JPH07138433A - Polystyrene resin composition - Google Patents

Abstract

(57) [Abstract] [Purpose] In addition to having excellent heat resistance, chemical resistance, mechanical strength, etc., the molded product has a decrease in mechanical strength and deterioration of color tone even when used at high temperature for a long time. It is an object of the present invention to provide a stable polystyrene resin resin composition with almost no deterioration. [Structure] A styrenic polymer (SPS) having a syndiotactic structure is optionally mixed with (modified) polyphenylene ether, another thermoplastic resin or a rubber-like elastic material, and a phenolic antioxidant or inorganic A polystyrene resin composition containing a filler.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polystyrene resin composition, and more particularly to a resin composition having excellent heat resistance, chemical resistance, mechanical strength, etc. The present invention relates to a stable polystyrene resin resin composition in which physical strength is not deteriorated, deterioration of color tone is hardly observed, and the molded product has no change in physical properties even when used at high temperature for a long time.

[0002]

2. Description of the Related Art Conventionally, a styrene polymer having a syndiotactic structure (hereinafter sometimes abbreviated as SPS).
Has excellent heat resistance, chemical resistance, water resistance, etc. and is used as a material for various molded products.

However, since the melting point of SPS is higher than that of conventional thermoplastic resins, thermoforming is performed at a high temperature. Thermoforming only SPS at relatively high temperatures results in a decrease in molecular weight due to thermal decomposition. As a result, there has been a problem of resin deterioration such as deterioration of mechanical strength and deterioration of color tone. Further, since SPS has high heat resistance, it is used as a material for molded products requiring heat resistance. However, in molded products containing only SPS, when exposed to high temperatures for a long time, the molecular weight decreases and The heat resistance and durability were not sufficient because the strength decreased and the color tone deteriorated.

[0004]

Therefore, the present inventors have found that
While maintaining the excellent properties of SPS, earnest studies were conducted to develop an SPS resin composition having improved heat resistance and durability suitable for thermoforming at high temperature and long-term use at high temperature. It was

[0005]

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

That is, the present invention is (1) (A) (a)
Styrene-based polymer having a syndiotactic structure (S
(PS) 100 parts by weight of (B) phenolic antioxidant 0.
A polystyrene resin composition comprising 005 to 5.0 parts by weight, and (2) (A) (a) SPS1 to
To 100 parts by weight of a resin consisting of 99% by weight and (b) a thermoplastic resin and / or a rubber-like elastic material 99 to 1% by weight,
(B) A polystyrene resin composition comprising 0.005 to 5.0 parts by weight of a phenolic antioxidant, and (3) (A) (a) SPS 99.9 to 9.0 parts by weight. % And (c) Polyphenylene ether and / or modified polyphenylene ether 0.1-10.0 wt% resin 1
(B) phenolic antioxidant 0.005
The present invention provides a polystyrene-based resin composition containing about 5.0 parts by weight of (4) (A) (a) SPS.
1 to 99% by weight and (b) 100 parts by weight of a resin composed of a thermoplastic resin and / or 99 to 1% by weight of a rubber-like elastic material, (c) polyphenylene ether and / or modified polyphenylene ether 0.1 to 10. The present invention provides a polystyrene resin composition comprising 100 parts by weight of a resin composition containing 0 parts by weight of (B) a phenolic antioxidant (0.005 to 5.0 parts by weight). Is (5) the resin composition 1 of the above (1), (2), (3) or (4)
The present invention provides a polystyrene resin composition comprising 1 to 350 parts by weight of the inorganic filler (C) with respect to 00 parts by weight.

In the resin composition of the present invention, the resin (A)
Is SPS as the component (a), a thermoplastic resin and / or a rubber-like elastic body as the component (b), and polyphenylene ether and / or modified polyphenylene ether as the component (c). Here, SPS as the component (a), that is, the syndiotactic structure in the styrene-based polymer having a syndiotactic structure, means that the stereostructure is a syndiotactic structure, that is, a main chain formed from carbon-carbon bonds. Has a three-dimensional structure in which phenyl groups and substituted phenyl groups, which are side chains, are alternately located in opposite directions, and the tacticity thereof is quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotopic carbon. . ^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), poly (tertiary-butylstyrene), poly (phenylstyrene), poly (vinylnaphthalene), There are poly (vinyl styrene) and the like, and as poly (halogenated styrene), there are poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene) and the like. The poly (halogenated alkylstyrene) includes poly (chloromethylstyrene), and the poly (alkoxystyrene) includes poly (methoxystyrene) and poly (ethoxystyrene).

