dialkylamino group having 2 to 20 carbon atoms, for example, a dimethylamino group,
Examples include a diethylamino group, a dipropylamino group, and a diisopropylamino group. Examples of the alkyl mercapto group having 1 to 10 carbon atoms include a methyl mercapto group, an ethyl mercapto group, and a propyl mercapto group.

Examples of the hydroxyalkyl group having 1 to 20 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxyisopropyl group, a hydroxybutyl group and the like. Examples of the carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and a carboxybutyl group. Examples of the acyl group having 1 to 10 carbon atoms of the alkyl group include, for example, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group,
Examples include an isovaleryl group and a pivaloyl group.

The alkoxy group having 1 to 20 carbon atoms includes, for example, a methoxy group, an ethoxy group, a propoxy group,
Butoxy group and the like. Examples of the alkoxycarbonyl group having 1 to 20 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, and the like. Examples of the group containing a heterocyclic ring include a furyl group, a thienyl group, a pyrrolyl group, a thiazolyl group, an indolyl group, and a quinolyl group.

The coumarin derivative represented by the general formula (I) of the component (C1) in the present invention can be obtained from the viewpoints of sensitivity, resolution and adhesion by using the general formulas (III) and (IV). Alternatively, a coumarin derivative represented by the general formula (V) is more preferable. Z ¹¹ , Z ¹² ,
Z ¹³ , Z ¹⁴ , Z ¹⁵ , Z ¹⁶ , Z ¹⁷ , Z ¹⁸ , Z ¹⁹ , Z ²⁰ , Z
²¹ and Z ²² each independently have the same meaning as Z ¹ in the formula (I), and include an alkoxy group having 1 to 6 carbon atoms and 1 carbon atom.
It is preferably an alkyl group having 1 to 6 carbon atoms or an alkoxycarbonyl group having 1 to 6 carbon atoms.

The coumarin derivatives represented by the general formula (I) of the component (C1) in the present invention include, for example, 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4
-Methylcoumarin, 7-methylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 4,6
-Dimethyl-7-ethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-dimethyl-
7-diethylaminocoumarin, 4,6-dimethyl-7-
Dimethylaminocoumarin, 4,6-diethyl-7-diethylaminocoumarin, 4,6-diethyl-7-dimethylaminocoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 7-dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 2,3
6,7,10,11-hexaanhydro-1H, 5H-
Cyclopenta [3,4] [1] benzopyrano [6,7,
8-ij] quinolizin 12 (9H) -one, 7-diethylamino-5 ', 7'-dimethoxy-3,3'-carbonylbiscoumarin, 3,3'-carbonylbis [7-
(Diethylamino) coumarin], 7-diethylamino-
3-thienoki silk marine, the following formula (VII)

Embedded image And the like.

Available coumarin derivatives include, for example, Coumarin 1, Coumarin 2, and Coumarin 2 manufactured by Acros.
4, Coumarin 6, Coumarin 7, Coumarin 30, Coum
arin102, Coumarin 106, Coumarin 120, Coum
arin 138, Coumarin 151, Coumarin 152, Cou
marin 153, Coumarin 307, Coumarin 314, Co
umarin 314T, Coumarin 334, Coumarin 33
7, Coumarin 338, Coumarin 339, Coumarin 5
00 and the like. These are used alone or in combination of two or more.

In the boron salt compound represented by the general formula (II), which is the component (C2) in the present invention, Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ in the formula And Z ¹⁰ each independently have the same meaning as Z ¹ in formula (I).

Examples of the boron salt compound represented by the general formula (II) as the component (C2) in the present invention include, for example, tetramethylammonium butyl triphenyl borate, tetraethyl ammonium butyl triphenyl borate, tetrabutyl ammonium butyl Triphenyl borate, tetramethylammonium tris (2-fluorophenyl) butyl borate, tetramethylammonium tris (3-fluorophenyl) butyl borate,
Tetramethylammonium tris (4-fluorophenyl) butyl borate, tetraethylammonium tris (2-fluorophenyl) butyl borate, tetraethylammonium tris (3-fluorophenyl) butyl borate, tetraethylammonium tris (4-fluorophenyl) butyl borate, tetra Methyl ammonium tris (2-fluorophenyl) hexyl borate, tetramethyl ammonium tris (3-fluorophenyl) hexyl borate, tetramethyl ammonium tris (4-fluorophenyl) hexyl borate, tetraethyl ammonium tris (2-fluorophenyl) hexyl borate, Tetraethylammonium tris (3-fluorophenyl) hexyl borate, tetraethylammonium tris Scan (4-fluorophenyl) hexyl borate, tetrabutyl ammonium tris (2
-Fluorophenyl) hexyl borate, tetrabutylammonium tris (3-fluorophenyl) hexyl borate, tetrabutylammonium tris (4-fluorophenyl) hexyl borate and the like. These are used alone or in combination of two or more.

