JP2003248308A - Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern and method for producing printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive element excellent in resolution, adhesion, sensitivity, low scumming property and plating resistance and to provide methods for producing a resist pattern and a printed wiring board. <P>SOLUTION: The photosensitive element comprises a photosensitive resin composition comprising (A) a binder polymer, (B) photopolymerizable compounds having at least one polymerizable ethylenically unsaturated group per molecule and (C) a photopolymerization initiator, wherein the component (B) essentially includes (b1) a bisphenol A type (meth)acrylate compound, (b2) a polypropylene glycol diacrylate and (b3) a phenoxypolyethyleneoxy (meth)acrylate compound represented by formula (I) (where R<SP>1</SP>is H or methyl; Z is a 1-10C alkyl; m is an integer of 2-10; and n is an integer of 0-5). The methods for producing a resist pattern and a printed wiring board uses the photosensitive element. <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 producing a resist pattern and a method for producing a printed wiring board.

[0002]

2. Description of the Related Art In the field of conventional printed wiring board manufacturing, as a resist material used for etching, plating, etc., a photosensitive resin composition and a photosensitive element obtained by using a support and a protective film therefor are widely used. ing.

In a printed wiring board, a photosensitive film is laminated on a copper substrate, and after pattern exposure, the cured portion is removed with a developing solution, and etching or plating treatment is applied to form a pattern, followed by curing. It is manufactured by a method of peeling and removing the portion from the substrate.

With the recent increase in the density of printed wiring boards, photosensitive films are required to have higher resolution and higher adhesion than conventional photosensitive films. On the other hand, from the viewpoint of improving workability, a photosensitive resin composition with high sensitivity and low plating bath contamination is desired, and these characteristics depend on the type and amount of the photopolymerization initiator used. It depends.

Highly sensitive photopolymerization initiators are described in German Patent No. 2,027,467 and European Patent Publication No. 1
1,786, European Patent Publication No. 220, European Patent Publication No. 589, JP-A-6
Although disclosed in Japanese Patent Publication No. 69631, these have a drawback that they have a plating bath contamination property.

In addition to this, a photosensitive resin composition having high sensitivity by combining a hydrogen donating compound with 2,4,5-triphenylimidazole dimer, which is a photopolymerization initiator, and has a low plating bath contamination property, is provided. U.S. Pat. No. 3,479,185, however, when the amount of 2,4,5-triphenylimidazole dimer used is increased when the sensitivity is adjusted to the required level, the resist line There is a drawback that the width becomes wide, and when the amount of the hydrogen donating compound used is increased, there is a drawback that the adhesion to copper and the storage stability become poor.

It is also possible to use a compound having a highly reactive ethylenically unsaturated group with 2,4,5-triphenylimidazole dimer (for example, polyethylene glycol dimethacrylate). It has the drawback of being extremely inferior in chemical resistance.

[0008]

[Patent Document 1] German Patent No. 2,027,467

[0009]

[Patent Document 2] European Patent Publication No. 11,786

[0010]

[Patent Document 3] European Patent Publication No. 220

[0011]

[Patent Document 4] European Patent Publication No. 589

[0012]

[Patent Document 5] Japanese Patent Laid-Open No. 6-96331

[0013]

[Patent Document 6] US Pat. No. 3,479,185

[0014]

SUMMARY OF THE INVENTION Claims 1, 2, 3,
4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 1
The invention described in 4 or 15 provides a photosensitive resin composition excellent in high resolution, high adhesion, high sensitivity, low scum generation, plating resistance and plating bath contamination.

The sixteenth aspect of the present invention is excellent in high resolution, high adhesion, high sensitivity, low scum generation, plating resistance, plating bath contamination, workability and productivity, and high printed wiring board. A photosensitive element effective for densification is provided.

The invention according to claim 17 is excellent in high resolution, high adhesion, high sensitivity, low scum generation, plating resistance, plating bath contamination, workability and productivity, and high printed wiring board. The present invention provides a method for producing a resist pattern effective for increasing the density.

The invention of claim 18 is excellent in high resolution, high adhesion, high sensitivity, low scum generation, plating resistance, plating bath contamination, workability and productivity, and high printed wiring board. It is intended to provide a method for manufacturing a printed wiring board which is effective in increasing the density.

[0018]

The present invention provides (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C) a photopolymerization initiator. In the photosensitive resin composition containing, the component (B) is (b1) bisphenol A-based (meth) acrylate compound, (b2) polypropylene glycol diacrylate and (b3) phenoxy polyethyleneoxy (meth) acrylate-based compound. It relates to a photosensitive resin composition containing as an essential component.

In the present invention, the (b1) bisphenol A-based (meth) acrylate compound is 2,2-bis (4-).
((Meth) acryloxypolyethoxy) phenyl) propane The above photosensitive resin composition.

The present invention also relates to (b2) the above-mentioned photosensitive resin composition in which the number of propylene glycol units of polypropylene glycol diacrylate is 2-10.

The present invention also provides (b3) a phenoxypolyethyleneoxy (meth) acrylate compound represented by the general formula (I).

[Chemical 3] (In the formula, R ¹ represents a hydrogen atom or a methyl group, Z represents an alkyl group having 1 to 10 carbon atoms, m is an integer of 2 to 15, and n is an integer of 0 to 5) And a photosensitive resin composition which is a compound.

The present invention also relates to the above-mentioned photosensitive resin composition in which (A) the binder polymer has a dispersity of 1.0 to 4.0.

Further, the present invention provides the (b1) component, (b2)
The blending amount of the component and the component (b3) is 30 to 85% by weight of the component (b1), 5 to 30% by weight of the component (b2), and 10 to 50% by weight of the component (b3) based on the total amount of the component (B). % Of the photosensitive resin composition.

