JPH1036640A - Photocurable resin composition and interlayer electric insulating material for multilayer printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photocurable resin compsn. which is excellent in adhesion to copper plating for circuit formation, has an excellent flexibility, and is useful for an interlayer electric insulating material for printed circuit boards by compounding a specific acid-pendant rubber-modified epoxy vinyl ester resin, a diluent, and a photopolymn. initiator as the essential ingredients. SOLUTION: This compsn. contains an acid-pendant rubber-modified epoxy vinyl ester resin (A), a diluent (B), and a photopolymn. initiator (C). as the essential ingredients. Resin A is obtd. by reacting a polyglycidyl ether of a compd. linked to a hydroxylated arom. compd. by a cycloaliph. hydrocarbon group as the linking group, a carboxylated rubbery polymer, and an ethylenically unsatd. monobasic acid and has a structure formed by reacting a polybasic acid anhydride with hydroxyl groups of a rubber-modified epoxy vinyl ester resin. The addition of a thermosetting ingredient (pref. an epoxy resin) to the compsn. improves the adhesion strength between conductor circuits.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photocurable resin composition and an interlayer electric insulating material for a multilayer printed wiring board. More specifically, an acid pendant type rubber-modified epoxy vinyl ester resin having a specific structure, a diluent, a photopolymerization initiator, and a thermosetting component are essential components, and have excellent adhesion to copper plating and flexibility. Electrical insulation for multi-layer printed wiring boards that can be developed with a dilute alkaline solution suitable for the production of multi-layer printed wiring boards and a photo-curable resin composition with a good balance of various properties such as heat resistance, solvent resistance, and electrical properties About the material.

[0002]

2. Description of the Related Art Recently, printed wiring boards have made remarkable progress, and in particular, the integration of printed wiring boards has been increasing at an accelerating rate due to the improvement of surface mounting technology, and higher density and higher reliability have been required. In particular, in the case of multilayer printed wiring boards, the thickness of each layer can be reduced, or from a conventional multilayer printed wiring board having only through holes to a multilayer printed wiring board having partial vias on the surface or inside of the board. Has been deployed.

However, in this multilayer printed wiring board, since there is a limit to the through-hole narrowing the wiring area or reducing the diameter of the through-hole, the high density required for the through-hole printed wiring board is required. Had a limit.

Therefore, at present, as a method of manufacturing a multilayer printed wiring board, a photosensitive resin is applied onto a printed wiring board, exposed,
After development, an interlayer electric insulating layer having a photo via hole is formed, and then the surface of the insulating layer is roughened with potassium permanganate, and electroless copper plating and electrolytic copper plating are performed.
A build-up method using a photoresist method has been proposed in which a dry film is laminated, exposure, development, etching, and stripping of the etching resist are performed to form a conductor circuit, and these steps are sequentially and repeatedly laminated.

The photoresist method is excellent in that a small-diameter via can be freely formed and a high-density multilayer printed wiring board can be obtained, and its development is in progress. One of the biggest problems in the build-up method by the photoresist method is to improve the adhesion strength between a circuit and an electric insulating layer.

At present, an acid pendant novolak epoxy vinyl ester resin is being studied as an interlayer electrical insulating material for a multilayer printed wiring board by a photoresist method.

[0007]

However, the above-mentioned conventional acid pendant novolak epoxy vinyl ester resin has insufficient adhesion with copper plating, and when used as an electrical insulating material for a multilayer printed wiring board, In addition to the problem that a sufficient adhesion strength between the conductor circuits cannot be obtained, there is also a problem that the conductor circuit is inferior in flexibility and is easily broken.

An object of the present invention is to provide a photocurable resin composition and a multilayer printed wiring board having excellent adhesion of copper plating for forming a circuit and also having excellent flexibility. An object of the present invention is to provide an interlayer electric insulating material for a multilayer printed wiring board which can be developed with a suitable diluted alkaline solution.

[0009]

The present inventors have conducted intensive studies on the above-mentioned problems of the interlayer electric insulating material for a multilayer printed wiring board, and have found that a specific acid pendant type rubber-modified epoxy vinyl ester resin, a diluent, By using a photopolymerization initiator and a thermosetting component, multilayer printed wiring is excellent in adhesion to copper plating and well-balanced in various properties such as flexibility, solder heat resistance, solvent resistance, and electrical properties. The present inventors have found that an interlayer insulating material for a multilayer printed wiring board which can be developed with a dilute alkali solution suitable for manufacturing a board can be obtained, and have completed the present invention.

