JP7615540B2 - Polyarylene sulfide resin composition and composite made thereof - Google Patents

Description

The present invention relates to a polyarylene sulfide resin composition that has a low dielectric constant and a low dielectric loss tangent, and therefore has excellent radio wave transmission in the megahertz to gigahertz ranges, exhibits little warping when integrated with a metal member, has excellent bonding properties with the metal member, and also has excellent impact resistance, and to a composite that integrates a polyarylene sulfide resin composition member with a metal member. More specifically, the present invention relates to a polyarylene sulfide resin composition that is particularly useful for electrical and electronic parts such as the housings of mobile terminal devices such as mobile personal computers, tablets, and mobile phones, and a composite made of the same.

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

By blending PAS with fibrous inorganic fillers such as glass fiber, or granular inorganic fillers such as calcium carbonate and talc, the mechanical strength, heat resistance, rigidity, etc. can be greatly improved. However, blending fibrous fillers causes warping in molded products, limiting their use in electronic and electrical component applications such as the housings of mobile terminal devices such as mobile PCs, tablets, and mobile phones, or electrical component applications such as automotive electrical components. In these applications, parts are becoming thinner due to the demand for more complex and smaller part shapes, and it is desirable to reduce warping when the parts are made thinner. Furthermore, there has been a limit to their use in applications requiring low dielectric constant and low dielectric loss tangent, such as the housings of mobile PCs, tablets, mobile phones, etc. that use radio waves in the megahertz to gigahertz range for communication.

Methods proposed for improving the warping of PAS include, for example, a PPS resin composition containing PPS, glass flakes, inorganic fillers other than glass flakes, and an olefin resin (see, for example, Patent Document 1), and a polyphenylene sulfide resin composition containing PPS, glass fiber, an olefin polymer containing specific functional groups, an epoxy resin, glass flakes, and/or calcium carbonate (see, for example, Patent Document 2).

In addition, there have been several studies on PAS resin compositions that have good adhesion to metals, and examples of such compositions include 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).

Further, as low dielectric glass, there is disclosed a low dielectric constant glass fiber (for example, see Patent Document 5) having a glass composition of, by weight, 53-57% SiO ₂ , 13-16% Al ₂ O ₃ , 15-19.5% B ₂ O ₃ , 3% or more but less than 6% MgO, 2-5% CaO, 1-4% TiO _{2 ,} 0-0.3% Li ₂ O, 0-0.3% Na ₂ O, 0-0.5% K ₂ O, and 0.2-1% F ₂ , with MgO+CaO 7-10% and LiO ₂ +Na ₂ O+K ₂ O 0.2-0.5%, a spinning temperature when the viscosity μ (poise) is log μ = 3.0 is 1340°C or less, and the amount of volatilization of B ₂ O ₃ during spinning is 4 ppm or less; Proposals have _{been made} for low _dielectric constant glass fibers _having a composition of 50-60% _CaO , 10-20% Al2O3, 20-30% B2O3, 0-5% CaO, 0-4% MgO, 0-0.5% _Li2O + _Na2O + _K2O , and 0.5-5% _TiO2 , and a dielectric loss tangent of 10 × ^10-4 or less at a frequency of 1 MHz (see, for example, Patent Document 6).

A glass fiber reinforced resin molded product having a low dielectric constant and a low dielectric tangent is a glass fiber reinforced resin molded product containing glass fiber in a range of 10 to 90 mass% and resin in a range of 90 to 10 mass% relative to the total amount of the glass fiber reinforced resin molded product, the glass fiber containing SiO ₂ in a range of 52.0 to 57.0 mass%, Al ₂ O ₃ in a range of 13.0 to 17.0 mass%, B ₂ O ₃ in a range of 15.0 to 21.5 mass%, MgO in a range of 2.0 to 6.0 mass%, CaO in a range of 2.0 to 6.0 mass%, TiO ₂ in a range of 1.0 to 4.0 mass%, and F ₂ less than 1.5 mass%, and further containing Li ₂ O, Na ₂ O, and K _{2 O.} A glass fiber reinforced resin molded product having a composition in which the total amount of O is less than 0.6 mass %, and the glass fibers have a number average fiber length of 30 to 5000 μm (see, for example, Patent Document 7), and the like have been proposed.

In addition, although for different purposes, a PPS resin composition made by blending a specific PPS and glass fibers having a flat cross-sectional shape (see, for example, Patent Document 8), and an insert molded product made of a resin composition blended with PPS resin, glass fibers having a flat cross-sectional shape, and a thermoplastic elastomer and a metal (see, for example, Patent Document 9) have been proposed.

JP 2002-129014 A JP 2005-306926 A JP 2010-070712 A JP 2010-284899 A Patent No. 6352186 Patent No. 3269937 JP 2017-52974 A JP 2006-328291 A JP 2005-161693 A

However, the resin compositions proposed in Patent Documents 1 and 2 had a problem in terms of warping when used as a component. In addition, the resin compositions proposed in Patent Documents 3 and 4 had good adhesion to metals, but no consideration was given to warping and weather resistance when used as a component, and there was a possibility of problems occurring. Furthermore, Patent Documents 5 and 6 propose low-dielectric constant glass fibers, but they are proposed for reinforcing printed wiring boards for high-density circuits, and there is no consideration or mention of reducing the dielectric constant of polyarylene sulfide. Furthermore, Patent Document 7 proposes a glass fiber reinforced resin molded product with a low dielectric constant and low dielectric loss tangent, but there is no consideration or mention of reducing the dielectric constant of polyarylene sulfide. And the resin compositions proposed in Patent Documents 8 and 9 had the possibility of having problems with the dielectric constant and dielectric loss tangent. That is, it was generally difficult for these proposed resin compositions to simultaneously achieve low warping when used as a component, good adhesion to metals, low dielectric constant and low dielectric loss tangent, and impact resistance.

The present invention relates to a polyarylene sulfide resin composition that exhibits little warping when used as a component, good adhesion to metals, low dielectric constant and low dielectric tangent, and excellent impact resistance, and to a composite that integrates a polyarylene sulfide resin composition component with a metal component. More specifically, the present invention provides a polyarylene sulfide resin composition and a composite made therefrom that are particularly useful for electrical and electronic components such as the housings of mobile terminal devices such as mobile PCs, tablets, and mobile phones because of these excellent properties.

