JP2001117224A - Photosensitive resin composition, photosensitive element using same, method for producing resist pattern and method for producing printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior productivity, work efficiency and tent reliability very useful for increasing the density of printed wiring and automatizing the production of a printed wiring board and to diminish development sludge. SOLUTION: The photosensitive resin composition contains a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond in one molecule and a photopolymerization initiator. The component B contains a compound having an isocyanuric ring and a phenolic compound as essential components. The composition is applied on a support, dried and laminated to obtain the objective photosensitive element. This element is laminated on a circuit forming substrate and irradiated with active light, the exposed part is photo-cured and the unexposed part is removed by development to produce the objective resist pattern. The circuit forming substrate is etched or plated to produce the objective printed wiring board.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, there are two methods of manufacturing a printed wiring board, a tenting method and a plating method. The above-mentioned tenting method protects a copper through-hole for mounting a chip with a resist, and performs etching and resist peeling to form an electric circuit, whereas the plating method deposits copper in a through-hole by electroplating, This is a method of forming an electric circuit by protecting with solder plating and removing and etching resist. As the resist, a photosensitive resin composition and a photosensitive element using the same are used, and an alkali developing type in which an uncured portion is removed with an alkaline aqueous solution is mainly used. Therefore, the photosensitive resin composition to be used is required to have a tenting property, that is, a tent reliability, which is not broken by a developing solution or a spray pressure of water washing.

[0003] The photopolymerizable compound represented by the general formula (I) has excellent mechanical strength, but tends to increase development sludge, which causes short-circuit failure. This is presumed to be because the isocyanate residue portion having a urethane bond is not so excellent in developability. Further, there is a disadvantage that the cured film is hard and brittle. To reduce the development sludge, to improve the solubility of the photosensitive resin composition in the developer, that is,
It is known that it is effective to introduce a hydrophilic group typified by a polyethylene glycol group or the like into the structure of the photopolymerizable compound, but if the hydrophilicity of the photosensitive resin composition is excessively improved, Since the cured film becomes brittle, there was a problem that tent reliability was reduced.

[0004]

SUMMARY OF THE INVENTION Claims 1, 2, 3,
4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 1
The inventions described in 4, 15 and 16 have excellent tent reliability,
Another object of the present invention is to provide a photosensitive resin composition having less development sludge. The invention according to claim 17 provides tent reliability,
An object of the present invention is to provide a photosensitive element which is excellent in workability and productivity and has little development sludge.

[0005] The invention according to claim 18 is a method for manufacturing a resist pattern having excellent tent reliability, workability and productivity, which is extremely useful for increasing the density of printed wiring and automating the manufacture of printed wiring boards, and having little development sludge. Is provided. The invention according to claim 19 is directed to a printed wiring board having a resist pattern excellent in tent reliability, workability, and productivity, which is extremely useful for increasing the density of printed wiring and automating the manufacture of printed wiring boards, and having less development sludge. It provides a manufacturing method.

[0006]

The present invention comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond in one molecule, and (C) a photopolymerization initiator. The present invention relates to a photosensitive resin composition wherein the component (B) comprises (B1) a compound having an isocyanuric ring and (B2) a phenolic compound as essential components.

[0007] The present invention also relates to the photosensitive resin composition wherein the binder polymer (A) contains a monomer having a carboxyl group as an essential copolymerization component. The present invention also relates to the photosensitive resin composition wherein (A) the binder polymer contains styrene or a styrene derivative as an essential copolymer component. The present invention also relates to the photosensitive resin composition, wherein (A) the binder polymer contains styrene or a styrene derivative in an amount of 0.1 to 30% by weight based on all copolymerized components.

[0008] The present invention also relates to the photosensitive resin composition, wherein (A) the carboxyl group content of the binder polymer is 12 to 50% by weight. Also, the present invention
(A) the weight average molecular weight of the binder polymer is 20,
000 to 300,000. In addition, the present invention provides (B1) a compound having an isocyanuric ring, wherein the (meth) acryloyl group has 3
The present invention relates to the above-mentioned photosensitive resin composition, which is a (meth) acrylate compound having at least one compound.

