Metal member-polyarylene sulfide member composite and manufacturing method thereof

Abstract

To provide a metal member-polyarylene sulfide member complex that has small warpage and excellent air-tightness between a metal member and a polyarylene sulfide member, and a production method therefor.SOLUTION: A metal member-polyarylene sulfide member complex is an integrally injection molded product of a metal member and a polyarylene sulfide member. The polyarylene sulfide member is formed by injection-molding a polyarylene sulfide composition satisfying all of the following: (1) a peak temperature at a melt crystallization peak is 200°C or more and 230°C or less; (2) a melt flow rate (MFR) is 20 g per 10 minutes or more and 150 g per 10 minutes or less; and (3) 5-25 pts.wt. of a modified ethylene-based copolymer (B), 1-15 pts.wt. of epoxy resin (C), glass fibers (D) and glass flakes (E) are contained with respect to 100 pts.wt. of polyarylene sulfide (A), with the glass fibers (D) / glass flakes (E) (weight ratio)=1 / 4-4 / 1, and the total amount of the glass fibers (D) and the glass flakes (E) is 40-150 pts.wt. with respect to 100 pts.wt. of the polyarylene sulfide (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composite that integrates a polyarylene sulfide member and a metal member, and more specifically to a metal member-polyarylene sulfide member composite that has little warping and excellent airtightness at the bonding surface, and is particularly useful for use in parts for transportation equipment such as automobiles and aircraft, or for use in electrical and electronic parts for portable devices and other devices that require waterproofing, and a method for producing the metal member-polyarylene sulfide member composite. [Background technology]

[0002] In order to reduce the weight of transportation equipment parts such as automobiles and aircraft, methods of replacing some metals with resins are being investigated. Also, as a method for integrating resin and metal into a composite, a method in which a metal member having a surface that has been subjected to physical and / or chemical treatment is inserted into a mold, and then resin is injection-molded to directly integrate the metal and resin (hereinafter, this method may be referred to as injection insert molding) has attracted attention from the viewpoints of good mass productivity, a small number of parts, low cost, high design flexibility, and a low environmental impact, and has been proposed for use in the manufacturing process of mobile electronic devices such as smartphones (see, for example, Patent Documents 1 to 3).

[0003] 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, as well as chemical resistance, and are widely used in a variety of electrical and electronic equipment components, automotive equipment components, and other office automation equipment components.

[0004] Furthermore, because PAS has excellent melt fluidity, it exhibits excellent bonding strength when used in injection insert molding with metal components having surfaces that have been subjected to physical and / or chemical treatments.

[0005] PAS can significantly improve 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 fillers can cause warping in molded products, limiting its use in electronic and electrical components such as the housings of mobile terminal devices like smartphones and tablet PCs, or in automotive parts. Furthermore, in these applications, demands for more complex part shapes and smaller sizes are driving thinner parts, and reducing warpage when thinner parts are used is desirable.

[0006] As methods for improving the warpage of PAS, for example, a PPS resin composition containing PPS, glass flakes, an inorganic filler other than glass flakes, and an olefin resin (see, for example, Patent Document 4), a polyphenylene sulfide resin composition containing PPS, glass fiber, an olefin polymer containing a specific functional group, an epoxy resin, glass flakes, and / or calcium carbonate (see, for example, Patent Document 5), and a polyarylene sulfide resin composition containing PPS, a modified ethylene copolymer, glass fiber having a fiber cross-sectional aspect ratio of 2 to 4, and an ultraviolet absorber (see, for example, Patent Document 6) have been proposed.

[0007] Furthermore, as a resin composition with high flatness and reduced dimensional variation between shots, a polyarylene sulfide resin composition consisting of PPS having a specific melt viscosity and crystallization temperature, a fibrous filler, and a non-fibrous filler has been proposed (see, for example, Patent Documents 7 and 8).