As a result of intensive research to solve the above problems, the present inventors discovered that a resin composition containing a polyarylene sulfide resin, at least an ethylene-based polymer, and a specific glass fiber in a specific blending ratio can be a polyarylene sulfide resin composition that, when used as a component, has low warping, good adhesion to metals, a low dielectric constant and low dielectric tangent, and excellent impact resistance, and thus completed the present invention.

That is, the present invention relates to a polyarylene sulfide resin composition comprising 30 to 70% by weight of polyarylene sulfide (A), 3 to 20% by weight of an ethylene-based polymer (B), and 30 to 60% by weight of glass fiber (C) having a dielectric constant of 5.5 or less at 2 GHz and a fiber cross-sectional aspect ratio of 2 to 4.

The present invention is described in detail below.

The polyarylene sulfide resin composition of the present invention comprises 30 to 70% by weight of polyarylene sulfide (A), 3 to 20% by weight of an ethylene-based polymer (B), and 30 to 60% by weight of glass fiber (C) having a dielectric constant of 5.5 or less at 2 GHz and a fiber cross-sectional aspect ratio of 2 to 4.

The polyarylene sulfide (A) constituting the polyarylene sulfide resin composition of the present invention may be any that belongs to the category generally referred to as polyarylene sulfide. Examples of the polyarylene sulfide include homopolymers or copolymers consisting 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 preferable because it results in a polyarylene sulfide resin composition that is particularly excellent in heat resistance and strength characteristics.

Furthermore, the polyarylene sulfide (A) is preferably a polyarylene sulfide having a melt viscosity of 50 to 1000 poise measured under conditions of a measurement temperature of 315°C and a load of 10 kg using a high-temperature flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm, and among these, a polyarylene sulfide having a melt viscosity of 100 to 700 poise is preferable since it results in a polyarylene sulfide resin composition having particularly excellent thin-wall fluidity and impact resistance. The polyarylene sulfide (A) can be produced by a method known as a method for producing polyarylene sulfide, and can be obtained, 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 forms of sodium sulfide, rubidium sulfide, and lithium sulfide. Examples of alkali metal sulfide salts include those obtained by reacting alkali metal hydrosulfide salts with alkali metal hydroxides. Examples of polyhalo aromatic compounds include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4'-dichlorodiphenylsulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenylether, and 4,4'-dichlorodibiphenyl.

The polyarylene sulfide (A) may be linear, or may be a polyarylene sulfide having a small amount of trihalogen or higher polyhalogen compound added during polymerization to introduce a slight crosslinking or branching structure, or may be a polyarylene sulfide having a molecular chain and/or an end modified with a functional group such as a carboxyl group, a carboxy metal salt, an alkyl group, an alkoxy group, an amino group, or a nitro group, or may be a polyarylene sulfide having a 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 a polyarylene sulfide having ions, oligomers, and other impurities reduced by deionization (acid washing, hot water washing, etc.) before or after heat curing, or by washing with an organic solvent such as acetone or methyl alcohol. The polyarylene sulfide (A) may be a polyarylene sulfide having a heat treatment in an inert gas or an oxidizing gas after the polymerization reaction is completed to cure.

The amount of polyarylene sulfide (A) constituting the polyarylene sulfide resin composition of the present invention is 30 to 70% by weight, and preferably 35 to 65% by weight. If the amount of polyarylene sulfide is less than 30% by weight, the resulting composition will have a high dielectric constant and dielectric tangent. On the other hand, if it exceeds 70% by weight, the resulting composition will be prone to warping when used as a resin composition for a component.

The ethylene-based polymer (B) constituting the polyarylene sulfide resin composition of the present invention improves the metal bonding properties of the polyarylene sulfide resin composition, and is preferably at least one modified ethylene-based polymer 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.

As the ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, any copolymer that falls within this category may be used, and among them, since the resulting polyarylene sulfide resin 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 Arkema Co., Ltd.), (trade name) Bondine TX8030 (manufactured by Arkema Co., Ltd.), (trade name) Bondine AX8390 (manufactured by Arkema Co., Ltd.), etc.

As the ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer, any copolymer that falls within this category may be used, and in particular, since the resulting polyarylene sulfide resin composition has excellent bonding properties with metals, it is preferable that the ethylene residue unit:α,β-unsaturated carboxylic acid glycidyl ester residue unit (weight ratio) 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 Arkema Co., Ltd.) and (trade name) Bondfast E (manufactured by Sumitomo Chemical Co., Ltd.).

As the ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer, any copolymer that falls within this category may be used, and among them, since the resulting polyarylene sulfide resin 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 (product name) Bondfast 2B (manufactured by Sumitomo Chemical Co., Ltd.) and (product name) Bondfast 7B (manufactured by Sumitomo Chemical Co., Ltd.).

As the ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer, any one that belongs to this category may be used, and among them, since the resulting polyarylene sulfide resin composition has excellent bonding properties with metals, it is preferable that the ethylene residue unit:α,β-unsaturated carboxylic acid glycidyl ester residue unit:α,β-unsaturated carboxylic acid alkyl ester residue unit (weight ratio) 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 Arkema Co., Ltd.), and (trade name) LOTADER AX8750 (manufactured by Arkema Co., Ltd.).

As the maleic anhydride grafted ethylene-α-olefin copolymer, any copolymer that falls within this category may be used, and among them, those having an ethylene residue unit:α-olefin residue unit:maleic anhydride residue unit (weight ratio) in the range of 50-98:45-1:5-1 are preferred because the resulting polyarylene sulfide resin composition has excellent bonding properties with metals, and specific examples include maleic anhydride grafted linear low-density polyethylene and maleic anhydride grafted ethylene-propylene rubber. 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.

The α-olefin constituting the modified ethylene polymer refers to an α-olefin having 3 or more carbon atoms, and examples thereof include propylene, butene-1, 4-methyl-pentene-1, hexene-1, and octene-1. Examples of α,β-unsaturated carboxylic acid alkyl esters include alkyl esters of acrylic acid and methacrylic acid, and specific examples thereof include 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 α,β-unsaturated carboxylic acid glycidyl esters include acrylic acid glycidyl ester and methacrylic acid glycidyl ester.

The amount of the ethylene polymer (B) to be blended is 3 to 20% by weight, preferably 4 to 18% by weight, since this results in a polyarylene sulfide resin composition that is particularly excellent in metal bonding and molding flowability. If the amount of the ethylene polymer (B) blended is less than 3% by weight, the resulting resin composition will have poor impact resistance and poor bonding to metals when made into a composite. On the other hand, if the amount blended exceeds 20% by weight, the resulting resin composition will have a high dielectric constant and dielectric tangent, which is not preferable.