Of these, particularly preferred styrene polymers are polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-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 polymer is not particularly limited in its molecular weight, but the weight average molecular weight is preferably 100.
It is at least 00, more preferably at least 50,000. Further, the molecular weight distribution is not limited in its width or width, and various kinds can be applied. Here, if the weight average molecular weight is less than 10,000, mechanical properties such as thermal properties and mechanical strength of the obtained composition or molded product may be deteriorated, which is not preferable.

Such SPS is obtained by using, for example, a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent, a styrenic monomer (the above styrene-based monomer). It can be produced by polymerizing a monomer corresponding to a polymer (JP-A-62-187708). Regarding poly (halogenated alkylstyrene), JP-A-1-46
No. 912, the above-mentioned hydrogenated polymer is described in JP-A 1-1785.
It can be obtained by the method described in Japanese Patent Publication No. 05.

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

Next, in the present invention, the component (b) is a thermoplastic resin and / or a rubber-like elastic material. Here, the thermoplastic resin is other than the component (a) and the component (c) described below, and various thermoplastic resins can be used without particular limitation. Specifically, polystyrene having an atactic structure, polystyrene having an isotactic structure, styrene polymers such as AS resin and ABS resin; polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polycarbonate; polyphenylene oxide, polyphenylene sulfide, poly Poly (thio) ether-based resins such as oxymethylene; sulfone-based resins such as polysulfone and polyethersulfone; acrylic-based polymers such as polyacrylic acid, polyacrylic acid ester, and polymethylmethacrylate;
Polyethylene, polypropylene, polybutene, poly-4
Examples include polyolefin polymers such as -methylpentene-1, ethylene-propylene copolymers; halogen-containing vinyl compound polymers such as polyvinyl chloride, polyvinylidene chloride, and polyvinylidene fluoride; polyamide resins. As the thermoplastic resin, these resins may be used alone or in combination of two or more kinds.

The rubber-like elastic body as the component (b) is, for example, styrene-butyl acrylate copolymer rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene. -Butadiene-styrene block copolymer (SB
S), 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-styrene block copolymer (SEP)
S), 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 (A
BS), methyl methacrylate-butadiene-styrene-core shell rubber (MBS), methyl methacrylate-
Butyl acrylate-styrene-core shell rubber (MA
S), octyl acrylate-butadiene-styrene-
Core shell rubber (MABS), alkyl acrylate-
Core-shell type particulate elastic bodies such as butadiene-acrylonitrile-styrene core-shell rubber (AABS) and butadiene-styrene-core-shell rubber (SBR),
Examples include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, silicone rubber, ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM), and rubber obtained by modifying these rubber-like elastic bodies with a modifier. . Further, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-methyl acrylate copolymer, ethylene-glycidyl methacrylate-ethyl acrylate copolymer, ethylene-glycidyl methacrylate-methyl methacrylate copolymer, ethylene-glycidyl methacrylate-ethyl methacrylate Copolymer,
Ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-maleic anhydride copolymer, ethylene-maleic anhydride-methyl methacrylate copolymer, ethylene-maleic anhydride-ethyl methacrylate copolymer, ethylene-maleic anhydride- Copolymer of olefin and polar vinyl monomer such as vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, nylon elastomer, Examples include polyester elastomers, urethane elastomers, polysulfide rubbers, thiochol rubbers, acrylic rubbers, epichlorohydrin rubbers, and chlorinated rubbers. Among these, especially SEB, SE
Core shell rubbers containing BS, SEPS and styrene units are preferably used. As the rubber-like elastic body, one kind or a combination of two or more kinds may be used. In the resin composition of the present invention, as the component (b),
It contains both or one of the above-mentioned thermoplastic resin and rubber-like elastic body.

