JPH08212832A - Layer-to-layer electric insulating material for multilayer printed board - Google Patents

Abstract

PURPOSE: To provide a layer-to-layer electric insulating coating film excellent in adhesion with a copper plating forming a circuit in a multilayer printed board obtained by build-up method. CONSTITUTION: This layer-to-layer electric insulating coating film for multilayer printed board contains (A) an acid pendant type rubber denaturated bisphenol A type epoxy vinyl ester resin having a structure in which a tetrahydromaleic anhydride is reacted with the hydroxyl group of a rubber denaturated bisphenol A type epoxy vinyl ester resin obtained by the reaction of a bisphenol A type epoxy resin; a polymer which is a linear copolymer of a conjugate diene vinyl monomer and acrylonitrile having carboxyl groups on both terminals of the molecule; and an acrylic acid, (B) a diluting agent, (C) an optical polymerization initiator, and (D) a cresol novolak type epoxy resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electric insulating material for a multilayer printed wiring board. More specifically, an acid pendant type rubber-modified bisphenol A type 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 The present invention relates to an interlayer electrical insulating material for a multilayer printed wiring board, which has a good balance of properties such as flexibility, solder heat resistance, solvent resistance, and electrical characteristics and which is suitable for manufacturing a multilayer printed wiring board and can be developed with a dilute alkaline solution.

[0002]

2. Description of the Related Art Recent advances in printed wiring boards have been remarkable, and in particular, due to improvements in surface mounting technology, high integration of printed wiring boards is accelerating, and higher density and higher reliability are required. Especially in the case of multilayer printed wiring boards, the thickness of each layer is reduced, or the conventional multilayer printed wiring board with only through holes is changed to a multilayer printed wiring board with partial vias on the surface or inside of the board. Has been deployed.

However, in this multilayer printed wiring board, there is a limit in narrowing the wiring area of the through hole and reducing the diameter of the through hole, so that the through hole printed wiring board is required to have a high density at present. There was a limit.

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

This photoresist method is excellent in that it can freely form a small-diameter via and obtain a high-density multilayer printed wiring board, and is under development. One of the biggest problems in the build-up method using the photoresist method is improvement of the adhesion strength between the circuit and the electric insulating layer.

Currently, an acid pendant type novolac epoxy vinyl ester resin is being investigated as an interlayer electrical insulating material for a multilayer printed wiring board by a photoresist method.

[0007]

However, the above-mentioned conventional acid pendant type novolac epoxy vinyl ester resin does not have sufficient adhesion to copper plating, and when used as an electric insulating material for a multilayer printed wiring board, In addition to the problem that sufficient adhesion strength between the conductor circuits cannot be obtained, it also has the problem of being liable to crack due to poor flexibility.

The problem to be solved by the present invention is to develop with a dilute alkaline solution suitable for the production of a multilayer printed wiring board, which has excellent adhesion of copper plating forming a circuit and also has excellent flexibility. An object is to provide a possible interlayer electric insulation material for a multilayer printed wiring board.

[0009]

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

That is, the present invention uses (A) a linear copolymer of a conjugated diene vinyl monomer and acrylonitrile, having a carboxyl group at both ends of the molecule as a rubber component, An acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin having a structure in which a polybasic acid anhydride is reacted with a hydroxyl group of a rubber-modified bisphenol A type epoxy vinyl ester resin modified by a reaction of a group and an epoxy group, (B ) A diluent, (C) a photopolymerization initiator, and (D) a thermosetting component as essential components, to an interlayer electrical insulating material for a multilayer printed wiring board.

Acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin (A) used in the present invention
Is a linear copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, which has as a rubber component a polymer having carboxyl groups at both ends of the molecule, and is modified by the reaction between the carboxyl group and the epoxy group. The rubber-modified bisphenol A-type epoxy vinyl ester resin has a structure in which a polybasic acid anhydride is reacted with the hydroxyl group of the rubber-modified bisphenol A-type epoxy vinyl ester resin.
It is preferably in the range of 140 mg KOH / g. Among them, the acid value is 40 because the solubility in an alkaline aqueous solution is good, the developability is excellent, and the characteristics of the interlayer electric insulation coating film are excellent.
Those in the range of to 120 mgKOH / g are particularly preferable.

