JPH06275929A - Molding material for printed wiring and printed wiring board using the same - Google Patents

Abstract

(57) [Abstract] [Purpose] Molding for printed wiring with excellent adhesiveness to metal layers and peeling strength without impairing the excellent heat resistance and high mechanical strength originally possessed by syndiotactic styrene resins. Development of materials and printed wiring boards using them. [Structure] (A) A molding material for a printed wiring comprising a styrene-based polymer having a highly syndiotactic structure having a polar group, or (B) a styrene-based polymer having a highly syndiotactic structure, (C) A mixture of rubber-like polymers having a product of the weight average molecular weight and the content of styrene-based monomer units of 30,000 or more, (D) a polyphenylene ether having a polar group, and (A) a high syndyne having a polar group. A molding material for printed wiring comprising a styrene resin composition obtained by mixing at least one of a styrene polymer having an tactic structure and a rubbery elastic body having a polar group, and a printed wiring board comprising the same.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding material for printed wiring and a printed wiring board using the same, and more specifically, it has good releasability in a high temperature mold and has a syndiotactic styrene structure. A molding material for printed wiring, which is excellent in adhesiveness to a metal layer and peeling strength, without impairing the excellent heat resistance and high mechanical strength originally possessed by a resin (hereinafter sometimes abbreviated as SPS), and the same. The present invention relates to a printed wiring board used.

[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. Therefore, in order to develop a styrene-based resin composition having more excellent physical properties, beyond the limit of improvement of physical properties inherent in conventional styrene-based resins, the inventors of the present invention have conducted research, and first, A high-impact styrenic resin composition prepared by blending a styrenic polymer having a high degree of syndiotactic structure with a rubber-like polymer containing a styrenic monomer unit as one component has been proposed (JP-A-1 −
146944). However, in this composition, as the rubber-like polymer, one having a product of the weight average molecular weight and the content of the styrene-based monomer unit as low as less than 30000 is used. The rigidity at the time of molding, which is considered to be caused, 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 found that a composition containing SPS and a specific rubber-like polymer in a predetermined ratio, and a composition obtained by surface-treating the composition with a polyphenylene ether having a polar group and a coupling agent. The above problem was solved by a composition in which a material and a flame retardant and a flame retardant auxiliary were mixed in a predetermined ratio, respectively, and a composition in which a flame retardant and a flame retardant auxiliary were each mixed in a predetermined ratio (Japanese Patent Application No. 4-46901). Specification). When molding a printed circuit board using such a styrene resin composition, 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. I 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.

[0004]

Therefore, the present inventors have
As a result of intensive studies to solve the above problems, only SPS having a polar group is used, or a polyphenylene ether having a polar group in a composition containing SPS and a specific rubber-like polymer in a predetermined ratio, SP with polar group
It has been found that the above problem can be solved by adding at least one rubber-like elastic body having S and a polar group. The present invention has been completed based on such findings. That is, the present invention provides a molding material for a printed wiring, which comprises (A) a styrene-based polymer having a polar group and a high syndiotactic structure. Further, the present invention provides (B) a styrene-based polymer having a highly syndiotactic structure in an amount of 20 to 95% by weight, and (C) the product of the weight average molecular weight and the content of the styrene-based monomer unit is 30000. (D) Polyphenylene ether having a polar group, (A) Styrene-based polymer having a polar group and having a high syndiotactic structure, relative to 100 parts by weight of the mixture of 80 to 5% by weight of the above rubbery polymer. Provided is a molding material for printed wiring, which comprises a styrene-based resin composition obtained by blending 0.1 to 60 parts by weight of at least one rubber-like elastic body having a polar group, and (B) provides a highly syndiotactic structure. Styrene-based polymer having 20 to 95% by weight
And (C) 100 parts by weight of a mixture 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, the (D) polar group At least one of a polyphenylene ether having (A), a styrene polymer having a highly syndiotactic structure having a polar group, and a rubber-like elastic body having a polar group.
Provided is a molding material for printed wiring, which comprises a styrene-based resin composition containing 0.1 to 60 parts by weight and (E) 1 to 350 parts by weight of a filler surface-treated with a coupling agent. ) 20 to 95% by weight of a styrenic polymer having a high syndiotactic structure, and (C) the product of the weight average molecular weight and the content of the styrenic monomer unit is 30,
000 or more rubbery polymer 80 to 5% by weight of mixture 10
At least one of (D) a polyphenylene ether having a polar group, (A) a styrene-based polymer having a highly syndiotactic structure having a polar group, and a rubber-like elastic body having a polar group is added to 0 part by weight. 0.1 to 60 parts by weight, (E) filler 1 surface-treated with a coupling agent 1
350 parts by weight, (F) flame retardant 3-60 parts by weight and (G)
The present invention also provides a molding material for printed wiring, which is made of a styrene resin composition containing 1 to 15 parts by weight of a flame retardant aid. Furthermore, the present invention also provides a printed wiring board in which a metal layer is adhered onto a molded body made of one of the above-mentioned printed wiring molding materials.