The (C2 ′) onium salt compound in the present invention includes, for example, ammonium salt compounds such as the boron salt compounds exemplified as the component (C2), iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, and the like. Arsonium salt compounds, stibonium salt compounds, oxonium salt compounds, selenonium salt compounds,
Stannonium salt compounds and the like. These are used alone or in combination of two or more.

As the above-mentioned iodonium salt compound, a diaryliodonium salt compound is preferable.

Embedded image (Wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom,
Which represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and X ⁻ represents a counter anion).

[0041] X in the general formula (VIII) ^- The, eg, Cl ^-, Br ^- halogen ions such, HSO ₄ ^-, B
F ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , ClO ₄ ⁻ , FSO ₃ ⁻ , F ₂ P
O ₂ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , B (C _{6
^{F 5) 4 -, CH 3}} SO 3 -, C 8 F 1 7 SO 3 -,

Embedded image And the like. These can be used alone or 2
Used in combination of more than one type.

Examples of the iodonium salt compound include diphenyliodonium salt, ditolyliodonium salt, phenyl (p-methoxyphenyl) iodonium salt, bis (p-tert-butylphenyl) iodonium salt, bis (p-cyanophenyl) Iodonium salt, 4-
Chloride such as isopropyl-4'-methyldiphenyliodonium salt, bromide, triflate, boron tetrafluoride, phosphorus hexafluoride, arsenic hexafluoride, antimony hexafluoride, benzene sulfonate, p- Toluenesulfonate, tetrakis (pentafluorophenyl)
Chlorides such as boron salts, bromide, triflate,
4-boron fluoride, 6-phosphorus fluoride, 6-arsenic fluoride, 6-antimony fluoride, benzenesulfonate, p-toluenesulfonate, tetrakis (pentafluorophenyl) boron And the like.

Preferred examples of these onium salt compounds include substances having the following structural formulas.

[0044]

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[0045]

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[0046]

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Component (C3) 2,4,5 in the present invention
-Triarylimidazole dimer is an essential component of the photopolymerization initiator system, and the aryl group has a halogen atom and 1 carbon atom.
Alkyl group having 20 to 20 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, amino group, 1 carbon atom
An alkylamino group having 10 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, and having 1 to 20 carbon atoms. A hydroxyalkyl group, a carboxyl group, a carboxyalkyl group having an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms.
Acyl group, an alkoxy group having 1 to 20 carbon atoms, 1 carbon atom
To 20 alkoxycarbonyl groups or groups containing a heterocyclic ring.

The 2,4,5-triarylimidazole dimer includes, for example, 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenylimidazole dimer, -(O-bromophenyl) -4,5-
Diphenylimidazole dimer, 2,2'-bis (o-
(Chlorophenyl) -4,4 ', 5,5'-tetra (p-
Chlorophenyl) imidazole dimer, 2- (o-chlorophenyl) -4,5-tetra (m-methoxyphenyl) imidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5 5'-tetra (p-fluorophenyl) imidazole dimer, 2,2'-bis (o
-Bromophenyl) -4,4 ', 5,5'-tetra (p
-Chloro p-methoxyphenyl) imidazole dimer,
2,2'-bis (o-chlorophenyl) -4,4 ',
5,5'-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2'-bis (o-chlorophenyl)
-4,4 ', 5,5'-tetra (o, p-dibromophenyl) imidazole dimer, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p -Chloronaphthyl) imidazole dimer, 2,2'-bis (o, m-dichlorophenyl) -4,4 ', 5,5'-
Tetraphenylimidazole dimer, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-
Tetraphenylimidazole dimer, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-
Tetra (m-methoxyphenyl) imidazole dimer,
2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)-
4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, -(2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2
-(P-methylmercaptophenyl) -4,5-diphenylimidazole dimer, 2,2'-bis (p-bromophenyl) -4,4 ', 5,5'-tetraphenylimidazole dimer, , 2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2'-bis (o-
(Bromophenyl) -4,4 ', 5,5'-tetra (p-
Iodophenyl) imidazole dimer, 2,2'-bis (m-bromophenyl) -4,4 ', 5,5'-tetraphenylimidazole dimer, 2,2'-bis (m, p
-Dibromophenyl) -4,4 ', 5,5'-tetraphenylimidazole dimer and the like. The substituents substituted on the two 2,4,5-triarylimidazoles may be the same or different. These are used alone or in combination of two or more.