The glass fiber (C) constituting the polyarylene sulfide resin composition of the present invention may be any (flat) glass fiber having a dielectric constant of 5.5 or less at 2 GHz and a fiber cross-sectional aspect ratio of 2 to 4. The type of glass fiber (C) is preferably NE glass or D glass, which have a dielectric constant of 5.5 or less at 2 GHz, and among these, NE glass is preferable because it results in a polyarylene sulfide resin composition with particularly excellent mechanical strength. Here, if the glass fiber has a dielectric constant of more than 5.5 at 2 GHz, the resulting resin composition will have a high dielectric constant, and there is a high possibility that its use as an electrical and electronic device component will be restricted.

The cross-sectional shape of the glass fiber (C) is a (flat) glass fiber having a fiber cross-sectional aspect ratio of 2 to 4, and specific cross-sectional shapes are preferably oval, elliptical, semicircular, cocoon-shaped, rectangular, or similar shapes. Here, if the fiber cross-sectional aspect ratio is less than 2, the amount of warping of the resulting molded product will be large. On the other hand, if it exceeds 4, problems may arise in terms of fluidity and molding processability. And, as for the fiber diameter of the glass fiber (C), it is preferable that the short diameter of the fiber cross section is 6 to 16 μm, since this will result in a polyarylene sulfide resin composition that is particularly excellent in mechanical strength and molding fluidity.

The glass fiber (C) may be in the form of chopped strand, milled fiber, roving, etc., with chopped strand being preferred since it is particularly easy to handle when forming a polyarylene sulfide resin composition. An example of a chopped strand having a dielectric constant of 5.5 or less at 2 GHz and a fiber cross-sectional aspect ratio of 4 is (product name) ECS309A-3-M4 (manufactured by Taishan Co., Ltd.). 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.

The amount of glass fiber (C) is 30 to 60% by weight. If it is less than 30% by weight, the resulting resin composition will be prone to warping when used in a component. On the other hand, if it exceeds 60% by weight, the resulting resin composition will have a high dielectric constant and dielectric tangent.

The polyarylene sulfide resin composition of the present invention exhibits particularly excellent electrical properties and can be used as a material for various electrical and electronic components. Therefore, it is preferable that the composition has a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.010 or less, measured at a measurement frequency of 2 GHz in accordance with JIS C-2565.

The polyarylene sulfide resin composition of the present invention is preferably further formulated with a release agent (D) since it has 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, and commercially available products can be used as the polyethylene wax, polypropylene wax, fatty acid amide lubricants, and carnauba wax. Examples of the fatty acid amide lubricants include polycondensates of higher fatty acid amides, ethylene bisstearamide, higher fatty acids, and diamines, and any lubricant that falls within this category can be used, such as (trade name) Light Amide WH-255 (manufactured by Kyoeisha Chemical Co., Ltd.), which is a polycondensate of stearic acid, sebacic acid, and ethylenediamine. In addition, the carnauba wax can be any wax generally known as carnauba wax, such as (trade name) Refined Carnauba Powder No. 1 (manufactured by Nikko Rica Co., Ltd.). The amount of the release agent (D) is preferably 0.1 to 3 parts by weight per 100 parts by weight of the total of the polyarylene sulfide (A), ethylene polymer (B), and glass fiber (C).

The polyarylene sulfide resin composition of the present invention may be, within the scope of the invention, a mixture of whiskers such as carbon fibers, silicon nitride whiskers, basic magnesium sulfate whiskers, barium titanate whiskers, potassium titanate whiskers, silicon carbide whiskers, boron whiskers, zinc oxide whiskers, etc.; inorganic fibers such as rock wool, zirconia, barium titanate, silicon carbide, silica, blast furnace slag, etc.; organic fibers such as fully aromatic polyamide fibers, phenolic resin fibers, fully aromatic polyester fibers, etc.; wollastonite, magnesium oxysulphide, etc. Mineral fibers such as phosphate may be added, and 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 may be added within a range that does not impair the effects of the present invention.

The polyarylene sulfide resin composition of the present invention may contain one or more of the following conventional additives, within the scope of the invention: a 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.

Furthermore, the polyarylene sulfide resin composition of the present invention may be made by mixing 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.

The method for producing the polyarylene sulfide resin composition of the present invention is not particularly limited, and any method known as a general mixing/kneading method can be used. For example, a method of blending all raw materials and melt-kneading them; a method of blending some of the raw materials and then melt-kneading them, and then blending the remaining raw materials and melt-kneading them; or a method of blending some of the raw materials and then melt-kneading them with a single-screw or twin-screw extruder, and then mixing the remaining raw materials using a side feeder. In addition, small amounts of added components may be used by blending other components using the above method or the like, pelletizing them, and then adding them before molding. As a method for melt-kneading, a conventionally used heating and melt-kneading method can be used, for example, a heating and melt-kneading method using a single-screw or twin-screw extruder, a kneader, a mill, a Brabender, or the like. In particular, a melt-kneading method using a twin-screw extruder with excellent kneading ability is preferable. In addition, the kneading temperature is not particularly limited, and can usually be selected from 260 to 350°C.

The polyarylene sulfide resin composition of the present invention exhibits excellent impact resistance and has excellent bonding properties with metals (members), and can therefore be used as a metal member-polyarylene sulfide resin composition member composite in which a polyarylene sulfide resin composition member and a metal member are directly integrated by injection molding.

The metal member may be made of any material as long as it falls within the category of metal members, and among these, aluminum members, aluminum alloy members, copper members, copper alloy members, magnesium members, magnesium alloy members, iron members, titanium members, titanium alloy members, and stainless steel members are preferred, since they can be adapted to various applications when made into a polyarylene sulfide resin composition member composite.