The present invention also comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C) a photopolymerization initiator. In the photosensitive resin composition, the component (A) has a dispersity of 1.0 to 4.0, the component (B) has (b4) HLB = 7.0 to 17.0, and A compound having at least two ethylenically unsaturated groups, (b5) HLB = 7.0 to 16.0,
A compound having at least one ethylenically unsaturated group in the molecule and (b6) HLB = 0 to 7.0, and a photosensitizer containing as an essential component a compound having at least one ethylenically unsaturated group in the molecule. Resin composition.

Further, according to the present invention, (b4) HLB = 7.0
The compound having ˜17.0 has two ethylenically unsaturated groups in the molecule, and the compound having (b5) HLB = 7.0 to 16.0 has one ethylenically unsaturated group in the molecule. The present invention relates to the photosensitive resin composition.

Further, according to the present invention, (b4) HLB = 7.0
~ 17.0 compounds are bisphenol A-based (meth)
It relates to the photosensitive resin composition which is an acrylate compound.

Further, according to the present invention, (b4) HLB = 7.0
The photosensitive resin composition has 2 to 30 ethylene glycol units in the molecule of the compound of 17.0 to 17.0. Moreover, this invention is (b5) HLB = 7.0-16.
The present invention relates to the photosensitive resin composition, wherein the number of ethylene glycol units in the molecule of compound 0 is 2 to 15.

Further, according to the present invention, (b6) HLB = 0 to
The above-mentioned photosensitive resin composition, wherein the compound of 7.0 is polypropylene glycol diacrylate.

The present invention also relates to the above-mentioned photosensitive resin composition in which the (A) binder polymer contains styrene or a styrene derivative as an essential copolymerization component.

The present invention also relates to the above-mentioned photosensitive resin composition in which the binder polymer (A) contains styrene or a styrene derivative in an amount of 0.1 to 30% by weight based on the total amount of the copolymerized components.

In the present invention, the weight average molecular weight of the (A) binder polymer is 20,000 to 300,000.
Which is the photosensitive resin composition.

The present invention also relates to the above-mentioned photosensitive resin composition (A) in which the binder polymer has an acid value of 30 to 200 mgKOH / g.

In the present invention, (C) the photopolymerization initiator is
The photosensitive resin composition is a 2,4,5-triarylimidazole dimer.

The present invention also relates to the above-mentioned photosensitive resin composition further containing (D) an oxetane compound.

In the present invention, the amount of the component (A), the component (B) and the component (C) is 100 parts by weight of the total amount of the components (A) and (B). 40 to 80 parts by weight, the component (B) is 20 to 60 parts by weight, and the component (C) is 0.1 to 10 parts by weight.

The present invention also relates to a photosensitive element formed by coating, drying and laminating the above-mentioned photosensitive resin composition on a support.

In the present invention, the above-mentioned photosensitive element is laminated on a circuit-forming substrate so that the photosensitive resin composition layer is in intimate contact therewith, and an actinic ray is imagewise irradiated, and the exposed portion is photocured. The present invention relates to a method for producing a resist pattern, characterized in that the unexposed portion is removed by development.

The present invention also relates to a method of manufacturing a printed wiring board, characterized in that the circuit forming substrate having the resist pattern manufactured by the method of manufacturing the resist pattern is etched or plated.

[0039]

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 and methacrylic acid corresponding thereto,
(Meth) acrylate means acrylate and corresponding methacrylate, and (meth) acryloyl group means acryloyl group and corresponding methacryloyl group.

The photosensitive resin composition of the present invention comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C) a photopolymerization initiator. And the component (B) contains (b1) bisphenol A (meth) acrylate compound, (b2) polypropylene glycol diacrylate and (b3) phenoxypolyethyleneoxy (meth) acrylate compound as essential components.

Further, the photosensitive resin composition of the present invention is
A dispersion of the component (A), which comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C) a photopolymerization initiator. The degree is 1.0 to 4.0, the component (B) is (b4) HLB = 7.0 to 17.0, and the compound has at least two ethylenically unsaturated groups in the molecule, ( b5) HLB = 7.0 to 16.0,
An essential component is a compound having at least one ethylenically unsaturated group in the molecule and (b6) HLB = 0 to 7.0 and a compound having at least one ethylenically unsaturated group in the molecule.

As the above-mentioned (A) binder polymer,
Examples thereof include acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, and phenol resin. From the viewpoint of alkali developability, acrylic resins are preferred. These may be used alone or in combination of two or more.

The binder polymer (A) can be produced, for example, by radically polymerizing a polymerizable monomer. Examples of the polymerizable monomer include styrene, vinyltoluene, α-methylstyrene,
Polymerizable styrene derivatives such as p-methylstyrene, p-ethylstyrene, p-methoxystyrene, p-ethoxystyrene, p-chlorostyrene, p-bromostyrene, acrylamides such as diacetone acrylamide, acrylonitrile, vinyl-n- Vinyl alcohol esters such as butyl ether, (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) acrylate,
2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β -Styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate and the like, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid , Crotonic acid, propiolic acid and the like.

Examples of the above-mentioned (meth) acrylic acid alkyl ester include those represented by the general formula (II)

[Chemical 4] (Wherein R ² represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 1 to 12 carbon atoms),
Examples thereof include compounds in which an alkyl group of these compounds is substituted with a hydroxyl group, an epoxy group, a halogen group or the like.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ³ in the above general formula (II) include a methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group,
Examples include undecyl group, dodecyl group and structural isomers thereof.

Examples of the monomer represented by the general formula (II) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth)
Examples thereof include butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. These may be used alone or in combination of two or more.

From the standpoint of alkali developability, the binder polymer (A) preferably contains a carboxyl group. For example, a polymerizable monomer having a carboxyl group and another polymerizable monomer are radically polymerized. It can be manufactured. Methacrylic acid is preferable as the polymerizable monomer having a carboxyl group.
In addition, it is preferable that the binder polymer (A) contains styrene or a styrene derivative as a polymerizable monomer from the viewpoint of flexibility.