Further, the photopolymerization initiator system (C) in the present invention may contain a photopolymerization initiator system other than the component (C1), the component (C2) and the component (C3).

Examples of photopolymerization initiator systems other than the components (C1), (C2) and (C3) 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-morpholino-propanone-
Aromatic ketones such as 1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone,
Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone,
Quinones such as 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantaraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl Benzoin ether compounds such as ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; benzyl derivatives such as benzyl dimethyl ketal; 9-phenylacridine; 1,7-bis (9,9 ′
Acridine derivatives such as -acridinyl) heptane;
Phenylglycine, N-phenylglycine derivatives and the like. These are used alone or in combination of two or more.

The amount of the component (A) in the present invention is as follows:
The total amount of the components (A) and (B) is preferably 40 to 80 parts by weight based on 100 parts by weight, and 40 to 6 parts by weight.
More preferably, it is 0 parts by weight. When this blending amount is 4
If the amount is less than 0 parts by weight, the photocured product tends to become brittle, and when used as a photosensitive element, tends to have poor coating properties.
If it exceeds 80 parts by weight, sensitivity tends to be insufficient.

The amount of the component (B) in the present invention 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 40 to 6 parts by weight.
More preferably, it is 0 parts by weight. This blending amount is 2
If the amount is less than 0 parts by weight, the sensitivity tends to be insufficient, and
If the amount exceeds 0 parts by weight, the photocured product tends to become brittle.

The content of the component (C1) in the present invention is as follows:
Preferably, the amount is 0.05 to 5.0 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
More preferably 0.05 to 1.0 parts by weight,
It is particularly preferred that the amount be 0.1 to 0.6 parts by weight. If the amount is less than 0.05 part by weight, the sensitivity tends to be insufficient, and if it exceeds 5.0 parts by weight, the resolution tends to deteriorate.

The content of the component (C2) in the present invention is as follows:
Preferably, the amount is 0.05 to 2.0 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
More preferably, the amount is 0.1 to 1.0 part by weight. If the amount is less than 0.05 part by weight, the effect of the present invention tends not to be obtained. If the amount exceeds 2.0 parts by weight, the resolution tends to be deteriorated and the development time tends to be longer.

The content of the component (C2 ') in the present invention is preferably 0.05 to 2.0 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
More preferably, the amount is 0.1 to 1.0 part by weight. If the amount is less than 0.05 part by weight, the effect of the present invention tends not to be obtained. If the amount exceeds 2.0 parts by weight, the resolution tends to be deteriorated and the development time tends to be longer.

The amount of the component (C3) in the present invention is as follows:
Preferably, the amount is 0.1 to 10.0 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
More preferably, the amount is 0.5 to 6.0 parts by weight. If the amount is less than 0.1 part by weight, the sensitivity tends to be insufficient, and the adhesion tends to decrease. If the amount exceeds 10.0 parts by weight, the line width of the resist pattern tends to be large.

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 be dissolved, if necessary, in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide or a mixture thereof. Then, it can be applied as 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, a copper-based alloy, nickel, chromium, iron, or 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 200 μm, more preferably from 1 to 100 μm, and more preferably from 1 to 30 μm in terms of thickness after drying. Is particularly preferred. If the thickness is less than 1 μm, it tends to be industrially difficult to apply,
If it exceeds 00 μm, the effect of the present invention tends to be small and the sensitivity tends to be insufficient. If it exceeds 200 μm, the photocurability at the bottom of the resist tends to deteriorate. When a liquid resist is coated with a protective film, the protective film is, for example, an inactive polyolefin film such as polyethylene and polypropylene.However, from the standpoint of releasability from the photosensitive resin composition layer, a polyethylene film is used. preferable.

