JP2000310855A - Photosensitive resin composition, photosensitive element using same, production of resist pattern and production of printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin composition having high resolution, high adhesion and high sensitivity and less liable to contaminate a plating bath by incorporating a binder polymer, a photopolymerizable compound having a polymerizable ethylenically unsaturated group in its molecule and a specified triarylimidazole dimer as a photopolymerization initiator. SOLUTION: The photosensitive resin composition contains (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in its molecule and (C) a 2,4,5-triarylimidazole dimer of the formula as a photopolymerization initiator. In the formula, X is H or F and R is 1-20C alkyl. The binder polymer preferably contains carboxyl groups from the viewpoint of alkali developability. In this case, the acid value of the binder polymer is preferably 30-200 mgKOH/g and the weight average molecular weight is preferably 20,000-300,000.

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. The printed wiring board is formed by laminating a photosensitive element on a copper substrate, exposing it in an image, removing the cured portion with a developing solution, producing a resist pattern, performing an etching or plating process, and performing a curing process. Is manufactured by a method of peeling off from the substrate. 2. Description of the Related Art With the recent increase in density of printed wiring boards, demands for high resolution and high adhesion 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. High-sensitivity photopolymerization initiators are described in German Patent No. 2,027,467, European Patent Publication No. 11,786, European Patent Publication No. 220, and European Patent Publication No. 58.
No. 9, JP-A-6-69631, etc., but they have the drawback 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. U.S. Pat. No. 3,479,185 describes that, when the required sensitivity is adjusted, the amount of 2,4,5-triphenylimidazole dimer used can be increased to increase the linearity of the resist. There is a disadvantage that the width is large, and when the amount of the hydrogen-donating compound used is increased, there is a disadvantage that adhesion to copper and storage stability are deteriorated. It is also conceivable to use a compound such as polyethylene glycol dimethacrylate having a 2,4,5-triphenylimidazole dimer and a highly reactive ethylenically unsaturated group, but the above-mentioned chemical resistance is extremely poor. There is a disadvantage that.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides a photosensitive resin excellent in high resolution, high adhesion, high sensitivity, plating bath contamination and the like. It is intended to provide a composition and a photosensitive element using the same. The inventions according to claims 1, 2, 3 and 4 provide a photosensitive resin composition which is extremely excellent in sensitivity, excellent in adhesion, chemical resistance, flexibility and plating bath contamination. The inventions of claims 5 and 6 exhibit the effects of the inventions of claims 1, 2, 3 and 4, and further provide a photosensitive resin composition having excellent developability with an alkali developing solution.
The invention according to claim 7 is extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards, having extremely excellent sensitivity, adhesion, chemical resistance, flexibility, plating bath contamination,
An object of the present invention is to provide a photosensitive element having excellent alkali developability, mechanical strength and workability.

The invention according to claim 8 is extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards, having extremely excellent sensitivity, adhesion, chemical resistance, flexibility, plating bath contamination, and alkali. An object of the present invention is to provide a method for producing a resist pattern having excellent developability, mechanical strength and workability. The invention according to claim 9 is extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards, having extremely high sensitivity, adhesion, chemical resistance, flexibility, plating bath contamination, alkali developability, An object of the present invention is to provide a method for manufacturing a printed wiring board having excellent mechanical strength and workability.

[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. Represented by the general formula (I)

Embedded image Wherein X represents a hydrogen atom or a fluorine atom, and R represents an alkyl group having 1 to 20 carbon atoms.
The present invention relates to a photosensitive resin composition containing a 5-triarylimidazole dimer.

