JP2869099B2 - Styrene resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a styrene-based resin composition, and more specifically, an electric / electronic material (for example, a printed circuit board connector, etc.), an industrial structural material, an automobile part (for example, a connector for mounting on a vehicle, a wheel cap, The present invention relates to a styrene-based resin composition suitable for molding industrial materials such as cylinder heads, home appliances, and various mechanical parts.

[Problems to be solved by conventional technology and invention]

In general, polyamide is excellent in moldability and heat resistance and has sufficient rigidity, so that it is used as a molding material for various products such as household goods, electric products, and mechanical parts.

However, although polyamide has such excellent properties, it has a drawback that it is hard to say that it is sufficient in terms of water resistance.

By the way, recently, the group of the present inventors succeeded in developing a styrenic polymer having high syndiotacticity, and further developed a thermoplastic resin composition in which other components were blended with this styrenic polymer ( JP-A-62-104818
JP-A-62-257950).

This styrenic polymer was blended with polyamide to try to improve the above drawbacks.However, a composition of a resin essentially incompatible with each other, such as polyamide and polystyrene, is caused by insufficient strength of the interface between phases. Since the reduction of mechanical properties cannot be avoided, there is a limit to the reforming effect by blending.

Therefore, the present inventor has solved the above-mentioned problems and improved the compatibility between the styrene-based polymer having a syndiotactic structure and the polyamide resin, so as not to impair the mechanical properties of the polyamide. Intensive research was conducted to develop a composition having greatly improved properties.

[Means for solving the problem]

As a result, they have found that the above-mentioned problems can be solved by blending a specific styrene-based polymer and a specific polyphenylene ether at a fixed ratio with a polyamide. The present invention has been completed based on such findings.

That is, the present invention comprises (A) 99 to 1% by weight of a styrene polymer having a syndiotactic structure and (B) polyphenylene ether or a mixture of polyphenylene ether and a styrene polymer having no functional group. A styrenic resin composition comprising 0.1 to 50% by weight having a polar group and 0.9 to 98.9% by weight of a polyamide (C).

In the present invention, the syndiotactic structure in the styrenic polymer having a syndiotactic structure used as the component (A) means that the stereochemical structure is a syndiotactic structure, that is, the main chain formed from carbon-carbon bonds. On the other hand, a phenyl group or a substituted phenyl group as a side chain has a three-dimensional structure in which the phenyl group and the substituted phenyl group are alternately located in opposite directions, and the tacticity is determined by a nuclear magnetic resonance method using isotope carbon (
¹³ C-NMR method).

Tacticity measured by the ¹³ C-NMR method can be represented by the abundance ratio of a plurality of continuous structural units, for example, a dyad for two, a triad for three, and a pentad for five. However, the styrenic polymer having a syndiotactic structure referred to in the present invention is usually 75% or more in racemic diad, preferably 85% or more, or 30% or more in racemic pentad, preferably
Polystyrene having a syndiotacticity of 50% or more, poly (alkylstyrene), poly (halogenated styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene), poly (vinylbenzoic ester), hydrogen of these A polymer or a mixture thereof or a copolymer containing these as a main component is referred to. Here, poly (alkylstyrene) includes poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiary butylstyrene), poly (phenylstyrene), poly (vinylnaphthalene), Examples include poly (vinyl styrene), and examples of poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene). Examples of poly (halogenated alkylstyrene) include poly (chloromethylstyrene), and examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).

Among these, particularly preferred styrene polymers include polystyrene, poly (p-methylstyrene),
Poly (m-methylstyrene), poly (p-tert-butylstyrene), poly (p-chlorostyrene), poly (m-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene and their structural units And a copolymer containing

The styrenic polymer is not particularly limited in molecular weight, but has a weight average molecular weight of 10,000 or more, preferably 50,000
00 or more. Further, the molecular weight distribution is not limited in its width, and various molecular weight distributions can be applied. Here, if the weight average molecular weight is less than 10,000,
The thermal and mechanical properties of the resulting composition or molded article are undesirably reduced.

Styrene-based polymers having such a syndiotactic structure can be produced, for example, by using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent. (A monomer corresponding to the styrene-based polymer) (JP-A-62-187708). In addition, poly (halogenated alkylstyrene) can be obtained by the method described in JP-A-1-46912, and hydrogenated polymers thereof can be obtained by the method described in JP-A-1-178505.

The compounding amount of the component (A) is 1 to 99% by weight, preferably 10 to 95% by weight, and more preferably 20 to 95% by weight. If the amount is less than 1% by weight, no effect of improving the water resistance of the composition obtained is obtained. If it exceeds 99% by weight, the mechanical strength is not different from that of the styrene polymer of the component (A).

