JPH07196868A - Polystyrene resin composition - Google Patents

Abstract

PURPOSE:To obtain a syndiotactic polystyrene resin composition markedly excellent in heat resistance and durability by mixing a syndiotactic styrene polymer with a phenolic antioxidant and a sulfur antioxidant in a specified mixing ratio. CONSTITUTION:The resin composition is prepared by mixing 100 pts.wt. syndiotactic styrene polymer with 0.005-5.0 pts.wt. phenolic antioxidant (e.g. 2,6-di-t-butyl-4-methylphenol or 2,2'-methylenebis (4-methyl-6-t-butylphenol)) and 0.005-5.0 pts.wt. sulfur antioxidant (e.g. dilauryl 3,3'-thiodipropionate or 2- mercaptobenzimidazole). Desirably, 100 pts.wt. this composition is mixed with 1-350 pts.wt. inorganic filler (e.g. alumina or silica).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polystyrene resin composition and a molded article thereof, and more specifically, it is made of a styrene polymer having a high syndiotactic structure, and is used for mechanical parts, electrical components, etc. The present invention relates to a polystyrene resin composition suitable for electronic parts, films, fibers and the like, and a molded product thereof.

[0002]

2. Description of the Related Art Conventionally, a styrene polymer having a syndiotactic structure (hereinafter sometimes abbreviated as SPS).
Has excellent heat resistance, chemical resistance, water resistance, etc. and is used as a material for various molded products. In particular, SPS is used as a material for molded products that require high heat resistance and durability because of its high heat resistance. However, molded products consisting only of SPS are exposed to heat and oxygen when exposed to high temperatures for a long time. It deteriorates due to such effects as described above, and unfavorable problems such as deterioration of mechanical strength and deterioration of color tone occur. In order to improve such a problem, a phenolic antioxidant is generally used as a stabilizer, but in the field where high heat resistance and durability are required, the effect is still not sufficient. It was

[0003]

Therefore, the present inventors
While maintaining the excellent properties of SPS, S has improved heat resistance, durability, etc. for long-term use at high temperatures.
Diligent studies were conducted to develop a PS resin composition.

[0004]

As a result, heat resistance, durability, etc. have been remarkably improved by blending SPS or SPS blended with another resin with a specific antioxidant within a certain range. It was found that an SPS resin composition can be obtained. The present invention has been completed based on such findings.

That is, the present invention provides (a) 100 parts by weight of (A) a styrene polymer having a syndiotactic structure, and (B) a phenolic antioxidant.
0.005-5.0 parts by weight, and (C) sulfur-based antioxidant
0.005 to 5.0 parts by weight of a polystyrene resin composition, (b) (A) 1 to 99% by weight of a styrene polymer having a syndiotactic structure, and (D) (A) component And a thermoplastic resin other than the component (E) and / or a rubber-like elastic body 99 to 1
% By weight, (B) a phenolic antioxidant,
0.005 per 100 parts by weight of the total of the component and the component (D)
To 5.0 parts by weight, and (C) a sulfur-based antioxidant, based on 100 parts by weight of the total of the components (A) and (D).
Styrene-based resin composition prepared by blending 005-5.0 parts by weight, (C) (A) styrene-based polymer having syndiotactic structure 90.0-99.9% by weight, (E) polyphenylene ether And / or modified polyphenylene ether 10.0
0.1% by weight, and (B) a phenolic antioxidant is added to 100 parts by weight of the total of the components (A) and (E).
005 to 5.0 parts by weight, and (C) a sulfur-based antioxidant in an amount of 0.005 to 5.0 parts by weight based on 100 parts by weight of the total of the components (A) and (E). (D) 1 to 99% by weight of (A) styrene polymer having syndiotactic structure, thermoplastic resin and / or rubber other than (D), (A) and (E) components Elastic body 99-1
% By weight of (E) polyphenylene ether and / or modified polyphenylene ether, relative to 100 parts by weight of the total of the components (A) and (D), 0.1 to 10.0 parts by weight,
(B) Phenol-based antioxidant was added to 100 parts by weight of the total of the above components (A), (D) and (E).
005 to 5.0 parts by weight, and (C) a sulfur-based antioxidant as a total of 100 of the above (A) component, (D) component and (E) component.
Polystyrene resin composition obtained by blending 0.005 to 5.0 parts by weight with respect to parts by weight, (e) 100 parts by weight of the polystyrene resin composition according to any one of (a) to (d) above. Inorganic filler for 1 part
To 350 parts by weight of the polystyrene resin composition according to any one of (a) to (d) above, or (f) the polystyrene resin according to any one of (a) to (e) above. The present invention provides a resin molded product made of the composition.