In the present invention, the photopolymerization initiator (C) preferably has the following formula (II):

Embedded image Wherein the photosensitive resin composition is a 2,4,5-triarylimidazole dimer represented by the formula:

In the present invention, the photopolymerization initiator (C) preferably has the following formula (III):

Embedded image Wherein the photosensitive resin composition is a 2,4,5-triarylimidazole dimer represented by the formula:

The present invention further relates to (D) a sensitizer represented by the general formula (IV):

Embedded image (Wherein, R ¹ and R ² each independently represent a hydrogen atom or a carbon atom
And R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 1 to 6 carbon atoms, and R ³ and R ⁴ are bonded to each other. Or a coumarin compound represented by the general formula (V)

Embedded image (Wherein, R ¹ and R ² are R ¹ and R ² in the general formula (IV)
And the above-mentioned photosensitive resin composition comprising an alkylaminobenzophenone-based compound represented by the formula:

[0011] The present invention also relates to the photosensitive resin composition, wherein (A) the binder polymer is a binder polymer containing a carboxyl group. Also, the present invention
(A) The photosensitive resin composition wherein the acid value of the component is 100 to 500 mgKOH / g and the weight average molecular weight is 20,000 to 300,000. The present invention also relates to a photosensitive element obtained by applying, drying and laminating the photosensitive resin composition on a support.

Further, the present invention provides a method for manufacturing a semiconductor device, comprising: laminating the photosensitive element on a circuit-forming substrate so that a photosensitive resin composition layer is in close contact with the photosensitive element; And a method of manufacturing a resist pattern, wherein unexposed portions are 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.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The binder polymer as the component (A) in the present invention is not particularly limited, and examples thereof include an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, and an alkyd resin. Resins, phenolic resins and the like. 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 radically polymerizing a polymerizable monomer. The polymerizable monomer is not particularly limited, for example, styrene, vinyl toluene, a polymerizable styrene derivative substituted at the α-position or an aromatic ring such as α-methylstyrene, 2,
Acrylamide such as 2,3,3-tetrafluoropropyl acrylate acrylamide, 2,2,3,3-tetrafluoropropyl methacrylate acrylamide, diacetone acrylamide, acrylonitrile, vinyl-
Esters of vinyl alcohol such as n-butyl ether, alkyl acrylate, alkyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, acryl Acid diethylaminoethyl ester, methacrylic acid diethylaminoethyl ester, 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-
Monoesters of maleic acid such as bromoacrylic acid, α-chloroacrylic acid, β-furylacrylic acid, β-styrylacrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate and the like, fumaral Acids, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like. Examples of the alkyl acrylate or alkyl methacrylate include, for example, those represented by the general formula (VI)

Embedded image (Wherein, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ 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.

R ⁶ in the above general formula (VI) includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Dodecyl groups and their structural isomers. As the monomer represented by the general formula (VI), for example, acrylic acid methyl ester,
Ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate Ester, undecyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, methacrylic acid Octyl ester, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate , Methacrylic acid undecyl ester, and methacrylic 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. 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, the acid value is from 30 to
200 mgKOH / g, preferably 50-100 mgK
Particularly preferred is OH / g. Acid value is 30mgKOH / g
If less than 200mgKO
If it exceeds H / g, the developer resistance of the photocured resist tends to decrease. The weight average molecular weight measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene was 20,000.
３００300,000, preferably 40,000
Particularly preferred is 〜150,000. If the weight average molecular weight is less than 20,000, the developer resistance tends to decrease, and if it exceeds 300,000, the development time tends to be long.

The (B) photopolymerizable compound having a polymerizable ethylenically unsaturated group in the present invention includes, for example,
Polyhydric alcohol, a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol, 2,2-bis (4
-(Acryloxypolyethoxy) phenyl) propane,
2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane, α-, β-
Compounds obtained by reacting unsaturated carboxylic acids, urethane monomers, 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 compound obtained by reacting the above polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example,
Polyethylene glycol diacrylate having 2 to 14 ethylene groups, polyethylene glycol dimethacrylate having 2 to 14 ethylene groups, polypropylene glycol diacrylate having 2 to 14 propylene groups, and the number of propylene groups 2-14 which are polypropylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropaneethoxytriacrylate, trimethylolpropaneethoxytrimethacrylate, tetramethylol Methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetraacrylate, Tiger methylol methane tetramethacrylate, polypropylene glycol diacrylate number of propylene is 2 to 14, polypropylene glycol dimethacrylate number of propylene is 2 to 14, dipentaerythritol pentaacrylate,
Examples thereof include dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate.