That is, the present invention relates to (A) polyglycidyl ether (a) of a compound in which a cyclic aliphatic hydrocarbon group (a-1) is bonded to a hydroxyl aromatic compound (a-2) as a bonding group, Acid pendant type having a structure in which hydroxyl groups of a rubber-modified epoxy vinyl ester resin obtained by reacting a group-containing rubbery polymer (b) and an ethylenically unsaturated monobasic acid (c) with polybasic anhydrides A photo-curable resin composition comprising a rubber-modified epoxy vinyl ester resin, (B) a diluent, and (C) a photopolymerization initiator as essential components; The present invention relates to an interlayer electric insulating material for a multilayer printed wiring board, comprising a curing component (D).

The acid pendant rubber-modified epoxy vinyl ester resin (A) used in the present invention is a compound in which a cyclic aliphatic hydrocarbon group (a-1) is bonded to a hydroxyl aromatic compound (a-2). Of the rubber-modified epoxy vinyl ester resin obtained by reacting the polyglycidyl ether (a) with the carboxyl group-containing rubbery polymer (b) and the ethylenically unsaturated monobasic acid (c) As long as it has a structure in which a product is reacted, it is not particularly limited.
It is preferably in the range of 140 to 140 mgKOH / g. Among them, the acid value is preferably 40 in terms of good solubility in an alkaline aqueous solution, excellent developability, and excellent characteristics of an interlayer electric insulating coating film.
Those having a range of １２０120 mgKOH / g are particularly preferred.

In order to obtain an acid pendant type rubber-modified epoxy vinyl ester resin (A) having the above-mentioned acid value range, for example, a rubber-modified epoxy vinyl ester resin is reacted with a polybasic anhydride as described above. The reaction ratio thereof is not particularly limited, and usually, the number of acid anhydride groups in the polybasic acid anhydride is 0.3 to 1.0 mol per 1 mol of hydroxyl groups in the rubber-modified epoxy vinyl ester resin. Ratio.

Above all, polybasic acid anhydride is used per mole of hydroxyl group in the rubber-modified epoxy vinyl ester resin because of its good solubility in an aqueous alkali solution, excellent developability, and excellent properties of an interlayer electric insulating coating film. It is preferred that the two are reacted at such a ratio that the number of acid anhydride groups therein becomes 0.4 to 0.9 mol.

Here, the rubber-modified epoxy vinyl ester resin is a polyglycidyl ether (a) of a compound in which a cyclic aliphatic hydrocarbon group (a-1) is bonded to a hydroxyl aromatic compound (a-2). ), A carboxyl group-containing rubbery polymer (b), and an ethylenically unsaturated monobasic acid (c), and a polyglycidyl ether (a) in the resin structure. And a carboxyl group-containing rubbery polymer (b) and an ethylenically unsaturated monobasic acid (c). In the present invention,
Among these ester bonds, the content of the ester structure site (including the rubbery polymer portion) based on the carboxyl group-containing rubbery polymer (b) is 3 to 60 in the acid pendant type rubber-modified epoxy vinyl ester resin. It is preferable that the content be in the range of weight% in that a resin excellent in adhesion to copper plating, flexibility, heat resistance, electrical characteristics, and the like can be obtained.

In producing the rubber-modified epoxy vinyl ester resin, the components of polyglycidyl ether (a), carboxyl group-containing rubbery polymer (b) and ethylenically unsaturated monobasic acid (c) are The reaction may be carried out simultaneously, or the polyglycidyl ether (a) may be reacted with the carboxyl group-containing rubbery polymer (b) followed by the reaction with the ethylenically unsaturated monobasic acid (c). .

At this time, polyglycidyl ether (a),
The reaction ratio of the carboxyl group-containing rubbery polymer (b) and the ethylenically unsaturated monobasic acid (c) is not particularly limited, but the carboxyl group per equivalent of epoxy group in the polyglycidyl ether (a) is not limited. It is preferable that the total carboxyl groups of the group-containing rubbery polymer (b) and the ethylenically unsaturated monobasic acid (c) be in the range of 0.8 to 1.1 equivalents, in particular, photocurability and storage stability. The range of 0.9 to 1.0 mol is preferable in that a resin having excellent properties is obtained.

The polyglycidyl ether (a) used in the present invention is a compound (a ') in which a cyclic aliphatic hydrocarbon group (a-1) is bonded to a hydroxyl aromatic compound (a-2) as a bonding group. Compounds obtained by glycidyl oxylation can be mentioned.

The compound (a ′) is a cyclic aliphatic hydrocarbon having two or more carbon-carbon double bonds in the molecule (a-
It is obtained by addition polymerization of 1 ′) and a hydroxyl aromatic compound (a-2) in the presence of an acid catalyst.

