Polyarylene sulfide composition

Abstract

To provide a polyarylene sulfide composition which is excellent in: mechanical property, heat resistance, and moldability; adhesion and bondability to a metal and a thermosetting resin; and at the same time chemical resistance and acid resistance.SOLUTION: A polyarylene sulfide composition comprises: 30-80 wt.% of a polyarylene sulfide (A) with melt viscosity of 50-2,000 poise; 0.5-10 wt.% of an epoxy resin (B) with an epoxy equivalent of 450-2,300 and a melting point of 50-135°C; and 10-60 wt.% of glass fiber (C) having boron oxide with a content of 1.5 wt.% or less, zirconium oxide with a content of 1.0 wt.% or less, and fluorine with a content of 0.1 wt.% or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyarylene sulfide composition that has improved adhesiveness and bonding properties to metals and thermosetting resins, and also has excellent chemical resistance and acid resistance, without impairing the heat resistance, mechanical strength, moldability, etc. that are inherent to polyarylene sulfide. [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 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] As a method for improving the rigidity, toughness, and hydrochloric acid resistance of PAS, for example, a PPS resin composition obtained by blending PPS, glass fiber containing 16% by mass or more of zirconium oxide, 5 to 10% by mass or less of titanium oxide, and 0.1 to 5% by mass of calcium oxide, and a silane coupling agent (see, for example, Patent Document 1) has been proposed. Also, as a method for improving heat and cold resistance and chemical resistance, a PPS resin composition obtained by blending PPS with a specific alumina and an ethylene copolymer (see, for example, Patent Document 2) has been proposed.

[0005] Furthermore, several studies have been conducted on PAS resin compositions that have good bonding properties with metals, and proposals have included, for example, a resin composition that combines (a) PAS, (b) a polar group-containing polyethylene copolymer, and (c) a triazine thiol (see, for example, Patent Document 3), and a resin composition that combines (a) PPS, (b) a polar group-containing polyolefin, and (c) a compatibilizer (see, for example, Patent Document 4).

[0006] Furthermore, as a PAS composition having excellent acid resistance, a PAS composition containing 30 to 70 wt % of PAS (A), 2 to 10 wt % of an ethylene polymer (B), and 20 to 60 wt % of glass fiber (C) having a boron oxide content of 1.5 wt % or less and a fluorine content of 0.1 wt % or less (see, for example, Patent Document 5) has been proposed. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 7024932 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-131896 [Patent Document 3] Patent No. 5003640 [Patent Document 4] Patent No. 5740805 [Patent Document 5] Japanese Patent Publication No. 2023-19030 Summary of the Invention [Problem to be solved by the invention]

[0008] However, the resin compositions proposed in Patent Documents 1 and 2 have problems with strength characteristics, making it difficult to simultaneously achieve mechanical properties, chemical resistance, and heat and cold resistance, and no consideration has been given to their bondability to metals. Furthermore, the resin compositions proposed in Patent Documents 3 and 4 have good bondability to metals, but no consideration has been given to their chemical resistance or acid resistance. Furthermore, the PAS composition proposed in Patent Document 5 shows improved acid resistance, but there is still room for improvement in its adhesion to metals, thermosetting resins, etc., and its mechanical properties. The emergence of a material that simultaneously satisfies mechanical properties, chemical resistance, heat and cold resistance, and adhesive / bonding properties is anticipated.

[0009] Therefore, the present invention provides a PAS composition that has excellent adhesive and bonding properties to metals and thermosetting resins, while also having excellent chemical and acid resistance, without compromising the mechanical properties, heat resistance, and moldability of PAS. [Means for solving the problem]

[0010] As a result of extensive research into the above-mentioned problems, the inventors of the present invention have discovered that a PAS composition containing PAS, a specific epoxy resin, and specific glass fibers exhibits excellent mechanical properties, heat resistance, moldability, and adhesive / bonding properties to metals and thermosetting resins, as well as excellent chemical resistance and acid resistance, and have thus completed the present invention.

[0011] Specifically, the present invention relates to a PAS composition comprising 30 to 80% by weight of a PAS (A) having a melt viscosity of 50 to 2000 poise under conditions of a measurement temperature of 315°C and a load of 10 kg, 0.5 to 10% by weight of an epoxy resin (B) having an epoxy equivalent of 450 to 2300 and a melting point of 50 to 135°C, and 10 to 60% by weight of glass fiber (C) having a boron oxide content of 1.5% by weight or less, a zirconium oxide content of 1.0% by weight or less, and a fluorine content of 0.1% by weight or less.