The metal member is preferably a metal member whose surface has been physically and/or chemically treated, and by carrying out the physical and/or chemical treatment, the metal member has excellent adhesion, bonding and airtightness when directly integrated with the polyarylene sulfide resin composition member. Any method can be used to physically and/or chemically treat the surface of the metal member, and among them, a composite with particularly excellent bonding and adhesion between the metal member and the polyarylene sulfide resin composition member can be obtained. Examples of physical treatment include a method of contacting or colliding fine solid particles with the surface, and a method of irradiating high-energy electromagnetic rays, and more specifically, a sandblasting treatment, a liquid honing treatment, a laser processing treatment, and the like. Furthermore, examples of abrasives for sandblasting and liquid honing treatment include sand, steel grid, steel shot, cut wire, alumina, silicon carbide, metal slag, glass beads, plastic beads, and the like. Examples of laser processing include the methods proposed in WO2007/072603, JP2015-142960A, and JP2016-132131A, and examples of methods of irradiating high-energy electromagnetic rays include the method proposed in JP2011-140167A.

In addition, since the composite has particularly excellent bonding and adhesion between the metal member and the polyarylene sulfide resin composition member, examples of chemical treatments include anodizing and chemical treatment with an acid or alkali aqueous solution.

Anodizing may be, for example, a method in which an electrochemical reaction is carried out in an electrolyte using a metal member as an anode to form an oxide film on the surface, and methods generally known as anodizing methods in fields such as plating can be used. More specifically, examples include 1) DC electrolysis, in which electrolysis is carried out by applying a constant DC voltage, and 2) bipolar electrolysis, in which electrolysis is carried out by applying a voltage in which an AC component is superimposed on a DC component. Specific examples of anodizing methods include the method proposed in WO2004/055248 and the like.

In addition, the method of chemically treating the metal member with an aqueous acid or alkali solution may be, for example, a method of immersing the metal member in an aqueous acid or alkali solution to chemically treat the surface of the metal member. Examples of the aqueous acid or alkali solution used in this case include phosphoric acid and other phosphoric acid compounds; chromic acid and other chromic acid compounds; hydrofluoric acid and other hydrofluoric acid compounds; nitric acid and other nitric acid compounds; hydrochloric acid and other hydrochloric acid compounds; sulfuric acid and other sulfuric acid compounds; aqueous alkali solutions such as sodium hydroxide and ammonia solution; trichloroethylene and the like. Examples of methods include chemical treatment using an aqueous solution of zincthiol or a triazinethiol derivative, and more specific examples include the methods proposed in JP-A-10-096088, JP-A-10-056263, JP-A-04-032585, JP-A-04-032583, JP-A-02-298284, WO2009/151099, WO2011/104944, and JP-A-2010-254793.

The physical and/or chemical treatments may be performed alone or in combination. For example, a metal member whose surface has been subjected to a physical treatment and then a chemical treatment may be used to form a metal member-polyarylene sulfide resin composition member composite.

As a method for producing the metal member-polyarylene sulfide resin composition member composite, any method can be used as long as it is possible to directly integrate the metal member whose surface has been physically and/or chemically treated with the polyarylene sulfide resin composition member by injection molding. Among these, it is preferable to integrate them by injection insert molding, since it is particularly possible to efficiently produce a composite. As an example of the injection insert molding method, a method can be mentioned in which a metal member whose metal surface has been physically and/or chemically treated is mounted in a mold, the metal member is filled with a molten polyarylene sulfide resin composition to form a polyarylene sulfide resin composition member, and a composite in which the metal member and the polyarylene sulfide resin composition member are directly integrated can be produced. The melting temperature of the polyarylene sulfide resin composition in this case can be 280 to 340°C, and as a molding machine for performing insert molding, it is preferable to perform insert injection molding using an injection molding machine, since it is particularly excellent in productivity.

The shape of the metal member-polyarylene sulfide resin composition member composite is preferably such that the thickness of the composite is in the range of 0.5 to 5 mm, and the ratio of the length and width to the thickness is 10 or more, since this provides excellent filling properties for the polyarylene sulfide resin composition when directly integrated by injection molding, and the composite has little warping when used as a component. Parts that include this shape include the housings of mobile terminal devices such as mobile PCs, tablets, and mobile phones, and in-vehicle capacitor cases.

The polyarylene sulfide resin composition of the present invention has low dielectric constant and dielectric loss tangent, particularly in the high frequency range, and when used as a component, it has low warping, good bonding properties with metal components, and excellent impact resistance. Therefore, it is suitable for use in electrical and electronic components such as the housings of mobile terminal devices, where thinner components are desired to meet the needs for more complex component shapes and smaller size, or in automotive electrical components.

The present invention provides a polyarylene sulfide resin composition that has a low dielectric constant and a low dielectric loss tangent, and therefore has excellent radio wave transmission in the megahertz to gigahertz ranges, has a small amount of warping when used as a component, has good bonding properties with metal components, and is also excellent in impact resistance. The composition is useful for electronic and electrical component applications such as housings for mobile terminal devices such as mobile PCs, tablets, and mobile phones, and electrical component applications such as automotive electrical components.

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

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

<Polyarylene sulfide (A)>
Poly(p-phenylene sulfide) (A-1) (hereinafter referred to as PPS (A-1)): melt viscosity of 500 poise.
Poly(p-phenylene sulfide) (A-2) (hereinafter referred to as PPS (A-2)): melt viscosity 150 poise.
Poly(p-phenylene sulfide) (A-3) (hereinafter referred to as PPS (A-3)): melt viscosity 400 poise.

<Ethylene-Based Polymer (B)>
Ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B-1) (hereinafter referred to as ethylene copolymer (B-1)): manufactured by Arkema Co., Ltd., (product 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 Sumitomo Chemical Co., Ltd., (product name) Bondfast 7M.
Ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer (B-3) (hereinafter referred to as ethylene-based copolymer (B-3)): manufactured by Arkema Co., Ltd., (product name) Bondine AX8840.
Ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (B-4) (hereinafter referred to as ethylene copolymer (B-4)): manufactured by Sumitomo Chemical Co., Ltd., (product name) Bondfast 7B.

<Glass fiber (C)>
Glass fiber (C-1): Taishan chopped strand, (product name) ECS309A-3-M4, dielectric constant at a measurement frequency of 2 GHz: 4.5, aspect ratio of fiber cross section: 4.
Glass fiber (C-2): chopped strand manufactured by Nitto Boseki Co., Ltd., (product name) CSG-3PA 830, dielectric constant at a measurement frequency of 2 GHz of 6.8, aspect ratio of fiber cross section of 4.
Glass fiber (C-3): Taishan chopped strand, (product name) TLD-T443, dielectric constant at a measurement frequency of 2 GHz: 4.5, aspect ratio of fiber cross section: 1.