The above invention will be described in more detail below.
The styrene-based polymer as the component (A) contained in the resin composition of each of the inventions (a) to (f) described above (hereinafter sometimes referred to as the invention) has a high syndiotactic structure. Here, the highly syndiotactic structure means that the steric structure is a syndiotactic structure, that is, a phenyl group or a substituted phenyl group which is a side chain with respect to the main chain formed from carbon-carbon bonds. Have a steric structure in which they are alternately located in opposite directions, and their tacticity is determined by the nuclear magnetic resonance method ( ¹³ C
-NMR method). ^The tacticity measured by the ¹³ C-NMR 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. However, the styrene-based polymer having a syndiotactic structure referred to in the present invention is usually 75% or more, preferably 85% or more in racemic dyad, or 30% or more, preferably 50% or more in racemic pentad. Polystyrene with syndiotacticity, poly (alkylstyrene), poly (halogenated styrene),
The term refers to poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (vinyl benzoic acid ester), hydrogenated polymers thereof and mixtures thereof, or copolymers containing these as the main components. 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. The poly (halogenated alkylstyrene) includes poly (chloromethylstyrene), and the poly (alkoxystyrene) includes poly (methoxystyrene) and poly (ethoxystyrene).

Of these, particularly preferred styrene polymers are 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 styrene-type polymer can be used individually by 1 type or in combination of 2 or more types. The styrene-based polymer is not particularly limited in molecular weight, but the weight average molecular weight is preferably 10,000 or more, more preferably 50,000 or more. Further, the molecular weight distribution is not limited in its width or width, and various kinds can be applied. Here, if the weight average molecular weight is less than 10,000, mechanical properties such as thermal properties and mechanical strength of the obtained composition or molded product may be deteriorated, which is not preferable.

Such an SPS is obtained by using, for example, 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 styrene-based monomer (the above-mentioned styrene-based monomer). It can be produced by polymerizing a monomer corresponding to a polymer (JP-A-62-187708). Regarding poly (halogenated alkylstyrene), JP-A-1-46
No. 912, the above-mentioned hydrogenated polymer is described in JP-A 1-1785.
It can be obtained by the method described in Japanese Patent Publication No. 05.

As the component (A), a styrene polymer having a syndiotactic structure having a functional group can be used. Here, the styrene-based polymer having a syndiotactic structure having a functional group is a modification of the styrene-based polymer having a syndiotactic structure, and includes, for example, (1) a copolymerization reaction during polymerization. It is obtained by introducing a functional group by (2), introducing a functional group when the polymerization reaction is stopped, (3) grafting using the functional group of the above (1) or (2), but is not limited to these methods. Not something. Further, the modification rate is not particularly limited.

The styrene-based polymer having a syndiotactic structure, which is the component (A), is 1 to 99% by weight, preferably 5 to 5% by weight in the resin composition in the above invention (B).
The content is 95% by weight, more preferably 20 to 80% by weight. Further, such a polymer in the invention (C) is 9 to 99.9% by weight in the resin composition, and in the invention (D) is 1 to 98% by weight in the resin composition, preferably 5 to 95% by weight, more preferably 20 to 80% by weight.

Specific examples of the phenolic antioxidant of the component (B) contained in the resin composition of the present invention are 2,
6-di-t-butyl-4-methylphenol, 2,6-
Di-t-butyl-4-ethylphenol, 2,6-di-
t-butyl-4-phenylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol),
2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-)
6-n-nonylphenol), 4,4′-butylidenebis (3-methyl-6-t-butylphenol), 4,
4'-thiobis (3-methyl-6-t-butylphenol), 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2-t-butyl-6- ( 3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2-
[1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, n-octadecyl-3- (3,5-di-
t-Butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, triethylene glycol-bis [3- (3-t-butyl-5- Methyl-4-hydroxyphenyl) propionate], 1,6
-Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate],
2,2-thio-diethylenebis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t
-Butyl-4-hydroxy-hydrocinnamide),
3,9-bis [1,1-di-methyl-2- [β- (3-
t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetrachiosasbiro [5,5] undecane, N, N'-bis [3- (3,3 5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis ( n-octylthio) -6- (4-hydroxy-3,5
-Di-t-butylanilino) -1,3,5-triazine, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, tris (4-t
-Butyl-2,6-di-methyl-3-hydroxybenzyl) isocyanurate and the like.