[0008] Furthermore, as resin compositions having excellent adhesion to epoxy resins, there have been proposed polyarylene sulfide compositions comprising PPS, a polyethylene copolymer, a modified polysiloxane compound, and an epoxy resin (see, for example, Patent Document 9), polyarylene sulfide compositions comprising PPS, a polyethylene copolymer, and a silane compound having a ketimine structure (see, for example, Patent Document 10), and polyarylene sulfide compositions comprising PPS, a polar group-containing polyethylene copolymer, and at least one coupling agent selected from the group consisting of organic titanates and organic aluminates (see, for example, Patent Document 11).

[0009] Furthermore, as a resin composition having excellent dimensional stability, thin-wall flowability, etc., a polyarylene sulfide resin composition comprising an amino group-containing PPS having a specific melt viscosity and crystallization temperature, a fibrous filler, a powdery granular filler, an ethylene copolymer, and a mold release agent (see, for example, Patent Document 12) has been proposed.

[0010] 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 13), and a resin composition that combines (a) PPS, (b) a polar group-containing polyolefin, and (c) a compatibilizer (see, for example, Patent Document 14).

[0011] Furthermore, as a metal-resin composite molding having a strong bonding strength between the insert metal member and the resin member, a good surface appearance, and excellent chemical resistance to acids, alkalis, etc., a metal-resin composite molding has been proposed in which the insert metal member has been subjected to physical and / or chemical treatment, and the resin member is made of a resin composition containing an inorganic filler selected from the group consisting of PPS, non-fibrous spherical silica, and glass beads, and an epoxy group-containing olefin copolymer (see, for example, Patent Document 15). [Prior art documents] [Patent documents]

[0012] [Patent Document 1] Patent No. 5701414 [Patent Document 2] Patent No. 5714193 [Patent Document 3] Patent No. 4020957 [Patent Document 4] Japanese Patent Application Laid-Open No. 2002-129014 [Patent Document 5] Japanese Patent Application Laid-Open No. 2005-306926 [Patent Document 6] Patent No. 6543965 [Patent Document 7] Japanese Patent Application Laid-Open No. 2007-204615 [Patent Document 8] Japanese Patent Application Laid-Open No. 2007-204616 [Patent Document 9] Japanese Patent Application Laid-Open No. 2008-144002 [Patent Document 10] Japanese Patent Application Laid-Open No. 2009-126884 [Patent Document 11] Japanese Patent Application Laid-Open No. 2009-143991 [Patent Document 12] Japanese Patent Application Laid-Open No. 2011-016942 [Patent Document 13] Japanese Patent Application Laid-Open No. 2010-070712 [Patent Document 14] Japanese Patent Application Laid-Open No. 2010-284899 [Patent Document 15] Patent No. 6132669 Summary of the Invention [Problem to be solved by the invention]

[0013] However, in the metal member-resin member composites obtained by the injection insert molding methods proposed in Patent Documents 1 to 3, the adhesion of the metal-resin joint surface is quantified in terms of joint strength to determine its superiority. However, even when the joint strength is excellent, the airtightness of the metal-resin joint surface is not necessarily excellent. Furthermore, no consideration has been given to warping, which may result in problems. In the resin compositions proposed in Patent Documents 4, 5, and 7 to 11, no consideration has been given to the joint strength or airtightness of the joint surface when the composite is formed with a metal member having a surface that has been subjected to physical and / or chemical treatment, which may result in problems. Furthermore, the resin composition proposed in Patent Document 6 has the problem that the airtightness and warping between the resin member and the metal member may not be fully satisfactory. Furthermore, in the resin composition proposed in Patent Document 9, a PPS having a specific melt viscosity and crystallization temperature is used, and an insert-molded composite member consisting of the resin composition and a metal member has excellent mold releasability, dimensional stability, and cold and heat resistance, but no consideration has been given to the melt viscosity and crystallization temperature of the resin composition that is actually bonded to the metal member in injection insert molding, resulting in a problem that the airtightness of the composite member may not be fully satisfied. Also, the resin compositions proposed in Patent Documents 6 and 12 have a problem that the bondability and warpage between the resin member and the metal member may not be fully satisfied.