The molding material for printed wiring according to the present invention is
The component (A) is composed of SPS having a polar group. Here, SPS is usually polystyrene, poly (alkylstyrene), poly (halogenated styrene) having a syndiotacticity of 85% or more for diads or 35% or more for pentads (racemic pentads), preferably 50% or more. , Poly (alkoxystyrene), poly (benzoic acid ester styrene) and mixtures thereof, or copolymers containing these as the main components. Here, as poly (alkylstyrene),
Poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (tertiary butyl styrene), etc., poly (halogenated styrene)
Examples include poly (chlorostyrene) and poly (bromostyrene). Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). The molecular weight and molecular weight distribution of this SPS are not particularly limited and may be appropriately determined according to the application of the composition to be produced. This SPS
Has a melting point of 260 to 270 ° C., and is significantly superior in heat resistance to a conventional styrene polymer having an atactic structure. The component (A) of the present invention is a product obtained by modifying the above SPS, and includes, for example, (1) introduction of a polar group by a copolymerization reaction at the time of polymerization, (2) introduction of a polar group at the time of termination of the polymerization reaction, ( 3) It can be obtained by grafting using the polar group of (1) or (2), but is not limited to these methods. Further, the modification rate is not particularly limited. Examples of (1) above include 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,
Examples include isocyanate groups, amino groups, hydroxyl groups, imide groups, thiol groups, oxazoline groups, and epoxy groups. 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 polyphenylene ether, and if it is less than 0.01% by weight, it is difficult to improve the mechanical strength. .

Further, in the molding material for printed wiring of the present invention, the product of SPS as the component (B) and the weight average molecular weight as the component (C) and the content of the styrene-based monomer unit is 3
A mixture of 20,000 or more rubbery polymers, polyphenylene ether having a polar group as component (D), S of (A)
At least one of rubber-like elastic bodies having PS and polar groups
And a styrene-based resin composition. Here, the component (B) is SPS having no polar group.
This is the same as the above-mentioned component (A) except that it does not have a polar group. Further, the rubber-like polymer used as the component (C) contains a styrene-based monomer unit, and examples of such a polymer include a styrene-butadiene block copolymer rubber and a styrene-butadiene block. Rubber in which the butadiene portion of the copolymer is partially or completely hydrogenated, styrene-butadiene copolymer rubber, methyl acrylate-butadiene-styrene copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber, methyl acrylate -Acrylic acid-2
-Ethylhexyl-styrene copolymer rubber and the like, since all of these have a styrene unit,
Good dispersibility in SPS as the component (B),
As a result, the effect of improving the physical properties 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 (C) has a product of the weight average molecular weight (Mw) and the content of the styrenic monomer unit of 30,000 or more, preferably 40,000. It is necessary to be 000 or more. This value is 3
When it is less than 0000, the composition obtained has insufficient releasability and rigidity, and also has poor heat resistance. Regarding the blending ratio of the component (B) and the component (C) in the composition, the component (B) is 20 to 95 wt% and the component (C) is 80.
It is necessary to mix both components so that the content becomes ˜5% by weight. Here, if the amount of the component (B) exceeds 95% by weight (the amount of the component (C) is less than 5% by weight), the effect of improving impact resistance is insufficient, and the amount is less than 20% by weight (the component (C)). When the amount exceeds 80% by weight), the elastic modulus is remarkably reduced.