To obtain the acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin (A) having the above acid value range, for example, a rubber modified bisphenol A type epoxy vinyl ester resin and a polybasic acid anhydride are used as described above. Although the reaction ratio is not particularly limited, the number of the acid anhydride groups in the polybasic acid anhydride is usually 1 mole of the hydroxyl group in the rubber-modified bisphenol A type epoxy vinyl ester resin. The ratio may be 0.3 to 1.0 mol. Among them, the acid value is 40 to 120 mg KO
When adjusting to the range of H / g, the number of acid anhydride groups in the polybasic acid anhydride is 0.4 to 0. 1 with respect to 1 mol of the hydroxyl groups in the rubber-modified bisphenol A type epoxy vinyl ester resin.
It is preferable to react both at a ratio of 9 mol.

In the present invention, these rubber-modified bisphenol A type epoxy vinyl ester resins may be used in combination with other acid pendant type epoxy vinyl ester resins, if necessary. As the other acid pendant type epoxy vinyl ester resin, any of those conventionally used in alkali developing type solder resist ink can be used. For example, acid pendant type novolac epoxy vinyl ester resin, acid pendant type bisphenol A type epoxy resin. Vinyl ester resin, acid pendant type bisphenol F type epoxy vinyl ester resin,
Examples thereof include acid pendant bisphenol S type epoxy vinyl ester resin and acid pendant type bixinol type epoxy vinyl ester resin.

Here, the rubber modified bisphenol A type epoxy vinyl ester resin is a bisphenol A type epoxy resin, a linear copolymer of a conjugated diene vinyl monomer and acrylonitrile, and has carboxyl groups at both ends of the molecule. A polymer having, and a structure obtained by reacting an ethylenically unsaturated monobasic acid, in the structure,
Bisphenol A type epoxy resin, linear copolymer of conjugated diene vinyl monomer and acrylonitrile, which has carboxyl groups at both ends of the molecule, and ester produced by reaction of ethylenically unsaturated monobasic acid A bond exists. In the present invention, among these ester bonds, an ester bond site (rubber-like polymer) based on a polymer which is a linear copolymer of a conjugated diene vinyl monomer and acrylonitrile and has a carboxyl group at both ends of the molecule. The content of (including a coalesced portion) is in the range of 3 to 60% by weight in the acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin (A), which is excellent in adhesiveness with copper plating, and ,
It is preferable in that a resin excellent in various properties such as flexibility, solder heat resistance, solvent resistance, and electrical properties can be obtained.

Further, in the production of this rubber-modified bisphenol A type epoxy vinyl ester resin, a bisphenol A type epoxy resin, a linear copolymer of a conjugated diene vinyl monomer and acrylonitrile, and having both ends of the molecule. The polymer having a carboxyl group and each component of the ethylenically unsaturated monobasic acid may be reacted at the same time, and a linear copolymer of a bisphenol A type epoxy resin, a conjugated diene vinyl monomer and acrylonitrile. It is also possible to react with a polymer having a carboxyl group at both ends of the molecule and then react with an ethylenically unsaturated monobasic acid.

At this time, a bisphenol A type epoxy resin, a linear copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group at both terminals of the molecule, and an ethylenically unsaturated monobasic acid. The reaction ratio with is not particularly limited, but is a linear copolymer of a conjugated diene vinyl monomer and acrylonitrile per one equivalent of the epoxy group of the bisphenol A type epoxy resin, and at both ends of the molecule. The content of the rubber-like polymer ester structure moiety is adjusted to the above range such that the total carboxyl group of the polymer having a carboxyl group and the ethylenically unsaturated monobasic acid is 0.8 to 1.1 equivalents. It is preferable from the viewpoint that it is easy to perform, and above all, the range of 0.9 to 1.0 mol is preferable from the viewpoint that a resin excellent in photocurability and storage stability is obtained. .

Although the structure of the bisphenol A type epoxy resin used in the present invention is not particularly specified, for example, an epoxy resin obtained by reacting bisphenol A with epichlorohydrin, or by reacting bisphenol A with epichlorohydrin is used. A high molecular weight type epoxy resin obtained by further reacting the obtained epoxy resin with bisphenol A may, for example, be mentioned. Among them, the melting point is 50
An epoxy resin having a temperature of not less than 0 ° C. is preferable because it can form a photopolymerizable film without tack after drying. The epoxy equivalent is not particularly limited, but is 250 to 40,000 from the viewpoint of forming a photopolymerizable film without tack after drying.
It is preferably 0 g / eq.