[0014] Furthermore, although the resin compositions proposed in Patent Documents 13 and 14 have good bondability to metal members, no consideration has been given to warping when they are formed into a composite, which may result in problems. Also, the metal resin composite molded product proposed in Patent Document 15 has no consideration given to warping, which may result in problems.

[0015] Therefore, the present invention relates to a metal member-polyarylene sulfide member composite that has little warping and excellent airtightness of the bonding surface, and more specifically, an object of the present invention is to provide a metal member-polyarylene sulfide member composite that is particularly useful for use in parts for transportation equipment such as automobiles and aircraft, or for use in electrical and electronic parts for portable devices and the like that require waterproofing. [Means for solving the problem]

[0016] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that a metal member-polyarylene sulfide member composite consisting of a polyarylene sulfide member and a metal member, which is made of a resin composition consisting of at least polyarylene sulfide, a modified ethylene copolymer, an epoxy resin, glass fiber, and glass flakes in a specific blending ratio and which has a specific melt crystallization peak temperature and melt viscosity, has little warping and excellent airtightness of the joint surface, and have thereby completed the present invention.

[0017] That is, the present invention relates to a metal member-polyarylene sulfide member composite which is an injection-molded integral body of a metal member and a polyarylene sulfide member, characterized in that the polyarylene sulfide member is an injection-molded member of a polyarylene sulfide composition that satisfies all of the following (1) to (3): (1) Using a differential scanning calorimeter (DSC), the sample is heated from 23°C to 330°C, held there for 5 minutes, and then cooled to 150°C at a rate of 20°C / min. The peak temperature of the melt crystallization peak obtained is 200°C or higher and 230°C or lower. (2) The melt flow rate (MFR) measured at 315°C in accordance with ISO 1133 is 20 g / 10 min or more and 150 g / 10 min or less. (3): Per 100 parts by weight of polyarylene sulfide (A), 5 to 25 parts by weight of at least one modified ethylene copolymer (B) selected from the group consisting of ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer, and maleic anhydride-grafted modified ethylene-α-olefin copolymer, 1 to 15 parts by weight of epoxy resin (C), glass fiber (D), and glass flake (E), wherein the weight ratio of glass fiber (D) / glass flake (E) is 1 / 4 to 4 / 1, and the total amount of glass fiber (D) and glass flake (E) is 40 to 150 parts by weight per 100 parts by weight of polyarylene sulfide (A).

[0018] The present invention will be described in detail below.

[0019] The metal member-polyarylene sulfide member composite of the present invention is a metal member-polyarylene sulfide resin member composite obtained by directly integrating a metal member and a polyarylene sulfide member by injection molding.

[0020] The polyarylene sulfide composition constituting the polyarylene sulfide member has a melt crystallization peak temperature (hereinafter sometimes referred to as melt crystallization temperature or Tc2) of 200°C or higher and 230°C or lower when measured using a differential scanning calorimeter (hereinafter sometimes referred to as DSC) by heating from 23°C to 330°C, holding for 5 minutes, and then cooling to 150°C at a rate of 20°C / min. The peak temperature (hereinafter sometimes referred to as melt crystallization temperature or Tc2) is 200°C or higher and 230°C or lower, and the resulting metal member-polyarylene sulfide member composite has excellent airtightness. Here, if the polyarylene sulfide composition has a Tc2 of less than 200°C, the mold releasability in injection insert molding is significantly reduced, and the productivity of the metal member-polyarylene sulfide member composite is poor. On the other hand, if the Tc2 exceeds 230°C, the bonding between the metal member and the polyarylene sulfide member is poor, and the resulting metal member-polyarylene sulfide member composite has poor airtightness.

