JP2003162052A - Photosensitive resin composition, photosensitive element using the same, method for forming resist pattern and method for manufacturing printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent not only in the adhesion property with a copper substrate, the sensitivity, the resolution and the contaminating property of a plating bath but particularly in the stability of the hue. <P>SOLUTION: The photosensitive resin composition contains (A) a binder polymer, (B) a photopolymerizable compound containing a bisphenol-A (meth) acrylate compound as the essential component, (C) a photopolymerization initiator and (D) a coloring agent containing a compound expressed by general formula (I) as the essential component. In formula (I), each of R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>independently represents an organic group such as an alkyl group or the like. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In the field of printed wiring board manufacturing,
As a resist material used for etching, plating, etc., a photosensitive resin composition and a photosensitive element in which the photosensitive resin composition is laminated on a support and covered with a protective film are widely used. In the case of manufacturing a printed wiring board using a photosensitive element, first, the photosensitive element is laminated on a copper substrate, and after pattern exposure, the unexposed portion is removed with a developing solution, and etching or plating is further performed. A process is performed to form a pattern, and finally the cured portion is peeled off from the substrate.

In recent years, the density of printed wiring boards has been rapidly increased, so that the contact area between the copper substrate and the patterned photosensitive resin composition layer tends to be small. The photosensitive resin composition and the photosensitive element are required to have excellent adhesive strength, mechanical strength, chemical resistance, flexibility and the like in the development, etching or plating treatment steps, and also high resolution.

When a pattern is formed by using a plating method, solder plating is generally used to protect a copper pattern formed by electroplating with copper sulfate or the like. The tin / lead ratio of the solder plating does not deviate significantly from the target ratio due to the soluble component from the photosensitive resin composition and the photosensitive element,
It is also necessary to ensure excellent plating bath contamination.

[0005]

By the way, a blue or green coloring agent (dye or pigment) is added to a photosensitive resin composition or a photosensitive element in order to prevent halation during exposure. However, even if the composition is known to have excellent chemical resistance, including a conventionally known photosensitive resin composition and photosensitive element (Japanese Patent Publication No. 7-27205, etc.), a colorant was added. In this case, the stability was low, the color fading occurred over time, the hue changed, and there was a problem in quality control of the photosensitive resin composition. There is also a problem in the production process such that stable production of the printed wiring board is difficult due to the change in hue.

The present invention has been made in view of the above problems of the prior art, and is a photosensitive resin composition containing a coloring agent, which has adhesion to copper substrate, sensitivity, resolution and plating bath contamination. It is an object of the present invention to provide a photosensitive resin composition which is not only excellent in color stability but also suppresses discoloration of a colorant and is particularly excellent in stability of hue. Another object of the present invention is to provide a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern and a method for manufacturing a printed wiring board.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have achieved the above object by using a specific photopolymerizable compound and a specific colorant in combination. The inventors have found that it is possible and completed the present invention.

That is, the photosensitive resin composition of the present invention is
Containing (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenic unsaturated bond in the molecule, (C) a photopolymerization initiator, and (D) a colorant And a bisphenol A-based (meth) acrylate compound as a component (B) and a compound represented by the following formula (I) as a component (D). Is.

[0009]

[Chemical 3] (In the formula, R ¹ , R ² , R ³ and R ⁴ each independently have 1 carbon atom.
~ 18 alkyl group, C2-18 alkenyl group,
C2-C18 alkynyl group, aryl group, carbon number 1
~ 18 carboxylate group, C1-18 alkoxyl group, C2-18 alkenyloxy group, C2-18 alkynyloxy group, C2-18 allyloxy group, C2-18 Alkoxycarbonyl group, C1-18 alkylthio group, C1-18
Is an alkylsulfonyl group or an alkylsulfinyl group having 1 to 18 carbon atoms. )

The photosensitive resin composition of the present invention has the above (A)
Adhesion to a copper substrate, since the component (D) is an essential component, the component (B) is a bisphenol A (meth) acrylate compound, and the component (D) is a compound represented by the general formula (I). In addition to excellent properties, sensitivity, resolution, and plating bath contamination, it is possible to stabilize the hue. As a result, the quality of the photosensitive element is stabilized, and it becomes possible to produce a high-resolution / high-density printed wiring board.

Since it is possible to further improve the adhesion and sensitivity to the copper substrate while stabilizing the hue, R ¹ , R ² , R ³ and R ⁴ in the general formula (I) are The same or different alkyl groups having 1 to 8 carbon atoms are preferable, and the bisphenol A (meth) acrylate compound is preferably a compound represented by the following general formula (II). Then, X and Y in the following general formula (II) are preferably ethylene groups.

[0012]

[Chemical 4] (In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are p + q = 4 to 40 Is a positive integer chosen to be.

From the viewpoint of further improving the adhesion and sensitivity to the copper substrate while stabilizing the hue, (A)
The component is preferably composed of one kind or two or more kinds of polymers having a carboxyl group, and the polymers having a carboxyl group are (meth) acrylic acid alkyl ester, (meth) acrylic acid and vinyl copolymerizable therewith. It is preferable to include a copolymer with a monomer. Further, as the component (B), it is preferable to contain a photopolymerizable compound having one polymerizable ethylenic unsaturated bond in the molecule, and regarding the compounding amounts of the components (A) to (D), ) Component 40 to 80 parts by weight and component (B) 20 to 6
The compounding amounts of the component (C) and the component (D) are 0.1 to 20 parts by weight and 0.001 to 5 parts by weight, respectively, relative to 100 parts by weight in total of 0 parts by weight, and The compounding amount of the bisphenol A (meth) acrylate compound based on the total weight is preferably 3 to 90% by weight.

The present invention also provides a photosensitive element comprising a support and a photosensitive resin composition layer formed on the support and comprising the above-mentioned photosensitive resin composition, and Provided is a photosensitive element characterized by further comprising a protective film on the photosensitive resin composition layer, the protective film covering the photosensitive resin composition layer.