Next, in the resin composition of the present invention,
The component (c) is polyphenylene ether and / or modified polyphenylene ether. Here, polyphenylene ether is a known compound and is disclosed in US Pat.
06,874, 3,306,875, 3,257,357
No. 3 and No. 3,257,358 can be referred to. Polyphenylene ethers are usually prepared by oxidative coupling reactions to form homopolymers or copolymers in the presence of copper amine complexes, one or more di- or tri-substituted phenols. Here, the copper amine complex may be a copper amine complex derived from primary, secondary and tertiary amines. Specifically, poly (2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-chloromethyl-)
1,4-phenylene ether), poly (2-methyl-6)
-Hydroxyethyl-1,4-phenylene ether),
Poly (2-methyl-6-n-butyl-1,4-phenylene ether), poly (2-ethyl-6-isopropyl-
1,4-phenylene ether), poly (2-ethyl-6)
-N-propyl-1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether), poly [2- (4'-methylphenyl) -1,4-
Phenylene ether], poly (2-bromo-6-phenyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2-phenyl-1,4-) Phenylene ether), poly (2-chloro-1,4-phenylene ether), poly (2-methyl-1,4-phenylene ether), poly (2-chloro-6-ethyl-1,4-phenylene ether), Poly (2-chloro-6-bromo-1,4-phenylene ether), poly (2,6-di-n-propyl-
1,4-phenylene ether), poly (2-methyl-6)
-Isopropyl-1,4-phenylene ether), poly (2-chloro-6-methyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2 , 6-dibromo-1,4-phenylene ether), poly (2,6-dichloro-1,4)
-Phenylene ether), poly (2,6-diethyl-)
1,4-phenylene ether) and poly (2,6-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.

The modified polyphenylene ether is obtained by modifying the polyphenylene ether as described above with a modifier, but the method is not limited to this method as long as it meets the object of the present invention. Examples of the modifier used for modifying these polyphenylene ethers include compounds having an ethylenic double bond and a polar group in the same molecule. Examples of such modifiers include maleic anhydride, maleic acid, fumaric acid, maleic acid esters,
Maleimide and its N-substituted compound, maleic acid salt, acrylic acid, acrylic acid ester, acrylic acid amide, acrylic acid salt, methacrylic acid, methacrylic acid ester, methacrylic acid amide, methacrylic acid salt, glycidyl methacrylate and the like can be mentioned. 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, for example, by reacting the above polyphenylene ether with a modifying agent in the presence of a solvent or another resin. The modification method is not particularly limited, and a known method, for example, a roll mill, a Banbury mixer, an extruder, etc.
A method of melt-kneading at a temperature in the range of 50 ° C. and reacting, or a method of heating and reacting in a solvent such as benzene, toluene or xylene can be used. Further, in order to facilitate these reactions, benzoyl peroxide; di-t-butyl peroxide; dicumyl peroxide; t-butyl peroxybenzoate; azobisisobutyronitrile; azobisisovalero are added to the reaction system. The presence of a radical generator such as nitrile; 2,3-diphenyl-2,3-dimethylbutane is effective. A preferable method is a method of melt-kneading in the presence of a radical generator. Among these modified polyphenylene ethers, maleic anhydride modified polyphenylene ethers are particularly preferably used. In the resin composition of the present invention, both or either of polyphenylene ether and modified polyphenylene ether may be blended as the component (c).

