JPH0931276A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition containing syndiotactic polystyrene(SPS), keeping the characteristic excellent heat-resistance of SPS, exhibiting good flame-retarding property and scarcely generating corrosive gas at high temperature. SOLUTION: This flame-retardant resin is produced by compounding (A) 100 pts.wt. of a resin or a resin mixture consisting of (a) 10-100wt.% of SPS, (b) 0-10wt.% of a polymer having polar group and exhibiting compatibility or affinity to the component (a) and (c) 0-90wt.% of other thermoplastic resin and/or rubbery elastomer with (B) 2-100 pts.wt. of a halogenated polystyrene resin generating <=1,000wt.ppm of halogen atom based on the total halogen atom contained in the resin when left standing for 15min in an atmosphere of 300 deg.C and (C) a flame-retarding assistant at a weight ratio B/C of 1-10.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition, and more specifically, it retains excellent heat resistance originally possessed by syndiotactic polystyrene, and has good flame retardancy and thermal stability. The present invention also relates to a syndiotactic polystyrene-containing flame-retardant resin composition in which generation of corrosive gas at high temperature is suppressed.

[0002]

2. Description of the Related Art Conventionally, various kinds of flame-retardant resin compositions having excellent heat resistance have been widely used as materials for parts of electric and electronic devices. In recent years, in the field of electric and electronic devices, with the miniaturization, high performance, and cost reduction,
As a molding method, hot runners have been adopted, and further thermal stability has been required.
Furthermore, due to the effects of miniaturization and the like, the operating environment is becoming more severe, and the requirements for material performance are becoming stricter. On the other hand, polystyrene having a syndiotactic structure (hereinafter sometimes abbreviated as SPS) is known to have excellent heat resistance and chemical resistance, and the excellent heat resistance of SPS is Many studies have been conducted on the retained flame-retardant resin composition. However, in the conventional flame-retardant resin composition containing SPS, when it is used in a high temperature environment by taking advantage of the high heat resistance characteristic of SPS, or when molding at a high temperature necessary for molding SPS. However, due to insufficient heat resistance, there are problems that physical properties and molecular weight are reduced, or halogen compounds are generated to corrode adjacent metal materials.

[0003]

The present invention overcomes the drawbacks of the conventional flame-retardant resin composition containing SPS, retains the excellent heat resistance originally possessed by SPS, and is excellent in An object of the present invention is to provide an SPS-containing flame-retardant resin composition having flame retardancy and thermal stability, and suppressing generation of corrosive gas at high temperatures.

[0004]

Means for Solving the Problems As a result of intensive studies to develop a flame-retardant resin composition having the above-mentioned preferable properties, the present inventors have found that SPS, or SPS and a specific heavy chain having a polar group. By blending a specific halogenated polystyrene-based resin and a flame retardant aid in a predetermined ratio to a resin mixture with a coalesce or other thermoplastic resin and / or a rubber-like elastic body, the object is achieved. I found that
The present invention has been completed based on such findings.
That is, the present invention comprises (A) 10 to 100% by weight of a polystyrene-based resin having a syndiotactic structure, and (b) having compatibility or affinity with the component (a) and having a polar group. 0 to 10% by weight of polymer and (c) the above (a),
Thermoplastic resin other than (b) and / or rubber-like elastic body 0 to
With respect to 100 parts by weight of the resin or resin mixture consisting of 90% by weight, (B) the halogenated polystyrene resin, the amount of halogen atoms in the halogen compound generated when left for 15 minutes in an atmosphere of 300 ° C. 2 to 100 parts by weight of 1000 ppm by weight or less with respect to all halogen atoms contained in the resin, and (C) the flame retardant aid is (B) /
The present invention provides a flame-retardant resin composition containing (C) = 1 to 10 in a weight ratio.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the flame-retardant resin composition of the present invention, (a) a polystyrene resin having a syndiotactic structure is used as a component (A). here,
The syndiotactic structure is a syndiotactic structure having a stereochemical structure, that is, a steric structure in which a phenyl group or a substituted phenyl group which is a side chain with respect to a main chain formed from a carbon-carbon bond is alternately located in opposite directions. And its tacticity is quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon. ¹³ C-NM
The tacticity measured by the R method can be indicated by the abundance ratio of a plurality of continuous structural units, for example, diad in the case of 2, triad in the case of 3, and pentad in the case of 5. The polystyrene-based resin having a syndiotactic structure referred to in the invention is usually 75% or more, preferably 85% or more, in racemic dyad, or 30% or more, preferably 50% or more, in racemic pentad. Having polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene), poly (vinyl benzoate), hydrogenated polymers thereof and mixtures thereof, Alternatively, a copolymer containing these as main components is referred to. Here, as poly (alkylstyrene), poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiary-butylstyrene), poly (phenylstyrene), poly (vinylnaphthalene), There are poly (vinyl styrene) and the like, and as poly (halogenated styrene), there are poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene) and the like. Examples of poly (halogenated alkylstyrene) include poly (chloromethylstyrene), and examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Of these, particularly preferable polystyrene resins include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tertiarybutylstyrene), poly (p-chlorostyrene), poly (m). -Chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene and copolymers containing these structural units. In addition, the said polystyrene resin can be used individually by 1 type or in combination of 2 or more types.

