JPH0762175A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. which is excellent in heat resistance, moldability, etc., and also in mechanical properties such as impact strength, stiffness, elongation, etc. CONSTITUTION:A resin compsn. is prepd. by compounding a compsn. comprising 85-99.9wt.% syndiotactic styrenic polymer, 0.1-10wt.% polar polymer having the compatibility with or affinity for the styrenic polymer (e.g. a modified syndiotactic polystyrene or a modified polyphenylene ether), and optionally 0.1-5wt.% polyphenylene ether with a polar rubbery elastomer (e.g. a maleic- anhydride-modified hydrogenated styrene-butadiene-styrene block copolymer) and if necessary a rubbery elastomer (e.g. a butadiene-styrene block copolymer). The objective thermoplastic resin compsn. is prepd. by compounding 100 pts.wt. above-prepd. resin compsn. with 1-350 pts.wt. inorg. filler.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition, and more specifically to a polystyrene-based thermoplastic resin composition having excellent heat resistance, chemical resistance, moldability, etc., and having significantly improved impact resistance and elongation. Regarding things.

[0002]

2. Description of the Related Art Conventionally, the mechanical properties, particularly impact resistance, rigidity, and heat resistance have been improved by blending various thermoplastic resins with an inorganic filler such as glass fiber. In recent years, a styrene-based polymer having a syndiotactic structure (hereinafter referred to as SPS) has been developed,
It has attracted attention as an engineered plastic with excellent water resistance, but it is not sufficient in terms of rigidity and impact strength.

Therefore, in order to improve mechanical properties, heat resistance, etc., JP-A-62-257948 discloses an SP.
A thermoplastic resin composition in which S is blended with an inorganic filler, and JP-A-1-182344 proposes a thermoplastic resin composition in which SPS is blended with a thermoplastic resin and / or rubber and an inorganic filler. . However, in these resin compositions, the adhesiveness between SPS and the inorganic filler was insufficient. Then, in JP-A-3-126747, it is further proposed that a composition excellent in impact resistance, heat resistance and mechanical properties can be obtained by adding maleic anhydride-modified polyphenylene ether. It was not sufficiently satisfactory in terms of toughness such as strength and elongation. Furthermore, in order to further improve the toughness of the resin composition, it is proposed in Japanese Patent Application No. 4-46901 to blend a rubber-like elastic body. However, in any case, a relatively large amount of rubber is required to improve toughness such as impact strength and elongation of SPS, and as a result, S
There is a problem that the heat resistance, rigidity, moldability, solvent resistance, etc., which are the inherent characteristics of PS, are reduced. Thus, a resin composition having excellent mechanical properties such as impact resistance, rigidity, and elongation while maintaining the properties, heat resistance, moldability, chemical resistance, etc. of the styrene-based polymer having a syndiotactic structure. Was not obtained.

In view of the above situation, the present inventors have earnestly sought to develop a thermoplastic resin composition having excellent mechanical properties, particularly impact strength, rigidity, long-term heat resistance, etc., without impairing the properties of SPS. Repeated research. As a result, it has been found that blending SPS with polyphenylene ether in a specific range is effective in improving toughness. Further, by using a rubber-like elastic body having a polar group as the rubber-like elastic body, or by using a rubber-like elastic body having a polar group and a rubber-like elastic body in combination, the effect of improving the rubber component such as impact strength and elongation can be obtained. Have been found to significantly improve. Furthermore, SP
By adding polyphenylene ether and a rubber-like elastic body having a polar group to S, it is possible to more effectively improve impact resistance, toughness such as elongation, and heat resistance, which is an inherent property,
It has been found that a resin composition can be obtained that does not reduce rigidity and the like.

[0005]

The present invention has been completed based on such findings. That is, the present invention provides (A) (a) 90 to 99.9% by weight of a styrene polymer having a syndiotactic structure, and (b) the above (a).
(B) a resin composition comprising 0.1 to 10.0% by weight of a polymer having compatibility or affinity with the components and having a polar group
(A) Resin 10 containing a rubber-like elastic body having a polar group
The present invention provides a thermoplastic resin composition (hereinafter, referred to as the first invention) in which 1 to 350 parts by weight of the inorganic filler (C) is mixed with 0 parts by weight. The present invention also provides (A)
(A) 90 to 99.9% by weight of a styrene polymer having a syndiotactic structure, and (b) a polymer having compatibility or affinity with the component (a) and having a polar group 0.1.
~ 10.0 wt% resin blend and (B) (a) polar group rubber-like elastic body 0.1 to 99.9 wt% and (b)
(C) Inorganic fillers 1 to 3 with respect to 100 parts by weight of a resin containing an elastic body composed of a rubber-like elastic body of 0.1 to 99.9% by weight.
A thermoplastic resin composition containing 50 parts by weight (hereinafter,
It is called the second invention. ), (A) (a) 85 to 99.8% by weight of a styrene polymer having a syndiotactic structure,
(B) Polymer having compatibility or affinity with the component (a) and having a polar group, 0.1 to 10.0% by weight, and (c)
Thermoplastic resin composition (hereinafter referred to as the third invention) in which 100 parts by weight of a resin compound consisting of 0.1 to 5.0% by weight of polyphenylene ether and 1 to 350 parts by weight of an inorganic filler (C) are compounded. 85% to 99.8% by weight of (A) (a) a styrene polymer having a syndiotactic structure, (b) a polymer having a compatibility or affinity with the component (a) and having a polar group. 100% by weight of a resin compound consisting of 0.1-10.0% by weight and (c) a polyphenylene ether of 0.1-5.0% by weight, and (B) a rubber-like elastic body having a polar group (a) (C) 1 to 350 parts by weight of an inorganic filler (hereinafter referred to as the fourth invention), (A) (a) a styrene-based polymer having a syndiotactic structure. Combined 85 to 99.8% by weight, (b) Compatibility with the above (a) component Alternatively, a resin compound comprising (A) a polymer having an affinity and having a polar group (0.1 to 10.0% by weight) and (c) a polyphenylene ether (0.1 to 5.0% by weight), and (B) and (b) a rubber. A thermoplastic resin composition (hereinafter referred to as the fifth invention) in which 1 to 350 parts by weight of the (C) inorganic filler is added to 100 parts by weight of the resin in which the elastic body is mixed,
And (A) (a) 85 to 99.8% by weight of a styrene polymer having a syndiotactic structure, (b) a polymer having a compatibility or affinity with the component (a) and having a polar group. (B) a resin blend consisting of 0.1-10.0 wt% and (c) polyphenylene ether 0.1-5.0 wt%
(A) 0.1 to 99.9% by weight of a rubber-like elastic body having a polar group
And (b) a thermoplastic resin in which 1 to 350 parts by weight of the inorganic filler (C) is added to 100 parts by weight of the resin in which the elastic material is 0.1 to 99.9% by weight of the rubber-like elastic material. The present invention also provides a composition (hereinafter referred to as the sixth invention).