Next, the component (B) of the present invention is a phenolic oxidizing agent. By blending this (B) component,
It is possible to improve heat resistance and durability while maintaining the physical properties that SPS originally has. Specific examples of the phenol-based oxidizing agent include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, and 2,6-di-t-butyl- 4-phenylphenol, 2,2'-methylenebis (4-methyl-6-
t-butylphenol), 2,2'-methylenebis (4
-Ethyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-n-nonylphenol), 4,4'-butylidenebis (3-methyl-6-t)
-Butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2-t -Butyl-6- (3-t-butyl-
2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-
3,5-Di-t-pentylphenyl) ethyl] -4,6
-Di-t-pentylphenyl acrylate, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxy-benzylphosphonate Nate-diethyl ester, triethylene glycol-bis [3- (3
-T-butyl-5-methyl-4-hydroxyphenyl)
Propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-dipropionate) -T-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,9-bis [1,1 -Di-methyl-2- [β- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy] ethyl] -2,
4,8,10-Tetrachiosasusbiro [5,5] undecane, N, N'-bis [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionyl] hydrazine,
Pentaerythrityl-tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-
Hydroxy-3,5-di-t-butylanilino) -1,
3,5-triazine, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate,
Examples include tris (4-t-butyl-2,6-di-methyl-3-hydroxybenzyl) isocyanurate.
Of these, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2- [1]
-(2-Hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, n-octadecyl-3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis [3- (3-t-butyl-
5-Methyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t
-Butyl-4-hydroxy-hydrocinnamide),
3,9-bis [1,1-di-methyl-2- [β- (3-
t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetrachiosasbiro [5,5] undecane, pentaerythrityl-tetrakis [3- (3,5) -Di-t-butyl-4
-Hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-
3,5-di-t-butylanilino) -1,3,5-triazine, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate is preferred.

Next, the component (C) of the present invention is an inorganic filler. As the inorganic filler, those subjected to a surface treatment with a coupling agent are preferably used in order to improve the adhesiveness with the styrene resin which is the component (A) (a). Here, there are various types of inorganic fillers such as fibrous, granular, and powdery ones. Examples of the fibrous filler include glass fiber, carbon fiber, whiskers, ceramic fiber, metal fiber and the like. Specifically, the whiskers include boron, alumina, silica, silicon carbide, etc., the ceramic fibers include gypsum, potassium titanate, magnesium sulfate, magnesium oxide, etc., and the metal fibers include copper, aluminum, steel, etc. Here, the shape of the filler is cloth, mat, bundle cutting, short fiber, filament,
There are whiskers. In the case of convergent cutting, the length is 0.05-
It is preferably 50 mm and the fiber diameter is 5 to 20 μm. In the case of a cloth or mat, the length is preferably 1 mm or more, more preferably 5 mm or more.

On the other hand, examples of the granular or powdery filler include talc, carbon black, graphite, titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, Examples thereof include tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flakes, and glass beads.
Among these fillers, especially glass fillers such as glass filaments, glass fibers, glass rovings,
Glass mats, glass powders, glass flakes and glass beads are preferred.

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

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

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

The resin composition (1) of the present invention contains 0.005 to 5.0 parts by weight of the above-mentioned component (B) in 100 parts by weight of the polystyrene polymer which is the above-mentioned component (A) (a). , And preferably a resin composition containing 0.01 to 3.0 parts by weight. When the amount of the component (B) is less than 0.005 part by weight, a sufficient antioxidant effect cannot be obtained, and the heat resistance and durability of the resin composition are not improved. If it exceeds 0.0 parts by weight, not only is it economically disadvantageous, but also bleeding of the antioxidant occurs, mechanical strength, heat resistance, appearance, etc. are deteriorated, which is not preferable.

The resin composition (2) of the present invention comprises the polystyrene-based polymers 1 to 99 which are the above-mentioned components (A) and (a).
% By weight, preferably 5 to 95% by weight, more preferably 20 to 80% by weight, and the above components (A) and (b) 99 to 1
%, Preferably 95 to 5% by weight, more preferably 80 to 20% by weight, and 100 parts by weight of the resin, which is the above-mentioned component (B) phenolic antioxidant.
The resin composition contains 0.005 to 5.0 parts by weight, preferably 0.01 to 3.0 parts by weight. Where (A)
In the addition ratio of the components (a) and (A) and (b),
If the added amount of the component is less than 1% by weight, the effect of improving the physical properties by the addition cannot be obtained, and if it exceeds 99% by weight, the styrene-based polymer as the component (a) has excellent properties such as mechanical strength and heat resistance. There is a problem that you can't expect enough. Further, the blending amount of the component (B) is specified for the same reason as the resin composition of (1).