Further, a linear copolymer of a conjugated diene vinyl monomer and acrylonitrile having a carboxyl group at both ends of the molecule is, for example, butadiene-acrylonitrile represented by the following structural formula 1. A polymer having a carboxyl group at the molecular end of the copolymer, and a polymer having a hydroxyl group at the molecular end of a butadiene-acrylonitrile copolymer represented by the following structural formula 2.
Examples thereof include half-esters with polybasic acid anhydrides such as maleic anhydride. Structural formula 1

[0019]

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.) Structural formula 2

[0021]

Embedded image

(Here, n and m are the average number of repeating units, n is an integer of 5 to 50, and m is an integer of 25 to 90.) Further, the conjugated diene vinyl monomer and acrylonitrile are added. As the conjugated diene vinyl monomer used in the polymer having a carboxyl group at both ends of the molecule, which is a linear copolymer, not only butadiene used in the above-mentioned exemplified polymers but also isoprene, chloroprene, etc. Although it may be used, butadiene is preferred. Also,
These compounds may be used alone,
Further, two or more kinds may be used in combination for polymerization, but in the latter case, it is preferable to use butadiene as one component.

Further, as the polybasic acid anhydride used as a half ester of a polybasic acid anhydride and a polymer having a hydroxyl group at the molecular end, which is a copolymer of a conjugated diene vinyl monomer and acrylonitrile, Specifically, maleic anhydride, succinic anhydride, itaconic anhydride, dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3- Methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic 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 anhydride, etc.

The number of carboxyl groups in the obtained rubber-like polymer is not particularly limited, but the number of carboxyl groups per molecule is 1 to 3 in the molecule, more preferably 1.5 to 2 It is desirable to be within the range of 5.

In the production of the rubber-modified bisphenol A type epoxy vinyl ester resin, examples of the ethylenically unsaturated monobasic acid used for the reaction with the bisphenol A type epoxy resin include (meth) acrylic acid, crotonic acid, Examples thereof include cinnamic acid, acrylic acid dimer, monomethylmalate, monopropylmalate, monobutylmalate, mono (2-ethylhexyl) malate, and sorbic acid. Among them, (meth) acrylic acid is preferable.

The rubber-modified bisphenol A type epoxy vinyl ester resin obtained by reacting each of the components described in detail above is not particularly limited in its structure, and can be used in a state in which various structures are mixed. However, for example, the carboxyl group and ethylenically unsaturated monobasic acid of the rubber-like polymer having a carboxyl group at the molecular end,
Examples thereof include those having a structure in which an ester bond is formed by reacting with an epoxy group in a bisphenol A type epoxy resin.

More specifically, for example, a linear rubber polymer having carboxyl groups at both ends of the molecule is used as a binding site, and the bisphenol A type epoxy resin structure is linked via an ester bond. Examples thereof include those having a structure in which an epoxy group at the terminal forms an ester structure with an ethylenically unsaturated monobasic acid.

Next, the polybasic acid anhydride to be reacted with the hydroxyl group of the rubber-modified bisphenol A type epoxy vinyl ester resin is not particularly limited, but specifically, maleic anhydride and succinic anhydride are used. Acid, itaconic anhydride, dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrate Hydrophthalic 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-Endomethylene tetrahydrophthalic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid anhydride, methylcyclohexene dicarboxylic acid Examples thereof include acid anhydrides, and among them, tetrahydrophthalic anhydride and hexahydrophthalic anhydride are preferable from the viewpoint of excellent electrolytic corrosion property.

The diluent (B) used in the present invention is dissolved in the acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin (A) and is suitable for various coating methods such as screen printing and roll coater method. It is an essential constitutional condition for forming a photopolymerizable film by coating so as to have a viscosity and then drying, and usually includes an organic solvent and a photopolymerizable vinyl monomer. May be used, or both may be used in combination.

