JP3516364B2 - Polystyrene resin composition and molded article thereof - Google Patents

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 molded articles thereof, more specifically, materials for industrial materials such as electric / electronic materials, industrial structural materials, automobile parts, home electric appliances and various machine parts. The present invention relates to a polystyrene resin composition excellent in rigidity, heat resistance, impact resistance, water resistance, and heat aging resistance, and a molded product thereof, which are preferably used as.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
A styrene polymer having a syndiotactic structure (hereinafter sometimes abbreviated as SPS), a polyamide resin and a compound containing a SPS and a polyamide resin as a compatibilizer as a main component are melt-blended to obtain strength, toughness, and heat resistance. Resistance, chemical resistance,
To obtain a composition excellent in balance of molding processability,
Already, JP-A-62-25795, JP-A-1-27
9944, JP-A-2-209938, JP-A-2-219843, JP-A-3-126744, and Japanese Patent Application No. 4-269893. And by utilizing such excellent properties,
Practical application is being considered for applications requiring strength and heat resistance such as electronic parts, automobile parts, mechanical parts and industrial parts. By the way, even with a resin composition having such many characteristics, resistance to long-term thermal oxidative deterioration,
That is, there is a problem that the heat aging resistance is still insufficient, and it is strongly desired to improve the long-term heat resistance of the resin molded product in order to improve the reliability of these parts. As means for solving such a problem, addition of a phenolic antioxidant (JP-A-5-289290) or combination of a phenolic antioxidant and a sulfur antioxidant (JP-A-6-384)
However, a sufficient improvement in heat aging resistance has not been obtained. Further, in order to improve the heat aging resistance of the polyamide resin, it has been proposed to use a copper compound and an iodine compound in combination and to add an amine antioxidant, but by adding these additives, the heat aging resistance is improved. Is not a satisfactory performance although it is improved to some extent, and there is a problem that the molded body turns yellow or brown over time, or metal damage occurs due to the copper compound, which causes corrosion of the extruder or the molding machine. . On the other hand, a polyamide resin composition containing a phenol-based antioxidant and a sulfur-based antioxidant has been proposed, but a sufficiently satisfactory result has not been obtained.

Under these circumstances, the present invention has little change in physical properties and color tone even when exposed to high temperature for a long time, and is excellent in heat aging resistance, and changes in color tone due to water absorption and electrical characteristics. The purpose of the present invention is to provide a polystyrene-based resin composition that can be suitably used as a material for various industrial materials and the like that does not cause problems such as deterioration and copper damage.

[0004]

[Means for Solving the Problems] The present inventors have earnestly studied to develop a polystyrene resin composition which is excellent in heat aging resistance, toughness, rigidity, heat resistance and chemical resistance. As a result, they have found an SPS / PA alloy-based resin composition that is excellent in heat aging resistance by adding a specific phenol compound. In addition, the present inventors
As a PS / PA alloy-based resin composition, the present inventors have found that the resin composition further excellent in heat aging resistance by containing a phenolic compound having a specific structure and / or a thiodipropionic acid ester-based compound. The present invention has been completed based on such findings. That is,
The first object of the present invention is (A) (a) racemic pentad
1 to 99% by weight of polystyrene-based resin having a syndiotacticity of 30% or more , (b) 1 to 99% by weight of polyamide resin, and (c) having compatibility with (a) component,
And a compatibilizer having a polar group capable of reacting with the component (b) 0.
1 to 10% by weight, (d) a rubber elastic body and / or a modified product thereof 0 to 50% by weight, a styrene polymer composition 1
(B) N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), (C) 3,9-bis [1, 1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5
-Methylphenyl) propionyloxy} ethyl]-
2,4,8,10-tetrachiosaspiro [5,5] undecane, (D) N, N'-bis [3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine And at least one of them is contained in an amount of 0.001 to 5.0 parts by weight.
[However, pentaerythrityl tetrakis (3-lauri
Other than sulfur-containing antioxidants other than ruthiopropionate)
Exclude cases. ] Is provided. Second of the present invention
The purpose of, in the polystyrene resin composition,
With respect to 100 parts by weight of the component (A), (E) the following general formula (I)

[0005]

[Chemical 2] [In the formula, R represents a methyl group or a t-butyl group, and X is 1
Shows the residue which removed n hydroxyl groups of the alcohol which has -4 hydroxyl groups, and n shows the integer of 1-4. ] It is to provide a polystyrene-based resin composition, characterized in that the phenol-based compound represented by the formula [5] is contained in an amount of 0.05 to 5.0 parts by weight. A third object of the present invention is that the above polystyrene resin composition contains (F) thiodipropionic ester compound in an amount of 0.005 to 5.0 parts by weight per 100 parts by weight of the component (A). Another object of the present invention is to provide a polystyrene resin composition characterized by the following. A fourth object of the present invention is to provide a polystyrene-based resin composition characterized in that (G) the inorganic filler is contained in an amount of 1 to 350 parts by weight with respect to 100 parts by weight of the polystyrene-based resin composition. Is. The object of the present invention is also to provide a molded article comprising the polystyrene resin composition.