The photosensitive element can be obtained by coating a photosensitive resin composition on a polymer film made of polyethylene terephthalate, polypropylene, polyethylene, polyester or the like as a support and drying the composition. The coating can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater. In addition, drying
The reaction can be performed at 80 to 150 ° C. for about 5 to 30 minutes.
In addition, since these polymer films must be removable from the photosensitive resin composition layer later, they may be surface-treated or made of a material that cannot be removed. must not. The thickness of these polymer films is preferably 5 to 100 μm,
It is more preferable that the thickness be 30 μm. This thickness is 5μ
If it is less than 30 m, the mechanical strength tends to decrease, and problems such as breakage of the polymer film during coating tend to occur.
If it exceeds μm, the resolution tends to decrease and the price tends to increase. Further, one of these polymer films may be laminated on both surfaces of the photosensitive resin composition layer as a support film of the photosensitive resin composition layer, and the other one may be used as a protective film of the photosensitive resin composition layer. .

The photosensitive element of the present invention comprising the two layers of the photosensitive resin composition layer and the polymer film thus obtained may be further provided with a protective film as it is or on the other surface of the photosensitive resin composition layer. They are stacked, wound into a roll, and stored.

In producing a resist pattern using a photosensitive element, if the above-mentioned protective film is present, the protective film is removed, and the substrate for circuit formation is heated while heating the photosensitive resin composition layer. And a method of laminating by pressure bonding, 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 70 to 130 ° C., and the pressure for pressing is 0.1 to 1.0 MPa (1 to 10 k
g / cm ² ), but these conditions are not particularly limited. In addition, 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 forming substrate in advance. Preheating of the substrate can also be performed.

The photosensitive resin composition layer thus laminated is irradiated imagewise with actinic rays 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. From the viewpoint of protecting the photosensitive resin composition layer, it is preferable that the polymer film is transparent, and that the polymer film is irradiated with actinic rays through the polymer film while remaining. 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. Sensitivity of the photopolymerization initiator contained in the photosensitive resin composition layer,
Since it is usually the maximum in the ultraviolet region, in that case,
It is preferable to use an actinic light source that should emit ultraviolet rays effectively.

Next, after the exposure, if a support is present on the photosensitive resin composition layer, the support is removed.
Using a developing solution such as an aqueous alkaline solution, the unexposed portion is removed and developed by a known method such as spraying, rocking immersion, brushing, and scraping to produce a resist pattern. As the developer, a safe and stable one having good operability, such as an alkaline aqueous solution, is used. As the base of the alkaline aqueous solution, for example, alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate, potassium phosphate, phosphoric acid Alkali metal phosphates such as sodium and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used.

The alkaline aqueous solution used for development includes a dilute solution of 0.1 to 5% by weight of sodium carbonate,
Dilute solution of 0.1-5% by weight potassium carbonate, 0.1-5%
Weight% dilute solution of sodium hydroxide, 0.1-5% by weight
A dilute solution of sodium tetraborate or the like is 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. Development methods include a dip method and a spray method, and a high-pressure spray method is most suitable for improving resolution.

As processing after development, 60-
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 of the metal surface performed after development, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution can be used. It is desirable to use a 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 or 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 is usually stripped with a more alkaline aqueous solution than the alkaline aqueous solution used for development. As the strong alkaline aqueous solution, for example, 1 to
A 5% by weight aqueous solution of sodium hydroxide, a 1 to 5% by weight aqueous solution of potassium hydroxide and the like are used. Further, the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board.

[0069]

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

Examples 1 to 9 and Comparative Examples 1 to 3 The materials shown in Table 1 were blended to obtain solutions.

[0071]

[Table 1]

[0072]

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Next, (C) shown in Table 2 was added to the obtained solution.
The components were dissolved to obtain a solution of the photosensitive resin composition. Coumarin derivatives and diethylaminobenzophenone 3
Table 3 shows the molecular absorption coefficient and the maximum absorption wavelength at 65 nm.

