JPH07142830A - Printed wiring board laminate material - Google Patents

Abstract

PURPOSE:To improve the adhesion to a metal layer and a delamination without deteriorating the heat-resistance and a mechanical strength by a method wherein glass cloth surface-treated with coupling agent is laminated with printed wiring board forming material composed of styrene resin having polar groups. CONSTITUTION:1-95wt.% of glass cloth surface-treated with coupling agent is laminated with 99-5wt.% of printed wiring board forming material composed of styrene polymer having polar groups and having high grade syndiotactic structures. The styrene resin (SPS) having polar groups is obtained by denaturing SPS. For instance, polar groups are introduced by a copolymerizing reaction at the time of polymerization, polar groups are introduced when a polymerizing reaction is stopped and graft copolymerization is proceeded by using the polar groups. With this constitution, the adhesion to a metal layer can be improved without deteriorating excellent heat-resistance properties and a high mechanical strength which SPS essentially has.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate for a printed wiring board, and more specifically, it has good releasability in a high temperature mold and has a high syndiotactic structure. (It may be abbreviated as SPS.) The printed wiring board laminate excellent in adhesiveness to a metal layer and peel strength without deteriorating the excellent heat resistance and high mechanical strength inherently possessed by SPS.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Styrene-based resins are widely used in various fields as general-purpose resins, but the styrene-based resins generally have a major drawback of poor impact resistance. Therefore, for the purpose of improving the impact resistance of the styrene resin, by blending polystyrene with a rubber-like polymer, or by polymerizing styrene in the presence of the rubber-like polymer, styrene is added to the rubber-like polymer. Partially graft-polymerized, and the balance of styrene becomes polystyrene so that a substantially rubber-like polymer / styrene graft copolymer and polystyrene are mixed to obtain a so-called rubber-like modified polystyrene resin composition. Is done industrially. In particular, it is known that impact strength is improved by using a complete block type styrene-butadiene type copolymer or a taper block type styrene-butadiene type copolymer as the rubber polymer. Impact-resistant polystyrene using a complete block type styrene-butadiene copolymer as a polymer (Japanese Patent Laid-Open No. 63-16541).
3), impact-resistant polystyrene using a taper block type styrene-butadiene copolymer (JP-A-52-
No. 71549, Japanese Patent Laid-Open No. 63-48317) and the like are disclosed.

However, these impact-resistant styrenic resins are not always sufficient in terms of balance of impact resistance, heat resistance, mechanical strength, etc., and these properties are highly balanced depending on the application. Styrenic resins are desired. By the way, the styrene resin generally used is obtained by radical polymerization, and its stereoregularity has an atactic structure and is amorphous. Therefore, it cannot be said that impact resistance and mechanical strength are sufficiently high, and there is a limit to improvement of these physical properties.

Under these circumstances, in order to develop a styrene-based resin composition having more excellent physical properties, overcoming the limit point of the improvement of physical properties inherent in conventional styrene-based resins,
The group of the present inventors has previously developed a high-impact styrene-based polymer obtained by blending a styrene-based polymer having a highly syndiotactic structure with a rubber-like polymer containing a styrene-based monomer unit as one component. A resin composition has been proposed (JP-A-1-146944). The composition of JP-A-1-146944 uses a rubber-like polymer having a low product of the weight average molecular weight and the content of the styrene-based monomer unit of less than 30000, so that the rubber dispersion The rigidity at the time of molding, which is considered to be caused by defects, is lowered, and the releasability is insufficient. Further, the obtained molded products have drawbacks such as insufficient improvement in Izod impact strength and low heat resistance (Vicat softening point).

Therefore, the researchers of the present invention have proposed a composition containing SPS and a specific rubber-like polymer in a predetermined ratio, and a surface treatment of this composition with a polyphenylene ether having a polar group and a coupling agent. The above problem was solved by providing a composition in which each of the above-mentioned fillers was blended in a predetermined ratio, and further, a composition in which a flame retardant and a flame retardant auxiliary were each blended in a predetermined ratio. (JP-A-5-247292). However, JP-A-5-247
When a printed circuit board is molded using the styrene resin composition of Japanese Patent No. 292, an adhesive is usually applied to the styrene resin composition and a metal layer is laminated, but the manufacturing process is complicated and the cost increases. Was invited. Also, if the step of molding the printed circuit board is simplified or the step of applying an adhesive is omitted to reduce the cost, the adhesion between the styrene resin composition and the metal layer becomes insufficient and the metal layer peels off. There was a problem that it was easy.

Therefore, the researchers of the present invention have further investigated a molding material for printed wiring, which is composed of SPS having a polar group,
SPS, specific rubbery polymer, and polyphenylene ether having polar group and / or SPS having polar group
And / or a molding material for printed wiring comprising a composition containing a rubber-like elastic material having a polar group, and a filler, a flame retardant or a flame retardant aid optionally surface-treated with a coupling agent. A molding material for printed wiring comprising the composition was proposed (Japanese Patent Application No. 5-63561). As a result, it was possible to prevent the peeling of the metal layer. However, the molding material for printed wiring of Japanese Patent Application No. 5-63561 easily causes deformation and peeling of the metal foil during the soldering resistance test, and still ensures sufficient peeling prevention of the metal layer in the solder resist process during mass production. It turns out that it has a problem that it cannot be obtained.

[0007]

Therefore, the present inventors have
As a result of earnest studies to solve the above problems, a glass cloth surface-treated with a coupling agent is laminated on a molding material for printed wiring boards, which is composed of SPS having a polar group, or is specified with SPS. Molding material for printed wiring board obtained by adding at least one of polyphenylene ether having a polar group, SPS having a polar group and rubber-like elastic body having a polar group to a composition containing a rubbery polymer in a predetermined ratio. On the other hand, it has been found that the above problems can be solved by laminating glass cloth surface-treated with a coupling agent. The present invention has been completed based on such findings.