There is no particular restriction on the molecular weight of this polystyrene resin, but the weight average molecular weight is preferably 10
It is 000 or more, more preferably 50,000 or more. Furthermore, the molecular weight distribution is not limited in its width, and various types can be applied. Here, if the weight average molecular weight is less than 10,000, the thermal properties and mechanical properties of the resulting composition or molded product may be deteriorated, which is not preferable. The polystyrene-based resin having such a syndiotactic structure is, for example, in an inert hydrocarbon solvent or in the absence of the solvent, using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst, a styrene-based monomer. It can be produced by polymerizing a body (a monomer corresponding to the polystyrene resin) (JP-A-62-187708). Regarding poly (halogenated alkylstyrene), JP-A-1-
No. 46912, the above hydrogenated polymer is disclosed in JP-A-1-17.
It can be obtained by the method described in Japanese Patent No. 8505.

Further, in the resin composition of the present invention,
As the component (A), in addition to the above component (a),
(B) a polymer having compatibility or affinity with the component (a) and having a polar group, and (c) a thermoplastic resin and / or a rubber-like elastic body other than the above (a) and (b) You may use in combination. The component (b), that is, the polymer having compatibility or affinity with the component (a) and having a polar group serves to improve the adhesiveness between the inorganic filler and the resin component, which are blended if necessary. have. Here, the polymer having compatibility or affinity with the component (a) refers to a polymer having a chain showing compatibility or affinity with the component (a) in the polymer chain. Examples of such a polymer include syndiotactic polystyrene, atactic polystyrene,
Isotactic polystyrene, styrene copolymer,
Examples thereof include those having polyphenylene ether, polyvinyl methyl ether, etc. as the main chain, block chain or graft chain. The polar group referred to here is (D)
There is no particular limitation as long as it is a group that improves the adhesiveness of the component to the inorganic filler. Specific examples of the polar group include an acid anhydride group, a carboxylic acid group, a carboxylic acid ester group, a carbonyl halide group, a carboxylic acid amide group, a carboxylic acid group, a sulfonic acid group, a sulfonic acid ester group, a sulfonyl chloride group, and a sulfonyl group. Examples thereof include amide group, sulfonate group, epoxy group, amino group, imide group, and oxazoline group.

Specific examples of the component (b) include styrene-maleic anhydride copolymer (SMA), styrene-glycidyl methacrylate copolymer, terminal carboxylic acid-modified polystyrene, terminal epoxy-modified polystyrene, terminal oxazoline-modified polystyrene, Terminal amine modified polystyrene, sulfonated polystyrene, styrene-based ionomer, styrene-methyl methacrylate graft polymer, (styrene-glycidyl methacrylate) -methyl methacrylate graft polymer, acid modified acrylic-styrene-graft polymer, (styrene-glycidyl methacrylate) -styrene graft Polymer, polybutylene terephthalate-polystyrene graft polymer,
Furthermore, maleic anhydride-modified syndiotactic polystyrene, fumaric acid-modified syndiotactic polystyrene, glycidyl methacrylate-modified syndiotactic polystyrene, amine-modified syndiotactic polystyrene, and other modified styrenic polymers, (styrene-maleic anhydride) -polyphenylene Examples thereof include ether graft polymers, maleic anhydride-modified polyphenylene ether, fumaric acid-modified polyphenylene ether, glycidyl methacrylate-modified polyphenylene ether, amine-modified polyphenylene ether, and other modified polyphenylene ether-based polymers. Among these, modified polyphenylene ether and modified syndiotactic polystyrene are particularly preferable.

The above modified polyphenylene ether can be obtained by modifying a known polyphenylene ether with a modifier, but the method is not limited to this method as long as it can be used for the purpose of the present invention. The polyphenylene ether is a known compound, and for this purpose, US Pat. Nos. 3,306,874 and 3,306,87 have been used.
No. 5, No. 3,257,357 and No. 3,257,358 can be referred to. Polyphenylene ethers are usually prepared by oxidative coupling reactions to form homopolymers or copolymers in the presence of copper amine complexes, one or more di- or tri-substituted phenols. Here, the copper amine complex may be a copper amine complex derived from primary, secondary and tertiary amines. Examples of suitable polyphenylene ethers include poly (2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-chloromethyl-
1,4-phenylene ether), poly (2-methyl-6)
-Hydroxyethyl-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-trimethyl-1,4-phenylene ether), poly [2- (4'-methylphenyl) -1,4-
Phenylene ether], poly (2-bromo-6-phenyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2-phenyl-1,4-) Phenylene ether), poly (2-chloro-1,4-phenylene ether), poly (2-methyl-1,4-phenylene ether), poly (2-chloro-6-ethyl-1,4-phenylene ether), Poly (2-chloro-6-bromo-1,4-phenylene ether), poly (2,6-di-n-propyl-
1,4-phenylene ether), poly (2-methyl-6)
-Isopropyl-1,4-phenylene ether), poly (2-chloro-6-methyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2 , 6-dibromo-1,4-phenylene ether), poly (2,6-dichloro-1,4)
-Phenylene ether), poly (2,6-diethyl-)
1,4-phenylene ether) and poly (2,6-dimethyl-1,4-phenylene ether).