Examples of the organic solvent used here 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 acetate, and cellosolve acetate Cyclohexanone,
Examples thereof include alicyclic hydrocarbons such as cyclohexanol and petroleum solvents such as petroleum ether and petroleum naphtha.
Among these, it is preferable to use the glycol derivative in combination with the petroleum-based solvent 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, isoboronyl (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, 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 dicyclopentanierdi (meth) acrylate, polypropoxylated dicyclopentanieldi Polyoxyalkylene glycol poly (meth) acrylates such as (meth) acrylate; hydroxypivalic acid neopentyl glycol ester di (meth) acrylate Ester-type poly (meth) acrylates such as salts; isocyanurate-type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate; N, N-dimethylaminoethyl (meth) acrylate, N , N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate and other aminoalkyl (meth) acrylates; (meth) acrylamide, N-methyl ( (Meth) acrylamide, N, N-dimethylacrylamide, N, N-dimethyl (meth) acrylamide,
(Meth) acrylamides such as (meth) acryloylmorpholine; vinylpyrrolidone and the like. Among these, trifunctional or higher functional acrylates are preferable from the viewpoint of the heat resistance of the insulating coating film.

The amount of the diluent (B) used is the above acid pendant type epoxy vinyl ester resin (A) 10
20-300 parts by weight, preferably 30
A proportion of up to 250 parts by weight is suitable.

Further, the photopolymerizable vinyl monomer promotes the photopolymerizability, and the water-soluble photopolymerizable vinyl monomer also plays a role of assisting the solubility in an alkaline aqueous solution, but the photopolymerizable vinyl monomer is reduced. It is possible to form a photopolymerizable film without tack after drying, the adhesion between the photopolymerizable film and the pattern film and the releasability of the pattern film after exposure are improved, and the resolution of the photovia hole pattern is improved. Can be improved, and further, chemical resistance and electrical characteristics are further improved. The amount used is preferably 50 parts by weight or less, and particularly preferably 2 to 20 parts by weight, based on 100 parts by weight of the acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin (A).

Next, examples of the photopolymerization initiator (C) 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-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-
Acetophenones such as (methylthio) phenyl] -2-morpholinopropan-1-one; methylanthraquinone, 2-ethylanthraquinone, 2-tacharybutylanthraquinone, 1-chloroanthraquinone, 2-
Anthraquinones such as amylanthraquinone; thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone,
Thioxanthones such as 2-methylthioxanthone and 2,4-diisopropylthioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone and azo compounds Among these, acetophenones are preferable.

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

In the present invention, a thermosetting component (D) is further used as a curing component to each of the above-mentioned components to provide an interlayer electrical insulation material for a multilayer printed wiring board which is excellent in solder heat resistance and electric characteristics. be able to.

The thermosetting component (D) used in the present invention is not particularly limited as long as it has an acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin (A) and a thermosetting functional group in the molecule, and is particularly specified. Although not included, examples thereof include epoxy resins, melamine compounds, urea compounds, oxazoline compounds, and phenol compounds. As the epoxy resin, specifically,
Bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin,
Glycidyl ethers such as cresol novolac type epoxy resin, brominated epoxy resin, bikylenol type epoxy resin, biphenol type epoxy resin; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate ,
Alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane; phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer Glycidyl esters such as acid glycidyl ester; tetraglycidyl diaminodiphenylmethane, triglycidyl P-
Glycidylamines such as aminophenol and N, N-diglycidylaniline; 1,3-diglycidyl-5,5
-Heterocyclic epoxy resins such as dimethylhydantoin and triglycidyl isocyanurate. Of these, an epoxy resin having a melting point of 50 ° C. or higher is preferable because it can form a photopolymerizable film without tack after drying.

Examples of the melamine compound include melamine and a melamine resin which is a polycondensation product of melamine and formalin. Examples of the urea compound include urea and a urea resin which is a polycondensation product of urea and formalin.

As the oxazoline compound, 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2oxazoline, 2,5-dimethyl-2oxazoline, 5-methyl-2-phenyl-2oxazoline, 2,
4-diphenyloxazoline and the like can be mentioned.

Examples of the phenol compound include phenol, cresol, kylenol, catechol, resorcin, hydroquinone, pyrogallol and resole.