[0012] The present invention will be described in detail below.

[0013] The PAS composition of the present invention comprises 30 to 80% by weight of PAS (A), 0.5 to 10% by weight of epoxy resin (B), and 15 to 60% by weight of glass fiber (C).

[0014] The PAS (A) constituting the PAS composition of the present invention is a PAS having a melt viscosity of 50 to 2000 poise under conditions of a measurement temperature of 315°C and a load of 10 kg, and may be any PAS that falls into the category generally referred to as PAS. For example, homopolymers or copolymers comprising 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 can be mentioned. Specific examples include PPS, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, and polyphenylene sulfide ether. Of these, PPS is preferred because of its excellent heat resistance and strength properties.

[0015] The PAS (A) has a melt viscosity of 50 to 2000 poise measured at a measurement temperature of 315°C under a load of 10 kg, and preferably a PAS of 100 to 800 poise, since this results in a PAS composition with particularly excellent mechanical strength and thin-wall flowability. If the PAS has a melt viscosity of less than 50 poise, the resulting composition will have poor mechanical strength. On the other hand, if the melt viscosity exceeds 2000 poise, the resulting composition will have poor molding flowability. The melt viscosity can be measured using, for example, a high-speed flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm.

[0016] The PAS (A) can be produced by a method known for producing PAS, for example, by polymerizing an alkali metal sulfide salt and a polyhaloaromatic compound in a polar solvent. Examples of polar organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexylpyrrolidone, dimethylformamide, and dimethylacetamide. Examples of alkali metal sulfide salts include anhydrous or hydrated sodium sulfide, rubidium sulfide, and lithium sulfide. Furthermore, the alkali metal sulfide salt may be a product of reacting an alkali metal hydrosulfide salt with 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'-dichlorodiphenyl.

[0017] PAS (A) may be linear, or may be a PAS obtained by adding a small amount of a trihalogen or higher polyhalogen compound during polymerization to introduce a slight crosslinking or branching structure, or may be a PAS obtained by modifying a portion and / or terminals of the molecular chain with functional groups such as carboxyl groups, carboxy metal salts, alkyl groups, alkoxy groups, amino groups, or nitro groups, or by heat treatment in a non-oxidizing inert gas such as nitrogen, or may be a mixture of these structures. Furthermore, the PAS (A) may be one in which impurities such as ions and oligomers have been reduced by deionization (such as acid washing or hot water washing) or washing with an organic solvent such as acetone or methyl alcohol before or after heat curing. Furthermore, the PAS (A) may be one that has been heat-treated in an inert or oxidizing gas after the polymerization reaction to cure.

[0018] The amount of PAS (A) contained in the PAS composition of the present invention is 30 to 80% by weight, preferably 40 to 70% by weight. If the amount of PAS is less than 30% by weight, the resulting composition will have poor fluidity. If the amount of PAS is more than 80% by weight, the resulting composition will have poor mechanical properties.

[0019] The epoxy resin (B) constituting the PAS composition of the present invention is an epoxy resin with an epoxy equivalent of 450 to 2300 and a melting point of 50 to 135°C, with an epoxy resin with an epoxy equivalent of 700 to 2100 and a melting point of 80 to 131°C being preferred. Furthermore, a solid bisphenol A-type epoxy resin containing two or more epoxy groups is preferred, as this results in a PAS composition with excellent adhesion and bonding properties, particularly with metals and thermosetting resins. If the epoxy resin has an epoxy equivalent of less than 450, the resulting composition will be subject to significant mold contamination when molded, and the molded article will have poor appearance. On the other hand, if the epoxy equivalent exceeds 2300, the resulting composition will have inconsistent adhesive strength improvement effects, making it difficult to handle. Furthermore, if the epoxy resin has a melting point of less than 50°C, the resulting composition will be subject to significant mold contamination when molded, and the molded article will have poor appearance. On the other hand, if the melting point of the epoxy resin exceeds 135°C, the adhesive strength of the resulting composition will vary, making it difficult to handle.

[0020] The amount of the epoxy resin (B) is 0.5 to 10% by weight, preferably 1.0 to 9% by weight, since this results in a PAS composition with excellent mechanical properties, heat resistance, and adhesiveness. If the amount of epoxy resin (B) is less than 0.5% by weight, the adhesiveness-improving effect of the resulting composition will not be achieved. On the other hand, if the amount of epoxy resin (B) is more than 10% by weight, the resulting composition will be prone to mold contamination.