Such a photosensitive element uses the above-mentioned photosensitive resin composition of the present invention which is not only excellent in adhesiveness to a copper substrate, sensitivity, resolution and plating bath contamination, but also stabilized in hue. Therefore, the quality is stabilized, which enables efficient production of high-resolution and high-density printed wiring boards.

The present invention further comprises stacking the photosensitive resin composition layer in the photosensitive element on a circuit-forming substrate, and irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray for exposure. Part is formed, and then a part other than the exposed part is removed to form a resist pattern, and the method for forming the resist pattern etches the circuit forming substrate on which the resist pattern is formed. Provided is a method for manufacturing a printed wiring board, which is characterized by plating.

Since the resist pattern forming method and the printed wiring board manufacturing method of the present invention use the above-described photosensitive element of the present invention, good exposure is achieved even when the pattern interval is narrowed. Also, etching or plating is possible, and high density can be realized.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The (meth) acrylic acid in the present invention means acrylic acid or methacrylic acid corresponding thereto,
The (meth) acrylate means an acrylate or a methacrylate corresponding thereto, and the (meth) acryloyl group means an acryloyl group or a methacryloyl group corresponding thereto.

As described above, the photosensitive resin composition of the present invention contains the following components (A) to (D):
Binder polymer (B) Photopolymerizable compound (C) photopolymerization initiator having at least one polymerizable ethylenically unsaturated bond in the molecule, (D) colorant, and (B) component as bisphenol A The (meth) acrylate compound is contained as an essential component, and the component (D) is a compound containing the compound represented by the general formula (I) as an essential component. The components (A) to (D) will be described in detail below.

First, the binder polymer as the component (A) will be described. In the present invention, the kind of the binder polymer used as the component (A) is not particularly limited, and examples of usable binder polymers include:
Polyester resin, acrylic resin, styrene resin,
Examples thereof include epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, urethane resin and the like. These binder polymers can be used alone or in combination of two or more.

The binder polymer can be produced, for example, by polymerizing a polymerizable monomer (radical polymerization or the like). Examples of the polymerizable monomer include styrene; styrene derivatives such as vinyltoluene and α-methylstyrene; acrylamide; acrylamide derivatives such as diacetone acrylamide; acrylonitrile; vinyl ethers such as vinyl-n-butyl ether; and (meth) acrylic acid. Alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl ( (Meth) acrylic acid ester such as (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate; (meth) acrylic acid; α-bromo (meth) acrylic acid, α-chloro (meth) acrylic Acid, β Substituted (meth) acrylic acids such as furyl (meth) acrylic acid and β-styryl (meth) acrylic acid; maleic acid; maleic anhydride; monoesters of maleic acid such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate. Other than these, fumaric acid, cinnamic acid,
Examples thereof include α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. In the present invention, the styrene derivative means a styrene in which a hydrogen atom is replaced with a substituent (an organic group such as an alkyl group or a halogen atom).

Examples of the (meth) acrylic acid alkyl ester include compounds represented by the general formula (III), compounds in which an alkyl group of such a compound is substituted with a hydroxyl group, an epoxy group, a halogen group or the like, General formula (II
Examples of the alkyl group having 1 to 12 carbon atoms represented by R ¹² in I) include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group,
Examples thereof include an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group and structural isomers thereof.

[0023]

[Chemical 5] (In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents an alkyl group having 1 to 12 carbon atoms)

Specific examples of the monomer represented by the general formula (III) include (meth) acrylic acid methyl ester,
(Meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth ) Acrylic acid octyl ester,
(Meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester and the like can be mentioned, and these are alone. Alternatively, two or more kinds can be used in combination.

The binder polymer in the present invention is preferably composed of one or more kinds of polymers having a carboxyl group, from the viewpoint of developability in the case of performing alkali development using a sodium hydrogen carbonate solution or the like, and a carboxyl group. More preferably, it is composed of two or more kinds of polymers having The polymer having a carboxyl group can be produced, for example, by polymerizing (radical polymerization or the like) a polymerizable monomer having a carboxyl group and another polymerizable monomer.

From the viewpoint of flexibility, the polymer having a carboxyl group as the binder polymer is (meth)
It is preferable to contain one or more copolymers of acrylic acid alkyl ester, (meth) acrylic acid, and a vinyl monomer copolymerizable with them.

Examples of vinyl monomers copolymerizable with (meth) acrylic acid alkyl ester and (meth) acrylic acid include (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, and (meth) acrylic acid. ) Acrylic acid diethylaminoethyl ester, methacrylic acid glycidyl ester, 2,2
2-trifluoroethyl (meth) acrylate, 2,
Examples thereof include styrene derivatives such as 2,3,3-tetrafluoropropyl (meth) acrylate acrylamide, diacetone acrylamide, styrene and vinyltoluene. Among them, styrene and / or styrene derivatives are preferable, and styrene is more preferable, because they are particularly excellent in flexibility.

In the copolymer of (meth) acrylic acid alkyl ester, (meth) acrylic acid and a vinyl monomer copolymerizable therewith, from the viewpoint of the adhesiveness and peeling property of the photosensitive resin composition, The total weight of styrene and / or styrene derivatives is preferably 0.1 to 30% by weight, based on the total weight of polymerizable monomers,
It is more preferably 1 to 28% by weight, and 1.5 to 2
It is particularly preferably 7% by weight. If the content is less than 0.1% by weight, the adhesion tends to be poor, and if it exceeds 30% by weight, the peeled pieces obtained when the photosensitive resin composition is peeled off after curing become large, or the peeling time is long. May become longer, resulting in inconvenience in the manufacturing process.

The acid value of the binder polymer as the component (A) is preferably 100 to 500 mgKOH / g, more preferably 100 to 300 mgKOH / g. If the acid value is less than 100 mgKOH / g, the developing time tends to be delayed, and 500 mgKOH
If it exceeds / g, the resistance of the photocured resist to the developing solution tends to decrease.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the binder polymer which is the component (A) can be measured by gel permeation chromatography (GPC) (converted by standard polystyrene). According to this measuring method, M of the binder polymer is
w is preferably 5,000 to 300,000, and 10,
000 to 150,000 is more preferable. Mw is 5,
If it is less than 000, the developer resistance tends to decrease, and
If it exceeds 10,000, the developing time tends to be long.
The dispersity (Mw / Mn) of the binder polymer is
It is preferably 1.0 to 3.0, and 1.0 to 2.0.
Is more preferable. When the dispersity exceeds 3.0, the adhesiveness and the resolution tend to decrease.