The above α, β-unsaturated carboxylic acids include:
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 glycidyl group-containing compound include, 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, for example, an acrylic monomer having an OH group at the β-position or a methacrylic monomer corresponding thereto and isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, and the like. And tris (methacryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane dimethacrylate, EO, PO-modified urethane dimethacrylate, and the like. Note that E
O represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of a propylene oxide group.

Examples of the 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.

X in the 2,4,5-triarylimidazole dimer represented by the general formula (I), which is the component (C) in the present invention, represents a hydrogen atom or a fluorine atom. From the standpoint of sensitivity characteristics, it is preferable that at least one of X is a fluorine atom, and examples of such a compound include 2,4,5- and -4,5-, which are represented by the general formula (II) or (III). And triarylimidazole dimers.

In the present invention, the components represented by the general formula (I), the general formula (II) and the general formula (II)
The 2,4,5-triarylimidazole dimer represented by I), the coumarin compound represented by the general formula (IV) as the component (D) in the present invention, and the compound represented by the general formula (V) The phenyl group in the alkylaminobenzophenone-based compound is a halogen atom, having 1 to 20 carbon atoms.
Alkyl group, cycloalkyl group having 3 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, amino group, 1 to 10 carbon atoms
Alkylamino group, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, mercapto group,
10 alkylmercapto groups, allyl groups, 1-2 carbon atoms
0 hydroxyalkyl group, alkyl group having 1 to 1 carbon atoms
10 carboxyalkyl groups, alkyl groups having 1 carbon atom
It may be substituted with an acyl group having 10 to 10, an alkoxy group having 1 to 20 carbon atoms, a group containing a heterocyclic ring or the like. Also,
The hydrogen atom of the alkyl group in the above substituent may be substituted with a halogen atom.

In formula (I), R has 1 to 20 carbon atoms.
Examples of the alkyl group include a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups. From the viewpoint of ease of production and availability, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferred. The five Xs may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine, iodine, and astatine.
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 nitro group, a cyano group, a mercapto group, an allyl group, an alkyl group having 1 to 20 carbon atoms, or the like. Examples of the alkylamino group having 1 to 10 carbon atoms include, for example,
Methylamino group, ethylamino group, propylamino group,
And an isopropylamino group.

Examples of the dialkylamino group having 2 to 20 carbon atoms include a dimethylamino group, 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 in the alkyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a pivaloyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. 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.

2,4,5 represented by the above general formula (I)
-As the triarylimidazole dimer, for example,
2,2'-bis (2-fluorophenyl) -4,4 ',
5,5'-tetrakis (3-methoxyphenyl) imidazole dimer, 2,2'-bis (2,3-difluoromethylphenyl) -4,4 ', 5,5'-tetrakis (3
-Methoxyphenyl) imidazole dimer, 2,2'-
Bis (2,4-difluorophenyl) -4,4 ', 5
5'-tetrakis (3-methoxyphenyl) imidazole dimer, 2,2'-bis (2,5-difluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) imidazole dimer Body, 2,2′-bis (2,
6-difluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) imidazole dimer,
2,2'-bis (2,3,4-trifluorophenyl)
-4,4 ', 5,5'-tetrakis (3-methoxyphenyl) imidazole dimer, 2,2'-bis (2,3
5-trifluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) imidazole dimer, 2,2'-bis (2,3,6-trifluorophenyl) -4,4 ', 5,5'-Tetrakis (3-methoxyphenyl) imidazole dimer, 2,2'-bis (2,
4,5-trifluorophenyl) -4,4 ', 5,5'
-Tetrakis (3-methoxyphenyl) imidazole dimer, 2,2'-bis (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) imidazole dimer Monomer, 2,2'-bis (2,3,4,5-tetrafluorophenyl) -4,
4 ', 5,5'-tetrakis (3-methoxyphenyl)
Imidazole dimer, 2,2'-bis (2,3,4,6
-Tetrafluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) imidazole dimer, 2,2'-bis (2,3,4,5,6-pentafluorophenyl)- 4,4 ', 5,5'-tetrakis (3
-Methoxyphenyl) imidazole dimer and the like. These are used alone or in combination of two or more.