That is, the present invention is, firstly, a molding material 99-5 for a printed wiring board comprising (A) a styrene-based polymer having a highly syndiotactic structure having a polar group.
It is intended to provide a laminate for a printed wiring board, which is obtained by laminating 1 to 95% by weight of glass cloth surface-treated with a coupling agent (B) with respect to% by weight. Further, the present invention secondly provides that (C) the styrene-based polymer having a highly syndiotactic structure of 20 to 95% by weight and (D) the product of the weight average molecular weight and the content of the styrene-based monomer unit. 30,0
100 parts by weight of a mixture consisting of 80 to 5% by weight of a rubbery polymer of 00 or more, (E) a polyphenylene ether having a polar group, (A) a styrene polymer having a highly syndiotactic structure having a polar group, and (F) 99 to 5% by weight of a molding material for a printed wiring board, which comprises 0.1 to 60 parts by weight of a resin containing at least one polar group selected from the group consisting of rubber-like elastic bodies having polar groups (B) A laminated body for a printed wiring board, which is obtained by laminating 1 to 95% by weight of glass cloth surface-treated with a coupling agent. Further, the present invention is, thirdly,
(C) 20-95% by weight of a styrene-based polymer having a high syndiotactic structure, and (D) a rubber-like polymer having a product of the weight average molecular weight and the content of the styrene-based monomer unit of 30,000 or more. Mixture 100 consisting of 80-5% by weight
Parts by weight, selected from the group consisting of (E) polar group-containing polyphenylene ether, (A) polar group-containing highly syndiotactic styrene polymer, and (F) polar group-containing rubber-like elastic material. 0.1 to 60 parts by weight of a resin containing at least one polar group, (G) flame retardant 3 to
60 parts by weight and (H) 1 to 15 parts by weight of a flame retardant aid, and 99 to 5% by weight of a molding material for a printed wiring board, (B) 1 to a glass cloth surface-treated with a coupling agent A laminated body for a printed wiring board, which is obtained by laminating 95% by weight.

First, the molding material for a printed wiring board used in the laminate for a printed wiring board of the present invention will be described. The molding material for a printed wiring board used in the first laminated body for a printed wiring board of the present invention comprises SPS having a polar group as the component (A). The SPS having a polar group is a modified SPS,
For example, (1) introduction of a polar group by a copolymerization reaction during polymerization,
(2) It can be obtained by introducing a polar group when the polymerization reaction is stopped, (3) grafting using the polar group of (1) or (2) above, but is not limited to these methods. Further, the modification rate is not particularly limited.

As an example of the above (1), styrene and p-
Examples thereof include copolymers with methylstyrene and divinylbenzene, and examples of (2) include terminal glycidyl methacrylate-modified SPS and terminal maleic anhydride-modified SPS. Examples of (3) include a copolymer of styrene and divinylbenzene grafted with glycidyl methacrylate, and a copolymer of styrene and p-methylstyrene with maleic anhydride in the presence of a radical generator. Examples include grafted products.
Examples of such polar groups include acid halides, carbonyl groups, acid anhydrides, acid amides, carboxylic acid esters, acid azides, sulfone groups, nitrile groups, cyano groups, isocyanic acid ester groups, amino groups, hydroxyl groups, imides. Groups, thiol groups, oxazoline groups, epoxy groups and the like. A particularly preferable polar group is an acid anhydride, and among them, a maleic anhydride group is preferable. The content of the polar group may be 0.01% by weight or more, preferably 0.1% by weight or more based on the SPS, and if the content is less than 0.01% by weight, it is difficult to improve the mechanical strength.

Here, SPS used for denaturation of SPS
Means that the stereochemical structure is mainly syndiotactic.
Structure, that is, for the main chain formed from carbon-carbon bonds
Side chains phenyl groups and substituted phenyl groups are alternately opposite
It has a three-dimensional structure located in the direction.
Tacticity of isotope carbon nuclear magnetic resonance method (
¹³C-NMR method).¹³For C-NMR method
The tacticity measured by
Existence ratio of constitutional units, for example, in case of two, diad,
Triad for 3 and pentad for 5.
It can be shown that
The styrene-based polymer having a tactic structure is usually
More than 85% by diad or pentad (racemic
35% or more, preferably 50% or more
Polystyrene, poly (acetic acid) with geotacticity
Rutile styrene), poly (halogenated styrene), poly
(Alkoxystyrene), poly (benzoic acid ester styrene)
Len) and their mixtures, or with these as the main components
Is a copolymer. Note that here, poly (alkyl)
As styrene, poly (methylstyrene), poly
(Ethyl styrene), poly (isopropyl styrene),
Poly (tertiary butyl styrene) etc.
As (halogenated styrene), poly (chlorostyrene)
), Poly (bromostyrene), etc. Also poly
As (alkoxystyrene), poly (methoxystyrene)
Len) and poly (ethoxystyrene).

Further, the molecular weight and the molecular weight distribution of the styrene polymer having a high syndiotactic structure are not particularly limited and may be appropriately determined depending on the use of the composition to be produced. This SPS has a melting point of 260-27.
The temperature is 0 ° C, and the heat resistance is remarkably superior to that of the conventional styrene polymer having an atactic structure. The SPS used for the above modification is also used as it is as a component (C) described later.

The printed wiring board molding material used in the second laminate for printed wiring boards of the present invention is (C) a styrene-based polymer 20 having a highly syndiotactic structure.
To 95% by weight and (D) 100 parts by weight of a mixture consisting of 80 to 5% by weight of a rubber-like polymer having a product of the weight average molecular weight and the content of styrenic monomer units of 30,000 or more, and (E) Polyphenylene ether having a polar group,
At least one polar group-containing resin 0.1 to 60 selected from the group consisting of (A) a styrene polymer having a highly syndiotactic structure having a polar group and (F) a rubber-like elastic body having a polar group It is made by blending parts by weight. The SPS of the component (C) is an SPS that does not have a polar group, and is the SPS before modification, which is a raw material for manufacturing the component (A).
It is the same as PS.

