JP4633390B2 - Polyarylene sulfide resin composition - Google Patents

Description

  The present invention relates to a polyarylene sulfide resin composition that is excellent in impact resistance and in which generation of mold deposits during molding is remarkably suppressed.

  Polyarylene sulfide (hereinafter abbreviated as PAS) resin represented by polyphenylene sulfide (hereinafter abbreviated as PPS) resin has high heat resistance, mechanical properties, chemical resistance, dimensional stability, and flame retardancy. For this reason, it is widely used for electrical / electronic equipment parts materials, automotive equipment parts materials, chemical equipment parts materials, and the like.

  However, PAS resins have a fundamental drawback that they have poor toughness and are fragile, and have insufficient mechanical properties represented by impact resistance.

As a conventional method for solving this problem, it is known to blend various elastomers. In particular, an olefin copolymer mainly composed of an α-olefin and a glycidyl ester of an α, β-unsaturated acid is excellent in compatibility with a PAS resin, and thus has improved impact resistance (Patent Document 1). ~ 4). However, since the processing temperature of the PAS resin is 300 ° C. or higher, the olefin copolymer component is thermally deteriorated and not only has a sufficient impact resistance improvement effect, but also decomposes and produces gas during molding. In addition, mold deposits may increase during molding.
JP 58-154757 A JP 59-152953 A JP 59-189166 JP 62-153343 A

  The object of the present invention is to provide a PAS resin composition that solves the above-mentioned problems of the prior art, is excellent in impact resistance, and has a significantly reduced generation of mold deposits during molding.

  As a result of intensive studies to solve the above problems, the present inventors have achieved excellent impact resistance by using a specific PAS resin with a reduced nitrogen content and a specific olefin copolymer, and a mold deposit at the time of molding. The present inventors have found that a PAS resin composition in which the generation of water is remarkably reduced can be obtained, and the present invention has been completed.

That is, the present invention
(A) For 100 parts by weight of polyarylene sulfide resin in which the content of nitrogen element is 0.55 g or less per kg of resin,
(B) A polyarylene sulfide resin composition comprising 0.5 to 50 parts by weight of an olefin copolymer mainly composed of an α-olefin and a glycidyl ester of an α, β-unsaturated acid.

The polyarylene sulfide resin having a nitrogen element content of 0.55 g or less per kg of the resin as described above can be obtained, for example, by a production method characterized by the following (1) and (2).
(1) A reaction vessel is charged with an organic amide solvent, a sulfur source containing an alkali metal hydrosulfide, and, if necessary, a part of the total charge of the alkali metal hydroxide, and the mixture containing these is heated. A dehydration step of discharging at least part of the distillate containing water from the system containing the mixture to the outside of the system, and
(2) Mixing the mixture remaining in the system after the dehydration step and the dihaloaromatic compound, heating the polymerization reaction mixture containing them, causing the sulfur source and the dihaloaromatic compound to undergo a polymerization reaction, and a polymerization reaction A polymerization step of adding alkali metal hydroxide continuously or in portions to the mixture and controlling the pH of the polymerization reaction mixture within the range of 7 to 12.5 from the start to the end of the polymerization reaction Process for producing polyarylene sulfide resin composition characterized in that

  Hereinafter, the constituent components of the present invention will be described in detail. The PAS resin is a polymer compound composed of-(Ar-S)-(where Ar is an arylene group) as a main repeating unit, and as the component (A) of the present invention, a generally known molecule is used. A PAS resin having a structure can be used, but it is essential that the content of nitrogen element is 0.55 g or less per kg of the resin.

  Examples of the arylene group include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p'-diphenylene sulfone group, p, p'-biphenylene group, p, p'- Examples include diphenylene ether group, p, p′-diphenylenecarbonyl group, naphthalene group and the like.

  The PAS resin used in the present invention may be a homopolymer consisting only of the above repeating units, or a copolymer containing the following different types of repeating units may be preferable from the viewpoint of processability.

