JPH08325339A - Interlaminar insulating material for multi-layer printed circuit board - Google Patents

Abstract

PURPOSE: To obtain an interlaminar insulating coating film having excellent adhesivity to a circuit-constituting copper plating and exhibiting excellent flame- retarding effect in a multi-layer printed circuit board manufactured by build-up method. CONSTITUTION: This electrically insulating material contains (A) an acid-pendant rubber-modified brominated epoxyvinyl ester resin having a structure obtained by reacting tetrahydromaleic anhydride with the hydroxyl group of a rubber- modified brominated epoxyvinyl ester resin produced by reacting acrylic acid with a brominated bisphenol A epoxy resin and a polymer having carboxyl groups at both molecular terminals and consisting of a straight-chain copolymer of a conjugated diene vinyl monomer and acrylonitrile, (B) a diluent, (C) a photopolymerization initiator and (D) a cresol novolak epoxy resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interlayer electrical insulating material for a multilayer printed wiring board having self-flame retardancy. More specifically, an acid pendant type rubber-modified halogenated epoxy vinyl ester resin having a specific structure, a diluent, a photopolymerization initiator, and a thermosetting component are essential components, and they have excellent adhesion to copper plating and Good balance of various characteristics such as flexibility, solder heat resistance, solvent resistance, electrical characteristics, flame retardancy, etc.
The present invention relates to a self-flame retardant 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.

[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 yet have sufficient adhesion strength between the interlayer electric insulation layer and the copper plating, so that a practical multilayer printed wiring board laminate is obtained. Not obtained,
Further, when flame retardancy is required, there is a problem that an additive flame retardant must be used.

The problem to be solved by the present invention is that it has a self-flame-retardant property and is excellent in the adhesiveness of copper plating for forming a circuit, and is suitable for the production of multilayer printed wiring boards. An object is to provide an interlayer electrical insulating material for a 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 an acid pendant type rubber-modified halogenated epoxy vinyl ester resin, a diluent, Multi-layer printing that uses a photopolymerization initiator and a thermosetting component as essential components, 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. It was found that an interlayer electrical insulating material for a multilayer printed wiring board, which can be developed with a dilute alkaline solution and is suitable for manufacturing a wiring board, can be obtained, and the present invention has been completed.

That is, the present invention provides (A) an acid pendant type rubber-modified halogenated epoxy vinyl ester resin having a structure in which a hydroxyl group of the rubber-modified halogenated epoxy vinyl ester resin is reacted with a polybasic acid anhydride, (B). 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.

The acid-pendant rubber-modified halogenated epoxy vinyl ester resin (A) used in the present invention has a structure in which a polybasic acid anhydride is reacted with the hydroxyl group of the rubber-modified halogenated epoxy vinyl ester resin, Those having an acid value in the range of 30 to 140 mgKOH / g are preferable. Among them, those having an acid value in the range of 40 to 120 mgKOH / g are particularly preferable in terms of good solubility in an alkaline aqueous solution, excellent developability, and excellent properties of an interlayer electrically insulating coating film.

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

Among them, the acid value is 40 to 120 mg KOH
When adjusted to the range of / g, the solubility in an alkaline aqueous solution is good, the developability is excellent, and the characteristics of the interlayer electric insulating coating film are also excellent, with respect to 1 mol of the hydroxyl group in the rubber-modified halogenated epoxy vinyl ester resin, It is preferable to react both of them in a ratio such that the number of acid anhydride groups in the polybasic acid anhydride is 0.4 to 0.9 mol.

Here, the rubber-modified halogenated epoxy vinyl ester resin is not particularly specified in its structure, but a halogenated epoxy resin, a carboxyl group-containing rubber polymer, and an ethylenically unsaturated monobasic acid are used. It has a reacted structure, and in this structure there is an ester bond formed by the reaction of the epoxy resin, the carboxyl group-containing rubbery polymer and the ethylenically unsaturated monobasic acid. In the present invention, among these ester bonds, the content of the ester structure portion (including the rubber-like polymer portion) based on the carboxyl group-containing rubber-like polymer is the acid pendant type rubber-modified halogenated epoxy vinyl ester resin ( In A), the content of 3 to 60% by weight is preferable from the viewpoint that a resin excellent in flexibility, adhesion, heat resistance, electric characteristics and the like can be obtained.