The present invention also relates to a compound (B1) having an isocyanuric ring represented by the general formula (I):

Embedded image [Wherein three R ¹ , R ² and R ³ are each independently

Embedded image (Wherein, R ⁴ represents a hydrogen atom or a methyl group, X ¹ represents an alkylene group having 2 to 6 carbon atoms, and m ¹ is an integer of ¹ to 14) or

Embedded image (Wherein, R ⁵ represents a hydrogen atom or a methyl group, X ² represents an alkylene group having 2 to 6 carbon atoms, n is an integer of 1 to 9, and m ² is an integer of 1 to 14) The photosensitive resin composition represented by the formula:

[0010] The present invention also relates to the photosensitive resin composition wherein X ¹ and X ² are ethylene groups. The present invention also relates to the photosensitive resin composition, wherein the phenolic compound (B2) has one benzene ring in one molecule. The present invention also relates to the photosensitive resin composition, wherein the (B2) phenolic compound is a (meth) acrylate compound having a block structure of an alkylene oxide group having 2 to 6 carbon atoms in one molecule. In addition, the present invention has two to two carbon atoms.
6 relates to the photosensitive resin composition, wherein the alkylene oxide group is an ethylene oxide group.

Further, the present invention provides a method for producing a phenolic compound represented by the formula (II):

Embedded image (Wherein, R ⁶ represents a hydrogen atom or a methyl group, X ³ represents an alkylene group having 2 to 6 carbon atoms, Z is an alkyl group having 1 to 20 carbon atoms, and p is an integer of 1 to 14 The present invention relates to the photosensitive resin composition represented by Also, the present invention
The present invention relates to the photosensitive resin composition wherein X ³ is an ethylene group and Z is a nonyl group. In addition, the present invention relates to the photosensitive resin composition, wherein the photopolymerization initiator (C) contains a 2,4,5-triarylimidazole dimer as an essential component.

In the present invention, the component (A), the component (B) and the component (C) are added in an amount of 100 parts by weight based on the total amount of the component (A) and the component (B). 40 to 80 parts by weight, the component (B) is 20 to 60 parts by weight, the component (C) is 0.1 to 20 parts by weight, and the component (B1) is 50 to 90% by weight in the component (B). Wherein the component (B2) is 10 to 50% by weight of the component (B). The present invention also relates to a photosensitive element obtained by applying, drying and laminating the photosensitive resin composition on a support.

Further, the present invention provides a method for manufacturing a semiconductor device, comprising: laminating the photosensitive element on a circuit-forming substrate so that the photosensitive resin composition layer is in close contact with the photosensitive element; And a method of manufacturing a resist pattern, wherein unexposed portions are removed by development. Further, the present invention relates to a method for manufacturing a printed wiring board, wherein a circuit forming substrate on which a resist pattern is manufactured is etched or plated by the method for manufacturing a resist pattern.

[0014]

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

The photosensitive resin composition of the present invention comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond in one molecule, and (C) a photopolymerization initiator. The component (B) is (B1)
A compound having an isocyanuric ring and (B2) a phenol compound are essential components.

The (A) binder polymer includes:
For example, acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin and the like can be mentioned. From the viewpoint of alkali developability, an acrylic resin is preferred. These can be used alone or in combination of two or more.

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

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

Embedded image (Wherein, R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an alkyl group having 1 to 12 carbon atoms), and the alkyl group of these compounds includes a hydroxyl group, an epoxy group, a halogen group, and the like. And the like. Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁸ in the general formula (III) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Examples include an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and structural isomers thereof.

Examples of the monomer represented by the general formula (III) include (meth) acrylic acid methyl ester,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meta) ) Octyl acrylate,
2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

The (A) binder polymer preferably contains a carboxyl group from the viewpoint of alkali developability. For example, the polymerizable monomer having a carboxyl group is radically polymerized with another polymerizable monomer. It can be manufactured by the following. The polymerizable monomer having a carboxyl group is preferably methacrylic acid.
The (A) binder polymer preferably contains styrene or a styrene derivative as a polymerizable monomer from the viewpoint of flexibility.

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

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

The carboxyl group content of the binder polymer (A) (the ratio of the polymerizable monomer having a carboxyl group to the total polymerizable monomers used) is determined from the viewpoint of the balance between alkali developability and alkali resistance. 12-50
%, More preferably 12 to 40% by weight, particularly preferably 15 to 30% by weight, and most preferably 15 to 25% by weight. If the carboxyl group content is less than 12% by weight, alkali developability tends to be poor, and if it exceeds 50% by weight, alkali resistance tends to be poor.