[0021] The glass fiber (C) constituting the PAS composition of the present invention is glass fiber having a boron oxide content of 1.0% by weight or less, a zirconium oxide content of 5.0% by weight or less, and a fluorine content of 0.1% by weight or less. Since this results in a PAS composition with higher mechanical strength and particularly excellent chemical resistance, glass fiber having a boron oxide content of 0.5% by weight or less and glass fiber having a fluorine content of 0.05% by weight or less is preferred, and glass fiber containing no boron oxide or no fluorine is particularly preferred, with glass fiber containing no boron oxide, zirconium oxide, or fluorine being even more preferred. Such glass fibers are not particularly limited as long as they satisfy the following requirements: a boron oxide content of 1.0 wt% or less, a zirconium oxide content of 5.0 wt% or less, and a fluorine content of 0.1 wt% or less. Examples include aluminosilicate glass fibers (e.g., S-glass fibers) and corrosion-resistant silicate glass fibers (e.g., ECR-glass fibers). Commercially available products include (trade name) ECS309C-3 (manufactured by Polycomp International Corp.) and (trade name) ECS10-03-584YF (manufactured by Jushi Group Co., Ltd.). Glass fibers with a boron oxide content exceeding 1.0 wt% or a fluorine content exceeding 0.1 wt% may result in poor chemical resistance in the resulting composition, which may be restricted for use as automotive parts or electrical and electronic equipment parts. Glass fibers with a zirconium oxide content exceeding 5.0 wt% may result in poor mechanical properties in the resulting composition, which may be restricted for use as automotive parts or electrical and electronic equipment parts.

[0022] 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, since this results in a PAS composition having particularly excellent mechanical strength and molding flowability.

[0023] The glass fiber (C) may be in the form of chopped strand, milled fiber, roving, etc., with chopped strand being preferred because it is particularly easy to handle when forming a PAS 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.

[0024] The blending amount of the glass fiber (C) is 10 to 65% by weight. If it is less than 10% by weight, the resulting composition will be inferior in mechanical properties and heat and cold resistance. On the other hand, if it exceeds 65% by weight, the resulting composition will be inferior in molding flowability.

[0025] The PAS composition of the present invention preferably contains an ethylene polymer or a thermoplastic elastomer, since it is a PAS resin composition that has excellent adhesion and bonding properties, particularly with metals and thermosetting resins, as well as excellent cold and heat resistance. In particular, it is preferred that the PAS composition contain an ethylene copolymer (D), which 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 ethylene-α-olefin copolymer.

[0026] 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, because the resulting PAS composition has excellent bonding properties to 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), (trade name) Bondine TX8030 (manufactured by SK Global Chemical), and (trade name) Bondine AX8390 (manufactured by SK Global Chemical).

[0027] 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 PAS composition has excellent bonding properties to metals, it is preferable that the weight ratio of ethylene residue units to 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.).

[0028] The ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer may be any copolymer that falls within this category, and in particular, because the resulting PAS composition has excellent bonding properties to 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.).

[0029] 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 PAS composition has excellent bonding properties to 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 be 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.).

[0030] 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 50-98:45-1:5-1 are preferred because the resulting PAS composition has excellent bonding properties to 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 presence of an ethylene-α-olefin copolymer, a peroxide, and maleic anhydride.

[0031] The α-olefin constituting the ethylene copolymer (D) 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.

[0032] The blending amount of the ethylene copolymer (D) is preferably 1 to 20% by weight, particularly 3 to 12% by weight, since it provides a PAS composition that is particularly excellent in heat and cold resistance and molding flowability.

[0033] The PAS composition of the present invention exhibits particularly excellent moldability, and therefore may further contain a release agent. The release agent is preferably one or more selected from 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 to be added is preferably 0.1 to 3 parts by weight per 100 parts by weight of the total of the PAS (A), the epoxy resin (B) and the glass fiber (C).

[0034] The PAS 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.The PAS composition of the present invention may also 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.

[0035] Furthermore, the PAS composition of the present invention may contain one or more conventional additives, such as conventionally known crystal nucleating agents such as talc, kaolin, and silica; plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds; antioxidants; heat stabilizers; lubricants; foaming agents; and silane coupling agents, within the scope of the present invention.

[0036] Furthermore, the PAS composition of the present invention may be a mixture of one or more of various thermosetting resins and thermoplastic resins, such as 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.