As the component (B) of the present invention, those having either a polyphenylene ether or a mixture of polyphenylene ether and a styrene polymer having no functional group and having a polar group are used. First, as a styrene polymer having no functional group, a general formula (Wherein R represents hydrogen or an alkyl group having 1 to 4 carbon atoms,
Z represents hydrogen, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and p is an integer of 1 to 5. The polymer having at least 25% by weight or more of the repeating structural unit derived from the vinyl aromatic compound represented by the formula (1) can be used. Such styrenic polymers include, for example, homopolymers of styrene or a derivative thereof and natural or synthetic elastomeric substances such as, for example, polybutadiene, polyisoprene, butyl rubber, EPDM, ethylene-propylene copolymer, natural rubber, epichlorohydrin. Styrene-based polymers, and styrene-containing copolymers such as styrene-methylstyrene copolymer and styrene-butadiene copolymer. Among them, in particular, styrene polymers having a syndiotactic structure, atactic polystyrene, isotactic polystyrene, polybutadiene-modified styrene polymers, butadiene-styrene copolymer, isoprene-styrene copolymer, high impact Functional polystyrene (HIPS) is preferred. Also, acrylonitrile, methyl methacrylate,
Styrene polymers into which at least one or more compounds such as methacrylonitrile are introduced are exemplified. The blending amount of the styrene-based polymer in the polyphenylene ether is preferably not more than 80% by weight, and if it exceeds this, the substantial blending amount of the polyphenylene ether with respect to the component (A) is not preferable.

Polyphenylene ether is a compound known per se. For this purpose, U.S. Patent No. 3,306,874
Nos. 3,306,875, 3,257,357 and 3,257,358 can be referred to. Polyphenylene ethers are usually prepared by an oxidative coupling reaction to form a homopolymer or copolymer in the presence of a copper amine complex, one or more two- or three-substituted phenols. Here, as the copper amine complex, a copper amine complex derived from primary, secondary and / or tertiary amines can be used. Examples of suitable polyphenylene ethers are poly (2,3-dimethyl-6-ethylphenylene-1,4-ether), poly (2-methyl-6-chloromethyl-1,4-phenylene) ether, poly (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-isopropylphenylene-1) ,Four
-Ether), poly (2-chloro-6-methylphenylene-1,4-ether), poly (2-methyl-6-ethylphenylene-1,4-ether), poly (2,6-dibromoferrene) 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).

Copolymers such as, for example, copolymers derived from two or more phenolic compounds as used in the preparation of said homopolymers are also suitable. Further, there are, for example, graft copolymers and block copolymers of the above-mentioned polyphenylene ether with a vinyl aromatic compound such as polystyrene.

The polar group contained in the component (B) includes acid halide, carbonyl group, acid anhydride, acid amide, carboxylic acid ester, acid azide, sulfone group, nitrile group,
Examples include a cyano group, an isocyanate group, 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, a maleic anhydride group is preferred. The content of the polar group is 0.01% by weight based on the polyphenylene ether.
If it is at least 0.01% by weight, improvement in mechanical strength cannot be expected.

As a method for obtaining the component (B), a method for obtaining a phenol compound having a polar group alone or by polymerizing two or more kinds thereof, a method for obtaining a phenol compound having a polar group alone or two or more kinds thereof, Examples thereof include a method of polymerizing a phenol compound having no polar group and a method of reacting a compound having both a polar group and an unsaturated group with polyphenylene ether.

The compound having both a polar group and an unsaturated group includes an unsaturated group, that is, a carbon-carbon double bond or a carbon-carbon triple bond, and a carboxylic acid group or a group derived from a carboxylic acid as a polar group, that is, a carboxyl group. Various hydrogen- or hydroxyl-substituted salts, esters, acid amides, acid anhydrides, imides, acid azides, acid halides or oxazolines, nitriles, epoxy groups, amino groups, hydroxyl groups or isocyanate groups of the same molecule It is a compound that also has

As compounds having both an unsaturated group and a polar group, 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, (However, R represents an aliphatic or aromatic group.) Those having a structure represented by, for example, methylnadic anhydride, dichloromaleic anhydride, maleic amide, itaconic acid, itaconic anhydride, soybean oil, tung oil , Castor oil,
Linseed oil, hemp seed oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil, sardine oil and other natural oils and fats, acrylic acid, butenoic acid, crotonic acid, vinyl acetate, methacrylic acid, pentenoic acid, angelic acid , Tebric acid, 2-pentenoic acid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2 -Pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-
Undecenoic acid, 10-undecenoic acid, 4-dotesenic acid, 5-dotesenic acid, 4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid,
Aicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid, myelibenic 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, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid,
Eicosapentaenoic acid, erucic acid, docosadienoic acid,
Unsaturated carboxylic acids such as docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacosenic acid, and traaconic acid, or esters, acid amides, anhydrides or allyl alcohols of these unsaturated carboxylic acids Crotyl alcohol; methyl vinyl carbinol; allyl carbinol; methyl propenyl carbinol; 4-penten-1-ol; 10-undecane-1-ol; propanegyl alcohol; 1,4-ventadien-3-ol; ,Four
-Hexadien-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; 2,6-
Unsaturated alcohols such as octadiene-4,5-diol, or unsaturated amines in which the OH groups of such unsaturated alcohols are replaced with NH ₂ groups, or low polymerization of butadiene or isoprene (for example, having an average molecular weight of 500 to 10000
) Or high molecular weight products (for example, those having an average molecular weight of 10,000 or more) to which maleic anhydride or phenols are added, or amino, carboxylic, hydroxyl, or epoxy groups, or isocyanate. Allyl acid and the like.