[0021] The metal member-polyarylene sulfide member composite of the present invention is a composite in which a metal member and a polyarylene sulfide member are firmly bonded by insert molding. A molten polyarylene sulfide composition is injected into a mold by injection molding, and the fine irregularities on the surface of the metal member are transferred within the mold, resulting in an anchoring effect. An important factor is that the irregularities on the metal surface are transferred reproducibly when the molten polyarylene sulfide composition solidifies. To achieve this, a polyarylene sulfide composition with an appropriate solidification rate enables excellent transferability. If the solidification rate is excessively fast, the resin composition solidifies before transferring the metal member surface, which can easily result in gaps called voids between the metal member surface and the resin member, resulting in poor airtightness. Furthermore, if the solidification rate is slow, the molding processability is poor, resulting in poor composite productivity. Therefore, if the Tc2 of the polyarylene sulfide member is less than 200°C, the solidification rate becomes excessively slow, significantly reducing releasability from the mold during composite production and resulting in poor productivity. On the other hand, if it exceeds 230°C, the solidification rate of the polyarylene sulfide composition becomes excessively fast, resulting in poor bonding between the metal member and the polyarylene sulfide member, and the resulting metal member-polyarylene sulfide member composite will have poor airtightness. Furthermore, since the Tc2 of the polyarylene sulfide member in the present invention is a unique Tc2 of 200°C or higher and 230°C or lower, which is lower than the Tc2 of general polyarylene sulfides, it is possible to control the solidification rate from the molten state, resulting in excellent productivity and airtightness.

[0022] Furthermore, the polyarylene sulfide member is made of a polyarylene sulfide composition having a melt flow rate (hereinafter sometimes referred to as MFR) of 20 g / 10 min or more and 150 g / 10 min or less, measured at 315 °C in accordance with ISO 1133. This results in the resulting metal member-polyarylene sulfide member composite having excellent airtightness at the joining surface. Here, if the polyarylene sulfide composition has a melt flow rate of less than 20 g / 10 min, the resin composition will have poor fluidity in the mold, making it difficult to efficiently transfer the metal member surface. This results in poor bonding between the metal member and the polyarylene sulfide member, and the resulting metal member-polyarylene sulfide member composite will have poor airtightness. On the other hand, if the melt flow rate exceeds 150 g / 10 min, drooling is likely to occur during injection insert molding, making molding difficult. The metal member-polyarylene sulfide member composite of the present invention has a specific fluidity in which the polyarylene sulfide member has an MFR of 20 g / 10 min or more and 150 g / 10 min or less, and therefore exhibits good processability during member molding and excellent airtightness.

[0023] In the present invention, airtightness refers to the airtightness of the joint surface between the metal member and the polyarylene sulfide member against, for example, water, water vapor, organic solvents; acetone, ethanol, dimethylformamide, tetrahydrofuran, ethyl acetate, ammonia, etc., various vehicle liquids; automatic transmission fluid, long-life coolant, battery fluid, engine oil, gasoline, diesel, gear oil, brake oil, silicone oil, etc., gases; helium, hydrogen, oxygen, nitrogen, air, carbon dioxide, ozone, methane, carbon monoxide, liquefied petroleum gas, hydrogen peroxide, hydrogen fluoride, etc., battery electrolyte, etc. The method for evaluating airtightness can be appropriately selected depending on the application and purpose, and an example of a helium leak test is the method proposed in JP 2020-68070 A.

[0024] The polyarylene sulfide member constituting the metal member-polyarylene sulfide member composite of the present invention comprises, with respect to 100 parts by weight of polyarylene sulfide (A), an ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, an ethylene-α,β-unsaturated carboxylic acid glycidyl ester 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 ... The composition contains 5 to 25 parts by weight of at least one modified ethylene copolymer (B) selected from the group consisting of an ethylene copolymer grafted with maleic anhydride and an ethylene-α-olefin copolymer grafted with maleic anhydride, 1 to 15 parts by weight of an epoxy resin (C), glass fibers (D) and glass flakes (E), wherein the weight ratio of the glass fibers (D) to the glass flakes (E) is 1 / 4 to 4 / 1, and the total amount of the glass fibers (D) and the glass flakes (E) is 40 to 150 parts by weight per 100 parts by weight of the polyarylene sulfide (A).