The resin composition (A) in the composition of the present invention is compatible or compatible with the styrene polymer (SPS) having a syndiotactic structure as the component (a) and (b) the component (a). In the case where it is composed of a polymer having properties and having a polar group (first and second inventions) and when the component (a) and component (b) are further added with (c) polyphenylene ether (third and fourth). , 5 and 6 inventions).

Here, the syndiotactic structure of the components (A) and (a) is a syndiotactic structure, that is, a phenyl group having a side chain with respect to the main chain formed from carbon-carbon bonds. And substituted phenyl groups have a three-dimensional structure in which they are alternately located in opposite directions, and their tacticity is determined by a nuclear magnetic resonance method using an isotope carbon ( ¹³ C-NM
R method). ^The tacticity measured by the ¹³ C-NMR method can be indicated by the abundance ratio of a plurality of continuous constitutional units, for example, diad in the case of two, triad in the case of 3, and pentad in the case of 5. However, the styrene-based polymer having a syndiotactic structure referred to in the present invention is usually 75% or more, preferably 85% or more in racemic dyad, or 30% or more, preferably 50% or more in racemic pentad. Polystyrene having syndiotacticity, 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. In addition, here, as poly (alkylstyrene), poly (methylstyrene),
There are poly (ethyl styrene), poly (isopropyl styrene), poly (tertiary butyl styrene), poly (phenyl styrene), poly (vinyl naphthalene), poly (vinyl styrene), etc., and as poly (halogenated styrene), Examples include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene).
Further, as poly (halogenated alkyl styrene),
Poly (chloromethylstyrene) and the like, and poly (alkoxystyrene) includes poly (methoxystyrene) and poly (ethoxystyrene). Among 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 An example is coalescence.

The styrene polymer is not particularly limited in molecular weight, but has a weight average molecular weight of 10000 or more,
It is 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, the weight average molecular weight is 10,0
If it is less than 00, the thermal properties and mechanical properties of the resulting composition or molded product are deteriorated, which is not preferable. The styrene-based polymer (SPS) having such a syndiotactic structure can be obtained, for example, by using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent. It can be produced by polymerizing a system monomer (a monomer corresponding to the above styrene polymer) (JP-A-62-187).
708). Further, poly (halogenated alkylstyrene) can be obtained by the method described in JP-A-1-46912, and these hydrogenated polymers can be obtained by the method described in JP-A-1-178505.

In the present invention, the polymer having compatibility or affinity with the above-mentioned component (A) (a) which is the component (A) (b) and having a polar group improves mechanical properties. (C) is added in order to improve the adhesiveness between the inorganic filler and the resin. Here, the polymer having compatibility or affinity with the component (A) (a) is a polymer having a chain showing compatibility or affinity with the component (A) (a) in the polymer chain. . Specific examples of such a polymer include those having syndiotactic polystyrene, atactic polystyrene, isotactic polystyrene, styrene copolymer, polyphenylene ether, polyvinyl methyl ether, etc. as a main chain, block or graft chain, etc. Is mentioned.

Further, the polar group of the polymer having a polar group may be any one which improves the adhesiveness to the inorganic filler of the component (C), specifically, an acid anhydride group, Carboxylic acid group, carboxylic acid ester group, carboxylic acid chloride group,
Carboxylic acid amide group, Carboxylic acid group, Sulfonic acid group,
Sulfonate group, Sulfonate group, Sulfonamide group, Sulfonate group, Epoxy group, Amino group,
Examples thereof include imide group and oxazoline group.

The content of the polar group is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight based on 100% by weight of the components (A) and (b). If the content is less than 0.01% by weight, it is necessary to add a large amount of the components (A) and (b), which lowers the mechanical properties, heat resistance, moldability, etc. of the resulting composition, which is not preferable. .
On the other hand, if it exceeds 20% by weight, the compatibility with the component (a) decreases.

Specific examples of the components (A) and (b) include styrene-maleic anhydride copolymer (SMA); styrene-
Glycidyl methacrylate copolymer; terminal carboxylic acid modified polystyrene; terminal epoxy modified polystyrene; terminal oxazoline modified polystyrene; terminal amine modified polystyrene; sulfonated polystyrene; styrene-based ionomers; 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 syndiotactic polystyrene, glycidyl methacrylate-modified Modification of syndiotactic polystyrene, amine-modified syndiotactic polystyrene, etc. Nji syndiotactic polystyrene;
(Styrene-maleic anhydride) -polyphenylene ether-graft polymer, maleic anhydride-modified polyphenylene ether, glycidyl methacrylate-modified polyphenylene ether, amine-modified polyphenylene ether and other modified polyphenylene ethers, and two or more kinds of these polymers. It is also possible to use them in combination.

Among these, modified syndiotactic polystyrene and modified polyphenylene ether are particularly preferable. A suitable method for producing the modified syndiotactic polystyrene and the modified polyphenylene ether will be described below. The components (A) and (b) are not limited by this.

First, in the case of modified syndiotactic polystyrene, syndiotactic polystyrene may be used as a raw material, and it is not particularly limited and may be the same as component (A) (a), but it is particularly compatible with styrene. A substituted styrene copolymer is preferably used. In this case, the composition ratio of the copolymer is not particularly limited, but the substituted styrene amount is preferably 3 to 50 mol%. 3 mol%
If it is less than 50%, the modification is difficult, and if it exceeds 50 mol%, the compatibility with the components (A) and (a) decreases.

Substituted styrenes suitable as comonomers include alkylstyrenes such as methylstyrene, ethylstyrene, isopropylstyrene, tert-butylstyrene, vinylstyrene; chlorostyrene, bromostyrene,
Halogenated styrenes such as fluorostyrene; halogenated alkylstyrenes such as chloromethylstyrene and bromomethylstyrene; alkoxystyrenes such as methoxystyrene and ethoxystyrene.

In the case of modified polyphenylene ether, polyphenylene ether is used as a raw material. Polyphenylene ether is a compound known per se,
For use for this purpose, U.S. Pat. No. 3,306,874,
Reference can be made to the specifications of 3,306,875, 3,257,357 and 3,257,358. Polyphenylene ethers are usually prepared by oxidative coupling reactions in the presence of copper amine complexes and one or more di- or tri-substituted phenols to form homopolymers or copolymers. Here, the copper amine complex may be a copper amine complex derived from primary, secondary and / or 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-hydroxydiethyl-1,4-phenylene ether), poly (2-methyl-6-n-butyl-1,4-phenylene ether), poly (2-ethyl-6-isopropyl-1,4-phenylene ether) , Poly (2-ethyl-6-n-propyl-1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether), poly [2- (4'-methylphenyl)
-1,4-phenylene ether], poly (2-bromo-
6-phenyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2-phenyl-1,4-phenylene ether), poly (2-chloro- 1,4-phenylene ether), poly (2-methyl-1,4-phenylene ether), poly (2-chloro-6-ethyl-1,4-phenylene ether), poly (2-chloro-6-bromo-) 1,
4-phenylene ether), poly (2,6-di-n-propyl-1,4-phenylene ether), poly (2-methyl-6-isopropyl-1,4-phenylene ether), poly (2-chloro- 6-methyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,
4-phenylene ether), poly (2,6-dibromo-)
1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether) and poly (2,2).
6-dimethyl-1,4-phenylene ether) and the like.