The binder polymers described above can be used alone or in combination of two or more kinds.
When two or more kinds are used in combination, the binder polymer may be, for example, two different copolymer components.
More than one type of binder polymer, two or more types of binder polymer with different Mw, different dispersity (Mw / Mn)
2 or more types of binder polymers and the like.

When two or more binder polymers are used in combination, one or more copolymers of alkyl (meth) acrylate and (meth) acrylic acid and (meth) acrylic are used. It is possible to combine one or more copolymers of an acid alkyl ester, (meth) acrylic acid and a vinyl monomer (preferably styrene and / or styrene derivative) copolymerizable therewith. .

Next, the component (B), a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule (hereinafter, simply referred to as "photopolymerizable compound") will be described.

The photosensitive resin composition of the present invention contains a bisphenol A (meth) acrylate compound as an essential component as the component (B). As long as such a compound is contained, the component (B) is bisphenol A. It may further contain a photopolymerizable compound other than the system (meth) acrylate compound. Further, the photopolymerizable compound other than the bisphenol A (meth) acrylate compound and the bisphenol A (meth) acrylate compound may be used alone or in combination of two or more kinds. In addition,
In the present invention, the bisphenol A (meth) acrylate compound means a (meth) acryloyl group or (meth)
Carbon derived from an acryloyl group - carbon unsaturated double bond, -C ₆ H ₄ -C derived from bisphenol A (C
_{H 3) 2 -C 6 H 4} - refers to a compound having a group, the.

The bisphenol A (meth) acrylate compound contained as the component (B) is preferably a compound represented by the following general formula (II).

[0036]

[Chemical 6]

In the general formula (II), R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, but it is preferable that both R ⁵ and R ⁶ are methyl groups. In addition, X and Y are each independently an alkylene group having 2 to 6 carbon atoms (ethylene group, propylene group, isopropylene group, butylene group, pentylene group, hexylene group, etc.), but in terms of resolution and plating resistance. Therefore, it is preferable that X and Y are each independently an ethylene group or a propylene group (further, an isopropylene group), and it is more preferable that both X and Y are an ethylene group.

In the general formula (II), p and q are p + q = 4 to
A positive integer chosen to be 40, but p + q
Is preferably 6 to 34, more preferably 8 to 30, still more preferably 8 to 28, particularly preferably 8 to 20, and most preferably 8 to 16. , 8-12 is most preferable. When p + q is less than 4, the compatibility with the component (A) decreases, and when the photosensitive element is laminated on the circuit-forming substrate, it tends to peel off. When p + q exceeds 40, a resist image is formed during development. It tends to peel off, and the plating resistance to solder plating and the like tends to decrease.

Specific examples of the compound represented by the general formula (II) include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-).
((Meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxy polyethoxy polypropoxy)
Phenyl) propane and the like.

As 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, for example, 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxytriethoxy) phenyl) propane,
2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxyheptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4
-((Meth) acryloxynonaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxyundecaethoxy) phenyl)
Propane, 2,2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecaethoxy) phenyl) propane, 2,
2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl) propane and the like can be mentioned.

In the general formula (II), R ⁵ and R ⁶
Is a methyl group, both X and Y are ethylene groups, and a compound of p + q = 10 is BPE-5.
It is commercially available as 00 (manufactured by Shin-Nakamura Chemical Co., Ltd.). Further, in the general formula (II), R ⁵ and R ⁶ are both methyl groups, X and Y are both ethylene groups, and the compound of p + q = 30 is BPE.
-1300N (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) is commercially available. BPE-500 is
(2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is contained as a main component, and
PE-1300N contains 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane as a main component.

Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl. ) Propane, 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,
2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like can be mentioned.

In the present invention, the derivative of the compound represented by the general formula (II) may be used in combination with the compound represented by the general formula (II). Examples of the derivative of the compound represented by the general formula (II) include compounds in which a hydrogen atom in the aromatic ring of the compound represented by the general formula (II) is substituted with a substituent. Examples of the substituent include , Halogen atom, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, aryl group having 6 to 18 carbon atoms, phenacyl group, amino group, alkylamino group having 1 to 10 carbon atoms, carbon number 2-20 dialkylamino group, nitro group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1-10 carbon atoms, allyl group, hydroxyl group, 1-2 carbon atoms
0 hydroxyalkyl group, carboxyl group, carboxyalkyl group having 1 to 10 carbon atoms of alkyl group, acyl group having 1 to 10 carbon atoms of alkyl group, alkoxyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms Substituted with an alkoxycarbonyl group, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, or a heterocyclic ring-containing group. Examples thereof include an aryl group. The above-mentioned substituents may form a condensed ring. Further, the hydrogen atom in these substituents may be substituted with the above-mentioned substituent such as a halogen atom. When the number of substituents is 2 or more, the 2 or more substituents may be the same or different.

As the substituent, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxyl group having 1 to 20 carbon atoms are preferable among the examples given above, and a halogen atom is more preferable.

As the photopolymerizable compound other than the bisphenol A (meth) acrylate compound, a compound obtained by further reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid; a glycidyl group-containing compound with α, β A compound obtained by reacting an unsaturated carboxylic acid; an esterified product of a polycarboxylic acid and a substance having a hydroxyl group and an ethylenically unsaturated group; (meth) acrylic acid alkyl ester; having a urethane bond in the molecule (meta ) Acrylate compounds; nonylphenoxypolyoxyalkylene (meth) acrylates such as nonylphenoxypolyethyleneoxyacrylate; γ-chloro-β-hydroxypropyl-
Examples thereof include phthalic acid compounds such as β ′-(meth) acryloyloxyethyl-o-phthalate and β-hydroxyalkyl-β ′-(meth) acryloyloxyalkyl-o-phthalate.

Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and propylene group. 2 to 14 polypropylene glycol di (meth) acrylate, 2 to 14 ethylene groups and 2 to 14 propylene groups polyethylene polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (Meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned.

Examples of the compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether triacrylate and bisphenol A diglycidyl ether acrylate.

Examples of the esterified product of a polyvalent carboxylic acid and a substance having a hydroxyl group and an ethylenically unsaturated group include an esterified product of phthalic anhydride and β-hydroxyethyl (meth) acrylate.

Examples of the (meth) acrylic acid alkyl ester include compounds represented by the above general formula (III), and specific examples thereof are the same as those described above.

Examples of the (meth) acrylate compound having a urethane bond in the molecule include (meth) acrylic monomers having an OH group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate and 2,4-
Toluene diisocyanate, addition reaction product with diisocyanate compound such as 1,6-hexamethylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, E
O, PO-modified urethane di (meth) acrylate and the like can be mentioned. Examples of the EO-modified urethane di (meth) acrylate include, for example, Shin-Nakamura Chemical Co., Ltd., product name UA-11.
Etc. Examples of the EO, PO-modified urethane di (meth) acrylate include Shin Nakamura Chemical Co., Ltd., product name UA-13 and the like.

EO represents ethylene oxide,
The EO-modified compound has a block structure of an ethylene oxide group. Further, PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide group.

Examples of nonylphenoxypolyethyleneoxyacrylate include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxy. Examples thereof include nonaethyleneoxy acrylate, nonylphenoxydecaethyleneoxy acrylate, and nonylphenoxyundecaethyleneoxy acrylate.

In the present invention, as the component (B), in addition to the bisphenol A (meth) acrylate compound,
It is preferable to contain a photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule. In addition to the bisphenol A (meth) acrylate compound,
It is preferable to contain a photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule and a photopolymerizable compound having two or more polymerizable ethylenically unsaturated bonds in the molecule. Therefore, as the component (B), for example, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, nonylphenoxypolyoxyalkylene (meth) acrylate, and a urethane bond in the molecule (meth) At least one selected from the group consisting of acrylate compounds and a bisphenol A (meth) acrylate compound can be used in combination. Each of the above compounds may be used alone or in combination.
It is possible to use more than one species.

Next, the photopolymerization initiator which is the component (C) will be described. As the photopolymerization initiator in the present invention,
For example, benzophenone, N, N'-tetramethyl-
4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-bis (diethylamino) benzophenone, 2- Benzyl-2-dimethylamino-1-
Aromatic ketones such as (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-tert.
-Butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-
Diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl 1,4
Quinones such as naphthoquinone and 2,3-dimethylanthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin, ethylbenzoin; benzyl derivatives such as benzyldimethylketal 2,4,5-triarylimidazole dimer; 9-phenylacridine,
Acridine derivatives such as 1,7-bis (9,9'-acridinyl) heptane; N-phenylglycine; N-phenylglycine derivatives; coumarin compounds; thioxanthone compounds such as a combination of diethylthioxanthone and dimethylaminobenzoic acid; and 3 A combination with a primary amine compound and the like can be mentioned.

In the 2,4,5-triarylimidazole dimer, the two 2,4 constituting the dimer are
The 5-triarylimidazoles may have the same structure or different structures. That is, the types of triaryl groups in the 2,4,5-triarylimidazole dimer may be the same or different.

Examples of the 2,4,5-triarylimidazole dimer include 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'. -Biimidazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5'-tetra (p-chlorophenyl) imidazole dimer, 2- (o-chlorophenyl) -4,5-di (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 Isomer, 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 (m, p-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 (o, p-dichlorophenyl)
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-
(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, 2,2'-
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 can be mentioned.

In these 2,4,5-triarylimidazole dimers, the aryl group is further a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 6 to 6 carbon atoms. 14 aryl group, amino group, alkylamino group having 1 to 10 carbon atoms, nitro group, cyano group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, allyl group, carbon A hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, and 1 to 20 carbon atoms
It may be substituted with an alkoxyl group or a group containing a heterocycle.

In the present invention, the photopolymerization initiator as the component (C) can be used alone or in combination of two or more kinds. From the viewpoints of adhesion and sensitivity, it is preferable to contain a 2,4,5-triarylimidazole dimer as a photopolymerization initiator, and a 2,4,5-triarylimidazole dimer and the dimer. It is more preferable to use in combination with a photopolymerization initiator other than. 2, 4,
As the photopolymerization initiator other than the 5-triarylimidazole dimer, 4,4′-bis (diethylamino) benzophenone is preferable.

Next, the colorant which is the component (D) will be described. The photosensitive resin composition of the present invention contains a compound represented by the following general formula (I) (hereinafter referred to as “compound I”) as an essential component as the component (D), and as long as the compound is contained, The component (D) may further contain a colorant other than the compound I.

[0060]

[Chemical 7]

In the general formula (I), R ¹ , R ² , R ³ ,
R ⁴ is independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group, a carboxylate group having 1 to 18 carbon atoms, and 1 to 1 carbon atoms. 18 alkoxyl groups with 2 to 1 carbon atoms
8 alkenyloxy group, C 2-18 alkynyloxy group, C 2-18 allyloxy group, C 2
A C18 to C18 alkoxycarbonyl group, a C1 to C18 alkylthio group, a C1 to C18 alkylsulfonyl group, or a C1 to C18 alkylsulfinyl group.

R ¹ , R ² , R ³ and R ⁴ are each independently
It is preferably an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms, or a carboxylate group having 1 to 18 carbon atoms, and an alkyl group having 1 to 18 carbon atoms. It is more preferable that the group is an alkoxyl group having 1 to 18 carbon atoms. R ¹ , R ² , R
³ and R ⁴ are more preferably the same or different alkyl groups having 1 to 18 carbon atoms, and the same or different C 1 to 1 4
Particularly preferred are alkyl groups having 8 carbon atoms, and more preferred are the same alkyl groups having 1 to 8 carbon atoms.