Examples of the cyclic aliphatic hydrocarbon (a-1 ′) include a chain conjugated diene compound such as butadiene, isoprene and piperylene; a cyclic conjugated diene compound such as cyclopentadiene and methylcyclopentadiene and a mixture thereof. Diels-Alder reaction products of selected compounds, specifically 4-vinylcyclohexene, 5-vinylcyclohexene, 4-isopropenyl-2-methylcyclohexene, 5-isopropenyl-2
-Methylcyclohexene, 6-methyl-4-vinylcyclohexene, 6-methyl-5-vinylcyclohexene,
6-methyl-4- (1-propenyl) cyclohexene,
6-methyl-5- (1-propenyl) cyclohexene,
5-vinyl-bicyclo [2,2,1] hept-2-ene, 6-vinyl-bicyclo [2,2,1] hept-2-ene
Ene, 3a, 4,7,7a-tetrahydroindene, dicyclopentadiene, 4-vinyl-tricyclo [6,
2,1,0 ^2,7] undec-9-ene, 5,5-cyclohexene - bicyclo [2,2,1] hept-2-ene, 4-vinyl - tetracyclo [6,2,1,1 ^{3 , 6} ,
0 ^2,7 ] dodec-9-ene, tetracyclo [9,2,
1,0 ^2,10, 0 ^4,9] tetradeca-5,12-diene,
Tetracyclo [9,2,1,0 ^{2, 10,} 0 ^3,8] tetradeca-5,12-diene, tetracyclo [6,5,1,0
^2,7, 0 ^9,13] tetradeca-4,10-diene, pentacyclo [6,5,1,1 ^3,6, 0 ^2,7, 0 ^9,13] 4,1
0-dienes or the like; or unsaturated terpene hydrocarbons such as limonene or 2,4-caradiene; and cyclic conjugated diene compounds such as cyclopentadiene or methylcyclopentadiene. These may be used alone or in combination of two or more. It can also be used.

The cyclic aliphatic hydrocarbon group (a-1) is
These compounds are divalent hydrocarbon groups based on double bonds in the molecular skeleton of these compounds. Among them, molecules of 3a, 4,7,7a-tetrahydroindene, dicyclopentadiene, and limonene having a cyclohexane ring or a cyclohexene ring A divalent hydrocarbon group based on a double bond in the skeleton is preferable because of excellent solder heat resistance.

The hydroxyl aromatic compound (a-2)
Represents a benzene ring, a naphthalene ring or an anthracene ring in which at least one hydroxyl group is substituted, and specifically, phenol, o-cresol, m-cresol, p-cresol, α-naphthol, β-naphthol, 1-anthracenol, 2-anthracenol, 9-anthracenol, bisphenol A, bisphenol F and the like.

The polyglycidyl ether (a) is a compound (a) obtained by addition polymerization of a cyclic aliphatic hydrocarbon (a-1 ') and a hydroxyl aromatic compound (a-2) in the presence of an acid catalyst. ') Can be obtained by glycidyloxylation, but the method is not particularly limited, and examples include a method of reacting compound (a') with epihalohydrin such as epichlorohydrin or epibromohydrin in the presence of an alkali.

Examples of the carboxyl group-containing rubbery polymer (b) include: a copolymer of an ethylenically unsaturated monobasic acid such as a polybutadiene-acrylic acid copolymer and a conjugated diene vinyl monomer; polybutadiene-acrylonitrile- Copolymer of ethylenically unsaturated monobasic acid such as acrylic acid copolymer, conjugated diene-based vinyl monomer and other vinyl monomer; carboxylic acid such as maleated polybutadiene represented by the following structural formula 1 or 2 A pendant conjugated diene-based vinyl polymer; or a rubber-like polymer having a carboxyl group at both molecular terminals of a linear polymer.

Structural formula 1

[0025]

Embedded image

(Here, n and m represent the average number of repeating units, n represents an integer of 10 to 100, and m represents an integer of 1 to 5, respectively.)

Structural formula 2

[0028]

Embedded image

(Where, n, m and l indicate the average number of repeating units, n is an integer of 10 to 80, m50 to 9
0 and 1 each represent an integer of 1 to 5. Here, examples of the rubber-like polymer having carboxyl groups at both molecular terminals of the latter linear polymer include, for example, a butadiene-acrylonitrile copolymer represented by the following structural formula 3 or structural formula 4. Copolymers of a conjugated diene-based vinyl monomer such as a polymer having a carboxyl group at a terminal and another vinyl monomer, and a polymer having a carboxyl group at both molecular terminals are exemplified.

Structural formula 3

[0031]

Embedded image

(Here, n and m indicate the average number of repeating units, and are integers of 1 or more.)

Structural formula 4

[0034]

Embedded image

(Here, n and m represent the average number of repeating units, n represents an integer of 5 to 50, and m represents an integer of 25 to 90.)