Also suitable are copolymers, such as copolymers derived from two or more of the phenolic compounds used, for example, in the preparation of said homopolymers. Further examples include graft copolymers and block copolymers of vinyl aromatic compounds such as polystyrene and the above-mentioned polyphenylene ether. Of these, poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferably used.

As the modifier used for modifying these polyphenylene ethers, compounds having an ethylenic double bond and a polar group in the same molecule can be used. Examples of such modifiers include maleic anhydride, maleic acid,
Maleic acid ester, maleimide and its N-substituted product, maleic acid such as maleic acid salt, fumaric acid, fumaric acid ester, fumaric acid such as fumarate, itaconic anhydride, itaconic acid, itaconic acid ester, itaconic acid salt, etc. Itaconic acid, acrylic acid, acrylic ester,
Examples thereof include (meth) acrylic acid such as acrylic acid amide, acrylic acid salt, methacrylic acid, methacrylic acid ester, methacrylic acid amide, methacrylic acid salt, and glycidyl methacrylate. Of these, maleic anhydride, fumaric acid and glycidyl methacrylate are particularly preferable. These modifiers may be used alone or in combination of two or more.

The modified polyphenylene ether can be obtained by reacting the polyphenylene ether with a modifying agent in the presence of a solvent or another resin. There is no particular limitation on the modification method, and a known method, for example, a roll mill, a Banbury mixer, an extruder, etc., is used.
A method of melt-kneading and reacting at a temperature in the range of to 350 ° C., a method of heating and reacting in a solvent such as benzene, toluene, xylene and the like can be used. Further, in order to facilitate these reactions, benzoyl peroxide; di-t-butyl peroxide; dicumyl peroxide; t-butyl peroxybenzoate; azobisisobutyronitrile; azobisisovalero are added to the reaction system. Nitrile; 2,3-diphenyl-2,3-
The presence of a radical generator such as dimethylbutane is effective. A preferable method is a method of melt-kneading in the presence of a radical generator. Among the modified polyphenylene ethers thus obtained, maleic anhydride modified polyphenylene ether, fumaric acid modified polyphenylene ether and glycidyl methacrylate modified polyphenylene ether are particularly preferable.

Further, a modified SPS having a polar group can be used as the component (b). The modified SPS can be obtained, for example, by modifying the SPS shown in the component (a) with a modifying agent, but the modified SPS is not limited to this method as long as it can be used for the purpose of the present invention. .
The SPS used for modification is not particularly limited, and the polymer shown in the component (a) can be used,
Particularly, a copolymer of styrene and substituted styrene is preferably used from the viewpoint of compatibility with other components. The composition ratio of the copolymer is not particularly limited, but the content of the substituted styrene unit is preferably in the range of 3 to 50 mol%. If this content is less than 3 mol%, modification is difficult, and if it exceeds 50 mol%, the compatibility with other components decreases, which is not preferable. Particularly preferred substituted styrenes include, for example, alkylstyrenes such as methylstyrene, ethylstyrene, isopropylstyrene, tert-butylstyrene and vinylstyrene, halogenated styrenes such as chlorostyrene, bromostyrene and fluorostyrene, halogenated styrenes such as chloromethylstyrene. Alkyl styrene,
Examples thereof include alkoxy styrene such as methoxy styrene and ethoxy styrene. These substituted styrenes may be used alone or in combination of two or more.
If the amount used is 5% by weight or less based on SPS,
The above polymer having an atactic structure can also be used.
If it is used in an amount of more than 5% by weight, the heat resistance of the composition is lowered, which is not preferable.

Examples of the modifying agent used for modifying the SPS include the same modifying agents as those exemplified in the description of the modified polyphenylene ether, and maleic anhydride, fumaric acid and glycidyl methacrylate are particularly preferable. These modifiers may be used alone or in combination of two or more. As the modification method, the same method as the modification method of the polyphenylene ether can be used. Among the modified SPS thus obtained, particularly maleic anhydride modified SPS, fumaric acid modified SPS and glycidyl methacrylate modified SPS
PS is preferred. In the present invention, the polymer as the component (b) may be used alone or in combination of two or more kinds. The content of polar groups in the polymer is 0.0
A range of 1 to 20% by weight is preferred. This content is 0.01
If it is less than 10% by weight, it is necessary to add a large amount of the component (b) in order to exert the adhesive effect with the inorganic filler, and as a result, the mechanical properties and heat resistance of the composition deteriorate, which is not preferable. Further, if it exceeds 20% by weight, the compatibility with the component (a) decreases, which is not preferable. From the viewpoints of the adhesiveness with the inorganic filler and the compatibility with the component (a), the polar group content in the polymer is preferably 0.05 to 10% by weight.
Further, the above (a) used as the component (c),
In the thermoplastic resin and / or rubber-like elastic body other than (b), examples of the thermoplastic resin include polystyrene having an atactic structure, polystyrene having an isotactic structure, styrene polymers such as AS resin and ABS resin, and polyethylene terephthalate. Polyester resin such as polyethylene naphthalate, polycarbonate, poly (thio) ether resin such as polyphenylene ether, polyphenylene sulfide, polyoxymethylene, polysulfone resin such as polysulfone and polyethersulfone, polyacrylic acid, polyacrylic ester , Polymethylmethacrylate and other acrylic polymers, polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, ethylene-propylene copolymer and other polyolefin-based polymers Body, polyvinyl chloride, polyvinylidene chloride, halogen-containing vinyl compound polymer such as polyvinylidene fluoride, nylon 6, nylon 46, and polyamide resins such as nylon 66 and the like.