The rubber-like polymer used as the component (D) contains a styrene-based monomer unit, and examples thereof include styrene-butadiene block copolymer rubber and styrene-butadiene. Rubber in which the butadiene portion of the block copolymer is partially or completely hydrogenated, styrene-butadiene copolymer rubber, methyl acrylate-butadiene-styrene copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber, acrylic acid Methyl-acrylic acid-2-ethylhexyl-styrene copolymer rubber and the like can be mentioned. Since all of them have a styrene unit, the dispersibility in SPS which is the component (C) is good, and as a result, the physical properties are improved. The effect is remarkable. Of these, a rubber-like polymer obtained by hydrogenating 95% or more of the butadiene portion of the styrene-butadiene block copolymer is particularly preferable. If the hydrogenation is less than 95%, the resulting composition has insufficient long-term heat resistance, and if it is subjected to heat for a long time, coloring and physical properties may deteriorate.

In the present invention, the rubber-like polymer as the component (D) has a product of the weight average molecular weight (Mw) and the content of the styrenic monomer unit of 30,000 or more, preferably 4 or more.
It is necessary to be at least 0000. This value is 30,0
When it is less than 00, the composition obtained has insufficient releasability and rigidity, and also has poor heat resistance. The upper limit of the above product is preferably less than 200,000, more preferably less than 150,000. If this value is more than 200,000, it may not work effectively as a rubbery polymer.

With respect to the mixing ratio of the mixture of the above-mentioned component (C) and component (D), both components are mixed so that the component (C) is 20 to 95% by weight and the component (D) is 80 to 5% by weight. It is necessary to blend. When the amount of the component (C) is less than 20% by weight (the amount of the component (D) exceeds 80% by weight), the deformation during the solder heat resistance test is remarkable, while
When the amount of the component (C) exceeds 95% by weight (the amount of the component (D) is less than 5% by weight), the plating coating after the through hole becomes insufficient.

The molding material for a printed wiring board used in the second laminated body for a printed wiring board of the present invention is (E) a polyphenylene ether having a polar group, in addition to the components (C) and (D). At least one of the rubber-like elastic body having the component (A) and the polar group (F) is blended.
The polar group in the polyphenylene ether having a polar group which is the component (E) is an acid halide, carbonyl group, acid anhydride, acid amide, carboxylic acid ester, acid azide, sulfone group, nitrile group, cyano group, isocyanic acid ester. Group, amino group, hydroxyl group, imide group, thiol group, oxazoline group, epoxy group and the like. A particularly preferable polar group is an acid anhydride, and among them, a maleic anhydride group is preferable. The content of this polar group may be 0.01% by weight or more with respect to the polyphenylene ether,
If it is less than 01% by weight, improvement in mechanical strength cannot be expected. The polyphenylene ether having the polar group is, for example, (1) a method of reacting a polyphenylene ether with a compound having both the polar group and an unsaturated group, (2) a phenol compound having the polar group, alone or in combination of two or more. Can be produced by, for example, (3) a method of polymerizing a phenol compound having a polar group alone or two or more kinds with a phenol compound having no polar group.

The polyphenylene ether is a compound known per se (US Pat. Nos. 3,306,874 and 3,306,875).
Nos. 3,257,357 and 3,257,358), which are usually copper amine complexes, and oxidative coupling to form homopolymers or copolymers in the presence of one or more 2- or 3-substituted phenols. It is produced by the reaction. Here, the copper amine complex may be a copper amine complex derived from a primary, secondary and / or tertiary amine. Specific examples of suitable polyphenylene ethers include poly (2,3-dimethyl-6-ethylphenylene-1,4-ether), poly (2-methyl-6-chloromethyl-1,4-phenylene) ether and poly (2-methyl-6-chloromethyl-1,4-phenylene) ether. (2-Methyl-6-hydroxydiethyl-1,4-phenylene)
Ether, poly (2-methyl-6-n-butyl-1,4
-Phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-
Ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,3,6-trimethylphenylene-1,
4-ether), poly [2- (4'-methylphenyl)
Phenylene-1,4-ether], poly (2-bromo-
6-phenylphenylene-1,4-ether), poly (2-methyl-6-phenylphenylene-1,4-ether), poly (2-phenylphenylene-1,4-ether), poly (2-chlorophenylene) -1,4-ether), poly (2-methylphenylene-1,4-ether), poly (2-chloro-6-ethylphenylene-1,
4-ether), poly (2-chloro-6-bromophenylene-1,4-ether), poly (2,6-di-n-propylphenylene-1,4-ether), poly (2-methyl-6). -Isopropylphenyl-1,4-ether), poly (2-chloro-6-methylphenylene-1,
4-ether), poly (2-methyl-6-ethylphenylene-1,4-ether), poly (2,6-dibromophenylene-1,4-ether), poly (2,6-dichlorophenylene-1, 4-ether), poly (2,6-diethylphenylene-1,4-ether) and poly (2,2)
6-dimethylphenylene-1,4-ether) and the like.