In the resin composition of the present invention, a styrene polymer having a syndiotactic structure is used as the component (a) of (A). Here, the syndiotactic structure in the styrene-based polymer having a syndiotactic structure is a syndiotactic structure in three-dimensional structure, that is, a phenyl group or a substitution which is a side chain to a main chain formed from a carbon-carbon bond. It has a steric structure in which phenyl groups are alternately located in opposite directions, and its tacticity is determined by a nuclear magnetic resonance method ( ¹³ C-NMR) using an isotope carbon.
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. Syndiotactic polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene), poly (vinyl benzoate), hydrogenated polymers thereof, and A mixture of these or a copolymer containing them as a main component is referred to. Here, as poly (alkylstyrene), poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene),
There are poly (tertiary-butyl styrene), poly (phenyl styrene), poly (vinyl naphthalene), poly (vinyl styrene), etc., and as poly (halogenated styrene), poly (chlorostyrene), poly (bromostyrene), Examples include poly (fluorostyrene). The poly (halogenated alkylstyrene) includes poly (chloromethylstyrene), and the poly (alkoxystyrene) includes poly (methoxystyrene) and poly (ethoxystyrene). Of these, particularly preferable styrene polymers 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 styrene-type polymer can be used individually by 1 type or in combination of 2 or more types.

The styrene polymer is not particularly limited in molecular weight, but the weight average molecular weight is preferably 100.
It is at least 00, more preferably at least 50,000. 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, the thermal properties and mechanical properties of the resulting composition or molded product may be deteriorated, which is not preferable. Such a styrene-based polymer having a syndiotactic structure is a styrene-based single polymer, for example, in an inert hydrocarbon solvent or in the absence of a solvent, using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst. It can be produced by polymerizing a monomer (a monomer corresponding to the styrene polymer) (JP-A-62-187708). Regarding poly (halogenated alkyl styrene), JP-A-1-46912.
The above-mentioned hydrogenated polymer can be obtained by the method described in JP-A-1-178505.

The blending amount of the above component (a) is 1 to 99% by weight, preferably 5 to 95% by weight based on the total weight of the resin components.
%, And more preferably 20 to 80% by weight. When the content is less than 1% by weight, the water resistance and stability against acid / alkali of the polyamide resin as the component (b) are the same as those of the components alone, and when it exceeds 99% by weight, the SPS or (a) as the component (a) is used. The effect of improving the mechanical strength of the modified SPS as the component) is not sufficiently exhibited.

In the resin composition of the present invention, all polyamides known as polyamide resins can be used as the component (b) of (A). Suitable polyamides include, for example, polyamide-4, polyamide-6, polyamide-6,6, polyamide-3,4, polyamide-12,
Polyamide-11, polyamide-6,10, polyamide obtained from terephthalic acid and 4,4'-diaminohexylmethane, azelaic acid, adipic acid and polyamide obtained from 2,2-bis (p-cyclohexyl) propane, adipic acid And a polyamide obtained from m-xylylenediamine and the like. The aromatic polyamide resin is a polyamide polymer containing an amide bond having an aromatic ring in the main chain as a repeating structural unit, and is obtained by reacting an aromatic diamine component and a dicarboxylic acid component by a conventional method. It is used by appropriately selecting from the polymer obtained by reacting the combined product and the dicarboxylic acid component with the dicarboxylic acid component having an aromatic ring by a conventional method.

As the aromatic diamine component, for example, 1,4-diaminobenzene; 1,3-diaminobenzene; 1,2-diaminobenzene; 2,4-diaminotoluene; 2,3-diaminotoluene; 2 , 5-diaminotoluene; 2,6-diaminotoluene; ortho, meta,
Para xylylenediamine; ortho, meta, para para 2,2′-diaminodiethylbenzene; 4,4′-diaminobiphenyl; 4,4′-diaminodiphenylmethane; 4,4′-diaminodiphenyl ether; 4,4 ′
Diamines having a benzene ring such as diaminodiphenyl thioether; 4,4′-diaminodiphenyl ketone; 4,4′-diaminodiphenyl sulfone are used, and the aromatic diamine component is the above-mentioned benzene ring-containing diamines alone. As long as it is contained, it may be a mixture with other diamines, for example, aliphatic diamines. Of course, two or more kinds of diamines having an aromatic ring may be mixed and used.

As the dicarboxylic acid component, for example, aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid,
Examples thereof include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid, as well as esters and acid chlorides of these dicarboxylic acids, which may be used alone or in combination of two kinds. The above may be used in combination. Furthermore, an aromatic polyamide resin can also be obtained by polymerizing an ω-amino-ω'-carboxyl compound having an aromatic ring, and such an ω-amino-ω'-carboxyl compound having an aromatic ring is, for example, 4 -Aminophenylcarboxymethane, 1- (4-aminophenyl) -2-carboxylethane, 3- (4-aminophenyl) -1-carboxylpropane, p- (3-amino-3'-carboxy) dipropylbenzene, etc. Can be mentioned. A preferred aromatic polyamide resin is a polyamide derived from a diamine having a benzene ring and an aliphatic dicarboxylic acid, and more preferable is a polyamide derived from xylylenediamine and adipic acid.

The polyamide as the component (b) may be used alone or in combination of two or more kinds.
The blending amount is 1 to 99% by weight, preferably 5 to 95% by weight, and more preferably 20% by weight based on the total weight of the resin components.
-80% by weight is selected. When the content of the component (b) is less than 1% by weight, there is no significant difference in properties from the case where the styrene-based polymer having the SPS structure is alone. When it exceeds 99% by weight, the styrene-based polymer having the SPS structure is used. Improvement of mechanical and thermal properties of coalescence cannot be expected.

