Polyarylene sulfide composition

Abstract

To provide a polyarylene sulfide composition having exceptional mechanical properties, acid resistance, and heat / cold resistance.SOLUTION: A polyarylene sulfide composition includes 30-70 wt.% of polyarylene sulfide (A), 2-10 wt.% of an ethylene polymer (B), and 20-60 wt.% of glass fiber (C). The boron oxide content of the glass fiber (C) is 1.5 wt.% or less and the fluorine content of it is 0.1 wt.% or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyarylene sulfide composition that has excellent chemical resistance, heat and cold resistance, fluidity, and acid resistance without impairing the inherent heat resistance, mechanical strength, electrical insulation, and other properties of polyarylene sulfide, and relates to a polyarylene sulfide composition that is particularly useful for applications such as automobile parts or electric / electronic parts. [Background technology]

[0002] Polyarylene sulfides (hereinafter sometimes abbreviated as PAS), such as poly(p-phenylene sulfide) (hereinafter sometimes abbreviated as PPS), have excellent mechanical, thermal, and electrical properties, and chemical resistance, and are widely used in many electrical and electronic equipment components, automotive equipment components, and other office automation equipment components.

[0003] PAS can significantly improve its mechanical strength, heat resistance, rigidity, etc. by blending it with fibrous inorganic fillers such as glass fiber, or granular inorganic fillers such as calcium carbonate and talc. However, blending fibrous or granular inorganic fillers significantly reduces low-temperature impact resistance, cold and heat resistance, and fluidity, and furthermore, there is the issue that the surface of molded products is corroded in certain strong acid environments, which has limited its use in some applications.

[0004] For example, as a method for improving heat and cold resistance and chemical resistance, a PPS resin composition obtained by blending a specific alumina and an ethylene copolymer with PPS (see, for example, Patent Document 1) has been proposed. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-131896 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the resin composition proposed in Patent Document 1 has problems with strength properties, and it is difficult to simultaneously obtain mechanical properties, chemical resistance, and heat and cold resistance.

[0007] Therefore, the present invention relates to a polyarylene sulfide composition that has excellent mechanical properties, acid resistance, and cold and heat resistance, and more specifically, to provide a polyarylene sulfide composition that has these excellent properties and is therefore particularly useful for electrical and electronic parts of automobiles. [Means for solving the problem]

[0008] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that a resin composition containing polyarylene sulfide, an ethylene-based copolymer, and a specific glass fiber in a specific blending ratio can become a polyarylene sulfide composition having excellent mechanical properties, acid resistance, and cold and heat resistance, and have thus completed the present invention.

[0009] That is, the present invention relates to a polyarylene sulfide composition comprising 30 to 70% by weight of polyarylene sulfide (A), 2 to 10% by weight of ethylene polymer (B), and 20 to 60% by weight of glass fiber (C), wherein the glass fiber (C) is a glass fiber having a boron oxide content of 1.5% by weight or less and a fluorine content of 0.1% by weight or less.

[0010] The present invention will be described in detail below.

[0011] The polyarylene sulfide composition of the present invention comprises 30 to 70% by weight of polyarylene sulfide (A), 2 to 10% by weight of ethylene polymer (B), and 20 to 60% by weight of glass fiber (C) having a boron oxide content of 1.5% by weight or less and a fluorine content of 0.1% by weight or less.

[0012] The polyarylene sulfide (A) constituting the polyarylene sulfide composition of the present invention may be any polyarylene sulfide that belongs to the category generally referred to as polyarylene sulfide. Examples of the polyarylene sulfide include homopolymers or copolymers composed of p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, and biphenylene sulfide units. Specific examples of the polyarylene sulfide include poly(p-phenylene sulfide), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, and polyphenylene sulfide ether. Among these, poly(p-phenylene sulfide) is preferred because it results in a polyarylene sulfide composition that is particularly excellent in heat resistance and strength properties.

[0013] The polyarylene sulfide (A) can be produced by a method known for producing polyarylene sulfides, for example, by polymerizing an alkali metal sulfide salt and a polyhaloaromatic compound in a polar solvent. Examples of the polar organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexylpyrrolidone, dimethylformamide, and dimethylacetamide. Examples of the alkali metal sulfide salt include anhydrous or hydrated sodium sulfide, rubidium sulfide, and lithium sulfide. Examples of the alkali metal sulfide salt include a reaction between an alkali metal hydrosulfide salt and an alkali metal hydroxide. Examples of polyhaloaromatic compounds include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, and 4,4'-dichlorodibiphenyl.