The photosensitive resin composition of the present invention further comprises (D) a coumarin compound represented by formula (IV) or an alkylaminobenzophenone compound represented by formula (V) as a sensitizer. Is preferable. R in the general formula (IV) and the general formula (V)
¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a cyclic group having 1 to 6 carbon atoms; It represents an alkyl group, and R ³ and R ⁴ may combine with each other to form a ring.

The coumarin compounds which are sensitizers which are component (D) in the present invention include 7-N, N-diethylamino-4-methylcoumarin, 7-N, N-ethylamino-4-methylcoumarin and 7-N, N-ethylamino-4-methylcoumarin. —N, N-diethylaminocyclopenta [c] coumarin and the like. In the present invention, the alkylaminobenzophenone-based compound as a sensitizer, which is the component (D), includes 4,4 ′-(N,
N-dimethyl) aminobenzophenone, 4,4'-
(N, N-diethyl) aminobenzophenone, 4,4 '
-(N-ethyl, N-methyl) aminobenzophenone and the like.

The photosensitive resin composition of the present invention may contain a photopolymerization initiator or a sensitizer other than the general formulas (I), (IV) and (V). Examples of such photopolymerization initiators or sensitizers include benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-
Aromatic ketones such as (4-morpholinophenyl) -butanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzoin methyl ether, benzoin Benzoin ether compounds such as ethyl ether and benzoin phenyl ether, benzoin compounds such as methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and 2,4,5-triarylimidazole represented by the general formula (I) 2,4,5-triarylimidazole dimer other than monomer, 9-phenylacridine, acridine derivative such as 1,7-bis (9,9'-acridinyl) heptane, N-phenylglycine, the general formula ( Coumarin compounds represented by IV) Etc. outside the coumarin compounds. 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.

In the present invention, the amount of the component (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 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 amount of the component (C) 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. When the amount is less than 0.1 part by weight, the effect obtained by the present invention tends to decrease, and when the amount exceeds 10 parts by weight, the resolution tends to deteriorate.

In the present invention, the amount of the component (D) is as follows:
The amount is preferably 0.03 to 1 part by weight based on 100 parts by weight of the total of the components (A) and (B), and is preferably 0.1 to 1 part by weight.
More preferably, it is set to 0.5 parts by weight. When the amount is less than 0.03 parts by weight, the resolution tends to be deteriorated due to the trailing of the pattern.
At the time of exposure, the absorption on the surface of the composition tends to increase and the photocuring inside tends to be insufficient.

The photosensitive resin composition of the present invention may contain, if necessary, a dye such as malachite green, a coloring agent such as leuco crystal violet, a thermal coloring inhibitor, a plasticizer, a pigment, a filler, an antifoam. Agents, flame retardants, stabilizers, adhesion promoters, leveling agents, release accelerators, antioxidants, fragrances,
Imaging agent, thermal crosslinking agent, etc.
Each component can be contained in an amount of about 0.01 to 20 parts by weight based on 100 parts by weight of the total amount of the components. These are used alone or in combination of two or more.

If necessary, the photosensitive resin composition of the present invention may contain a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, N, N-dimethylformamide, or a mixture thereof. It can be dissolved in a solvent and 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, copper-based alloy, nickel, chromium, iron, and stainless steel, and preferably copper or 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 is used as a support,
It can be obtained by applying and drying a photosensitive resin composition on a polymer film having heat resistance and solvent resistance, such as polyethylene terephthalate, polypropylene, polyethylene and polyester. From the viewpoint of transparency, it is preferable to use a polyethylene terephthalate film. 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, a bar coater, and a sleigh coater. Also,
Drying can be performed at 70 to 150 ° C. for about 5 to 30 minutes. In addition, the amount of the residual organic solvent in the photosensitive resin composition layer is 2 to prevent diffusion of the organic solvent in a later step.
% By weight or less.