Among these thermosetting components (D), particularly the acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin (A) is excellent in reactivity with the carboxyl group in the resin and also has good adhesion to copper plating. The epoxy resin is preferable from the viewpoint of

A suitable range of the amount of the thermosetting component (D) used is usually the thermosetting component (D) per one carboxyl group in the acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin (A). The ratio is such that the functional group group of D) becomes 0.2 to 3.0 equivalents. Above all, a ratio of 1.0 to 1.5 equivalents is preferable from the viewpoint of excellent solder heat resistance and electric characteristics when used as a printed wiring board.

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

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

The thus obtained interlayer electrical insulating material for a multilayer printed wiring board of the present invention is applied onto 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 photopolymerizable film obtained by drying with active energy rays such as ultraviolet rays, a photo-via hole pattern is formed by removing the unexposed portion with a dilute alkaline aqueous solution, and further post-cured by heat to form an interlayer electrical insulation layer. Formed, then roughen the surface of the insulating layer with potassium permanganate, electroless copper plating,
Electrolytic copper plating is applied, then dry film is laminated, exposure, development, etching, etching resist is peeled off to form a conductor circuit, and these steps are sequentially and repeatedly laminated to form the intended multilayer printed wiring board. Can be

[0046]

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 thereto. All parts and% in the examples are on a weight basis.

Example 1 260 parts of a bisphenol A type epoxy resin "Epiclon 8600" (manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 260, a molecular weight of 3500, bound acrylonitrile of 27% by weight, and a carboxyl group of 1. HYCARCTBN 1 having carboxyl groups at both ends of a molecule of a copolymer of butadiene and acrylonitrile of 9 molecules / molecule
300X13 [B. F. Goodrich Che
160 parts of acrylic acid, 65 parts of acrylic acid (the number of epoxy groups: the number of total carboxyl groups = 1: 1), and 485 parts of rubber-modified bisphenol A type epoxy vinyl ester resin obtained by reaction with tetrahydro. 178 parts of phthalic anhydride (number of hydroxyl groups: number of acid anhydride groups = 1: 0.
9) is reacted with 284 parts of butyl carbitol acetate to give 70% of a resin component having an acid value of 99 mgKOH / g.
The resin solution (A-1) containing was obtained.

A photopolymerization initiator, an organic solvent and a filler were blended together with this resin solution (A-1) as follows, and 3
The main ingredient was prepared by kneading using this roll mill. Then, an epoxy resin, an organic solvent and a filler were blended according to the following formulation, and kneaded using a three-roll to prepare a curing agent.

(Compounding) Main agent Resin solution (A-1) 50 parts 2,2-Dimethoxy-2-phenylacetophenone 5 parts Solvesso 150 15 parts Barium sulfate 30 parts Main agent total 100 parts

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

Next, after mixing the base material and the curing agent, the mixture is applied on the entire surface by a screen printing method so as to have a thickness of 30 to 40 μm on a copper through-hole printed wiring board on which a circuit is formed in advance. 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 device manufactured by Oak Manufacturing Co., Ltd. Then, a 1% sodium carbonate aqueous solution at a liquid temperature of 30 ° C was used. Development was performed for 60 seconds, and then heat treatment was performed for 30 minutes at 150 ° C. using a hot air dryer to obtain a printed wiring board having a photovia hole pattern formed.

Then, the printed wiring board having the photo via holes formed therein is treated with an alkaline potassium permanganate solution at 60%.
The surface of the interlayer electric insulation coating was roughened at -80 ° C to neutralize residual alkali, washed with water and dried.

Next, the printed wiring board having the roughened inter-layer electrical insulating coating film on its surface is sequentially subjected to conditioner treatment, micro etching, pickling, catalysis, and accelerator treatment, and electroless copper plating is performed. A thin copper plating with a thickness of 3 μm was applied on the surface-roughened interlayer electrical insulation coating.

Next, a printed wiring board plated with electroless copper is placed in a plating bath containing a copper plating bath to serve as a cathode.
Place the anodes on both sides of the printed wiring board and apply an electric current.
An electrolytic copper plating having a thickness of μm was performed, followed by washing with water and drying to obtain a sample (1-a) having copper plating on one surface.

The obtained sample (1-a) was polished and surface-polished with a buff roll, the dry film was pressure-bonded with a hot roll, and then a pattern film of IPC-B-25 of IPC-TM-650 was brought into close contact, UV light exposure, then liquid temperature 30
Development was performed using a 1% sodium carbonate aqueous solution at 0 ° C., and an etching solution containing ferric chloride as a main component was sprayed to dissolve unnecessary copper other than the resist pattern. Then, the dry film is peeled off using an aqueous solution of sodium hydroxide, then washed with water and dried to obtain IPC-TM.
A sample (1-b) having a pattern of -650 IPC-B-25 was obtained.