Among these, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,
4'-thiobis (3-methyl-6-t-butylphenol), 2- [1- (2-hydroxy-3,5-di-t-
Pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, n-octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, triethylene glycol-bis [3-
(3-t-Butyl-5-methyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,9 -Bis [1,1-di-methyl-2
-[Β- (3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4
8,10-tetraoxaspiro [5,5] undecane,
Pentaerythrityl-tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4
-Hydroxy-3,5-di-t-butylanilino)-
1,3,5-triazine, 1,3,5-trimethyl-
2,4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Tris (3,5-di-t)
-Butyl-4-hydroxybenzyl) isocyanurate is preferred.

The phenolic antioxidant as the component (B) is the component (A) 100 according to the invention (a).
0.005-5.0 parts by weight, preferably 0.0
The amount is 1 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight. Further, such a compound is 100 parts by weight in total of the component (A) and the component (D) in the invention (b), whereas the compound (c) in the invention (c) is 100 parts by weight.
0 to 100 parts by weight of the total of the components and the component (E), and in the invention (d), 100 parts by weight of the total of the components (A), (D) and the components (E). .00
The amount is 5 to 5.0 parts by weight, preferably 0.01 to 2.0 parts by weight. In the present invention, these compounds may be used alone or in combination of two or more.

As the sulfur-based antioxidant of the component (C) contained in the resin composition of the present invention, various ones are used, and specifically, for example, dilauryl 3,3'-thiodipropionate. , Ditridecyl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate,
Bis2-methyl-4- (3-n-alkyl (C ₁₂ or C
₁₄ ) Thiopropionyloxy) -5-t-butylphenyl sulfide, pentaerythrityl-tetrakis (3
-Laurylthiopropionate), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (3-methyl-6) -T-butylphenol), 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole and the like.

The sulfur-based antioxidant as the component (C) is
In the said invention (a), 0.005-5.0 weight part is preferable with respect to 100 weight part of said (A) component, Preferably it is 0.01-.
The amount is 3.0 parts by weight, and more preferably 0.01 to 2.0 parts by weight. Further, such a compound is 100 parts by weight in total of the component (A) and the component (D) in the invention (b), while the compound (A) and (E) in the invention (c). ) Component in total 100 parts by weight, and in the above-mentioned invention (d), in each of the above components (A), (D) and (E) 100 parts by weight, 0.005
To 5.0 parts by weight, preferably 0.01 to 3.0 parts by weight, and more preferably 0.01 to 2.0 parts by weight. These compounds may be used alone or in combination of two or more. When the amount of the above-mentioned (B) component phenol-based antioxidant and (C) component sulfur-based antioxidant is less than 0.005 parts by weight, sufficient antioxidant effect cannot be obtained, and more than 5.0 parts by weight. Not only is it economically disadvantageous, but it is also not preferable because it adversely affects the bleeding, mechanical properties, heat resistance and appearance of the antioxidant.

Among the thermoplastic resin and / or the rubber-like elastic body of the component (D) contained in the resin composition of the present invention,
As the thermoplastic resin, various thermoplastic resins can be used without particular limitation as long as they are other than the above-mentioned components (A) and (C). Specifically, polystyrene having an atactic structure, polystyrene having an isotactic structure, styrene polymers such as AS resin and ABS resin; polyethylene terephthalate, polyethylene naphthalate,
Polyester resins such as polycarbonate; poly (thio) ether resins such as polyphenylene oxide, polyphenylene sulfide, polyoxymethylene; sulfone resins such as polysulfone and polyethersulfone;
Acrylic polymers such as polyacrylic acid, polyacrylic acid ester, polymethylmethacrylate; polyethylene,
Polyolefin-based polymers such as polypropylene, polybutene, poly-4-methylpentene-1, ethylene-propylene copolymer; polyvinyl chloride, polyvinylidene chloride,
Halogen-containing vinyl compound polymers such as polyvinylidene fluoride; polyamide resins and the like. As the thermoplastic resin, these resins may be used alone or in combination of two or more kinds.