In order to improve both the adhesiveness and the peeling property of the styrene or styrene derivative as a copolymerization component, the content is preferably 0.1 to 30% by weight and 1 to 28% by weight.
It is more preferable that the content is 1.5% by weight, and particularly preferably 1.5 to 27% by weight. If this content is less than 0.1% by weight, the adhesion tends to be poor, and if it exceeds 30% by weight, the peeled pieces tend to be large and the peeling time tends to be long.

These binder polymers may be used alone or in combination of two or more. Examples of the binder polymer in the case of using two or more kinds in combination include two or more kinds of binder polymers composed of different copolymerization components, two or more kinds of binder polymers having different weight average molecular weights, and two or more kinds of different dispersities. Examples include binder polymers.

The dispersity of the binder polymer (A) is preferably 1.0 to 4.0, and 1.0 to 3.5.
Is more preferable, and 1.0 to 3.0 is particularly preferable. If this dispersity exceeds 4.0, the resolution tends to decrease.

The polydispersity in the present invention means the value of weight average molecular weight / number average molecular weight, and the weight average molecular weight and number average molecular weight are measured by gel permeation chromatography and standard polystyrene is used. It is converted by the calibration curve created by.

The weight average molecular weight of the (A) binder polymer is preferably 20,000 to 300,000, and more preferably 25,000 to 200,000, from the viewpoint of coatability and resolution. More preferably, it is more preferably 30,000 to 150,000. If the weight average molecular weight is less than 20,000, the developing solution resistance tends to decrease, and if it exceeds 300,000, the developing time tends to be long.

The acid value of the component (A) is 30 to 200 m.
Preferably gKOH / g, 40-150 mg
More preferably KOH / g. This acid value is 30
If it is less than mgKOH / g, the developing time tends to be long, and if it exceeds 200 mgKOH / g, the developing solution resistance of the photocured resist tends to decrease.

The photopolymerizable compound (B) is (b1) a bisphenol A-based (meth) acrylate compound, (b1)
2) Polypropylene glycol diacrylate and (b
3) A phenoxy polyethyleneoxy (meth) acrylate compound is an essential component.

The above (b1) bisphenol A type (meth)
The acrylate compound is not particularly limited as long as it has a bisphenol A skeleton, and examples thereof 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) acryloxypolyethoxy) Examples thereof include polypropoxy) phenyl) propane, etc., which preferably have an ethylene glycol unit in the molecule, and more preferably 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane. These are used alone or in combination of two or more.

Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 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) acry) Roxydodecaethoxy) 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, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is B
PE-500 (Shin-Nakamura Chemical Co., Ltd., product name) is commercially available, and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is
BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) is commercially available. These are used alone or in combination of two or more.

As the above 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane,
For example, 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentapropoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2
-Bis (4-((meth) acryloxyheptapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth ) Acryloxynonapropoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydodeca) Propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,
2-bis (4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-
Examples include ((meth) acryloxypentadecapropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexadecapropoxy) phenyl) propane. These are used alone or in combination of two or more.

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

Examples of the polypropylene glycol diacrylate (b2) include dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate,
Pentapropylene glycol diacrylate, hexapropylene glycol diacrylate, heptapropylene glycol diacrylate, octapropylene glycol diacrylate, nonapropylene glycol diacrylate, decapropylene glycol diacrylate, undecapropylene glycol diacrylate, dodecapropylene glycol diacrylate, tri Decapropylene glycol diacrylate, tetradecapropylene glycol diacrylate, pentadecapropylene glycol diacrylate, hexadecapropylene glycol diacrylate, heptadecapropylene glycol diacrylate, octadecapropylene glycol diacrylate, nonadecapropylene glycol diacrylate, eicosapropi Glycol diacrylate and the like, propylene glycol units in the molecule 2 to 1
It is preferable to have zero.

The isopropylene group in the component (b2) is a group represented by --CH (CH ₃ ) CH _2- , and the bonding direction is when the methylene group is bonded to oxygen or when the methylene group is oxygen. There are two types when they are not bound to each other, and one type of binding direction may be used, or two types of binding directions may be mixed.

Examples of the phenoxypolyethyleneoxy (meth) acrylate compound (b3) include compounds represented by the above general formula (I).

In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

In the general formula (I), Z has 1 to 10 carbon atoms.
Is an alkyl group. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s
ec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, structural isomers thereof, and the like, and may be nonyl group. preferable.

In the above general formula (I), m is an integer of 2 to 15, preferably 4 to 13, and more preferably 6 to 10.

In the general formula (I), n is an integer of 0-5, preferably 0-4, more preferably 1-3, and most preferably 1-2. 1
Is most preferable.

The phenyl group in the general formula (I) may have a substituent other than Z, and examples of the substituent include a halogen atom, an alkyl group having 11 to 20 carbon atoms, and a carbon number of 3. -10 cycloalkyl groups, 6 carbon atoms
~ 18 aryl group, phenacyl group, amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, 1 to 10 carbon atoms Alkyl mercapto group,
Allyl group, hydroxyl group, hydroxyalkyl group having 1 to 20 carbon atoms, carboxyl group, alkyl group having 1 to 10 carbon atoms
Carboxyalkyl group, the alkyl group has 1 to 1 carbon atoms
0 acyl group, C 1-20 alkoxy group, C 1-20 alkoxycarbonyl group, C 2-10 alkylcarbonyl group, C 2-10 alkenyl group, C 2-10 N Examples thereof include an alkylcarbamoyl group, a group containing a heterocycle, and an aryl group substituted with these substituents. 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 there are plural substituents, the plural substituents may be the same or different.