On the other hand, examples of the rubber-like elastic material include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, silicone rubber, shrimp chlorohydrin rubber, and styrene-butadiene block copolymer. Polymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEB)
S), styrene-isoprene block copolymer (SI
R), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-
Styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene random copolymer, ethylene propylene rubber (EPR),
Ethylene propylene diene rubber (EPDM), or butadiene-acrylonitrile-styrene-core shell rubber (ABS), methyl methacrylate-butadiene-
Styrene-core shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core shell rubber (MAS), octyl acrylate-butadiene-styrene-core shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene core shell rubber (AABS), butadiene -Styrene-core shell rubber (SBR), core-shell type particulate elastic bodies such as siloxane-containing core shell rubbers such as methyl methacrylate-butyl acrylate-siloxane, or rubbers obtained by modifying these. Among these, especially SBR, SBS, SEB, SEB
S, SIR, SEP, SIS, SEPS, core shell rubber and rubbers modified with these are preferably used.

The thermoplastic resin or the rubber-like elastic body as the component (c) may be used alone or in combination of two or more kinds. In the composition of the present invention, the blending ratio of each component in the component (A) is such that the component (a) is 10 to 10 based on the total amount of the component (a), the component (b) and the component (c).
100% by weight, 0 to 10% by weight of component (b) and (c)
The components are in the range of 0 to 90% by weight. If the amount of the component (a) is less than 10% by weight, the composition obtained will not exhibit the SPS characteristics sufficiently and the object of the present invention will not be achieved.
In order to effectively exhibit the characteristics of SPS, the content of the component (a) is preferably in the range of 30 to 100% by weight, and particularly 4
A range of 0 to 100% by weight is suitable. Further, if the amount of the component (b) compounded exceeds 10% by weight, the resulting composition has poor mechanical properties and solvent resistance. Furthermore, when the content of the component (c) exceeds 90% by weight, the composition obtained is SPS.
Is not fully exhibited and heat resistance and the like are reduced. S
In order to effectively exhibit the characteristics of PS, the content of the component (c) is preferably in the range of 0 to 70% by weight, particularly 0 to 60%.
A range of weight percent is preferred.

In the resin composition of the present invention, a halogenated polystyrene resin is used as the component (B). This halogenated polystyrene-based resin has a function as a flame retardant, and has at least one hydrogen atom of the benzene ring of the polystyrene-based resin and / or at least one hydrogen atom other than the benzene ring substituted with a halogen atom. Is. In this halogenated polystyrene resin, the halogen atom bonded to the site other than the benzene ring is eliminated at a temperature of about 200 ° C. to become a halogen compound and evaporate, but the halogen atom bonded to the benzene ring is It is known that desorption does not occur even at a temperature of about 300 ° C.

In the present invention, the halogenated polystyrene resin as the component (B) is used in an atmosphere of 300 ° C.
The amount of halogen atoms in the halogen compound generated when the resin is left for 10 minutes is 10 with respect to all the halogen atoms contained in the resin.
It is not more than 00 ppm by weight. The amount of this halogen atom is 1
If the amount exceeds 000 ppm by weight, unfavorable situations such as metal corrosion during molding of the composition and deterioration of residence stability of the composition are brought about. From the viewpoint of corrosion resistance and thermal stability, the amount of halogen atoms is preferably 800 ppm by weight or less, and particularly preferably 600 ppm by weight or less. As such a halogen-containing polystyrene-based resin, a resin in which a halogen atom is bound to only the benzene ring is practically used. Here, “having a halogen atom bound to only the benzene ring” means that an impurity having a halogen atom bound to a site other than the benzene ring is included as an impurity in a range satisfying the above conditions. Means good. Further, the content of halogen atoms in the halogen-containing polystyrene resin is preferably 30% by weight or more, particularly 40% in order to exhibit good flame retardancy.
% By weight or more is preferred. The halogenated polystyrene-based resin is preferably a brominated polystyrene-based resin in which a bromine atom is bonded only to the benzene ring. In addition,
This brominated polystyrene-based resin can be produced, for example, by polymerizing a brominated styrene-based monomer in which all bromine is attached only to the benzene ring. In addition, this brominated polystyrene-based resin contains a bromine atom bound to a site other than a benzene ring as an impurity, which is contained in a bromine compound generated when the resin is left in an atmosphere of 300 ° C. for 15 minutes. The content of bromine atoms may be 1000 ppm by weight or less based on all bromine atoms contained in the resin.