Separately, after mixing the main agent and the curing agent, the mixture was preliminarily compliant with JIS K 5400 and the surface thereof was polished with No. 280 polishing paper to a 0.8 mm-thick steel plate to a thickness of 30 to 40 μm. So that it is applied to the entire surface by the screen printing method and dried at 80 ° C. for 20 minutes, and then exposed for 60 seconds using a metal halide lamp exposure device manufactured by Oak Manufacturing Co., Ltd., and then at 150 ° C. using a hot air dryer.
Specimens for flexibility test (1-
c) was obtained.

Then, according to the evaluation test method described below,
The peeling strength, solder heat resistance, and trichlene resistance of the copper foil were measured using the sample (1-a), the insulation resistance was measured using the sample (1-b), and the flexibility test was performed using the sample (1-a).
Measurement was carried out using c), and the results are shown in Table 1.

Example 2 Bisphenol A type epoxy resin "Epiclon 4050" having an epoxy equivalent of 475 [Dainippon Ink and Chemicals, Inc.]
Made] and HYCAR CTBN 1300X1
820 parts of rubber-modified bisphenol A type epoxy vinyl ester resin obtained by reacting 80 parts of 3 and 65 parts of acrylic acid (the number of epoxy groups: the number of total carboxyl groups = 1: 0.95), and tetrahydroanhydrophthalic acid 95 parts of acid (the number of hydroxyl groups: the number of acid anhydride groups = 1: 0.3) is reacted in 306 parts of butyl carbitol acetate,
A resin solution (A-2) containing 70% of a resin component having an acid value of 49 mgKOH / g was obtained.

Then, the composition of the present invention was prepared in the same manner as in Example 1 except that the following components were added, and then the test pieces (2-a, 2-b, 2-
c) was obtained.

(Compounding) Main agent Resin solution (A-2) 50 parts 2,2-Dimethoxy-2-phenylacetophenone 5 parts Solvesso 150 15 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 acetate 5 parts Barium sulfate 10 parts Curing agent total 30 parts Next, as in Example 1. Table 1 shows the results of measurement according to the following evaluation test methods.

Example 3 Bisphenol A type epoxy resin "Epiclon 850" having an epoxy equivalent of 188 [Dainippon Ink and Chemicals, Inc.]
Made] 188 parts, HYCAR CTBN 1300X1
321 parts of 3 and 58 parts of acrylic acid (the number of epoxy groups:
559 parts of a rubber-modified bisphenol A type epoxy vinyl ester resin obtained by reacting with a total number of carboxyl groups = 1: 1, and 117 parts of tetrahydrophthalic anhydride (the number of hydroxyl groups: the number of acid anhydride groups = 1) : 0.7) in 290 parts of butyl carbitol acetate,
A resin solution (A-3) containing 70% of a resin component having an acid value of 64 mgKOH / g was obtained.

Then, the composition of the present invention was prepared in the same manner as in Example 1 except that the ingredients were mixed as described below, and then the sample (3-a, 3-b, 3-
c) was obtained.

(Compounding) Main agent Resin solution (A-3) 50 parts 2,2-Dimethoxy-2-phenylacetophenone 5 parts Solvesso 150 12 parts Dipentaerythritol hexaacrylate 3 parts Barium sulfate 30 parts Main agent total 100 parts

Curing agent "Epiclone N-680" 15 parts Butyl cellosolve acetate 5 parts Barium sulfate 10 parts Curing agent total 30 parts Next, in the same manner as in Example 1, the results of measurement according to the following evaluation test methods are shown in Table 1. Shown in.

Example 4 "Epiclone N-680" 215 with an epoxy equivalent of 215
Part and acrylic acid 72 parts (the number of epoxy groups: the total number of carboxyl groups = 1: 1) to obtain 287 parts of an epoxy vinyl ester resin, and 91 parts of tetrahydrophthalic anhydride (the number of hydroxyl groups: acid anhydride). Number of physical objects = 1: 0.6)
And were reacted in 162 parts of butyl carbitol acetate to obtain a resin solution (B-1) containing 70% of a resin component having an acid value of 89 mgKOH / g.