The polymerization average molecular weight of the binder polymer (A) is preferably from 20,000 to 300,000, and more preferably from 40,000 to 200,000, from the viewpoint of balance between mechanical strength and alkali developability. Is more preferable, and it is especially preferable that it is 60,000 to 120,000. This weight average molecular weight is 20,000
If it is less than 3, mechanical strength tends to be inferior, and if it exceeds 300,000, alkali developability tends to be inferior. The weight average molecular weight in the present invention is a value measured by a gel permeation chromatography method and converted by a calibration curve created using standard polystyrene.

The compound (B1) having an isocyanuric ring is not particularly limited, but is preferably a (meth) acrylate compound having three or more (meth) acryloyl groups in one molecule, and preferably one compound in one molecule. A (meth) acrylate compound having 3 to 6 (meth) acryloyl groups is more preferable, and a (meth) acrylate compound having 3 (meth) acryloyl groups in one molecule is particularly preferable.

The compound (B1) having an isocyanuric ring is not particularly limited, but preferably includes, for example, a compound represented by the above general formula (I). R ¹ , R ² and R ³ in the general formula (I) are each independently

Embedded image (Wherein, R ⁴ represents a hydrogen atom or a methyl group, X ¹ represents an alkylene group having 2 to 6 carbon atoms, and m1 is an integer of 1 to 14) or

Embedded image (Wherein, R ⁵ represents a hydrogen atom or a methyl group, X ² represents an alkylene group having 2 to 6 carbon atoms, n is an integer of 1 to 9, and m2 is an integer of 1 to 14) is there.

The alkylene group having 2 to 6 carbon atoms in X ¹ and X ² includes, for example, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group,
Examples thereof include a pentylene group, a neopentylene group, and a hexylene group, and an ethylene group is preferable. The isopropylene _{group, -CH (CH 3) CH 2} - is a group represented by the R ^1, R ² and R ³ in the general formula ^{(I) - (X 1 -O} ) - and - There are two types of bonding directions for (X ² —O) —, where the methylene group is bonded to oxygen and when the methylene group is not bonded to oxygen. May be mixed. Further, when each of the repeating units of-(X ¹ -O)-and-(X ² -O)-is 2 or more, two or more X ¹ and two or more X ² are
Each may be the same or different, and when X ¹ and X ² are composed of two or more types of alkylene groups, two or more types of-(X ¹
-O) - and - (X ² -O) - it may exist at random or may be present blockwise.

On the other hand, it is preferable that m ¹ and m ² are each independently 1 to 14. When m ¹ or m ² exceeds 14, the hydrophilicity becomes too high, and the development resistance of the obtained resist tends to decrease. Further, n is preferably 1 to 9. If n exceeds 9, the hydrophilicity tends to decrease, and the development sludge tends to increase.

Compounds available as the component (B1) include, for example, UA-21 manufactured by Shin-Nakamura Chemical Co., Ltd.
[In the general formula (I), R ¹ , R ² and R ³ are

Embedded image (Compound wherein n is 6 and m ² is 4 (average value)), UA
-41 [in the general formula (I), R ¹ , R ² and R ³ are

Embedded image (Compound in which n is 6 and m ² is 5 (average value)), UA
-42 [in the general formula (I), R ¹ , R ² and R ³ are

Embedded image (Compound in which n is 6 and m2 is 9 (average value)), UA
-44 [in the general formula (I), R ¹ , R ² and R ³ are

Embedded image (N is 6 and m2 is 6 (average value)). These are used alone or in combination of two or more.

The phenolic compound (B2) is not particularly limited, but preferably has one benzene ring in one molecule and has a block structure of an alkylene oxide group having 2 to 6 carbon atoms. Is preferred. Examples of the alkylene oxide group having 2 to 6 carbon atoms include an ethylene oxide group, a propylene oxide group, an isopropylene oxide group, a butylene oxide group, an isobutylene oxide group, a pentylene oxide group, a neopentylene oxide group, and a hexylene oxide group. However, from the viewpoint of hydrophilicity, an ethylene oxide group is preferable. These are used alone or in combination of two or more.

When a plurality of bonding directions are present in the alkylene oxide group, only one bonding direction may be used, or a plurality of bonding directions may be mixed. When the number of repeating units of the alkylene oxide group is two or more, the two or more alkylene oxides may be the same or different, and when two or more alkylene oxide groups are used, two or more alkylene oxide groups are used. The groups may be present randomly or in blocks.