The method for producing the halogenated polystyrene resin used as the component (B) is not particularly limited. For example, a halogenated styrene monomer having a halogen atom bonded to only the benzene ring is homopolymerized or otherwise. Examples thereof include a method of copolymerizing with the above monomer, a method of halogenating the polymerized styrene resin, a method of blending the products obtained by these methods, and the like. Among these methods, a method of homopolymerizing a halogenated styrenic monomer in which a halogen atom is bonded only to the benzene ring is preferable. In the composition of the present invention, the halogenated polystyrene-based resin as the component (B) is based on 100 parts by weight of the resin as the component (A) or the resin mixture.
It is compounded at a ratio of 2 to 100 parts by weight. If this amount is less than 2 parts by weight, the flame retardant performance of the composition will be insufficient, and 100
If it exceeds the weight part, the effect of improving the flame retardancy is not seen for the amount, but rather the mechanical properties are deteriorated. From the viewpoints of flame retardancy and mechanical properties, etc., the preferable amount of the component (B) is 5 to 100 parts by weight, particularly 10 to 80 parts by weight.

In the composition of the present invention, the flame retardant aid used as the component (C) is not particularly limited, and any of those conventionally used as a flame retardant aid for polystyrene resins can be selected. It can be selected and used. Examples of the flame retardant aids include antimony oxides such as antimony trioxide and antimony pentoxide, alkali metal salts of antimonic acid such as sodium antimonate,
Alkaline earth metal salts of antimonic acid, metal antimony,
Examples thereof include antimony-based flame retardant aids such as antimony trichloride, antimony pentachloride, antimony trisulfide and antimony pentasulfide, as well as zinc borate, barium metaborate, zirconium oxide, iron oxide and zinc oxide. Among these, antimony oxide, an alkali metal salt of antimonic acid, an alkaline earth metal salt of antimonic acid, iron oxide and zinc oxide are preferable from the viewpoint of performance and economical efficiency, and diantimony trioxide is particularly preferable. The flame retardant aid of the component (C) may be used alone or in combination of two or more. The blending amount is selected in the range of 1 to 10 in the weight ratio of the (B) / (C) component. If this weight ratio is less than 1, the effect as a flame retardant aid is insufficient, and 10
If it exceeds the above range, the effect as a flame retardant aid is not improved for its amount, and rather other physical properties may be impaired.

In the composition of the present invention, if desired,
An inorganic filler may be added for the purpose of further improving the mechanical properties and heat resistance of the composition. As this inorganic filler, those subjected to surface treatment with a coupling agent are preferably used in order to enhance the adhesiveness with the resin component. Here, there are various inorganic filler materials such as fibrous, granular, and powdery materials. Examples of the fibrous filler include glass fiber, carbon fiber, whiskers, ceramic fiber, metal fiber and the like. Specifically, as whiskers, boron, alumina, silica, silicon carbide, etc., as ceramic fibers, gypsum, potassium titanate, magnesium sulfate, magnesium oxide, etc., as metal fibers, copper,
There are aluminum, steel, etc. Here, the shape of the filler includes cloth, mat, bundle cutting, short fiber, filament, and whiskers. In the case of the bundle cutting, the length is preferably 0.05 to 50 mm and the fiber diameter is 5 to 20 μm. In the case of a cloth or mat, the length is preferably 1 mm or more, more preferably 5 mm or more.

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, Examples thereof include tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flakes and glass beads. Among these fillers, especially glass fillers such as glass filaments, glass fibers, glass rovings, glass mats, glass powders, glass flakes,
Glass beads are preferred.

Further, as the surface-treated inorganic filler,
Examples include those obtained by surface-treating the above-mentioned inorganic filler with a coupling agent usually used for surface treatment, such as a silane coupling agent or a titanium coupling agent.
Specific examples of the silane coupling agent include triethoxysilane and vinyltris (β-methoxyethoxy).
Silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β
-(1,1-Epoxycyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)
-Γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-
Aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl-tris (2-methoxy-ethoxy) silane, N-methyl-γ -Aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, triaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane,
Examples include 3-4,5 dihydroimidazolepropyltriethoxysilane, hexamethyldisilazane, N, N-bis (trimethylsilyl) urea and the like. Of these, preferred are γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and β- (3,4- Epoxy cyclohexyl)
Aminosilanes such as ethyltrimethoxysilane and epoxysilanes.