In producing the rubber-modified halogenated epoxy vinyl ester, the halogenated epoxy resin, the carboxyl group-containing rubber-like polymer and the ethylenically unsaturated monobasic acid may be reacted simultaneously. Alternatively, the halogenated epoxy resin may be reacted with the carboxyl group-containing rubbery polymer, and then the ethylenically unsaturated monobasic acid may be reacted.

At this time, the reaction ratio of the halogenated epoxy resin, the carboxyl group-containing rubbery polymer and the ethylenically unsaturated monobasic acid is not particularly limited, but the epoxy group 1 of the halogenated epoxy resin is not limited. The content ratio of the rubbery polymer ester structure moiety is that the total carboxyl groups of the carboxyl group-containing rubbery polymer and the ethylenically unsaturated monobasic acid are in the range of 0.8 to 1.1 equivalents per equivalent. The acid pendant type epoxy vinyl ester resin (A) is preferably 3 to 60% by weight in terms of easy preparation,
Among them, the range of 0.9 to 1.0 mol is preferable from the viewpoint of obtaining a resin having excellent photocurability and storage stability.

Although the structure of the halogenated epoxy resin used in the present invention is not particularly limited, for example, tetrabromobisphenol A type epoxy resin, tetrachlorobisphenol A type epoxy resin, tetrabromobisphenol F type epoxy resin. Halogenated bisphenol type epoxy resins such as tetrachlorobisphenol F type epoxy resins; halogenated novolac type epoxy resins such as brominated cresol novolac type epoxy resins and brominated phenol novolac type epoxy resins. The halogen content of these halogenated epoxy resins is not particularly limited, but usually 15 to 6
It is preferably 0% by weight. Of these, an epoxy resin having a melting point of 50 ° C. or higher is preferable because it can form a tack-free photopolymerizable film after drying.

The structure of the carboxyl group-containing rubbery polymer is not particularly limited, but for example, an ethylenically unsaturated monobasic acid such as a polybutadiene-acrylic acid copolymer and a conjugated diene vinyl are used. Copolymer with monomer; Copolymer of ethylenically unsaturated monobasic acid such as polybutadiene-acrylonitrile-acrylic acid copolymer, conjugated diene vinyl monomer and other vinyl monomer; structural formula 1 or structural formula 2 below. Carboxylic acid-suspended conjugated diene-based vinyl polymers such as maleated polybutadiene represented by ## STR3 ##; rubber-like polymers in which carboxyl groups are suspended on the above-mentioned molecular side chains, or carboxyl groups at both molecular ends of linear polymers A rubbery polymer having

Structural formula 1

[0020]

Embedded image (Where n and m represent the average number of repeating units,
Each is an integer of 1 or more. )

Structural formula 2 (where n, m and l represent the average number of repeating units, each being an integer of 1 or more.)

[0022]

Embedded image Examples of the latter rubber-like polymer having a carboxyl group at both terminals of the linear polymer include, for example, a diene having a carboxyl group at both terminals of a molecule such as polybutadiene dicarboxylic acid represented by the following structural formula 3. -Based vinyl polymer; a copolymer of a conjugated diene-based vinyl monomer such as a polymer having a carboxyl group at both ends of the molecule of a butadiene-acrylonitrile copolymer represented by the following structural formula 4 and acrylonitrile and both ends of the molecule A polymer having a carboxyl group in the following; a half ester of a conjugated diene vinyl monomer such as a copolymer of polybutadiene glycol represented by the following structural formula 5 with maleic anhydride and an acid anhydride; represented by the following structural formula 6 Of butadiene-acrylonitrile copolymer with a hydroxyl group-terminated polymer and maleic anhydride Half esters and the like of the polymer and a polybasic acid anhydride with a hydroxyl group at the molecular terminal of the copolymer of a conjugated diene-based vinyl monomer and acrylonitrile such as esters.

Structural formula 3

[0024]

Embedded image (Here, n represents the average number of repeating units and is an integer of 1 or more.)