[0074]

[Table 2]

[0075]

[Table 3]

Next, the solution of the photosensitive resin composition was
A 16 μm-thick polyethylene film was uniformly coated on a polyethylene terephthalate film and dried with a hot air convection dryer at 100 ° C. for 10 minutes to obtain a photosensitive element. The thickness of the photosensitive resin composition layer was 20 μm.

On the other hand, a copper-clad laminate (Hitachi Kasei Kogyo Co., Ltd.) which is a glass epoxy material in which a copper foil having a thickness of 35 μm is laminated on both sides.
The copper surface of MCL-E-61 (trade name, manufactured by Co., Ltd.) was # 60
The surface of the copper-clad laminate is polished with a polishing machine having a brush equivalent to 0 (manufactured by Sankei Co., Ltd.), washed with water, and dried in an air stream. Then, the photosensitive resin composition layer was laminated while being heated to 110 ° C.

Next, using an exposure machine (manufactured by Oak Co., Ltd.) 590 having a high-pressure mercury lamp, a 41-step stofer step tablet was placed on the test piece as a negative, and the
Exposure was performed at 0 mJ / cm ² . Next, the polyethylene terephthalate film was peeled off, and an unexposed portion was removed by spraying a 1% by weight aqueous solution of sodium carbonate at 30 ° C. for 20 seconds. The minimum developing time was defined as the developing time in which the unexposed portion of the resist could be completely and quickly removed.

Further, by measuring the number of steps of the step tablet of the photocurable film formed on the copper-clad laminate,
The sensitivity of the photosensitive resin composition was evaluated, and the results are shown in Table 4. The 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 sensitivity. The pattern after development was observed, and the resolution (μm) was determined from the line width (μm) remaining as a line and space. The line width (μm) of the floating island pattern remaining without peeling after the development was measured, and the results were shown in Table 4 as adhesion. The smaller the value of the adhesion is, the smaller the line is, the more closely it is adhered to the copper-clad laminate without peeling off from the copper-clad laminate, and the higher the adhesion is.

[0080]

[Table 4]

Example 7 As the component (C2) and the component (C2 '), instead of 0.15 g of trimethylammonium tris (3-fluorophenyl) hexyl borate,
A photosensitive resin composition was obtained and evaluated in the same manner as in Example 1 except that 0.15 g of 4'-bis (tert-butyl) phenyliodonium triflate (trade name: BBI105, manufactured by Midori Kagaku Co., Ltd.) was used. did. As a result, the sensitivity is 2
5 (ST / 41), resolution 22 (μm), adhesion 2
0 (μm) and the development time was 8 (μm).

Example 8 In addition to 0.15 g of trimethylammonium tris (3-fluorophenyl) hexyl borate as components (C2) and (C2 '), 4,4'-bis (tert-butyl) phenyliodonium was further added. Triflate (trade name BBI10 manufactured by Midori Kagaku Co., Ltd.)
A photosensitive resin composition was obtained and evaluated in the same manner as in Example 1 except that 0.15 g of 5) was used. As a result, the sensitivity was 30 (ST / 41), the resolution was 22 (μm), the adhesion was 20 (μm), and the development time was 8 (μm).

Example 9 7-Diethylamino-4-methylcoumarin was not added as the component (C1).
Component and (C2 ') component are 4,4'-bis (tert-butyl) instead of 0.15 g of trimethylammonium tris (3-fluorophenyl) hexyl borate.
Using 0.15 g of phenyliodonium triflate (trade name: BBI105, manufactured by Midori Kagaku Co., Ltd.), N, N'-
A photosensitive resin composition was obtained and evaluated in the same manner as in Example 3 except that 0.15 g of tetraethyl-4,4'-diaminobenzophenone was used. As a result, the sensitivity is 2
3 (ST / 41), resolution 25 (μm), adhesion 8
(Μm) and the development time was 10 (μm).

[0084]

The photosensitive resin compositions according to the first, sixth, seventh and eighth aspects are extremely excellent in sensitivity, adhesion, chemical resistance, flexibility and plating bath contamination. The photosensitive resin composition according to the second aspect exhibits the effects of the invention according to the first aspect, and further has extremely excellent sensitivity. The photosensitive resin composition according to the third aspect has the effects of the invention according to the first or second aspect, and further has extremely excellent resolution and adhesion. The photosensitive resin composition according to the fourth aspect has extremely excellent peeling properties in addition to the effects of the invention according to the first, second or third aspect. The photosensitive resin composition according to the fifth aspect has extremely excellent alkali developability in addition to the effects of the invention according to the first, second, third or fourth aspect.