<Release Agent (D)>
Fatty acid amide lubricant (D-1) (hereinafter, sometimes referred to as mold release agent (D-1)): manufactured by Kyoeisha Chemical Co., Ltd., (trade name) Lightamide WH-255.
Carnauba wax (D-2) (hereinafter, sometimes referred to as release agent (D-2)): product name: Refined Carnauba Powder No. 1, manufactured by Nikko Rica Corporation.

<Synthesis Example 1 (Synthesis of PPS (A-1))>
In a 50-liter autoclave equipped with a stirrer, 6214 g of flake sodium sulfide (Na ₂ S.2.9H ₂ O) and 17,000 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 205° C. while stirring under a nitrogen stream, and 1,355 g of water was distilled off. After cooling this system to 140° C., 7,150 g of p-dichlorobenzene, 47 g of 3,5-dichloroaniline, 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, polymerized at 225° C. for 2 hours, then heated to 250° C. over 30 minutes, and further polymerized at 250° C. for 3 hours. After the polymerization was completed, the system was cooled to room temperature, and the polymer was isolated by a centrifuge. The solid polymer was repeatedly washed with warm water and dried overnight at 100° C. to obtain an amino group-substituted poly(p-phenylene sulfide) having a melt viscosity of 250 poise. The dried amino group-substituted poly(p-phenylene sulfide) was then loaded into a batch-type rotary kiln-type calciner and cured for 5 hours at 250° C. in a nitrogen atmosphere to obtain PPS (A-1) having a melt viscosity of 500 poise and an amino group content of 0.6 mol % relative to the phenyl groups.

<Synthesis Example 2 (Synthesis of PPS (A-2))>
In a 15-liter autoclave equipped with a stirrer, 1814 g of flake sodium sulfide (Na ₂ S.2.9H ₂ O), 48 g of 30% caustic soda solution (30% NaOHaq), and 3679 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised 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, polymerized at 225° C. for 1 hour, then heated to 250° C. over 25 minutes, and further polymerized at 250° C. for 3 hours. After polymerization, N-methyl-2-pyrrolidone was recovered from the polymerization slurry by distillation under reduced pressure. The final temperature was 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 to raise the temperature to 175°C, washing the poly(p-phenylene sulfide) twice in total. The resulting polyphenylene sulfide was dried at 105°C for a whole day and night. The dried polyphenylene sulfide was then loaded into a batch-type rotary kiln-type baking apparatus, heated to 235°C under a nitrogen atmosphere, and held for 1 hour to perform a curing treatment, thereby obtaining PPS (A-2) with a melt viscosity of 150 poise.

<Synthesis Example 3 (Synthesis of PPS (A-3))>
In a 15-liter autoclave equipped with a stirrer, 1814 g of flake sodium sulfide (Na ₂ S.2.9H ₂ O), 8.7 g of granular caustic soda (100% NaOH: Wako Pure Chemical special grade) and 3232 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 200°C while stirring under a nitrogen stream, and 340 g of water was distilled off. After cooling to 190°C, 2107 g of p-dichlorobenzene and 1783 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, polymerized at 225°C for 1 hour, then heated to 250°C over 25 minutes, and polymerized at 250°C for 2 hours. Next, 509 g of distilled water was injected into the system at 250°C, and the system was heated to 255°C and polymerized for another 1 hour. After the polymerization, N-methyl-2-pyrrolidone was recovered from the polymerization slurry by distillation under reduced pressure. The final temperature reached was 170°C and the pressure was 4.7 kPa. The obtained cake was washed by adding hot water at 80°C to make the slurry concentration 20%, and hot water was added again in the same manner to raise the temperature to 175°C, and washing of poly(p-phenylene sulfide) was performed twice in total. The obtained poly(p-phenylene sulfide) was dried at 105°C for one day to obtain PPS (A-3) having a melt viscosity of 400 poise.

The evaluation and measurement methods for the obtained polyarylene sulfide resin and polyarylene sulfide resin composition are shown below.

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

～Measurement of dielectric constant and dielectric tangent～
The polyarylene sulfide resin composition was injection molded using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (product name) SE-75D) with a cylinder temperature of 310°C and a mold temperature of 135°C to prepare a molded plate of 70 mm x 70 mm x 1 mm thickness, and a test piece for measuring dielectric constant of 70 mm x 3 mm x 1 mm thickness was prepared from this molded plate by cutting. The dielectric constant and dielectric loss tangent of this test piece were measured at a measurement frequency of 2 GHz using a dielectric constant measuring device (manufactured by AET Corporation, (product name) Cavity Resonator) in accordance with JIS C-2565. A dielectric constant of 3.5 or less and a dielectric loss tangent of 0.010 or less were judged to have sufficiently low dielectric properties for practical use.

～Impact resistance measurement～
A test piece for measuring Charpy impact strength was prepared from the polyarylene sulfide resin 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, and a notch was inserted using a notching machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., (product name) A-3 type), and the Charpy impact strength was measured in accordance with ISO179 using a Charpy impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., (product name) DG-CB type). A Charpy impact strength of more than 10 kJ/ ^m2 was determined to have impact properties sufficiently high for practical use.

- Evaluation of metal bonding and warpage -
A metal plate (70 mm (longitudinal) × 70 mm (lateral) × 1 mm (thickness) or 20 mm (longitudinal) × 20 mm (lateral) × 1 mm (thickness)) having a surface that had been subjected to a physical and/or chemical treatment was placed in an injection molding machine mold set at a mold temperature of 150°C, and a polyarylene sulfide resin composition was placed in a hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (product name) SE75S) heated to 310°C, and injection insert molding was performed to obtain a metal member-polyarylene sulfide resin composition member composite of 70 mm × 70 mm × 2 mm (thickness) (the ratios of the longitudinal and lateral dimensions to the thickness direction of the laminate layer were each 35) or 20 mm × 20 mm × 2 mm (thickness) (the ratios of the longitudinal and lateral dimensions to the thickness direction of the laminate layer were each 10).

The interface of the metal member-polyarylene sulfide resin composition member composite 24 hours after molding was visually inspected.
◯: No peeling was observed at the interface of the metal member-polyarylene sulfide resin composition member composite.
×: Peeling was observed at the interface of the metal member-polyarylene sulfide resin composition member composite.