[0014] The polyarylene sulfide (A) may be linear, or may be polyarylene sulfide having a slight crosslinking or branching structure introduced by adding a small amount of a trihalogen or higher polyhalogen compound during polymerization, or polyarylene sulfide having a molecular chain and / or terminals modified with functional groups such as carboxyl groups, carboxy metal salts, alkyl groups, alkoxy groups, amino groups, or nitro groups, or may be polyarylene sulfide having been subjected to heat treatment in a non-oxidizing inert gas such as nitrogen, or may be a mixture of these structures. The polyarylene sulfide (A) may be deionized (such as by acid washing or hot water washing) or washed with an organic solvent such as acetone or methyl alcohol before or after heat curing to reduce impurities such as ions and oligomers. Furthermore, the polyarylene sulfide (A) may be cured by heat treatment in an inert gas or oxidizing gas after the polymerization reaction.

[0015] The blending amount of polyarylene sulfide (A) constituting the polyarylene sulfide composition of the present invention is 30 to 70% by weight, preferably 35 to 65% by weight. If the blending amount of polyarylene sulfide is less than 30% by weight, the resulting composition will have poor molding flowability. On the other hand, if it exceeds 70% by weight, the resulting composition will have poor mechanical properties.

[0016] The ethylene copolymer (B) constituting the polyarylene sulfide composition of the present invention may be any copolymer as long as it belongs to the category of ethylene copolymers, and among them, it is preferable that it is at least one modified ethylene copolymer selected from the group consisting of ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer, and maleic anhydride-grafted modified ethylene-α-olefin copolymer, since it is particularly effective in improving the cold and heat resistance of the polyarylene sulfide composition.

[0017] Any ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer may be used as long as it falls within this category, and in particular, since the resulting polyarylene sulfide composition has excellent bonding properties with metals, it is preferable that the weight ratio of ethylene residue units:α,β-unsaturated carboxylic acid alkyl ester residue units:maleic anhydride residue units is in the range of 50 to 98:40 to 1:10 to 1. Specific examples of the ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer include (trade name) Bondine LX4110 (manufactured by SK Global Chemical Co., Ltd.), (trade name) Bondine TX8030 (manufactured by SK Global Chemical Co., Ltd.), and (trade name) Bondine AX8390 (manufactured by SK Global Chemical Co., Ltd.).

[0018] Any ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer may be used as long as it falls within this category, and in particular, since the resulting polyarylene sulfide composition has excellent bonding properties with metals, it is preferable that the weight ratio of ethylene residue units:α,β-unsaturated carboxylic acid glycidyl ester residue units is in the range of 85 to 99:15 to 1. Specific examples of the ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer include (trade name) Bondine AX8840 (manufactured by SK Global Chemical Co., Ltd.) and (trade name) Bondfast E (manufactured by Sumitomo Chemical Co., Ltd.).

[0019] Any ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer may be used as long as it falls within this category, and in particular, since the resulting polyarylene sulfide composition has excellent bonding properties with metals, it is preferable that the weight ratio of ethylene residue units:α,β-unsaturated carboxylic acid glycidyl ester residue units:vinyl acetate residue units is in the range of 50 to 98:15 to 1:35 to 1. Specific examples of the ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer include (trade name) Bondfast 2B (manufactured by Sumitomo Chemical Co., Ltd.) and (trade name) Bondfast 7B (manufactured by Sumitomo Chemical Co., Ltd.).

[0020] The ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer may be any copolymer that falls within this category, and in particular, because the resulting polyarylene sulfide composition has excellent bonding properties with metals, it is preferable that the weight ratio of ethylene residue units:α,β-unsaturated carboxylic acid glycidyl ester residue units:α,β-unsaturated carboxylic acid alkyl ester residue units is in the range of 50 to 98:10 to 1:40 to 1. Specific examples of the ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer include (trade name) Bondfast 7L (manufactured by Sumitomo Chemical Co., Ltd.), (trade name) Bondfast 7M (manufactured by Sumitomo Chemical Co., Ltd.), (trade name) LOTADER AX8700 (manufactured by SK Global Chemical Co., Ltd.), and (trade name) LOTADER AX8750 (manufactured by SK Global Chemical Co., Ltd.).