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

The surface treatment of the above-mentioned inorganic filler using such a coupling agent may be carried out by an ordinary known method without any particular limitation. For example, a sizing treatment method in which an organic solvent solution or suspension of the above coupling agent is applied to a filler as a so-called sizing agent, or drying using a Henschel mixer, super mixer, Loedige mixer, V-type blender or the like. The mixing method, the spray method, the integral blending method, the dry concentrate method, or the like can be performed by an appropriate method depending on the shape of the filler, but the sizing treatment method, the dry mixing method, and the spray method are preferable. Further, a film-forming substance for glass can be used together with the above coupling agent. The film-forming substance is not particularly limited, and examples thereof include polyester-based, urethane-based, epoxy-based, acrylic-based, vinyl acetate-based, and polyether-based polymers.

In the composition of the present invention, the inorganic filler as the component (D) may be used alone or in combination of two or more kinds. Further, the blending amount thereof is selected in the range of 1 to 350 parts by weight per 100 parts by weight of the total amount of the above-mentioned components (A), (B) and (C). If this amount is less than 1 part by weight, the effect of improving mechanical properties such as tensile strength will not be sufficiently exerted, and if it exceeds 350 parts by weight, toughness and impact resistance will tend to be reduced. From the viewpoint of mechanical properties such as tensile strength, toughness, impact resistance, etc., the preferable blending amount of the inorganic filler is in the range of 5 to 300 parts by weight, and particularly 1
A range of 0 to 250 parts by weight is preferred. In the resin composition of the present invention, various additives such as a halogen scavenger, a nucleating agent, an antioxidant, a light stabilizer, a lubricant, a plasticizer, an electrostatic charge may be added, if necessary, within a range not impairing the object of the present invention. Inhibitors, release agents, colorants, etc. may be added.

Here, the halogen scavenger improves the thermal stability of the halogenated polystyrene resin as the component (B), which is a flame retardant, and improves the corrosion resistance of the mold and the retention stability of the composition. Therefore, for example, hydrotalcites and the like are preferably used. As the nucleating agent, a general organic nucleating agent or an inorganic nucleating agent can be used. For example, di-p
-Tert-butylbenzoic acid metal salt, p-tert-
Butylbenzoic acid metal salt, cyclohexanecarboxylic acid sodium salt, β-naphthoic acid sodium salt and other carboxylic acid metal salts, 2,2′-methylenebis (4,6-di-t-butylphenyl) metal phosphate Examples thereof include organic phosphorus compounds such as salts. Examples of the antioxidant include pentaerythrityl-tetrakis [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate], n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate,
Examples include (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite. Examples of the light stabilizer include di- (2,2,6,6-
Tetramethyl-4-piperidyl) sebacate; 4-benzoyloxy-2,2,6,6-tetramethylpiperidine; 1,2,3,4-tetra- (2,2,6,6-tetramethyl-4- Hindered amine compounds such as piperidyl) butanetetracarboxylate, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2
-(2-Hydroxy-5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t
Examples thereof include benzotriazole-based compounds such as -butylphenyl) benzotriazole.

Examples of the lubricant include fatty acids such as stearic acid and behenic acid, fatty acid metal salts such as zinc stearate, calcium stearate and magnesium stearate, and ethylenebisstearamide. Examples of the plasticizer include polyethylene. Examples thereof include glycol, polyamide oligomer, phthalate ester, polystyrene oligomer, polyethylene wax, mineral oil, silicone oil and the like. The method for preparing the resin composition of the present invention is not particularly limited and can be prepared by a known method. For example, the component (A),
Component (B), component (C), and optionally component (D) and various additives, ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single screw extruder, twin screw extruder ，
270 by using a co-kneader or multi-screw extruder
The resin composition of the present invention can be obtained by melt-kneading at a temperature of about 320 ° C.

[0029]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The components used for the preparation of the resin composition are shown below. (A) Component (a) SPS: 1,2,4-trichlorobenzene as a solvent,
Polystyrene-equivalent weight average molecular weight Mw = 225,000, measured by GPC method at 150 ° C., weight average molecular weight / number average molecular weight (Mw / Mn) = 2.70 (A) (b) component MA-PPE: maleic anhydride modified Polyphenylene ether. Prepared in Production Example 1 (A) (c) component G1651: Hydrogenated SEBS manufactured by Shell Chemical Co., Ltd., trade name “Clayton G1651” 2015B: Nylon 66 manufactured by Ube Industries, trade name “20”
15B "