Then, the composition of the present invention was prepared in the same manner as in Example 1 except that the following components were mixed, and then the test pieces (4-a, 4-b, 4-
c) was obtained.

(Compounding) Main agent Resin solution (A-1) 25 parts Resin solution (B-1) 25 parts 2,2-Dimethoxy-2-phenylacetophenone 5 parts Solvesso 150 12 parts Dipentaerythritol hexaacrylate 3 parts Barium sulfate 30 parts Total 100 parts

Curing agent "Epiclone N-680" 15 parts Butyl cellosolve acetate 5 parts Barium sulfate 10 parts Curing agent total 30 parts Next, in the same manner as in Example 1, the results of measurement according to the following evaluation test methods are shown in Table 1. Shown in.

Comparative Example 1 Then, the composition of the present invention was prepared in the same manner as in Example 1 except that the resin solution (B-1) synthesized in Example 4 was used and the composition was as follows. Further, a sample (1'-a, 1'-b, 1'-c) was obtained in the same manner as in Example 1.

(Compounding) Main agent Resin solution (B-1) 50 parts 2,2-Dimethoxy-2-phenylacetophenone 5 parts Solvesso 150 15 parts Barium sulfate 30 parts Main agent total 100 parts

Curing agent "Epiclone N-680" 15 parts Butyl cellosolve acetate 5 parts Barium sulfate 10 parts Curing agent total 30 parts Then, in the same manner as in Example 1, the results of measurement according to the following evaluation test method are shown in Table 1. Shown in.

Comparative Example 2 332 parts of an epoxy vinyl ester resin obtained by reacting 260 parts of "Epiclone 860" with 72 parts of acrylic acid (the number of epoxy groups: the number of carboxyl groups = 1: 1) and tetrahydrophthalic anhydride. Acid 158 parts (number of hydroxyl groups:
The number of acid anhydride groups = 1: 0.8) was reacted with 210 parts of butyl carbitol acetate to give an acid value of 91 mg.
A resin solution containing 70% KOH / g resin (B-
2) was obtained.

Then, a comparative composition was prepared in the same manner as in Example 1 except that the following components were mixed, and then the test pieces (2'-a, 2'-) were prepared in the same manner as in Example 1. b,
2'-c) was obtained.

(Compounding) Main agent Resin solution (B-2) 50 parts 2,2-Dimethoxy-2-phenylacetophenone 5 parts Solvesso 150 15 parts Barium sulfate 30 parts Main agent total 100 parts

Curing agent "Epiclone N-680" 15 parts Butyl cellosolve acetate 5 parts Barium sulfate 10 parts Curing agent total 30 parts Next, in the same manner as in Example 1, the results of measurement according to the following evaluation test methods are shown in Table 1. Shown in.

Comparative Example 3 260 parts of an epoxy vinyl ester resin obtained by reacting 188 parts of "Epiclone 850" with 72 parts of acrylic acid (the number of epoxy groups: the number of carboxyl groups = 1: 1) and tetrahydroanhydrophthalic anhydride. 117 parts of acid (number of hydroxyl groups:
The number of acid anhydride groups = 1: 0.7) was reacted with 162 parts of butyl carbitol acetate to give an acid value of 104 m.
Resin solution containing 70% of resin content of gKOH / g (B-
3) was obtained.

Then, a comparative composition was prepared in the same manner as in Example 1 except that the following components were used, and then the test pieces (3'-a, 3'-) were prepared in the same manner as in Example 1. b,
3'-c) was obtained. (Compounding) Main agent Resin solution (B-3) 50 parts 2,2-Dimethoxy-2-phenylacetophenone 5 parts Solvesso 150 15 parts Barium sulfate 30 parts Main agent total 100 parts

Curing agent "Epiclone N-680" 15 parts Butyl cellosolve acetate 5 parts Barium sulfate 10 parts Curing agent total 30 parts Then, in the same manner as in Example 1, the results of measurement according to the following evaluation test methods are shown in Table 1. Shown in.

[Evaluation test method] Peel strength: JIS C 6481 was used by using a test piece with copper plating on one side.
According to, grasp the tip of the peeled copper foil with a gripping tool and peel it in the direction in which the pulling direction is perpendicular to the copper foil surface, and the minimum value at this time is the peeling strength of the copper foil.