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

Next, as a modifier for modifying the above-mentioned raw materials, a compound containing an ethylenic double bond and a polar group in the same molecule can be used. Examples of such a compound include maleic anhydride, maleic acid, maleic acid salt, maleic acid ester, maleimide and its N-substituted compound, acrylic acid, acrylic acid salt, acrylic acid ester, acrylic acid amide, methacrylic acid, methacrylic acid. Examples thereof include acid ester, methacrylic acid amide, and glycidyl methacrylate. Of these, maleic anhydride and glycidyl methacrylate are particularly preferable.

Modification is carried out using the above raw materials and modifier. The modification method can be performed by a known method. For example, a method of melt-kneading at a temperature of 150 to 350 ° C. for reaction using a roll mill, a Banbury mixer, an extruder, or the like, a method of heating reaction in a solvent such as benzene, toluene, xylene, and the like can be mentioned. Furthermore, in order to make these reactions proceed rapidly, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate,
A radical generator such as azobisisobutyronitrile, azobisisovaleronitrile, 2,3-diphenyl-2,3-dimethylbutane may be present. A preferable method is a method in which the mixture is melt-kneaded and modified in the presence of a radical generator.

The modified syndiotactic polystyrene thus obtained is particularly preferably maleic anhydride modified syndiotactic polystyrene, and the modified polyphenylene ether is particularly preferably maleic anhydride modified polyphenylene ether.

In the first and second aspects of the invention, the proportion of each component of the (A) resin blend is 90 to 99.9% by weight of the (A) (a) component and 0.1 to 10 of the (A) (b) component. %, More preferably 92 to 99.5% by weight of component (A) (a) and 0.5 to 8% by weight of component (A) (b). here,
If the amount of the components (A) and (b) is less than 0.1% by weight, the effect of adhering to the inorganic filler (C) is low, and if it exceeds 10% by weight, the adhesiveness of the components (A) and (a) decreases. It is not preferable because the heat resistance and moldability of the composition are significantly reduced.

In the third, fourth, fifth and sixth inventions, (A)
The blending ratio of each component of the resin blend is (A) (a) component 85
To 99.8% by weight, component (A) (b) 0.1 to 10% by weight and component (A) (c) 0.1 to 5% polymerized, more preferably (A) each component of the resin formulation. The blending ratio is 87 to 99.0% by weight of the component (A) (a), 0.5 to 8% by weight of the component (A) and (b) and 0.5 to 5% by weight of the component (A) and (c). If the amount of the components (A) and (c) is less than 0.1% by weight, the effect of improving the toughness is low, and if it exceeds 5% by weight, the crystallinity of the components (A) and (a) is lowered, and the heat resistance of the composition is reduced. And moldability are significantly reduced, which is not preferable.

Next, the polyphenylene ether which is the component (A) (c) is the same as the known polyphenylene ether described in the modification raw material of the component (A) (b). Particularly preferred is poly (2,6-dimethyl-1,
4-phenylene ether). The molecular weight of polyphenylene ether is not particularly limited, but it is preferable that the intrinsic viscosity measured at 25 ° C in chloroform is 0.2 dl / g or more. If the intrinsic viscosity is less than 0.2 dl / g, the effect of improving the toughness by adding the polyphenylene ether is not sufficient.

Further, the (B) elastic body of the present invention is (B)
(A) a rubber-like elastic body having a polar group (first and fourth inventions), (B) (b) a rubber-like elastic body (fifth invention), (B) (a) a polar group When the rubber-like elastic body has (B) and (b) the rubber-like elastic body (second and sixth)
Invention). Examples of such (B) and (b) rubber-like elastic materials include styrene-butyl acrylate copolymer rubber and styrene-butadiene block copolymer (SB).
R), 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 (SIS),
Hydrogenated styrene-isoprene block-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene random Copolymers such as copolymers; butadiene-acrylonitrile-styrene-core shell rubber (ABS), methyl methacrylate-butadiene-styrene-core shell rubber (MB
S), methyl methacrylate-butyl acrylate-styrene-core shell rubber (MAS), octyl acrylate-butadiene-styrene-core shell rubber (MAB)
S), alkyl acrylate-butadiene-acrylonitrile-styrene-core shell rubber (AABS), butadiene-styrene-core shell rubber (SBR) and other core-shell type particulate elastic materials; polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, epi Ethylene-polar vinyl monomer copolymerization such as chlorohydrin rubber, chlorinated rubber, styrene-butyl acrylate copolymer rubber, ethylene-methyl methacrylate-glycidyl methacrylate copolymer rubber, ethylene-methyl methacrylate-maleic anhydride copolymer rubber Combined rubber; natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, silicone rubber, ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), etc. The recited may be used them in combination one kind or two kinds or more.

Among these, especially butadiene-styrene-core shell rubber (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene -Styrene block copolymer (S
EBS), styrene-isoprene block copolymer (S
IR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene block-styrene block copolymer (SEPS) or core shell containing styrene. Rubber is preferred.

The components (B) and (a) are the same as the components (B) and (b) above.
A rubber-like elastic body obtained by modifying a rubber-like elastic body with a modifier having a polar group, or a rubber originally having a polar group.
(B) Specific examples of the component (a) include polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, epichlorohydrin rubber, chlorinated rubber, styrene-butyl acrylate copolymer rubber, ethylene-methyl methacrylate- Rubbers having polar groups such as ethylene-polar vinyl monomer copolymer rubbers such as glycidyl methacrylate copolymer rubbers, ethylene-methyl methacrylate-maleic anhydride copolymer rubbers, natural rubbers,
Polybutadiene, polyisoprene, polyisobutylene,
Neoprene, silicone rubber, styrene-butadiene block copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEB
S), styrene-isoprene block-styrene block copolymer (SIS), hydrogenated styrene-isoprene block-styrene block copolymer (SEPS), ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM) as polar groups Examples thereof include rubber modified with a modifying agent having Among them, especially SEB
A rubber modified with S, SBR, SBS, SEPS, SIS is preferably used. Specific examples include maleic anhydride-modified SEBS, maleic anhydride-modified EPR, epoxy-modified SEBS, and epoxy-modified SEBS. The rubber-like elastic body may be used alone or in combination of two or more.

When the components (B) and (a) and (B) and (b) are blended, that is, in the second and sixth inventions, (B)
As the components (a) and (B) and (b), it is preferable to use elastic bodies having the same skeleton or those having good compatibility with each other.

In the second and sixth inventions, the mixing ratio of the components (B) (a) and (B) (b) of the elastic body (B) is
(B) (a) component 0.1 to 99.9% by weight and (B) (b)
Ingredients 0.1 to 99.9% by weight, preferably (B) (a) ingredients 1 to 50% by weight and (B) (b) ingredients 50 to 99% by weight
Is. If the amount of the components (B) and (a) is 1% by weight, the effect of improving impact strength and elongation is low, and if it exceeds 50% by weight, there is a problem in economic efficiency.