[0025] The polyarylene sulfide (A) may be any one that falls within the category generally referred to as polyarylene sulfide. Examples of the polyarylene sulfide (A) include homopolymers or copolymers composed of p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, and biphenylene sulfide units. Specific examples of the polyarylene sulfide (A) include poly(p-phenylene sulfide), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, and polyphenylene sulfide ether. Among these, poly(p-phenylene sulfide) is preferred because it provides a polyarylene sulfide member that is particularly excellent in heat resistance and strength properties.

[0026] Furthermore, the polyarylene sulfide (A) is preferably a polyarylene sulfide having a melt viscosity of 90 to 2000 poise as measured using a high-temperature flow tester 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, since this makes it possible to efficiently obtain a metal member-polyarylene sulfide member composite having excellent airtightness at the joining surface.

[0027] The polyarylene sulfide (A) can be produced by a method known for producing polyarylene sulfides, for example, by polymerizing an alkali metal sulfide salt and a polyhaloaromatic compound in a polar solvent. Examples of the polar organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexylpyrrolidone, dimethylformamide, and dimethylacetamide. Examples of the alkali metal sulfide salt include anhydrous or hydrated sodium sulfide, rubidium sulfide, and lithium sulfide. Examples of the alkali metal sulfide salt include a reaction between an alkali metal hydrosulfide salt and an alkali metal hydroxide. Examples of polyhaloaromatic compounds include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, and 4,4'-dichlorobiphenyl.

[0028] Examples of polyarylene sulfides include linear polyarylene sulfides, polyarylene sulfides having a slight crosslinking or branching structure introduced by adding a small amount of a trihalogen or higher polyhalogen compound during polymerization, polyarylene sulfides modified at a portion and / or at the end of the molecular chain 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, and polyarylene sulfides heat-treated in a non-oxidizing inert gas such as nitrogen. Mixtures of these polyarylene sulfides are also acceptable. The polyarylene sulfide (A) may be one in which impurities such as sodium atoms, oligomers of polyarylene sulfide resins, sodium chloride, or sodium salt of 4-(N-methyl-chlorophenylamino)butanoate have been reduced by acid washing, hot water washing, or washing with an organic solvent such as acetone or methyl alcohol.

[0029] The polyarylene sulfide member constituting the metal member-polyarylene sulfide member composite of the present invention, which enables efficient production of a metal member-polyarylene sulfide member composite with excellent airtightness at the bonding surface, contains 5 to 25 parts by weight of at least one modified ethylene copolymer (B) 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, per 100 parts by weight of polyarylene sulfide (A). Here, if the blending amount of the modified ethylene copolymer (B) is less than 5 parts by weight, the resulting metal member-polyarylene sulfide member composite will have poor airtightness at the bonding surface. On the other hand, if the blending amount exceeds 25 parts by weight, the resulting metal member-polyarylene sulfide member composite will have poor airtightness at the joint surface, and gas generation and mold contamination during injection insert molding will become significant, which is undesirable.