In the resin composition of the present invention, as the component (c) of (A), a compatibilizing agent having compatibility with the component (a) and having a polar group capable of reacting with the component (b). Is used. This compatibilizer is added for the purpose of improving the compatibility between the components (a) and (b), finely dispersing the domains, and improving the interfacial strength. The polar group capable of reacting with the component (b) refers to a functional group capable of reacting with the polar group of the component (b), and specifically, for example, an acid anhydride group, a carboxylic acid group, a carboxylic acid ester group, Carboxylic acid halide groups, carboxylic acid amides, carboxylic acid groups, sulfonic acid groups, sulfonic acid ester groups, sulfonic acid chloride groups, sulfonic acid amide groups, sulfonic acid groups, epoxy groups, amino groups, imide groups, oxazoline groups, etc. Can be mentioned. Further, the one having compatibility with the component (a) is one having a chain showing the compatibility with the component (a) in a polymer chain, and examples thereof include syndiotactic polystyrene, atactic polystyrene, and isotactic polystyrene. Examples thereof include polymers having tactic polystyrene, styrene-based polymers, polyphenylene ether, polyvinyl methyl ether, etc. as the main chain, block chains or graft chains.

Specific examples of the component (c) 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 copolymer, acid-modified acrylic-styrene-graft polymer, (styrene-glycidyl Methacrylate) -styrene-graft polymer,
Polybutylene terephthalate-polystyrene-graft polymer, maleic anhydride modified SPS, fumaric acid modified S
Modified styrene polymers such as PS, glycidyl methacrylate modified SPS, amine modified SPS, (styrene-maleic anhydride) -polyphenylene ether-graft polymer, maleic anhydride modified polyphenylene ether,
Examples thereof include modified polyphenylene ether-based polymers such as fumaric acid-modified polyphenylene ether, glycidyl methacrylate-modified polyphenylene ether, and amine-modified polyphenylene ether. Among these, modified polyphenylene ether and modified SPS 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.

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. Specific examples thereof include maleic anhydride, maleic acid and fumaric acid. Acid, maleic acid ester, fumaric acid ester, maleimide and its N-substituted product, maleate, fumarate, acrylic acid,
Acrylic acid esters, acrylic acid amides, acrylic acid salts, methacrylic acid, methacrylic acid esters, methacrylic acid amides, methacrylic acid salts, glycidyl methacrylate and the like can be mentioned. Among them, maleic anhydride, fumaric acid and glycidyl methacrylate are particularly preferable. Used. The above various modifiers may be used alone,
You may use it in combination of 2 or more type.

The modified polyphenylene ether can be obtained by reacting the polyphenylene ether with a modifier in the presence of a solvent or another resin, for example. 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.

Further, a modified SPS having a polar group can be used as the component (c). 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.

As the modifier used for modifying the SPS, a compound 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, fumaric acid, maleic acid ester, fumaric acid ester, maleimide and its N.
Substitutes, maleate, fumarate, acrylic acid, acrylic acid ester, acrylic acid amide, acrylic acid salt, methacrylic acid, methacrylic acid ester, methacrylic acid amide, methacrylate, glycidyl methacrylate, etc. Among them, maleic anhydride, fumaric acid and glycidyl methacrylate are particularly preferably used. These modifiers may be used alone or in combination of two or more.

The modified SPS can be obtained, for example, by reacting the SPS 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 method of melt-kneading at a temperature in the range of 150 to 350 ° C. using a roll mill, a Banbury mixer, an extruder or the like to cause a reaction, or benzene, toluene,
It is possible to use a method such as heating reaction in a solvent such as xylene. Furthermore, 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 or 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 SPS, especially maleic anhydride modified SP
S, fumaric acid-modified SPS, and glycidyl methacrylate-modified SPS are preferably used.

The polar group content in component (c) is 0.0.
It is desirable to be in the range of 1 to 20% by weight, preferably 0.05 to 10% by weight. If this content is less than 0.01% by weight, it is necessary to add a large amount of component (c) in order to exert the effect as a compatibilizer, and as a result, the mechanical properties and heat resistance of the composition decrease, Not preferable. Further, if it exceeds 20% by weight, the compatibility with the component (a) decreases, which is not preferable.

The component (c) may be used alone or in combination of two or more, and the polar group content in the component (c) is 0.01 to 20% by weight, preferably 0.0
It is preferably in the range of 5 to 10% by weight. If this content is less than 0.01% by weight, it is necessary to add a large amount of component (c) in order to exert the effect as a compatibilizer.
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. The blending amount of the component (c) is selected in the range of 0.1 to 10% by weight, preferably 0.5 to 8% by weight, based on the total weight of the resin component. If the blending amount is less than 0.1% by weight, the toughness improving effect is not sufficient, and
When the content exceeds the weight%, the crystallinity of the component (a) is lowered, and the heat resistance and moldability of the composition are lowered, which is not preferable.

In the resin composition of the present invention, a rubber elastic body and / or a modified body thereof is used as the component (d) of (A). This rubber elastic material is blended to improve impact resistance and toughness such as elongation. Examples of the rubber elastic body used as the component (d) include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, silicone rubber, shrimp chlorohydrin rubber, styrene-butadiene. Block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene -Isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SI
S), 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 (AB
S), methylmethacrylate-butadiene-styrene-
Core shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core shell rubber (MA
S), octyl acrylate-butadiene-styrene-
Core shell rubber (MABS), alkyl acrylate-
Core-shell type particulate elastic bodies such as butadiene-acrylonitrile-styrene core-shell rubber (AABS), butadiene-styrene-core-shell rubber (SBR), and siloxane-containing core-shell rubbers such as methylmethacrylate-butyl acrylate siloxane, or modified these. Examples include rubber. Among these,
In particular, SBR, SBS, SEB, SEBS, SIR, S
EP, SIS, SEPS, core shell rubber, rubber modified with these, and the like are preferably used.