Examples of the vinyl compound 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.

Needless to say, the definition of a compound having both an unsaturated group and a polar group in the present invention includes a compound containing two or more unsaturated groups and two or more (same or different) polar groups. It is also possible to use two or more compounds.

As a specific method for obtaining the component (B), a compound having both a polyphenylene ether and a polar group is roll milled.
A method of melt-kneading and reacting at a temperature of 150 ° C. to 350 ° C. using a Banbury mixer, an extruder, etc.
A method in which polyphenylene ether and a compound having both a polar group and an unsaturated group are heated and reacted in a solvent such as toluene or xylene can be used. In order to further facilitate these reactions, an organic peroxide such as benzoyl peroxide, di-t-butyl-peroxide, dicumyl peroxide, t-butyl peroxybenzoate, or azobisisobutyro It is effective to use a radical initiator represented by an azo compound such as nitrile and azobisisovaleronitrile. A more effective method is a method of melt-kneading in the presence of a radical initiator.

Further, it may be produced by melt-kneading the styrene-based polymer as a part of the component (B), polyphenylene ether, a compound having both a polar group and an unsaturated group, and a radical initiator in the coexistence. it can.

The amount of the component (B) is 0.1 to 50% by weight, preferably 0.5 to 40% by weight, particularly preferably 1 to 30% by weight. The component (B) or the polyphenylene ether as a part thereof has very good compatibility with the styrene-based polymer as the component (A), but if the content is less than 0.1% by weight, the mechanical strength of the obtained resin is improved. I can't hope. If added in excess of 50% by weight, heat resistance and moldability will decrease.

In producing the resin composition of the present invention, it is not necessary to prepare only the component (B) in advance,
After mixing a styrene-based polymer as a component and a part of the component (B), a polyphenylene ether serving as the component (B), a compound having both a polar group and an unsaturated group, and an additive such as a filler, a roll mill is used. It can also be produced by melt-kneading at a temperature of 150 to 350 ° C. using a Banbury mixer, an extruder or the like.

As the polyamide as the component (C) of the present invention, all known thermoplastic polyamides can be used. Suitable polyamides are, for example, polyamide-4; polyamide 6; polyamide-4,6; polyamide-6,6; polyamide-3,4; polyamide-12; polyamide-11; polyamide-6,10; terephthalic acid and 4 Polyamides purified from 4,4'-diaminocyclohexylmethane; azelaic acid, adipic acid and 2,2 '
Polyamide purified from bis (p-aminocyclohexyl) propane; polyamide purified from adipic acid and metaxylylenediamine; polyamide purified from terephthalic acid and trimethylhexamethylenediamine.

In addition, aromatic polyamide resin (hereinafter abbreviated as PA)
Is a polyamide polymer containing an amide bond having an aromatic nucleus in the main chain as a repeating structural unit. More specifically, the aromatic polyamide resin of the present invention is obtained by reacting a polymer obtained by reacting an aromatic diamine component and a dicarboxylic acid component by a conventional method and an aromatic ω′-carboxyl compound by a conventional method. The polymer is appropriately selected from polymers obtained by the reaction.

Here, as the aromatic diamine component, 1,4-diaminobenzene; 1,3-diaminobenzene; 1,2-diaminobenzene; 2,4-diaminotoluene; 2,3-diaminotoluene;
2,5-diaminotoluene; 2,6-diaminotoluene; ortho, meta or para xylylenediamine; ortho,
Meta or para 2,2'-diaminodiethylbenzene, respectively;
4,4'-diaminobiphenyl;4,4'-diaminodiphenylmethane;4,4'-diaminodiphenylether;4,4'-
Diamino diphenyl thioether; 4,4'-diamino diphenyl ketone; a diamine compound having a benzene ring which can be typically exemplified by 4,4'-diamino diphenyl sulfone is used, and the aromatic diamine component has the benzene ring described above. The diamine compound may be used alone, or may be a mixture with another diamine compound, for example, an aliphatic diamine, as long as it contains 50 mol% or more. Of course, two or more diamine compounds having a benzene ring may be used as a mixture.

Next, as dicarboxylic acid components, aliphatic dicarboxyl compounds exemplified by glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like, and phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid And the like, and acid chlorides of these dicarboxyl compounds. These compounds may be used in combination.

Further, examples of the ω-amino-ω′-carboxy compound having an aromatic nucleus include 4-aminophenylcarboxylmethane, 1- (4-aminophenyl) -2-carboxylethane, and 3- (4-aminophenyl)-. Examples thereof include 1-carboxylpropane and para- (3-amino-3'-hydroxy) dipropylbenzene. The preferred aromatic polyamide resin used in the present invention is a polyamide derived from a diamine compound having a benzene ring and an aliphatic dicarboxylic acid, and a more preferred example is a polyamide derived from xylylenediamine and adipic acid.