The compound I is, for example, R ¹ , R ² ,
4- (p- (diethylamino) -α-phenylbenzylidene) -2,5-, in which all of R ³ and R ⁴ are ethyl groups
Cyclohexadiene-1-ylidene sulfate (N-
[4-[[4- (diethylamino) phenyl] phenylmethylene] -2,5-cyclohexadiene-1-ylidene] -N-ethyl-ethanaminium sulfate),
4- (p- (dimethylamino) -α-phenylbenzylidene) -2,5-cyclohexadiene-1-ylidene sulfate (N- [4-[[4- (dimethylamino) phenyl] phenylmethylene] -2, 5-cyclohexadiene-1-ylidene] -N-ethyl-ethanaminium sulphate). 4- (p- (diethylamino) -α-phenylbenzylidene) -2,5-cyclohexadiene-1-ylidene sulfate is known as Basic Green 1 or Brilliant Green and is easily available. It is preferably used as compound I.

Compound I can be used alone or in combination of two or more kinds. Further, at least one kind of colorants other than the compound I can be used in combination. Compound I
Other colorants include triphenylmethane dyes such as malachite green, ethyl violet, and acid magenta, styryl dyes, metalocyanine dyes, and oxonol dyes.

Next, the compounding amounts of the components (A) to (D) in the photosensitive resin composition of the present invention will be described. (A)
The weight of the component (A), which accounts for 100 parts by weight of the total weight of the component and the component (B), is preferably 40 to 80 parts by weight, and more preferably 45 to 70 parts by weight. If the weight of the component (A) is less than 40 parts by weight, the photocured product tends to be brittle, and when used as a photosensitive element, the film-forming property tends to be poor. If it exceeds 80 parts by weight, the photosensitivity is insufficient. Tends to become.

Total weight of component (A) and component (B) 1
The weight of the component (B) in 20 parts by weight is 20 to 60.
Part by weight is preferable, and 30 to 55 parts by weight is more preferable.
If the weight of the component (B) is less than 20 parts by weight, the photosensitivity tends to be insufficient, and if it exceeds 60 parts by weight, the photocured product tends to become brittle.

The compounding amount of the component (C) is 0.1 to 2 with respect to 100 parts by weight of the total weight of the components (A) and (B).
It is preferably 0 part by weight, more preferably 0.2 to 10 parts by weight. The blending amount of component (C) is 0.1
If the amount is less than 20 parts by weight, the photosensitivity tends to be insufficient.
If the amount is more than parts by weight, absorption on the surface of the composition during exposure tends to increase, and internal photocuring tends to be insufficient.

The blending amount of the component (D) is 0.001 based on 100 parts by weight of the total weight of the components (A) and (B).
Is preferably 5 to 5 parts by weight, more preferably 0.005 to 1 part by weight. If the blending amount of the component (D) is less than 0.001 part by weight, the effect of preventing halation tends to be low and the resolution tends to be low. If it exceeds 5 parts by weight, the degree of coloring is too high, and The contrast with the film tends to be low, and workability in forming a circuit tends to decrease.

Next, the components other than the components (A) to (D) that can be contained in the photosensitive resin composition of the present invention will be described. In the photosensitive resin composition of the present invention, if necessary, a photo-coloring agent such as tribromophenyl sulfone or leuco crystal violet, a thermal color-developing agent, a plasticizer such as p-toluene sulfonamide, a pigment, a filler, A foaming agent, a flame retardant, a stabilizer, an adhesion-imparting agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal cross-linking agent, etc. (A) component and (B) component 100 parts by weight in total. With respect to each, about 0.01 to 20 parts by weight can be contained. These are used alone or in combination of two or more.

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

The above-mentioned photosensitive resin composition of the present invention has a metal surface such as copper, copper alloy, nickel, chromium, iron,
On the surface of iron-based alloys such as stainless steel, preferably copper, copper-based alloys, iron-based alloys, it is applied as a liquid resist and dried, and then a protective film is coated if necessary, or the photosensitivity described below is used. It is preferably used in the form of an element.

Next, the photosensitive element of the present invention will be described. The photosensitive element of the present invention comprises a support and a photosensitive resin composition layer formed on the support and comprising the photosensitive resin composition, and the photosensitive resin composition layer is provided on the photosensitive resin composition layer. May further include a protective film that covers the photosensitive resin composition layer.

The photosensitive resin composition layer is prepared by dissolving the photosensitive resin composition of the present invention in the above-mentioned solvent (or mixed solvent) to form a solution having a solid content of about 30 to 60% by weight, and then supporting the solution. It is preferably formed by coating on the body. The thickness of the photosensitive resin composition layer varies depending on the use, but the thickness after drying is preferably 1 to 100 μm, and 1 to 5 μm.
It is more preferably 0 μm. If this thickness is less than 1 μm, it tends to be difficult to coat industrially, and 100 μm
If it exceeds, the adhesive strength and resolution tend to decrease.

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

The support in the photosensitive element preferably has a thickness of 5 to 25 μm, more preferably 8 to 20 μm, and particularly preferably 10 to 16 μm. When the thickness is less than 5 μm, the support tends to be easily broken at the time of peeling the support before development, and the thickness is 25 μm.
If it exceeds m, the resolution tends to decrease.

The support is polyethylene terephthalate,
It is preferably made of a polymer film having heat resistance and solvent resistance such as polypropylene, polyethylene, polyester, and the haze thereof is preferably 0.001 to 5.0, and 0.001 to 2.0. Is more preferable and 0.01 to 1.8 is particularly preferable. If this haze exceeds 2.0, the resolution tends to decrease. The haze is measured according to JIS K 7105, and can be measured with a commercially available turbidimeter such as NDH-1001DP (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.).

The protective film used for the photosensitive element preferably has a thickness of 5 to 30 μm,
The thickness is more preferably 28 μm, particularly preferably 15 to 25. If the thickness is less than 5 μm, the protective film tends to tear during lamination,
If the thickness exceeds μm, the price tends to be poor.

