JP2003248306A - Photosensitive resin composition, photosensitive element using the same, resist pattern forming method and method for producing printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having high tent strength and excellent in adhesion to a substrate for forming a circuit. <P>SOLUTION: The photosensitive resin composition comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond per molecule and (C) a photopolymerization initiator, wherein a compound having one cycloalkylene group, one or more polyoxyalkylene (2-6C) skeletons and two (meth)acryloyl groups composes the component (B). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art As a method for manufacturing a printed wiring board, a tenting method is known in which a through hole in a copper clad laminate is protected by a resist, and an electric circuit is formed through etching and resist stripping.

The resist used in such a manufacturing method is generally a photosensitive resin composition or a photosensitive element formed by laminating a photosensitive resin composition on a film.
Further, the development of the uncured portion is mainly the alkaline development type using an alkaline aqueous solution. Therefore, the photosensitive resin composition and the photosensitive element to be used are required to have tenting property, that is, tent reliability, which is not broken by the developing solution or the spray pressure of water washing. Furthermore,
With the recent increase in the density of printed wiring boards, the patterned photosensitive resin composition has a small contact area with the copper substrate, so that excellent adhesion is required in the development, etching or plating treatment step. Resolution and chemical resistance are also required.

[0004]

However, the existing photosensitive resin compositions and photosensitive elements have a problem that the tent reliability is not sufficient. There is also a problem that the adhesion to a circuit-forming board such as a copper-clad laminate used for manufacturing a printed wiring board is insufficient.

The present invention has been made in view of the above problems of the prior art, and is a photosensitive resin composition used for manufacturing a printed wiring board or the like, which covers a through hole on a circuit forming substrate. When the coating part (tent part) is formed and cured, the strength of the tent part after curing (tent strength) is sufficiently high, and the adhesiveness to the circuit forming substrate after curing is also excellent. The purpose of the present invention is to provide a resin composition. Another object of the present invention is to provide a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a printed wiring board.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that one cycloalkylene group and one or more polyoxyalkylenes (having 2 carbon atoms). The present invention has been completed by finding that the above objects can be achieved by a photosensitive resin composition containing a skeleton and a compound having a (meth) acryloyl group of 2 as an essential component.

That is, the photosensitive resin composition of the present invention is
A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule, and (C) a photopolymerization initiator. Accordingly, the component (B) contains a compound represented by the following general formula (I) and / or a compound represented by the following general formula (II).

[Chemical 4]

[Chemical 5] [In the formula, R ¹ and R ¹¹ each independently represent a cycloalkylene group or a substituted cycloalkylene group, and R ² , R ³ , R ¹² and R ¹³ each independently represent a hydrogen atom or a methyl group, A,
B and X each independently represent an alkylene group having 2 to 6 carbon atoms, and n, m and l each independently represent an integer of 1 to 30. ]

Since the photosensitive resin composition of the present invention has the above-mentioned constitution, it is used to form a coating portion (tent portion) for covering the through hole on the substrate and cure it, and then the cured tent. The strength of the portion (tent strength) becomes sufficiently high, and the adhesion after curing with the substrate also becomes excellent.

The photosensitive resin composition of the present invention preferably further contains a bisphenol A (meth) acrylate compound as the component (B), and the bisphenol A (meth) acrylate compound is represented by the following general formula ( II
It is preferable to include the compound represented by I).

[Chemical 6] [In the formula, R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, Y and Z each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are p + q = 4 to 40. Denotes a positive integer chosen as ]

With the above-mentioned constitution, the photosensitive resin composition of the present invention is excellent not only in tent strength and adhesiveness but also in resolution, peeling property and chemical resistance.

(A) in the photosensitive resin composition of the present invention
The component is preferably a binder polymer having a carboxyl group. With such a configuration, alkali developability is improved in addition to tent strength and adhesion.