Structural formula 4

[0026]

[Chemical 4] (Where n and m represent the average number of repeating units,
Each is an integer of 1 or more. )

Structural formula 5

[0028]

Embedded image (Here, n represents the average number of repeating units and is an integer of 1 or more.)

Structural formula 6

[0030]

[Chemical 6] (Where n and m represent the average number of repeating units,
n is an integer of 5 to 50 and m is an integer of 25 to 90. )

The conjugated diene vinyl monomer used in the carboxyl group-containing rubbery polymer may be butadiene, isoprene, chloroprene or the like, in addition to butadiene used in the above-mentioned exemplified polymers. Further, the ethylenically unsaturated monobasic acid that can be copolymerized with the conjugated diene-based vinyl monomer is not limited to those listed as the above exemplified polymers, and examples thereof include (meth) acrylic acid, crotonic acid, and cinnamic acid. , Acrylic acid dimer, monomethylmalate, monopropylmalate, monobutylmalate, mono (2-ethylhexyl) malate, sorbic acid, etc., among which (meth) acrylic acid is preferred. Further, other vinyl monomers are not limited to the above exemplified compounds, and acrylic acid, methacrylic acid, acrylonitrile, styrene, vinyltoluene and the like can be used.

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 5 per molecule, more preferably 1.5 to 3 per molecule. It is desirable to be within the range.

Among these, especially, a polymer having a carboxyl group at the molecular end of a copolymer of a conjugated diene vinyl monomer and acrylonitrile, and a hydroxyl group at a molecular end of a copolymer of a conjugated diene vinyl monomer and acrylonitrile. Half-esters of the polymers and polybasic acid anhydrides are preferable because the effects of the present invention are remarkable.

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 5 per molecule, more preferably 1.5 to 3. It is desirable to be within the range.

The ethylenically unsaturated monobasic acid used in the reaction with the halogenated epoxy resin in the production of the rubber-modified halogenated epoxy vinyl ester resin is, for example, (meth) acrylic acid, crotonic acid, cinnamic acid. ,
Acrylic acid dimers, monomethylmalate, monopropylmalate, monobutylmalate, mono (2-ethylhexyl) malate, sorbic acid and the like can be mentioned, with preference given to (meth) acrylic acid.

The rubber-modified halogenated epoxy vinyl ester resin obtained by reacting each of the components described in detail above is not particularly specified in its structure, but can be used in a mixed state of various structures. But, for example,
A rubbery polymer having multiple carboxyl groups in its molecular chain is reacted with an epoxy resin having multiple epoxy groups on the carboxyl groups to form a rubbery polymer ester of the epoxy resin, and the residual epoxy group in this compound is formed. The thing of the structure which ethylenically unsaturated monobasic acid reacted was mentioned.

More specifically, for example, a halogenated epoxy resin reacts with a rubber-like polymer having a plurality of carboxyl groups in its molecular chain and a carboxyl group present at the terminal of the molecule of the rubber polymer, respectively. Examples thereof include those having an ester structure and having (meth) acrylic acid reacted with the unreacted epoxy groups in each halogenated epoxy resin portion.

The polybasic acid anhydride used in the present invention is a copolymer of the conjugated diene vinyl monomer and acrylonitrile, which is a polymer having a hydroxyl group at the molecular end and a polybasic acid anhydride. The polybasic acid anhydride used for the half ester may be mentioned. 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- Endomethylene tetrahydrophthalic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride,
Examples thereof include benzophenone tetracarboxylic acid anhydride and methylcyclohexene dicarboxylic acid anhydride. Among them, tetrahydrophthalic anhydride and hexahydrophthalic anhydride are preferable from the viewpoint of excellent electrolytic corrosion property.

The halogen content of the acid pendant type rubber-modified halogenated epoxy vinyl ester resin (A) is preferably 10 to 40% by weight.