Component (B) (brominated polystyrene) poly (MBS): In toluene, 4 mol / liter of monobromostyrene (manufactured by Aldrich) and 8.84 mmol / liter of azobisisobutyronitrile (AIBN). Monobromostyrene polymer obtained by polymerization at 60 ° C (Mw 203000, Br content 43.6% by weight, bromine generation amount after standing at 300 ° C for 15 minutes 50% by weight p
pm) poly (DBS): in toluene, dibromostyrene [synthesized and purified by the method described in "Journal of the Chemical Society of Japan", page 633 (1992)] 2 mol / liter and AIBN 9.19 mmol / liter were used. , A dibromostyrene polymer polymerized at 60 ° C. (Mw 199000, B
r content 61.0% by weight, bromine generation amount after standing for 15 minutes at 300 ° C. 55% by weight) poly (TBS): tribromostyrene (FR803 manufactured by Bromochem Far East Co., Ltd., purified with methanol) in toluene ) 0.8 mol / l and AIBN
Tribromostyrene polymer (Mw 211000, Br content 70.3 wt%, bromine generation amount 80 wt ppm after standing at 300 ° C. for 15 minutes) polymerized at 60 ° C. using 4.61 mmol / liter PDBS-80: Brominated polystyrene manufactured by Great Lakes (Mw 54000, Br content 59.0% by weight, 30
The amount of bromine generated after standing at 0 ° C. for 15 minutes of 250 ppm by weight) The above is a brominated polystyrene with a small amount of bromine compounds generated. Next, Br-poly (TBS): poly (TBS) as described above
Polymer Journal Vol. 26, No. 7 (1994), 823
Brominated polystyrene with bromine added to the chain by the method described on the page (Mw = 210,000, Br content 71.1% by weight,
Generation of bromine after standing at 300 ° C for 15 minutes 8100 weight p
pm) Pyrocheck 68PB (68PBC): Brominated polystyrene manufactured by Nissan Ferro Co., Ltd. (Mw = 241000, Br content 67.0% by weight, bromine generation amount after standing at 300 ° C. for 15 minutes 5200 ppm by weight) The amount was calculated as follows. First, 1
0 g of brominated polystyrene was placed in a sealed glass container of 1 liter, heated at 300 ° C. for 15 minutes, bubbling an internal gas with 100 ml of pure water to dissolve the generated bromine compound, and quantified by titration. Next, based on this quantification result, it was calculated by the following formula. Bromine generation amount (ppm) = (bromine amount determined by the above method)
/ (Amount of bromine in brominated polystyrene) x 1,000,000

Component (C) ATOX-S: Antimony trioxide manufactured by Nippon Seiko Co., Ltd., trade name "ATOX-S" (D) Component JAFT712: Glass fiber manufactured by Asahi Fiber Glass Co., Ltd.
Product name "JAFT712" JAFT-2A: glass fiber manufactured by Asahi Fiber Glass Co., Ltd.,
Trade name "JAFT-2A" FB74: fused silica manufactured by Denki Kagaku Kogyo Co., Ltd., trade name "FB"
74 "Other additives Irganox 1010: Antioxidant manufactured by Ciba Geigy, trade name" Irganox 1010 ", pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-
4-Hydroxyphenyl) propionate] DHT-4A: Kyowa Chemical Co., Ltd. halogen scavenger, trade name "DHT-4A", basic aluminum magnesium carbonate hydrate NA11: ADEKA ARGUS antioxidant, trade name " N
A11 "phosphoric acid 2,2'-methylene-bis- (4,6-
Di-t-butylphenyl) sodium

Production Example 1 Production of maleic anhydride-modified polyphenylene ether Polyphenylene ether (intrinsic viscosity 0.47 deciliter / g, in chloroform, 25 ° C.) 1 kg, maleic anhydride 60 g, 2,3-dimethyl-as a radical generator
Dry blend of 10 g of 2,3-diphenylbutane [NOFMER BC, trade name] manufactured by NOF CORPORATION, 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 polyphenylene ether. To measure the denaturation rate, 1 g of the obtained modified polyphenylene ether was dissolved in ethylbenzene and then reprecipitated in methanol, and the recovered polymer was Soxhlet extracted with methanol. After drying, the denaturation rate was determined by titration and carbonyl absorption intensity of IR spectrum. I asked. At this time, the modification rate was 2.0% by weight.

Example 1 (A) SPS (Mw225000, as component (a),
Mw / Mn 2.70) 100 parts by weight, flame retardant poly (MBS) as component (B) (monobromostyrene polymer in which bromine is bonded only to the benzene ring) 36.70 parts by weight, as component (C) Flame retardant auxiliary agent ATOX-S (manufactured by Nippon Seiko Co., Ltd., antimony trioxide) 4.3 parts by weight and Irganox 1010 (manufactured by Ciba Geigy) as an antioxidant.
5 parts by weight are mixed, and the resin temperature is set to 300 by using a twin-screw extruder.
The resin composition was prepared by kneading at 0 ° C. and pelletizing. With respect to this resin composition, retention stability, corrosion inhibition and flame retardancy were evaluated according to the following methods.

(1) Retention stability Pellets were formed on an injection molding machine at a cylinder temperature of 290 ° C.
The tensile strength of the dumbbell molded under the conditions of a mold temperature of 80 ° C. and the dumbbell molded under the same conditions as above after being retained in the cylinder of the molding machine for 10 minutes was measured according to JIS K-711.
The retention stability was obtained from the following equation. Retention stability (%) = (10 minutes retention dumbbell tensile strength) / (dumbbell non-retention tensile strength) x 100 (2) Corrosion prevention 5g sample pellets were placed in a 50 milliliter Erlenmeyer flask, and a silver plate was added. After hanging and sealing so as not to touch the pellets, the discoloration of the silver plate after holding at 200 ° C. for 1 week was visually observed, and corrosion inhibition was evaluated according to the following criteria. ◯: No discoloration Δ: Slight discoloration ×: Significant discoloration (3) Flame retardance: 5 inch × 1/2 inch × 1/32 according to UL94
Combustion test was conducted using 5 inch test pieces, and V
The flame retardancy was evaluated by classifying into −0, V-1, V-2 and HB. Table 1 shows the results.