The most preferred example is a polyamide derived from meta-xylylenediamine and adipic acid.

The amount of the component (C) is 0.9 to 98.9% by weight, preferably 5 to 90% by weight, and more preferably 5 to 65% by weight. If the amount is less than 0.9% by weight, the effect of improving mechanical strength is not seen. If it exceeds 98.9% by weight, the water resistance is no different from that of polyamide.

The resin composition of the present invention basically comprises the above (A),
Although it is composed of the components (B) and (C), a filler that has been surface-treated with a coupling agent may be further added as the component (D) in some cases. The filler used in the present invention may be fibrous or granular or powdery. Examples of the fibrous filler include glass fiber, carbon fiber, organic synthetic fiber, whisker, ceramic fiber, metal fiber, and natural plant fiber. Specific organic synthetic fibers include wholly aromatic polyamide fibers,
Fibers such as polyimide fibers, whiskers include whiskers such as boron, alumina, silica, and silicon carbide; ceramic fibers include gypsum, potassium titanate;
Fibers such as magnesium sulfate and magnesium oxide and metal fibers include fibers such as copper, aluminum, and steel, and glass fibers and carbon fibers are particularly preferable. Here, the shape of the filler includes cloth, mat, bundle cut, short fiber, filament, and whisker. In the case of bundle cut, the length is 0.05 mm to 50 mm and the fiber diameter is 5 to 5. 20 μm is preferred. Further, as the carbon fiber, a polyacrylonitrile (PAN) -based carbon fiber is preferable.

On the other hand, as the granular or powdery filler, for example, 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, and the like. Particularly, talc, calcium carbonate and mica are preferred. The preferred average particle size of talc is 0.3 to 20 μm, more preferably 0.6 to 10
μm is better. The preferred average particle size of the calcium carbonate is 0.1 to 20 μm. The preferred average particle size of mica is from 40 to 250 μm, more preferably from 50 to 150 μm.

Among the various fillers described above, glass fillers such as glass powder, glass flake, glass beads, glass filament, glass fiber, glass lobing, and glass mat are particularly preferable.

The coupling agent used for the surface treatment of the filler described above is used for improving the adhesion between the filler and the polyphenylene ether having a polar group as the component (B), and is a so-called silane-based coupling agent. Coupling agent,
As the titanium-based coupling agent, any one of conventionally known ones can be selected and used. Specific examples of the silane coupling agent include triethoxysilane, vinyl tris (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 dihydroimidazolepropyltriethoxysilane, Hexamethyldisilazane, N, O- (bistrimethylsilyl) amide, N, N-bis (trimethylsilyl) urea and the like. Among them, γ-aminopropyltriethoxysilane, N-
Aminosilanes such as β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferred. In particular, it is preferable to use the above-mentioned aminosilane.

Specific examples of the titanium-based coupling agent include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditrityl) (Decylphosphite) titanate, tetra (1,1-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctate Noyl titanate, isopropyl dimethacryl isostearyl titanate, isopropyl isostearyl diacryl Titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- amidoethyl, aminoethyl) titanate, dicumyl phenyloxy acetate titanate, etc. diisostearoyl ethylene titanate and the like. Among them, isopropyl tri (N-amidoethyl, aminoethyl) titanate is preferable.

The surface treatment of the filler using such a coupling agent can be performed by a usual method, and there is no particular limitation. For example, a sizing treatment in which an organic solvent solution or suspension of the above-mentioned coupling agent is applied to a filler as a so-called sizing agent, or dry mixing using a Henschel mixer, a super mixer, a Reedige mixer, a V-type blender, or the like, It can be performed by an appropriate method depending on the shape of the filler, such as a spraying method, an integral blending method, a dry concentrate method, and the like, but is preferably performed by a sizing treatment, dry mixing, and a spraying method.

Further, a film-forming substance for glass can be used in combination with the above-mentioned coupling agent. The film-forming substance is not particularly limited, and examples thereof include polymers of polyester type, urethane type, epoxy type, acrylic type, vinyl acetate type and isocyanate type.

In the present invention, the above-mentioned surface treatment filler component is blended. The blending ratio is such that the surface treatment filler component is added to the total of 100 parts by weight of the components (A), (B) and (C). The content is 1 to 350 parts by weight, preferably 5 to 200 parts by weight.
If the blending amount of the surface-treated filler is less than 1 part by weight, a sufficient blending effect as a filler is not recognized. On the other hand, 350
If the amount is more than 10 parts by weight, the dispersibility is poor and molding becomes difficult.

Further, in the present invention, the styrene polymer having a syndiotactic structure as the component (A) and the styrene polymer having no functional group with the polyphenylene ether (B ') or the polyphenylene ether as the component (B) are used as the component (B). Having a maleic anhydride group, that is, 0.1 to 50% by weight of a polyphenylene ether modified with maleic anhydride, and further subjected to surface treatment with (D ') aminosilane coupling agent as a component (D). By blending the filler and the polyamide of component (C) as described above, the adhesiveness between the styrene polymer having a syndiotactic structure and the filler can be improved, and the resin composition having more excellent properties Can be obtained.