The component (D) comprises at least one of a polyphenylene ether having a polar group, the component (A) and a rubber-like elastic material. Here, as the polar group in the polyphenylene ether having a polar group, 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 is
It is sufficient if it is 0.01% by weight or more based on the polyphenylene ether, and if it is less than 0.01% by weight, improvement in mechanical strength cannot be expected. The polyphenylene ether having the polar group is, for example, (1) polyphenylene ether,
A method of reacting a compound having both the polar group and an unsaturated group, (2) a method of polymerizing the phenol compound having the polar group alone or a method of polymerizing two or more kinds thereof, (3) a method of only the phenol compound having the polar group. Alternatively, it can be produced by a method of polymerizing 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-dibromoferulene-1,4-ether), poly (2,6-dichlorophenylene-1) , 4-ether), poly (2,6-diethylphenylene-1,4-ether) and poly (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)

[0011]

[Chemical 1]

(Wherein Y represents an aliphatic residue or an aromatic residue) and the like, methylnadic 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
-Bentadiene-3-ol; 1,4-hexadiene-
3-ol; 3,5-hexadiene-2-ol; 2,
4-hexadiene-1-ol; 3-butene-1,2-
Diol; 2,5-dimethyl-3-hexene-2,5-
Diol; 1,5-hexadiene-3,4-diol;
Unsaturated alcohols such as 2,6-octadiene-4,5-diol or OH of such unsaturated alcohols
Anhydrous to unsaturated amines whose groups are replaced by NH ₂ groups, low polymers such as butadiene and isoprene (for example, those having an average molecular weight of about 500 to 10,000) and high molecular weight substances (for example, those having an average molecular weight of 10,000 or more) Examples thereof include maleic acid, those to which phenols are added, those in which an amino group, a carboxylic acid group, a hydroxyl group, an epoxy group and the like have been introduced, and further allyl isocyanate.

Examples of vinyl compounds having an epoxy group include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, and glycidyl itaconate. 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 material having a polar group is used for improving 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 (SEBS), styrene-isoprene block copolymer (SIR), styrene-isoprene-styrene block copolymer (SIS),
Hydrogenated styrene-isoprene-styrene block copolymer (SEPS), ethylene propylene rubber (EP
M), ethylene propylene diene rubber (EPDM), ethylene butylene rubber (EBM) and the like are modified with a modifier having a polar group. Among these, rubber-like elastic bodies modified from SEBS, SBR, SBS, SEPS, and SIS are preferable. The rubber-like elastic body having a polar group may be used alone or in combination of two or more. Here, the polar group is not particularly limited, and examples thereof include acid halides, carbonyl groups, acid anhydrides, acid amides, carboxylic acid esters,
Examples thereof include acid azide, sulfone group, nitrile group, cyano group, isocyanic acid ester group, amino group, hydroxyl group, imide group, thiol group, oxazoline group and 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. As the rubbery elastic body having a polar group of the present invention, SEBS having a maleic anhydride group and an epoxy group is particularly preferably used. The component (A) used as the component (D) is as described above.

The component (D) is 0.1 to 6 with respect to 100 parts by weight of the mixture of the components (B) and (C).
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 composition will not be sufficiently exerted,
If the amount is more than parts by weight, the crystallization rate at the time of molding becomes slow, resulting in poor release and increased productivity due to increased cooling time.

Further, the molding material for printed wiring according to the present invention contains a filler surface-treated with a coupling agent as the above-mentioned component (B), component (C), component (D) and component (E). And a styrene resin composition. Here, a filler surface-treated with a coupling agent is used as the component (E), but 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. Specific organic synthetic fibers include wholly aromatic polyamide fibers and polyimide fibers, whiskers include boron, alumina, silica, silicon carbide and other whiskers, and ceramic fibers include gypsum, potassium titanate and magnesium sulfate. Examples of the fiber such as magnesium oxide and the metal fiber include fibers such as copper, aluminum and steel, and particularly glass fiber and carbon fiber are preferable. Here, the shape of the filler includes cloth, mat, bundled cut, short fiber, filament, and whiskers. In the bundled cut, the length is 0.05 mm.
A fiber having a diameter of -50 mm and a fiber diameter of 5-20 µm is preferable.
Also, as the carbon fiber, polyacrylonitrile (PA
N) type is preferable.