Furthermore, the metal member-polyarylene sulfide resin composition member composite 24 hours after molding was evaluated using a 3D scanner type coordinate measuring machine (Keyence Corporation, product name: VL-350) to determine the amount of warping by taking the three vertices of the composite as reference points and setting them as reference planes, and the amount of deviation of the remaining vertex from the reference plane. A deviation of less than 1 mm was determined to have little warping for practical use.

Example 1
85.8% by weight of PPS (A-1) obtained in Synthesis Example 1, 13.4% by weight of ethylene copolymer (B-1), and 0.8% by weight of release agent (D-1) were mixed uniformly 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. On the other hand, glass fiber (C-1) was charged from the hopper of the side feeder of the twin-screw extruder, melt-kneaded, and pelletized to obtain a polyarylene sulfide resin composition. The composition ratio of the polyarylene sulfide resin composition at that time was 51.5% by weight of PPS (A-1), 8% by weight of ethylene copolymer (B-1), 40% by weight of glass fiber (C-1), and 0.5% by weight of release agent (D-1).

On the other hand, an aluminum alloy (A5052) flat plate (70 mm × 70 mm × 1 mm (thickness)) was immersed in acetone to clean the surface, and then the test piece was immersed in a 1 wt % aqueous sodium hydroxide solution, then in a 10 wt % aqueous sulfuric acid solution, and further anodized in a 15 wt % aqueous sulfuric acid solution at a current density of 0.5 A/ ^cm3 , thereby obtaining an aluminum alloy (A5052) plate with a chemically treated aluminum alloy surface.

The obtained aluminum alloy (A5052) plate was placed in an injection molding machine mold set at a mold temperature of 150°C, and the obtained polyarylene sulfide resin composition was placed in the hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (product name) SE75S) heated to 310°C, and injection insert molding was performed to obtain an aluminum alloy member-polyarylene sulfide resin composition member composite of 70 mm x 70 mm x 2 mm (thickness) (the ratio of the length and width to the thickness direction of the laminate layer was 35 each).

The resulting polyarylene sulfide resin composition and aluminum alloy member-polyarylene sulfide resin composition member composite were evaluated for dielectric constant, dielectric tangent, impact resistance, metal bondability, and amount of displacement. The evaluation results are shown in Table 1.

The obtained polyarylene sulfide resin composition and aluminum alloy member-polyarylene sulfide resin composition member composite also had good metal bonding properties and warpage. In addition, the dielectric constant, dielectric tangent, and impact resistance also showed values sufficient for practical use.

Example 2
87.3% by weight of PPS (A-2) obtained in Synthesis Example 2, 11.1% by weight of ethylene copolymer (B-2), and 1.6% by weight of release agent (D-2) were mixed uniformly 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. On the other hand, glass fiber (C-1) was charged from the hopper of the side feeder of the twin-screw extruder, melt-kneaded, and pelletized to obtain a polyarylene sulfide resin composition. The composition ratio of the polyarylene sulfide resin composition at that time was 39.3% by weight of PPS (A-2), 5% by weight of ethylene copolymer (B-2), 55% by weight of glass fiber (C-1), and 0.7% by weight of release agent (D-2).

On the other hand, an aluminum die-cast alloy (ADC12) plate (70 mm x 70 mm x 1 mm (thickness)) was immersed in acetone to clean the surface, and then the test piece was subjected to laser processing in which a laser with a wavelength of 1.064 μm was used to scan the test piece 120,000 times in the orthogonal direction with a hatching width of 0.2 mm, a frequency of 6 KHz, and a speed of 100 mm/sec, to obtain an aluminum die-cast alloy (ADC12) plate with a physically treated aluminum die-cast alloy surface.

The obtained aluminum die-cast alloy (ADC12) plate was placed in an injection molding machine mold set at a mold temperature of 150°C, and the obtained polyarylene sulfide resin composition was placed in the hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (product name) SE75S) heated to 310°C, and injection insert molding was performed to obtain an aluminum die-cast alloy member-polyarylene sulfide resin composition member composite of 70 mm x 70 mm x 2 mm (thickness) (ratio of length and width to thickness of the laminate layer: 35).

The resulting polyarylene sulfide resin composition and aluminum die-cast alloy member-polyarylene sulfide resin composition member composite were evaluated for dielectric constant, dielectric tangent, impact resistance, metal bondability, and amount of displacement. The evaluation results are shown in Table 1.

The obtained polyarylene sulfide resin composition and aluminum die-cast alloy member-polyarylene sulfide resin composition member composite also had good metal bonding properties and warpage. In addition, the dielectric constant, dielectric tangent, and impact resistance also showed values sufficient for practical use.

Example 3
71.4% by weight of PPS (A-1) obtained in Synthesis Example 1, 27.7% by weight of ethylene copolymer (B-3), and 0.9% by weight of release agent (D-1) were mixed uniformly 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. On the other hand, glass fiber (C-1) was charged from the hopper of the side feeder of the twin-screw extruder, melt-kneaded, and pelletized to obtain a polyarylene sulfide resin composition. The composition ratio of the polyarylene sulfide resin composition at that time was 46.4% by weight of PPS (A-1), 18.0% by weight of ethylene copolymer (B-3), 35% by weight of glass fiber (C-1), and 0.6% by weight of release agent (D-1).

On the other hand, an aluminum alloy (A6063) plate (70 mm x 70 mm x 1 mm (thickness)) was immersed in acetone to clean the surface, and then the test piece was subjected to liquid honing treatment with #800 alumina and then #2000 alumina to obtain an aluminum alloy (A6063) plate with a physically treated aluminum alloy surface.

The obtained aluminum alloy (A6063) plate was placed in an injection molding machine mold set at a mold temperature of 150°C, and the obtained polyarylene sulfide resin composition was placed in the hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (product name) SE75S) heated to 310°C, and injection insert molding was performed to obtain an aluminum alloy member-polyarylene sulfide resin composition member composite of 70 mm x 70 mm x 2 mm (thickness) (ratio of length and width to thickness of the laminate layer: 35).

The resulting polyarylene sulfide resin composition and aluminum alloy member-polyarylene sulfide resin composition member composite were evaluated for dielectric constant, dielectric tangent, impact resistance, metal bondability, and amount of displacement. The evaluation results are shown in Table 1.

The obtained polyarylene sulfide resin composition and aluminum alloy member-polyarylene sulfide resin composition member composite also had good metal bonding properties and warpage. In addition, the dielectric constant, dielectric tangent, and impact resistance also showed values sufficient for practical use.