Examples of the modified rubber elastic material used as the component (d) include styrene-butyl acrylate copolymer rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer. Polymer (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),
Examples thereof include rubbers obtained by modifying ethylene propylene diene rubber (EPDM) with a modifier having a polar group. Among these, especially SEB, SEBS, SE
A rubber modified with P, SEPS, EPR, or EPDM is preferably used. Specifically, maleic anhydride modified SE
Examples thereof include BS, maleic anhydride-modified SEPS, maleic anhydride-modified EPR, maleic anhydride-modified EPDM, epoxy-modified SEBS, and epoxy-modified SEPS. The rubber elastic body of the component (d) may be used alone or in combination of two or more, and the compounding amount thereof is selected in the range of 0 to 50% by weight based on the total weight of the resin component. Be done. If the blending amount exceeds 50% by weight, the elastic modulus and heat resistance of the composition are significantly lowered, which is not preferable.

Next, in the resin composition of the first object of the present invention, as the component (B), N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocin) is used. Namami) [Ciba Geigy Co., Ltd. product name IRG
ANOX1098], (C) 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl]
-2,4,8,10-Tetrachiosaspiro [5,5] undecane [Asahi Denka Co., Ltd. product name ADEKASTAB
AO-80], (D) N, N'-bis [3,5-di-t
-Butyl-4-hydroxyphenyl) propionyl] hydrazine [Ciba Geigy Co., Ltd. trade name IRGANO
XMP-1024] is used. The blending amount thereof is 0.05 to 5.0 parts by weight based on 100 parts by weight of the (A) styrene polymer composition,
Preferably, it is from 0.01 to 3.0 parts by weight, more preferably,
It is contained in an amount of 0.01 to 2.0 parts by weight. If it is less than 0.005 part by weight, the toughness is largely decreased by the heat aging test, and the effect of addition is not sufficient. If it exceeds 5.0 parts by weight, the molded surface will be poor due to blooming of the surface, the surface hardness will be lowered, the mechanical properties and heat resistance will be lowered, and the effect of addition will be saturated, which is economically unfavorable.

In the resin composition of the second object of the present invention, as the component (E), the following general formula (I) is used.

[Chemical 3]

[Wherein R represents a methyl group or a t-butyl group, X represents a residue of an alcohol having 1 to 4 hydroxyl groups excluding n hydroxyl groups, and n is an integer of 1 to 4] Indicates. ] A phenolic compound represented by Specific examples of this phenolic compound include, for example, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (product name: IRGANOX 1076, ADEKASTA
B AO-50 or Sumilizer BP-76), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (Product name: IRGANOX 245),
1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate] (Product name: IRGA
NOX 259), 2,2-thio-diethylenebis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate] (Product name: IRGANOX 1035), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Product name: IRGANOX 1010 ， ADEKASTAB AO-6
0 or SUMILIZER BP-101) and the like, among which pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], n-octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate is preferred. The above phenolic compounds may be used alone or in combination of two or more, and the addition amount thereof is 0.0005 with respect to 100 parts by weight of the component (A) in 100 parts by weight of the resin composition. ~
It is in the range of 5.0 parts by weight, preferably 0.01 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight. If it is less than 0.005 parts by weight, the physical properties will be largely deteriorated by the heat aging test and the effect of addition will be insufficient, and if it exceeds 5.0 parts by weight, surface defects of the molded product due to blooming on the surface, deterioration of surface hardness or dynamics will occur. The physical properties and heat resistance are deteriorated, the effect of addition is saturated, and it is economically disadvantageous, which is not preferable.

In the resin composition of the third object of the present invention, a thiodipropionic ester compound is used as the component (F). Specific examples of the thiodipropionate compound include dilauryl-3,3'-thiodipropionate (product name: SUMILIZER TPL-R, Yoshitomi DLTP), ditridecyl-3,3'-thiodipropionate. (Product name: SUMILIZER TL or ADEKASTAB AO-503A), Dimyristyl-3,3'-thiodipropionate (Product name: SUMI
LIZER TPM), distearyl-3,3'-thiodipropionate (product name: SUMILIZER TPS), distearyl-3,3'-methyl-3,3'-thiodipropionate, tetrakis [methylene-3- (Hexylthio) propionate] methane, tetrakis [methylene-3- (dodecylthio) propionate] methane (Product name: Sumilizer TP-D or Adekastab AO-412S
), Tetrakis [methylene-3- (octadecylthio) propionate] methane and the like, among which tetrakis [methylene-3- (dodecylthio) propionate] is particularly preferable.
Methane is preferred. The thiodipropionate compound may be used alone or in combination of two or more, and the addition amount thereof is 0.1 parts by weight per 100 parts by weight of the component (A) in the resin composition. The range is from 0.05 to 5.0 parts by weight, preferably from 0.01 to 3.0 parts by weight, more preferably from 0.01 to 2.0 parts by weight. If it is less than 0.05 parts by weight, the physical properties are greatly deteriorated by the heat aging test, and the effect of addition is insufficient, and if it exceeds 5.0 parts by weight, the surface of the molded product is poor due to plumming to the surface, the surface hardness is lowered, or the mechanical strength is deteriorated. The physical properties and heat resistance are deteriorated, the effect of addition is saturated, and it is economically disadvantageous, which is not preferable.