[0021] The maleic anhydride-grafted ethylene-α-olefin copolymer may be any copolymer that falls within this category, and among these, those having a weight ratio of ethylene residue units:α-olefin residue units:maleic anhydride residue units of 50 to 98:45 to 1:5 to 1 are preferred because the resulting polyarylene sulfide composition has excellent bonding properties with metals, and specific examples include maleic anhydride-grafted linear low-density polyethylene, maleic anhydride-grafted ethylene-propylene rubber, etc. The maleic anhydride-grafted ethylene-α-olefin copolymer can be obtained, for example, by carrying out a grafting reaction in the coexistence of an ethylene-α-olefin copolymer, a peroxide, and maleic anhydride.

[0022] The α-olefin constituting the ethylene copolymer (B) refers to an α-olefin having 3 or more carbon atoms, such as propylene, butene-1, 4-methyl-pentene-1, hexene-1, and octene-1. Examples of the α,β-unsaturated carboxylic acid alkyl ester include alkyl esters of acrylic acid and methacrylic acid, specifically methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. Examples of the α,β-unsaturated carboxylic acid glycidyl ester include acrylic acid glycidyl ester and methacrylic acid glycidyl ester.

[0023] The blending amount of the ethylene copolymer (B) is 2 to 10% by weight, preferably 3 to 8% by weight, since this results in a polyarylene sulfide composition with particularly excellent heat and cold resistance and molding flowability. If the blending amount of the ethylene copolymer (B) is less than 2% by weight, the resulting resin composition will have poor heat and cold resistance. On the other hand, if the blending amount exceeds 10% by weight, the resulting resin composition will have poor mechanical properties, which is not preferred.

[0024] The glass fiber (C) constituting the polyarylene sulfide composition of the present invention is a glass fiber having a boron oxide content of 1.5% by weight or less and a fluorine content of 0.1% by weight or less. If the boron oxide content exceeds 1.5% by weight or the fluorine content exceeds 0.1% by weight, the resulting composition will have poor chemical resistance, which will likely limit its use as automotive parts and electrical and electronic equipment parts. Furthermore, in order to obtain a polyarylene sulfide composition with higher strength and excellent chemical resistance, glass fibers having a boron oxide content of 1% by weight or less are preferred, and glass fibers containing no boron oxide are particularly preferred. Furthermore, glass fibers having a fluorine content of 0.05% by weight or less are preferred, and glass fibers containing no fluorine are particularly preferred.

[0025] The glass fiber (C) is not particularly limited as long as it is a glass fiber that satisfies the requirements of a boron oxide content of 1.5% by weight or less and a fluorine content of 0.1% by weight or less, and examples thereof include aluminosilicate glass fibers (e.g., S-glass fibers), corrosion-resistant silicate glass fibers (e.g., ECR-glass fibers), and alkali-resistant glass fibers (e.g., AR-glass fibers).

[0026] The cross-sectional shape of the glass fiber (C) may be round or may be a (flat) glass fiber having a fiber cross-sectional aspect ratio of 2 to 8. Specific cross-sectional shapes are preferably oval, elliptical, semicircular, cocoon-shaped, rectangular, or shapes similar thereto. The fiber diameter of the glass fiber (C) is preferably 6 to 16 μm in order to provide a polyarylene sulfide composition having excellent mechanical strength and molding flowability.

[0027] The glass fibers (C) may be in the form of chopped strands, milled fibers, rovings, etc., and are preferably chopped strands because they are easier to handle when forming a polyarylene sulfide composition. If necessary, these glass fibers (C) may be surface-treated in advance with a functional compound or polymer such as an epoxy compound, an isocyanate compound, a silane compound, or a titanate compound.

[0028] The blending amount of the glass fiber (C) is 20 to 60% by weight. If it is less than 20% by weight, the resulting composition will be inferior in mechanical properties and heat and cold resistance. On the other hand, if it exceeds 60% by weight, the resulting composition will be inferior in molding flowability.