The resin composition of the present invention comprises the above-mentioned styrene-based polymer and polyphenylene ether having a polar group, and further comprises a filler surface-treated with a coupling agent, if necessary. As long as the object of the present invention is not impaired, various additives or other thermoplastic resins and rubber-like elastic materials can be blended as required. Here, as the additive, for example, JP-A-63-28
No. 4244, phosphites, antioxidants of phosphate esters, ultraviolet absorbers, JP-A-1-2013
No. 50, JP-A-1-22587, aliphatic carboxylic acid ester type and paraffin type external lubricants, nucleating agents such as organic acid metal salts and organic phosphorus compounds, release agents, antistatic agents , Coloring agents, flame retardants, flame retardant auxiliaries and the like.

Examples of the thermoplastic resin include polyphenylene ethers having no polar group, polyolefins such as polyethylene, polypropylene, polybutene and polypentene; polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polythioethers such as polyphenylene sulfide; polycarbonate; Arylate, polysulfone, polyetheretherketone, polyethersulfone, polyimide, polyamideimide, polymethylmethacrylate, ethylene-acrylic acid copolymer, acrylonitrile-styrene copolymer, acrylonitrile-chlorinated polyethylene-styrene copolymer, ethylene -Vinyl acetate copolymer, ethylene-
Examples include vinyl alcohol copolymer, acrylonitrile-butadiene-styrene copolymer, vinyl chloride resin, chlorinated polyethylene, fluorinated polyethylene, polyacetal, thermoplastic polyurethane elastomer, 1,2-polybutadiene, styrene-maleic anhydride, and the like. it can. Preferred thermoplastic resins include thermoplastic resins having affinity or reactivity with the polar group of the polyphenylene ether having a polar group as the component (B),
(B) Polyethylene, polypropylene, polybutene, polypentene, etc., in which a compound having both a polar group and an unsaturated group used for introducing a polar group of a polyphenylene ether having a polar group as a component is introduced by a melting reaction, a solution reaction or polymerization. Polyolefins and polyphenylene sulfides, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polycarbonate, polyarylate, polysulfone, polyetheretherketone, polyethersulfone, polyimide, polyamideimide, polymethyl methacrylate, ethylene-acrylic acid Copolymer, acrylonitrile-styrene copolymer, acrylonitrile-chlorinated polyethylene-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene Vinyl acetate copolymer, ethylene -
Vinyl alcohol copolymer, acrylonitrile-butadiene-styrene copolymer, polyacetal, styrene-
Maleic anhydride copolymers and the like can be mentioned. Particularly preferred thermoplastic resins include maleic anhydride-modified polyethylene, polypropylene, styrene-maleic anhydride copolymer, polyarylate, polycarbonate, epoxy group-containing polyphenylene sulfide, amino group-containing polyphenylene sulfide, and the like.

Also, various types of rubber-like elastic bodies can be cited, but the most preferable one is a rubber-like copolymer containing a styrene-based compound as one component. For example, styrene
Butadiene copolymer rubber (SBR), styrene-butadiene block copolymer (SB, SBS, BSB, etc.), styrene-hydrogenated butadiene block copolymer (SEBS, SEB, etc.), styrene-isoprene block copolymer (SI , SIS, ISI), styrene-hydrogenated isoprene block copolymers (SEP, SEPS, etc.) or alkyl acrylate, alkyl methacrylate and conjugated diene double bonds as described in Japanese Patent Application No. 63-121700. Elastic granular material obtained by polymerizing a vinyl monomer in the presence of a polymer obtained by polymerizing one or more monomers selected from the group consisting of polyfunctional monomers having For example, acrylonitrile-styrene grafted butadiene rubber (AB
S), acrylonitrile-styrene grafted butadiene-butyl acrylate copolymer rubber (AABS), methyl methacrylate-styrene grafted butyl acrylate rubber (MAS), styrene grafted butadiene rubber (S
B), methyl methacrylate-styrene grafted butadiene rubber (MBS), and methyl methacrylate-styrene grafted butadiene-butyl acrylate copolymer rubber (MABS).

Further, one or more blocks or graft copolymers selected from AB type block copolymers, A grafted B copolymers and B grafted A copolymers (where A is an attack Tic polystyrene, acrylonitrile-styrene random copolymer, styrene-maleic anhydride random copolymer, styrene-acrylonitrile-maleimide anhydride random copolymer, styrene-methyl methacrylate random copolymer and styrene-methacrylic acid random copolymer Represents one or more selected styrene-based polymers or styrene-based copolymers, and B represents one or more selected from polybutadiene, polyisoprene, hydrogenated polybutadiene, hydrogenated polyisoprene and polycarbonate, and Polyamide, polymethyl methacrylate Polyethylene terephthalate,
One or two or more types of polymers selected from polybutylene terephthalate are shown. ).