Further, a copolymer derived from two or more phenol compounds used for producing the homopolymer, a graft copolymer of a vinyl aromatic compound such as styrene and the polyphenylene ether, and a block copolymer. Coalition can also be mentioned. Of these, poly (2,6-dimethylphenylene-1,4-ether) is particularly preferable. The compound having both the polar group and the unsaturated group means an unsaturated group, that is, a carbon-carbon double bond or a carbon-carbon triple bond, and a carboxylic acid group as a polar group, a group derived from a carboxylic acid, that is, Various salts or esters in which hydrogen atom or hydroxyl group of carboxyl group is substituted, acid amide, acid anhydride, imide, acid azide, acid halide or oxazoline, nitrile, epoxy group, amino group, hydroxyl group, and isocyanic acid ester group It is a compound having both of the same in the same molecule. Compounds having both an unsaturated group and a polar group include unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, unsaturated epoxy compounds,
Unsaturated alcohols, unsaturated amines and unsaturated isocyanates are mainly used. Specifically, maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, a reaction product of maleic anhydride and a diamine, for example, general formula (I) or (II)

[0020]

[Chemical 1]

(Wherein Y represents an aliphatic residue or an aromatic residue), methyl nadic acid anhydride, dichloromaleic anhydride, maleic acid amide, itaconic acid, anhydride Itaconic acid, soybean oil, tung oil, castor oil, linseed oil, hempseed oil, cottonseed oil, sesame oil, rapeseed oil,
Natural oils and fats such as peanut oil, camellia oil, olive oil, coconut oil, sardine oil, acrylic acid, butenoic acid, crotonic acid, vinylacetic acid, methacrylic acid, pentenoic acid, angelic acid, tebulinic acid, 2-pentenoic acid, 3-pentene Acid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl-2-pentenoic acid, 3
-Methyl-2-pentenoic acid, α-ethyl crotonic acid,
2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2
-Octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10
-Undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4
-Tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid,
Mayeribenic acid, 2,4-pentadienoic acid, 2,4-hexadienoic acid, diallylacetic acid, geranic acid, 2,4-
Decadienoic acid, 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12-octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, octadecatrienoic acid, eicosadienic acid, eicosatrieen Acid, eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid , Octacosenoic acid, traaconic acid, etc. or esters of these unsaturated carboxylic acids, acid amides, anhydrides or allyl alcohols; crotyl alcohol; methyl vinyl carbinol; allyl carbinol; methyl propenyl carbinol; 4 Penten-1-ol; 10-undecane-1-ol; propargyl alcohol; 1,4
-Pentadien-3-ol; 1,4-hexadiene-
3-ol; 3,5-hexadiene-2-ol; 2,
4-hexadiene-1-ol; formula _{C n H 2n-5 OH,} C n H 2n-7 OH, C n H 2n-9 OH ( where, n is a positive integer) the alcohol represented by; 3-
Butene-1,2-diol; 2,5-dimethyl-3-hexene-2,5-diol; 1,5-hexadiene-
3,4-diol; unsaturated alcohol such as 2,6-octadiene-4,5-diol or an unsaturated amine in which the OH group of such an unsaturated alcohol is replaced with an NH ₂ group, or butadiene, isoprene, etc. A low polymer (for example, one having an average molecular weight of about 500 to 10,000) or a high molecular weight substance (for example, one having an average molecular weight of 10,000 or more) to which maleic anhydride or a phenol is added, an amino group, a carboxylic acid group, a hydroxyl group, Examples thereof include those introduced with an epoxy group and the like, and allyl isocyanate.

As the vinyl compound having an epoxy group, for example, glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, glycidyl itaconate, etc. Of these, glycidyl methacrylate is particularly preferred. Examples of the method for reacting the compound having both polar group and unsaturated group with the polyphenylene ether include (1) a compound having both polar group and unsaturated group and polyphenylene ether by roll mill, Banbury mixer, extrusion. Melt kneading at a temperature of 150 ° C to 350 ° C using a machine and reacting, (2) polyphenylene ether and a compound having both a polar group and an unsaturated group in a solvent such as benzene, toluene or xylene. Examples thereof include a method of reacting by heating. Further, in order to easily proceed these reactions, the reaction system is provided with an organic peroxide such as benzoyl peroxide, di-t-butyl-peroxide, dicumyl peroxide, t-butyl peroxybenzoate or azobisisobutyroate. The presence of radical initiators represented by azo compounds such as nitrile and azobisisovaleronitrile is effective. A more effective method is a method of melt kneading in the presence of a radical initiator.

The rubber-like elastic body having a polar group, which is the component (F), is used to improve the impact resistance of the resin composition of the present invention. Various materials can be used as such a rubber-like elastic material, for example, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, epichlorohydrin rubber, chlorinated rubber, styrene-butyl acrylate rubber, ethylene-methyl methacrylate-
Ethylene-polar vinyl monomer copolymer rubber such as glycidyl methacrylate copolymer rubber, ethylene-methyl methacrylate-maleic anhydride copolymer rubber, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, silicone rubber, styrene-butadiene Block copolymer rubber (SBR), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (S
EBS), styrene-isoprene block copolymer (S
IR), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), ethylene propylene rubber (EPM), ethylene propylene diene rubber (E
Examples thereof include rubbers obtained by modifying PDM), ethylene butylene rubber (EBM) and the like with a modifier having a polar group. Among these, SEBS, SBR, SBS, SEP are preferable.
It is a rubber-like elastic body obtained by modifying S and SIS.

Here, the polar group is not particularly limited, and examples thereof include acid halides, carbonyl groups, acid anhydrides,
Acid amide, carboxylic acid ester, acid azide, sulfone group, nitrile group, cyano group, isocyanic acid ester group,
Examples thereof include an amino group, a hydroxyl group, an imide group, a thiol group, an oxazoline group and an epoxy group. Particularly preferred polar groups are acid anhydrides, and among them, maleic anhydride groups and epoxy groups are preferred. The content of the polar group is preferably 0.1% by weight or more based on the rubber-like elastic body having the polar group, and if it is less than 0.1% by weight, improvement in mechanical strength may not be expected. In the present invention, SEBS having a maleic anhydride group and an epoxy group is particularly preferably used as the rubber-like elastic body having a polar group. In addition,
The component (A) is as described above.