On the other hand, 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 and oxysulfate. , Tin oxide,
Alumina, kaolin, silicon carbide, metal powder, glass powder, glass flakes, glass beads and the like can be mentioned. Particularly preferred are talc, calcium carbonate and mica.
The preferable average particle size of talc is 0.3 to 20 μm, and more preferably 0.6 to 10 μm. The preferable average particle size of calcium carbonate is 0.1 to 20 μm. The average particle size of mica is preferably 40 to 250 μm, more preferably 50 to 150 μm. Among these various fillers, glass fillers such as glass powder, glass flakes, glass beads, glass filaments, glass fibers, glass rovings, and glass mats are particularly preferable.

The coupling agent used for the surface treatment of the filler is used to improve the adhesion between the filler and the component (D), and is a so-called silane coupling agent or titanium-based coupling agent. As the coupling agent, any one can be selected and used from conventionally known 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 Silane; 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 dihydroimidazolepropyltriethoxysilane; hexamethyldisilazane; N, O-
(Bistrimethylsilyl) amide; N, N-bis (trimethylsilyl) urea and the like can be mentioned. Among these, γ-aminopropyltriethoxysilane; N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane;
Aminosilanes and epoxysilanes such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferred. It is particularly preferable to use the above aminosilane.

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 (ditridecyl phosphite) titanate; Tetra (1,1-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate; Bis (dioctyl pyrophosphate) oxyacetate titanate; Bis (dioctyl pyrophosphate) 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. Among these, isopropyl tri (N-amidoethyl, aminoethyl) titanate is preferable.

The surface treatment of the filling material using such a coupling agent can be carried out by an ordinary method without any particular limitation. For example, a sizing treatment in which an organic solvent solution or suspension of the coupling agent is applied to a filler as a so-called sizing agent, or a Henschel mixer, a super mixer, a Loedige mixer,
Dry mixing using V type blender, spray method,
Although it can be performed by an appropriate method such as an integral blend method or a dry concentrate method depending on the shape of the filler, it is preferably performed by a sizing treatment, dry mixing, or a spray method. 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.

In the present invention, the filler surface-treated with the coupling agent of the component (E) is preferably 1 to 100 parts by weight of the mixture of the components (B) and (C). The amount is 350 parts by weight, particularly preferably 1 to 200 parts by weight. If the amount is less than 1 part by weight, the effect of adding the filler is not sufficiently exerted,
If it exceeds the weight part, the dispersibility may be deteriorated, and kneading and molding may be difficult.

Furthermore, the molding material for printed wiring according to the present invention is a component (B), a component (C), a component (D), a component (E), a flame retardant (F) and a flame retardant (G). It is composed of a styrene resin composition containing an auxiliary agent. Here, various flame retardants are used as the component (F), and halogen-based flame retardants and phosphorus-based flame retardants are particularly preferable. Examples of halogen-based flame retardants include tetrabromobisphenol A; tetrabromophthalic anhydride; hexabromobenzene; tribromophenyl allyl 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,
Examples thereof include brominated polystyrene such as polytribromostyrene, poly (dibromophenylene oxide), and bis (tribromophenoxy) ethane.

On the other hand, examples of the phosphorus-based flame retardant include ammonium phosphate, tricresyl phosphate, triethyl phosphate, acidic phosphate ester, triphenylphosphene oxide and the like. As a flame retardant,
Among these, polytribromostyrene, poly (dibromophenylene oxide), decabromodiphenyl ether, bis (tribromophenoxy) ethane, ethylene-bis- (tetrabromophthalimide), tetrabromobisphenol A, and brominated polycarbonate oligomer are particularly preferable. In the composition, the flame retardant of the component (F) is the mixture 10 of the component (B) and the component (C).
The amount is preferably 3 to 60 parts by weight, particularly preferably 5 to 40 parts by weight, relative to 0 parts by weight.
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 used as the component (G) include antimony trioxide, antimony pentoxide, sodium antimonate,
Antimony flame-retardant aids such as metallic antimony, antimony trichloride, antimony pentachloride, antimony trisulfide, antimony pentasulfide and the like can be mentioned. 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 of the component (G) is 1 to 1 with respect to 100 parts by weight of the mixture of the components (B) and (C).
It is necessary to add 5 parts by weight, preferably 2 to 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. Even if only one of the above-mentioned component (F) or component (G) is used, the effect of imparting flame retardancy is not sufficiently exhibited.