In the first, second, fourth, fifth and sixth inventions, the compounding ratio of the above-mentioned (A) resin compound and (B) elastic material is not particularly limited, but it is 100 parts by weight of the (A) resin compound. On the other hand, the elastic body (B) is 1 to 100 parts by weight, preferably 5 to 80 parts.
Parts by weight. When the amount of the elastic body (B) is less than 1 part by weight, the effect of improving the impact resistance of the obtained composition is insufficient, and 1
If the amount exceeds 100 parts by weight, the elastic modulus, heat resistance, etc. of the resulting composition are significantly reduced, which is not preferable.

Next, as the inorganic filler which is the component (C) of the present invention, there are various ones such as fibrous, granular and powdery ones. Examples of the fibrous filler include glass fiber, carbon fiber, whiskers, ceramic fiber, metal fiber and the like.
Specifically, the whiskers are boron, alumina, silica, silicon carbide, etc., the ceramic fibers are gypsum,
Examples of metal fibers such as potassium titanate, magnesium sulfate, and magnesium oxide include copper, aluminum, and steel. Here, the shape of the filler includes cloth, mat, bundle cutting, short fiber, filament, and whiskers. In the case of focused cutting, the length is 0.05 to 50
mm, and the fiber diameter is preferably 1 to 20 μm.

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, glass fillers such as glass mats, glass powders, glass flakes, glass beads, glass filaments, glass fibers, and glass lobings are particularly preferable.

Further, in order to enhance the adhesiveness with the resin which is the component (A), those subjected to surface treatment are preferably used. The coupling agent used for the surface treatment of the above-mentioned inorganic filler can be appropriately selected and used from those known as so-called silane coupling agents and titanium coupling agents. 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 dihydroimidazolepropyltriethoxysilane, hexamethyldisilazane , N, O- (bistrimethylsilyl) amide, N, N
-Bis (trimethylsilyl) urea and the like. Of these, preferred are γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and β- (3,4- Aminosilane such as epoxycyclohexyl) ethyltrimethoxysilane,
Epoxy silane.

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. Further, as the surface treatment agent, a film former can be used in combination with the above coupling agent.
As the film former, various kinds such as urethane type, isocyanate type, epoxy type, acrylic type and polyether type are used. Of these, preferred are polyether film formers and epoxy film formers. Further, these film formers can be used alone or in combination of two or more.

In the present invention, the amount of the inorganic filler (C) compounded is 100 parts by weight of the above-mentioned (A) resin compound (third invention), or (A) resin compound and (B) elasticity. The amount is 1 to 350 parts by weight, preferably 5 to 200 parts by weight, based on 100 parts by weight of the whole body (first, second, fourth, fifth and sixth inventions). Here, if the compounding amount of the inorganic filler (C) is less than 1 part by weight, the effect of adding the filler is not sufficiently observed, and if it exceeds 350 polymerized parts, the dispersibility is poor and molding becomes difficult. Is not preferable.

The resin composition of the present invention is basically a thermoplastic resin composition comprising the above-mentioned (A) resin composition and (C) inorganic filler, (A) resin composition, (B) elastic body and ( C) A thermoplastic resin composition comprising an inorganic filler, which is an antioxidant, a nucleating agent, a plasticizer, a release agent, a flame retardant, a pigment, carbon black, an antistatic agent, as long as the object of the present invention is not impaired. Additives such as agents or other thermoplastic resins can be blended. The thermoplastic resin composition of the present invention can be obtained by blending the above-mentioned components in the above-specified amounts. The compounding method is not particularly limited and may be a known method. Usually, after blending (A) the resin blend and (B) the elastic body, (C) the inorganic filler is blended.

[0036]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Production Example 1 (Production of SPS) Purified styrene (1.0 liter) and triethylaluminum (1 mmol) were added to a 2 liter reaction vessel, heated to 80 ° C., and then premixed with catalyst (pentamethylcyclopentadienyl titanium trimethoxide 90 Micromol, dimethylanilinium tetra (pentafluorophenyl) borate 90 micromol, toluene 29.1 mmol, triisobutylaluminum 1.8 mmol) 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 380 g of polystyrene. The weight average molecular weight of this polymer is 1,2,4-trichlorobenzene as a solvent, 1
When measured by gel permeation chromatography at 30 ° C., it was 320,000. The weight average molecular weight / number average molecular weight was 2.60. From the melting point and ¹³ C-NMR measurement, it was confirmed that this polymer was polystyrene (SPS) having a syndiotactic structure.

Production Example 2 (Production of SPS) 0.9 liter of purified styrene in a 2 liter reaction vessel, p
-Methylstyrene 0.1 liter and triethylaluminum 1 mmol were added and heated to 80 ° C., then premixed catalyst (pentamethylcyclopentadienyl titanium trimethoxide 90 micromol, dimethylanilinium tetra (pentafluorophenyl) borate) 90 μmol, toluene 29.1 mmol, triisobutylaluminum 1.8 mmol) 16.5 ml were added, and 80
Polymerization was carried out at ℃ for 5 hours. After the reaction was completed, the product was repeatedly washed with methanol and dried to obtain 390 g of a styrene-p-methylstyrene copolymer. The weight average molecular weight of this polymer was 328,000 as measured by gel permeation chromatography at 130 ° C. using 1,2,4-trichlorobenzene as a solvent. The weight average molecular weight / number average molecular weight was 2.60. Further, from the melting point and ¹³ C-NMR measurement, this polymer was a styrene-p-methylstyrene copolymer (SPS) having a syndiotactic structure, and p-methylstyrene was 12%.
It was confirmed that the content was mol%.

Production Example 3 (Production of Maleic Anhydride Modified SPS) 1 kg of the styrene-p-methylstyrene copolymer obtained in Production Example 2, 30 g of maleic anhydride, 2,3-dimethyl-2,2 as a radical generator, 10 g of 3-diphenylbutane (NOFMER BC, manufactured by NOF CORPORATION) was dry-blended and melt-kneaded using a 30 mm 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 SPS.
The obtained maleic anhydride-modified SPS (1 g) was dissolved in ethylbenzene and then reprecipitated in methanol. The recovered polymer was subjected to Soxhlet extraction with methanol, and after drying, the modification ratio was measured by the carbonyl absorption intensity of the IR spectrum and titration. The modification rate was 1.05% by weight.

Production Example 4 (Production of maleic anhydride-modified polyphenylene ether) 1 kg of polyphenylene ether (intrinsic viscosity 0.47 dl / g, measured at 25 ° C. in chloroform), maleic anhydride 6
0 g, 2,3-dimethyl-2,3 as a radical generator
-Diphenylbutane (NOFMER B, manufactured by NOF CORPORATION)
C) 10 g was dry blended, and the screw rotation speed was 200 rpm and the set temperature was 300 using a 30 mm twin screw extruder.
Melt kneading was performed at ℃. At this time, the resin temperature is about 330 ° C.
Met. The strand was cooled and then pelletized to obtain maleic anhydride-modified polyphenylene ether. The modification ratio of the obtained maleic anhydride-modified polyphenylene ether was measured in the same manner as in Production Example 3. The modification rate was 2.0% by weight.