Examples of the compound represented by the general formula (I) include nonylphenoxypolyethyleneoxy (meth) acrylate, nonylphenoxypolypropyleneoxy (meth) acrylate, butylphenoxypolyethyleneoxy (meth) acrylate, butylphenoxypolypropyleneoxy. (Meth) acrylate etc. are mentioned.

Examples of the nonylphenoxypolyethyleneoxy (meth) acrylate include nonylphenoxytetraethyleneoxy (meth) acrylate, nonylphenoxypentaethyleneoxy (meth) acrylate, nonylphenoxyhexaethyleneoxy (meth) acrylate, nonylphenoxyhepta. Ethyleneoxy (meth) acrylate, nonylphenoxyoctaethyleneoxy (meth) acrylate, nonylphenoxynonaethyleneoxy (meth) acrylate, nonylphenoxydecaethyleneoxy (meth) acrylate, nonylphenoxyundecaethyleneoxy (meth) acrylate, nonylphenoxide Decaethyleneoxy (meth) acrylate etc. are mentioned.

Examples of the butylphenoxypolyethyleneoxy (meth) acrylate include butylphenoxytetraethyleneoxy (meth) acrylate, butylphenoxypentaethyleneoxy (meth) acrylate, butylphenoxyhexaethyleneoxy (meth) acrylate, butylphenoxyhepta. Examples include ethyleneoxy (meth) acrylate, butylphenoxyoctaethyleneoxy (meth) acrylate, butylphenoxynonaethyleneoxy (meth) acrylate, butylphenoxydecaethyleneoxy (meth) acrylate, butylphenoxyundecaethyleneoxy (meth) acrylate. To be

The photosensitive resin composition of the present invention has the above (b)
A photopolymerizable compound other than the component (1), the component (b2) and the component (b3) can be contained. Examples thereof include compounds obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, and urethane. Urethane monomers such as (meth) acrylate compounds having a bond, nonylphenyldioxylene (meth) acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o
-Phthalate, β-hydroxyethyl-β '-(meth)
Acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, (meth) acrylic acid alkyl ester and the like can be mentioned, but (meth) acrylate compounds having a urethane bond are used. It is preferable to use it as an essential component. These are used alone or in combination of two or more.

Examples of the compound obtained by reacting the above polyhydric alcohol with an α, β-unsaturated carboxylic acid include:
Polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, 2 to 14 ethylene groups
And the number of propylene groups is 2 to 14 polyethylene polypropylene glycol glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate , Trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri ( (Meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythri Ruhekisa (meth) acrylate.

As the above α, β-unsaturated carboxylic acid,
For example, (meth) acrylic acid or the like can be fisted.

Examples of the glycidyl group-containing compound include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meth) acryloxy-2-hydroxy-propyloxy).
Phenyl etc. can be fisted.

As the urethane monomer, for example,
(Meth) acrylic monomer having OH group at β-position and isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-
Examples thereof include addition reaction products with diisocyanate compounds such as hexamethylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, and the like.

Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid 2-ethylhexyl ester. Is mentioned.

On the other hand, the photopolymerizable compound (B) is a compound (b4) HLB = 7.0 to 17.0,
(B5) HLB = 7.0 to 16.0 and (b6) HLB = 0 to 7.0 are essential components.

The HLB in the present invention is an index of hydrophilicity of the photopolymerizable compound and can be calculated by the mathematical formula (1). Incidentally, the hydrophilic group in the present invention,

[Chemical 5] Represents a group represented by.

[0078]

[Equation 1] E: total molecular weight of hydrophilic groups in molecule M: molecular weight of photopolymerizable compound The compound (b4) HLB = 7.0 to 17.0 has at least two ethylenically unsaturated groups in the molecule. It is necessary to have two ethylenically unsaturated groups in the molecule. In addition, (b5) HLB =
The compound of 7.0 to 16.0 needs to have at least one ethylenically unsaturated group in the molecule, and more preferably has one ethylenically unsaturated group in the molecule.

The HLB of the component (b4) is 7.0-1.
It is necessary to be 7.0, preferably 7.5 to 16.0, more preferably 8.0 to 15.0, and particularly preferably 8.3 to 14.0. Preferably 8.6 to 13.0, and very preferably,
Very preferably, it is 9.0 to 12.0.

The HLB of the component (b5) is 7.0-1.
It is necessary to be 6.0, preferably 7.5 to 15.0, more preferably 8.0 to 14.0, and particularly preferably 8.0 to 13.0. It is highly preferable that it is 9.0 to 12.5, and 1
It is extremely preferable that it is 0.0 to 12.0.
Very preferably, between 5 and 11.5.

The HLB of the component (b6) is 0 to 7.0.
Is more preferable, 0 to 5.0 is more preferable, 0 to 3.0 is particularly preferable, and 0 is
Very preferably 1.0 and very preferably 0.

In order to adjust the HLB of the photopolymerizable compound within the above range, it is preferable to adjust the number of hydrophilic groups in the molecule, and it is preferable to adjust the number of ethylene glycol chains in production. For the above adjustment, the number of ethylene glycol units in the molecule of the component (b4) is preferably adjusted to 2 to 30, more preferably 4 to 25, and more preferably 6 to 15. Particularly preferred. Further, the number of ethylene glycol units in the molecule of the component (b5) is preferably adjusted to 2 to 15, and 4 to 1
It is more preferable to adjust to 3, and it is particularly preferable to adjust to 6 to 10.

The component (b4) is not particularly limited, but the above-mentioned 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2
-Bis (4-((meth) acryloxypolypropoxy))
Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2
-Bisphenol A such as bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane
System (meth) acrylate compound, polyethylene glycol di (meth) acrylate, polyethylene glycol polypropylene glycol di (meth) acrylate, EO
Examples include modified trimethylolpropane tri (meth) acrylate, EO, PO modified trimethylolpropane tri (meth) acrylate, EO modified urethane di (meth) acrylate, and EO, PO modified urethane di (meth) acrylate. It is selected by adjusting the number of ethylene glycol units so as to be 0-16.0. These are used alone or in combination of two or more.