One or more of the components (E), (A) and (F) are added in an amount of 0.1 parts by weight per 100 parts by weight of the mixture of the components (C) and (D). 1-6
The amount is 0 parts by weight, preferably 0.1 to 10 parts by weight. If this amount is less than 0.1 part by weight, the effect of improving the mechanical strength of the obtained molding material for printed wiring board cannot be sufficiently exerted, and if it exceeds 60 parts by weight, the crystallization rate at the time of molding becomes slow and Productivity decreases due to mold defects and increased cooling time. The components (E), (A) and (F)
The combination of components is arbitrary, and for example, two or more types of component (E) may be blended.

The molding material for a printed wiring board used in the third laminated body for a printed wiring board of the present invention is the same as the molding material for a printed wiring board used in the above-mentioned second laminated body for a printed wiring board. It contains G) flame retardant and (H) flame retardant aid. It is preferable to use both the components (G) and (H) together, because the flame retardancy imparting effect cannot be sufficiently exhibited even if only one of them is used.

As the flame retardant which is the component (G), various flame retardants can be mentioned, but a halogen flame retardant and a phosphorus flame retardant are particularly preferable. Examples of halogen-based flame retardants include tetrabromobisphenol A; tetrabromophthalic anhydride; hexabromobenzene; tribromophenylallyl ether; pentabromotoluene; pentabromophenol; tribromophenyl-2,3-dibromo-propyl ether; Tris (2,3-dibromopropyl) phosphate; Tris (2-chloro-3-bromopropyl) phosphate; Octabromodiphenyl ether;
Decabromodiphenyl ether; octabromobiphenyl; pentachloropentacyclodecane; hexabromocyclododecane; hexachlorobenzene; pentachlorotoluene; hexabromobiphenyl; decabromobiphenyl; tetrabromobutane; decabromodiphenyl ether; hexabromodiphenyl ether; ethylene-bis- (Tetrabromophthalimide); tetrachlorobisphenol A; tetrabromobisphenol A; tetrachlorobisphenol A or an oligomer of tetrabromobisphenol A; halogenated polycarbonate oligomer such as brominated polycarbonate oligomer, halogenated epoxy compound, polychlorostyrene, Brominated polystyrene such as polytribromostyrene, poly (dibromophenyleneoxy) ), Bis (tri-bromophenoxy)
Examples include ethane.

Examples of the phosphorus-based flame retardant include ammonium phosphate, tricresyl phosphate, triethyl phosphate, acidic phosphoric acid ester, triphenylphosphene oxide and the like. Among these flame retardants, polytribromostyrene, poly (dibromophenylene oxide), decabromodiphenyl ether, bis (tribromophenoxy) ethane, ethylene-
Bis- (tetrabromophthalimide), tetrabromobisphenol A and brominated polycarbonate oligomer are preferred.

The flame retardant as the component (G) is preferably 3 to 60 parts by weight, particularly preferably 5 to 40 parts by weight, based on 100 parts by weight of the mixture of the components (C) and (D). It is to be blended in a ratio. If the amount is less than 3 parts by weight, the composition obtained is not sufficiently flame-retardant, and if it exceeds 60 parts by weight, the effect of improving the flame retardancy is not found in comparison with the amount, and rather the mechanical properties and The chemical resistance tends to be impaired.

On the other hand, examples of the flame retardant aid as the component (H) include antimony trioxide, antimony pentaoxide, sodium antimonate, metal antimony, antimony trichloride, antimony pentachloride, antimony trisulfide, antimony pentasulfide and the like. Antimony flame-retardant aids are available. Also,
Other than these, zinc borate, barium metaborate, zirconium oxide and the like can be mentioned, and among these, antimony trioxide is particularly preferable.

The flame retardant aid which is the component (H) is the same as described in the above (C).
1 to 100 parts by weight of the mixture of the component and the component (D)
It is necessary to blend in a proportion of -15 parts by weight, preferably 2-10 parts by weight. If this amount is less than 1 part by weight, the effect of blending the flame retardant aid will not be sufficiently exerted, and if it exceeds 15 parts by weight, the effect of blending the flame retardant aid will not be improved in proportion to that, and rather the machine Practical physical properties such as physical properties, chemical resistance, and creep properties tend to be impaired.

In addition to the above-mentioned essential components, the molding composition for printed wiring of the present invention may optionally contain (I) various additives such as stabilizers, antioxidants, and photopolymerizable components, as long as the object of the present invention is not impaired. Stabilizers, lubricants, plasticizers, antistatic agents, release agents, colorants, and other thermoplastic resins can be added. Of course, it is also possible to mix a flame retardant and / or a flame retardant aid in the printed wiring board molding material used for the first laminate for printed wiring boards. Furthermore, various different molding material sheets may be laminated during or after molding of the printed wiring board molding material.

One of such desired components is a filler surface-treated with a coupling agent. The shape of the filler is not particularly limited and may be fibrous, granular or powdery. As the fiber filler, for example,
Examples include glass fibers, carbon fibers, organic synthetic fibers, whiskers, ceramic fibers, metal fibers, and natural plant fibers. Examples of the granular or powdery filler include talc, carbon black, graphite, titanium dioxide,
Silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flakes, glass beads, etc. .
Among these various fillers, especially glass fillers such as glass powder, glass flakes, glass beads,
Glass filament, glass fiber, glass lobing, glass mat and the like are preferable.

The coupling agent used for the surface treatment of the filler is used for improving the adhesiveness between the filler and the components (E), (A) and (F),
As the so-called silane coupling agent and titanium coupling agent, conventionally known ones can be used. Specific examples of the silane coupling agent include, for example, γ-
Examples include aminopropyltriethoxysilane.
Specific examples of the titanium-based coupling agent include isopropyl tri (N-amidoethyl, aminoethyl) titanate and the like.