The photosensitive resin composition of the present invention preferably contains a 2,4,5-triarylimidazole dimer as the component (C). With such a configuration, the photosensitive resin composition of the present invention is excellent not only in tent strength and adhesion, but also in photosensitivity and resolution.

The present invention is also characterized by comprising (1) a support and a photosensitive resin composition layer formed on the support and comprising the above-mentioned photosensitive resin composition of the present invention. On the photosensitive element, (2) the circuit-forming substrate, the photosensitive resin composition layer in the photosensitive element is laminated, and a predetermined portion of the photosensitive resin composition layer is irradiated with an actinic ray to expose the exposed portion. Forming the resist pattern, and then removing the portion other than the exposed portion to form a resist pattern, and (3) etching the circuit forming substrate on which the resist pattern is formed by the resist pattern forming method. Provided is a method for manufacturing a printed wiring board, which is characterized by plating.

Since the above-mentioned photosensitive element has a layer made of the photosensitive resin composition of the present invention, it is possible to easily form a coating film having excellent tent strength and adhesion on a substrate. Become. Therefore, the resist pattern forming method and the printed wiring board manufacturing method have excellent workability and productivity.

[0015]

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

(Photosensitive resin composition) The (A) binder polymer (hereinafter also referred to as "(A) component") contained in the photosensitive resin composition of the present invention is, for example, an acrylic resin or a styrene resin. , Epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin and the like. From the viewpoint of alkali developability, acrylic resins are preferred. These alone or 2
A combination of two or more species can be used.

The component (A) can be produced by polymerizing (radical polymerizing) a polymerizable monomer.
Examples of the polymerizable monomer include styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-
Polymerizable styrene derivative such as ethylstyrene, acrylamide, acrylonitrile, vinyl alcohol esters such as vinyl-n-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 Products, monomethyl maleate, male Phosphate, monoethyl maleate monoesters such as maleic acid monoisopropyl, fumaric acid, cinnamic acid, alpha-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid. These are used alone or in combination of two or more.

Examples of the above-mentioned (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, structural isomers thereof, etc. Is mentioned. These may be used alone or in combination of two or more.

From the viewpoint of alkali developability, the component (A) is preferably a polymer containing a carboxyl group. For example, a polymerizable monomer having a carboxyl group and another polymerizable monomer are polymerized ( It can be produced by radical polymerization). The polymerizable monomer having a carboxyl group is preferably acrylic acid or methacrylic acid, more preferably methacrylic acid. That is, the component (A) is preferably a polymer containing (meth) acrylic acid as a monomer unit, and from the viewpoint of flexibility, styrene and / or a styrene derivative is used as a polymerizable monomer. It is preferable to contain it. In the present invention, the styrene derivative means a styrene in which a hydrogen atom is replaced with a substituent (an organic group such as an alkyl group or a halogen atom).

In order to improve both the adhesiveness and the peeling property, the content ratio of styrene and / or styrene derivative based on the total weight of the polymerizable monomer is preferably 3 to 30% by weight, It is more preferably 4 to 28% by weight, and particularly preferably 5 to 27% by weight. If the content is less than 3% by weight, the adhesion tends to be poor,
If it exceeds 5% by weight, the peeling pieces tend to be large and the peeling time tends to be long.

The acid value of the component (A) is 50 to 250 mgK.
OH / g is preferred, 60-150 mg KO
More preferably, it is H / g. This acid value is 50 mg
If it is less than KOH / g, the developing time tends to be long,
When it exceeds 50 mgKOH / g, the developing solution resistance of the photocured photosensitive resin composition tends to decrease. When solvent development is performed as the development step, it is preferable to prepare a small amount of the polymerizable monomer having a carboxyl group.

The weight average molecular weight of the component (A) (measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene) is 20,
It is preferably 000 to 300,000, and 25,
It is more preferably 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. In addition, if necessary (A)
The component may have a photosensitive group.