In the resin composition of the fourth object of the present invention, an inorganic filler is used as the component (G). As the inorganic filler, those subjected to a surface treatment with a coupling agent are preferably used in order to enhance the adhesiveness with the styrene resin which is the component (A) (a). Here, there are various types of inorganic fillers such as fibrous, granular, and powdery ones. The fibrous filler includes glass fiber, carbon fiber,
Examples include whiskers, ceramic fibers, and metal fibers. Specifically, the whiskers include boron, alumina,
Silica, silicon carbide and the like, ceramic fibers include gypsum, potassium titanate, magnesium sulfate, magnesium oxide and the like, and metal fibers 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 focused cutting, the length is 0.05 to 50
mm, and the fiber diameter is preferably 5 to 20 μm. Also,
In the case of a cloth shape or a mat shape, 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 and glass beads are preferred.

The surface-treated inorganic filler is a surface-treated inorganic filler as described above using a coupling agent usually used for surface treatment, such as a silane coupling agent or a titanium coupling agent. is there. 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-dihydro Examples include imidazolepropyltriethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) amide, N, N-bis (trimethylsilyl) urea and the like. Of these, preferred are γ-aminopropyltrimethoxysilane and N-β.
Aminosilanes such as-(aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and epoxysilanes.

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

The surface treatment of the filler using such a coupling agent may be carried out by a commonly 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, and polyether-based polymers.

Furthermore, in the present invention, an organic filler can be added in addition to the inorganic filler (G). 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.
The inorganic fillers may be used alone or in combination of two or more, and the addition amount thereof is 1 to 350 parts by weight, preferably 5 to 200 parts by weight, relative to 100 parts by weight of the resin composition. Is the range. If it is less than 1 part by weight, a sufficient effect of addition as a filler cannot be obtained, and if it exceeds 350 parts by weight, dispersibility is poor and moldability is deteriorated, which is not preferable. In addition, the resin composition of the present invention contains various additive components such as a nucleating agent, a plasticizer, a release agent, a flame retardant, an antistatic agent, a foaming agent, a pigment, and the like, as long as the object of the present invention is not impaired. Carbon black, processing aids, additives such as metal soaps, or other thermoplastic resins can be blended.

[0036]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Incidentally, the component (B), the component (C), the component (D), the component (E) of the present invention in Examples and Comparative Examples,
The amounts of each of the components (F) and (G) are shown in Tables 1 and 2
Shown in the table. Moreover, the conditions of the physical property evaluation in the examples and comparative examples were based on the following methods. (1) The tensile strength / elongation test was performed according to JIS K-7113. The test piece has a thickness of 1 mm, or 3
mm ASTM No. 4 piece is used, the pulling speed is 50 mm / min for 1 mm, and the pulling speed is 5 m for 3 mm.
m / min. (2) Thermal aging resistance is 1 in an air oven at a given temperature.
Tensile strength and elongation after standing for 000 hours were evaluated.

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) 1 kg of polyphenylene ether (intrinsic viscosity 0.47 deciliter / g, in chloroform, 25 ° C.), 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. The recovered polymer was subjected to Soxhlet extraction with methanol, and the denaturation rate was determined by titration and carbonyl absorption intensity of IR spectrum after drying. I asked. At this time, the modification rate was 2.0% by weight.

Example 1 33% by weight of SPS, polyamide 66 [Ube Industries, Ltd.]
Manufactured by 2015B, trade name] 60% by weight, maleic anhydride-modified polyphenylene ether 2% by weight, maleic anhydride-modified SEBS [manufactured by Asahi Kasei Corp., MX-072, trade name] 5% by weight, taken as 100 parts by weight. On the other hand, 0.5 parts by weight of IRGANOX 1098 (manufactured by Ciba-Geigy Co., Ltd.) as a phenolic compound was dry-blended with a Hensyl mixer, and then a twin-screw extruder (TEM-35 manufactured by Toshiba Machine Co., Ltd.) was used. ) In the cylinder temperature 28
The mixture was melt-kneaded at 0 ° C. and pelletized. Injection molding of the obtained pellets (IS55F manufactured by Toshiba Machine Co., Ltd.)
PA), the cylinder temperature was set to 290 ° C., and a tensile test piece having a thickness of 1 mm was molded. It was left to stand in an air oven at 150 ° C. for 1000 hours, and the tensile strength and elongation were measured. The results are shown in Table 2.

Example 2 In Example 1, 0.5 parts by weight of ADEKASTAB AO-80 (manufactured by Asahi Denka Co., Ltd.) was used as a phenol compound instead of 0.5 parts by weight of IRGANOX 1098 (manufactured by Ciba Geigy Co., Ltd.). The same procedure as in Example 1 was carried out except that the addition was made. The results are shown in Table 2.

Example 3 In Example 1, 0.5 parts by weight of IRGANOX MD9824 (manufactured by Ciba-Geigy Co., Ltd.) was added as a phenolic compound instead of 0.5 parts by weight of IRGANOX 1098 (manufactured by Ciba-Geigy Co., Ltd.). Example 1 except
I went in the same way. The results are shown in Table 2.

Example 4 33% by weight of SPS, polyamide 66 [Ube Industries, Ltd.]
Manufactured by 2015B, trade name] 60% by weight, maleic anhydride-modified polyphenylene ether 2% by weight, maleic anhydride-modified SEBS [manufactured by Asahi Kasei Corp., MX-072, trade name] 5% by weight, taken as 100 parts by weight. On the other hand, 0.5 parts by weight of IRGANOX 1098 (manufactured by Ciba-Geigy Co., Ltd.) and IRGANOX 24 as phenol compounds
5 [Ciba-Geigy Co., Ltd.] 0.3 part by weight was added, and after dry blending with a Hensil mixer, the cylinder temperature was adjusted with a twin-screw extruder (Toshiba Machinery Co., Ltd. TEM-35). The mixture was melt-kneaded at 280 ° C. and pelletized. The obtained pellets are injection molded (IS55FPA manufactured by Toshiba Machine Co., Ltd.) and the cylinder temperature is set to 29.
The tensile test piece having a thickness of 1 mm was molded by setting the temperature to 0 ° C.
It was left to stand in an air oven at 150 ° C. for 1000 hours, and the tensile strength and elongation were measured. The results are shown in Table 2.