  As the homopolymer, one having a p-phenylene sulfide group as a repeating unit (PPS) using a p-phenylene group as an arylene group is particularly preferably used. As the copolymer, among the arylene sulfide groups comprising the above-mentioned arylene groups, two or more different combinations can be used, and among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used. It is done. Among these, those containing 70 mol% or more, preferably 80 mol% or more of p-phenylene sulfide groups are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties. The m-phenylene sulfide group preferably contains 5 to 30 mol%, particularly 10 to 20 mol%, as a copolymer. In this case, the repeating unit of the component is contained in a block rather than a random one (for example, the one described in JP-A-61-1228) has excellent workability, heat resistance, machine The physical properties are also excellent and can be preferably used. Further, among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional halogen aromatic compound can be particularly preferably used.

  Such a linear PAS resin having substantially no branch is a target resin suitable for the purpose of the present invention in terms of excellent fluidity and mechanical properties.

  In addition to the linear PAS resin, a partially branched or crosslinked structure is formed by using a small amount of a monomer such as a polyhaloaromatic compound having 3 or more halogen substituents when performing condensation polymerization. A polymer having a low molecular weight linear structure polymer heated at a high temperature in the presence of oxygen or the like to increase the melt viscosity by oxidative crosslinking or thermal crosslinking to improve molding processability, or Mixtures of these can also be used.

The melt viscosity (310 ° C., shear rate 1200 sec ⁻¹ ) of the PAS resin as the base resin used in the present invention is preferably 10 to 500 Pa · s, including the above mixed system, and more preferably in the range of 20 to 300 Pa · s. In this case, the balance between mechanical properties and fluidity is excellent, and it is particularly preferable. An excessively low melt viscosity is not preferable because the mechanical strength is not sufficient. On the other hand, when the melt viscosity exceeds 500 Pa · s, the flowability of the resin composition is poor at the time of injection molding, and the molding operation becomes difficult.

  The content of nitrogen element in the PAS resin is 0.55 g or less, preferably 0.4 g or less, per 1 kg of the resin. Excessive nitrogen content means that NMP (N-methyl-2-pyrrolidone), sodium methylaminobutanoate, chlorophenylmethylaminobutanoic acid, or methylaminobutanoic acid group at the PAS terminal, etc. remaining in the PAS resin. This means that there is a large amount, and it is thought that this is due to the thermal decomposition of these substances, the occurrence of mold deposits during molding increases, frequent mold maintenance, or the thermal stability of the resulting PAS resin composition. The problem that it falls is caused.

  In addition, content of the nitrogen element in PAS resin can be measured with a normal method using commercially available apparatuses, such as a trace amount nitrogen sulfur analyzer.

Such a PAS resin used in the present invention does not depend on the production method if the nitrogen content is 0.55 g or less per kg of the resin, but is obtained by the production method characterized by the following (1) and (2). It is done.
(1) A reaction vessel is charged with an organic amide solvent, a sulfur source containing an alkali metal hydrosulfide, and, if necessary, a part of the total charge of the alkali metal hydroxide, and the mixture containing these is heated. A dehydration step of discharging at least part of the distillate containing water from the system containing the mixture to the outside of the system, and
(2) Mixing the mixture remaining in the system after the dehydration step and the dihaloaromatic compound, heating the polymerization reaction mixture containing them, causing the sulfur source and the dihaloaromatic compound to undergo a polymerization reaction, and a polymerization reaction A polymerization step of adding alkali metal hydroxide continuously or in portions to the mixture and controlling the pH of the polymerization reaction mixture within the range of 7 to 12.5 from the start to the end of the polymerization reaction Further, the PAS resin used in the present invention only needs to have a nitrogen content in the above range, and may be a blend having a high nitrogen content and a low nitrogen content as long as this condition is satisfied.

  Next, the (B) olefin copolymer used in the present invention is an olefin copolymer mainly composed of α-olefin and a glycidyl ester of α, β-unsaturated acid. Examples of the α-olefin that is one of the components include ethylene, propylene, and butylene, with ethylene being preferred. Two or more of these α-olefins can be used. Further, the glycidyl ester of α, β-unsaturated acid which is the other component constituting the olefin copolymer is represented by the general formula (2).