The component (b5) is not particularly limited, but the above-mentioned nonylphenoxypolyethyleneoxy (meth) acrylate, nonylphenoxypolypropyleneoxy (meth) acrylate, butylphenoxypolyethyleneoxy (meth) acrylate, butylphenoxypolypropyleneoxy. Examples thereof include phenoxypolyethyleneoxy (meth) acrylate compounds such as (meth) acrylate, phenoxypolyethyleneoxypolypropyleneoxy (meth) acrylate compounds, EO-modified phthalic acid compounds, and EO, PO-modified phthalic acid compounds, but HLB is 7 It is selected by adjusting the number of ethylene glycol units so as to be 0.0 to 14.0. These are used alone or in combination of two or more.

The component (b6) is not particularly limited as long as it does not contain an ethylene glycol unit in the molecule,
For example, the above-mentioned polypropylene glycol diacrylate and the like can be mentioned. These are used alone or in combination of two or more.

Further, in the photosensitive resin composition of the present invention, (b
Photopolymerizable compounds other than the component (4), the component (b5) and the component (b6) can be used.

Examples of the photopolymerization initiator (C) include benzophenone, N, N'-tetramethyl-4,
4'-diaminobenzophenone (Michler's ketone),
N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4
-Morpholinophenyl) -butanone-1,2-methyl-
Aromatic ketones such as 1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone,
1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2
-Methylanthraquinone, 1,4-naphthoquinone, 9,
Quinones such as 10-phenantharaquinone, 2-methyl 1,4-naphthoquinone and 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and other benzoin ether compounds, benzoin, methylbenzoin, ethylbenzoin Benzoin compounds such as benzyl dimethyl ketal, benzyl derivatives such as benzyl dimethyl ketal, 2,4,5-triarylimidazole dimer, 9-phenylacridine, 1,7-
Examples include acridine derivatives such as bis (9,9'-acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds.

The substituents on the aryl groups of the two 2,4,5-triarylimidazoles may be the same and may give the target compound, or may be different and give asymmetric compounds.

Also, a thioxanthone compound and a tertiary amine compound may be combined, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid.

From the viewpoint of adhesion and sensitivity,
More preferred is a 4,5-triarylimidazole dimer.

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

Examples of the 2,4,5-triarylimidazole dimer include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2-chlorophenyl) -4,2 2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5 ' -Tetraphenylbisimidazole, 2,2'-bis (2,5-dichlorophenyl)
-4,4 ', 5,5'-Tetraphenylbisimidazole, 2,2'-bis (2,6-dichlorophenyl)-
4,4 ', 5,5'-Tetraphenylbisimidazole, 2,2'-bis (2,3,4-trichlorophenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2,2 ′ -Bis (2,3,5-trichlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole, 2,2′-bis (2,3,6-trichlorophenyl) -4,4 ′ , 5,5'-Tetraphenylbisimidazole, 2,2'-bis (2,4,5-trichlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis ( 2-fluorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4-difluorophenyl) -4,4', 5,5'-tetraphenylbisimidazole , 2,2'-bis ( , 3-Difluorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,5-difluorophenyl) -4,4', 5,5'-tetraphenylbis Imidazole, 2,2'-bis (2,6-difluorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,3,4-trifluorophenyl)- 4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,3,5-trifluorophenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2, 2'-bis (2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4,5-trifluorophenyl) -4 , 4 ', 5,5'-Tet Phenyl bisimidazole, 2,2'-bis (2,4,6
-Trifluorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2 , 2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,3-dibromophenyl) -4,4', 5 , 5'-Tetraphenylbisimidazole, 2,2'-bis (2,5-dibromophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,6- Dibromophenyl)
-4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,3,4-tribromophenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2 , 2'-bis (2,3,5-tribromophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,3,6-tribromophenyl)- 4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4,5-tribromophenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2, 2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2-fluorophenyl) -4,4', 5 , 5'-Tetrakis (3-methoxyphenyl) bisimid Tetrazole, 2,2'-bis (2,4
-Difluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) bisimidazole, 2,
2'-bis (2,3-difluorophenyl) -4,
4 ', 5,5'-tetrakis (3-methoxyphenyl)
Bisimidazole, 2,2'-bis (2,5-difluorophenyl) -4,4 ', 5,5'-tetrakis (3-
Methoxyphenyl) bisimidazole, 2,2'-bis (2,6-difluorophenyl) -4,4 ', 5,5'
-Tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2,3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) bisimidazole, 2 , 2'-bis (2,
3,5-trifluorophenyl) -4,4 ', 5,5'
-Tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) bisimidazole, 2 , 2'-bis (2,
4,5-trifluorophenyl) -4,4 ', 5,5'
-Tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) bisimidazole, etc. Can be mentioned. These are used alone or in combination of two or more.

Further, the photosensitive resin composition of the present invention may contain a sensitizer, and examples of the sensitizer include 7-amino-4-methylcoumarin and 7-dimethylamino-4-. Methylcoumarin, 7-diethylamino-4-
Methylcoumarin, 7-methylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 7-dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [ c] Coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin 4,6-diethyl-7-diethylaminocoumarin,
4,6-diethyl-7-dimethylaminocoumarin, 4,
6-dimethyl-7-ethylaminocoumarin, 4,4'-
Examples thereof include bis (diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (methylethylamino) benzophenone. These are used alone or in combination of two or more.