Solder heat resistance: A printed wiring board plated with electrolytic copper was used, and the copper foil was floated down so that the entire surface was immersed in solder according to JIS C 6481. Boil or peel off the copper foil surface and interlayer insulation layer surface after floating for 10 seconds
The presence or absence of abnormalities such as cracks was observed.

Trichlorethylene resistance: A test piece with copper plating on one side was prepared in accordance with JIS C 6481, immersed in boiling trichlorethylene for 5 minutes, and then taken out. Investigate changes in the appearance of the copper foil surface.

A: No change in appearance X: There is a change in appearance (whitening or cracks on the insulating layer surface; peeling or blistering on the copper foil surface). Insulation resistance: IPC of IPC standard IPC-TM-650
-Using a specimen having a pattern of B-25, IPC-
SM-840B 3.8.2 A test piece was prepared according to Class 3, a DC voltage of 100 V was applied and maintained for 1 minute, and then the insulation resistance was measured under the applied voltage.

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

[0085]

[Table 1]

[0086]

According to the present invention, development is performed with a dilute alkaline solution, which has excellent adhesion to copper plating and has a good balance of various characteristics such as flexibility, solder heat resistance, solvent resistance, and electrical characteristics. Interlayer electrical insulation layers of possible multilayer printed wiring boards can be formed.

Front page continuation (72) Inventor Makoto Yanagawa 16-2 Sayamagahara, Kumaga City, Saitama Prefecture Tamura Kaken Co., Ltd. (72) Masato Hoshino 16-2 Sayamagahara, Kukuma City, Saitama Prefecture Tamura Kaken Co., Ltd. In-house

Claims (6)

[Claims] 1. A linear copolymer of (A) a conjugated diene-based vinyl monomer and acrylonitrile, wherein a polymer having carboxyl groups at both ends of the molecule is used as a rubber component, and An acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin having a structure in which a hydroxyl group of a rubber-modified bisphenol A type epoxy vinyl ester resin modified by the reaction of a carboxyl group and an epoxy group is reacted with a polybasic acid anhydride, ( An interlayer electrical insulating material for a multilayer printed wiring board, which comprises B) a diluent, (C) a photopolymerization initiator, and (D) a thermosetting component as essential components. 2. A rubber-modified bisphenol A type epoxy vinyl ester resin is a bisphenol A type epoxy resin, which is a linear copolymer of a conjugated diene vinyl monomer and acrylonitrile and has carboxyl groups at both ends of the molecule. The electrical insulating material for a multilayer printed wiring board according to claim 1, which has a structure in which a polymer is reacted with an ethylenically unsaturated monobasic acid. 3. An acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin (A) is a linear copolymer of a conjugated diene vinyl monomer and acrylonitrile and has a carboxyl group at both ends of the molecule. The interlayer electrical insulation for a multilayer printed wiring board according to claim 1 or 2, wherein a rubber-like polymer ester structure site with the polymer is contained in the epoxy vinyl ester resin (A) in a proportion of 3 to 60% by weight. material. 4. An acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin (A) is 30 to 14
A polymer having an acid value of 0 mgKOH / g.
2. The interlayer electric insulating material for a multilayer printed wiring board according to 2 or 3. 5. A rubber-modified bisphenol A type epoxy vinyl ester resin is a linear copolymer of a conjugated diene vinyl monomer and acrylonitrile per one equivalent of epoxy group of the bisphenol A type epoxy resin, and has both molecular terminals. 5. The reaction according to claim 4, wherein the total amount of the carboxyl group present in the polymer having a carboxyl group and the carboxyl group of the ethylenically unsaturated monobasic acid is 0.8 to 1.1 equivalents. Interlayer electrical insulation material for multilayer printed wiring boards. 6. The acid pendant type rubber-modified bisphenol A type epoxy vinyl ester resin (A) has 0 hydroxyl group in the polybasic acid anhydride per 1 mole of the hydroxyl group of the rubber modified bisphenol A type epoxy vinyl ester resin. .3
The interlayer electrical insulating material for a multilayer printed wiring board according to claim 5, which has a structure that is reacted at a ratio of about 1.0 mol.