[0037] The manufacturing method for producing the PAS composition of the present invention is not particularly limited, and any commonly known mixing and kneading method can be used. For example, any method may be used, such as blending all raw materials and melt-kneading them together; blending some of the raw materials and then melt-kneading them, followed by 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 blending 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. Conventional heat-melt-kneading methods can be used for melt-kneading, such as those using a single-screw or twin-screw extruder, kneader, mill, or Brabender. Melt-kneading using a twin-screw extruder is particularly preferred, due to its excellent kneading capabilities. The kneading temperature is not particularly limited, and can generally be selected from the range of 260 to 350°C.

[0038] The PAS resin composition of the present invention has excellent adhesiveness and bonding properties, particularly with respect to metals, and is therefore preferably used as a composite bonded to a metal. The metal used in this case may be any metal within the scope of the metal category. Among these, aluminum, magnesium, stainless steel, copper, titanium, and iron are preferred because they are particularly adaptable to a variety of applications, with aluminum, magnesium, stainless steel, and copper being particularly preferred, and aluminum or copper being even more preferred. The metal may be a simple metal or an alloy in which one or more metals or nonmetals are added to the simple metal. The metal may also be a wrought or cast material.

[0039] Furthermore, in order to improve adhesion to resins, it is preferable that the metal surface has a large surface area, and specifically, that the surface is roughened. Examples of roughening treatments for metal surfaces include chemical treatments using chemicals or physical treatments using laser devices.

[0040] The PAS composition of the present invention is suitable for use in automobile parts or electric / electronic parts because it has excellent acid resistance, heat and cold resistance, and mechanical strength, as well as excellent metal bonding properties. [Effects of the Invention]

[0041] The present invention relates to a PAS composition that has improved bonding and adhesion properties to metals and thermosetting resins, while also exhibiting excellent chemical and acid resistance, without impairing the mechanical properties, heat resistance, and moldability of PAS. [Example]

[0042] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples in any way.

[0043] The PAS (A), epoxy resin (B), glass fiber (C), and ethylene copolymer (D) used in the examples and comparative examples are shown below.

[0044] <PAS(A)> PPS (A-1); melt viscosity 200 poise. PPS (A-2); melt viscosity 600 poise. PPS (A'-3); melt viscosity 2400 poise.

[0045] <Epoxy resin (B)> Epoxy resin (B-1): bisphenol A type epoxy resin, manufactured by DIC Corporation, (trade name) Epiclon 3050; epoxy equivalent 780, melting point 95°C. Epoxy resin (B-2): cresol novolac epoxy resin, manufactured by DIC Corporation, trade name Epiclon 7050; epoxy equivalent: 2000, melting point: 125°C. Epoxy resin (B'-3): bisphenol A type epoxy resin, manufactured by DIC Corporation, trade name Epiclon 855; epoxy equivalent 185, liquid at room temperature (25°C).

[0046] <Glass fiber (C)> Glass fiber (C-1): chopped strand manufactured by Chongqing Polycomp International Corp., trade name ECS309C-3 (0% by weight boric acid, 0% by weight zirconium oxide, 0% by weight fluorine). Glass fiber (C-2): Chopped strand manufactured by Jushi Group Co., Ltd., (product name) ECS10-03-584YF (0% by weight boric acid, 0% by weight zirconium oxide, 0% by weight fluorine). Glass fiber (C'-3): chopped strand manufactured by Nippon Electric Glass Co., Ltd., (trade name) ACS6H-103 (0% by weight of boric acid oxide, 15 to 20% by weight of zirconium oxide, 0% by weight of fluorine). Glass fiber (C'-4): Chopped strand manufactured by Nitto Boseki Co., Ltd., (trade name) CS3J-962 (boric acid oxide 5 to 10% by weight, zirconium oxide 0% by weight, fluorine content 0.2 to 1.0% by weight).

[0047] <Ethylene-based copolymer (D)> Ethylene copolymer (D-1): ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, manufactured by SK Global Chemical Co., Ltd., (trade name) Bondine AX8390. Ethylene copolymer (D-2): ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer, manufactured by SK Global Chemical Co., Ltd., trade name: Rotader AX8700.

[0048] <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 while 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 resulting cake was washed with 80°C hot water to a slurry concentration of 20%, and then hot water was added again in the same manner, and the temperature was raised to 175°C, washing the PPS twice in total. The resulting PPS (a) was dried overnight at 105°C. The dried PPS (a) was then loaded into a batch-type rotary kiln-type calciner, heated to 235°C in a nitrogen atmosphere, and held for 1 hour for curing, yielding PPS (A-1) with a melt viscosity of 600 poise.