(However, R ₁ represents hydrogen or a lower alkyl group.)
And glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, with glycidyl methacrylate being preferred.

  An olefin copolymer comprising an α-olefin (for example, ethylene) and a glycidyl ester of an α, β-unsaturated acid can be obtained by copolymerization by a well-known radical polymerization reaction. (B) The olefin copolymer is preferably copolymerized using 1 to 40 parts by weight of a glycidyl ester of an α, β-unsaturated acid with respect to 100 parts by weight of the α-olefin.

  Further, (B) the olefin copolymer is one or more of a polymer or copolymer composed of a repeating unit represented by the following general formula (1) for improving impact resistance and heat resistance. A graft copolymer that is chemically bonded in a branched or crosslinked structure is preferred.

(However, R is hydrogen or a lower alkyl group, X is -COOCH ₃ , -COOC ₂ H ₅ , -COOC ₄ H ₉ , -COOCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ , -C ₆ H ₅ , One or more groups selected from —CN are shown.)
The polymer or copolymer segment to be graft copolymerized as a branched or cross-linked chain may be one or two selected from acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile and styrene. Examples include polymers or copolymers composed of more than one species. Preferred are a methacrylic acid polymer, a copolymer of acrylonitrile and styrene, a copolymer of methyl methacrylate and butyl acrylate, and the like, particularly preferably a copolymer of methyl methacrylate and butyl acrylate. These polymers or copolymers are usually prepared by well-known radical polymerization.

  In addition, the branching or crosslinking reaction of these polymers or copolymers can be easily prepared by radical reaction. For example, by generating free radicals in these polymers or copolymers with peroxides or the like, and melting and kneading an olefin copolymer of α-olefin and a glycidyl ester of α, β-unsaturated acid, Graft copolymers can be prepared.

  The polymer or copolymer that becomes a branched or crosslinked chain branches or crosslinks 10 to 100 parts by weight with respect to 100 parts by weight of an olefin copolymer of glycidyl ester of α-olefin and α, β-unsaturated acid. Is preferred.

  (B) As a compounding quantity of an olefin type copolymer, 0.5-50 weight part with respect to 100 weight part of (A) PAS resin, Preferably 1-20 weight part is used.

  In the present invention, a stabilizer such as a phenolic antioxidant, a thioether antioxidant, a phosphorus stabilizer, or an amine stabilizer is used to obtain the desired impact resistance, heat resistance, and moldability. Can do.

  In addition, the resin composition of the present invention may be blended with an inorganic filler as component (C) in order to improve performance such as mechanical strength, heat resistance, dimensional stability (deformation resistance, warpage), and electrical properties. This can be done using fibrous, granular or plate-like fillers depending on the purpose.

  Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum, titanium, copper, brass, etc. Examples thereof include inorganic fibrous materials such as metal fibrous materials. Particularly typical fibrous fillers are glass fibers or carbon fibers. High melting point organic fiber materials such as polyamide, fluororesin and acrylic resin can also be used. On the other hand, as granular fillers, carbon black, silica, quartz powder, glass beads, glass powder, calcium oxalate, aluminum oxalate, kaolin, talc, clay, diatomaceous earth, wollastonite such as wollastonite, oxidation Metal oxides such as iron, titanium oxide, zinc oxide and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, other silicon carbide, silicon nitride, boron nitride, Various metal powders are mentioned. Examples of the plate-like filler include mica, glass flakes, and various metal foils. These inorganic fillers can be used alone or in combination of two or more.

  In using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary. Examples of this are functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, and titanate compounds. These compounds may be used after being subjected to surface treatment or convergence treatment in advance, or may be added at the same time as material preparation.

  The amount of the inorganic filler used is 10 to 300 parts by weight per 100 parts by weight of the component (A) PAS resin. If it is too small, the mechanical strength is slightly inferior. If it is too large, the molding operation becomes difficult, and there is also a problem in mechanical strength.

  Moreover, the silane compound can be mix | blended with the resin composition of this invention in order to improve a burr | flash etc. in the range which does not impair the effect of this invention. The silane compound includes various types such as vinyl silane, methacryloxy silane, epoxy silane, amino silane, mercapto silane, etc., for example, vinyl trichloro silane, γ-methacryloxy propyl trimethoxy silane, γ-glycidoxy propyl trimethoxy silane. , Γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like, but are not limited thereto.