Further, since these polymer films must be removable from the photosensitive resin composition layer later, they may be subjected to a surface treatment that makes removal impossible, or may be made of a material. Don't be. The thickness of these polymer films is preferably 1 to 100 μm, more preferably 1 to 30 μm. If the thickness is less than 1 μm, the mechanical strength tends to decrease, and problems such as breakage of the polymer film during coating tend to occur. If the thickness exceeds 30 μm, the resolution tends to decrease and the price tends to increase. One of these polymer films may be laminated on both surfaces of the photosensitive resin composition layer as a support film for the photosensitive resin composition layer, and the other as a protective film for the photosensitive resin composition layer. As the protective film, one having a smaller adhesive force between the photosensitive resin composition layer and the protective film than the adhesive force between the photosensitive resin composition layer and the support is preferable.

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 the photosensitive element, if the above-mentioned 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 set to 70 to 130 ° C., and the pressing pressure is set to 0.1 to 1.0 MPa (1 to 1.0 MPa).
It is preferably 10 kg / 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 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. 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. In contrast, when a photopolymerizable initiator such as 9,10-phenanthrenequinone which is highly sensitive to visible light is used in combination, an actinic light source that should emit visible light effectively should be used. Is preferred.

Next, after 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.
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 is 0.1 to 5% by weight.
A dilute solution of sodium carbonate, a dilute solution of 0.1 to 5% by weight of potassium carbonate, a dilute solution of 0.1 to 5% by weight of sodium hydroxide, a dilute solution of 0.1 to 5% by weight of sodium tetraborate and the like are preferable. . 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 accelerating development, and the like may be mixed in the alkaline aqueous solution. The aqueous developer comprises water or an aqueous alkaline solution and one or more organic solvents. Here, as the alkaline substance, other than the above substances, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, , 3-diaminopropanol-2, morpholine and the like. Developer pH
Is preferably as small as possible within a range where the development of the resist can be sufficiently performed, preferably pH 8 to 12, and more preferably pH 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, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monoethyl ether. Butyl ether and the like. These are used alone or in combination of two or more.

The concentration of the organic solvent is usually 2 to 90% by weight.
The temperature can be adjusted in accordance with the developing property. Further, a small amount of a surfactant, an antifoaming agent and the like can be mixed in the aqueous developer. As the organic solvent-based developer used alone, for example, 1,1,1
-Trichloroethane, N-methylpyrrolidone, N, N-
Examples include dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone, and the like. 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 a dip method, a battle method, a spray method, brushing, and slapping, and a high-pressure spray method is most suitable for improving 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 . The order of performing these exposure and heating is not particularly limited. In the case where development is performed using an alkaline substance, a step of neutralizing and removing the remaining alkaline substance after the development can be added. For neutralization, both inorganic and organic acids can be used, but usually,
Organic acids are used. Examples of the organic acid used for neutralization include saturated fatty acids, unsaturated fatty acids, aliphatic dibasic acids, aromatic dibasic acids, aliphatic tribasic acids, and aromatic tribasic acids.

Specifically, for example, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, propionic acid,
Oxalic acid, malonic acid, methyl malonic acid, ethyl malonic acid, succinic acid, methyl succinic acid, adipic acid, methyl adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid Acids, terephthalic acid, trimellitic acid, citric acid and the like. Among these, from the point of high neutralization effect,
Oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, succinic acid, methylsuccinic acid, citric acid and the like are preferable, and oxalic acid, malonic acid, citric acid and the like are more preferable.
These are used alone or in combination of two or more. Further, after the neutralization step, a water washing step may be added.

For the etching of the metal surface after the 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 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 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 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.

[0054]

The present invention will be described below with reference to examples. Examples 1 and 2 and Comparative Examples 1 and 2 The materials shown in Table 1 were blended to obtain a solution. Next, the components (C) and (D) shown in Table 2 were dissolved in the obtained solution to obtain a solution of the photosensitive resin composition.