[0049] <Synthesis Example 2 (Synthesis of PPS (A-2))> The PPS (a) obtained in Synthesis Example 1 was loaded into a batch rotary kiln-type calciner, heated to 250°C in a nitrogen atmosphere, and held for 4 hours for curing treatment to obtain PPS (A-2) with a melt viscosity of 850 poise.

[0050] <Synthesis Example 3 (Synthesis of PPS (A-3))> A 50-liter autoclave equipped with a stirrer was charged with 6214 g of sodium sulfide 2.9 hydrate and 17,000 g of N-methyl-2-pyrrolidone. The mixture was gradually heated to 205°C while stirring under a nitrogen stream, and 1,355 g of water was distilled off. After cooling the system to 140°C, 7,115 g of p-dichlorobenzene and 5,000 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 2 hours, then heated to 250°C over 30 minutes and polymerized at 250°C for another 3 hours. After polymerization, the mixture was cooled to room temperature and the solids were isolated using a centrifuge. The solids were repeatedly washed with warm water and dried overnight at 100°C to obtain PPS with a melt viscosity of 400 poise. The dried PPS was then loaded into a batch rotary kiln-type calciner and cured in an air atmosphere at 250°C for 5 hours to obtain PPS (A-3) with a melt viscosity of 3,000 poise.

[0051] The measurement and evaluation methods for PAS and PAS compositions in the examples and comparative examples are shown below.

[0052] ~Melt viscosity measurement of PAS~ The melt viscosity was measured using a high-temperature 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.

[0053] ~Measurement of tensile strength~ Test pieces for measuring tensile strength were prepared from the PAS composition using an injection molding machine (SE-75S, manufactured by Sumitomo Heavy Industries, Ltd.) 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 (AG-5000B, manufactured by Shimadzu Corporation) in accordance with ISO 527. Tensile strengths exceeding 150 MPa were considered to be sufficient for practical use.

[0054] ~Acid resistance measurement~ A test piece for measuring tensile strength was impregnated in an aqueous solution of hydrofluoric acid adjusted to a concentration of 1% by weight in an environment of 60°C, and then measured using a tensile tester (Shimadzu Corporation, product name Autograph AG-5000B) in accordance with ISO 527. The measured value after impregnation was divided by the initial value and multiplied by 100 to obtain the strength retention rate, and a strength retention rate of more than 80% after 300 hours of impregnation was determined to have good acid resistance.

[0055] ~Measuring the bond strength with metal~ A rectangular aluminum (A5052) plate measuring 50 mm long, 12 mm wide, and 1.5 mm thick was degreased with acetone, then immersed in a 1% sodium hydroxide solution, then in a 10% sulfuric acid solution, and then in a 15% sulfuric acid solution at a current density of 0.5 A / cm. 3 The aluminum plate was anodized with 0.5% NaOH to obtain a chemically treated aluminum plate.

[0056] The resulting aluminum plate was placed in a mold, and the PAS composition was molded into a plate using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name SE75S) set at a cylinder temperature of 310°C and a mold temperature of 150°C to prepare a bond strength test piece with a bond area of ​​60 mm. A tensile test was performed on the bond strength test piece using a measuring device (manufactured by Shimadzu Corporation, product name Autograph AG-5000B) at a tension speed of 10 mm / min. A bond strength of more than 30 MPa was determined to be sufficient for practical use.

[0057] ~Measuring adhesive strength to metal after heat cycle testing~ The bond strength test pieces were subjected to a thermal cycle consisting of 30 minutes at 150°C followed by 30 minutes at -40°C. The cycle was continued until cracks were visually observed, and the number of thermal cycles at which cracks were observed was evaluated as thermal resistance. Test pieces with 100 or more thermal cycles were judged to have excellent thermal resistance. The bond strength test pieces were subjected to a tensile test at a tensile speed of 10 mm / min using a measuring device (Shimadzu Corporation, product name Autograph AG-5000B). Test pieces with a bond strength retention rate of over 90% after the heat cycle were judged to be good.

[0058] ~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 maximum, the injection time to 1.5 seconds, and the mold temperature set to 135°C, and injected. The length of the molten material flowing through the spiral groove in the mold was measured as molding fluidity. A molding fluidity of more than 150 mm was deemed to exhibit sufficient fluidity for practical use.