The rubber-like elastic material is, for example, styrene-butyl acrylate copolymer rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block. Copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (S
EBS), styrene-isoprene block copolymer (S
IR), 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, 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 ( AAB
S), butadiene-styrene-core shell rubber (SB
R) and other core-shell type particulate elastic materials, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, silicone rubber, ethylene propylene rubber (EPR), ethylene propylene diene rubber (EP
DM), and rubbers obtained by modifying these rubber-like elastic bodies with a modifying agent.

Further, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-
Methyl acrylate copolymer, ethylene-glycidyl methacrylate-ethyl acrylate copolymer, ethylene-glycidyl methacrylate-methyl methacrylate copolymer, ethylene-glycidyl methacrylate-ethyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, Ethylene-maleic anhydride copolymer, ethylene-maleic anhydride-methyl methacrylate copolymer, ethylene-maleic anhydride-ethyl methacrylate copolymer, ethylene-maleic anhydride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer Copolymers of olefins and polar vinyl monomers such as polymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, chlorinated polyethylene, Ron elastomer, polyester elastomer, urethane elastomer, polysulfide rubber, Thiokol rubber, acrylic rubber, epichlorohydrin rubber, chlorinated rubber. Of these, the core-shell rubber containing SEB, SEBS, SEPS, and styrene units is particularly preferably used. As the rubber-like elastic body, one kind or a combination of two or more kinds may be used.

The thermoplastic resin and / or rubber-like elastic body of the component (D) in the invention (b) and invention (c) is 1 to 99% by weight, preferably 5 to 95% by weight,
More preferably, it is blended in an amount of 20 to 80% by weight. When the blending amount is less than 1% by weight, no significant difference from the properties of the styrene polymer having the SPS structure alone is observed, and 9
If it exceeds 9% by weight, improvement in mechanical and thermal properties due to the styrene polymer having an SPS structure cannot be expected, which is not preferable. The resin composition of the present invention contains both or one of the above-mentioned thermoplastic resin and rubber-like elastic body as the component (D).

The polyphenylene ether and / or the modified polyphenylene ether as the component (E) contained in the resin composition of the present invention are known compounds and are disclosed in US Pat.
The compounds described in the specifications of 6,874, 3,306,875, 3,257,357 and 3,257,358 can be used. 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. Specifically, 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 (2,2).
6-dimethyl-1,4-phenylene ether) and the like.

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. The modified polyphenylene ether is obtained by modifying the polyphenylene ether as described above with a modifier, but the modified polyphenylene ether is not limited to this method as long as it meets the object of the present invention. Examples of the modifier used for modifying these polyphenylene ethers include compounds having an ethylenic double bond and a polar group in the same molecule. Examples of such modifiers include maleic anhydride, maleic acid, fumaric acid, maleic acid ester, maleimide and its N-substituted product, maleic acid salt, acrylic acid, acrylic acid ester, acrylic acid amide, acrylic acid salt, methacrylic acid salt. Examples thereof include acids, methacrylic acid esters, methacrylic acid amides, methacrylic acid salts, and glycidyl methacrylate. Of these, maleic anhydride and glycidyl methacrylate are particularly preferably used. These modifiers may be used alone,
You may use it in combination of 2 or more type.

The modified polyphenylene ether can be obtained, for example, by reacting the above polyphenylene ether with a modifying agent in the presence of a solvent or another resin. The modification method is not particularly limited, and a known method, for example, a roll mill, a Banbury mixer, an extruder, etc.
A method of melt-kneading at a temperature in the range of 50 ° C. and reacting, or a method of heating and reacting in a solvent such as benzene, toluene or xylene 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. The presence of a radical generator such as nitrile; 2,3-diphenyl-2,3-dimethylbutane is effective. A preferable method is a method of melt-kneading in the presence of a radical generator. Among these modified polyphenylene ethers, maleic anhydride modified polyphenylene ethers are particularly preferably used. In the resin composition of the present invention, both or either of polyphenylene ether and modified polyphenylene ether may be blended as the component (E).