The phenolic compound (B2) is not particularly limited, but is preferably, for example, a compound represented by the general formula (II). The general formula (I
In I), X ³ represents an alkylene group having 2 to 6 carbon atoms, and is preferably an ethylene group. In the general formula (II), Z
Represents an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, sec-
Butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group,
Examples include a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, and structural isomers thereof. From the viewpoint of hydrophobicity, a nonyl group is preferable.

In the general formula (II), p is an integer of 1 to 14, preferably 3 to 13, more preferably 5 to 13, particularly preferably 5 to 11, Very preferably 5-10, 6-10
Is very preferable, and it is very very preferable that it is 7-9.

The benzene ring of the component (B2) may have substituents as long as the effects of the present invention are not impaired. These substituents include, for example, a halogen atom and a carbon atom having 1 to 20 carbon atoms. An alkyl group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, nitro Group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, allyl group, hydroxyl group, 1 to 2 carbon atoms
0 hydroxyalkyl group, carboxyl group, carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, acyl group having 1 to 10 carbon atoms in the alkyl group, alkoxy group having 1 to 20 carbon atoms, 1 to 20 carbon atoms An alkoxycarbonyl group, an alkylcarbonyl group having 2 to 10 carbon atoms,
And alkenyl groups having 10 to 10 carbon atoms, N-alkylcarbamoyl groups having 2 to 10 carbon atoms, groups containing a heterocyclic ring, and aryl groups substituted with these substituents. The above substituent may form a condensed ring, and a hydrogen atom in the above substituent may be substituted with the above substituent such as a halogen atom. When the number of the substituents is two or more, the two or more substituents may be the same or different.

Compounds available as component (B2) include, for example, NP-8EA manufactured by Kyoeisha Chemical Co., Ltd.
(In the general formula (II), R ⁶ is a hydrogen atom, X ³ is an ethylene group, Z is a nonyl group, and p is 8). These are used alone or in combination of two or more.

As the component (B) other than the component (B1) and the component (B2), for example, a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-
Bisphenol A-based (meth) acrylate compounds such as ((meth) acryloxypolypropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, and glycidyl group-containing compounds , A compound obtained by reacting an α, β-unsaturated carboxylic acid, a urethane monomer such as a (meth) acrylate compound having a urethane bond, γ-chloro-
β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β ′-(meth) acryloyl Oxyethyl-o-phthalate, (meth) acrylic acid alkyl ester and the like can be mentioned, and it is preferable to use a bisphenol A (meth) acrylate compound or a (meth) acrylate compound having a urethane bond as an essential component. These are used alone or in combination of two or more.

The 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane includes, 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) acryl) Roxide decaethoxy) 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 represented by B
It is commercially available as PE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name), and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is
It is commercially available as BPE-1300 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.). These are used alone or in combination of two or more.

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

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

Examples of the 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, 9,10-
Quinones such as phenantaraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether,
Benzoin ether compounds such as benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, 2- (o-chlorophenyl) -4,
5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-
Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2
2,4,5-triarylimidazole dimer such as-(p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9,9'-acridinyl) Examples include acridine derivatives such as heptane, N-phenylglycine, N-phenylglycine derivatives, and coumarin-based compounds.

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

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

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

The amount of the component (B1) in the component (B) is preferably 50 to 90% by weight, more preferably 55 to 85% by weight, based on the total amount of the component (B). , 60 to 80% by weight. If the amount is less than 50% by weight, tent reliability tends to be insufficient, and if it exceeds 90% by weight, development sludge tends to increase.

The amount of component (B2) in component (B) is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, based on the total amount of component (B). It is particularly preferred that the content is 20 to 40% by weight. If the amount is less than 10% by weight, development sludge tends to increase, and if it exceeds 50% by weight, tent reliability tends to decrease.

The amount of the component (C) is 0.01 to 20 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B) from the viewpoint of the balance between sensitivity and resolution. Is preferably 0.01 to 10 parts by weight, particularly preferably 0.01 to 5 parts by weight, very preferably 0.05 to 4 parts by weight, and 0.1 to 10 parts by weight. It is extremely preferred to use 3 parts by weight. 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.