  The resin composition of the present invention can be used in combination with a small amount of other thermoplastic resins in addition to the above components depending on the purpose. Other thermoplastic resins include, for example, ester resins such as polyphenylene ether, polyethersulfone, polysulfone, polycarbonate, polyacetal, etc., liquid crystalline polymers, aromatic polyesters, polyarylate, polyethylene terephthalate, polybutylene terephthalate; polyethylene Olefin resins such as polypropylene and poly-4-methylpentene-1; amide resins such as nylon 6, nylon 66 and aromatic nylon; polymethyl (meth) acrylate, polyacrylonitrile styrene (AS resin), polystyrene, norbornene resin And the like, and the like. These thermoplastic resins can be used in combination of two or more.

  Further, the resin composition of the present invention also includes known substances generally added to thermoplastic resins, that is, flame retardants, coloring agents such as dyes and pigments, lubricants and crystallization accelerators, crystal nucleating agents, and the like. Depending on the case, it can be added appropriately.

  The resin composition of the present invention can be prepared by facilities and methods generally used for preparing a synthetic resin composition. In general, necessary components can be mixed, melt-kneaded using a single-screw or twin-screw extruder, and extruded to form pellets for molding. The resin temperature during this melt-kneading is preferably 360 ° C. or lower in order to prevent thermal degradation of the olefin copolymer. It is also a preferred method to melt-extrude the resin component and add and mix an inorganic component such as glass fiber in the middle.

  The material pellets thus obtained can be molded using generally known thermoplastic resin molding methods such as injection molding, extrusion molding, vacuum molding, compression molding, etc., but injection molding is most preferred. .

Next, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these. The specific substances of the components (A), (B) and (C) used in the examples and comparative examples are as follows.
(A) PAS resin
(A-1)
Into a 20 L autoclave, 5700 g of NMP (N-methyl-2-pyrrolidone) was charged, and after replacing with nitrogen gas, the temperature was raised to 100 ° C. while stirring at a rotation speed of 250 rpm for about 1 hour. After reaching 100 ° C., 1170 g of an aqueous NaOH solution having a concentration of 74.7% by weight, 1990 g of an aqueous sulfur source solution (including NaSH = 21.8 mol and Na ₂ S = 0.50 mol) and NMP 1000 g were added, and gradually increased to 200 ° C. over about 2 hours. Then, 945 g of water, 1590 g of NMP, and 0.31 mol of hydrogen sulfide were discharged out of the system.

  After the dehydration step, the mixture was cooled to 170 ° C. and 3283 g of p-dichlorobenzene, 2800 g of NMP, 133 g of water, and 23 g of NaOH having a concentration of 97% by weight were added. As a result, the temperature in the can became 130 ° C. and the pH became 13.2. Subsequently, while stirring at a rotational speed of 250 rpm of the stirrer, the temperature was raised to 180 ° C. over 30 minutes, and further between 180 ° C. and 220 ° C. over 60 minutes. After reacting at that temperature for 60 minutes, the temperature was raised to 230 ° C. over 30 minutes, and the reaction was carried out at 230 ° C. for 90 minutes to perform pre-stage polymerization.

  Immediately after completion of the pre-polymerization, the rotation speed of the stirrer was increased to 400 rpm, and 340 g of water was injected. After water injection, the temperature was raised to 260 ° C. over 1 hour, and the reaction was carried out at that temperature for 5 hours to carry out post polymerization. The pH of the system at the end of the latter polymerization was 10.1.