Examples 2 to 13 and Comparative Examples 1 to 6 Resin compositions having the composition shown in Table 1 were prepared in the same manner as in Example 1 and their performances were evaluated. The results are shown in Table 1.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

[0041]

[Table 6]

As can be seen from Table 1, all of the resin compositions of the present invention (Examples 1 to 13) have good retention stability and corrosion resistance, and also good flame retardancy. On the other hand, in Comparative Examples 1 to 5 in which the amount of halogen generation (the amount of bromine generation) after standing at 300 ° C. for 15 minutes exceeds 1000 ppm by weight, Comparative Examples 1 to 5 have poor retention stability and corrosion resistance. Since the retention stability and the corrosion preventive property of Comparative Example 6 containing no flame retardant are good, it is clear that the above-mentioned defective phenomenon is caused by the flame retardant of Comparative Example. Further, the effect of the present invention is sufficiently exhibited even in Example 11 in which a large amount of the inorganic filler is blended. Furthermore, comparing Examples 3 and 5 and Examples 4 and 6, Examples 5 and 6 in which a halogen scavenger is blended have the same flame retardancy, but better retention stability.

[0043]

The flame-retardant resin composition of the present invention retains the excellent heat resistance inherent in SPS, has good flame retardancy, and suppresses the generation of corrosive gas at high temperatures. Moreover, it has characteristics such as good retention stability at high temperature. The resin composition of the present invention is suitably used as a material for parts such as connectors in the electric and electronic fields, parts such as connectors in the field of automobiles, and other useful parts. In particular, it is suitable for using hot runners to improve productivity and for materials of parts that insert metal and are exposed to high temperature atmosphere.

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[Procedure amendment]

[Submission date] September 12, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

In the composition of the present invention, the flame retardant aid used as the component (C) is not particularly limited, and any of those conventionally used as a flame retardant aid for polystyrene resins can be selected. It can be selected and used. Examples of the flame retardant aids include antimony oxides such as antimony trioxide and antimony pentoxide, alkali metal salts of antimonic acid such as sodium antimonate,
Alkaline earth metal salts of antimonic acid, metal antimony,
Examples thereof include antimony-based flame retardant aids such as antimony trichloride, antimony pentachloride, antimony trisulfide and antimony pentasulfide, as well as zinc borate, barium metaborate, zirconium oxide, iron oxide and zinc oxide. Among these, antimony oxide, an alkali metal salt of antimonic acid, an alkaline earth metal salt of antimonic acid, iron oxide and zinc oxide are preferable from the viewpoint of performance and economical efficiency, and diantimony trioxide is particularly preferable. The flame retardant aid of the component (C) may be used alone or in combination of two or more. The blending amount is selected in the range of 1 to 10 in the weight ratio of the (B) / (C) component. This weight ratio is 10
If it exceeds, the effect as a flame retardant aid is insufficient, and
If it is less than 1 , the effect as a flame retardant aid is not improved relative to the amount, and rather other physical properties may be impaired.

Claims (6)

[Claims] 1. (A) (a) 10 to 100% by weight of a polystyrene resin having a syndiotactic structure, and (b)
0 to 10% by weight of a polymer having compatibility or affinity with the component (a) and having a polar group, and (c) the above (a) and (b)
Other than 100 parts by weight of a resin or resin mixture containing 0 to 90% by weight of a thermoplastic resin and / or a rubber-like elastic body other than (B) halogenated polystyrene resin,
The amount of halogen atoms in the halogen compound generated when left in an atmosphere of 00 ° C for 15 minutes is 1000 ppm by weight or less based on all halogen atoms contained in the resin 2.
~ 100 parts by weight, and (C) flame retardant aid is (B) / (C)
A flame-retardant resin composition prepared by blending a weight ratio of 1 to 10. 2. The flame-retardant resin composition according to claim 1, wherein the halogenated polystyrene resin as the component (B) contains 30 wt% or more of halogen atoms. 3. The flame-retardant resin composition according to claim 1, wherein the halogenated polystyrene resin as the component (B) is a brominated polystyrene resin in which a bromine atom is bonded only to the benzene ring. 4. The brominated polystyrene resin as the component (B), which is a brominated polystyrene resin obtained by polymerizing a brominated styrene monomer in which all bromine is attached only to the benzene ring. Flame-retardant resin composition. 5. The flame retardant aid of component (C) is at least one selected from antimony oxide, alkali metal salts of antimonic acid, alkaline earth metal salts of antimonic acid, iron oxide and zinc oxide. The flame-retardant resin composition according to claim 1. 6. The (D) inorganic fillers 1 to 3 per 100 parts by weight of the total amount of the (A) component, (B) component and (C) component.
The flame-retardant resin composition according to claim 1, which comprises 50 parts by weight.