These acid pendant type rubber-modified halogenated epoxy vinyl ester resins (A) are acid pendant type epoxy vinyl ester resins conventionally used in alkali developing type solder resist inks, for example, acid pendant type novolaks. Epoxy vinyl ester resin, acid pendant bisphenol A epoxy vinyl ester resin, acid pendant bisphenol F epoxy vinyl ester resin, acid pendant bisphenol S epoxy vinyl ester resin, acid pendant bixinol epoxy vinyl ester resin, etc. It is preferable to do.

As the diluent (B) used in the present invention, a viscosity suitable for various coating methods such as screen printing and roll coater method is dissolved in the acid pendant type rubber-modified halogenated epoxy vinyl ester resin (A). It is an essential constitutional condition for forming a photopolymerizable film by coating so as to be followed by drying, usually, an organic solvent and a photopolymerizable vinyl monomer, and in the use thereof,
Each may be used alone, 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.

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 20 to 300 parts by weight, preferably 30 to 250 parts by weight, based on 100 parts by weight of the acid pendant type rubber-modified halogenated epoxy vinyl ester resin (A). Is appropriate.

The photopolymerizable vinyl monomer also promotes photopolymerizability, and the water-soluble photopolymerizable vinyl monomer also plays a role of assisting solubility in an alkaline aqueous solution. It is possible to form a photopolymerizable film without tack after drying, it is possible to adhere the photopolymerizable film and the pattern film, it is possible to improve the resolution of the photovia hole pattern, further chemical resistance and In order to improve electric characteristics and the like, the amount of use is preferably 50 parts by weight or less, and more preferably 2 to 20 parts by weight, relative to 100 parts by weight of the acid pendant type rubber-modified halogenated epoxy vinyl ester resin (A). .

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 acids 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.

According to the present invention, a thermosetting component (D) is further used as a curing component for each of the above-mentioned components to provide an interlayer electrical insulating material for a multilayer printed wiring board having excellent solder heat resistance and electrical characteristics. You can

As the thermosetting component (D) used in the present invention, an acid pendant type rubber modified halogenated epoxy vinyl ester resin (A) and an epoxy resin having a thermosetting functional group in the molecule, a melamine compound, a urea compound, Examples thereof include oxazoline compounds and phenol compounds. Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated epoxy resin, biquinenol type epoxy resin, and biphenol type epoxy resin. Glycidyl ethers; 3,4-epoxy-6
-Methylcyclohexylmethyl-3,4-epoxy-6
-Methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,
Alicyclic epoxy resins such as 4-epoxycyclohexane; glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; tetraglycidyl diaminodiphenylmethane, triglycidyl P-aminophenol, N, N -Glycidyl amines such as diglycidyl aniline; and heterocyclic epoxy resins such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate. Above all,
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.

Examples of the oxazoline compound include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 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, chylenol, catechol, resorcin, hydroquinone, pyrogallol and resole.

The preferred range of the amount of the thermosetting component (D) used is usually 1 carboxyl group in the acid pendant type rubber-modified halogenated epoxy vinyl ester resin (A).
The functional group group of the thermosetting component (D) is 0.2 to
The ratio is 3.0 equivalents. Above all, it is 1.0 because it has excellent solder heat resistance and electrical characteristics when used as a printed wiring board.
A ratio of up to 1.5 equivalents is preferable.

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

Further, in the present invention, the above acid pendant type rubber modified halogenated epoxy vinyl ester resin (A), diluent (B), photopolymerization initiator (C), and
In addition to the thermosetting component (D), if necessary, various additives such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay, and other fillers;
Thixotropic agents such as Aerosil; colorants such as phthalocyanine blue, phthalocyanine green and titanium oxide; silicone, fluorine-based leveling agents and defoamers; polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether; It can be added for the purpose of enhancing the performance.

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

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

Example 1 Tetrabromobisphenol A having an epoxy equivalent of 400
Type epoxy resin "Epiclon 153" [Dainippon Ink and Chemicals, Inc., bromine content 48% by weight] 400 parts,
HYCAR CTBN 1300X13 [B.C.] having a carboxyl group at both ends of a copolymer of butadiene and acrylonitrile having a molecular weight of 3500, 27% by weight of bound acrylonitrile, and 1.9 carboxyl groups / molecule.
F. Made by Goodrich Chemical Company] 1
645 parts of a rubber-modified brominated epoxy vinyl ester resin obtained by reacting 80 parts and 65 parts of acrylic acid (the number of epoxy groups: the number of total carboxyl groups = 1: 1), and 153 parts of tetrahydrophthalic anhydride (Number of hydroxyl groups: number of acid anhydride groups = 1: 0.9) is reacted in 342 parts of butyl carbitol acetate to give a bromine content of 24% by weight,
A resin solution (A-1) containing 70% of a resin component having an acid value of 71 mgKOH / g was obtained.