Example 5 In Example 4, 0.5 parts by weight of IRGANOX 1098 (manufactured by Ciba-Geigy Co., Ltd.) and IRGANOX 24 were used.
5 IRGANOX 1098 [manufactured by Ciba-Geigy Co., Ltd.] and IRGANOX as a phenol compound instead of 0.3 part by weight of Ciba-Geigy Co., Ltd.
The same procedure as in Example 4 was carried out except that 0.36 part by weight of 1076 (manufactured by Ciba-Geigy Co., Ltd.) was added. The results are shown in Table 2.

Example 6 In Example 4, 0.5 parts by weight of IRGANOX 1098 [manufactured by Ciba-Geigy Co., Ltd.] and IRGANOX 24 were used.
5 IRGANOX 1098 [manufactured by Ciba-Geigy Co., Ltd.] and IRGANOX as a phenol compound instead of 0.3 part by weight of Ciba-Geigy Co., Ltd.
The same procedure as in Example 4 was carried out except that 0.310 parts by weight of 1010 (manufactured by Ciba-Geigy Co., Ltd.) was added. The results are shown in Table 2.

Example 7 In Example 4, 0.5 parts by weight of IRGANOX 1098 (manufactured by Ciba-Geigy Co., Ltd.) and IRGANOX 24 were used.
5 [manufactured by Ciba-Geigy Co., Ltd.] ADEKASTAB AO-8 as a phenolic compound instead of 0.3 part by weight
0 [Asahi Denka Co., Ltd.] 0.5 parts by weight and IRGANOX
The same procedure as in Example 4 was carried out except that 0.310 parts by weight of 1010 (manufactured by Ciba-Geigy Co., Ltd.) was added. The results are shown in Table 2.

Example 8 33% by weight of SPS, polyamide 66 [Ube Industries, Ltd.]
Manufactured by 2015B, trade name] 60% by weight, maleic anhydride-modified polyphenylene ether 2% by weight, maleic anhydride-modified SEBS [manufactured by Asahi Kasei Corp., MX-072, trade name] 5% by weight, taken as 100 parts by weight. On the other hand, 0.5 parts by weight of IRGANOX 1098 (manufactured by Ciba-Geigy Co., Ltd.) as a phenol compound and 0.3 parts by weight of SUMILISER TP-D (manufactured by Sumitomo Chemical Co., Ltd.) as a thiodipropionate compound were added. After dry blending with a Hensyl mixer, the mixture was melt-kneaded with a twin-screw extruder [TEM-35 manufactured by Toshiba Machine Co., Ltd.] at a cylinder temperature of 280 ° C., and pelletized. The obtained pellets are injection-molded [Toshiba Machine Co., Ltd. I
S55FPA], the cylinder temperature was set to 290 ° C., and a tensile test piece having a thickness of 1 mm was molded. Fifteen it
It was left in an air oven at 0 ° C. for 1000 hours, and the tensile strength and elongation were measured. The results are shown in Table 2.

Example 9 IRGA was used as the phenolic compound in Example 8.
NOX 1098 [manufactured by Ciba-Geigy Co., Ltd.] 0.5 part by weight, SUM as thiodipropionate compound
ILIZER TP-D [Sumitomo Chemical Co., Ltd.] ADEKAST as a phenolic compound instead of 0.3 parts by weight
AB AO-80 [manufactured by Asahi Denka Co., Ltd.] 0.5 part by weight, SUMILIS as a thiodipropionate compound
ER TP-D (manufactured by Sumitomo Chemical Co., Ltd.) was added in the same manner as in Example 8 except that 0.5 part by weight was added. Second result
Shown in the table.

Comparative Example 1 33% by weight of SPS, polyamide 66 [Ube Industries, Ltd.]
Manufactured by 2015B, trade name] 60% by weight, maleic anhydride-modified polyphenylene ether 2% by weight, maleic anhydride-modified SEBS [manufactured by Asahi Kasei Corp., MX-072, trade name] 5% by weight, dry blended with a Hensil mixer. After that, a twin-screw extruder [TEM-35 manufactured by Toshiba Machine Co., Ltd.]
With the cylinder temperature set at 280 ° C., melt kneading was performed to pelletize. The obtained pellets were injection-molded [IS55FPA manufactured by Toshiba Machine Co., Ltd.] at a cylinder temperature of 290 ° C. to form a tensile test piece having a thickness of 1 mm. It was left to stand in an air oven at 150 ° C. for 1000 hours, and the tensile strength and elongation were measured. The results are shown in Table 2.