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

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

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

The thickness of the photosensitive resin composition layer depends on the intended use, but is preferably 1 to 200 μm, more preferably 1 to 100 μm, and more preferably 1 to 30 μm in terms of the thickness after drying. Is particularly preferred. If the thickness is less than 1 μm, it tends to be difficult to coat industrially,
If it exceeds 00 μm, the effect of the present invention is small, the sensitivity is insufficient, and the photocurability at the bottom of the resist tends to deteriorate. When a liquid resist is coated with a protective film, the protective film is, for example, an inactive polyolefin film such as polyethylene and polypropylene.However, from the standpoint of releasability from the photosensitive resin composition layer, a polyethylene film is used. preferable.

The photosensitive element is prepared, for example, by coating a photosensitive resin composition on a heat-resistant and solvent-resistant polymer film such as polyethylene terephthalate, polypropylene, polyethylene or polyester as a support, and drying. can get. From the viewpoint of transparency, it is preferable to use a polyethylene terephthalate film. The coating can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater, and a sleigh coater. Drying is performed at 70 to 150 ° C. and 5 to 30 ° C.
It can be done in about a minute. Further, 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 a later step.

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

The photosensitive element of the present invention comprising two layers of the photosensitive resin composition layer and the polymer film thus obtained can be used, for example, as it is or on the other surface of the photosensitive resin composition layer on a protective film. Are further laminated, wound up in a roll shape, and stored.

In producing a resist pattern using the photosensitive element, if the above-mentioned protective film is present, the protective film is removed, and the photosensitive resin composition layer is heated while forming a circuit. For example, a method of laminating by press-bonding to a substrate may be mentioned, and it is preferable to laminate under reduced pressure from the viewpoint of adhesion and followability. The surface to be laminated is usually a metal surface, but is not particularly limited.
The heating temperature of the photosensitive resin composition layer is preferably from 70 to 130 ° C., and the pressing pressure is preferably from about 0.1 to 1 MPa (about from 1 to 10 kgf / cm ² ). Is not particularly limited. Further, if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the circuit formation substrate in advance,
In order to further improve the lamination property, a pre-heat treatment of the circuit forming substrate may be performed.

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

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

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

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

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

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

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

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

When manufacturing a printed wiring board using the photosensitive element of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching and plating using the developed resist pattern as a mask. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate, solder plating such as high-throw solder plating,
There are nickel plating such as Watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and gold plating such as hard gold plating and soft gold plating. Next, the resist pattern can be stripped with, for example, a more alkaline aqueous solution than the alkaline aqueous solution used for development. As this strongly alkaline aqueous solution,
For example, a 1 to 10% by weight aqueous sodium hydroxide solution,
A 10% by weight aqueous solution of potassium hydroxide or the like is used. Examples of the peeling method include an immersion method and a spray method. The immersion method and the spray method may be used alone or in combination. Further, the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole.

[0064]

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

Examples 1 and 2 and Comparative Examples 1 to 3 The materials shown in Table 1 (component (A), component (C), additives and solvents) were blended, and the components (B) shown in Table 2 were added thereto. By dissolving, a solution of the photosensitive resin composition was obtained.

[0066]

[Table 1]

[0067]

[Table 2]

The components (B) in Table 2 are shown below. * 1: In the general formula (I), R ¹ , R 2 and R ³ are

Embedded image [N is 6, m2 is 4 (average value)] (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.) * 2: In the general formula (II), R ⁶ is a hydrogen atom, X ³ is an ethylene group, Z Is a nonyl group and p is 8 (product name manufactured by Kyoeisha Chemical Co., Ltd.) * 3: Heptapropylene glycol diacrylate (product name manufactured by Shin-Nakamura Chemical Co., Ltd.) * 4: γ-chloro-β-hydroxypropyl -Β'-methacryloyloxyethyl-ο-phthalate (product name, manufactured by Hitachi Chemical Co., Ltd.)

Next, the solution of the photosensitive resin composition was uniformly applied on a 25 μm thick polyethylene terephthalate film (manufactured by Teijin Limited, GS type) using a knife coat method, and then dried with a hot air convection dryer at 100 ° C. for 10 minutes. After drying for a minute, a photosensitive element was obtained. The dried film thickness of the photosensitive resin composition layer was 40 μm.