[0029] The polyarylene sulfide composition of the present invention preferably further contains a release agent (D) because it exhibits particularly excellent moldability. The release agent (D) is preferably one or more selected from, for example, polyethylene wax, polypropylene wax, fatty acid amide lubricants, and carnauba wax. Commercially available polyethylene wax, polypropylene wax, fatty acid amide lubricants, and carnauba wax can be used. Examples of the fatty acid amide lubricant include polycondensates of higher fatty acid amides, ethylene bisstearamide, higher fatty acids, and diamines. Any lubricant within this category can be used, such as Light Amide WH-255 (manufactured by Kyoeisha Chemical Co., Ltd.), a polycondensate of stearic acid, sebacic acid, and ethylenediamine. The carnauba wax can be any wax commonly known as carnauba wax, such as Refined Carnauba Powder No. 1 (manufactured by Nikko Rica Corporation). The amount of the release agent (D) to be added is preferably 0.1 to 3 parts by weight per 100 parts by weight of the total of the polyarylene sulfide (A), the ethylene polymer (B) and the glass fiber (C).

[0030] The polyarylene sulfide composition of the present invention may be added with whiskers such as carbon fibers, silicon nitride whiskers, basic magnesium sulfate whiskers, barium titanate whiskers, potassium titanate whiskers, silicon carbide whiskers, boron whiskers, and zinc oxide whiskers; inorganic fibers such as rock wool, zirconia, barium titanate, silicon carbide, silica, and blast furnace slag; organic fibers such as wholly aromatic polyamide fibers, phenolic resin fibers, and wholly aromatic polyester fibers; or mineral fibers such as wollastonite and magnesium oxysulfate, within the range not impairing the effects of the present invention. Alternatively, the polyarylene sulfide composition of the present invention may be added with calcium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, mica, silica, talc, clay, calcium sulfate, kaolin, wollastonite, zeolite, silicon oxide, magnesium oxide, zirconium oxide, tin oxide, magnesium silicate, calcium silicate, calcium phosphate, magnesium phosphate, carbon black, hydrotalcite, glass powder, glass balloons, and glass flakes within the range not impairing the effects of the present invention.

[0031] Furthermore, the polyarylene sulfide composition of the present invention may contain one or more conventional additives, such as a conventionally known crystal nucleating agent such as talc, kaolin, or silica; a plasticizer such as a polyalkylene oxide oligomer compound, a thioether compound, an ester compound, or an organic phosphorus compound; an antioxidant; a heat stabilizer; a lubricant; a foaming agent; or a silane coupling agent, within the range that does not impair the effects of the present invention.

[0032] Furthermore, the polyarylene sulfide composition of the present invention may be a mixture of one or more of various thermosetting resins and thermoplastic resins, such as epoxy resins, cyanate ester resins, phenolic resins, polyimides, silicone resins, polyesters, polyamides, polyphenylene oxides, polycarbonates, polysulfones, polyetherimides, polyethersulfones, polyetherketones, polyetheretherketones, polyamideimides, polyamide-based elastomers, polyester-based elastomers, and polyalkylene oxides, within the scope of the object of the present invention.

[0033] The method for producing the polyarylene sulfide composition of the present invention is not particularly limited, and any method known as a general mixing and kneading method can be used. For example, any method may be used, such as blending all raw materials and melt-kneading them; blending some of the raw materials and then melt-kneading them, and then blending and melt-kneading the remaining raw materials; or blending some of the raw materials and then melt-kneading them using a single-screw or twin-screw extruder, while mixing the remaining raw materials using a side feeder. Small amounts of additional components may be added by blending other components using the above-mentioned methods, pelletizing them, and then adding them before molding. The melt-kneading method may be a conventionally used heat-melt-kneading method, such as a heat-melt-kneading method using a single-screw or twin-screw extruder, kneader, mill, or Brabender. Melt-kneading using a twin-screw extruder, which has excellent kneading capabilities, is particularly preferred. The kneading temperature is not particularly limited, and can usually be selected from the range of 260 to 350°C.

[0034] The polyarylene sulfide composition of the present invention is particularly excellent in acid resistance, and also has excellent properties such as resistance to cold and heat and mechanical strength, and is therefore suitable for use in automobile parts or electric / electronic parts. [Effects of the Invention]

[0035] The present invention provides a polyarylene sulfide composition that has been endowed with acid resistance, heat and cold resistance, and fluidity without impairing the inherent heat resistance, mechanical strength, electrical insulation, etc. of polyarylene sulfide, and is useful for use in automobile parts or electrical / electronic parts. [Example]

[0036] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0037] The polyarylene sulfide (A), ethylene copolymer (B), glass fiber (C), and release agent (D) used in the examples and comparative examples are shown below.