The resin composition (3) of the present invention comprises the styrene-based polymer 99.9 to 90.
0% by weight, preferably 99.5 to 92.0% by weight and the above-mentioned component (A) (c) 0.1 to 1.0% by weight, preferably 0.5
To 100 parts by weight of resin containing ~ 8.0% by weight,
Component (B) 0.005 to 5.0 parts by weight, preferably 0.01 to
A polystyrene-based resin composition containing 3.0 parts by weight. Here, in the blending ratio of the components (A) (a) and (A) (c), if the blending amount of the component (c) is less than 0.1% by weight, toughness improvement by blending the component (c) The effect is insufficient, and when it exceeds 1.0% by weight, the crystallinity of the component (a) is lowered, and the heat resistance and moldability of the resulting composition are lowered, which is not preferable. Further, the blending amount of the component (B) is specified for the same reason as the resin composition of (1).

Further, the resin composition (4) of the present invention is
Styrene-based polymers 1 to 9 which are the above-mentioned components (A) and (a)
9% by weight, preferably 5 to 95% by weight, more preferably 20 to 80% by weight, and the above components (A) and (b) 99 to 99% by weight.
1% by weight, preferably 95 to 5% by weight, and more preferably 80 to 20% by weight, based on 100% by weight of the resin, 0.1 to 10. 0 parts by weight, preferably 0.5 to 8.0 parts by weight, is added, and 100 parts by weight of the resin thus blended is added with 0.005 parts of the component (B).
To 5.0 parts by weight, preferably 0.01 to 3.0 parts by weight, is a polystyrene resin composition. here,
In the addition ratio of the components (A) (a) and (A) (b),
If the addition amount of the component (b) is less than 1% by weight, the effect of improving the physical properties cannot be obtained by the addition, and if it exceeds 99% by weight, the mechanical strength and heat resistance of the styrene-based polymer as the component (a) can be reduced There is a problem that excellent characteristics cannot be expected sufficiently. Further, the blending amount of the components (A) and (c) is 0.
If the amount is less than 1 part by weight, the effect of improving the toughness by blending the component (c) is insufficient, and if the amount exceeds 1 part by weight, the crystallinity of the component (a) is lowered, and the heat resistance of the resulting composition is reduced. Properties and moldability are deteriorated, which is not preferable. Further, the blending amount of the component (B) is specified for the same reason as the resin composition of (1).

Next, the resin composition (5) of the present invention is
1 to 350 of the above-mentioned component (C) is added to 100 parts by weight of the resin composition of (1), (2), (3) or (4) above.
It is a resin composition containing 5 parts by weight, preferably 5 to 200 parts by weight. Here, if the amount of the component (C) is less than 1 part by weight, sufficient effects of improving heat resistance, rigidity, impact resistance, etc. are not observed, and if it exceeds 350 parts by weight, dispersibility deteriorates. Then, molding becomes difficult, which is not preferable.

Further, in the present invention, an organic filler can be added in addition to the above-mentioned (C) inorganic filler. Here, examples of the organic filler include organic synthetic fibers and natural plant fibers. Specific examples of the organic synthetic fibers include wholly aromatic polyamide fibers and polyimide fibers.

In the resin composition of the present invention, various addition components such as a nucleating agent, a plasticizer, a release agent, a flame retardant, an antistatic agent, and a foaming agent are used as long as the object of the present invention is not impaired. , Pigments, carbon black, processing aids, metal soaps, etc. can be added.

The resin composition of the present invention is a composition in which the above-mentioned components are blended in the above-mentioned proportions, and there is no particular limitation on the blending method and the like. It can be produced by a method such as melt kneading at a specific ratio. In this way, the resin composition of the present invention produced is a resin composition having significantly improved heat resistance and durability while maintaining characteristics such as original mechanical strength as compared with conventional SPS resins. is there.