As the conjugated diene-based vinyl monomer used in the carboxyl group-containing rubbery polymer (b), not only butadiene used in the above-described exemplified polymers but also isoprene and chloroprene may be used. In addition, the ethylenically unsaturated monobasic acid that can be copolymerized with the conjugated diene-based vinyl monomer is not limited to those exemplified above as the polymer, and includes, for example, (meth) acrylic acid, crotonic acid, cinnamic acid, Acrylic acid dimer, monomethylmalate, monopropylmalate, monobutylmalate, mono (2-ethylhexyl) malate, sorbic acid and the like can be mentioned, among which (meth) acrylic acid is preferable. Further, the other vinyl monomer is not limited to the above exemplified compounds, and acrylonitrile, styrene, vinyl toluene and the like can be used.

The number of carboxyl groups in the obtained carboxyl group-containing rubbery polymer (b) is not particularly limited, but the number of carboxyl groups per molecule is preferably 1 to 5, more preferably 1 molecule. Is preferably in the range of 1.5 to 3.

In the production of the rubber-modified epoxy vinyl ester resin, examples of the ethylenically unsaturated monobasic acid used for the reaction with the epoxy resin include (meth) acrylic acid, crotonic acid, cinnamic acid and acrylic acid dimer. ,
Monomethyl malate, monopropyl malate, monobutyl malate, mono (2-ethylhexyl) malate, sorbic acid and the like are mentioned, and among them, (meth) acrylic acid is preferable.

The structure of the rubber-modified epoxy vinyl ester resin obtained by reacting each of the components (a) to (c) described above is not particularly limited, but those having various structures can be used. Although it can be used in a mixed state, for example, the polyglycidyl ether (a) having a plurality of epoxy groups has reacted with the carboxyl group of the carboxyl group-containing rubbery polymer (b) having a plurality of carboxyl groups. Forming a rubbery polymer ester of epoxy resin,
Examples include those having a structure in which an ethylenically unsaturated monobasic acid has reacted with the remaining epoxy group in this reaction product. More specifically, for example, as the carboxyl group-containing rubbery polymer (b), a rubbery polymer having carboxyl groups at both molecular terminals of a linear polymer is used, and as the polyglycidyl ether (a) When a bisphenol-type epoxy resin is used, the bisphenol-type epoxy resin reacts with the carboxyl groups at both terminals of the rubbery polymer to form an ester structure, and unreacted in each bisphenol-type epoxy resin portion. Examples include those having a structure in which (meth) acrylic acid has reacted with an epoxy group that is present as it is.

The polybasic acid anhydride which forms an acid pendant structure by reacting with a hydroxyl group of the rubber-modified epoxy vinyl ester resin is not particularly limited. For example, maleic anhydride, succinic anhydride, etc. , Itaconic anhydride, dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydro Phthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, 3-butenyl-5,6
-Dimethyltetrahydrophthalic anhydride, 3,6-endomethylene-tetrahydrophthalic anhydride, 7-methyl-
3,6-endomethylenetetrahydrophthalic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, methylcyclohexene dicarboxylic acid Examples thereof include acid anhydrides, and among them, tetrahydrophthalic anhydride and hexahydrophthalic anhydride are preferred from the viewpoint of excellent electrolytic corrosion.

Next, the diluent (B) used in the present invention is dissolved in the acid pendant type rubber-modified epoxy vinyl ester resin (A) and is suitable for various coating methods such as an electrostatic coating method and a roll coater method. It is an essential component for forming a photopolymerizable film by applying the composition so as to have a viscosity, followed by drying, and usually includes an organic solvent and a photopolymerizable vinyl monomer. Or both may be used together.

Examples of the organic solvent used herein include aromatic hydrocarbons such as toluene and xylene; methanol,
Alcohols such as isopropyl alcohol; esters such as ethyl acetate and butyl acetate; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycol derivatives such as cellosolve, butyl cellosolve and cellosolve acetate; Examples include alicyclic hydrocarbons such as cyclohexanone and cyclohexanol, and petroleum solvents such as petroleum ether and petroleum naphtha. Among these, it is preferable to use a glycol derivative and a petroleum-based solvent in combination from the viewpoint of excellent workability.