The tensile strength of the protective film in the longitudinal direction of the film is preferably 13 MPa or more and 13 to 1
More preferably 00 MPa, 14 to 100 M
Pa is more preferable, 15 to 100 MPa is particularly preferable, and 16 to 100 MPa is extremely preferable. Tensile strength in the longitudinal direction of the film
If it is less than 3 MPa, the protective film tends to be easily torn during lamination.

The tensile strength of the protective film in the film width direction is preferably 9 MPa or more, and 9 to 100 M.
Pa is more preferable, 10 to 100 MPa is still more preferable, 11 to 100 MPa is particularly preferable, and 12 to 100 MPa is extremely preferable. If the tensile strength in the film width direction is less than 9 MPa, the protective film tends to break during lamination.

The tensile strength is JIS C 2318-199.
7 (5.3.3), and can be measured with a commercially available tensile strength tester such as Tensilon under the trade name of Toyo Baldwin Co., Ltd., for example.

The support and the protective film must be capable of being removed from the photosensitive resin composition layer later, and therefore must not be surface-treated so that they cannot be removed. If necessary, surface treatment such as corona discharge treatment may be applied. Further, the support and the protective film may be subjected to antistatic treatment.

The photosensitive element of the present invention can be stored, for example, in the form of a sheet, or after interposing a protective film, wound around a winding core in a roll shape. And on the end face of the photosensitive element wound into a roll, it is preferable to install an end face separator from the viewpoint of end face protection,
It is preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. In addition, as a packing method, it is preferable to wrap and wrap in a black sheet having low moisture permeability.

Next, the method of forming the resist pattern of the present invention will be described. The method for forming a resist pattern according to the present invention comprises laminating a photosensitive resin composition layer in the photosensitive element on a circuit-forming substrate, irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray and exposing the same. Part is formed, and then the part other than the exposed part is removed. The circuit-forming board is an insulating layer and a conductor layer formed on the insulating layer (copper, copper-based alloy, nickel, chromium,
A substrate provided with an iron-based alloy such as iron or stainless steel, preferably copper, a copper-based alloy, or an iron-based alloy).

As a lamination method, when the photosensitive element has a protective film, the film is removed, and then the photosensitive resin composition layer is heated and pressure-bonded to the circuit-forming substrate for lamination. Examples thereof include a method, and it is preferable to laminate under reduced pressure from the viewpoint of adhesion and followability. The surface to be laminated is usually the surface of the conductor layer of the circuit-forming substrate, but it may be a surface other than this surface. The heating temperature of the photosensitive resin composition layer is preferably 70 to 130 ° C., and the pressure bonding is preferably about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). There are no particular restrictions on the conditions. Further, if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, it is not necessary to preheat the circuit forming substrate in advance, but in order to further improve the stacking property, the circuit forming is required. It is also possible to perform a preheat treatment of the substrate.

After the lamination is completed in this way, an actinic ray is irradiated to a predetermined portion of the photosensitive resin composition layer to form an exposed portion. Examples of the method of forming the exposed portion include a method of irradiating an actinic ray imagewise through a negative or positive mask pattern called an artwork. At this time, when the support present on the photosensitive resin composition layer is transparent to actinic rays, it can be irradiated with actinic rays through the support, and when the support is opaque to actinic rays. First, after removing the support, the photosensitive resin composition layer is irradiated with actinic rays.

As the light source of the actinic ray, for example, a known light source such as a carbon arc lamp, a mercury vapor arc lamp,
Ultra-high pressure mercury lamps, high pressure mercury lamps, xenon lamps, etc. that effectively radiate ultraviolet rays are used. In addition, a flood light bulb for photography, a solar lamp or the like that effectively radiates visible light is also used.

Then, after the exposure, if the support is present on the photosensitive resin composition layer, after removing the support,
A portion other than the exposed portion is removed by wet development, dry development, or the like, and development is performed to form a resist pattern. In the case of wet development, using a developing solution corresponding to the photosensitive resin composition such as an alkaline aqueous solution, an aqueous developing solution, an organic solvent-based developing solution, for example, known spraying, rocking dipping, brushing, scraping, etc. Develop according to the method.

As the developing solution, an alkaline aqueous solution or the like which is safe and stable and has good operability is used.
Examples of the base of the alkaline aqueous solution include lithium,
Alkali hydroxide such as sodium or potassium hydroxide, alkali carbonate such as lithium, sodium, potassium or ammonium carbonate or bicarbonate, potassium phosphate, alkali metal phosphate such as sodium phosphate,
Alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used. As the alkaline aqueous solution used for development, a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% potassium carbonate, a dilute solution of 0.1 to 5 wt% sodium hydroxide, A dilute solution of 0.1 to 5% by weight sodium tetraborate 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. Further, a surface active agent, a defoaming agent, a small amount of an organic solvent for accelerating development may be mixed in the alkaline aqueous solution.

The water-based developer comprises water or an aqueous alkaline solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution, other than those described above, for example,
Examples include borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2 and morpholine. P of developer
H is preferably as small as possible within the range where the resist can be sufficiently developed, and is preferably pH 8 to 12, more preferably pH 9 to 10.

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

As the organic solvent type developing solution, for example, 1,
1,1-trichloroethane, N-methylpyrrolidone,
Examples thereof include N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone and the like. These organic solvents are 1 to 20 to prevent ignition.
Water is preferably added in the range of wt%.

In the present invention, if necessary, two or more of the above-mentioned developing methods may be used in combination. Development methods include dip method, battle method, spray method, brushing, slapping, etc., and the high pressure spray method is most suitable for improving resolution.

As the processing after development, 60 to 60
The resist pattern may be further cured and used by heating at about 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² .

The resist pattern is formed as described above. However, in the resist pattern forming method of the present invention, the use of the above-described photosensitive element of the present invention makes it possible to form a narrow pattern well. Become.

Next, a method for manufacturing the printed wiring board of the present invention will be described. The method for producing a printed wiring board of the present invention is the method for forming a resist pattern of the present invention,
The circuit forming substrate on which a resist pattern is formed is etched or plated.