The component (A) is used alone or in combination of two or more kinds. As a method of using two or more kinds in combination, for example, a method of combining two or more kinds of binder polymers composed of different copolymerization components,
Examples thereof include a method of combining two or more kinds of binder polymers having different weight average molecular weights, a method of combining two or more kinds of binder polymers having different dispersities. Further, a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.

Next, the photopolymerizable unsaturated compound (hereinafter referred to as "component (B)") containing at least one ethylenically unsaturated group (B) contained in the photosensitive resin composition of the present invention. explain.

The component (B) is a compound represented by the general formula (I) (hereinafter referred to as "compound I") and / or a compound represented by the general formula (II) (hereinafter referred to as "compound II"). It is contained as an essential component. In Compound I and Compound II, A, B and X each independently represent 2 to 6 alkylene groups, but preferably at least an ethylene group, and more preferably an ethylene group or a propylene group. Further, R ² and R ³ , R ¹² and R ¹³ are preferably the same group, and more preferably all are methyl groups.

In compound I and compound II, m, n and l are each independently an integer of 1 to 30. M in compound I
And n are preferably 4 to 30 in total (m + n), and 1 in the compound II is preferably 4 to 30. And, m + n or l is more preferably 8 to 20, and particularly preferably 10 to 15.
When m + n or l is less than 4, the flexibility of the cured product tends to be insufficient, and when it exceeds 30, the crosslink density tends to be low and the adhesion and resolution tend to be low.

R ¹ and R in compound I and compound II
¹¹ are each independently a cycloalkylene group or a substituted cycloalkylene group, and the number of carbon atoms in the cycloalkylene group is 3 to
8 is preferable and 6 is more preferable. That, cycloalkylene group cyclohexylene group (-C ₆ H ₁₀ -) are preferable. As cyclohexylene 1,4-cyclohexylene group is more preferable. The substituted cycloalkylene group is preferably the above-mentioned suitable cycloalkylene group having a substituent.

As the substituent, for example, a halogen atom,
C1-C20 alkyl group, C3-C10 cycloalkyl group, C6-C18 aryl group, phenacyl group, amino group, C1-C10 alkylamino group, C2-C20 Dialkylamino group, 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 of alkyl group, acyl group having 1 to 10 carbon atoms of alkyl group, alkoxyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms Substituted with an alkoxycarbonyl group, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, or a heterocyclic ring-containing group. Examples thereof include an aryl group. The above-mentioned substituents may form a condensed ring. Further, the hydrogen atom in these substituents may be substituted with the above-mentioned substituent such as a halogen atom. When the number of substituents is 2 or more, the 2 or more substituents may be the same or different.

Further, carbon in the cyclohexane ring in the compounds I and II may be substituted with another atom.
For example, as an atom substituting a carbon atom, an oxygen atom,
Examples thereof include sulfur atom and nitrogen atom.

The compound I is, for example, a compound in which A is an isopropylene group, B is an ethylene group, m = 3 and n = 5,
A is an isopropylene group, B is an ethylene group, m = 5, n =
5, A is an isopropylene group, B is an ethylene group,
Examples thereof include compounds in which m = 5 and n = 3, and these are used alone or in combination of two or more kinds.

The compound II is, for example, a compound in which X is an ethylene group and l = 2 (manufactured by Hitachi Chemical Co., Ltd., sample name: CHDM-4EO-DM), X is an ethylene group, and 1 =
4 compounds (manufactured by Hitachi Chemical Co., Ltd., sample name: CH
DM-8EO-DM), X is an isopropylene group, l = 5
And the compounds may be used alone or in combination of two or more.

The component (B) preferably contains a bisphenol A (meth) acrylate compound. Here, bisphenol A residues bisphenol A-based (meth) acrylate compounds (e.g., -O-C ₆ H ₄ -C
_{(CH 3) 2 -C 6 H} 4 -O-) and (meth) acrylic acid residues (e.g., (meth) refers to a compound having an acryloyl group).