[0030] The polyarylene sulfide member constituting the metal member-polyarylene sulfide member composite of the present invention contains 1 to 15 parts by weight of epoxy resin (C) per 100 parts by weight of polyarylene sulfide (A), since this makes it possible to efficiently obtain a metal member-polyarylene sulfide member composite having excellent airtightness at the joining surface. As the epoxy resin (C), any resin may be used as long as it belongs to the category called epoxy resin. Specific examples include 2,2-bis(4'-hydroxyphenyl)propane (bisphenol A), bis(2-hydroxyphenyl)methane (bisphenol F), 4,4'-dihydroxydiphenyl sulfone (bisphenol S), 4,4'-dihydroxybiphenyl, resorcinol, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylolethane, halogen-substituted and alkyl-substituted derivatives thereof, butanediol, ethylene glycol, erythritol, novolak, glycerin, polyoxyalkylene, and compounds containing two or more hydroxyl groups in the molecule, such as those synthesized from epichlorohydrin. Examples of epoxy resins include glycidyl ether epoxy resins synthesized from compounds containing two or more hydroxyl groups in the molecule and glycidyl phthalate ester; glycidyl group-containing epoxy resins such as glycidylamine epoxy resins synthesized from primary or secondary amines such as aniline, diaminodiphenylmethane, metaxylenediamine, and 1,3-bisaminomethylcyclohexane and epichlorohydrin; and glycidyl group-free epoxy resins such as epoxidized soybean oil, epoxidized polyolefins, vinylcyclohexene dioxide, and dicyclopentadiene dioxide. Among these, bisphenol-type epoxy resins, such as glycidyl ether-type epoxy resins and glycidyl ester-type epoxy resins of bisphenols such as bisphenol A, bisphenol F, and bisphenol S, are preferred because they provide particularly excellent airtightness at the bonded surfaces of the resulting metal member-polyarylene sulfide member composite. Bisphenol A-type epoxy resins are even more preferred.If the amount of the epoxy resin (C) is less than 1 part by weight, the resulting metal member-polyarylene sulfide member composite will have poor airtightness at the joining surface, whereas if the amount is more than 15 parts by weight, drooling may occur during injection insert molding, making molding difficult, and gas generation and mold contamination during injection insert molding will be significant, which is undesirable.

[0031] The polyarylene sulfide member constituting the metal member-polyarylene sulfide member composite of the present invention contains 40 to 150 parts by weight of glass fiber (D) and glass flakes (E) in total relative to 100 parts by weight of polyarylene sulfide (A), since this allows for efficient production of a metal member-polyarylene sulfide member composite with little warpage and excellent mechanical strength. The blending ratio of glass fiber (D) to glass flakes (E) is 1 / 4 to 4 / 1 by weight. Any material generally known as glass fiber may be used as the glass fiber (D).

[0032] Specific examples of the glass fibers include chopped strands having an average fiber diameter of 6 to 14 μm, chopped strands made of flat glass fibers having an aspect ratio of 2 to 4 in the fiber cross section, milled fibers, glass fibers such as roving, silane fibers, aluminosilicate glass fibers, hollow glass fibers, and non-hollow glass fibers. Among these, chopped strands having an average fiber diameter of 6 to 14 μm or chopped strands made of flat glass fibers having an aspect ratio of 2 to 4 in the fiber cross section are preferred, as they result in a metal member-polyarylene sulfide member composite with fewer defects in the bonding surface and excellent impact resistance. Two or more of these glass fibers can be used in combination, and if necessary, they 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.

[0033] The glass flakes (E) are typically scaly glass flakes having an average thickness of 2 to 5 μm and an average particle size of 10 to 4000 μm, and are classified into C glass, which contains an alkali component, and E glass, which contains almost no alkali component. Among these, glass flakes having an average particle size of 100 to 1000 μm are preferred, as they significantly reduce warpage of the resulting metal member-polyarylene sulfide member composite.

[0034] Here, if the total amount of the glass fiber (D) and the glass flakes (E) is less than 40 parts by weight, or if the weight ratio of the glass fiber (D) to the glass flakes (E) is greater than 4 / 1, the resulting metal member-polyarylene sulfide member composite will exhibit significant warpage. On the other hand, if the total amount exceeds 150 parts by weight, or if the weight ratio of the glass fiber (D) to the glass flakes (E) is less than 1 / 4, the fluidity of the polyarylene sulfide composition will decrease, and the airtightness of the joint surface of the metal member-polyarylene sulfide member composite will decrease.