The surface treatment of the filler using such a coupling agent can be carried out by an ordinary method without any particular limitation. For example, it is desirable to perform sizing treatment, dry mixing, and spraying. Further, a film-forming substance for glass can be used in combination with the above coupling agent. The film-forming substance is not particularly limited, and examples thereof include polyester-based, urethane-based, epoxy-based, acrylic-based, vinyl acetate-based, and isocyanate-based polymers.

The molding material for a printed wiring board used in the laminated body for a printed wiring board of the present invention is a mixture of the above-mentioned essential components and optional components used if desired, for example, a Banbury mixer, a single screw. Depending on the extruder, twin-screw extruder, co-kneader, multi-screw extruder, etc., appropriate temperature, for example, 270-320
It can be prepared by sufficiently kneading at a temperature in the range of ° C.

The laminate for a printed wiring board of the present invention comprises (B) a glass cloth surface-treated with a coupling agent, laminated on the molding material for a printed wiring board prepared as described above. . The weaving method of the glass cloth is not particularly limited. For example, a plain weave, a twill weave, a punched plain weave, etc. can be arbitrarily selected, but a plain weave is preferred because the surface smoothness is easily obtained. The thickness of the glass cloth layer and the ratio of the thickness of the glass cloth layer to the thickness of the entire laminate are not particularly limited. The amount of glass cloth used is required to be 1% by weight or more, preferably 10% by weight or more, based on the total weight of the laminate for a printed wiring board. When the weight of the glass cloth is less than 1% by weight, the rigidity when heat is applied to the printed wiring board laminate is lowered. The amount of glass cloth used is 9 weights of the total weight of the laminate for a printed wiring board.
It is also necessary to be 5% by weight or less, preferably 80% by weight or less. When the weight of the glass cloth exceeds 95% by weight, the molding material may start to exhibit an unfavorable tendency such as becoming porous or impairing the strength.

The coupling agent used for the surface treatment of the above-mentioned glass cloth can be appropriately selected and used from those known as so-called silane coupling agents and titanium coupling agents. Specific examples of the silane coupling agent include triethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (1,1). -Epoxycyclohexyl) ethyltrimethoxysilane, N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl-tris (2-methoxy-ethoxy) silane, N-methyl-γ-aminopropyltrimethoxysilane , N-vinylbenzyl-γ-aminopropyltriethoxysilane,
Triaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3- (4,5-dihydroimidazole) propyltriethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) amide, N, N-bis (Trimethylsilyl) urea and the like can be mentioned. Of these, preferred is γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)-
Aminosilanes such as γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and epoxysilanes.

Specific examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl. Bis (ditridecylphosphite) titanate, tetra (1,1-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, Isopropyl trioctanoyl titanate,
Isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate,
Isopropyltri (N-amidoethyl, aminoethyl)
Examples thereof include titanate, dicumylphenyloxyacetate titanate, diisostearoyl ethylene titanate and the like. Preferred among these is isopropyl tri (N-amidoethyl, aminoethyl) titanate.

The surface treatment of the glass cloth using such a coupling agent can be carried out by an ordinary known method, and there is no particular limitation. For example, a method such as a sizing treatment in which an organic solvent solution or suspension of the coupling agent is applied as a so-called sizing agent can be exemplified. Further, a film-forming substance for glass can be used together with the above coupling agent. The film-forming substance is not particularly limited, and examples thereof include polyester-based, urethane-based, epoxy-based,
Examples thereof include acrylic type and vinyl acetate type polymers.

The method for laminating the glass cloth on the molding material for a printed wiring board is not particularly limited, and any conventionally known method can be arbitrarily selected. For example, dry-blending each component of the molding material for printed wiring boards, pelletizing by a usual method, and then forming a molding material sheet by extrusion molding method, and then extruding molding method or compression molding method on the obtained molding material sheet. By laminating glass cloth by the above, the laminate for a printed wiring board of the present invention can be manufactured. Here, the extrusion molding method is a method in which several layers of a molding material sheet and a glass cloth are inserted between a pair of metal belts, heated and melted, and then cooled to mold a laminate. The compression molding method is a method of molding a laminate by mounting a molding material sheet and glass cloth in a mold. Note that glass cloth pre-impregnated with a molding material such as SPS may be used.

By providing a metal layer on the laminate of the present invention, an excellent printed wiring board can be obtained. The metal layers used here include copper, aluminum, silver, gold, zinc,
Examples thereof include thin films of tin and the like, and copper and aluminum are particularly preferably used. There are various methods for producing a printed wiring board. For example, a metal layer may be laminated with or without applying an adhesive to a laminate of the present invention that has been manufactured in advance, or a metal layer may be formed simultaneously with the production of the laminate of the present invention without using an adhesive. Can be stacked.
In general, the latter is selected from the viewpoints of simplification of the manufacturing process and cost reduction.

When the molding material sheet, the glass cloth, and the metal layer are laminated simultaneously by the method of (3), the molding material sheet, the glass cloth, and the metal layer are inserted into the mold and compression molding is performed. Should be done. Also, after dry-blending each component of the molding material for printed wiring boards and pelletizing by a usual method, sheet molding for laminated compression molding is carried out by extrusion molding method, and the obtained molding material sheet and glass cloth are paired. The metal-clad laminate can be directly molded by inserting metal foils on both sides or one side while inserting several layers between the metal belts, heating and melting, and then cooling. Further, this molding method can be continuously performed while forming a sheet for laminated compression molding by an extrusion molding method.

[0044]

The present invention will be described in more detail with reference to Reference Examples, Production Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.