As the bisphenol A (meth) acrylate compound, a compound represented by the above general formula (III) (hereinafter referred to as "compound III") is preferable. Compound I
R ²¹ and R ²² in II are preferably the same groups, and more preferably both are methyl groups.

In compound III, Y and Z each independently represent an alkylene group having 2 to 6 carbon atoms, preferably an ethylene group or a propylene group, and more preferably an ethylene group. And p and q are p + q = 4-40
Is a positive integer selected so that p + q is 6 to
34 is preferable, 8 to 30 is more preferable, 8 to 28 is further preferable, and 8 to 2
It is more preferably 0, particularly preferably 8 to 16, and most preferably 8 to 12. p
When + q is less than 4, the compatibility with the component (A) tends to decrease, and when the photosensitive element is laminated on the circuit-forming substrate, it tends to peel off. When p + q exceeds 40, hydrophilicity increases, The resist image is easily peeled off during development,
Plating resistance to solder plating and the like also tends to decrease.

In the present invention, instead of compound III or together with compound III, a compound having a substituent on the aromatic ring in compound III can be used. Examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 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 alkoxyl group, C 1-20 alkoxycarbonyl group, C 2-10
And an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms or a group containing a heterocycle, an aryl group substituted with these substituents, and the like. The above-mentioned substituents may form a condensed ring. Further, the hydrogen atom in these substituents may be substituted with the above-mentioned substituent such as a halogen atom. When the number of substituents is 2 or more, the 2 or more substituents may be the same or different.

Examples of the compound III include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl). Bisphenol A type such as propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane Examples thereof include (meth) acrylate compounds.

Examples of the 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), 2,2-bis (4-
((Meth) acryloxyundecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxydodecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxytridecaethoxy) ) Phenyl), 2,
2-bis (4-((meth) acryloxytetradecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl), 2,2-bis (4-(( (Meth) acryloxyhexadecaethoxy)
Phenyl) and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BP.
E-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) is commercially available, and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) 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),
2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl), 2,2-bis (4-((meth))
Acryloxide dodecapropoxy) phenyl), 2,2-
Bis (4-((meth) acryloxytridecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxytetradecapropoxy) phenyl), 2,2-bis (4-((meth)) Examples thereof include acryloxypentadecapropoxy) phenyl) and 2,2-bis (4-((meth) acryloxyhexadecapropoxy) phenyl). 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 can be mentioned. These are used alone or in combination of two or more.

The component (B) may contain a photopolymerizable compound other than the compounds I, II and III. Examples of the photopolymerizable compound include a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, and a compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid. , Urethane monomers such as (meth) acrylate compounds having a urethane 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, EO-modified nonylphenyl (meth) acrylate and the like can be mentioned, but one polymerizable ethylenic unsaturated bond is included in the molecule. It is preferable to use the photopolymerizable compound which it has together. These are used alone or in combination of two or more.

Examples of the compound obtained by reacting the above polyhydric alcohol with α, β-unsaturated carboxylic acid include:
Polyethylene glycol di (meth) acrylate having 2-14 ethylene groups, 2-1 propylene groups
4, polypropylene 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, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate , Polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) ac Rate, dipentaerythritol hexa (meth) acrylate.

Next, the photopolymerization initiator which is the component (C) (hereinafter also referred to as "component (C)") will be described.
Examples of the component (C) include benzophenone, N,
N, N'-tetraalkyl-, such as N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone)
4,4'-diaminobenzophenone, 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)-
Butanone-1,2-methyl-1- [4- (methylthio)
Phenyl] -2-morpholino-propanone-1 and other aromatic ketones, quinones such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethylketal,
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
-2,4,5-triarylimidazole dimer such as diphenylimidazole dimer and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-
Examples thereof include acridine derivatives such as phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds. In addition, the substituents of the aryl groups of the two 2,4,5-triarylimidazoles may be the same and may give a target compound, or may be different and give an asymmetric compound. Also, from the viewpoint of adhesion and sensitivity,
It is more preferable that the component (C) contains a 2,4,5-triarylimidazole dimer as an essential component.
The component (C) exemplified above is used alone or in combination of two or more kinds.