The polyphenylene ether and / or modified polyphenylene ether as the component (E) in the above invention (c) is 0.1 to 10.0% by weight, preferably 0.1.
5 to 8.0 wt% is compounded. Further, in the invention (d), such a compound is used in an amount of 0.1 to 10.0 parts by weight based on 100 parts by weight of the total of the components (A) and (D).
The amount is preferably 0.5 to 8.0 parts by weight. These compounds may be used alone or in combination of two or more. The polyphenylene ether and / or modified polyphenylene ether of the component (E) is
If the content is less than 0.1% by weight (part), the effect of improving the toughness due to the component (E) is low, and if it exceeds 10.0% by weight (part),
It is not preferable because it lowers the crystallinity of the component (A) and adversely affects the heat resistance and moldability of the resin composition.

As the inorganic filler contained in the composition of the present invention, those which have been surface-treated with a coupling agent in order to enhance the adhesiveness with the styrene polymer as the component (A) are preferably used. To be Here, there are various types of inorganic fillers such as fibrous, granular, and powdery ones. Examples of the fibrous filler include glass fiber, carbon fiber, whiskers, ceramic fiber, metal fiber and the like. Specifically, the whiskers include boron, alumina, silica, silicon carbide, etc.
Ceramic fibers are gypsum, potassium titanate,
Examples of metal fibers such as magnesium sulfate and magnesium oxide include copper, aluminum and steel. Here, the shape of the filler includes a cloth shape, a mat shape, a bundle cutting shape, a short fiber, a filament shape, and whiskers. In the case of convergent cutting, the length is 0.05 to 50 mm and the fiber diameter is 5 to 2.
It is preferably 0 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, examples of the granular or powdery filler include talc, carbon black, graphite, titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, 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 and glass beads are preferred.

Further, as the surface-treated inorganic filler,
The inorganic filler is surface-treated 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, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β.
-(1,1-Epoxycyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)
-Γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-
Aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl-tris (2-methoxy-ethoxy) silane, N-methyl-γ -Aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, triaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane,
3-4,5 dihydroimidazole propyltriethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) amide, N, N-bis (trimethylsilyl) urea and the like can be mentioned. Of these, preferred are γ-aminopropyltrimethoxysilane and N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
Aminosilanes and epoxysilanes such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

Specific examples of titanium coupling agents include isopropyltriisostearoyl titanate, isopropyltridodecylbenzenesulfonyl 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 filler using such a coupling agent may be carried out by an ordinary known method without any particular limitation. For example, a sizing treatment in which an organic solvent solution or suspension of the above coupling agent is applied to the filler as a so-called sizing agent, or dry mixing using a Henschel mixer, super mixer, Loedige mixer, V-type blender or the like. The spraying 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 sizing treatment, dry mixing, or spraying method is 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,
Examples thereof include polyester-based, urethane-based, epoxy-based, acrylic-based, vinyl acetate-based polymers and the like. The inorganic filler is added in an amount of 1 to 350 parts by weight, preferably 5 to 200 parts by weight, based on 100 parts by weight of the resin composition of the present invention. If the blending amount is less than 1 part by weight, a sufficient addition effect as a filler cannot be exhibited, and if it exceeds 350 parts by weight, dispersibility is poor and moldability is difficult, which is not preferable.

Further, in the present invention, an organic filler can be added in addition to the above inorganic filler. Here, examples of the organic filler include organic synthetic fibers and natural plant fibers. Specific examples of the organic synthetic fibers include wholly aromatic polyamide fibers and polyimide fibers. Further, in the resin composition of the present invention, various addition components such as a nucleating agent, a plasticizer, a release agent, a flame retardant, an antistatic agent, a foaming agent, and a pigment are used as long as the object of the present invention is not impaired. , Carbon black, processing aids, metal soaps, etc. can be added.
The resin composition of the present invention is a composition in which the above components are blended in the above proportions, and there is no particular limitation on the blending method and the like, and a known method that is usually performed, for example, each component in a specific proportion. It can be produced by a method such as melt kneading. In this way, the resin composition of the present invention produced is a resin composition having significantly improved heat resistance and durability while maintaining characteristics such as original mechanical strength as compared with conventional SPS resins. is there. The resin molded product of the present invention is obtained from the resin composition of the present invention.