[0038] <Polyarylene sulfide (A)> Poly(p-phenylene sulfide) (A) (hereinafter referred to as PPS (A-1)): melt viscosity 200 poise.

[0039] <Ethylene-based copolymer (B)> Ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B-1) (hereinafter referred to as ethylene copolymer (B-1)): SK Global Chemical Co., Ltd., (trade name) Bondine AX8390. Ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer (B-2) (hereinafter referred to as ethylene copolymer (B-2)): manufactured by SK Global Chemical Co., Ltd., (trade name) Rotader AX8700.

[0040] <Glass fiber (C)> Glass fiber (C-1); corrosion-resistant silicate glass fiber (ECR glass fiber), Taishan chopped strand, (trade name) ECS319C-3; Glass fiber (C-2); Aluminosilicate glass fiber (S-glass fiber), Taishan chopped strand, (trade name) ECS329A-3, Aluminosilicate glass fiber Glass fiber (C-3); alumina borosilicate glass fiber (E glass fiber), Taishan chopped strand, (trade name) ECS309A-3-H.

[0041] <Release agent (D)> Fatty acid amide lubricant (D-1) (hereinafter referred to as mold release agent (D-1)): manufactured by Kyoeisha Chemical Co., Ltd., (trade name) Lightamide WH-255.

[0042] <Synthesis Example 1 (Synthesis of PPS (A-1))> A 15-liter autoclave equipped with a stirrer was charged with 1814 g of flake sodium sulfide (NaS·2.9H2O), 48 g of 30% caustic soda solution (30% NaOH aq), and 3679 g of N-methyl-2-pyrrolidone. The mixture was gradually heated to 200°C with stirring under a nitrogen stream, and 380 g of water was distilled off. After cooling to 190°C, 2107 g of p-dichlorobenzene and 985 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225°C over 2 hours and polymerized at 225°C for 1 hour. The temperature was then raised to 250°C over 25 minutes, and polymerization continued at 250°C for another 3 hours. After polymerization, N-methyl-2-pyrrolidone was recovered from the polymerization slurry by distillation under reduced pressure. The final temperature reached 170°C and the pressure was 4.7 kPa. The resulting cake was washed with 80°C hot water to a slurry concentration of 20%, and hot water was added again in the same manner, raising the temperature to 175°C, and the poly(p-phenylene sulfide) was washed twice in total. The resulting polyphenylene sulfide was dried overnight at 105°C. The dried polyphenylene sulfide was then loaded into a batch-type rotary kiln-type calciner, heated to 235°C in a nitrogen atmosphere, and held there for 1 hour for curing, yielding PPS (A-1) with a melt viscosity of 200 poise.

[0043] ~Melt viscosity measurement of polyarylene sulfide~ The melt viscosity was measured using a high-performance flow tester (Shimadzu Corporation, product name CFT-500) equipped with a die having a diameter of 1 mm and a length of 2 mm, under the conditions of a measurement temperature of 315°C and a load of 10 kg.

[0044] ~Measurement of tensile strength~ The polyarylene sulfide composition was used to prepare test pieces for measuring tensile strength using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name SE-75S) with a cylinder temperature of 310°C and a mold temperature of 135°C, and the tensile strength was measured using a tensile testing machine (manufactured by Shimadzu Corporation, product name Autograph AG-5000B) in accordance with ISO527.

[0045] ~Acid resistance measurement~ Test pieces for tensile strength measurement were prepared from the polyarylene sulfide composition using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name SE-75S) with a cylinder temperature of 310°C and a mold temperature of 135°C. The test pieces were then impregnated in a hydrofluoric acid aqueous solution adjusted to a concentration of 5% by weight at 60°C, and the strength was measured using a tensile tester (manufactured by Shimadzu Corporation, product name Autograph AG-5000B) in accordance with ISO 527. The strength retention was calculated by dividing the measured value after impregnation by the initial value and multiplying the result by 100. Test pieces with a strength retention of more than 90% after 100 hours of impregnation and more than 70% after 250 days of impregnation were judged to have good acid resistance.

[0046] ~Measurement of molding flowability~ A mold with a spiral groove 1 mm deep and 10 mm wide was attached to an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name SE75S), and the PPS composition was then loaded into the hopper of the injection molding machine, with the cylinder temperature set to 310°C, the injection pressure to 190 MPa, the injection speed set to the maximum, the injection time to 1.5 seconds, and the mold temperature set to 135°C, and injected. The length of the melt flowing through the spiral groove in the mold was measured as molding fluidity. A molding fluidity of more than 180 mm was deemed to exhibit sufficient fluidity for practical use.