Next, 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 with a copper foil (thickness: 35 μm) laminated on both sides, was brushed with a brush equivalent to # 600. Using a polishing machine (manufactured by Sankeisha) with
After washing with water, drying with an air stream, the obtained copper-clad laminate was
After heating to ℃, using the photosensitive element obtained above, a layer of the photosensitive resin composition on the copper surface 120
Laminated at 0.4 ° C. and 0.4 MPa.

After the lamination, the copper-clad laminate was cooled, and when the temperature of the copper-clad laminate reached 23 ° C., a photo tool (Stoffer 21-step tablet was brought into close contact with the polyethylene terephthalate surface; Using an exposure machine manufactured by Oak Manufacturing Co., Ltd. (model HMW-201GX, 5kW ultra-high pressure mercury lamp), a 21-step step tablet of stofer and a wiring pattern with a line / space of 30/400 to 250/400 (adhesion, unit: μm) The exposed photo tool was brought into close contact with the stoker and exposed with an energy amount such that the number of remaining steps after development of the 21-step tablet of the stofer was 8.0.

After exposure, the film was allowed to stand at room temperature for 15 minutes, then the polyethylene terephthalate film was peeled off from the copper-clad laminate, and developed by spraying a 1.0% by weight aqueous solution of sodium carbonate at 30 ° C. Thereafter, based on this result, the exposure amount (sensitivity) at which the number of remaining steps after development became 8.0 was accurately obtained. The amount of development sludge was determined by separating the sludge generated in this development step by a centrifugal separator, filtering, and further drying at 150 ° C. for 4 hours.
The weight of the sludge was measured and evaluated.

The tent reliability was measured by using a laminate of a photosensitive resin composition on a base material (see FIGS. 1 and 2) in which three holes each having a diameter of 4 mm were continuously formed in a 1.6 mm-thick copper-clad laminate. Was laminated on both sides, and exposed at the above energy amount (the exposure amount at which the number of remaining steps after development becomes 8.0), and development was performed twice for 60 seconds. After the development, the number of broken holes in the triple holes shown in FIG. 2 (a total of 18 triple-diameter φ4 mm holes) was measured and evaluated as a deformed tent breaking ratio (the following formula), which was defined as tent reliability.

[0074]

(Equation 1) Table 3 summarizes the above results.

[0075]

[Table 3]

As is clear from Table 3, Comparative Examples 1 and 3
It was expected that the photosensitive resin composition used in (1) had a large amount of development sludge and the yield would be deteriorated. In addition, the photosensitive resin compositions used in Comparative Examples 2 and 3 had broken tents, resulting in low tent reliability. In contrast, the photosensitive resin compositions used in Examples 1 and 2 were:
The deformed tent had no tear and excellent tent reliability, and the amount of developing sludge was greatly reduced.

[0077]

According to the present invention, claims 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, and 16
The photosensitive resin composition described has excellent tent reliability and low development sludge. The photosensitive element according to claim 17 is excellent in tent reliability, workability, and productivity, and has little development sludge. The method for manufacturing a resist pattern according to claim 18 has excellent tent reliability, workability, and productivity, which are extremely useful for increasing the density of printed wiring and automating the manufacture of printed wiring boards, and has less development sludge. The method for manufacturing a printed wiring board according to the nineteenth aspect has excellent tent reliability, workability, and productivity extremely useful for increasing the density of printed wiring and automating the manufacture of the printed wiring board, and has less development sludge.

[Brief description of the drawings]

FIG. 1 is an external view of an evaluation board used to evaluate a deformed tent tear rate in Examples.

FIG. 2 is an enlarged view of a triple hole in an evaluation board used for evaluating a deformed tent tear rate in Examples.

[Explanation of Codes] Evaluation board 2. Three holes 3. 3. Triple hole diameter (4mm) Triple hole length (8mm)

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takeshi Ohashi 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Hitachi Chemical Co., Ltd. Yamazaki Office (72) Inventor Satoshi Otomo 4--13 Higashimachi, Hitachi City, Ibaraki Prefecture No. 1 Hitachi Chemical Co., Ltd. Yamazaki Office F-term (reference) 2H025 AA03 AA04 AA13 AB11 AB15 AC01 BC14 BC34 BC38 BC43 BC49 CA28 CB14 CB16 CB42 CB43 CB55 FA40 FA43 5E339 BE11 CC01 CC10 CD01 CE12 CE16 CF16 CF17 DD02 GG01A02 AA12 BB21 BB71 CC62 DD32 ER16 ER18 GG03

