JP3531683B2 - Polystyrene resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polystyrene resin composition, more specifically, as a material 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 syndiotactic polystyrene resin composition which is suitably used and has excellent rigidity, heat resistance, impact resistance, water resistance and the like.

[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, and acid / alkali resistance, but its range of application as a material was limited due to its low impact resistance. On the other hand, a polymer having a polar group such as polyamide is excellent in moldability and heat resistance, but it has been desired to be improved because its properties in water absorption and water absorption are significantly changed and its properties are remarkably deteriorated by acid / alkali. In order to solve such a problem, alloying of SPS and polyamide has been conventionally proposed (Japanese Patent Laid-Open No. 62-2579).
No. 5). However, a composition composed of an essentially incompatible resin such as SPS and polyamide cannot avoid a decrease in mechanical properties due to poor dispersibility and insufficient interfacial strength between phases, and thus a simple composition There was a limit to the modifying effect of the compounding.

Further, in order to improve dispersibility and interfacial strength, a compatibilizer or a rubber-like elastic body also serving as a compatibilizer is used.
For example, styrene-polyamide block copolymer (JP-A-1-279944), styrene-glycidyl methacrylate copolymer, styrene-maleic anhydride copolymer (JP-A-2-209938), maleic anhydride-modified styrene block. Copolymer rubber (JP-A-2-219
843), maleic anhydride-modified polyphenylene ether (JP-A-3-126744), maleic anhydride-modified SPS (Japanese Patent Application No. 4-269893), and the like. However, in any case, it could not be said that the mechanical properties and the balance between the mechanical properties and the heat resistance were still sufficient.

[0004]

Under the circumstances, the present invention provides excellent rigidity, heat resistance, impact resistance, water resistance, etc., which are suitably used as materials for various industrial materials. The purpose of the present invention is to provide a syndiotactic polystyrene resin composition having the same.

[0005]

Means for Solving the Problems As a result of intensive studies to develop a syndiotactic polystyrene resin composition having excellent rigidity, heat resistance, impact resistance and water resistance, the present inventors have A composition containing a predetermined proportion of SPS, a thermoplastic resin having a reactive polar group, a particular rubber-like elastic body, and a particular compatibilizer, or a predetermined proportion of modified S
A composition containing a thermoplastic resin having a polar group reactive with PS, a specific rubber-like elastic body, and optionally a compatibilizing agent,
Alternatively, it has been found that a composition obtained by further mixing these compositions with an inorganic filler in a predetermined ratio has excellent properties such as rigidity, heat resistance, impact resistance and water resistance. The present invention has been completed based on such findings.

That is, the present invention provides (1) (a) 1 to 95% by weight of a styrene polymer having a syndiotactic structure, (b) 1 to 95% by weight of polyamide , and (c) hydrogenated.
Styrene-butadiene-styrene block copolymer or
Is methyl acrylate-butyl acrylate-siloxa
-Styrene-core shell rubber 1 to 50% by weight, and a compatibilizing agent having a polar group capable of reacting with the component (d) and the component (b) and 0.1 to 10% by weight. % Polystyrene resin composition, (2) (a ′)
1-95% by weight of a styrene-based polymer having a modified syndiotactic structure having a polar group capable of reacting with the component (b), 1-95% by weight of a polyamide (b), and (c ') (a
1) 50% by weight of a rubber-like elastic material having an affinity for the component
And a polystyrene resin composition comprising (3) the component (a ') 1 to 95% by weight, the component (b) 1 to 95% by weight, the component (c') 1 to 50% by weight, and the component (d '). ) A polystyrene resin composition comprising 0.1 to 10% by weight of a compatibilizing agent having a polar group capable of reacting with the component (b) and having compatibility with the component (a '). . The present invention also provides a polystyrene resin composition obtained by mixing (e) 1 to 350 parts by weight of the inorganic filler with 100 parts by weight of the resin compositions (1) to (3). Is.

In the first resin composition of the present invention,
A styrene-based polymer having a syndiotactic structure is used as the component (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 preferred styrene polymers are polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), 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, the thermal properties and mechanical properties of the resulting composition or molded product may be deteriorated, which is not preferable.