[0047] ~Cold and heat resistance~ Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name SE-75S), insert molding was performed by inserting a rectangular parallelepiped steel material (carbon steel) measuring 30 mm × 20 mm × 10 mm, and a test piece for cold and heat resistance was produced by covering it with a polyarylene sulfide composition having a wall thickness of 1 mm. The obtained test piece was subjected to a cold and heat cycle, with one cycle consisting of holding at 150 ° C for 30 minutes and then holding at -40 ° C for 30 minutes. This cycle was continued until cracks were visually observed, and the number of cold and heat cycles at which cracks were observed was evaluated as cold and heat resistance. Test pieces that had been subjected to the cold and heat cycle treatment 100 times or more were judged to have excellent cold and heat resistance.

[0048] ~Method for measuring element content in glass fiber~ After applying an osmium coating to the glass fiber as a conductive treatment, each element was quantified using energy dispersive X-ray spectroscopy (JEOL Ltd. FE-SEM JSM-7100F / EDS JED-2300) at an accelerating voltage of 15 kV, and the content in the glass fiber was expressed as % by weight. When the element content was below the detection limit, the content was expressed as 0% by weight. The evaluation results are shown in Table 1.

[0049] [Table 1]

[0050] Example 1 85.2 wt% of the PPS (A-1) obtained in Synthesis Example 1, 14 wt% of the ethylene copolymer (B-1), and 0.8 wt% of the release agent (D-1) were homogeneously mixed in advance and charged into the hopper of a twin-screw extruder (Toshiba Machine, product name: TEM-35-102B) heated to a cylinder temperature of 300°C. Meanwhile, glass fiber (C-1) was charged into the hopper of the side feeder of the twin-screw extruder, melt-kneaded, and pelletized to obtain a polyarylene sulfide composition. The polyarylene sulfide composition consisted of 42.6 wt% of PPS (A-1), 7 wt% of the ethylene copolymer (B-1), 50 wt% of the glass fiber (C-1), and 0.4 wt% of the release agent (D-1). The resulting PPS composition was evaluated for cold and heat resistance, fluidity, and acid resistance. The evaluation results are shown in Table 2.

[0051] Examples 2 to 4 PPS compositions were prepared in the same manner as in Example 1, except that the polyarylene sulfide (A), ethylene copolymer (B), glass fiber (C), and release agent (D) were blended in the proportions shown in Table 2, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0052] Comparative Example 1 Compositions were prepared in the same manner as in Example 1, except that the polyarylene sulfide (A), ethylene copolymer (B), glass fiber (C-3), and release agent (D) were blended in the proportions shown in Table 2, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0053] The resulting composition had low acid resistance and poor retention.

[0054] Comparative Example 2 PPS compositions were prepared in the same manner as in Example 1, except that the polyarylene sulfide (A), ethylene copolymer (B), glass fiber (C), and release agent (D) were blended in the proportions shown in Table 2, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0055] The resulting composition was poor in cold and heat resistance.

[0056] [Table 2] [Industrial Applicability]

[0057] The polyarylene sulfide composition of the present invention has excellent acid resistance, chemical resistance, cold and heat resistance, and fluidity without impairing the inherent heat resistance, mechanical strength, electrical insulation properties, etc. of polyarylene sulfide, and is therefore expected to be a resin composition used in applications such as automobile parts or electrical and electronic parts.

Claims

1. A polyarylene sulfide composition comprising 30 to 70% by weight of a polyarylene sulfide (A), 2 to 10% by weight of an ethylene-based polymer (B), and 20 to 60% by weight of glass fibers (C), wherein the ethylene-based polymer (B) is an ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, and the glass fibers (C) are glass fibers having a boron oxide content of 1.5% by weight or less and a fluorine content of 0.1% by weight or less, and are aluminosilicate glass fibers and / or corrosion-resistant silicate glass fibers.

2. The polyarylene sulfide composition according to claim 1, further comprising at least one release agent (D) selected from the group consisting of polyethylene wax, polypropylene wax, carnauba wax, and fatty acid amide wax.

3. 3. The polyarylene sulfide composition according to claim 1, which is a hydrofluoric acid-resistant polyarylene sulfide composition.

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