A photopolymerization initiator, an organic solvent and a filler were blended together with the 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 ────────────── ─────────────────── Total base agent 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 to the entire surface of the 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 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.

Next, the printed wiring board having the photo via holes formed therein is treated with an alkaline potassium permanganate solution to 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 was sequentially subjected to conditioner treatment, micro etching, pickling, catalysis and accelerator treatment, and electroless copper plating was performed to obtain a thickness of 0. A thin copper plating with a thickness of 3 μm was applied on the surface-roughened interlayer electrical insulation coating.

Next, the electroless copper-plated printed wiring board was 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 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 in conformity 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 following evaluation test method,
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 2 800 parts of a brominated bisphenol A type epoxy resin having an epoxy equivalent of 800 obtained by reacting 711 parts of "Epiclone 153" having an epoxy equivalent of 400 with 89 parts of bisphenol A and HYCAR CTBN 1300X1
Rubber-modified brominated epoxy 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: 1.0) in 514 parts of butyl carbitol acetate. 958 parts of vinyl ester resin,
Tetrahydrophthalic anhydride was reacted with 242 parts (the number of hydroxyl groups: the number of acid anhydride groups = 1: 0.8) to give 70 parts of a resin component having a bromine content of 29% by weight and an acid value of 37 mgKOH / g.
% To obtain a resin solution (A-2).

Then, the composition of the present invention was prepared in the same manner as in Example 1 except that the components were mixed as described below, and then the sample (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 ─────────────── ─────────────────── Total base agent 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

Then, in the same manner as in Example 1, the results measured according to the following evaluation test methods are shown in Table 1.

Example 3 280 parts of brominated phenol novolac type epoxy resin "Epiclon N-135" (manufactured by Dainippon Ink and Chemicals, Inc., bromine content 35% by weight) having an epoxy equivalent of 280 and HYCAR CTBN 1300X13 90 copies,
68 parts of acrylic acid (number of epoxy groups: total number of carboxyl groups = 1: 1) and butyl carbitol acetate 2
Rubber-modified brominated phenol novolac epoxy vinyl ester resin 438 parts obtained by reacting in 20 parts,
By reacting with 76 parts of tetrahydrophthalic anhydride (the number of hydroxyl groups: the number of acid anhydride groups = 1.0: 0.5), a resin component having a bromine content of 19% by weight and an acid value of 55 mgKOH / g is obtained. A resin solution (A-3) containing 70% 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 mixed, and then the test pieces (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 ─────── ────────────────────────── Total 100 parts of active ingredient

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 measured according to the following evaluation test methods are shown in Table 1.

Comparative Example 1 21 of "Epiclone N-680" having an epoxy equivalent of 215
287 parts of cresol novolac epoxy vinyl ester resin obtained by reacting 5 parts with 72 parts of acrylic acid (the number of epoxy groups: the number of carboxyl groups = 1.0: 1.0) in 162 parts of butyl carbitol acetate And tetrahydrophthalic anhydride 91 parts (number of hydroxyl groups: number of acid anhydride groups = 1.0: 0.6) are reacted to give an acid value of 89.
Resin solution containing 70% resin content in mgKOH / g (B-
1) 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 (1'-a, 1'-) were prepared in the same manner as in Example 1. b,
1'-c) was obtained.

(Blending) Main agent Resin solution (B-1) 50 parts 2,2-dimethoxy-2-phenylacetophenone 5 parts Solvesso 150 15 parts Barium sulfate 30 parts ─────────────── ─────────────────── Total base agent 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 measured according to the following evaluation test methods are shown in Table 1.