Styrene-based polymers having such a syndiotactic structure can be prepared, for example, in an inert hydrocarbon solvent,
Alternatively, it is produced by polymerizing a styrene-based monomer (a monomer corresponding to the above-mentioned styrene-based polymer) using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in the absence of a solvent. Can be performed
No. 187708). The poly (halogenated alkylstyrene) can be obtained by the method described in JP-A-1-46912, and the hydrogenated polymer can be obtained by the method described in JP-A-1-178505.

In the second and third resin compositions of the present invention, as the component (a '), a modified SPS having a polar group capable of reacting with the component (b) described later is used. This modified SPS can be obtained, for example, by modifying the SPS shown in the above component (a) with a modifying agent, but 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 it is possible to use the polymer shown in the above component (a). In particular, the copolymer of styrene and substituted styrene is compatible with other components. It is preferably used. 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 are, for example, alkylstyrenes such as methylstyrene, ethylstyrene, isopropylstyrene, tert-butylstyrene and vinylstyrene, halogenated styrenes such as chlorostyrene, bromostyrene and fluorostyrene, halogenated chloromethylstyrene and the like. Alkyl styrene, methoxy styrene, alkoxy styrene, such as ethoxy styrene, etc. are mentioned. These substituted styrenes may be used alone or in combination of two or more. Further, the above-mentioned polymer having an atactic structure can be used as long as the amount is 5% by weight or less based on SPS. 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, 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, methacrylic acid. Examples thereof include 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 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.

Of these modified SPS, maleic anhydride modified SPS is particularly preferably used. Further, the modified SPS as the component (a ′) may be used alone or in combination of two or more kinds. The blending amount of the component (a) or the component (a ′) is based on the total weight of the resin components,
1 to 95% by weight, preferably 3 to 90% by weight, more preferably 5 to 85% by weight is selected. When the content is less than 1% by weight, the water resistance and the stability against acid / alkali of the thermoplastic resin as the component (b) are the same as when they are used alone, and when the content exceeds 95% by weight, the SPS of the component (a) or ( The effect of improving the mechanical strength of the modified SPS as the component a ') is not sufficiently exhibited.

In the first, second and third resin compositions of the present invention, a thermoplastic resin having a reactive polar group is used as the component (b). The thermoplastic resin having a reactive polar group is a thermoplastic resin containing at least one polar group such as a carboxyl group, a hydroxyl group and an amino group. Examples of such a thermoplastic resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyoxyethoxybenzoate, polyethylene naphthalate, or the above polyester constituent components and other acid components and / or glycol components. , Acid components such as isophthalic acid, p-oxybenzoic acid, adipic acid, sebacic acid, glutaric acid, diphenylmethanedicarboxylic acid, dimer acid, hexamethylene glycol, diethylene glycol, neopentyl glycol, bisphenol A, neopentyl glycol alkylene oxide addition Obtained by copolymerizing a glycol component such as a product, an aromatic polyester-polyether block copolymer, Examples include aromatic polyester-polylactone block copolymers, polyesters in a broad sense such as polyarylate, and polyamides, polycarbonates, polyolefins such as polar group-modified polyethylene and polar group-modified polypropylene, and polyarylene sulfides. Of these, polyamide is particularly preferred.

As the polyamide, all known polyamides can be used. 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.

Next, 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 and the like. 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 thermoplastic resin having a reactive polar group of the component (b) may be used alone or in combination of two or more, and the blending amount thereof is the total weight of the resin component. 1 to 95% by weight, preferably 3 to 90% by weight, and more preferably 5 to 85% by weight. If the blending amount of this component (b) is less than 1% by weight, (a)
The effect of improving the mechanical strength of the component SPS or the modified SPS of the component (a ') is not sufficiently exerted, and when it exceeds 95% by weight, the water resistance and the stability against acid / alkali are different from those of the component (b) alone. It won't change.

In the first resin composition of the present invention,
As the component (c), a rubber-like elastic body having an affinity with the component (a) is used. In addition, in the second and third resin compositions, a rubber-like elastic body having an affinity with the component (a ′) is used as the component (c ′). This rubber-like elastic material is blended to improve impact resistance and toughness such as elongation. Here, the component (a) or (a ′)
Affinity with the component means that SPS of the component (a)
Or (a ') having a chain having affinity with the modified SPS of the component, specifically having a styrene chain, a styrene copolymer segment, a polyphenylene ether segment as the main chain, block or graft chain, Examples thereof include a random copolymer rubber containing a styrene-based monomer unit and a core-shell rubber having a shell of a styrene-based polymer.