Example 1 10 g of polyphenylene ether (intrinsic viscosity 0.45 dl / g, measured in chloroform at 25 ° C.), relative to 960 g of polystyrene having a syndiotactic structure obtained in Production Example 1, Production Example 4 30 g of maleic anhydride-modified polyphenylene ether obtained in 1., sodium methylenebis (2,4-di-t-butylphenol) acid phosphate as a nucleating agent (NA-1 manufactured by ADEKA ARGUS CORPORATION)
1) 5 g, 1 g of (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by Adeka Argus, PEP-36) as an antioxidant,
After adding 1 g of tetrakis (methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl)) propionate (ADEKA ARGUS MARK AO60), after dry blending with a Henschel mixer , Glass fiber treated with aminosilane as a filler (13
2m while side-feeding 430g (μm / 3mm)
Pelletized with a shaft extruder. Using the obtained pellets, injection molding was performed to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile strength and flexural modulus tests were performed. The results are shown in Table 1.

Example 2 Example 1 was repeated except that the amounts of SPS and polyphenylene ether were changed to those shown in Table 1. The results are shown in Table 1.

Example 3 In Example 1, the maleic anhydride-modified polyphenylene ether of Production Example 4 was replaced by the maleic anhydride-modified SPS of Production Example 3, and the compounding amounts of SPS and polyphenylene ether were the amounts shown in Table 1. The same procedure as in Example 1 was carried out except that The results are shown in Table 1.

Example 4 10 g of polyphenylene ether (intrinsic viscosity 0.45 dl / g, measured at 25 ° C. in chloroform) was added to 860 g of the polystyrene having a syndiotactic structure obtained in Production Example 1 and Production Example 4 30 g of maleic anhydride-modified polyphenylene ether obtained in step 3, SE as a rubber elastic body
BS (Kraton G-1651, manufactured by Shell Chemical Co., Ltd.) 1
00 g, methylenebis (2,4-di-t-butylphenol) acid phosphate sodium (NA-11, manufactured by ADEKA ARGUS CORPORATION) as a nucleating agent, and (2,6-di-t-butyl-4-) as an antioxidant. Methylphenyl)
1 g of pentaerythritol diphosphite (manufactured by ADEKA ARGUS CORPORATION, PEP-36), tetrakis (methylene-
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl)) propionate (Made by Adeka Argus, MAR
KAO60) 1 g was added, and after dry blending with a Henschel mixer, aminosilane-treated glass fiber (13 μm / 3 mm) 430 g as a filler.
Was side-fed and pelletized with a twin-screw extruder. Using the obtained pellets, injection molding was performed to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile strength and flexural modulus tests were performed. The results are shown in Table 1.

Example 5 Example 4 was repeated except that the amounts of SPS and polyphenylene ether were changed to those shown in Table 1. The results are shown in Table 1.

Example 6 In Example 4, the maleic anhydride-modified polyphenylene ether of Production Example 4 was replaced by the maleic anhydride-modified SPS of Production Example 3, and the compounding amounts of SPS and polyphenylene ether were as shown in Table 1. Example 4 was repeated except that The results are shown in Table 1.

Example 7 To 870 g of the polystyrene having a syndiotactic structure obtained in Production Example 1, 30 g of the maleic anhydride-modified polyphenylene ether obtained in Production Example 4 and anhydrous as a rubber-like elastic body having a polar group were obtained. Maleic acid modified SEB
S (manufactured by Asahi Kasei Corporation, Tuftec M-1913) 10
0 g, methylenebis (2,4-di-t-butylphenol) acid phosphate sodium (NA-11, manufactured by ADEKA ARGUS CORPORATION) as a nucleating agent, and (2,6-di-t-butyl-4-) as an antioxidant. Methylphenyl) pentaerythritol diphosphite (manufactured by ADEKA ARGUS CORPORATION, PEP-36) 1 g, tetrakis (methylene-3)
-(3 ', 5'-di-t-butyl-4'-hydroxyphenyl)) propionate (Made by Adeka Argus, MAR
KAO60) 1 g was added, and after dry blending with a Henschel mixer, aminosilane-treated glass fiber (13 μm / 3 mm) 430 g as a filler.
Was side-fed and pelletized with a twin-screw extruder. Using the obtained pellets, injection molding was performed to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile strength and flexural modulus tests were performed. The results are shown in Table 1.

Example 8 The procedure of Example 7 was repeated except that the maleic anhydride-modified SPS of Production Example 3 was used in place of the maleic anhydride-modified polyphenylene ether of Production Example 4. The results are shown in Table 1.

Example 9 30 g of the maleic anhydride-modified polyphenylene ether obtained in Production Example 4 was added to 870 g of the polystyrene having a syndiotactic structure obtained in Production Example 1 and SEBS (Shell Chemical Co., Ltd. as a rubber elastic body). ), Kraton G
-1651) 90 g, maleic anhydride-modified SEBS (Tuftec M-1913 manufactured by Asahi Kasei Co., Ltd.) 10 g as a rubber-like elastic body having a polar group, and methylenebis (2,4-di-t-butylphenol) acid as a nucleating agent. Sodium phosphate (manufactured by Adeka Argus, NA-1)
1) 5 g, 1 g of (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by Adeka Argus, PEP-36) as an antioxidant,
After adding 1 g of tetrakis (methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl)) propionate (ADEKA ARGUS MARK AO60), after dry blending with a Henschel mixer , Glass fiber treated with aminosilane as a filler (13
2m while side-feeding 430g (μm / 3mm)
Pelletized with a shaft extruder. Using the obtained pellets, injection molding was performed to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile strength and flexural modulus tests were performed. The results are shown in Table 1.

Example 10 The procedure of Example 9 was repeated, except that the maleic anhydride-modified SPS of Production Example 3 was used in place of the maleic anhydride-modified polyphenylene ether of Production Example 4. The results are shown in Table 1.

Example 11 10 g of polyphenylene ether (intrinsic viscosity 0.45 dl / g, measured in chloroform at 25 ° C.), relative to 860 g of the polystyrene having a syndiotactic structure obtained in Production Example 1, Production Example 4 30 g of maleic anhydride-modified polyphenylene ether obtained in 1., 100 g of maleic anhydride-modified SEBS (Tuftec M-1913 manufactured by Asahi Kasei Co., Ltd.) as a rubber-like elastic body having a polar group, and methylenebis (2,4- 5 g of sodium diphosphate (di-t-butylphenol) acid phosphate (NA-11, manufactured by ADEKA ARGUS CORPORATION) as an antioxidant (2,6
-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by ADEKA ARGUS CORPORATION, PE
P-36) 1 g, tetrakis (methylene-3- (3 ', 5'
-Di-t-butyl-4'-hydroxyphenyl)) propionate (MARK AO6, manufactured by ADEKA ARGUS CORPORATION)
0) 1 g was added and dry blended with a Henschel mixer, and then 430 g of aminosilane-treated glass fiber (13 μm / 3 mm) as a filler was side-fed and pelletized with a twin-screw extruder. Using the obtained pellets, injection molding was performed to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile strength and flexural modulus tests were performed. The results are shown in Table 1.