Comparative Example 2 Brominated epoxy vinyl ester resin 47 obtained by reacting 400 parts of "Epiclone 153" with 72 parts of acrylic acid (the number of epoxy groups: the number of carboxyl groups = 1: 1)
2 parts and 153 parts of tetrahydrophthalic anhydride (the number of hydroxyl groups: the number of acid anhydride groups = 1.0: 0.9) are reacted in 268 parts of butyl carbitol acetate to give a bromine content of 31% by weight. %, And a resin solution (B-2) containing 70% of a resin component having an acid value of 81 mgKOH / g 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 (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 ─────────────── ─────────────────── Total base agent 100 parts

Hardener "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 measured according to the following evaluation test methods are shown in Table 1. The flame retardancy was measured according to UL standards.

[Evaluation test method] Peeling strength: Using a test piece having one surface plated with copper, the tip of the peeled copper foil was gripped with a gripper according to JIS C 6481, and the pulling direction was copper foil. Peel in the direction perpendicular to the surface, and the minimum value at this time is the peel strength of the copper foil.

Solder heat resistance: A printed wiring board plated with electrolytic copper is used, and the copper foil is floated down so that the entire surface is immersed in the 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: In accordance with JIS K 5400, an Erichsen tester was used to extrude a steel ball from the back surface of the test piece, and when the test piece was deformed, cracking and peeling of the coating film occurred. The extrusion distance was measured.

[0092]

[Table 1]

[0093]

The problem to be solved by the present invention is that it has a self-flame retardant property and is excellent in the adhesiveness of copper plating for forming a circuit, and can be developed with a dilute alkaline solution suitable for the production of multilayer printed wiring boards. An interlayer electrical insulation material for a multilayer printed wiring board can be provided.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C09D 163/10 C09D 163/10

Claims (7)

[Claims] 1. An acid pendant type rubber modified halogenated epoxy vinyl ester resin having a structure in which a hydroxyl group of the rubber modified halogenated epoxy vinyl ester resin is reacted with a polybasic acid anhydride, (B) a diluent, An interlayer electrical insulating material for a multilayer printed wiring board, which comprises C) a photopolymerization initiator and (D) a thermosetting component as essential components. 2. The rubber-modified halogenated epoxy vinyl ester resin has a structure in which a halogenated epoxy resin is reacted with a carboxyl group-containing rubber-like polymer and an ethylenically unsaturated monobasic acid. Inter-layer electrical insulation material for multilayer printed wiring boards. 3. The multi-layer according to claim 2, wherein the carboxyl group-containing rubbery polymer is a linear copolymer of a conjugated diene vinyl monomer and acrylonitrile and has carboxyl groups at both ends of the molecule. Interlayer electrical insulation material for printed wiring boards. 4. The acid pendant type rubber-modified halogenated epoxy vinyl ester resin (A) has a rubber-like polymer ester structure site based on a carboxyl-group-containing rubber-like polymer, in the epoxy vinyl ester resin (A). ~ 60
The interlayer electrical insulating material for a multilayer printed wiring board according to claim 2, 3 or 4, which is contained in a weight percentage. 5. The rubber-modified halogenated epoxy vinyl ester resin comprises a carboxyl group present in a carboxyl group-containing rubber-like polymer and a carboxyl group of an ethylenically unsaturated monobasic acid per equivalent of epoxy group of the halogenated epoxy resin. And a total of 0.8 to 1.1 equivalents are reacted, the interlayer electrical insulating material for a multilayer printed wiring board according to claim 4. 6. An acid pendant type rubber-modified halogenated epoxy vinyl ester resin (A) is used, relative to 1 mol of a hydroxyl group of the rubber-modified halogenated epoxy vinyl ester resin.
6. The multilayer printed wiring board according to claim 1, wherein the polybasic acid anhydride has a structure in which it is reacted with a non-hydroxyl group in a proportion of 0.3 to 1.0 mol. Interlayer electrical insulation material. 7. An acid pendant type rubber-modified halogenated epoxy vinyl ester resin (A) is 30 to 140 mgK.
The interlayer electrical insulating material for a multilayer printed wiring board according to claim 6, which has an acid value of OH / g.