Examples of the rubber-like elastic material used as the component (c) or the component (c ') include 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 (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, 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
Examples thereof include core-shell type particulate elastic bodies such as R). Among these, especially SEB, SEBS, SEP
A core shell rubber containing S and styrene units is preferably used. Particularly, as the core shell rubber, methyl acrylate-butyl acrylate-siloxane-styrene-core shell rubber (MASS), MAS, MBS and the like are preferable. The particle size of these core-shell rubbers is not particularly limited, but should be selected within the range of preferably 0.05 to 1.5 μm, particularly preferably 0.1 to 1.0 μm. If the particle size of the core-shell rubber is less than 0.05 μm, the impact resistance improving effect is not always sufficient, and conversely 1.5 μm.
If it exceeds, the dispersed state will not be good, and as a result, impact resistance may not be effectively improved.
The mixing ratio of the core-shell rubber is not particularly limited, but the core-shell rubber is preferably contained in the rubber-like elastic body which is the component (c) or the component (c ') in an amount of 5 to 95% by weight, particularly preferably It may be blended so as to occupy 20 to 80% by weight. Outside of these ranges, the effect of using the core-shell rubber may not be sufficiently exhibited.

The rubber-like elastic body of the component (c) or the component (c ') may be used alone or in combination of two or more, and the compounding amount thereof is based on the total weight of the resin component. It is selected in the range of 1 to 50% by weight, preferably 5 to 40% by weight. If the content is less than 1% by weight, the effect of improving impact resistance will not be sufficiently exerted, and if it exceeds 50% by weight, the elastic modulus and heat resistance of the composition will be significantly reduced.

In the composition of the present invention, the rubber-like elastic material of the above-mentioned component (c) or component (c ') is used in combination,
If desired, another rubber-like elastic material may be blended.
Examples of the other rubber-like elastic body include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, ethylene propylene rubber (EPR) or Examples thereof include ethylene propylene diene rubber (EPDM). When these rubber-like elastic bodies are used in combination, the compounding ratio is 50% by weight from the viewpoint of elastic modulus and heat resistance. % Or less is desirable.

In the first resin composition of the present invention,
The component (d) has compatibility with the component (a),
In addition, a compatibilizing agent having a polar group capable of reacting with the component (b) is used. Further, in the third resin composition,
As the component (d ′), a compatibilizing agent having compatibility with the component (a ′) and 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 component (a) or the component (a ') and the component (b), finely dispersing the domain, and improving the interfacial strength. In the component (d) or the component (d ′), 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), specifically, an acid anhydride. Group, carboxylic acid group, carboxylic acid ester group, carboxylic acid chloride group, carboxylic acid amide group, carboxylic acid base, sulfonic acid group, sulfonic acid ester group, sulfonic acid chloride group, sulfonic acid amide group, sulfonic acid base, Examples thereof include epoxy group, amino group, imide group, oxazoline group and the like.

Further, those having a compatibility with the component (a) or the component (a ') are those having a skeleton compatible with the SPS of the component (a) or the modified SPS of the component (a'). Specifically, a styrene chain, a styrene-based copolymer segment, a polyphenylene ether segment, etc. are main chains,
Examples thereof include those having a block or graft chain. Specific examples of the compatibilizing agent used as the component (d) include a styrene-maleic anhydride copolymer (SM
A), a styrene-glycidyl methacrylate copolymer,
Terminal carboxylic acid modified polystyrene, terminal oxazoline modified polystyrene, terminal amine modified polystyrene, sulfonated polystyrene, styrene-based ionomer, styrene-methyl methacrylate graft copolymer, (styrene-glycidyl methacrylate) -methyl methacrylate graft copolymer, acid modified acrylic -Styrene graft copolymer, (styrene-glycidyl methacrylate)-
Styrene graft copolymer, polybutylene terephthalate-polystyrene graft copolymer, maleic anhydride modified SPS, glycidyl methacrylate modified SP
S, modified SPS such as amine-modified SPS, (styrene-
Maleic anhydride) -polyphenylene ether graft copolymer, maleic anhydride modified polyphenylene ether,
Examples thereof include modified polyphenylene ethers such as glycidyl methacrylate modified polyphenylene ether and amine modified polyphenylene ether. Among these,
In particular, modified SPS and modified polyphenylene ether are suitable.