Further, as the photopolymerizable vinyl monomer,
For example, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isophoronyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxydiethylene glycol Esters of (meth) acrylic acid such as (meth) acrylate; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and pentaerythritol tri (meth) acrylate; methoxyethyl (meth) ) Acrylate,
Alkoxyalkylene glycol mono (meth) acrylates such as ethoxyethyl (meth) acrylate; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di Alkylene polyol poly (meth) acrylates such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol Di (meta)
Acrylate, polyethylene glycol 200 di (meth) acrylate, polyethoxylated trimethylolpropane tri (meth) acrylate, polypropoxylated trimethylolpropane tri (meth) acrylate, polyethoxylated bisphenol A di (meth) acrylate, polypropoxylated bisphenol A di (Meth) acrylate, polyethoxylated hydrogenated bisphenol A di (meth) acrylate, polypropoxylated hydrogenated bisphenol A di (meth) acrylate, polyethoxylated dicyclopentanieldi (meth) acrylate, polypropoxylated dicyclopentanieldi Polyoxyalkylene glycol poly (meth) acrylates such as (meth) acrylate; neopentyl glycol hydroxypivalate di (meth) acrylate Ester-type poly (meth) acrylates such as nitrate; isocyanurate-type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate; N, N-dimethylaminoethyl (meth) acrylate; N Aminoalkyl (meth) acrylates such as N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate and t-butylaminoethyl (meth) acrylate; (meth) acrylamide, N-methyl ( (Meth) acrylamide, N, N-dimethylacrylamide, N, N-dimethyl (meth) acrylamide,
(Meth) acrylamides such as (meth) acryloylmorpholine; and vinylpyrrolidone. Among them, acrylates having three or more functional groups are preferable from the viewpoint of excellent heat resistance of the interlayer electric insulating coating film.

The amount of the diluent (B) used is not particularly limited, but may be 20 to 30 parts by weight based on 100 parts by weight of the acid pendant type epoxy vinyl ester resin.
The proportion is preferably 0 parts by weight, especially 30 to 250 parts by weight.

The photopolymerizable vinyl monomer promotes the photopolymerizability, and the water-soluble photopolymerizable vinyl monomer also has a function of assisting the solubility in an aqueous alkali solution. After drying, a tack-free photopolymerizable film can be formed after drying, the photopolymerizable film can be in close contact with the resist pattern film, the resolution of the resist pattern can be improved, and chemical resistance and In order to improve the electrical properties and the like, the amount of use is preferably 50 parts by weight or less, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the rubber-modified epoxy vinyl ester resin.

Next, the photopolymerization initiator (C) used in the present invention
Examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy -2-methyl-1
-Phenylpropan-1-one, diethoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4
Acetophenones such as-(methylthio) phenyl] -2-morpholinopropan-1-one; methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone,
Anthraquinones such as amylanthraquinone; thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone and 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal Benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; and azo compounds. Among them, acetophenones are preferable.

These can be used alone or as a mixture of two or more kinds. Further, tertiary amines such as triethanolamine and methyldiethanolamine; benzoic acids such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate It can be used in combination with a photoinitiating auxiliary such as a derivative. The amount of the acid pendant epoxy vinyl ester resin and the diluent (B)
The proportion is preferably 0.5 to 20 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the total weight.

The photocurable resin composition of the present invention contains the above components (A) to (C) as essential components. In the present invention, these components are further added to a thermosetting component (D).
By using together, it is possible to provide an interlayer electric insulating material for a multilayer printed wiring board excellent in adhesion strength between conductor circuits and flexibility.

The thermosetting component (D) used here includes:
As long as it has a functional group capable of thermosetting with the acid pendant type rubber-modified epoxy vinyl ester resin (A) in the molecule, it is not particularly limited, and examples thereof include an epoxy resin, a melamine compound, a urea compound and an oxazoline compound. And phenol compounds. As the epoxy resin, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, brominated epoxy resin, biquilenol type epoxy resin, biphenol type epoxy resin, etc. Glycidyl ethers; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl Alicyclic epoxy resins such as -3,4-epoxycyclohexane; glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate and glycidyl dimer S; tetraglycidyl diaminodiphenylmethane, triglycidyl P- aminophenol, N,
Glycidylamines such as N-diglycidylaniline;
Examples thereof include heterocyclic epoxy resins such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate. Above all, melting point is 50 ℃
The above epoxy resin is preferable because it can form a tack-free photopolymerizable film after drying.

Examples of the melamine compound include melamine and a melamine resin which is a polycondensate of melamine and formalin. Examples of the urea compound include urea and urea resins which are polycondensates of urea and formalin.

Examples of the oxazoline compound include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 5-methyl-2-phenyl-2-oxazoline, 2,
4-diphenyloxazoline and the like.

Examples of the phenol compound include phenol, cresol, chilenol, catechol, resorcin, hydroquinone, pyrogallol, resol and the like.

Among these thermosetting components (D), particularly, they have excellent reactivity with carboxyl groups in the acid pendant type rubber-modified epoxy vinyl ester resin (A) and good adhesion with copper plating. And an epoxy resin is preferred.

The preferred range of the amount of the thermosetting component (D) used is usually per carboxyl group in the acid pendant type rubber-modified epoxy vinyl ester resin (A).
The ratio is such that the functional group of the thermosetting component (D) is 0.2 to 3.0 equivalents. Above all, a ratio of 1.0 to 2.0 equivalents is preferred from the viewpoint of excellent solder heat resistance and electrical characteristics when formed into a printed wiring board.