Example 12 Example 11 was repeated except that the amounts of SPS and polyphenylene ether were changed to those shown in Table 1.
I went the same way. The results are shown in Table 1.

Example 13 In Example 11, the maleic anhydride-modified SPS of Production Example 3 was used in place of the maleic anhydride-modified polyphenylene ether of Production Example 4, and the amounts of SPS and polyphenylene ether were as shown in Table 1. Example 1 except that
The same procedure as 1 was performed. The results are shown in Table 1.

Example 14 To 860 g of the polystyrene having a syndiotactic structure obtained in Production Example 1, 10 g of polyphenylene ether (intrinsic viscosity 0.45 dl / g, measured at 25 ° C. in chloroform), Production Example 4 30 g of the obtained maleic anhydride-modified polyphenylene ether, SEB as a rubber elastic body
S (Shell Chemical Co., Ltd., Kraton G-1651) 90
g, maleic anhydride-modified SEBS as a rubber-like elastic body having a polar group (Tuftec M-19 manufactured by Asahi Kasei Corp.)
13) 10 g, methylenebis (2,4-di-
5 g of sodium t-butylphenol) acid phosphate (NA-11, manufactured by Adeka Argus Co., Ltd.), (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite as an antioxidant (Adeka.
Argus, PEP-36) 1 g, tetrakis (methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl)) propionate (Adeka Argus,
1 g of MARK AO60) was added, dry blended with a Henschel mixer, and aminosilane-treated glass fiber (13 μm / 3 mm) 4 was used as a filler.
While side feeding 30 g, it was pelletized by a twin-screw extruder. Using the obtained pellets, injection molding was performed to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile strength and flexural modulus tests were performed. The results are shown in Table 1.

Example 15 Example 14 was repeated except that the amounts of SPS and polyphenylene ether were changed to those shown in Table 1.
I went the same way. The results are shown in Table 1.

Example 16 In Example 14, the maleic anhydride-modified SPS of Production Example 3 was used in place of the maleic anhydride-modified polyphenylene ether of Production Example 4, and the compounding amounts of SPS and polyphenylene ether were the amounts shown in Table 1. Example 1 except that
The same procedure as in 4 was performed. The results are shown in Table 1.

Comparative Example 1 To 970 g of the polystyrene having a syndiotactic structure obtained in Production Example 1, 30 g of maleic anhydride-modified polyphenylene ether obtained in Production Example 4 and methylenebis (2,4-diene) as a nucleating agent were added. 5 g of sodium t-butylphenol) acid phosphate (NA-11, manufactured by ADEKA ARGUS CORPORATION) as an antioxidant (2,6
-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by ADEKA ARGUS CORPORATION, PE
P-36) 1 g, tetrakis (methylene-3- (3 ', 5'
-Di-t-butyl-4'-hydroxyphenyl)) propionate (MARK AO6, manufactured by ADEKA ARGUS CORPORATION)
0) 1 g was added and dry blended with a Henschel mixer, and then 430 g of aminosilane-treated glass fiber (13 μm / 3 mm) as a filler was side-fed and pelletized with a twin-screw extruder. Using the obtained pellets, injection molding was performed to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile strength and flexural modulus tests were performed. The results are shown in Table 1.

Comparative Example 2 The procedure of Comparative Example 1 was repeated except that the maleic anhydride-modified polyphenylene ether of Production Example 4 was replaced by the maleic anhydride-modified SPS of Production Example 3. The results are shown in Table 1.

Comparative Example 3 30 g of the maleic anhydride-modified polyphenylene ether obtained in Production Example 4 was added to 870 g of the polystyrene having a syndiotactic structure obtained in Production Example 1, and SEBS (Shell Chemical Co., Ltd. as a rubber elastic body was used. ), Kraton G
-1651) 100 g, methylenebis (2,2 as a nucleating agent
4-di-t-butylphenol) acid phosphate sodium (manufactured by Adeka Argus Co., NA-11) 5
g, as an antioxidant (2,6-di-t-butyl-4-
1 g of methylphenyl) pentaerythritol diphosphite (manufactured by ADEKA ARGUS CORPORATION, PEP-36), tetrakis (methylene-3- (3 ′, 5′-di-t-butyl-4′-)
1 g of (hydroxyphenyl)) propionate (MARK AO60, manufactured by ADEKA ARGUS CORPORATION) was added and dry blended with a Henschel mixer, and then aminosilane-treated glass fibers (13 μm /
(3 mm) 430 g was side-fed and pelletized by a twin-screw extruder. Using the obtained pellets, injection molding was performed to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile strength and flexural modulus tests were performed. The results are shown in Table 1.

Comparative Example 4 The procedure of Comparative Example 3 was repeated, except that the maleic anhydride-modified SPS of Production Example 3 was used in place of the maleic anhydride-modified polyphenylene ether of Production Example 4. The results are shown in Table 1.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

In the table, the symbols of raw materials are as follows. SPS: Syndiotactic polystyrene MA-SPS: Maleic anhydride modified syndiotactic polystyrene MA-PPE: Maleic anhydride modified polyphenylene ether PPE: Polyphenylene ether MA-SEBS: Maleic anhydride modified hydrogenated styrene-butadiene-styrene block copolymer Combined SEBS: Hydrogenated styrene-butadiene-styrene block copolymer GF: Glass fiber Each test in the above Table 1 was conducted under the following conditions. Izod impact strength test: Based on JIS-K-7110. Tensile strength test: Based on JIS-K-7113. Flexural modulus: based on JIS-K-7203.

From the results of Examples and Comparative Examples, (A)
(C) By adding polyphenylene ether,
Mechanical properties such as impact strength and elongation can be improved without lowering the elastic modulus and moldability of the composition. As the elastic body (B), a rubber-like elastic body having a polar group is used alone or in combination with the rubber-like elastic body to obtain (A)
It is possible to obtain the same effect as in the case of adding (c) polyphenylene ether. Further, by adding (A) (c) polyphenylene ether and (B) (a) a rubber-like elastic body having a polar group, a thermoplastic resin composition having significantly improved physical properties such as impact strength and elongation is obtained. be able to.