The modified SPS may be the same as the modified SPS described as the component (a '). The 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 3,306,875 are known.
Nos. 3,257,357 and 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, for example copolymers derived from two or more of the phenolic compounds used for the preparation of said homopolymers. Further examples include graft copolymers and block copolymers of vinyl aromatic compounds such as polystyrene and the above-mentioned polyphenylene ether. Of these, poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferably used. As the modifier used for modifying these polyphenylene ethers, compounds having an ethylenic double bond and a polar group in the same molecule can be used. Examples of such modifiers include maleic anhydride, maleic acid, maleic acid ester, maleimide and its N-substituted product, maleic acid salt, acrylic acid, acrylic acid ester, acrylic acid amide, acrylic acid salt, methacrylic acid, methacrylic acid. Examples thereof include 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 or in combination of two or more.

The modified polyphenylene ether can be obtained 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.

On the other hand, as the compatibilizing agent used as the component (d '), the same as the compatibilizing agent exemplified as the compatibilizing agent for the component (d) except the modified SPS are the same. it can. The compatibilizing agent of the component (d) or the compatibilizing agent of the component (d ′) may be used alone or in combination of two or more, and the component (d) or the component (d ′) may be used. It is desirable that the polar group content therein is in the range of 0.01 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 (d) or component (d ') in order to exert the effect as a compatibilizer, and as a result, the mechanical properties of the composition and The heat resistance is lowered, which is not preferable. Also, 20% by weight
When it exceeds, the compatibility with the component (a) or the component (a ′) decreases, which is not preferable. The blending amount of the component (d) or the component (d ′) 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 amount is less than 0.1% by weight, the effect as a compatibilizer is not sufficiently exerted, resulting in poor dispersion and insufficient interfacial strength. If it exceeds 10% by weight, the heat resistance of the composition is remarkably reduced. . An inorganic filler may be added to the first, second and third resin compositions as the component (e) for the purpose of further improving the elastic modulus and heat resistance of the resin compositions.

The shape of the inorganic filler is not particularly limited and may be fibrous, granular or powdery. Examples of the fibrous filler include glass fiber, carbon fiber, whiskers, and the like, and the shapes include cloth, mat, focused cut, short fiber, filament, and whiskers. , Length is 0.05-5
It is preferably 0 mm and the fiber diameter is 5 to 20 μm. On the other hand, examples of granular or powdery fillers include talc, carbon black, graphite, titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, calcium oxysulfate, tin oxide. , Alumina, kaolin, silicon carbide, metal powder, glass powder, glass flakes, glass beads and the like.
Among these fillers, glass fillers such as glass powder, glass flakes, glass beads, glass filaments, glass fibers, glass rovings, and glass mats are particularly preferable.

The filler is preferably surface-treated with a coupling agent. The coupling agent used for the surface treatment is used to improve the adhesiveness between the filler and the resin, and is selected from conventionally known ones such as so-called silane coupling agents and titanium coupling agents. Any one can be selected and used. Among them, γ-aminopropyltrimethoxysilane, N-β- (aminomethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)
Aminosilanes such as ethyltrimethoxysilane, epoxysilanes, and isopropyltri (N-amidoethyl, aminoethyl) titanate are preferred.

The above-mentioned inorganic filler may be used alone or in combination of two or more kinds, and the compounding amount thereof is 1 to 350 parts by weight with respect to 100 parts by weight of the resin composition,
It is preferably selected in the range of 5 to 200 parts by weight. If the blending amount is less than 1 part by weight, a sufficient blending effect as a filler cannot be exhibited, and if it exceeds 350 parts by weight, dispersibility is poor and molding becomes difficult. In addition, the resin composition of the present invention contains various additive components such as an antioxidant, a nucleating agent, a plasticizer, a release agent, a flame retardant, a pigment, carbon black, an electrostatic charge as long as the object of the present invention is not impaired. Additives such as inhibitors, or other thermoplastic resins can be blended. By using the resin composition of the present invention, a molded article having excellent physical properties can be obtained regardless of the molding method. Examples thereof include injection-molded products, extrusion-molded sheets and films, extrusion-molded and thermoformed containers and trays, extrusion-molded and stretched uniaxially and biaxially stretched films and sheets, and spun fiber-shaped molded products.