In the present invention, the blending amount of the component (C) is 0.1 to 20 parts by weight (preferably 0.2 to 10 parts by weight) based on 100 parts by weight of the total of the components (A) and (B). It is preferable that the blending amount of the component (A) is 40 to 80 parts by weight (preferably 45 to 70 parts by weight) based on 100 parts by weight of the total of the components (A) and (B).
In addition, since the compounding amount of the component (B) in the total 100 parts by weight of the component (A) and the component (B) is the amount excluding the compounding amount of the component (A), a suitable compounding amount is 20 to 60 parts by weight ( It is preferably 30 to 55 parts by weight). When the contents of the components (A), (B) and (C) are in the above ranges, the photosensitive resin composition exhibits not only excellent tent strength and adhesiveness but also high photosensitivity and resolution. Like

If the amount of the component (C) is less than 0.1 parts by weight per 100 parts by weight of the total of the components (A) and (B), the photosensitivity tends to be insufficient, and if it exceeds 20 parts by weight. When exposed to light, absorption on the surface of the composition increases, and internal photocuring tends to be insufficient. Further, if the amount of the component (A) is less than 40 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B), the photocured product tends to become brittle, and thus the photocurable element has a coating property When the amount exceeds 80 parts by weight, the photosensitivity tends to be insufficient.

In the photosensitive resin composition, if necessary, a photopolymerizable compound (oxetane compound etc.) having at least one cationically polymerizable cyclic ether group in the molecule,
Cationic polymerization initiators, dyes such as malachite green, photo-coloring agents such as tribromophenyl sulfone and leuco crystal violet, thermal color inhibitors, plasticizers such as p-toluene sulfonamide, pigments, fillers, defoaming agents, difficult Fuel,
Stabilizers, adhesion promoters, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. are each added to 0.01 parts of the total of 100 parts by weight of the (A) component and the (B) component. Can be contained in an amount of about 20 parts by weight.
These are used alone or in combination of two or more.

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

(Photosensitive Element) The photosensitive element of the present invention comprises a support and a photosensitive resin composition layer formed of the above-mentioned photosensitive resin composition on the support, A protective film may be further provided on the photosensitive resin composition layer to cover the photosensitive resin composition layer.

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

The support in the photosensitive element preferably has a thickness of 5 to 25 μm. When the thickness is less than 5 μm, the support tends to be broken at the time of peeling the support before development, and when it exceeds 25 μm, the resolution tends to decrease. The support is preferably composed of a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, polyester and the like.

The protective film used for the photosensitive element preferably has a thickness of 1 to 100 μm. If the thickness is less than 1 μm, the protective film tends to be easily broken during lamination, and if it exceeds 100 μm, the cost tends to be poor. The protective film preferably has a smaller adhesive force with the photosensitive resin composition layer than the adhesive force between the photosensitive resin composition layer and the support, and is preferably a low fish eye film.

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

(Method for forming resist pattern) The method for forming a resist pattern according to the present invention comprises:
Laminating a photosensitive resin composition layer in the photosensitive element, irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to form an exposed portion, and then removing a portion other than the exposed portion. Is. The circuit-forming substrate is
Insulating layer and conductor layer formed on the insulating layer (copper, copper-based alloy,
A substrate provided with an iron-based alloy such as nickel, chromium, iron or stainless steel, preferably copper, a copper-based alloy or an iron-based alloy).

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

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

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

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

As the developing solution, an alkaline aqueous solution which is safe and stable and has good operability is used.
As the alkaline aqueous solution, a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% potassium carbonate, a dilute solution of 0.1 to 5 wt% sodium hydroxide, 0.1 to 5 A dilute solution of wt% sodium tetraborate is preferred. In addition, p of the alkaline aqueous solution used for development is
H 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, a small amount of an organic solvent for accelerating development may be mixed in the alkaline aqueous solution.