When an epoxy resin is used as the thermosetting component (D), the epoxy resin is cured in order to accelerate the reaction with the carboxyl group in the acid pendant type rubber-modified epoxy vinyl ester resin (A). Preferably, an accelerator is used. Specific examples of the curing accelerator for the epoxy resin include 2-methylimidazole, 2-ethyl-3-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, and 1-cyanoethyl-2.
Imidazole compounds such as ethylimidazole, 1-cyanoethyl-2undecylimidazole, etc .; melamine, guanamine, acetoguanamine, benzoguanamine, ethyldiaminotriazine, 2,4 diaminotriazine,
Triazine derivatives such as 2,4 diamino-6-tolyl triazine, 2,4 diamino-6-xylyl triazine; trimethylamine, triethanolamine, N, N
-Tertiary amines such as dimethyloctylamine, pyridine and m-aminophenol; polyphenols and the like. These curing accelerators can be used alone or in combination.

Further, in the present invention, the acid pendant rubber-modified epoxy vinyl ester resin (A), diluent (B), photopolymerization initiator (C), and thermosetting component (D) are further required. Various additives, for example, fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica and clay; thixotropy-imparting agents such as Aerosil; phthalocyanine blue, phthalocyanine green And a coloring agent such as titanium oxide; a silicone, a fluorine-based leveling agent or a defoaming agent; a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether, and the like can be added for the purpose of enhancing various properties of the interlayer insulating material.

The thus obtained interlayer electric insulating material for a multilayer printed wiring board of the present invention is applied on a printed wiring board by a screen printing method, an electrostatic coating method, a roll coater method, a curtain coater method, or the like. After irradiating the dried photopolymerizable film with active energy rays such as ultraviolet rays, the unexposed portions are removed with a dilute aqueous alkali solution to form a photovia hole pattern, and further post-cured with heat to form an interlayer electric insulating layer. Formed, then roughen the surface of the insulating layer with potassium permanganate, electroless copper plating,
Applying electrolytic copper plating, laminating a dry film, exposing, developing, etching, and stripping the etching resist to form a conductor circuit, and repeating these steps in order to repeatedly laminate the desired multilayer printed wiring board It can be.

[0058]

EXAMPLES The present invention will be described below with reference to examples and comparative examples, but this is only one mode and the present invention is not limited to these. All parts and percentages in the examples are on a weight basis.

Example 1 Dicyclopentadiene-phenol polyaddition type epoxy resin "Epiclon HP-7200" having an epoxy equivalent of 260, a softening point of 62 ° C. and an average number of functional groups of 2.3 [Dai Nippon Ink Chemical Industry Co., Ltd. 260 parts and a molecular weight of 350
0, HYCAR CTBN1300X13 having 27% by weight of bound acrylonitrile and 1.9 carboxyl groups / molecule
[B. F. Goodrich Chemical Co., Ltd.], 509 parts of a rubber-modified epoxy vinyl ester resin obtained by reacting 184 parts with 65 parts of acrylic acid (the number of epoxy groups: the total number of carboxyl groups = 1: 1), and tetrahydrophthalic anhydride 137 parts (the number of hydroxyl groups: the number of acid anhydride groups = 1: 0.9) was added to 277 of Solvesso 150
The resin solution (A-1) containing 70% of a resin component having a rubber component content of 28.5% and an acid value of 78 mgKOH / g was obtained.

A photopolymerization initiator, an organic solvent and a filler were blended together with the resin solution (A-1) as follows.
The main ingredient was prepared by kneading using this roll. Then
An epoxy resin, an organic solvent and a filler were blended according to the following formulation, and kneaded using a three-roll mill to prepare a curing agent.

(Blending) Main agent Resin solution (A-1) 50 parts 2,2-Dimethoxy-2-phenylacetophenone 5 parts Butyl cellosolve 15 parts Barium sulfate 30 parts Main agent total 100 parts

Curing agent Cresol novolac epoxy resin “Epiclon N-673” (manufactured by Dainippon Ink and Chemicals, Inc.) 15 parts Butyl cellosolve 5 parts Barium sulfate 10 parts Curing agent total 30 parts

Next, after mixing the main agent and the curing agent, the mixture is applied to the entire surface of a copper through-hole printed wiring board on which a circuit is formed in advance by a screen printing method so as to have a thickness of 30 to 40 μm. After drying at 80 ° C. for 20 minutes, the pattern film of the photo via hole was brought into close contact with the coated surface, and exposed for 60 seconds using a metal halide lamp exposure apparatus manufactured by Oak Manufacturing Co., Ltd. And then subjected to a heat treatment at 150 ° C. for 30 minutes using a hot air drier to obtain a printed wiring board on which a photo via hole pattern was formed.

Next, the printed wiring board in which the photo via hole was formed was washed with an alkaline potassium permanganate solution for 60 hours.
The surface of the interlayer insulating film was roughened at -80 ° C to neutralize the remaining alkali, washed with water and dried.