Further, as the rubber-like elastic body, in addition to the above, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, ethylene-propylene copolymer rubber,
Polysulfide rubber, thiocol rubber, acrylic rubber,
Examples include urethane rubber, silicone rubber, and epichlorohydrin rubber.

As such a rubber-like elastic body, a rubber-like elastic body modified by reacting with a compound having a polar group and an unsaturated group used for introducing a polar group of polyphenylene ether having a polar group may be used.

In addition, various flame retardants can be mentioned, and halogen-based flame retardants and phosphorus-based flame retardants are particularly preferred. As the halogen-based flame retardant, for example, tetrabromobisphenol
A, tetrabromophthalic anhydride, hexabromobenzene, tribromophenyl allyl ether, pentabromotoluene, pentabromophenol, tribromophenyl-2,3-dibromopropyl ether, tris (2,3-dibromopropyl) phosphate, tris ( 2-chloro-
3-bromopropyl) phosphate, octabromodiphenyl ether, decabromodiphenyl ether, octabromobiphenyl, pentachloropentacyclodecane, hexabromocyclododecane, hexachlorobenzene, pentachlorotoluene, hexabromobiphenyl,
Decabromobiphenyl, decabromobiphenyl oxide, tetrabromobutane, decabromodiphenyl ether, hexabromodiphenyl ether, ethylene-bis- (tetrabromophthalimide), tetrachlorobisphenol A, tetrabromobisphenol A, tetrachlorobisphenol A or tetrabromobisphenol A
Oligomers, halogenated polycarbonate oligomers such as brominated polycarbonate oligomers, halogenated epoxy compounds, halogenated polystyrenes such as polychlorostyrene and polytribromostyrene, poly (dibromophenylene oxide), bis (tribromophenoxy)
Ethane and the like.

On the other hand, examples of the phosphorus-based flame retardant include ammonium phosphate, tricresyl phosphate, triethyl phosphate, acid phosphate, triphenyl phosphene oxide, and the like.

Among the flame retardants, among them, polytribromostyrene, poly (dibromophenylene oxide), decabromodiphenyl ether, bis (tribromophenoxy) ethane, ethylene-bis- (tetrabromophthalimide), tetrabromobisphenol A, brominated Polycarbonate oligomers are preferred.

The flame retardant is used in an amount of 3 to 40 parts by weight, preferably 5 to 100 parts by weight of the total of the components (A), (B) and (C).
It is blended in a proportion of up to 35 parts by weight. Here, if the blending ratio is less than 3 parts by weight, the obtained effect is small. On the other hand, if it exceeds 40 parts by weight, the flame retardancy does not improve according to the proportion, and conversely other mechanical properties are impaired. Not preferred.

Further, in the present invention, it is preferable to use a flame retardant auxiliary together with the above-mentioned flame retardant. Here, as the flame retardant aid,
There are various types, for example, antimony trioxide, antimony pentoxide, sodium antimonate, metal antimony, antimony trichloride, antimony pentachloride, antimony trisulfide,
An antimony flame retardant such as antimony pentasulfide is exemplified. In addition to these, zinc borate, barium metaborate, zirconium oxide and the like can be mentioned. Among these, antimony trioxide is particularly preferred. The flame retardant aid is blended in an amount of 1 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the total of the components (A), (B) and (C). Here, when the compounding ratio of the flame retardant auxiliary is less than 1 part by weight, the effect as the flame retardant auxiliary is not sufficient. on the other hand,
If the amount exceeds 15 parts by weight, the effect as a flame retardant aid does not improve in accordance with the proportion, and other physical properties may be impaired.

Further, in the present invention, a tetrafluoroethylene polymer can be used to prevent the molten dripping. Specific examples of the tetrafluoroethylene polymer include a tetrafluoroethylene homopolymer (polytetrafluoroethylene), a copolymer of tetrafluoroethylene and hexafluoropropylene, and a copolymerizable ethylenically unsaturated polymer. Examples include a tetrafluoroethylene copolymer containing a small amount of a monomer. As this tetrafluoroethylene polymer, those having a fluorine content of 65 to 76% by weight, preferably 70 to 76% by weight are used. The tetrafluoroethylene polymer is 0.003 to 10 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C),
Preferably 0.02 to 2 parts by weight, more preferably 0.1 to 2 parts by weight
It is blended in parts by weight.

〔Example〕

Next, examples and comparative examples of the present invention will be described in more detail.

Glass container of Reference Example 1 was replaced with argon internal volume 500 ml, put copper sulfate pentahydrate _{(CuSO 4 · 5H 2 O)} 17.8g (71 mmol), toluene 200ml and trimethylaluminum 24 ml (250 mmol), 40 ° C. For 8 hours. Thereafter, toluene was further distilled off from the solution obtained by removing the solid portion under reduced pressure at room temperature to obtain 6.7 g of a contact product. Its molecular weight measured by freezing point depression method was 610.