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

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

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

(Method for Manufacturing Printed Wiring Board) The method for manufacturing a printed wiring board according to the present invention comprises etching or plating a circuit forming substrate having a resist pattern formed thereon by the above method for forming a resist pattern. is there.

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

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

A printed wiring board is obtained as described above,
In the printed wiring board manufacturing method of the present invention, since the photosensitive element of the present invention is used, the adhesion is high even when the pattern interval is narrowed. Also,
Since the tent strength is high, the tent part is not easily broken by the developer or the spray pressure of water washing.

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

[0066]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. (Examples 1 to 3 and Comparative Examples 1 to 3)

The materials shown in Table 1 were blended to obtain a solution.

[Table 1]

The component (B) shown in Table 2 was dissolved in the obtained solution to obtain a solution of a photosensitive resin composition. The unit of numerical values in Table 2 is gram (g).

[Table 2]

Then, the solution of the obtained photosensitive resin composition was uniformly applied on a polyethylene terephthalate film (trade name G2-16, manufactured by Teijin Ltd.) having a thickness of 16 μm, which was a support, at 100 ° C. After drying for 10 minutes with a hot air convection dryer, it was covered with polyethylene (trade name: NF-15, Tama Poly Co., Ltd.), which is a protective film, to obtain a photosensitive element. The film thickness of the photosensitive resin composition layer after drying was 25 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 sides,
Polished with a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to 600, washed with water, dried with an air stream, and heat the obtained copper-clad laminate to 80 ° C. The above-mentioned photosensitive resin composition layer was laminated at a speed of 1.5 m / min using a heat roll at 110 ° C. while peeling off the protective film.

The exposure was carried out using an exposure machine (Oak Co., Ltd.) EXM-1201 having a high pressure mercury lamp at 140
It was carried out by irradiation with mJ / cm ² . This corresponds to the amount of energy at which the number of remaining step steps after development of the 21-step stoffer step tablet is 4.0. The development was performed by peeling off the polyethylene terephthalate film and spraying a 1 wt% sodium carbonate aqueous solution at 30 ° C. for 60 seconds.

Using the circuit-forming substrate having the cured photosensitive resin composition layer obtained by the above method, the cross-cutting property (adhesion) was evaluated by the following method.
The tent strength and tent elongation were evaluated.

(Cross-Cut Property) A cross-cut test (JIS-K-) was carried out on the photosensitive resin composition layer of the circuit-forming substrate having the cured photosensitive resin composition layer obtained by the above method. 5400) and the adhesion was evaluated. The cross-cut test is performed by using a cutter guide at the center of a circuit-forming substrate provided with a cured photosensitive resin composition layer to form 1 m of vertical and horizontal 11 parallel lines.
This is a test in which the state of scratches is evaluated by making a grid-like cut so that 100 squares are formed in 1 cm ² by drawing at intervals of m. In addition, the cut may be such that the blade edge of the cutter knife is kept at a constant angle in the range of 35 to 45 degrees with respect to the photosensitive resin composition layer, and penetrates the photosensitive resin composition layer to reach the circuit forming substrate. For one cut, it was pulled at a constant speed over 0.5 seconds. Then, the cross-cut property was evaluated based on the criteria shown in Table 3 below.

[Table 3]

(Tent strength and tent extension) Diameter 6 mm
The photosensitive resin composition layer in the photosensitive element is laminated on both sides of a 1.6 mm-thick copper-clad laminate having 100 holes in the same manner as described above, and the both surfaces are exposed and exposed under the same conditions as above. It was developed. And a diameter of 1.5 mm
The breaking strength and elongation of the photosensitive resin composition layer in the tent portion were measured with a rheometer (manufactured by FUDOH) using a cylinder having an insertion diameter of. The higher the tent strength and the greater the elongation, the better the mechanical strength.