The present invention will be described below with reference to Examples and Comparative Examples.
A more specific description will be given. The following physical properties of the pellets or the formed test pieces obtained in Examples and Comparative Examples were measured by the following methods. (1) Tensile strength of test piece: JIS K7113
(2) YI of test piece: JIS K7103
(3) Long-term heat resistance of test piece After being held at 160 ° C. for 1000 hours, the tensile strength, its holding rate, and the YI of the test piece Note that the holding rate of the tensile strength is derived from the following formula. Retention rate of tensile strength (%) = (tensile strength after high temperature treatment)
/ (Tensile strength before high temperature treatment) x 100

Production Example 1 (Production of SPS) 1.0 liter of purified styrene was added to a 2 liter reaction vessel.
After adding 1 mmol of triethylaluminum and heating to 80 ° C., a premixed catalyst [pentamethylcyclopentadienyl titanium trimethoxide 90 micromol, dimethylanilinium tetrakis (pentafluorophenyl) borate 90 micromol, toluene 29.1] was added. Mmol, triisobutylaluminum 1.8 mmol] 16.5
After adding milliliter, polymerization was carried out at 80 ° C. for 5 hours.
After the reaction was completed, the product was repeatedly washed with methanol and dried to obtain 380 g of a polymer. The weight average molecular weight of this polymer is 1,2,4-trichlorobenzene as a solvent,
It was 400,000 when measured by gel permeation chromatography at 130 ° C. The weight average molecular weight / number average molecular weight was 2.60. Further, by melting point and ¹³ C-NMR measurement, this polymer shows S
It was confirmed to be PS.

Production Example 2 (Production of modified polyphenylene ether (MAPPO)) Polyphenylene ether (intrinsic viscosity 0.47 deciliter / g, in chloroform, 25 ° C.) 1 kg, maleic anhydride 60 g, 2,3-dimethyl as 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.

Examples 1 to 5 To 100 parts by weight of SPS obtained in Production Example 1, the phenol-based antioxidant and the sulfur-based antioxidant shown in Table 1 were added and dried with a Hensyl mixer. After blending, the mixture was melt-kneaded with a twin screw extruder at a cylinder temperature of 300 ° C. to form pellets. Injection molding was performed using the obtained pellets to obtain a test piece. The physical properties of the obtained pellets and test pieces were measured as described above. Second result
Shown in the table.

Examples 6 to 9 80% by weight of SPS obtained in Production Example 1 and SEBS (Sh
ell Chem. Co. LTD .; Kraton G-1651) 20% by weight to 100 parts by weight, to which phenol-based antioxidants and sulfur-based antioxidants shown in Table 1 were added, and Hensyl was added. After dry blending with a mixer, the mixture was melt-kneaded with a twin-screw extruder at a cylinder temperature of 300 ° C. to form pellets. Injection molding was performed using the obtained pellets to obtain a test piece. The physical properties of the obtained pellets and test pieces were measured as described above. The results are shown in Table 2.

Examples 10 to 14 90% by weight of SPS obtained in Production Example 1 and SEBS (Sh
ell Chem. Co. LTD .; Kraton G-1651) 10% by weight as 100 parts by weight, and MAPP obtained in Preparation Example 2
3 parts by weight of O was added. Furthermore, 100 parts by weight of these were added, to which phenol-based antioxidants and sulfur-based antioxidants shown in Table 1 were added, and after dry blending with a Hensil mixer, a cylinder was added with a twin-screw extruder. At a temperature of 300 ° C., 30% by weight of glass fiber ECS03T-051 / P (manufactured by Nippon Electric Glass Co., Ltd .; surface treatment with aminosilane) was side-fed, melt-kneaded and pelletized. Injection molding was performed using the obtained pellets to obtain a test piece.
The physical properties of the obtained pellets and test pieces were measured as described above. The results are shown in Table 2.

Comparative Examples 1 and 2 Pellets and test pieces were obtained in the same manner as in Example 1 except that the antioxidants shown in Table 1 were used. Physical properties of the obtained pellets and test pieces were measured in the same manner as in Example 1. The results are shown in Table 2. Comparative Examples 3 and 4 Pellets and test pieces were obtained in the same manner as in Example 6 except that the antioxidants shown in Table 1 were used. Physical properties of the obtained pellets and test pieces were measured in the same manner as in Example 6. The results are shown in Table 2. Comparative Examples 5 and 6 Example 10 except that the antioxidants were as shown in Table 1.
Pellets and test pieces were obtained in the same manner as in. Physical properties of the obtained pellets and test pieces were measured in the same manner as in Example 10. The results are shown in Table 2.