Production Example 1 Purified styrene 1, 7.5 mmol of the contact product obtained in Reference Example 1 as an aluminum atom, 7.5 mmol of triisobutylaluminum, 7.5 mmol of pentamethylcyclopentadienyl titanium trimethoxy The polymerization reaction was carried out at 90 ° C. for 5 hours using 0.038 mmol of the compound. After completion of the reaction, the product was decomposed with a methanol solution of sodium hydroxide to decompose a catalyst component, washed repeatedly with methanol, and dried to obtain 466 g of a polymer.

The weight average molecular weight of this polymer measured by gel permeation chromatography at 130 ° C. using 1,2,4-trichlorobenzene as a solvent was 290,000, and the ratio of weight average molecular weight / number average molecular weight was 2.72. Was. Further, the polymer was confirmed to be a polystyrene (SPS) having a syndiotactic structure by the melting point and ¹³ C-NMR measurement.

Production Example 2 Purified styrene 1, 5 mmol of the contact product obtained in Reference Example 1 as an aluminum atom, 5 mmol of triisobutylaluminum, 5 mmol of pentamethylcyclopentadienyl titanium trimethoxy The polymerization reaction was carried out at 90 ° C. for 5 hours using 0.025 mmol of the compound. After completion of the reaction, the product was decomposed with a methanol solution of sodium hydroxide to decompose the catalyst component, washed repeatedly with methanol, and dried to obtain a polymer 308.

The weight average molecular weight of this polymer measured by gel permeation chromatography at 130 ° C. using 1,2,4-trichlorobenzene as a solvent was 389,000, and the weight average molecular weight / number average molecular weight was 2.64. Was. Further, the polymer was confirmed to be a polystyrene having a syndiotactic structure by the melting point and ¹³ C-NMR measurement.

Production Example 3 In a reaction vessel having an inner volume of 2, purified styrene 1, 7.5 mmol of the contact product obtained in Reference Example 1 as aluminum atom, 7.5 mmol of triisobutylaluminum, pentamethylcyclopentadienyl titanium trimethoxy The polymerization reaction was carried out at 70 ° C. for 3 hours using 0.038 mmol of the polymer. After completion of the reaction, the product was decomposed with a methanol solution of sodium hydroxide to decompose the catalyst component, washed repeatedly with methanol, and dried to obtain 580 g of a polymer.

The weight average molecular weight of this polymer measured by gel permeation chromatography at 130 ° C. using 1,2,4-trichlorobenzene as a solvent was 592,000, and the weight average molecular weight / number average molecular weight was 2.81. Was. Further, the polymer was confirmed to be a polystyrene having a syndiotactic structure by the melting point and ¹³ C-NMR measurement.

Production Example 4 Poly (2,6-dimethyl-1,4-phenylene) ether (PPO) (manufactured by Aldrich, catalog No. 18178-1) 1
00 parts by weight of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., S
Grade) 5 parts by weight, 0.2 part by weight of t-butyl hydroperoxide (manufactured by NOF CORPORATION, trade name: Perbutyl H) as a peroxide, mixed with a Henschel mixer,
The mixture was kneaded while being heated and melted by a twin-screw extruder at a temperature of 320 ° C. to obtain maleic anhydride-modified PPO. The resulting modified PPO was dissolved in toluene and purified by dropwise reprecipitation in methanol. After press-molding the purified modified PPO, the infrared (I
R) The peak based on the carbonyl group was observed by the measurement, and it was confirmed that maleic anhydride modification was performed.

Production Example 5 Styrene-grafted polyphenylene ether (PPE) having an intrinsic viscosity of 0.45 in chloroform at 25 ° C (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Copiace CPX100) 100
0.5 parts by weight of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., S grade) and 0.4 parts by weight of cumene hydroperoxide (manufactured by Nippon Oil & Fats Co., Ltd., trade name: Parkmill H) are added to parts by weight. 300 ℃ after mixing with Henschel mixer
The mixture was heated and melted by a twin-screw extruder under the above temperature to obtain maleic anhydride-modified PPE. It was confirmed that the obtained modified PPE was modified with maleic anhydride in the same manner as in Production Example 4.

Production Example 6 Poly (2,6-dimethyl-1,4-phenylene) ether (PP
O) 15 parts by weight of the SPS obtained in Production Example 1, 0.5 part by weight of maleic anhydride (S grade, manufactured by Wako Pure Chemical Industries, Ltd.) based on 85 parts by weight of (Aldrich, Catalog No. 18178-1)
As a peroxide, 0.2 part by weight of t-butylhydroxyperoxide (manufactured by NOF CORPORATION, trade name: Perbutyl H) is mixed by a Henschel mixer, and then heated by a twin-screw extruder at a temperature of 300 to 320 ° C. The mixture was kneaded under melting to obtain maleic anhydride-modified PPO. It was confirmed that the obtained modified PPO was modified with maleic anhydride in the same manner as in Production Example 4.