[0032]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The physical properties of the resin composition were determined as follows. (1) Izod impact strength: JISK 7110
(2) Elongation: JISK 7113
(3) Flexural modulus: JISK 7203
(4) Heat distortion temperature: JISK 7207
(5) Water absorption: JISK 7209
Complies with

Production Example 1 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 320,000 when measured by gel permeation chromatography at 130 ° C. The weight average molecular weight / number average molecular weight was 2.60. further,
According to melting point and ¹³ C-NMR measurement, this polymer was found to be SPS.
Was confirmed.

Production Example 2 0.9 liter of purified styrene was added to a 2 liter reaction vessel.
After adding 0.1 liter of p-methylstyrene and 1 mmol of triethylaluminum and heating to 80 ° C., a premixed catalyst [pentamethylcyclopentadienyl titanium trimethoxide 90 μmol, dimethylanilinium tetrakis (pentafluorophenyl)] was added. 90 micromoles of borate, 29.1 mmol of toluene, 1.8 mmol of triisobutylaluminum] 16.5 ml were added, and 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 a polymer 390.
g was obtained. The weight average molecular weight of this polymer is 1, 2, 4
-Measured by gel permeation chromatography at 130 ° C using trichlorobenzene as a solvent,
It was 328,000. The weight average molecular weight / number average molecular weight was 2.60. In addition, melting point and ¹³ C-NM
By R measurement, it was confirmed that this polymer was SPS and contained 12 mol% of p-methylstyrene unit.

Production Example 3 Styrene-p-methylstyrene copolymer of Production Example 2 (p
-Methylstyrene unit content 12 mol%) 1 kg, maleic anhydride 30 g, and a radical generator 2,3-dimethyl-2,3-diphenylbutane [NOFMER BC, trade name] 10 g, dry blend And then 30
Screw rotation speed of 200 rp using mm twin screw extruder
Melt kneading was performed at a temperature of 300 ° C. At this time, the resin temperature was about 330 ° C. After the strand was cooled, it was reprecipitated in methanol, the recovered polymer was subjected to Soxhlet extraction with methanol, and after drying, the carbonyl absorption intensity of the IR spectrum and the modification rate were determined by titration. At this time, the modification rate was 1.05% by weight.

Production Example 4 1 kg of polyphenylene ether (intrinsic viscosity 0.47 deciliter / g, in chloroform, 25 ° C.), 60 g of maleic anhydride, 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 (modified PPO). 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 SPS of Production Example 1 (weight average molecular weight 320,000, weight average molecular weight / number average molecular weight 2.60) 22.2 wt%, polyamide 66 [manufactured by Ube Industries, 2015B, trade name] 70 wt%, SEBS [Glass Chemical Co., Ltd., G-1651, trade name] 6.0 wt% as a rubber-like elastic body, and maleic anhydride-modified SPS1 of Production Example 3 as a compatibilizer.
(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by ADEKA ARGUS CORPORATION, PEP-36, trade name) as an antioxidant based on 100 parts by weight of 8 wt% .1 part by weight, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'
-Hydroxyphenyl)] propionate (trade name: MARK AO60, manufactured by Adeka Argus Co., Ltd.) 0.1 part by weight was added, dry blended with a Henschel mixer, and then melt-kneaded with a twin-screw extruder to form pellets. Using the obtained pellets, injection molding was performed to obtain tensile test pieces, bending test pieces and Izod test pieces. The obtained test pieces were used for Izod impact strength, elongation, elastic modulus, and heat distortion temperature. The water absorption and the elastic modulus after water absorption were measured, and the results are shown in Table 1.

Examples 2 and 3 Example 1 was repeated except that the composition was changed as shown in Table 1.
I went in the same way. The results are shown in Table 1.

Example 4 The procedure of Example 1 was repeated, except that 1.8 wt% of the maleic anhydride-modified polyphenylene ether of Production Example 4 was used as the compatibilizing agent of the component (d). The results are shown in Table 1.

Examples 5 and 6 Example 4 was changed except that the composition was changed as shown in Table 1.
I went in the same way. The results are shown in Table 1.

Example 5A In Example 5, SEBS [Shell Chemical Co., Ltd., G
The same operation as in Example 5 was performed, except that a core-shell type MASS [S-2001, trade name, manufactured by Mitsubishi Rayon Co., Ltd.] was used instead of -1651, trade name. The results are shown in Table 1.