After the post-polymerization is completed, the reaction mixture is cooled to near room temperature, the contents are passed through a 100 mesh screen, the particulate polymer is filtered off, then washed three times with acetone, three times with water, and 0.3% acetic acid. After that, washing with water was performed 4 times to obtain a washed granular polymer. The granular polymer was dried at 105 ° C. for 13 hours. The granular polymer thus obtained had a melt viscosity (310 ° C., shear rate of 1200 sec ⁻¹ ) of 140 Pa · s. This operation was repeated 5 times to obtain the required amount of polymer.
(A-2)
Into a 20 L autoclave, 5700 g of NMP (N-methyl-2-pyrrolidone) was charged, and after replacing with nitrogen gas, the temperature was raised to 100 ° C. while stirring at a rotation speed of 250 rpm for about 1 hour. After reaching 100 ° C., 1990 g of sulfur source aqueous solution (including NaSH = 21.9 mol and Na ₂ S = 0.4 mol) and NMP 1000 g were added, and the temperature was gradually raised to 200 ° C. over about 2 hours. Water 729 g, NMP 1370 g , And 0.70 mol of hydrogen sulfide was discharged out of the system.

  After the dehydration step, the mixture was cooled to 170 ° C., and 3236 g of p-dichlorobenzene and 2800 g of NMP were added. As a result, the inside temperature of the can reached 130 ° C. After heating up to 180 ° C. over 30 minutes, addition of sodium hydroxide (NaOH) was started, and the pH of the polymerization reaction system was controlled to 11.5 to 12.0. Subsequently, while stirring at a rotation speed of 250 rpm of the stirrer, the temperature was raised to 180 ° C. over 30 minutes, and further between 180 ° C. and 220 ° C. over 60 minutes. After reacting at that temperature for 60 minutes, the temperature was raised to 230 ° C. over 30 minutes, and the reaction was carried out at 230 ° C. for 90 minutes to perform pre-stage polymerization.

  Through the previous polymerization step, 1180 g of a 73.7 wt% NaOH aqueous solution was continuously added using a pump so as to maintain the pH of the polymerization reaction system in the range of 11.5 to 12.0.

  Immediately after completion of the pre-polymerization, the rotation speed of the stirrer was increased to 400 rpm, and 340 g of water was injected. After water injection, the temperature was raised to 260 ° C. over 1 hour and reacted at that temperature for 4 hours to carry out post polymerization. The pH of the system at the end of the latter polymerization was 10.0.

After the post-polymerization is completed, the reaction mixture is cooled to near room temperature, the contents are passed through a 100 mesh screen, the particulate polymer is filtered off, then washed three times with acetone, three times with water, and 0.3% acetic acid. After that, washing with water was performed 4 times to obtain a washed granular polymer. The granular polymer was dried at 105 ° C. for 13 hours. The granular polymer thus obtained had a melt viscosity (310 ° C., shear rate of 1200 sec ⁻¹ ) of 151 Pa · s. This operation was repeated 5 times to obtain the required amount of polymer.
(B) Olefin copolymer
(B-1) Ethylene / glycidyl methacrylate copolymer (Nippon Polyolefin Co., Ltd., Lexpearl RA3150)
(B-2) A copolymer obtained by grafting 30 parts by weight of a styrene / acrylonitrile copolymer to 70 parts by weight of an ethylene / glycidyl methacrylate copolymer (manufactured by NOF Corporation, Modiper A4400)
(B-3) A copolymer obtained by grafting 30 parts by weight of a methyl methacrylate / butyl acrylate copolymer (9/21) to 70 parts by weight of an ethylene / glycidyl methacrylate copolymer (Nippon Yushi Co., Ltd., Modiper A4300)
(C) Inorganic filler
(C-1) Glass fiber (13 μmφ chopped strand (manufactured by Nippon Electric Glass Co., Ltd., ECS303T-717))
(C-2) Calcium carbonate (Toyo Fine Chemical, Whiten P-30)
Moreover, the evaluation method in an Example and a comparative example is as follows.
[Analytical method of nitrogen content]
The nitrogen content in the PAS resin was measured using a trace nitrogen sulfur analyzer (ANTEK 7000, manufactured by ANTEK) (a calibration curve for the nitrogen content was prepared using an ethylbenzene solution of triphenylamine).