[0059] ~Evaluation of mold contamination~ The PAS compositions obtained in the examples were molded into ASTM No. 1 tensile test pieces, and the tensile test pieces were molded 100 times, after which the mold was visually inspected for contamination.

[0060] The evaluation criteria are as follows: ○: No adhesion to the mold surface. ×: Brown deposits found on the mold surface.

[0061] Example 1 PPS (A-1), epoxy resin (B-1), and ethylene copolymer (D-1) were charged into the hopper of a twin-screw extruder with a screw diameter of 25 mm (trade name: TEX-25αIII, manufactured by The Japan Steel Works, Ltd.). Meanwhile, glass fiber (C-1) was charged into the hopper of the side feeder of the twin-screw extruder and melt-kneaded at a cylinder temperature of 300°C to obtain a pelletized PPS composition (43 wt% PPS (A-1), 2 wt% epoxy resin (B-1), 50 wt% glass fiber (C-1), and 5 wt% ethylene copolymer (D-1)).

[0062] The resulting PPS composition was dried at 150°C for 5 hours and then molded into test specimens using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name SE75S) set at a cylinder temperature of 310°C and a mold temperature of 140°C. Test specimens were then evaluated for tensile strength, metal bond strength, mold contamination, etc. The results are shown in Table 1.

[0063] Examples 2 to 8 PPS compositions were obtained and evaluated in the same manner as in Example 1, except that the blending amounts of PPS (A-1, 2), epoxy resin (B-1, 2), glass fiber (C-1, 2), and ethylene copolymer (D-1, 2) were changed to those shown in Table 1. The results are shown in Table 1.

[0064] [Table 1]

[0065] Comparative Examples 1 to 8 Compositions were obtained and evaluated in the same manner as in Example 1, except that the amounts of PPS (A-1, 2, A'-3), epoxy resin (B-1, 2, B'-3), glass fiber (C-1, 2, C'-3, 4), and ethylene copolymer (D-1) were changed as shown in Table 2. The results are shown in Table 2.

[0066] The resin composition obtained in Comparative Example 1 was poor in bonding strength. The resin composition obtained in Comparative Example 2 was poor in bonding strength, bonding strength after heat cycles, and mold contamination resistance. The resin composition obtained in Comparative Example 3 was poor in tensile strength and bonding strength. The resin composition obtained in Comparative Example 4 was poor in acid resistance. The resin composition obtained in Comparative Example 5 was poor in tensile strength, bonding strength, and bonding strength after heat cycles. The resin composition obtained in Comparative Example 6 was poor in tensile strength and bonding strength. The resin composition obtained in Comparative Example 7 was poor in mold contamination resistance. The resin composition obtained in Comparative Example 8 was poor in bonding strength and bonding strength after heat cycles.

[0067] [Table 2] [Industrial Applicability]

[0068] The PAS composition of the present invention has improved bonding and adhesion to metals and thermosetting resins without impairing the mechanical properties, heat resistance, and moldability of PAS, and at the same time has excellent chemical resistance and acid resistance, making it suitable for use in various parts, particularly automotive parts or electrical and electronic parts.

Claims

1. A polyarylene sulfide composition comprising: 30 to 80% by weight of a polyarylene sulfide (A) having a melt viscosity of 50 to 2,000 poise under conditions of a measurement temperature of 315°C and a load of 10 kg; 0.5 to 10% by weight of an epoxy resin (B) having an epoxy equivalent of 450 to 2,300 and a melting point of 50 to 135°C; and 10 to 60% by weight of a glass fiber (C) having a boron oxide content of 1.5% by weight or less, a zirconium oxide content of 1.0% by weight or less, and a fluorine content of 0.1% by weight or less.

2. The polyarylene sulfide composition according to claim 1, further comprising an ethylene polymer (D) which is at least one modified ethylene polymer selected from the group consisting of ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymers, ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymers, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymers, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymers, and maleic anhydride-grafted modified ethylene polymers.

3. 3. The polyarylene sulfide composition according to claim 1, wherein the epoxy resin (B) is a bisphenol A type epoxy resin.

4. 3. The polyarylene sulfide composition according to claim 1, wherein the glass fiber (C) is a glass fiber that does not contain boron oxide or zirconium oxide.

5. 3. The polyarylene sulfide composition according to claim 1, wherein the glass fiber (C) is a glass fiber that does not contain boron oxide, zirconium oxide, or fluorine.

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