In the molding material for printed wiring of the present invention, in addition to the above-mentioned essential components, various additives such as stabilizers, antioxidants, light stabilizers, and the like may be added as necessary within the range not impairing the object of the present invention. Lubricants, plasticizers, antistatic agents, release agents, coloring agents, and other thermoplastic resins can be added. This molding material for printed wiring is prepared by blending the above-mentioned essential components and optional components used as desired in a predetermined ratio, for example, Banbury mixer, single-screw extruder, twin-screw extruder, co-kneader, multi-screw extrusion. Depending on the machine, etc., an appropriate temperature, for example, 270-32
It can be prepared by sufficiently kneading at a temperature in the range of 0 ° C.

The printed wiring board of the present invention has a metal layer provided on a molded body made of the molding material for printed wiring obtained as described above. Examples of the metal layer used here include thin films of copper, aluminum, silver, gold, zinc, tin and the like, and copper and aluminum are particularly preferably used. There are various methods for creating a printed wiring board,
For example, it is general that the molding material for printed wiring is dry blended, then pelletized by a usual method, and then injection molding, extrusion molding, or compression molding. Here, the injection molding method is a method in which a metal foil is inserted into both inner surfaces or one surface of a mold and the metal-bonded substrate is directly molded by insert molding. The extrusion molding method is a method in which a metal foil is inserted between a pair of metal belts on both sides or one side and a plate-like melt is sandwiched between them to directly form a metal-bonded substrate.
The compression molding method is the obtained pellet or injection molding method,
In this method, a flat plate formed by extrusion molding, compression molding, or the like is mounted in a mold, and a metal foil is inserted into both sides or one side of the mold to directly mold a metal-bonded substrate.

[0027]

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 1 liter of purified styrene in a reaction vessel having an internal volume of 2 liters, 7.5 mmol of the contact product obtained in Reference Example 1 as an aluminum atom, and 7.3 of triisobutylaluminum.
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. Moreover, it was confirmed by melting point and ¹³ C-NMR measurement that this polymer was SPS.

Production Example 2 500 g of SPS obtained in Production Example 1 and 500 polyphenylene ether (manufactured by Mitsubishi Gas Chemical Co., Ltd .; YPX-100L)
g, maleic anhydride (Wako Pure Chemical Industries, Ltd., S grade)
33 g and 2,3-dimethyl-as a radical initiator
2,3-Diphenylbutane (manufactured by Nihon Yushi; Nofmer B
C) After mixing 20 g with a Henschel mixer, 300-
The mixture was kneaded under heating and melting with a twin-screw extruder at a temperature of 320 ° C. to obtain maleic anhydride-modified PPE. Obtained modified P
After dissolving PE in toluene, it was purified by dropping into PE and reprecipitation. After press-molding the purified modified PPE, peaks based on carbonyl groups were observed by infrared (IR) measurement, and it was confirmed that the modified PPE was modified with maleic anhydride.

Production Example 3 1000 g of SPS obtained in Production Example 1, 30 g of maleic anhydride and 10 g of 2,3-dimethyl-2,3-diphenylbutane (NOFMER BC Co., Ltd .; NOFMER BC) were dry-blended to 30 mm. Melt kneading was performed using a 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 was cooled and then pelletized to obtain maleic anhydride-modified SPS.
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 drying, denaturation was confirmed by carbonyl absorption of IR spectrum.