The photosensitive element according to the ninth aspect is extremely excellent in sensitivity, adhesion, chemical resistance, flexibility, plating bath contamination and workability. The method for producing a resist pattern according to claim 10 has extremely high sensitivity, adhesion, chemical resistance, flexibility, plating bath contamination and workability, which are extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards. Excellent. The method for manufacturing a printed wiring board according to the eleventh aspect has sensitivity, adhesion, chemical resistance, flexibility, plating bath contamination, and workability that are extremely useful for increasing the density of printed wiring and automating the manufacture of printed wiring boards. Very good.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/027 502 G03F 7/027 502 7/029 7/029 7/033 7/033 H05K 3/00 H05K 3/00 FF term (reference) 2H025 AA01 AA06 AA07 AA08 AA14 AB15 AC01 AD01 BC32 BC42 CA20 CA28 CB13 CB14 CB16 CB43 CB51 CB55 EA08 FA03 FA17 FA40 FA43 4J011 PA65 PA69 PA85 PA86 PA96 PB39 Q08AA QA13 QA13 RA19 SA62 SA82 UA01 VA01 WA01 4J026 AA17 AA31 AA42 AA43 AA45 AA46 AA47 AA49 AA50 AA53 AB01 AB04 AB11 AB28 BA24 BA27 BA28 BA30 DB06 DB11 DB36 GA01

Claims (8)

[Claims] 1. A binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in a molecule, and (C) a photopolymerization initiator system comprising (C1) a compound represented by the general formula (1): I) (Wherein, Z ¹ and Z ² each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amino group, -10 alkylamino group, C2-C20 dialkylamino group, mercapto group, C1-C10 alkylmercapto group, allyl group, C1-C20 hydroxyalkyl group, carboxyl group, carbon of alkyl group A carboxyalkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or a group containing a heterocyclic group; Further, Z ¹ and Z ² may form a ring, a plurality of Z ¹ or a plurality of Z ² may be bonded to form a ring, and m is an integer of 0 to 2. Yes, n is 0
A photosensitive resin composition containing a coumarin derivative represented by the following formula: 2. The component (C1) having the general formula (III):(Where Z¹¹, Z¹², Z¹³And Z¹⁴Are each independently said
Z in the general formula (I) ¹And p is 0 to 2
And g is an integer of 0 to 3), and a general formula (I
V) embedded image(Where Z^Fifteen, Z¹⁶, Z¹⁷And Z¹⁸Are each independently said
Z in the general formula (I) ¹And i is 0 to 8
And h is an integer of 0 to 3) or a general formula
(V)(Where Z¹⁹, Z²⁰, Z^{twenty one}And Z^{twenty two}Are each independently said
Z in the general formula (I) ¹And a is 0 to 6
B is an integer from 0 to 6, and c is an integer from 0 to 2.
Is an integer, and d is an integer of 0 to 1).
2. The photosensitive resin composition according to claim 1, which is a marine derivative.
object. 3. The photosensitive resin composition according to claim 1, further comprising (C3) a 2,4,5-triarylimidazole dimer as the photopolymerization initiator system (C). 4. The photosensitive resin composition according to claim 1, wherein the component (A) is a carboxyl group-containing binder polymer containing styrene or a styrene derivative as a copolymer component. 5. An acid value of the component (A) is from 30 to 200 mgKOH /
g and a weight average molecular weight of 20,000 to 300,00.
The photosensitive resin composition according to claim 1, 2, 3, or 4, which is 0. 6. A photosensitive element obtained by applying the photosensitive resin composition according to claim 1, 2, 3, 4 or 5 on a support and drying. 7. The photosensitive element according to claim 6, which is laminated on the circuit-forming substrate such that the photosensitive resin composition layer is in close contact with the circuit element while peeling off the protective film in some cases. Irradiate and light cure the exposed area,
A method for producing a resist pattern, wherein an unexposed portion is removed by development. 8. 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 7.