The present invention will be described in detail below with reference to examples and comparative examples. The following physical properties of the pellets or the formed test pieces obtained in Examples and Comparative Examples were measured by the following methods. (1) MI of pellet: JIS K7210
(Measured at 300 ° C, 2.16kg) (2) Tensile strength of test piece: JIS K7113
(3) YI of test piece: JIS K7203
(4) Long-term heat resistance of test piece After being held at 150 ° C. for 1000 hours, tensile strength, its holding rate and YI of the test piece Here, the holding rate of tensile strength is derived from the following formula. Retention rate of tensile strength (%) = (tensile strength after high temperature treatment)
/ (Tensile strength before high temperature treatment) x 100

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

Production Example 2 (Production of modified polyphenylene ether) 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. To measure the denaturation rate, 1 g of the obtained modified polyphenylene ether was dissolved in ethylbenzene and then reprecipitated in methanol, and the recovered polymer was Soxhlet extracted with methanol. After drying, the denaturation rate was determined by titration and carbonyl absorption intensity of IR spectrum I asked. At this time, the modification rate was 2.0% by weight.

Example 1 100 parts by weight of SPS (weight average molecular weight 40,000, weight average molecular weight / number average molecular weight 2.60) of Production Example 1 was used as an antioxidant pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by ADEKA ARGUS CORPORATION, trade name AO-20) was blended in an amount of 0.3 parts by weight and dry-blended with a Henschel mixer, followed by twin-screw extrusion. Melt kneading was carried out at a cylinder temperature of 300 ° C. in a machine to form pellets. Injection molding was performed using the obtained pellets to obtain a test piece.
The physical properties of the obtained pellets and test pieces were measured. The results are shown in Table 1.

Example 2 In Example 1, except that 4,4'-thiobis (3-methyl-6-t-butylphenol) (Adeka Argus Co., trade name AO-40) was used as an antioxidant. A pellet and a test piece were obtained in the same manner as in Example 1.
The results are shown in Table 1.

Example 3 In Example 1, except that 2,2'-methylenebis (4-methyl-6-t-butylphenol) (Sumitomo Chemical Co., trade name Sumilizer MDP-S) was used as an antioxidant. A pellet and a test piece were obtained in the same manner as in Example 1. The results are shown in Table 1.

Example 4 Example 4 was repeated except that n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenylpropionate (trade name Irg1076) was used as the antioxidant. Pellets and test pieces were obtained in the same manner as in Example 1. The results are shown in Table 1.

Example 5 In Example 1, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-) was used as an antioxidant.
Hydroxyphenyl) propionate] (trade name Irg
Pellets and test pieces were obtained in the same manner as in Example 1 except that 1010) was used. The results are shown in Table 1.

Comparative Example 1 Pellets and test pieces were obtained in the same manner as in Example 1 except that the antioxidant was not used.
The results are shown in Table 1.

Example 6 80% by weight of SPS (weight average molecular weight of 40,000, weight average molecular weight / number average molecular weight of 2.60) of Production Example 1 and SEBS as a rubber-like elastic body (manufactured by Shell Chemical Co., Ltd., trade name)
Kraton G-1651] 20 wt% was added to 100 parts by weight, while 2,4-bis (n-octylthio) -6- (4-hydroxy-3,
5-di-t-butylanilino) -1,3,5-triazine (trade name Irg565) (0.3 parts by weight) was blended and dry blended with a Henschel mixer, and then melted with a twin screw extruder at a cylinder temperature of 300 ° C. Kneading was performed and pelletized. Injection molding was performed using the obtained pellets to obtain a test piece. The physical properties of the obtained pellets and test pieces were measured. The results are shown in Table 1.

Example 7 Example 6 was repeated except that n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenylpropionate (trade name Irg1076) was used as an antioxidant. Pellets and test pieces were obtained in the same manner as in Example 6. The results are shown in Table 1.

Example 8 In Example 6, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-) was used as an antioxidant.
Hydroxyphenyl) propionate] (trade name Irg
Pellets and test pieces were obtained in the same manner as in Example 6 except that 1010) was used. The results are shown in Table 1.

Example 9 In Example 6, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) (trade name Irg1098) was used as an antioxidant. Pellets and test pieces were obtained in the same manner as in Example 6 except for the above. The results are shown in Table 1.

Example 10 In Example 6, 2- [1- (2-
Hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate (Sumitomo Chemical Co., Ltd., trade name Sumilizer GS) was used in the same manner as in Example 6. To obtain pellets and test pieces. The results are shown in Table 1.