Claims (19)

[Claims] 1. A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond in one molecule, and (C) a photopolymerization initiator. Wherein the component (B) comprises (B1) a compound having an isocyanuric ring and (B2) a phenolic compound as essential components. 2. The photosensitive resin composition according to claim 1, wherein (A) the binder polymer comprises a monomer having a carboxyl group as an essential copolymerization component. 3. The method according to claim 1, wherein (A) the binder polymer comprises styrene or a styrene derivative as an essential copolymer component.
Or the photosensitive resin composition according to 2. 4. A method according to claim 1, wherein the binder polymer comprises styrene or a styrene derivative in an amount of from 0.1 to 0.1% based on all copolymerized components.
4. The photosensitive resin composition according to claim 3, which contains 30% by weight. 5. The photosensitive resin composition according to claim 2, wherein (A) the carboxyl group content of the binder polymer is from 12 to 50% by weight. 6. The photosensitive resin composition according to claim 1, wherein (A) the binder polymer has a weight average molecular weight of 20,000 to 300,000. 7. The compound according to claim 1, wherein (B1) the compound having an isocyanuric ring is a (meth) acrylate compound having three or more (meth) acryloyl groups in one molecule.
7. The photosensitive resin composition according to 3, 4, 5, or 6. 8. The compound (B1) having an isocyanuric ring is represented by the following general formula (I): Wherein the three R ¹ , R ² and R ³ are each independently (Wherein, R ⁴ represents a hydrogen atom or a methyl group, X ¹ represents an alkylene group having 2 to 6 carbon atoms, and m ¹ is an integer of ¹ to 14) or (Wherein, R ⁵ represents a hydrogen atom or a methyl group, X 2 represents an alkylene group having 2 to 6 carbon atoms, n is an integer of 1 to 9, and m 2 is an integer of 1 to 14). The photosensitive resin composition according to claim 1, 2, 3, 4, 5, 6, or 7. 9. The photosensitive resin composition according to claim 8, wherein X ¹ and X ² are ethylene groups. 10. The method according to claim 1, wherein (B2) the phenolic compound has one benzene ring in one molecule.
The photosensitive resin composition according to 5, 6, 7, 8 or 9. 11. The (B2) phenol compound is a (meth) acrylate compound having a block structure of an alkylene oxide group having 2 to 6 carbon atoms in one molecule. 11. The photosensitive resin composition according to 7, 8, 9, or 10. 12. The photosensitive resin composition according to claim 11, wherein the alkylene oxide group having 2 to 6 carbon atoms is an ethylene oxide group. (B2) The phenolic compound is represented by the general formula (II): (Wherein, R ⁶ represents a hydrogen atom or a methyl group, X ³ represents an alkylene group having 2 to 6 carbon atoms, Z is an alkyl group having 1 to 20 carbon atoms, and p is an integer of 1 to 14 1, 2, 3, 4, 5, 6, 7, 8, 9, 1
13. The photosensitive resin composition according to 0, 11 or 12. 14. The photosensitive resin composition according to claim 13, wherein X ³ is an ethylene group and Z is a nonyl group. 15. The photopolymerization initiator (C) is 2,4,5-
Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, comprising a triarylimidazole dimer as an essential component.
15. The photosensitive resin composition according to 12, 13, or 14. 16. The compounding amount of the component (A), the component (B) and the component (C) is a total amount of the component (A) and the component (B) of 100.
Component (A) is 40 to 80 parts by weight, and (B)
20 to 60 parts by weight of component and 0.1 to 20 of component (C)
Parts by weight, and the component (B1) is 5% of the component (B).
0 to 90% by weight, and the component (B2) accounts for 10 to 50% by weight of the component (B).
6, 7, 8, 9, 10, 11, 12, 13, 14 or 1
6. The photosensitive resin composition according to 5. 17. The method of claim 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, or 16
A photosensitive element obtained by applying, drying and laminating the photosensitive resin composition as described above on a support. 18. The photosensitive element according to claim 17, which is laminated on a circuit-forming substrate so that the photosensitive resin composition layer is in close contact with the photosensitive element, and is irradiated with actinic rays in an image-like manner, and the exposed portion is photocured. And removing unexposed portions by development. 19. A method for manufacturing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern has been manufactured by the method for manufacturing a resist pattern according to claim 18.