[0065]

INDUSTRIAL APPLICABILITY As described above, the thermoplastic resin composition of the present invention is a resin composition having high heat resistance, moldability, etc. and excellent mechanical properties, particularly impact resistance, rigidity, elongation, etc. It can be expected to be effectively used for various purposes as a molding material for industrial materials such as electrical / electronic materials, industrial structural materials, automobile parts, home appliances, and various machine parts.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 21, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

Example 1 10 g of polyphenylene ether (intrinsic viscosity 0.45 dl / g, measured in chloroform at 25 ° C.), relative to 960 g of polystyrene having a syndiotactic structure obtained in Production Example 1, Production Example 4 30 g of maleic anhydride-modified polyphenylene ether obtained in 1., sodium methylenebis (2,4-di-t-butylphenol) acid phosphate as a nucleating agent (NA-1 manufactured by ADEKA ARGUS CORPORATION)
1) 5 g, 1 g of (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by Adeka Argus, PEP-36) as an antioxidant,
After adding 1 g of tetrakis (methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl)) propionate (ADEKA ARGUS MARK AO60), after dry blending with a Henschel mixer , Glass fiber treated with aminosilane as a filler (13
2m while side-feeding 430g (μm / 3mm)
Pelletized with a shaft extruder. Using the obtained pellets, injection molding was carried out to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile elongation and flexural modulus tests were conducted. The results are shown in Table 1.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

Example 4 10 g of polyphenylene ether (intrinsic viscosity 0.45 dl / g, measured at 25 ° C. in chloroform) was added to 860 g of the polystyrene having a syndiotactic structure obtained in Production Example 1 and Production Example 4 30 g of maleic anhydride-modified polyphenylene ether obtained in step 3, SE as a rubber elastic body
BS (Kraton G-1651, manufactured by Shell Chemical Co., Ltd.) 1
00 g, methylenebis (2,4-di-t-butylphenol) acid phosphate sodium (NA-11, manufactured by ADEKA ARGUS CORPORATION) as a nucleating agent, and (2,6-di-t-butyl-4-) as an antioxidant. Methylphenyl)
1 g of pentaerythritol diphosphite (manufactured by ADEKA ARGUS CORPORATION, PEP-36), tetrakis (methylene-
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl)) propionate (Made by Adeka Argus, MAR
KAO60) 1 g was added, and after dry blending with a Henschel mixer, aminosilane-treated glass fiber (13 μm / 3 mm) 430 g as a filler.
Was side-fed and pelletized with a twin-screw extruder. Using the obtained pellets, injection molding was carried out to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile elongation and flexural modulus tests were conducted. The results are shown in Table 1.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

Example 7 To 870 g of the polystyrene having a syndiotactic structure obtained in Production Example 1, 30 g of the maleic anhydride-modified polyphenylene ether obtained in Production Example 4 and anhydrous as a rubber-like elastic body having a polar group were obtained. Maleic acid modified SEB
S (manufactured by Asahi Kasei Corporation, Tuftec M-1913) 10
0 g, methylenebis (2,4-di-t-butylphenol) acid phosphate sodium (NA-11, manufactured by ADEKA ARGUS CORPORATION) as a nucleating agent, and (2,6-di-t-butyl-4-) as an antioxidant. Methylphenyl) pentaerythritol diphosphite (manufactured by ADEKA ARGUS CORPORATION, PEP-36) 1 g, tetrakis (methylene-3)
-(3 ', 5'-di-t-butyl-4'-hydroxyphenyl)) propionate (Made by Adeka Argus, MAR
KAO60) 1 g was added, and after dry blending with a Henschel mixer, aminosilane-treated glass fiber (13 μm / 3 mm) 430 g as a filler.
Was side-fed and pelletized with a twin-screw extruder. Using the obtained pellets, injection molding was carried out to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile elongation and flexural modulus tests were conducted. The results are shown in Table 1.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

Example 9 30 g of the maleic anhydride-modified polyphenylene ether obtained in Production Example 4 was added to 870 g of the polystyrene having a syndiotactic structure obtained in Production Example 1 and SEBS (Shell Chemical Co., Ltd. as a rubber elastic body). ), Kraton G
-1651) 90 g, maleic anhydride-modified SEBS (Tuftec M-1913 manufactured by Asahi Kasei Co., Ltd.) 10 g as a rubber-like elastic body having a polar group, and methylenebis (2,4-di-t-butylphenol) acid as a nucleating agent. Sodium phosphate (manufactured by Adeka Argus, NA-1)
1) 5 g, 1 g of (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by Adeka Argus, PEP-36) as an antioxidant,
After adding 1 g of tetrakis (methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl)) propionate (ADEKA ARGUS MARK AO60), after dry blending with a Henschel mixer , Glass fiber treated with aminosilane as a filler (13
2m while side-feeding 430g (μm / 3mm)
Pelletized with a shaft extruder. Using the obtained pellets, injection molding was carried out to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile elongation and flexural modulus tests were conducted. The results are shown in Table 1.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

Example 11 10 g of polyphenylene ether (intrinsic viscosity 0.45 dl / g, measured in chloroform at 25 ° C.), relative to 860 g of the polystyrene having a syndiotactic structure obtained in Production Example 1, Production Example 4 30 g of maleic anhydride-modified polyphenylene ether obtained in 1., 100 g of maleic anhydride-modified SEBS (Tuftec M-1913 manufactured by Asahi Kasei Co., Ltd.) as a rubber-like elastic body having a polar group, and methylenebis (2,4- 5 g of sodium diphosphate (di-t-butylphenol) acid phosphate (NA-11, manufactured by ADEKA ARGUS CORPORATION) as an antioxidant (2,6
-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by ADEKA ARGUS CORPORATION, PE
P-36) 1 g, tetrakis (methylene-3- (3 ', 5'
-Di-t-butyl-4'-hydroxyphenyl)) propionate (MARK AO6, manufactured by ADEKA ARGUS CORPORATION)
0) 1 g was added and dry blended with a Henschel mixer, and then 430 g of aminosilane-treated glass fiber (13 μm / 3 mm) as a filler was side-fed and pelletized with a twin-screw extruder. Using the obtained pellets, injection molding was carried out to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile elongation and flexural modulus tests were conducted. The results are shown in Table 1.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction content]

Example 14 To 860 g of the polystyrene having a syndiotactic structure obtained in Production Example 1, 10 g of polyphenylene ether (intrinsic viscosity 0.45 dl / g, measured at 25 ° C. in chloroform), Production Example 4 30 g of the obtained maleic anhydride-modified polyphenylene ether, SEB as a rubber elastic body
S (Shell Chemical Co., Ltd., Kraton G-1651) 90
g, maleic anhydride-modified SEBS as a rubber-like elastic body having a polar group (Tuftec M-19 manufactured by Asahi Kasei Corp.)
13) 10 g, methylenebis (2,4-di-
5 g of sodium t-butylphenol) acid phosphate (NA-11, manufactured by Adeka Argus Co., Ltd.), (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite as an antioxidant (Adeka.
Argus, PEP-36) 1 g, tetrakis (methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl)) propionate (Adeka Argus,
1 g of MARK AO60) was added, dry blended with a Henschel mixer, and aminosilane-treated glass fiber (13 μm / 3 mm) 4 was used as a filler.
While side feeding 30 g, it was pelletized by a twin-screw extruder. Using the obtained pellets, injection molding was carried out to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile elongation and flexural modulus tests were conducted. The results are shown in Table 1.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