The oxetane compound (D) optionally used in the photosensitive resin composition of the present invention is not particularly limited as long as it has an oxetane ring in the molecule.
Alkyl oxetane such as oxetane, 2-methyl oxetane, 2,2-dimethyl oxetane, 3-methyl oxetane, 3,3-dimethyl oxetane, 3-methyl-3-
Methoxymethyl oxetane, 3,3′-di (trifluoromethyl) perfluorooxetane, 2-chloromethyl oxetane, 3,3-bis (chloromethyl) oxetane, OXT-101 (trade name of Toagosei Co., Ltd.), OXT
-121 (trade name manufactured by Toagosei Co., Ltd.) and the like. These are used alone or in combination of two or more.

From the viewpoint of the balance between coating property and photocurability, the amount of the component (A) is 40 to 80 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). The amount is preferably 50 to 70 parts by weight, more preferably 55 to 65 parts by weight.
If the blending amount is less than 40 parts by weight, the resulting photosensitive resin composition tends to be inferior in coating property, and if it exceeds 80 parts by weight, the photocurability tends to be insufficient.

The blending amount of the component (B) is 20 to 60 relative to 100 parts by weight of the total amount of the components (A) and (B).
The amount is preferably parts by weight, more preferably 30 to 50 parts by weight, particularly preferably 35 to 45 parts by weight. If the content is less than 20 parts by weight, the photocurability tends to be insufficient, and if it exceeds 60 parts by weight, the coating property tends to deteriorate.

In addition, the component (b1) in the component (B),
The blending amounts of the component (b2) and the component (b3) are 30 to 85% by weight of the component (b1) based on the total amount of the component (B).
It is preferable that (b2) is 5 to 30% by weight and (b3) is 10 to 50% by weight.

From the viewpoint of the balance between sensitivity and resolution, the amount of the component (C) blended is 0.01 to 10 parts by weight per 100 parts by weight of the total amount of the components (A) and (B). Is more preferable, 0.01 to 5 parts by weight is more preferable, 0.05 to 4 parts by weight is very preferable, and 0.1 to 3 parts by weight is very preferable. If the amount is less than 0.01 part by weight, the sensitivity tends to be insufficient, and if it exceeds 20 parts by weight, the resolution tends to deteriorate.

From the viewpoint of the balance between sensitivity and resolution, the compounding amount of the component (D) used as necessary in the present invention is 2 with respect to 100 parts by weight of the total amount of the components (A) and (B). It is preferably from 50 to 50 parts by weight.
It is more preferably 5 to 40 parts by weight, particularly preferably 3 to 30 parts by weight, very preferably 3.5 to 25 parts by weight, and most preferably 4 to 20 parts by weight. . If the blending amount is less than 2 parts by weight, the effect such as shortening of the peeling time tends to be unobtainable.
If it exceeds the weight part, the shape of the pattern becomes an inverted trapezoid, which tends to facilitate the flow.

If necessary, the photosensitive resin composition contains a photopolymerizable compound having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, a dye such as malachite green, and tribromo. Photo-coloring agents such as phenyl sulfone and leuco crystal violet, thermal color inhibitors, plasticizers such as p-toluene sulfonamide, pigments, fillers, defoamers, flame retardants, stabilizers, adhesion promoters, leveling agents, A peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent, etc. are each added in an amount of 0.01 to 100 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B).
About 20 parts by weight can be contained. These are used alone or in combination of two or more.

The photosensitive resin composition, if necessary,
Methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene,
It can be dissolved in a solvent such as N, N-dimethylformamide or propylene glycol monomethyl ether or a mixed solvent thereof to be applied as a solution having a solid content of about 30 to 60% by weight.

The photosensitive resin composition is not particularly limited, but is applied as a liquid resist on a metal surface such as copper, copper-based alloy, iron, iron-based alloy, etc., dried, and if necessary, a protective film. Is preferably used as coated or is used in the form of a photosensitive element.

Although the thickness of the photosensitive resin composition layer varies depending on the use, it is preferable that the thickness after drying is about 1 to 100 μm. When the liquid resist is coated with a protective film, examples of the protective film include polymer films such as polyethylene and polypropylene.

The above-mentioned photosensitive element can be obtained, for example, by applying a photosensitive resin composition on a polymer film of polyethylene terephthalate, polypropylene, polyethylene, polyester or the like as a support and drying it. The coating can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater. The 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 preferably 2% by weight or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent steps.

The thickness of these polymer films is from 1 to 1
It is preferably set to 00 μm. One of these polymer films may be laminated on both sides of the photosensitive resin composition layer as a support for the photosensitive resin composition layer, and the other as a protective film of the photosensitive resin composition layer. The protective film preferably has 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, and is preferably a low fish eye film.

The photosensitive element has an intermediate layer and a protective layer such as a cushion layer, an adhesive layer, a light absorbing layer and a gas barrier layer in addition to the photosensitive resin composition layer, the support and the protective film. May be.

The photosensitive element is stored, for example, as it is or on another surface of the photosensitive resin composition layer by further laminating a protective film, and wound around a cylindrical core. At this time, it is preferable that the support is wound so that the support is on the outermost side. An end face separator is preferably installed on the end face of the roll-shaped photosensitive element roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance. In addition, as a packing method, it is preferable to wrap the product in a black sheet having low moisture permeability.

Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer).

In producing a resist pattern using the above-mentioned photosensitive element, when the above-mentioned protective film is present, after removing the protective film, the photosensitive resin composition layer is heated to about 70 to 130 ° C. About 0.1 to 1 MPa (1 to 10 kgf / c) on the circuit forming substrate while heating.
Examples of the method include laminating by pressure bonding under a pressure of about m ² ), and laminating under reduced pressure is preferable. The surface to be laminated is usually a metal surface, but there is no particular limitation.

The photosensitive resin composition layer thus laminated is irradiated with actinic rays imagewise through a negative or positive mask pattern.

As the light source of the above-mentioned actinic rays, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp or the like that effectively radiates ultraviolet rays and visible light is used.