[0055]

[Table 1]

* 1:

Embedded image

[0057]

[Table 2]

Next, the solution of the photosensitive resin composition is
The composition was uniformly coated on a 16 μm-thick 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, 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 made of # 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. Then, the photosensitive resin composition layer was laminated while being heated to 110 ° C.
Next, an exposure machine equipped with a high-pressure mercury lamp (Oak Co., Ltd.)
As a negative, a 41-step tablet was placed on the test piece and exposed at 60 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. Furthermore, the sensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step tablet of the photocurable film formed on the copper-clad laminate, and the results are shown in Table 3. 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.

[0060]

[Table 3]

[0061]

The photosensitive resin compositions according to the first, second, third and fourth aspects are extremely excellent in sensitivity, excellent in adhesion, chemical resistance, flexibility and plating bath contamination, and are suitable for liquid resists and photosensitive compositions. It is extremely suitable for use as an element. The photosensitive resin composition according to any one of claims 5 and 6,
And 4 exhibit the effects of the photosensitive resin composition described above, and are further excellent in developability with an alkali developing solution, and are extremely suitable for use as a liquid resist and a photosensitive element. The photosensitive element according to claim 7 is extremely excellent in sensitivity, excellent in adhesion, chemical resistance, flexibility, plating bath stainability, alkali developability, mechanical strength and workability, high density of printed wiring and printing. It is extremely useful for automation of wiring board production.

The method for producing a resist pattern according to the eighth aspect has extremely excellent sensitivity, which is extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards, and has excellent adhesion, chemical resistance, flexibility, and plating bath contamination. This is a method for producing a resist pattern having excellent properties, alkali developability, mechanical strength and workability. The method for producing a printed wiring board according to claim 7 is extremely excellent in sensitivity, which is extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards, and has excellent adhesion, chemical resistance, flexibility, plating bath contamination, This is a method for producing a printed wiring board having excellent alkali developability, mechanical strength and workability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/18 H05K 3/18 D

Claims (9)

[Claims] 1. A photopolymerizable compound having (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in a molecule, and (C) a photopolymerization initiator represented by the general formula (I): 1) Wherein X represents a hydrogen atom or a fluorine atom, and R represents an alkyl group having 1 to 20 carbon atoms.
A photosensitive resin composition comprising a 5-triarylimidazole dimer. 2. The photopolymerization initiator (C) has the following formula (II): The photosensitive resin composition according to claim 1, which is a 2,4,5-triarylimidazole dimer represented by the following formula: (C) The photopolymerization initiator is represented by the following formula (III): The photosensitive resin composition according to claim 1, which is a 2,4,5-triarylimidazole dimer represented by the following formula: 4. A sensitizer of the general formula (IV): (Wherein, R ¹ and R ² each independently represent a hydrogen atom or a carbon atom
And R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 1 to 6 carbon atoms, and R ³ and R ⁴ are bonded to each other. A coumarin compound represented by the general formula (V): (Wherein, R ¹ and R ² are R ¹ and R ² in the general formula (IV)
The photosensitive resin composition according to claim 1, which comprises an alkylaminobenzophenone-based compound represented by the following formula: 5. The method according to claim 1, wherein (A) the binder polymer is a binder polymer containing a carboxyl group.
5. The photosensitive resin composition according to 2, 3 or 4. 6. The component (A) having an acid value of 100 to 500 mg KO.
H / g, and a weight average molecular weight of 20,000 to 300,0
The photosensitive resin composition according to claim 5, which is 00. 7. A photosensitive element obtained by applying, drying and laminating the photosensitive resin composition according to claim 1, 2, 3, 4, 5 or 6 on a support. 8. The photosensitive element according to claim 7, which is laminated on the substrate for circuit formation so that the photosensitive resin composition layer is in close contact with the photosensitive element, and is irradiated with actinic rays in an image-like manner, and the exposed portion is photocured. And removing unexposed portions by development. 9. 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 8.