Reference Example 1 Copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) 17.8 was placed in a glass container having an inner volume of 500 ml replaced with argon.
g (71 mmol), 200 ml of toluene and 24 ml (250 mmol) of trimethylaluminum were added, and the mixture was reacted at 40 ° C. for 8 hours. Then, toluene was distilled off under reduced pressure at room temperature from the solution obtained by removing the solid portion to obtain 6.7 g of a contact product. The molecular weight of this product was 610 as measured by the freezing point depression method.

Production Example 1 [Production of (C) SPS] In a reaction vessel having an internal volume of 2 liters, 1 liter of purified styrene, 7.5 mmol of the contact product obtained in Reference Example 1 as an aluminum atom, triisobutylaluminum To 7.
5 mmol at 90 ° C. with 5 mmol and 0.038 mmol pentamethylcyclopentadienyl titanium trimethoxide.
The polymerization reaction was carried out for a time. After completion of the reaction, the product was decomposed with sodium hydroxide in methanol to decompose the catalyst component, repeatedly washed with methanol and dried to obtain 466 g of a polymer. When the weight average molecular weight of this polymer was measured by gel permeation chromatography at 130 ° C. using 1,2,4-trichlorobenzene as a solvent, it was 290,00.
And the weight average molecular weight / number average molecular weight is 2.72.
Met. In addition, by melting point and ¹³ C-NMR measurement, this polymer was found to have polystyrene (S
It was confirmed to be PS).

Production Example 2 [(E) Production of Polyphenylene Ether Having Polar Group] 500 g of SPS obtained in Production Example 1 and polyphenylene ether (manufactured by Mitsubishi Gas Chemical Co., Ltd .; YPX-100L) 500
g, maleic anhydride (Wako Pure Chemical Industries, Ltd., S grade)
33 g and 2,3-dimethyl-as a radical initiator
2,3-Diphenylbutane (NOFMER B, manufactured by NOF CORPORATION)
C) After mixing 20 g with a Henschel mixer, 300-
The mixture was kneaded under heating and melting by a twin-screw extruder at a temperature of 320 ° C. to obtain maleic anhydride-modified PPE (polyphenylene ether having a polar group). The modified PPE thus obtained was dissolved in toluene and then added dropwise to methanol for reprecipitation for purification. After press-molding the purified modified PPE, infrared rays (I
R) A peak based on a carbonyl group was observed by measurement, and it was confirmed that the derivative was modified with maleic anhydride.

Production Example 3 [(A) Production of SPS having polar group] Production of SPS 1.0 liter of purified styrene was added to a 2 liter reaction vessel.
0.1 liter of p-methylstyrene, 5 mmol of methylaluminoxane as an aluminum atom, 5 mmol of triisobutylaluminum, 0.025 mmol of pentamethylcyclopentadienyl titanium trimethoxide were added, and a polymerization reaction was carried out at 90 ° C. for 5 hours. It was After completion of the reaction, the product was decomposed with sodium hydroxide in methanol to decompose the catalyst component, washed repeatedly with methanol, and dried to obtain polymer 3
20 g was obtained. The weight average molecular weight of this polymer is 1,
When measured by gel permeation chromatography at 130 ° C. using 2,4-trichlorobenzene as a solvent, it was 39,000. The weight average molecular weight / number average molecular weight was 2.60. In addition, melting point and ¹³ C-
By NMR measurement, it was confirmed that this polymer was SPS and contained 12 mol% of p-methylstyrene unit. Production of SPS having polar group 100 parts by weight of SPS obtained as described above, 3 parts by weight of maleic anhydride, 2,3-dimethyl-2,3-diphenylbutane (NOFMER BC, manufactured by NOF CORPORATION) 1 Parts by weight were dry blended, and melt kneading was carried out using a 30 mm twin screw extruder at a screw rotation speed of 200 rpm and a set temperature of 300 ° C. At this time, the resin temperature was about 330 ° C.
The strand is cooled and then pelletized into maleic anhydride-modified S
PS (SPS with polar groups) was obtained. To measure the denaturation rate, 1 g of the obtained modified SPS was dissolved in chloroform and then reprecipitated in methanol. The recovered polymer was subjected to Soxhlet extraction with methanol, and after denaturation, denaturation was confirmed by carbonyl absorption of IR spectrum.

Production Example 4 [(F) Production of rubber-like elastic body having polar group] SEBS (Shell Chem. Co. Kraton)
G-1651) 1000 g, maleic anhydride 3
0 g was dry-blended and melt-kneaded using a 30 mm twin-screw extruder at a screw rotation speed of 200 rpm and a set temperature of 300 ° C. to obtain maleic anhydride-modified SEBS (rubber-like elastic body having a polar group). To measure the denaturation rate, the maleic anhydride-modified SEBS obtained was dissolved in chloroform. Then, the polymer recovered by reprecipitation in methanol was Soxhlet extracted with methanol, dried and then I
The denaturation rate was determined by the intensity of carbonyl absorption in the R spectrum and titration. The modification ratio of this maleic anhydride-modified SEBS was 0.8% by weight.

Examples 1 to 12 and Comparative Examples 1 to 2 The predetermined amounts of the raw materials (A), (C) to (I) shown in Table 1 were dry blended with a Henschel mixer, and then the cylinder temperature was kept at 300 ° C. Melt-kneading was performed with a twin-screw extruder to form pellets. The obtained pellets were extrusion-molded to prepare a resin sheet (thickness 5 mm) for laminated compression molding. A predetermined amount of this sheet and (B) glass cloth was loaded into a mold, and compression molding was performed together with a copper foil (thickness 10 ± 0.1 mm) to prepare a test piece of a laminate for a printed wiring board. The obtained test piece was used to measure the peel strength and observe the deformation and peeling during the soldering resistance test. The results are shown in Table 2. Each test was conducted as follows.