Example 6 Example 4 except that the composition was changed as shown in Table 1.
I went in the same way. The results are shown in Table 1.

Example 6A In Example 6, SEBS [Shell Chemical Co., G
The same operation as in Example 6 was performed, except that a core-shell type MASS [S-2001, trade name, manufactured by Mitsubishi Rayon Co., Ltd.] was used instead of -1651, trade name. The results are shown in Table 1.

Example 7 Maleic anhydride-modified SPS of Production Example 3 as component (a ')
Example 1 was repeated except that 22.2 wt% was used. The results are shown in Table 1.

Example 8 100 parts by weight of the composition of Example 4 was used as a nucleating agent for sodium-2,2'-methylene-bis- (4,6-di-t).
-Butylphenyl) phosphate (trade name: NA-1
The same operation as in Example 4 was performed, except that 0.5 part by weight of Adeka Argus Co., Ltd.) was added. The results are shown in Table 1.

Example 8A SEBS [Shell Chemical Co., Ltd., G
The same operation as in Example 8 was performed except that a core-shell type MASS [S-2001, trade name, manufactured by Mitsubishi Rayon Co., Ltd.] was used in place of the -1651, trade name. The results are shown in Table 1.

Comparative Examples 1 and 2 Example 1 was repeated except that 100% by weight of SPS and 100% of polyamide were used. The results are shown in Table 1.

Comparative Examples 3 to 5 The compatibilizing agent of the component (d) was not added, and the compounding composition was the first.
The same procedure as in Example 1 was repeated except that the changes were made as shown in the table. The results are shown in Table 1.

Comparative Examples 6 to 11 The rubber-like elastic body of the component (c) was not added and the compounding composition was changed to the first composition.
The same procedure as in Example 1 or 4 was repeated except that the changes were made as shown in the table. The results are shown in Table 1.

Comparative Example 12 The procedure of Example 7 was repeated except that the rubber-like elastic material as the component (c ') was not added and the compounding composition was changed as shown in Table 1. The results are shown in Table 1.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

As is clear from Table 1, the impact is larger than the case where only (a) + (c), (a) + (d) and (a ') are added to the component (b). It is possible to obtain a heat resistant / water resistant resin composition having significantly improved strength and elongation.

Example 9 SPS of Production Example 1 (weight average molecular weight 320,000, weight average molecular weight / number average molecular weight 2.60) 22.2 wt%, polyamide 66 [manufactured by Ube Industries, Ltd., 2015B, trade name]
70 wt%, SEBS as a rubber-like elastic body [Kraton G-1651, manufactured by Shell Chemical Co., Ltd., trade name] 6.0 w
t% and 1.8% by weight of maleic anhydride-modified SPS of Production Example 3 as a compatibilizer, a total of 100 parts by weight, and (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diester as an antioxidant. 0.1 parts by weight of phosphite (manufactured by Adeka Agas, PEP-36, trade name), tetrakis [methylene-3- (3 ', 5'-di-t-butyl-
4'-hydroxyphenyl)] propionate (manufactured by ADEKA ARGUS CORPORATION, MARK AO60, trade name] 0.1 part by weight was added, and dry blending was performed with a Henschel mixer. Part was side-fed and melt-kneaded to form pellets, and the obtained pellets were injection-molded to obtain tensile test pieces, bending test pieces and Izod test pieces. The Izod impact strength, elongation, elastic modulus, thermal deformation humidity, water absorption and elastic modulus after water absorption were measured, and the results are shown in Table 2.

Examples 10 and 11 Example 9 except that the compounding composition was changed as shown in Table 2.
I went in the same way. The results are shown in Table 2.

Example 12 Example 12 was carried out in the same manner as in Example 9 except that 1.8 wt% of the maleic anhydride-modified polyphenylene ether of Production Example 4 was used as the compatibilizing agent of the component (d). The results are shown in Table 2.

Example 12A SEBS [Shell Chemical Co., Ltd.,
The same operation as in Example 12 was carried out except that a core-shell type MASS [S-2001, trade name, manufactured by Mitsubishi Rayon Co., Ltd.] was used instead of G-1651, trade name]. The results are shown in Table 2.

Example 13 Example 1 except that the compounding composition was changed as shown in Table 2.
It carried out similarly to 2. The results are shown in Table 2.