Comparative Example 1 To 970 g of the polystyrene having a syndiotactic structure obtained in Production Example 1, 30 g of maleic anhydride-modified polyphenylene ether obtained in Production Example 4 and methylenebis (2,4-diene) as a nucleating agent were added. 5 g of sodium t-butylphenol) acid phosphate (NA-11, manufactured by ADEKA ARGUS CORPORATION) as an antioxidant (2,6
-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by ADEKA ARGUS CORPORATION, PE
P-36) 1 g, tetrakis (methylene-3- (3 ', 5'
-Di-t-butyl-4'-hydroxyphenyl)) propionate (MARK AO6, manufactured by ADEKA ARGUS CORPORATION)
0) 1 g was added and dry blended with a Henschel mixer, and then 430 g of aminosilane-treated glass fiber (13 μm / 3 mm) as a filler was side-fed and pelletized with a twin-screw extruder. Using the obtained pellets, injection molding was carried out to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile elongation and flexural modulus tests were conducted. The results are shown in Table 1.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0058

[Correction method] Change

[Correction content]

Comparative Example 3 30 g of the maleic anhydride-modified polyphenylene ether obtained in Production Example 4 was added to 870 g of the polystyrene having a syndiotactic structure obtained in Production Example 1, and SEBS (Shell Chemical Co., Ltd. as a rubber elastic body was used. ), Kraton G
-1651) 100 g, methylenebis (2,2 as a nucleating agent
4-di-t-butylphenol) acid phosphate sodium (manufactured by Adeka Argus Co., NA-11) 5
g, as an antioxidant (2,6-di-t-butyl-4-
1 g of methylphenyl) pentaerythritol diphosphite (manufactured by ADEKA ARGUS CORPORATION, PEP-36), tetrakis (methylene-3- (3 ′, 5′-di-t-butyl-4′-)
1 g of (hydroxyphenyl)) propionate (MARK AO60, manufactured by ADEKA ARGUS CORPORATION) was added and dry blended with a Henschel mixer, and then aminosilane-treated glass fibers (13 μm /
(3 mm) 430 g was side-fed and pelletized by a twin-screw extruder. Using the obtained pellets, injection molding was carried out to obtain tensile test pieces and Izod test pieces, and Izod impact strength, tensile elongation and flexural modulus tests were conducted. The results are shown in Table 1.

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[Table 3]

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In the table, the symbols of raw materials are as follows. SPS: Syndiotactic polystyrene MA-SPS: Maleic anhydride modified syndiotactic polystyrene MA-PPE: Maleic anhydride modified polyphenylene ether PPE: Polyphenylene ether MA-SEBS: Maleic anhydride modified hydrogenated styrene-butadiene-styrene block copolymer Combined SEBS: Hydrogenated styrene-butadiene-styrene block copolymer GF: Glass fiber Each test in the above Table 1 was conducted under the following conditions. Izod impact strength test: Based on JIS-K-7110. Tensile elongation test: Based on JIS-K-7113. Flexural modulus: based on JIS-K-7203.

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Claims (11)

[Claims] 1. (A) (a) 90 to 99.9% by weight of a styrene polymer having a syndiotactic structure, and (b)
(B) Rubber-like elasticity having a polar group (B) in a resin composition comprising 0.1 to 10.0% by weight of a polymer having a polar group and having compatibility or affinity with the component (a). (C) Inorganic fillers 1 to 35 relative to 100 parts by weight of the resin added with the body
A thermoplastic resin composition containing 0 part by weight. 2. (A) 90 to 99.9% by weight of (a) a styrene polymer having a syndiotactic structure, and (b)
(B) Rubber-like elasticity having a polar group (B) in a resin composition comprising 0.1 to 10.0% by weight of a polymer having a polar group and having compatibility or affinity with the component (a). Body 0.1-9
9.9% by weight and (b) rubber-like elastic body 0.1 to 99.9% by weight
1 to 350 parts by weight of the inorganic filler (C) is mixed with 100 parts by weight of the resin containing the elastic body of 1. 3. (A) (a) 85 to 99.8% by weight of a styrene polymer having a syndiotactic structure, (b) a polar group having compatibility or affinity with the component (a). 1. A resin blend 1 comprising 0.1% to 10.0% by weight of a polymer having (a) and (c) 0.1% to 5.0% by weight of polyphenylene ether.
A thermoplastic resin composition comprising 100 parts by weight of (C) and 1 to 350 parts by weight of the inorganic filler (C). 4. (A) (a) 85 to 99.8% by weight of a styrene polymer having a syndiotactic structure, (b) a polar group having compatibility or affinity with the component (a). (B) (a) a rubber-like elastic material having a polar group is added to a resin mixture consisting of 0.1 to 10.0% by weight of a polymer having (b) and 0.1 to 5.0% by weight of (c) a polyphenylene ether. A thermoplastic resin composition obtained by mixing 1 to 350 parts by weight of the inorganic filler (C) with 100 parts by weight of the resin. 5. (A) (a) 85 to 99.8% by weight of a styrene polymer having a syndiotactic structure, (b) a polar group having compatibility or affinity with the component (a). (B) (b) a rubber-like elastic material added to a resin blend consisting of 0.1 to 10.0% by weight of a polymer having (b) and 0.1 to 5.0% by weight of (c) polyphenylene ether 1 to 350 parts by weight of the inorganic filler (C) with respect to 1 part by weight of the thermoplastic resin composition. 6. (A) (a) 85 to 99.8% by weight of a styrene polymer having a syndiotactic structure, (b) a polar group having compatibility or affinity with the component (a). (B) (a) a rubber-like elastic material having a polar group in a resin blend consisting of 0.1 to 10.0% by weight of a polymer having (b) and 0.1 to 5.0% by weight of (c) a polyphenylene ether. 1-99.9
(C) with respect to 100 parts by weight of a resin to which an elastic body composed of 0.1% to 99.9% by weight and (b) a rubber-like elastic body is added.
A thermoplastic resin composition containing 1 to 350 parts by weight of an inorganic filler. 7. 100 parts by weight of (A) resin compound (B)
The elastic body is compounded in a ratio of 1 to 100 parts by weight.
The thermoplastic resin composition according to 2, 4, 5 or 6. 8. A polymer having compatibility with or affinity for the components (A) and (b) and the polar group is a modified syndiotactic polystyrene or a modified polyphenylene ether. Item 7. The thermoplastic resin composition according to any one of Items 1 to 6. 9. A rubber-like elastic body having a polar group as component (B) (a) is a maleic anhydride-modified hydrogenated styrene-butadiene-styrene block copolymer, maleic anhydride-modified ethylene-propylene rubber or epoxy-modified. The thermoplastic resin composition according to claim 1, 2, 4, or 6, which is a hydrogenated styrene-butadiene-styrene block copolymer. 10. A rubber-like elastic body of components (B) and (b),
Butadiene-styrene-block copolymer (SBR),
Hydrogenated styrene-butadiene block copolymer (SE
B), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer A core-shell rubber containing a polymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene block-styrene block copolymer (SEPS) or styrene. The thermoplastic resin composition described. 11. The thermoplastic resin composition according to claim 1, wherein the inorganic filler (C) is a surface-treated inorganic filler.