Production Example 7 Poly (2,6-dimethyl-1,4-phenylene) ether (PP
O) 85 parts by weight (Aldrich, Catalog No. 18178-1), 15 parts by weight of Idemitsu polystyrene HT-54 (HIPS), maleic anhydride (S grade, manufactured by Wako Pure Chemical Industries, Ltd.)
Parts by weight, t-butylhydroxyperoxide (trade name: Perbutyl H, manufactured by NOF Corporation) as peroxide.
After mixing 2 parts by weight with a Henschel mixer, 260-270 ° C
The mixture was heated and melted and kneaded with a twin-screw extruder at the temperature described above to obtain maleic anhydride-modified PPO. It was confirmed that the obtained modified PPO was modified with maleic anhydride in the same manner as in Production Example 4.

Example 1 85% by weight of polystyrene (SPS) having a syndiotactic structure obtained in Production Example 1, 5% by weight of maleic anhydride-modified PPO obtained in Production Example 4, N nylon-6,6 (Ube Industries, Ltd. ), Ube nylon 2020B) 10% by weight, total 100
(2,6-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by Adeka Argus Co., trade name: PEP-36) was used as an antioxidant.
7 parts by weight, 0.1 part by weight of 2,6-di-t-butyl-4-phenol (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer BHT) and p
After adding 1 part by weight of aluminum-(t-butyl) benzoate and dry-blending with a Henschel mixer, the mixture was melt-kneaded with a twin-screw extruder at a cylinder temperature of 300 ° C to form pellets.

Using the obtained pellets, injection molding was performed to obtain a tensile test specimen, and the tensile elastic modulus, water absorption, and retention of the tensile elastic modulus after water absorption were measured. The results are shown in Table 1.

Examples 2 to 5 and Comparative Examples 1 to 3 The same procedures as in Example 1 were carried out except that the styrene-based polymer, polyphenylene ether, polyamide, and additives were blended in the proportions shown in Table 1, and the tensile elastic modulus, water absorption, The retention of the tensile modulus after water absorption was measured. The results are shown in Table 1. For Example 3 and Comparative Example 3, the bending strength was also measured.

Example 6 85% by weight of polystyrene (SPS) having a syndiotactic structure obtained in Production Example 1, 5% by weight of maleic anhydride-modified PPO obtained in Production Example 4, nylon-6,6 (Ube Industries, Ltd.) (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by Adeka Argus Co., Ltd.) Name: PEP-36) 0.7
Parts by weight, tetrakis [methylene-3- (3 ', 5'-di-
t-butyl-4'-hydroxyphenyl)] propionate (trade name: MARK AO 60, manufactured by Adeka Argus) 0.1
Parts by weight and 1 part by weight of p- (t-butyl) benzoic acid were added, and dry blending was performed using a Henschel mixer. Then, aminosilane-treated glass fiber was used as a filler in a twin-screw extruder at a cylinder temperature of 300 ° C. While side-feeding 43 parts by weight, the mixture was melt-kneaded to form pellets.

Using the obtained pellets, injection molding was performed to obtain a tensile test piece and a bending test piece, and the tensile elasticity, water absorption, retention of tensile elasticity after water absorption, and thermal deformation temperature were measured. The results are shown in Table 2.

Examples 7 to 15 The same procedures as in Example 6 were carried out except that the styrene-based polymer, polyphenylene ether, polyamide, filler and additives were blended in the proportions shown in Table 3, to obtain a tensile modulus, water absorption,
The retention of the tensile modulus after water absorption and the heat distortion temperature were measured. The results are shown in Table 2.

For Example 10 and Comparative Example 4, the Izod impact value was also measured.

[Effects of the Invention] As described above, the styrenic resin composition of the present invention is excellent in impact resistance, water resistance, and mechanical properties, and is suitable for electric / electronic materials, industrial structural materials, automobile parts, home electric appliances, It is expected to be effective for various uses such as molding of industrial materials such as machine parts.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁶ , DB name) C08L 1/00-101/14 C08K 1/00-13/08

Claims (5)

(57) [Claims] 1. A composition comprising: (A) 99 to 1% by weight of a styrene polymer having a syndiotactic structure; and (B) polyphenylene ether or a mixture of polyphenylene ether and a styrene polymer having no functional group. A styrene resin composition comprising 0.1 to 50% by weight having a polar group and (C) 0.9 to 98.9% by weight of a polyamide. 2. The styrenic resin composition according to claim 1, wherein the polar group of the component (B) is an acid derivative. 3. A styrene resin composition comprising 100 parts by weight of the styrene resin composition according to claim 1 or 2 and 1 to 350 parts by weight of a filler surface-treated with (D) a coupling agent. 4. The styrene resin composition according to claim 3, wherein the coupling agent used for the surface treatment of the filler as the component (D) is a silane coupling agent. 5. A method comprising: (A ') 99 to 1% by weight of a styrene polymer having a syndiotactic structure and (B') polyphenylene ether or a mixture of polyphenylene ether and a styrene polymer having no functional group. Having a maleic anhydride group of 0.1
(C) polyamide 0.9 to 98.9% by weight (D ') A filler surface-treated with an aminosilane coupling agent is added to the above (A'), (B ') and (C) components in a total amount of 100%. A styrenic resin composition formulated in a proportion of 1 to 350 parts by weight with respect to parts by weight.