Comparative Example 2 33% by weight of SPS, polyamide 66 [Ube Industries, Ltd.]
Manufactured by 2015B, trade name] 60% by weight, maleic anhydride-modified polyphenylene ether 2% by weight, maleic anhydride-modified SEBS [manufactured by Asahi Kasei Corp., MX-072, trade name] 5% by weight, taken as 100 parts by weight. After adding 0.5 parts by weight of IRGANOX 1010 (manufactured by Ciba-Geigy Co., Ltd.) as a phenolic compound, dry blending was performed with a Hensil mixer, and then a twin-screw extruder [TEM manufactured by Toshiba Machine Co., Ltd.] -35], the cylinder temperature was set to 280 ° C., and the mixture was melt-kneaded and pelletized. The obtained pellets are injection-molded [Toshiba Machine Co., Ltd. I
S55FPA], the cylinder temperature was set to 290 ° C., and a tensile test piece having a thickness of 1 mm was molded. Fifteen it
It was left in an air oven at 0 ° C. for 1000 hours, and the tensile strength and elongation were measured. The results are shown in Table 2.

Comparative Example 3 33% by weight of SPS, polyamide 66 [Ube Industries, Ltd.]
Manufactured by 2015B, trade name] 60% by weight, maleic anhydride-modified polyphenylene ether 2% by weight, maleic anhydride-modified SEBS [manufactured by Asahi Kasei Corp., MX-072, trade name] 5% by weight, taken as 100 parts by weight. 0.5 parts by weight of IRGANOX 1010 (manufactured by Ciba-Geigy Co., Ltd.) as a phenol compound and 0.3 parts by weight of SUMILIZER TP-D (manufactured by Sumitomo Chemical Co., Ltd.) as a thiodipropionate compound were added. After dry blending with a Hensyl mixer, the mixture was melt-kneaded with a twin-screw extruder [TEM-35 manufactured by Toshiba Machine Co., Ltd.] at a cylinder temperature of 280 ° C., and pelletized. The obtained pellets are injection-molded [Toshiba Machine Co., Ltd. I
S55FPA], the cylinder temperature was set to 290 ° C., and a tensile test piece having a thickness of 1 mm was molded. Fifteen it
It was left in an air oven at 0 ° C. for 1000 hours, and the tensile strength and elongation were measured. The results are shown in Table 2.

Comparative Example 4 33% by weight of SPS, polyamide 66 [Ube Industries, Ltd.]
Manufactured by 2015B, trade name] 60% by weight, maleic anhydride-modified polyphenylene ether 2% by weight, maleic anhydride-modified SEBS [manufactured by Asahi Kasei Corp., MX-072, trade name] 5% by weight, taken as 100 parts by weight. After adding 0.03 part by weight of cuprous iodide and 0.15 part by weight of potassium iodide to the above mixture and dry blending with a Hensil mixer, a twin-screw extruder [manufactured by Toshiba Machine Co., Ltd.] TEM-3
5], the cylinder temperature was set to 280 ° C., melt kneading was performed, and pelletization was performed. The obtained pellets were injection-molded [IS55FPA manufactured by Toshiba Machine Co., Ltd.] at a cylinder temperature of 290 ° C. to form a tensile test piece having a thickness of 1 mm. 1000 in an air oven at 150 ° C
The sample was left for a time and the tensile strength and elongation were measured. The results are shown in Table 2.

Example 10 44% by weight of SPS, polyamide 66 [Ube Industries, Ltd.]
Manufactured by 2015B, trade name] 50% by weight, maleic anhydride-modified polyphenylene ether 6% by weight to 100 parts by weight, and IRGAN as a phenolic compound
OX 1098 (manufactured by Ciba-Geigy Co., Ltd.) was added with 0.5 part by weight, and after dry blending with a Hensil mixer, a twin-screw extruder [TEM-3 manufactured by Toshiba Machine Co., Ltd.]
5] at glass fiber [Asahi Fiber Co., Ltd.
, 03JAFT2A] was side-fed, and the temperature of the cylinder was set to 280 ° C. to melt-knead and pelletize. The obtained pellets are injection molded [IS55FPA manufactured by Toshiba Machine Co., Ltd.] and the cylinder temperature is set to 29.
The tensile test piece having a thickness of 3 mm was molded by setting the temperature to 0 ° C.
It was left to stand in an air oven at 160 ° C. for 1000 hours, and the tensile strength and elongation were measured. The results are shown in Table 2.

Example 11 44% by weight of SPS, polyamide 66 [Ube Industries, Ltd.]
Manufactured by 2015B, trade name] 50% by weight, maleic anhydride-modified polyphenylene ether 6% by weight to 100 parts by weight, and ADEKA as a phenolic compound
STAB AO-80 [manufactured by Asahi Denka Co., Ltd.] 0.5 parts by weight and IRGANOX 1010 [manufactured by Ciba Geigy Co., Ltd.]
0.3 parts by weight, SUMILISER TP-D [manufactured by Sumitomo Chemical Co., Ltd.] as a thiodipropionate compound
After adding 0.3 part by weight of the mixture, dry blending was performed with a Hensyl mixer, and then glass fiber [Asahi Fiber Co., Ltd. 03JAFT2A] was used with a twin-screw extruder [Toshiba Machine Co., Ltd. TEM-35]. ] Was side-fed and the cylinder temperature was set to 280 ° C. to melt-knead and pelletize. The obtained pellets were injection-molded [IS55FPA manufactured by Toshiba Machine Co., Ltd.] at a cylinder temperature of 290 ° C. to form a tensile test piece having a thickness of 3 mm. It was left to stand in an air oven at 160 ° C. for 1000 hours, and the tensile strength and elongation were measured. The results are shown in Table 2.