Next, the printed wiring board having the roughened interlayer electric insulating coating film is sequentially subjected to conditioner treatment, microetching, pickling, catalysis, and accelerator treatment, and electroless copper plating. A thin copper plating having a thickness of 3 μm was applied on the roughened interlayer electric insulating coating film.

Next, the printed wiring board having been subjected to electroless copper plating is placed in a plating tank containing a copper plating bath to serve as a cathode.
An anode is placed on both sides of the printed wiring board to allow current to flow, and
A test piece (1-a) having a thickness of μm, subjected to electrolytic copper plating, washed with water and dried to obtain a copper plating on one surface was obtained.

The specimen (1-a) thus obtained was polished and polished with a buff roll, the dry film was pressed with a hot roll, and then a pattern film of IPC-B-25 of IPC-TM-650 was brought into close contact therewith. Exposure to UV light, then 30
Development was carried out using a 1% aqueous solution of sodium carbonate at ℃, and an etching solution containing ferric chloride as a main component was sprayed thereon to dissolve unnecessary copper other than the resist pattern. Next, the dry film is peeled off using an aqueous solution of sodium hydroxide, and then washed with water and dried, and then subjected to IPC-TM.
A specimen (1-b) having a pattern of IPC-B-25 of -650 was obtained.

Separately, after mixing the main agent and the curing agent, the mixture is preliminarily polished to a thickness of 30 to 40 μm on a 0.8 mm-thick steel plate whose surface has been polished with No. 280 abrasive paper in accordance with JIS K5400. After being applied to the entire surface by a screen printing method and dried at 80 ° C. for 20 minutes, exposure was performed for 60 seconds using a metal halide lamp exposure device manufactured by Oak Manufacturing Co., Ltd., and then 150 ° C. using a hot air drier.
Heat-treated for 30 minutes in a test specimen for the flexibility test (1-
c) was obtained.

Next, according to the following evaluation test method,
The test piece (1-a) was used for the copper foil peeling strength, solder heat resistance and trichlene resistance, the test piece (1-b) was used for the insulation resistance, and the test piece (1-b) was used for the flexibility test.
The measurement was performed using c), and the results are shown in Table 1.

Example 2 Dicyclopentadiene-phenol polyaddition type epoxy resin "Epiclon HP-7200H" having an epoxy equivalent of 280, a softening point of 83.degree. C. and an average functional group of 3.0 [Dainippon Ink Chemical Industry Co., Ltd. )] And 280 parts with a molecular weight of 350
0, dipole DN-601 which is a copolymer of acrylic acid and acrylonitrile with butadiene having 27% by weight of bound acrylonitrile and 1.9 carboxyl groups / molecule.
Rubber-modified epoxy vinyl ester resin 4 obtained by reacting 55 parts of [Nippon Zeon Co., Ltd.] with 70 parts of acrylic acid (the number of epoxy groups: the total number of carboxyl groups = 1: 1).
05 parts and 77 parts of hexahydrophthalic anhydride (the number of hydroxyl groups: the number of acid anhydride groups = 1: 0.5) are reacted in 206 parts of butyl carbitol acetate to give a rubber component content of 11 parts. A resin solution (A-2) containing 0.4% and 70% of a resin having an acid value of 58 mgKOH / g was obtained. Then, after preparing the composition of the present invention in the same manner as in Example 1 except that the following blending was carried out, the specimens (2-a, 2-b, 2-c) were further processed in the same manner as in Example 1. ) Got.

(Blending) Main agent Resin solution (A-2) 50 parts 2,2-Dimethoxy-2-phenylacetophenone 5 parts Solvesso 150 10 parts Pentaerythritol triacrylate 5 parts Barium sulfate 30 parts Main agent total 100 parts

Curing agent Cresol novolac type epoxy resin “Epiclon N-680” (manufactured by Dainippon Ink and Chemicals, Inc.) 15 parts Butyl cellosolve 5 parts Barium sulfate 10 parts Curing agent total 30 parts Next, according to the following evaluation test method Table 1 shows the measurement results.

Comparative Example 1 215 parts of “Epiclone N-680” and 68 parts of acrylic acid (number of epoxy groups: total number of carboxyl groups = 1: 0.9)
5) and 283 parts of an epoxy vinyl ester resin obtained by reacting with 70 parts of succinic anhydride (number of hydroxyl groups: number of acid anhydride groups = 1: 0.7) in 151 parts of butyl carbitol acetate. The acid value is 111mgK
Resin solution containing 70% OH / g resin (A'-
3) was obtained.

Then, a composition of the present invention was prepared in the same manner as in Example 1 except that the following composition was adopted, and then the test pieces (1′-a, 1′- b,
1′-c) was obtained.