Then, after the exposure, if the support is present on the photosensitive resin composition layer, after removing the support,
A resist pattern can be produced by removing the unexposed area by development such as wet development with a developing solution such as an alkaline aqueous solution, an aqueous developing solution or an organic solvent, and dry development.

Examples of the alkaline aqueous solution include:
0.1-5 wt% dilute sodium carbonate solution, 0.1
Examples thereof include a dilute solution of 5 wt% potassium carbonate and a dilute solution of 0.1 to 5 wt% sodium hydroxide.

The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and its temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surface active agent, a defoaming agent, an organic solvent and the like may be mixed in the alkaline aqueous solution.

Examples of the developing method include dipping method, spraying method, brushing, and slapping.

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

For etching the metal surface after the development, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution or the like can be used.

When a printed wiring board is manufactured using the photosensitive element of the present invention, the surface of the circuit-forming board 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, solder plating, nickel plating and gold plating.

Next, the resist pattern can be stripped with, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used for the development.

The above-mentioned strong alkaline aqueous solution is, for example, 1 to 10% by weight aqueous sodium hydroxide solution, 1 to 10
A weight% potassium hydroxide aqueous solution or the like is used. Examples of the peeling method include a dipping method and a spray method. Further, the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole.

[0122]

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

Examples 1 to 6 and Comparative Examples 1 to 5 The materials shown in Table 1 were blended to obtain a solution.

[0124]

[Table 1] Then, the components (B) and (D) shown in Tables 2 and 3 were dissolved in the obtained solution to obtain a solution of the photosensitive resin composition.

[0125]

[Table 2]

[Table 3] The components used in Tables 2 and 3 are shown below.

^* 1: FA-321M (2,2-bis (4
-(Methacryloxypentaethoxy) phenyl) propane, trade name manufactured by Hitachi Chemical Co., Ltd. ^* 2: APG200 (tripropylene glycol diacrylate, trade name manufactured by Shin-Nakamura Chemical Co., Ltd.) ^* 3: APG400 (heptapropylene) Glycol diacrylate, trade name manufactured by Shin-Nakamura Chemical Co., Ltd.) ^* 4: NP-8EA (nonylphenoxyoctaethyleneoxy acrylate: R ¹ = in the general formula (I))
A hydrogen atom, Z = nonyl group, a compound of m = 8 and n = 1,
Kyoeisha Chemical Co., Ltd. product name) ^* 5: NP-4EA (tetraphenoxyoctaethyleneoxy acrylate: R ¹ = in the general formula (I))
A hydrogen atom, Z = nonyl group, a compound of m = 4 and n = 1,
Kyoeisha Chemical Co., Ltd. product name) ^* 6: OXT-101 (Oxetane compound, Toa Gosei Co., Ltd. product name) ^* 7: OXT-121 (Oxetane compound, Toa Gosei)
Then, a solution of this photosensitive resin composition is uniformly applied on a polyethylene polyethylene terephthalate film having a thickness of 16 μm, and dried for 10 minutes in a hot air convection dryer at 100 ° C. A sex element was obtained. The film thickness of the photosensitive resin composition layer was 30 μm.

On the other hand, the copper surface of a copper-clad laminate (trade name: MCL-E-61 manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material in which copper foil (thickness: 35 μm) is laminated on both surfaces, is # 6.
Polished using a polishing machine (manufactured by Sankei Co., Ltd.) with a brush equivalent to 00, washed with water, dried with an air stream, and heat the obtained copper-clad laminate to 80 ° C. Then, the photosensitive resin composition layer was laminated while being heated to 110 ° C.

Next, using an exposure device (manufactured by Oak Co., Ltd.) 590 having a high pressure mercury lamp, a stouffer 41-step step tablet was placed on the test piece as a negative for 3 minutes.
Exposure was performed at 0, 60 and 120 mJ / cm ² .

Then, the polyethylene terephthalate film was peeled off, and an unexposed portion was removed by spraying a 1 wt% sodium carbonate aqueous solution 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 photo-cured film formed on the copper-clad laminate, and the 41-step step tablet (OD = 0. The exposure amount (mJ / cm ² ) required to cure the 21st layer of the optical disc (.05) was defined as the sensitivity. The results are shown in Tables 4 and 5. The lower this number, the higher the sensitivity.

The pattern after development was observed, and the resolution (μm) was determined from the line width (μm) remaining as a line and space.

The peeling time was measured as follows. The sample irradiated with the exposure dose (21 steps / 41) corresponding to each sensitivity was developed with a 1 wt% sodium carbonate aqueous solution. After standing for 1 day and night, add 3% by weight sodium hydroxide solution to 4
While maintaining the temperature at 5 ° C. and stirring with a stirrer, the time (sec) when immersion was started and peeling started was measured. The shorter the peeling time, the better.

Next, a layer of the unexposed photosensitive resin composition 0.5
m ² was dissolved in 1 liter of a 1 wt% sodium carbonate aqueous solution, and the solution was circulated in a spray developing machine at 30 ° C. for 90 minutes. After standing for 2 minutes, the oily product adhering to the wall surface of the developing machine was observed, and the scum generating property was evaluated according to the following criteria. The larger the number, the better in terms of characteristics.

3: No oily product 2: Small amount of oily product 1: Large amount of oily product The plating resistance was evaluated as follows. An exposure amount (21 steps / 41) corresponding to each sensitivity was exposed using a mask and developed with a 1 wt% sodium carbonate aqueous solution. This sample was degreased, washed with water, plated with copper sulfate at 3.0 A / dm ² for 30 minutes, washed with water and immersed in borofluoric acid,
It was solder-plated at 1.5 A / dm ² for 10 minutes and washed with water. Water was removed with an airbrush, and Cellotape (registered trademark) (manufactured by Sekisui Chemical Co., Ltd., 24 mm width) was brought into close contact with it and rapidly peeled off to examine the presence or absence of peeling.