Comparative Example 2 Pellets and test pieces were obtained in the same manner as in Example 6 except that the antioxidant was not used.
The results are shown in Table 1.

Example 11 90% by weight of SPS (weight average molecular weight 400,000, weight average molecular weight / number average molecular weight 2.60) of Production Example 1 and SEBS as a rubber-like elastic body [manufactured by Shell Chemical Co., Ltd., trade name Kraton G-1651] 10% by weight was added to 100 parts by weight, and 3 parts by weight of the modified polyphenylene ether obtained in Production Example 2 was added to 100 parts by weight of triethylene glycol as an antioxidant. Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate (trade name Irg245) 0.
After mixing 3 parts by weight and dry blending with a Henschel mixer, the mixture was melt-kneaded with a twin-screw extruder at a cylinder temperature of 300 ° C., and pelletized. Injection molding was performed using the obtained pellets to obtain a test piece. The physical properties of the obtained pellets and test pieces were measured. The results are shown in Table 1.

Example 12 Example 12 was repeated except that n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenylpropionate (trade name Irg1076) was used as the antioxidant. Pellets and test pieces were obtained in the same manner as in Example 11. The results are shown in Table 1.

Example 13 In Example 11, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4) was used as an antioxidant.
-Hydroxyphenyl) propionate] (trade name Ir
Pellets and test pieces were obtained in the same manner as in Example 11 except that g1010) was used. The results are shown in Table 1.

Example 14 In Example 11, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (commercial product was used as an antioxidant. First name Irg
Pellets and test pieces were obtained in the same manner as in Example 11 except that 1330) was used. The results are shown in Table 1.

Example 15 In Example 11, as the antioxidant, 3,9-bis [1,1-di-methyl-2- [β- (3-t-butyl-
4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetrachiosasbiro [5,5] undecane (manufactured by Adeka Argus Co., Ltd., trade name AO-80) was used. Pellets and test pieces were obtained in the same manner as in Example 11 except for the above. The results are shown in Table 1.

Comparative Example 3 Pellets and test pieces were obtained in the same manner as in Example 11 except that the antioxidant was not used. The results are shown in Table 1.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

As described above, the resin composition of the present invention is
It is a resin composition having remarkably improved heat resistance and durability while maintaining the water resistance, impact resistance, mechanical strength and the like that PS originally has. Therefore, the resin composition of the present invention can be used in various applications such as products for which heat resistance and durability are particularly required, specifically, various molded products such as mechanical parts, electric and electronic parts, films and fibers. Expected effective use.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 71:12)

Claims (5)

[Claims] 1. A polystyrene resin comprising (A) (a) 100 parts by weight of a styrene polymer having a syndiotactic structure and (B) a 0.005 to 5.0 parts by weight of a phenolic antioxidant. Composition. 2. 100% by weight of a resin comprising (A) 1 to 99% by weight of (a) a styrene polymer having a syndiotactic structure and (b) 99 to 1% by weight of a thermoplastic resin and / or a rubber-like elastic material. A polystyrene resin composition obtained by blending 0.005 to 5.0 parts by weight of (B) a phenolic antioxidant in 10 parts by weight. 3. A) (A) (a) Styrene-based polymer having a syndiotactic structure 99.9 to 90.0% by weight and (c) polyphenylene ether and / or modified polyphenylene ether 0.1 to 10.0% by weight. % Resin 10
0 parts by weight of (B) phenolic antioxidant 0.005
A polystyrene resin composition containing 5.0 parts by weight. 4. 100% by weight of (A) (a) 1 to 99% by weight of a styrene polymer having a syndiotactic structure and (b) 99 to 1% by weight of a thermoplastic resin and / or a rubber-like elastic material. (C) polyphenylene ether and / or modified polyphenylene ether 0.1 to 10 parts by weight
To 100 parts by weight of resin obtained by adding 10.0 parts by weight,
(B) A polystyrene resin composition containing 0.005 to 5.0 parts by weight of a phenolic antioxidant. 5. Inorganic fillers (C) 1 to 35 relative to 100 parts by weight of the resin composition according to claim 1, 2, 3 or 4.
A polystyrene resin composition containing 0 part by weight.