The etching and plating of the circuit-forming board are performed on the conductor layer and the like of the circuit-forming board using the formed resist pattern as a mask. Examples of the etching solution used for etching include cupric chloride solution, ferric chloride solution, alkaline etching solution, and hydrogen peroxide-based etching solution. Preference is given to using iron solutions. Moreover, as a plating method when performing plating,
For example, copper sulfate plating, copper plating such as copper pyrophosphate, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate plating, hard gold plating, soft gold plating Etc., such as gold plating. In the present invention, solder plating may be further performed in order to protect the copper pattern formed by copper sulfate plating or the like.

After completion of etching or plating, the resist pattern can be stripped with, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used for development.
As the strongly alkaline aqueous solution, for example, 1 to 10
A weight% sodium hydroxide aqueous solution, a 1 to 10 weight% potassium hydroxide aqueous solution and the like are used. Examples of the peeling method include a dipping method and a spray method. The dipping method and the spray method may be used alone or in combination.

A printed wiring board is obtained as described above,
In the method for producing a printed wiring board of the present invention, since the photosensitive element of the present invention described above is used, good exposure and etching or plating are possible even when the pattern interval is narrowed, It becomes possible to realize densification. Further, since elution of the photosensitive element into the plating bath is suppressed, the tin / lead ratio of the solder plating does not deviate significantly from the target ratio. As a result, it is possible to ensure excellent plating bath contamination.

The method of manufacturing a printed wiring board according to the present invention is applicable not only to the manufacture of a single-layer printed wiring board but also to the manufacture of a multilayer printed wiring board. Further, since the method for producing a printed wiring board of the present invention has the above-mentioned effects, the obtained printed wiring board can be suitably used in a field requiring high density.

[0100]

EXAMPLES The present invention will be described below with reference to examples. First, the materials shown in Table 1 were blended to obtain a solution. Then, the component (B) shown in Table 2 was dissolved in the obtained solution to obtain a solution of the photosensitive resin composition. The numerical values in Table 1 and Table 2 mean parts by weight.

[0101]

[Table 1]

[0102]

[Table 2]

Then, the solution of the obtained photosensitive resin composition was treated with polyethylene terephthalate (PE) having a thickness of 16 μm.
T) film (haze: 1.7%, trade name GS-16,
Teijin Co., Ltd.) and then dried for 10 minutes with a hot air convection dryer at 100 ° C., and then a polyethylene protective film (tensile strength in longitudinal direction of film: 16 MPa, tensile strength in transverse direction of film: 12 MPa). , Product name: NF-1
5, Tama Poly Co., Ltd.) to obtain a photosensitive element.

Next, with respect to each of the obtained photosensitive elements, those stored under the following conditions (1) and (2) were used as evaluation samples, and the photosensitive resin was applied to the copper-clad laminate by the following method. The composition layers were laminated to obtain a laminate. (1) 4 ° C in a room at 23 ° C ± 2 ° C RH60% with light shielding
Stored for 2 hours (2) 23 ° C ± 2 ° C RH 60% in a light-shielded state 9
One stored for 0 days, that is, a copper-clad laminate which is a glass epoxy material with copper foil (thickness 35 μm) laminated on both sides (manufactured by Hitachi Chemical Co., Ltd.,
The copper surface of the product name MCL-E-61) was polished using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, washed with water, and then dried with an air stream to obtain a copper-clad laminate. The plate was heated to 80 ° C., and the photosensitive resin composition layer was laminated on the copper surface while peeling off the protective film of the photosensitive element to obtain a laminate. The laminate is 120 ° C.
Was performed at a pressure of 0.4 MPa and a speed of 3 m / min.

<Sensitivity> On the resulting laminate, a 21-step stoffer negative tablet was placed as a negative, and an exposure machine having a high pressure mercury lamp (HMW5 manufactured by Oak Co., Ltd.) was used.
90) was used and exposed at 30, 60 and 120 mJ / cm ² . Then, the polyethylene terephthalate film was peeled off, and a 1 wt% sodium carbonate aqueous solution was added at 60 ° C.
The unexposed areas were removed by spraying for 2 seconds.
Further, the sensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step tablet of the photo-cured film formed on the copper-clad laminate, and the sensitivity of the photosensitive resin composition was evaluated.
The exposure amount (mJ / cm ² ) required to cure the 0th step was defined as the sensitivity. The lower the exposure amount, the higher the sensitivity.

<Adhesiveness / Resolution> A phototool having a wiring pattern having a line width / space width of 30/30 to 200/200 (unit: μm) was brought into close contact with the obtained laminated body, and 21 steps of a stouffer were attached. Exposure was performed with a step tablet at an energy amount such that the remaining step number after development was 8.0. After that, the polyethylene terephthalate film was peeled off, the unexposed portion was removed, and then the resolution was evaluated by the smallest value of the space width between the line widths which was able to remove the unexposed portion cleanly by the developing treatment. In addition, the line width remaining without peeling was defined as the adhesiveness. The smaller the numerical value is, the better the evaluation of the adhesiveness and the resolution is.

<Polting bath contamination> The above (1) and (2)
After exposing the photosensitive element stored under the conditions described above under the step tablet with an energy amount of 8.0 steps, the polyethylene terephthalate film was peeled off, and the exposed photosensitive resin composition was treated with a solder plating bath (45% by weight). Tin borofluoride 64 ml / liter, 45 wt% lead borofluoride 22 ml / liter, 42 wt% borofluoric acid 20
0 ml / liter, Pultin LA Conductivity Salt (Meltex Co., Ltd.) 20 g / liter, Pultin LA Starter (Meltex Co., Ltd. 41 ml / liter) was added to 0.1 m ² / liter at 40 ° C. for 7 days. I left it.