(1) Measurement of Peel Strength The test piece was dimensioned as shown in FIG. Then JIS
According to C6481, one end of the copper foil peeled off from the test piece was fixed to a tensile tester, and the peel strength when the copper foil was peeled off at a speed of 50 mm / min in the direction perpendicular to the test piece was measured. . The outline of the operation method of the test is shown in FIG.

(2) Solder resistance test The test pieces were dimensioned as shown in FIG. Then JIS
According to C6481, the copper foil surface was made to face down and floated on a molten solder bath (260 to 262 ° C.), and the time (seconds) until the copper foil surface and the resin sheet were blistered was measured. The outline of the operating method of the test is shown in FIG.

[0053]

[Table 1]

[0054]

[Table 2]

* 1: SPS obtained in Production Example 1 * 2: SEBS (Kuraray Co., Ltd .; Septon 8006) * 3: Maleic anhydride modified PPE obtained in Production Example 2 * 4: Production Example 3 Obtained maleic anhydride-modified SPS * 5: Maleic anhydride-modified SEBS obtained in Production Example 4 * 6: Flame retardant (Nissan Ferro Organic Chemical Co., Ltd .; Pyrocheck 68PB) * 7: Flame retardant aid ( Made by Nippon Seiko Co., Ltd .; Antimony trioxide, ATOX-S) * 8: Glass fiber (made by Nippon Electric Glass Co., Ltd .; EC
S03T-051 / P) was blended in a weight% conversion amount based on the weight of the resin sheet for laminated compression molding. * 9: Filler (Kindaira Mining Co., Ltd .; calcium carbonate,
KS 1300) * 10: Glass cloth (manufactured by Asahi Schwebel KK; AS
637AV)

[0056]

The laminate for a printed wiring board according to the present invention is S
It has significantly improved adhesiveness to the metal layer without deteriorating the excellent heat resistance and high mechanical strength that PS originally has. Especially, it is mass-produced by reducing deformation and peeling of metal layer during soldering resistance test. The problems in the solder resist process at that time are solved and the insulation is excellent. Therefore, the laminate of the present invention is preferably used not only for manufacturing a printed wiring board, but also as a material for general structural materials, electric / electronic parts, automobile parts, etc., and also for films, fibers, sheets, etc.

[Brief description of drawings]

FIG. 1 shows a side view of a test piece for a peel strength test.

[Explanation of symbols]

 1: Test piece, 2: Resin sheet, 3: Copper foil.

FIG. 2 shows an outline of an operation method of a peel strength test.

[Explanation of symbols]

 1: Test piece, 2: Resin sheet, 3: Copper foil.

FIG. 3 shows a plan view of a test piece for a solder resistance test.

[Explanation of symbols]

 1: Test piece.

FIG. 4 shows an outline of a method of operating a solder resistance test.

[Explanation of symbols]

1: Test piece, 2: Resin sheet, 3: Copper foil, 4: Molten solder bath, 5: Molten solder, 6: L-type thermometer.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 8, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

The method for laminating the glass cloth on the molding material for a printed wiring board is not particularly limited, and any conventionally known method can be arbitrarily selected. For example, dry-blending each component of the molding material for printed wiring boards, pelletizing by a usual method, and then forming a molding material sheet by extrusion molding method, and then extruding molding method or compression molding method on the obtained molding material sheet. By laminating glass cloth by the above, the laminate for a printed wiring board of the present invention can be manufactured. Here, the extrusion molding method is a method in which several layers of a molding material sheet and a glass cloth are inserted between a pair of metal belts, heated and melted, and then cooled to mold a laminate. The compression molding method is a method of molding a laminate by mounting a molding material sheet and glass cloth in a mold. In addition, a glass cloth and a metal foil are laminated by heating, compressing and cooling with a roll and a roll or a double belt press or a single belt press while extruding a raw material containing SPS into a film by a T-die extrusion method or the like. Good. Note that glass cloth pre-impregnated with a molding material such as SPS may be used.

Claims (3)

[Claims] 1. A surface treatment with a coupling agent (B) is applied to 99-5% by weight of a molding material for a printed wiring board, which comprises (A) a styrene-based polymer having a highly syndiotactic structure having a polar group. A laminated body for a printed wiring board, which is obtained by laminating 1 to 95% by weight of glass cloth. 2. (C) 20 to 95% by weight of a styrenic polymer having a highly syndiotactic structure, and (D)
100 parts by weight of a mixture consisting of 80 to 5% by weight of a rubber-like polymer having a product of a weight average molecular weight and a content of styrene-based monomer units of 30,000 or more, and (E) a polyphenylene ether having a polar group, ( 0.1 to 60% by weight of a polar group-containing resin selected from the group consisting of A) a styrene polymer having a highly syndiotactic structure having a polar group and (F) a rubber-like elastic body having a polar group 1 to 95% by weight of the glass cloth surface-treated with the coupling agent (B) is laminated on 99 to 5% by weight of the molding material for a printed wiring board. 3. (C) 20 to 95% by weight of a styrenic polymer having a highly syndiotactic structure, and (D)
100 parts by weight of a mixture consisting of 80 to 5% by weight of a rubber-like polymer having a product of the weight average molecular weight and the content of styrene-based monomer units of 30,000 or more, (E) a polyphenylene ether having a polar group (A) ) Styrenic polymer having a highly syndiotactic structure having a polar group and (F)
0.1-60 parts by weight of at least one polar group-containing resin selected from the group consisting of rubber-like elastic bodies having polar groups,
(G) Flame retardant 3 to 60 parts by weight and (H) Flame retardant aid 1 to
Molding material for printed wiring board 9 containing 15 parts by weight
A laminated body for a printed wiring board, which is obtained by laminating (B) 1 to 95% by weight of a glass cloth surface-treated with a coupling agent with respect to 9 to 5% by weight.