Example 4
80% by weight of PPS (A-3) obtained in Synthesis Example 3, 18.2% by weight of ethylene copolymer (B-4), and 1.8% by weight of release agent (D-2) were mixed uniformly 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. On the other hand, glass fiber (C-1) was charged from the hopper of the side feeder of the twin-screw extruder, melt-kneaded, and pelletized to obtain a polyarylene sulfide resin composition. The composition ratio of the polyarylene sulfide resin composition at that time was 44% by weight of PPS (A-3), 10% by weight of ethylene copolymer (B-4), 45% by weight of glass fiber (C-1), and 1% by weight of release agent (D-1).

On the other hand, a stainless steel (SUS316) plate (70 mm x 70 mm x 1 mm (thickness)) was immersed in acetone to clean the surface, and then the test piece was subjected to laser processing in which a laser with a wavelength of 1.064 μm was used to scan the test piece 120,000 times in the perpendicular direction with a hatching width of 0.2 mm, a frequency of 6 kHz, and a speed of 200 mm/sec, thereby obtaining a stainless steel (SUS316) plate with a physically treated stainless steel surface.

The obtained stainless steel (SUS316) plate was placed in an injection molding machine mold set at a mold temperature of 150°C, and the obtained polyarylene sulfide resin composition was placed in the hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, (product name) SE75S) heated to 310°C, and injection insert molding was performed to obtain a stainless steel member-polyarylene sulfide resin composition member composite of 70 mm x 70 mm x 2 mm (thickness) (ratio of length and width to thickness of the laminate layer: 35).

The resulting polyarylene sulfide resin composition and the stainless steel member-polyarylene sulfide resin composition member composite were evaluated for dielectric constant, dielectric tangent, impact resistance, metal bondability, and amount of displacement. The evaluation results are shown in Table 1.

The obtained polyarylene sulfide resin composition and stainless steel member-polyarylene sulfide resin composition member composite also had good metal bonding properties and warpage. In addition, the dielectric constant, dielectric tangent, and impact resistance also showed values sufficient for practical use.

Example 5
91.4% by weight of PPS (A-2) obtained in Synthesis Example 2, 8% by weight of ethylene copolymer (B-1), and 0.6% by weight of release agent (D-2) were mixed uniformly in advance and charged into the hopper of a twin-screw extruder (manufactured by Toshiba Machine, (product name) TEM-35-102B) heated to a cylinder temperature of 300° C. On the other hand, glass fiber (C-1) was charged from the hopper of the side feeder of the twin-screw extruder, melt-kneaded, and pelletized to obtain a polyarylene sulfide resin composition. The composition ratio of the polyarylene sulfide resin composition at that time was 45.7% by weight of PPS (A-2), 4.0% by weight of ethylene copolymer (B-1), 50% by weight of glass fiber (C-1), and 0.3% by weight of release agent (D-2).

On the other hand, an aluminum (A1050) plate (70 mm x 70 mm x 1 mm (thickness)) was immersed in ethanol to clean the surface, and then the test piece was roughened by sandblasting using 0.1 mm and then 0.01 mm alumina powder. The test piece was then immersed in a 1 wt% aqueous sodium hydroxide solution, and then in a 1 wt% aqueous sulfuric acid solution. Finally, the test piece was immersed for 10 minutes in a distilled water mixture containing 1 wt% ethanolamine at 95°C to subject the surface to boehmite treatment, thereby obtaining an aluminum (A1050) plate whose surface had been physically and then chemically treated.

The resulting aluminum (A1050) plate was placed in an injection molding machine mold set at a mold temperature of 150°C, and the resulting polyarylene sulfide resin composition was placed in the hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, (product name) SE75S) heated to 310°C, and injection insert molding was performed to obtain an aluminum member-polyarylene sulfide resin composition member composite of 70 mm x 70 mm x 2 mm (thickness) (ratio of length and width to thickness of the laminate layer: 35).

The resulting polyarylene sulfide resin composition and aluminum member-polyarylene sulfide resin composition member composite were evaluated for dielectric constant, dielectric tangent, impact resistance, metal bondability, and amount of displacement. The evaluation results are shown in Table 1.

The obtained polyarylene sulfide resin composition and aluminum member-polyarylene sulfide resin composition member composite also had good metal bonding properties and warpage. In addition, the dielectric constant, dielectric tangent, and impact resistance also showed values sufficient for practical use.

Example 6
78.3% by weight of PPS (A-3) obtained in Synthesis Example 3, 20% by weight of ethylene copolymer (B-3), and 1.7% by weight of release agent (D-1) were mixed uniformly 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. On the other hand, glass fiber (C-1) was charged from the hopper of the side feeder of the twin-screw extruder, melt-kneaded, and pelletized to obtain a polyarylene sulfide resin composition. The composition ratio of the polyarylene sulfide resin composition at that time was 47% by weight of PPS (A-3), 12% by weight of ethylene copolymer (B-2), 40% by weight of glass fiber (C-1), and 1% by weight of release agent (D-1).

On the other hand, an aluminum alloy (A5052) plate (20 mm x 20 mm x 1 mm (thickness)) was immersed in ethanol to clean the surface, and then the test piece was immersed in a distilled water mixture containing 0.5% by weight of ethanolamine at 95°C for 5 minutes to perform a boehmite treatment, thereby obtaining an aluminum alloy (A5052) plate with a chemically treated aluminum alloy surface.

The obtained aluminum alloy (A5052) plate was placed in an injection molding machine mold set at a mold temperature of 150°C, and the obtained polyarylene sulfide resin composition was placed in the hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, (product name) SE75S) heated to 310°C, and injection insert molding was performed to obtain an aluminum alloy member-polyarylene sulfide resin composition member composite of 20 mm x 20 mm x 2 mm (thickness) (ratio of length and width to thickness of the laminate layer: 10).

The resulting polyarylene sulfide resin composition and aluminum alloy member-polyarylene sulfide resin composition member composite were evaluated for dielectric constant, dielectric tangent, impact resistance, metal bondability, and amount of displacement. The evaluation results are shown in Table 1.

The obtained polyarylene sulfide resin composition and aluminum alloy member-polyarylene sulfide resin composition member composite also had good metal bonding properties and warpage. In addition, the dielectric constant, dielectric tangent, and impact resistance also showed values sufficient for practical use.