Then, the above standing plating solution was put into a Hull cell tank (made by Yamamoto Plating Tester Co., Ltd.) and a current of 1 A was applied to 5 hours.
It flowed for a minute and plated on a copper plate. The current density was calculated using the conversion table, and the current density on the copper plate was 0.5 A / dm ² , 1
X-ray fluorescence microanalysis film thickness meter at the position where the A / dm ² and 2A / dm ² (Seiko Denshi Kogyo SFT-158V) Sn ratio using the (content of tin to the total content of lead and tin The weight ratio) was measured. At this time, a blank was measured in advance with a plating solution to which no photosensitive element was added, and the value obtained by dividing the measured value with the lowest Sn ratio in the above measurement by the blank was used as an index of contamination. The obtained value means that the closer it is to 1, the lower the staining property.

<Hue> The photosensitive element stored under the conditions (1) and (2) above was evaluated for change in hue over time using a color difference meter TC-8600A manufactured by Tokyo Denshoku Co., Ltd. In this case, the measurement was performed so that the PET film side of the photosensitive element was the light source side. Note that the hue change is the b value indicating the degree of green / blue and the total light transmittance L.
(%) Was used as an index.

The results of evaluation of sensitivity, adhesion, resolution, plating bath contamination and hue are shown in Table 3 for the photosensitive element stored under the above condition (1) and the photosensitivity stored under the above condition (2). The elements are shown in Table 4.

[0111]

[Table 3]

[0112]

[Table 4]

As is clear from Tables 3 and 4, the photosensitive elements of Examples 1 to 4 showed little change in hue even after 90 days had passed after preparation. Also, the resolution, adhesion and plating bath contamination are good.

[0114]

As described above, according to the present invention,
A photosensitive resin composition containing a colorant, which is not only excellent in adhesion to a copper substrate, sensitivity, resolution and plating bath stain resistance, but also suppresses discoloration of the colorant and is particularly excellent in hue stability. It is possible to provide the photosensitive resin composition. Further, it becomes possible to provide a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a printed wiring board.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/028 G03F 7/028 7/033 7/033 7/11 501 7/11 501 7/40 521 7 / 40 521 H05K 3/00 H05K 3/00 F 3/06 3/06 J 3/18 3/18 D (72) Inventor Katsutoshi Itagaki 4-13-1 Higashimachi, Hitachi City, Ibaraki Hitachi Chemical Co., Ltd. Yamazaki Plant (72) Inventor Tatsuya Ichikawa 4-13-1 Higashimachi, Hitachi City, Ibaraki Hitachi Chemical Co., Ltd. Yamazaki Plant F-term (reference) 2H025 AA01 AA02 AA14 AB11 AB15 AC01 AD01 BC42 BC43 CA03 CA27 CA28 CB13 CB14 CB43 CC11 DA01 FA03 FA17 FA40 FA43 2H096 AA26 BA05 BA20 CA20 EA02 GA08 HA17 HA27 JA04 4J027 AC02 AC03 AC04 AC06 BA07 BA19 BA24 BA25 BA26 BA27 BA28 CA25 CA34 CC05 CD10 5E339 BE13 CC01 CC02 CD01 CE11 CF05 CF04 CF17 CG GG10 5E343 CC63 DD33 DD43

Claims (12)

[Claims] 1. A binder polymer (A), a photopolymerizable compound (B) having at least one polymerizable ethylenically unsaturated bond in the molecule, and (C) a photopolymerization initiator.
A photosensitive resin composition containing (D) a colorant, which contains a bisphenol A (meth) acrylate compound as a component (B) and is represented by the following general formula (I) as a component (D). A photosensitive resin composition comprising a compound. [Chemical 1] (In the formula, R ¹ , R ² , R ³ and R ⁴ each independently have 1 carbon atom.
~ 18 alkyl group, C2-18 alkenyl group,
C2-C18 alkynyl group, aryl group, carbon number 1
~ 18 carboxylate group, C1-18 alkoxyl group, C2-18 alkenyloxy group, C2-18 alkynyloxy group, C2-18 allyloxy group, C2-18 Alkoxycarbonyl group, C1-18 alkylthio group, C1-18
Is an alkylsulfonyl group or an alkylsulfinyl group having 1 to 18 carbon atoms. ) 2. The photosensitive resin composition according to claim ¹ , wherein R ¹ , R ² , R ³ and R ⁴ are the same or different alkyl groups having 1 to 8 carbon atoms. 3. The photosensitive resin composition according to claim 1, wherein the bisphenol A (meth) acrylate compound is a compound represented by the following general formula (II). [Chemical 2] (In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are p + q = 4 to 40 Is a positive integer chosen to be. 4. The photosensitive resin composition according to claim 3, wherein X and Y are ethylene groups. 5. The component (B), which contains a photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule, according to any one of claims 1 to 4. The photosensitive resin composition of. 6. The photosensitive resin composition according to claim 1, wherein the component (A) is composed of one kind or two or more kinds of polymers having a carboxyl group. 7. The polymer having a carboxyl group contains a copolymer of (meth) acrylic acid alkyl ester, (meth) acrylic acid, and a vinyl monomer copolymerizable therewith. The photosensitive resin composition described. 8. A total of 100 parts by weight of 40 to 80 parts by weight of component (A) and 20 to 60 parts by weight of component (B),
The blending amounts of the component (C) and the component (D) are each 0.
1 to 20 parts by weight and 0.001 to 5 parts by weight, and the bisphenol A is based on the total weight of the component (B).
The photosensitive resin composition according to any one of claims 1 to 7, wherein the compounding amount of the system (meth) acrylate compound is 3 to 90% by weight. 9. A support, and a photosensitive resin composition layer formed on the support, the photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 8. And a photosensitive element. 10. The photosensitive element according to claim 9, further comprising a protective film on the photosensitive resin composition layer, the protective film covering the photosensitive resin composition layer. 11. The circuit forming substrate according to claim 9 or 1.
The photosensitive resin composition layer in the photosensitive element according to 0, is laminated, and a predetermined portion of the photosensitive resin composition layer is irradiated with an actinic ray to form an exposed portion, and then a portion other than the exposed portion is exposed. A method for forming a resist pattern, which comprises removing the resist pattern. 12. A method of manufacturing a printed wiring board, which comprises etching or plating a circuit-forming substrate having a resist pattern formed thereon by the method of forming a resist pattern according to claim 11.