As a result, the nitrogen content of PAS resin (A-1) produced as described above was 850 ppm (0.850 g per kg of resin), and the nitrogen content of PAS resin (A-2) was 320 ppm (0.320 g per kg of resin). )Met.
[Evaluation of mold deposit]
With an injection molding machine, a molded product having a specific shape shown in FIG. 1 was continuously molded under the following conditions, and the amount of mold deposits was evaluated. Specifically, 500 shots of the test piece were molded, a mold deposit adhering to the gas vent part (operation side only) was collected, and the weight (μg) was measured.
(Molding condition)
Injection molding machine; Toshiba IS30FPA (manufactured by Toshiba Machine)
Cylinder temperature: 335-340-325-310 ° C
Injection pressure: 74MPa
Injection speed: 1m / min
Injection time: 2 sec
Cooling time: 5 sec
Molding cycle: 12sec
Mold temperature: 60 ℃
[Measurement of impact strength]
With an injection molding machine, Izod impact test specimens were molded according to ASTM D-256 at a cylinder temperature of 320 ° C and a mold temperature of 150 ° C, and allowed to stand in a predetermined temperature atmosphere for 2 hours or more, and the notch side impact strength was measured. .
Examples 1-6, Comparative Examples 1-4
The component (A) shown in Table 1 was premixed for 5 minutes with a Henschel mixer (omitted for one type). Further, the components (B) and (C) were added in the amounts shown in Table 1, mixed for 2 minutes, and charged into a twin-screw extruder having a cylinder temperature of 320 ° C. to produce pellets of a polyphenylene sulfide resin composition. About the obtained pellet, evaluation about a mold deposit and impact strength was performed by the above-mentioned method.

  The results are shown in Table 1.

It is a schematic diagram which shows the molded product for evaluation of the mold deposit performed in the Example, and the evaluation condition.

Claims (4)

(A) For 100 parts by weight of polyarylene sulfide resin in which the content of nitrogen element is 0.55 g or less per kg of resin,
(B) A polyarylene sulfide resin composition comprising 0.5 to 50 parts by weight of an olefin copolymer mainly composed of an α-olefin and a glycidyl ester of an α, β-unsaturated acid ,
A polyarylene sulfide resin composition wherein the polyarylene sulfide resin (A) or a part thereof is a polyarylene sulfide resin obtained by a production method characterized by the following (1) and (2).
(1) A reaction vessel is charged with an organic amide solvent, a sulfur source containing an alkali metal hydrosulfide, and, if necessary, a part of the total charge of the alkali metal hydroxide, and the mixture containing these is heated. A dehydration step of discharging at least part of the distillate containing water from the system containing the mixture to the outside of the system, and
(2) Mixing the mixture remaining in the system after the dehydration step and the dihaloaromatic compound, heating the polymerization reaction mixture containing them, causing the sulfur source and the dihaloaromatic compound to undergo a polymerization reaction, and a polymerization reaction A polymerization step of adding alkali metal hydroxide continuously or in portions to the mixture and controlling the pH of the polymerization reaction mixture within the range of 7 to 12.5 from the start to the end of the polymerization reaction
Process for producing polyarylene sulfide resin composition characterized in that (B) A polymer in which the olefin copolymer is composed of a repeating unit represented by the following general formula (1) in an olefin copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid. The polyarylene sulfide resin composition according to claim 1, wherein the polyarylene sulfide resin composition is a graft copolymer in which one or more of the copolymers are chemically bonded in a branched or crosslinked structure.

(Where R is hydrogen or a lower alkyl group, X is -COOCH _Three , -COOC ₂ H _Five , -COOC _Four H ₉ , -COOCH ₂ CH (C ₂ H _Five ) C _Four H ₉ , -C ₆ H _Five , Or one or more groups selected from —CN. ) (B) The olefin copolymer is an olefin copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid, and acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate. A polyarylene sulfide according to claim 1 or 2, which is a graft copolymer in which one or more polymers or copolymers selected from butyl methacrylate, acrylonitrile and styrene are chemically bonded in a branched or cross-linked structure. Resin composition. (B) The polyarylene according to any one of claims 1 to 3, wherein the olefin copolymer is a graft copolymer obtained by chemically bonding a copolymer of methyl methacrylate and butyl acrylate as a branched chain. A sulfide resin composition.

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