Production Example 4 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. Obtained maleic anhydride-modified SEB for measuring the modification rate
S was dissolved in chloroform. Then, the polymer recovered by reprecipitation in methanol was subjected to Soxhlet extraction with methanol, dried, and the modification rate was determined by titration and the intensity of carbonyl absorption in the IR spectrum. The modification ratio of this maleic anhydride-modified SEBS was 0.8% by weight.

Examples 1 to 14 and Comparative Examples 1 to 3 The raw materials shown in Table 1 were dry blended with a Henschel mixer, and then melt-kneaded with a twin-screw extruder having a cylinder temperature of 300 ° C. to form pellets. . The obtained pellet was injection-molded to prepare a test piece, and the peel strength was determined. The results are shown in Table 1.

[0033]

[Table 1]

[0034]

[Table 2]

* 1: SPS obtained in Production Example * 2: SEBS (manufactured by Shell Kagaku Co .; Kraton G1)
651) * 3: Maleic anhydride-modified PPE obtained in Production Example 2 * 4: Maleic anhydride-modified SPS obtained in Production Example 3 * 5: Maleic anhydride-modified SEBS obtained in Production Example 4 * 6: Glass fiber (Nippon Electric Glass Co., Ltd .; EC
S03T-051 / P) * 7: Filler (Kawatetsu Kogyo Co., Ltd .; Kaliwhisker titanate, Tybrex) * 8: Flame retardant (Nissan Ferro Organic Chemicals Co., Ltd .; Pyrocheck 68PB) * 9: Flame retardant aid Agent (Nippon Seiko Co., Ltd .; antimony trioxide, ATOX-S)

[0036]

The molding material for printed wiring according to the present invention is S
The peel strength is greatly improved without impairing the excellent heat resistance and high mechanical strength inherent in PS.
In addition to these characteristics, excellent flame retardancy is imparted. Therefore, the molding material for printed wiring according to the present invention is suitably used not only as a printed wiring board but also as a material for general structural materials, electric / electronic parts, automobile parts, etc., as well as films, fibers, sheets, etc.

Claims (5)

[Claims] 1. A molding material for printed wiring, which comprises (A) a styrene-based polymer having a highly syndiotactic structure having a polar group. 2. The product of (B) 20 to 95% by weight of a styrene-based polymer having a highly syndiotactic structure, and (C) the product of the weight average molecular weight and the content of the styrene-based monomer unit is 30000 or more. 100% by weight of a mixture of 80 to 5% by weight of the rubbery polymer, (D) a polyphenylene ether having a polar group, (A) a styrene polymer having a highly syndiotactic structure having a polar group and a polar A molding material for printed wiring, comprising a styrene-based resin composition obtained by blending 0.1 to 60 parts by weight of at least one rubber-like elastic body having a base. 3. The product of (B) 20 to 95% by weight of a styrene polymer having a highly syndiotactic structure, and (C) the product of the weight average molecular weight and the content of styrene monomer units is 30000 or more. 100% by weight of a mixture of 80 to 5% by weight of the rubbery polymer, (D) a polyphenylene ether having a polar group, (A) a styrene polymer having a highly syndiotactic structure having a polar group and a polar A styrene resin composition comprising 0.1 to 60 parts by weight of at least one rubber-like elastic body having a base and 1 to 350 parts by weight of a filler (E) surface-treated with a coupling agent. Molding material for printed wiring. 4. The product of (B) 20 to 95% by weight of a styrene polymer having a highly syndiotactic structure, and (C) the product of the weight average molecular weight and the content of the styrene monomer unit is 30000 or more. 100% by weight of a mixture of 80 to 5% by weight of the rubbery polymer, (D) a polyphenylene ether having a polar group, (A) a styrene polymer having a highly syndiotactic structure having a polar group and a polar Filler 1 in which 0.1 to 60 parts by weight of at least one rubber-like elastic body having a base is surface-treated with (E) a coupling agent
˜350 parts by weight, (F) 3 to 60 parts by weight of flame retardant, and (G) 1 to 15 parts by weight of flame retardant auxiliary agent, a molding material for printed wiring, which is made of a styrene resin composition. 5. A printed wiring board in which a metal layer is brought into close contact with a molded body made of one of the molding materials for printed wiring according to any one of claims 1 to 4.