Example 7
86.4% by weight of PPS (A-1) obtained in Synthesis Example 1, 12.7% by weight of ethylene copolymer (B-2), and 0.9% by weight of release agent (D-2) were mixed uniformly in advance and charged into the hopper of a twin-screw extruder (manufactured by Toshiba Machine, (product name) TEM-35-102B) heated to a cylinder temperature of 300° C. On the other hand, glass fiber (C-1) was charged from the hopper of the side feeder of the twin-screw extruder, melt-kneaded, and pelletized to obtain a polyarylene sulfide resin composition. The composition ratio of the polyarylene sulfide resin composition at that time was 47.5% by weight of PPS (A-1), 7% by weight of ethylene copolymer (B-2), 45% by weight of glass fiber (C-1), and 0.5% by weight of release agent (D-2).

On the other hand, an aluminum die-cast alloy (ADC12) plate (20 mm x 20 mm x 1 mm (thickness)) was immersed in acetone to clean the surface, and then the test piece was subjected to laser processing in which a laser with a wavelength of 1.064 μm was used to scan the test piece 120,000 times in the orthogonal direction with a hatching width of 0.2 mm, a frequency of 6 KHz, and a speed of 100 mm/sec, to obtain an aluminum die-cast alloy (ADC12) plate with a physically treated aluminum die-cast alloy surface.

The obtained aluminum die-cast alloy (ADC12) plate was placed in an injection molding machine mold set at a mold temperature of 150°C, and the obtained polyarylene sulfide resin composition was placed in the hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, (product name) SE75S) heated to 310°C, and injection insert molding was performed to obtain an aluminum die-cast alloy member-polyarylene sulfide resin composition member composite of 20 mm x 20 mm x 2 mm (thickness) (ratio of length and width to thickness of the laminate layer: 10).

The resulting polyarylene sulfide resin composition and aluminum die-cast alloy member-polyarylene sulfide resin composition member composite were evaluated for dielectric constant, dielectric tangent, impact resistance, metal bondability, and amount of displacement. The evaluation results are shown in Table 1.

The obtained polyarylene sulfide resin composition and aluminum die-cast alloy member-polyarylene sulfide resin composition member composite also had good metal bonding properties and warpage. In addition, the dielectric constant, dielectric tangent, and impact resistance also showed values sufficient for practical use.

Comparative Examples 1 to 6
PPS (A-1), ethylene copolymer (B-1), and release agent (D-1) were mixed in the composition ratio shown in Table 2 and charged into the hopper of a twin-screw extruder. Glass fibers (C-1 to C-3) were charged into the hopper of the side feeder of the twin-screw extruder so as to have the composition ratio shown in Table 2. A resin composition was obtained in the same manner as in Example 1.

Meanwhile, an aluminum alloy (A5052) plate was obtained with the aluminum alloy surface chemically treated in the same manner as in Example 1.

An aluminum alloy member-resin composition member laminate was obtained in the same manner as in Example 1, except that the obtained resin composition was used.

The obtained resin composition and the aluminum alloy member-resin composition member laminate were evaluated for dielectric constant, dielectric tangent, impact resistance, metal bonding, and amount of displacement. The evaluation results are shown in Table 2.

The resin composition obtained in Comparative Example 1 was inferior in dielectric constant and dielectric tangent. The resin composition obtained in Comparative Example 2 was inferior in dielectric constant and dielectric tangent. The resin composition obtained in Comparative Example 3 was inferior in the amount of warping. The resin composition obtained in Comparative Example 4 was inferior in dielectric constant and dielectric tangent. The resin composition obtained in Comparative Example 5 was inferior in the amount of warping. The resin composition obtained in Comparative Example 6 was inferior in metal bonding and impact resistance.

The polyarylene sulfide resin composition of the present invention has a low dielectric constant and a low dielectric loss tangent, and therefore has excellent radio wave permeability from the megahertz band to the gigahertz band, and when integrated with a metal member, it has a small amount of warping, good bonding properties with the metal member, and excellent impact resistance. It is expected to be used as a resin composition and a composite made of the same for electronic and electrical component applications such as the housings of mobile terminal devices such as mobile PCs, tablets, and mobile phones that use radio waves in the megahertz band to the gigahertz band during communication, or for electrical component applications such as automotive electrical components.

Claims (5)

A polyarylene sulfide resin composition comprising 39.3 to 51.5% by weight of polyarylene sulfide (A), 4.0 to 10.0% by weight of an ethylene polymer (B) which is at least one modified ethylene polymer 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-vinyl acetate copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer, and maleic anhydride graft-modified ethylene polymer, and 40.0 to 55.0% by weight of glass fiber (C) having a dielectric constant of 5.5 or less at 2 GHz and a fiber cross-sectional aspect ratio of 2 to 4, wherein the polyarylene sulfide resin composition has a dielectric constant of 3.5 or less and a dielectric dissipation factor of 0.010 or less as measured at a measurement frequency of 2 GHz in accordance with JIS C-2565, and the polyarylene sulfide (A) is an amino group-modified polyarylene sulfide . The polyarylene sulfide resin 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. The polyarylene sulfide resin composition according to claim 1 or 2, characterized in that the polyarylene sulfide (A) is a polyarylene sulfide having a melt viscosity of 100 to 700 poise when measured at a temperature of 315°C and a load of 10 kg using a high-temperature flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. a metal member having a surface which has been subjected to a physical and/or chemical treatment; 39.3 to 51.5% by weight of a polyarylene sulfide (A); 4.0 to 10.0% by weight of an ethylene polymer (B) which is at least one modified ethylene polymer selected from the group consisting of an ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, an ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer, an ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer, and a maleic anhydride graft-modified ethylene polymer; and 40.0 to 55.0% by weight of a glass fiber (C) having a dielectric constant of 5.5 or less at 2 GHz and a fiber cross-sectional aspect ratio of 2 to 4, A metal member-polyarylene sulfide resin composition member composite is characterized in that the metal member-polyarylene sulfide resin composition member composite has a dielectric constant of 3.5 or less and a dielectric dissipation factor of 0.010 or less, as measured at a measurement frequency of 2 GHz in accordance with C-2565, and is a direct integration product of an injection-molded member and a polyarylene sulfide resin composition in which the polyarylene sulfide (A) is an amino group-modified polyarylene sulfide. The metal member-polyarylene sulfide resin composition member composite according to claim 4, characterized in that it includes a laminate having a thickness of 0.5 to 5 mm and a ratio of length to thickness and width to thickness of 10 or more .