◯: No peeling x: Peeling occurred Evaluation results of Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Table 4.
And shown in Table 5.

[0136]

[Table 4]

[Table 5]

[0137]

The effects of the present invention are set forth in claims 1, 2, 3, 4, 5, 6, 7.
The photosensitive resin composition described in 8, 9, 10, 11, 12, 13, 14, or 15 has high resolution, high adhesion, high sensitivity, low scum generation, plating resistance, and plating bath stain resistance. Excel.

The photosensitive element according to claim 16 has high resolution, high adhesion, high sensitivity, low scum generation, plating resistance, plating bath contamination, workability and productivity, and a printed wiring board. It is effective for high density.

The method of manufacturing a resist pattern according to claim 17 is characterized by high resolution, high adhesion, high sensitivity, low scum generation,
It has excellent plating resistance, plating bath contamination, workability and productivity, and is effective in increasing the density of printed wiring boards.

The method for producing a printed wiring board according to claim 18 is excellent in high resolution, high adhesion, high sensitivity, low scum generation, plating resistance, plating bath contamination, workability and productivity.
Effective for increasing the density of printed wiring boards.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/06 H05K 3/06 J 3/18 3/18 DF term (reference) 2H025 AA01 AA02 AA14 AB11 AB15 AC01 AD01 BC14 BC32 BC42 CA28 CB16 FA03 FA17 FA40 FA43 4J011 QA03 QA12 QA13 QB16 RA10 RA19 SA78 UA06 VA01 WA01 5E339 CD01 CE16 CF15 DD02 5E343 AA02 CC62 ER16 ER18 GG16

Claims (18)

[Claims] 1. A photosensitive resin comprising (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C) a photopolymerization initiator. In the composition, the component (B) is a photosensitive resin containing (b1) bisphenol A (meth) acrylate compound, (b2) polypropylene glycol diacrylate, and (b3) phenoxypolyethyleneoxy (meth) acrylate compound as essential components. The composition (b3) is a compound represented by the general formula (I): (In the formula, R ¹ represents a hydrogen atom or a methyl group, Z represents an alkyl group having 1 to 10 carbon atoms, m is an integer of 2 to 10, and n is an integer of 0 to 5) Photosensitive resin composition which is a compound to be prepared. 2. The binder polymer (A) contains styrene or a styrene derivative as an essential copolymerization component.
The photosensitive resin composition described. 3. The binder polymer (A) contains styrene or a styrene derivative in an amount of 0.1 to 0.1 with respect to all copolymer components.
The photosensitive resin composition according to claim 2, which contains 30% by weight. 4. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (C) is a 2,4,5-triarylimidazole dimer. 5. A binder polymer (A) containing styrene or a styrene derivative as an essential copolymerization component, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C). In a photosensitive resin composition containing a photopolymerization initiator containing a 2,4,5-triarylimidazole dimer, the component (B) is (b).
1) Bisphenol A (meth) acrylate compound,
A photosensitive resin composition comprising (b2) polypropylene glycol diacrylate and (b3) phenoxypolyethyleneoxy (meth) acrylate compound as essential components. 6. A binder polymer comprising (A) styrene or a styrene derivative as an essential copolymerization component, wherein (A) a binder polymer comprises styrene or a styrene derivative relative to all copolymerization components.
The photosensitive resin composition according to claim 5, which contains 0.1 to 30% by weight. 7. The (b3) phenoxypolyethyleneoxy (meth) acrylate compound is represented by the general formula (I): (In the formula, R ¹ represents a hydrogen atom or a methyl group, Z represents an alkyl group having 1 to 10 carbon atoms, m is an integer of 2 to 10, and n is an integer of 0 to 5) 7. The photosensitive resin composition according to claim 5 or 6, which is a compound that is produced. 8. The method according to claim 1, wherein the (b1) bisphenol A-based (meth) acrylate compound is 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane. The photosensitive resin composition described. 9. The number of propylene glycol units of (b2) polypropylene glycol diacrylate is 2 to 10.
The photosensitive resin composition according to any one of claims 1 to 8. 10. The photosensitive resin composition according to claim 1, wherein the dispersion degree of the binder polymer (A) is 1.0 to 4.0. 11. A component (b1), a component (b2) and a component (b)
The blending amount of component 3) is (b) relative to the total amount of component (B).
1) component is 30 to 85% by weight, (b2) component is 5 to 30
The photosensitive resin composition according to any one of claims 1 to 10, wherein the content of the component (b3) is 10 to 50% by weight. 12. The photosensitive resin composition according to claim 1, wherein the binder polymer (A) has a weight average molecular weight of 20,000 to 300,000. 13. The acid value of the (A) binder polymer is
It is 30-200 mgKOH / g.
2. The photosensitive resin composition according to any one of 2. 14. The photosensitive resin composition according to claim 1, further comprising (D) an oxetane compound. 15. The blending amount of the component (A), the component (B) and the component (C) is 100, which is the total amount of the component (A) and the component (B).
40 to 80 parts by weight of the component (A), (B)
20 to 60 parts by weight of component and 0.1 to 10 of component (C)
It is a weight part, The photosensitive resin composition in any one of Claims 1-14. 16. A photosensitive element obtained by applying, drying and laminating a photosensitive resin composition according to any one of claims 1 to 15 on a support. 17. The photosensitive element according to claim 16 is laminated on a circuit-forming substrate so that the photosensitive resin composition layer is in intimate contact with the substrate, and an actinic ray is imagewise irradiated to the exposed portion to be photocured. Then, the method for producing a resist pattern, characterized in that the unexposed portion is removed by development. 18. A method of manufacturing a printed wiring board, which comprises etching or plating a circuit-forming substrate having a resist pattern manufactured by the method of manufacturing a resist pattern according to claim 17.