(Blending) Main agent Resin solution (A'-3) 50 parts 2,2-Dimethoxy-2-phenylacetophenone 5 parts Butyl cellosolve 15 parts Barium sulfate 30 parts Main agent total 100 parts

Curing Agent “Epiclon N-673” 15 parts Butyl cellosolve 5 parts Barium sulfate 10 parts Curing agent total 30 parts Next, the results measured in accordance with the following evaluation test method are shown in Table 1.

[Evaluation Test Method] Peeling strength: Using a test piece having copper plating on one side, the tip of the peeled copper foil is gripped with a gripper in accordance with JIS C 6481, and the pulling direction is copper foil. Peeling in the direction perpendicular to the surface, the lowest value at this time is the peeling strength of the copper foil.

Solder heat resistance: Using a printed wiring board plated with electrolytic copper, according to JIS C 6481, with the copper foil facing down and floating so that the entire surface is immersed in the solder, and soldering at 260 ° C. Float or peel off the copper foil surface and interlayer insulating layer surface after taking out for 10 seconds,
The occurrence of abnormalities such as cracks was observed.

：: No change in appearance. ×: Appearance change (whitening or cracking of insulating layer surface; peeling or blistering of copper foil surface). Trichlorethylene resistance: A test piece prepared by subjecting a copper-plated specimen to one side in accordance with JIS C 6481,
After being immersed in boiling trichlorethylene for 5 minutes, it is taken out and examined for changes in the appearance of the interlayer insulating layer surface and the copper foil surface.

：: No change in appearance. ×: Appearance change (whitening or cracking of insulating layer surface; peeling or blistering of copper foil surface). Insulation resistance: IPC of IPC-TM-650 of IPC standard
Using a specimen having a pattern of -B-25, IPC-
Specimens were prepared according to SM-840B 3.8.2 Class 3 and a DC voltage of 100 V was applied and maintained for 1 minute, and then the insulation resistance was measured with the voltage applied.

Flexibility test: A steel ball was extruded from the back surface of a test piece using an Erichsen tester according to JIS K 5400, and when the test piece was deformed, the coating film was cracked and peeled off. The extrusion distance was measured.

[0082]

[Table 1]

[0083]

According to the present invention, development with a dilute alkali solution having excellent adhesion to copper plating and a good balance of various properties such as flexibility, solder heat resistance, solvent resistance, and electrical properties. It is possible to form an interlayer electric insulating coating film of a possible multilayer printed wiring board.

The resin composition of the present invention is not only used for the interlayer insulating material of a multilayer printed wiring board,
It can be used as solder resist ink for printed wiring boards.

Claims (7)

[Claims] (A) a cyclic aliphatic hydrocarbon group (a-1)
Is reacted with a polyglycidyl ether (a), a carboxyl group-containing rubbery polymer (b) and an ethylenically unsaturated monobasic acid (c) of a compound bonded to a hydroxyl aromatic compound (a-2) as a bonding group. An acid pendant type rubber-modified epoxy vinyl ester resin having a structure in which a hydroxyl group of a rubber-modified epoxy vinyl ester resin obtained by the reaction is reacted with a polybasic anhydride, (B) a diluent, and (C) a photopolymerization initiator, A photocurable resin composition comprising: 2. The composition according to claim 1, wherein the acid pendant rubber-modified epoxy vinyl ester resin (A) has an acid value of 30 to 140 mg KOH / g. 3. An acid pendant type rubber-modified epoxy vinyl ester resin (A) has an acid anhydride group in a polybasic acid anhydride of 0.3 to 1.0 per mole of hydroxyl group of the rubber-modified epoxy vinyl ester resin. 3. The composition according to claim 2, wherein the composition has a structure reacted by using it in a molar ratio. 4. The acid pendant type rubber-modified epoxy vinyl ester resin (A) has a rubber-like polymer ester structure based on the carboxyl group-containing rubber-like polymer (b) in the epoxy vinyl ester resin (A). 3-60% by weight
The composition according to claim 1, 2 or 3, wherein the composition is contained at a ratio of: 5. A rubber-modified epoxy vinyl ester resin comprising a carboxyl group present in a carboxyl group-containing rubbery polymer (b) and an ethylenically unsaturated monobasic acid per one equivalent of an epoxy group of a polyglycidyl ether (a). The composition according to any one of claims 1 to 4, wherein the composition is reacted at a ratio of a total of 0.8 to 1.1 equivalents of the carboxyl group (c). 6. A carboxyl group-containing rubbery polymer (b)
The composition according to any one of claims 1 to 5, wherein the composition has from 1 to 5 carboxyl groups per molecule of the polymer. 7. An interlayer electric insulating material for a multilayer printed wiring board, further comprising a thermosetting component (D) in the composition according to any one of claims 1 to 6.