Example 13A SEBS [Shell Chemical Co., Ltd.,
The same operation as in Example 13 was performed except that a core shell type MASS [S-2001, trade name, manufactured by Mitsubishi Rayon Co., Ltd.] was used instead of G-1651, trade name. The results are shown in Table 2.

Example 14 Example 1 except that the compounding composition was changed as shown in Table 2.
It carried out similarly to 2. The results are shown in Table 2.

Example 14A In Example 14, SEBS [Shell Chemical Co., Ltd.,
The same operation as in Example 14 was performed, except that a core-shell type MASS [S-2001, trade name, manufactured by Mitsubishi Rayon Co., Ltd.] was used instead of G-1651, trade name. The results are shown in Table 2.

Example 15 Maleic anhydride-modified SPS of Production Example 3 as component (a ')
Example 9 was repeated except that 22.2 wt% was used. The results are shown in Table 2.

Comparative Examples 13 and 14 The procedure of Example 9 was repeated except that SPS and polyamide were each used in an amount of 100 wt%. The results are shown in Table 2.

Comparative Examples 15 to 17 The compatibilizer of the component (d) was not added, and the compounding composition was the second.
Example 9 was carried out in the same manner as in Example 9 except that the changes were made as shown in the table. The results are shown in Table 2.

Comparative Examples 18 to 23 The rubber-like elastic body as the component (c) was not added and the compounding composition was changed to the second composition.
It carried out like Example 9 or 12 except having changed as shown in a table. The results are shown in Table 2.

Comparative Example 24 The procedure of Example 15 was repeated except that the rubber-like elastic material as the component (c ') was not added and the compounding composition was changed as shown in Table 2. The results are shown in Table 2.

[0069]

[Table 5]

[0070]

[Table 6]

[0071]

[Table 7]

[0072]

[Table 8]

As is clear from Table 2, the impact strength is higher than that in the case where only (a) + (c), (a) + (d) and (a ') are added to the component (b). It is possible to obtain a highly rigid, heat resistant and water resistant resin composition having significantly improved elongation.

[0074]

The polystyrene resin composition of the present invention is
Excellent rigidity, toughness, compatibility, heat resistance, impact resistance, acid resistance
It has alkalinity and water resistance. For example, electrical / electronic materials (connectors, printed boards, etc.), industrial structural materials, automobile parts (vehicle-mounted connectors, wheel caps, cylinder head covers, etc.), home appliances, various machine parts, etc. It is preferably used as a material for industrial materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (6)

(57) [Claims] 1. (a) 1 to 95% by weight of a styrene polymer having a syndiotactic structure, and (b) a polyamide 1
~ 95% by weight, (c) hydrogenated styrene-butadiene-
Styrene block copolymer or methyl acrylate
Cyl acrylate-siloxane-styrene-core shell
Polystyrene system comprising 1 to 50% by weight of rubber and 0.1 to 10% by weight of a compatibilizing agent having compatibility with (d) and (a) components and having a polar group capable of reacting with (b) component. Resin composition. 2. A styrene-based polymer having a modified syndiotactic structure having a polar group capable of reacting with the components (a ′) and (b), 1 to 95% by weight, (b) a polyamide, 1 to 95% by weight, and ( c ') A polystyrene resin composition comprising 1 to 50% by weight of a rubber-like elastic material having an affinity with the component (a'). 3. A styrene-based polymer having a modified syndiotactic structure having a polar group capable of reacting with the components (a ′) and (b), 1 to 95% by weight, (b) a polyamide, 1 to 95% by weight, and (c). ') 1 to 50% by weight of a rubber-like elastic material having an affinity with the component (a'), and compatibility with the components (d ') and (a') and capable of reacting with the component (b) A polystyrene resin composition comprising 0.1 to 10% by weight of a compatibilizing agent having a polar group. 4. The (e) inorganic fillers 1 to 3 relative to 100 parts by weight of the resin composition according to claim 1.
A polystyrene resin composition containing 50 parts by weight. 5. (c) Hydrogenated styrene-butadiene-
5-9 core shell rubber in styrene block copolymer
The polystyrene resin composition according to claim 1, containing 5% by weight. 6. The polystyrene-based resin composition according to claim 2, wherein the rubber-like elastic body (c ′) contains a core-shell rubber in an amount of 5 to 95% by weight.