[0037]

[Table 1]

* 1: Phenolic antioxidant Irg. 245 (manufactured by Ciba Geigy): triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] Irg. 259 (manufactured by Ciba Geigy): 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Irg. 1010 (manufactured by Ciba Geigy): pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Irg. 1076 (manufactured by Ciba Geigy): n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate Irg. 565 (manufactured by Ciba Geigy): 2,4-bis (n-octylthio) -6- (4-hydroxy-3,
5-di-t-butylanilino) -1,3,5-triazine Irg. 3114 (manufactured by Ciba Geigy): tris (3,5-di-t-butyl-4-hydroxybenzyl)
-Isocyanurate ADK. AO-80 (manufactured by Asahi Denka Co., Ltd.): 3,9-
Bis [1,1-di-methyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5 , 5] Undecane * 2: Sulfur-based antioxidant Sumi. TPM (Sumitomo Chemical Co., Ltd.): Dimyristyl 3,3′-thiodipropionate Sumi. TPL (Sumitomo Chemical Co., Ltd.): Dilauryl 3,3′-thiodipropionate Sumi. TP-D (manufactured by Sumitomo Chemical Co., Ltd.): pentaerythrityl-tetrakis (3-laurylthiopropionate) Sumi. TPS (Sumitomo Chemical Co., Ltd.): Distearyl 3,3′-thiodipropionate

[0039]

[Table 2]

[0040]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, the machine is used under the condition that heat resistance and durability are required while maintaining the heat resistance, water resistance and impact resistance that SPS originally has, especially when used at high temperature. It is possible to obtain a resin composition in which the deterioration of the mechanical strength and the deterioration of the color tone are significantly improved. Therefore, the resin composition of the present invention,
Products that require particularly high heat resistance, durability, low specific gravity, high strength, chemical resistance, hydrolysis resistance, low dielectric constant, etc.,
Specifically, it is expected to be effectively used for various purposes as materials for various molded products such as mechanical parts, electric and electronic parts, films and fibers.

Claims (6)

[Claims] 1. (A) 100 parts by weight of a styrene polymer having a syndiotactic structure, (B) 0.005 to 5.0 parts by weight of a phenolic antioxidant, and (C) a sulfuric antioxidant 0 A polystyrene resin composition comprising 0.005 to 5.0 parts by weight. 2. A synthetic resin having a syndiotactic structure (A) 1 to 99% by weight, a thermoplastic resin other than the components (A) and (E) and / or a rubber-like elastic material 99 to (A). 1% by weight of (B) a phenolic antioxidant with respect to a total of 100 parts by weight of the components (A) and (D).
0.005 to 5.0 parts by weight, and (C) a sulfur-based antioxidant in an amount of 0.005 to 5.0 parts by weight based on 100 parts by weight of the total of the components (A) and (D). A polystyrene-based resin composition blended. 3. (A) Styrene-based polymer having a syndiotactic structure 90.0 to 99.9% by weight, (E) polyphenylene ether and / or modified polyphenylene ether 10.0 to 0.1% by weight, B) Phenol-based antioxidant is 0.005-5.0 parts by weight per 100 parts by weight of the above-mentioned components (A) and (E), and (C) sulfur-based antioxidant is added in the above-mentioned (A). A polystyrene resin composition comprising 0.005 to 5.0 parts by weight based on 100 parts by weight of the total of the components and the component (C). 4. (A) 1 to 99% by weight of a styrene-based polymer having a syndiotactic structure, a thermoplastic resin other than the components (D) and (A) and (E) and / or a rubber-like elastic material 99 to. 1% by weight, (E) polyphenylene ether and /
Alternatively, the modified polyphenylene ether is 0.1 to 10.0 parts by weight based on 100 parts by weight of the total of the components (A) and (D), and (B) the phenolic antioxidant is (A) and ( For 100 parts by weight of the total of the component (D) and the component (E)
0.005 to 5.0 parts by weight, and (C) a sulfur-based antioxidant as a total of 10 of the above-mentioned components (A), (D) and (E).
A polystyrene-based resin composition containing 0.005 to 5.0 parts by weight based on 0 parts by weight. 5. An inorganic filler in an amount of 1 to 350 parts by weight is added to 100 parts by weight of the polystyrene resin composition according to any one of claims 1 to 4. The polystyrene-based resin composition as described. 6. A resin molded product comprising the polystyrene resin composition according to claim 1.