Comparative Example 5 SPS 44% by weight, polyamide 66 [Ube Industries, Ltd.]
Manufactured by 2015B, trade name] 50% by weight and 6% by weight of maleic anhydride-modified polyphenylene ether were dry-blended with a Hensyl mixer, and then twin-screw extruder [TEM-35 manufactured by Toshiba Machine Co., Ltd.]. While the glass fiber [03JAFT2A manufactured by Asahi Fiber Co., Ltd.] was side-fed, the cylinder temperature was set to 280 ° C., the mixture was melt-kneaded, and pelletized. The obtained pellets are injection molded [IS55FPA manufactured by Toshiba Machine Co., Ltd.] with a cylinder temperature of 290 ° C. and a thickness of 3 mm.
Was formed into a tensile test piece. It was left to stand in an air oven at 160 ° C. for 1000 hours, and the tensile strength and elongation were measured. The results are shown in Table 2.

Comparative Example 6 SPS 44% by weight, polyamide 66 [Ube Industries, Ltd.]
Manufactured by 2015B, trade name] 50% by weight, maleic anhydride-modified polyphenylene ether 6% by weight to 100 parts by weight, and IRGAN as a phenolic compound
OX 1010 [manufactured by Ciba-Geigy Co., Ltd.] 0.5 part by weight,
SUMIL as thiodipropionate compound
IZER TP-D (manufactured by Sumitomo Chemical Co., Ltd.) 0.3 part by weight was added, and after dry blending with a Hensil mixer, a twin-screw extruder [TEM-3 manufactured by Toshiba Machine Co., Ltd.] was used.
5] glass fiber [Asahi Fiber Co., Ltd., 0
3JAFT2A] while side-feeding, the cylinder temperature was set to 280 ° C., melt kneading was performed, and pelletization was performed. The obtained pellets were injection-molded [IS55FPA manufactured by Toshiba Machine Co., Ltd.] at a cylinder temperature of 290 ° C. to form a tensile test piece having a thickness of 3 mm. It 1
It was left to stand in an air oven at 60 ° C. for 1000 hours, and the tensile strength and elongation were measured. The results are shown in Table 2.

Comparative Example 7 SPS 44% by weight, polyamide 66 [Ube Industries, Ltd.]
Manufactured by 2015B, trade name] 50% by weight, maleic anhydride-modified polyphenylene ether 6% by weight to 100 parts by weight, to which cuprous iodide 0.03 parts by weight and potassium iodide 0.15 parts by weight are added. After dry-blending the added product with a Hensil mixer, while side-feeding glass fiber [03JAFT2A manufactured by Asahi Fiber Co., Ltd.] with a twin-screw extruder [TEM-35 manufactured by Toshiba Machine Co., Ltd.] The cylinder temperature was set to 280 ° C., and the mixture was melt-kneaded and pelletized. The obtained pellets were injection-molded [IS55FPA manufactured by Toshiba Machine Co., Ltd.] at a cylinder temperature of 290 ° C. to form a tensile test piece having a thickness of 3 mm. 100 in an air oven at 160 ° C
It was left for 0 hours and the tensile strength and elongation were measured. Second result
Shown in the table.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

[0061]

The polystyrene resin composition of the present invention is
It has excellent properties such as little change in physical properties and color tone even after being exposed to high temperature for a long time, and excellent heat aging resistance, and no problems such as color tone change due to water absorption, deterioration of electrical properties, copper damage, etc. Further, since it is excellent in toughness, rigidity, water resistance, etc., it is preferably used as a material for industrial materials such as electric / electronic materials, industrial structural materials, automobile parts, home electric appliances, and various machine parts.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 77/00 C08L 77/00 101/00 101/00 (56) Reference JP-A-6-345923 (JP, A) JP JP-A-7-48488 (JP, A) JP-A-7-48487 (JP, A) JP-A-6-116461 (JP, A) JP-A-6-220274 (JP, A) JP-A-6-184430 (JP , A) JP 7-18179 (JP, A) JP 7-196868 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (5)

(57) [Claims] 1. (A) (a) 30% of racemic pentad
Polystyrene resin having the above syndiotacticity 1 to 99% by weight, (b) polyamide resin 1 to 99
%, A compatibilizer having compatibility with the components (c) and (a) and having a polar group capable of reacting with the component (b) 0.1 to
Styrene-based polymer composition 10 comprising 10% by weight, (d) 0 to 50% by weight of a rubber-like elastic material and / or a modified product thereof.
(B) N, N'-hexamethylene bis (3,5-di-t-
Butyl-4-hydroxy-hydrocinnamamide),
(C) 3,9-bis [1,1-dimethyl-2- {β-
(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10
-Tetrachiosaspiro [5,5] undecane, (D)
Polystyrene containing at least 0.05 to 5.0 parts by weight of at least one selected from N, N'-bis [3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine. -Based resin composition [however, penta
Erythrityl tetrakis (3-lauryl thiopropione
Other than sulfur-containing antioxidants other than
Ku. ]. 2. The polystyrene resin composition according to claim 1, wherein (E) the following general formula (I): [In the formula, R represents a methyl group or a t-butyl group, and X is 1
Shows the residue which removed n hydroxyl groups of the alcohol which has -4 hydroxyl groups, and n shows the integer of 1-4. ] The polystyrene type resin composition characterized by containing 0.0005-5.0 weight part of the phenolic compounds represented by these. 3. The polystyrene resin composition according to claim 1 or 2, wherein (F) thiodipropionate compound is 0.0005 with respect to 100 parts by weight of the component (A).
A polystyrene-based resin composition, characterized in that it is contained in an amount of up to 5.0 parts by weight. 4. A polystyrene resin containing (G) 1 to 350 parts by weight with respect to 100 parts by weight of the polystyrene resin composition according to claim 1. Composition. 5. A molded article made of the polystyrene resin composition according to claim 1.