The cross-cut properties, tent strength and tent elongation are shown in Table 4 below.

[Table 4]

[0076]

As described above, according to the present invention,
A photosensitive resin composition used for manufacturing a printed wiring board or the like, which comprises a coating portion (tent portion) for covering a through hole on a circuit-forming board, and curing the tent portion after curing. The strength (tent strength) is high enough,
Furthermore, it becomes possible to provide a photosensitive resin composition having excellent adhesion to the circuit-forming substrate after curing. Further, it becomes possible to provide a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for producing a printed wiring board.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/029 G03F 7/029 5E339 7/031 7/031 5E343 7/033 7/033 7/40 521 7 / 40 521 H05K 3/06 H05K 3/06 J 3/18 3/18 D (72) Inventor Akihiro Kobayashi 14 Goi South Coast, Ichihara City, Chiba Hitachi Chemical Co., Ltd. Goi Plant (72) Inventor Katsunori Hayashi F-term in the Goi Works, Hitachi Chemical Co., Ltd., Ichihara City, Chiba Prefecture 2H025 AA13 AA14 AB11 AB15 AC01 AD01 BC14 BC42 BC43 CA14 CA28 CB10 CB13 CB14 CB16 CB43 FA03 FA17 FA40 FA43 2H096 AA26 BA05 BA20 CA20 CA20 CA20 CA20 CA20 CA20 CA20 HA17 HA27 JA04 4J011 PA63 PA83 PC02 4J026 AA17 AA45 AB01 AB04 AB07 AB28 BA30 BA50 DB26 DB36 FA05 4J027 AC01 AC02 AC03 AC07 BA07 CB10 CC03 5E339 BC02 BE13 CC01 CC02 CD 01 CE11 CE14 CF16 CF17 CG04 DD04 GG10 5E343 BB24 CC63 DD32 GG03 GG08

Claims (8)

[Claims] 1. A binder polymer (A), a photopolymerizable compound (B) having at least one polymerizable ethylenically unsaturated bond in the molecule, and (C) a photopolymerization initiator.
And a compound represented by the following general formula (I) and / or a compound represented by the following general formula (II) as a component (B). Photosensitive resin composition. [Chemical 1] [Chemical 2] [In the formula, R ¹ and R ¹¹ each independently represent a cycloalkylene group or a substituted cycloalkylene group, and R ² , R ³ , R ¹² and R ¹³ each independently represent a hydrogen atom or a methyl group, A,
B and X each independently represent an alkylene group having 2 to 6 carbon atoms, and n, m and l each independently represent an integer of 1 to 30. ] 2. Bisphenol A as the component (B)
The photosensitive resin composition according to claim 1, which contains a system (meth) acrylate compound. 3. The photosensitive resin composition according to claim 2, wherein the bisphenol A (meth) acrylate compound contains a compound represented by the following general formula (III). [Chemical 3] [In the formula, R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, Y and Z each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are p + q = 4 to 40. Denotes a positive integer chosen as ] 4. The component (A) is a binder polymer having a carboxyl group.
The photosensitive resin composition as described in any one of 3 above. 5. The photosensitive resin composition according to claim 1, which comprises 2,4,5-triarylimidazole dimer as the component (C). 6. A support, and a photosensitive resin composition layer comprising the photosensitive resin composition according to claim 1 formed on the support. And a photosensitive element. 7. A photosensitive resin composition layer of the photosensitive element according to claim 6 is laminated on a circuit-forming substrate, and a predetermined portion of the photosensitive resin composition layer is exposed to actinic rays for exposure. A resist pattern is formed, and then a portion other than the exposed portion is removed. 8. A method for manufacturing a printed wiring board, which comprises etching or plating a circuit-forming substrate on which a resist pattern has been formed by the method for forming a resist pattern according to claim 7.