[0035] The polyarylene sulfide member may also contain a mold release agent (J) to improve mold releasability and appearance when molded into a molded product. Suitable examples of the mold release agent (J) include polyethylene wax, polypropylene wax, and fatty acid amide wax. Commonly available commercial products can be used as the polyethylene wax and polypropylene wax. The fatty acid amide wax is a polycondensate of a higher aliphatic monocarboxylic acid, a polybasic acid, and a diamine. Any wax 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.

[0036] Furthermore, the polyarylene sulfide member 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; and mineral fibers such as wollastonite and magnesium oxysulfate, within the range not impairing the effects of the present invention.Also, the polyarylene sulfide member may be added with calcium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, mica, silica, talc, clay, calcium sulfate, kaolin, wollastonite, zeolite, silicon oxide, magnesium oxide, zirconium oxide, tin oxide, magnesium silicate, calcium silicate, calcium phosphate, magnesium phosphate, hydrotalcite, glass powder, or glass balloons within the range not impairing the effects of the present invention.

[0037] Furthermore, the polyarylene sulfide material may contain one or more conventional additives such as plasticizers such as conventionally known polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds; antioxidants; heat stabilizers; lubricants; and foaming agents, within the scope of not impairing the effects of the present invention.

[0038] Furthermore, the polyarylene sulfide member may be made by mixing 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 present invention.

[0039] The metal member constituting the metal member-polyarylene sulfide member composite of the present invention 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 because they can be adapted to various uses when made into a composite with a polyarylene sulfide member, and aluminum members, aluminum alloy members, magnesium members, magnesium alloy members, titanium members, and titanium alloy members are particularly preferred, as they are excellent in terms of weight reduction, and aluminum members and aluminum alloy members are more preferred. Furthermore, the metal member may be a wrought material such as a plate, a cast material such as a die-cast, or a forged material.

[0040] Furthermore, the metal member is preferably a metal member whose surface has been physically and / or chemically treated. By subjecting the metal member to such physical and / or chemical treatment, when directly integrated with the polyarylene sulfide member, a metal member-polyarylene sulfide member composite with excellent airtightness, etc., can be obtained. Any method can be used to physically and / or chemically treat the surface of the metal member. Examples of physical treatments include contacting or impacting the surface with fine solid particles, or irradiating the surface with high-energy electromagnetic radiation. More specifically, examples of such methods include sandblasting, liquid honing, and laser processing. Examples of abrasives used in sandblasting and liquid honing include sand, steel grit, steel shot, cut wire, alumina, silicon carbide, metal slag, glass beads, and plastic beads. Examples of laser processing methods include those proposed in WO 2007 / 072603 and JP 2015-142960 A.

[0041] Examples of chemical treatments include anodizing and chemical treatments using an acid or alkaline aqueous solution. Anodizing may involve, for example, using a metal member as the anode to carry out an electrochemical reaction in an electrolyte to form an oxide film on the surface, and may be a method commonly known as anodizing in fields such as plating. More specific examples include 1) direct current electrolysis, in which electrolysis is carried out by applying a constant direct current voltage, and 2) bipolar electrolysis, in which electrolysis is carried out by applying a voltage in which an alternating current component is superimposed on a direct current component. Specific examples of anodizing include the method proposed in WO2004 / 055248. Furthermore, the method of chemically treating with an acid or alkali aqueous solution may be, for example, a method of immersing a metal member in an acid or alkali aqueous solution to chemically treat the surface of the metal member. Examples of the acid or alkali aqueous solution 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; alkaline aqueous solutions such as sodium hydroxide and ammonia aqueous solutions; triazine thiol aqueous solutions, triazine thiol derivative aqueous solutions, etc. Examples include methods of chemical treatment using a solution, and more specific examples include methods proposed in JP 2017-132243 A, JP 2019-188651 A, WO2008 / 133296 A, Japanese Patent No. 5622785, JP 10-096088 A, JP 10-056263 A, JP 04-032585 A, JP 04-032583 A, JP 02-298284 A, WO2009 / 151099 A, WO2011 / 104944 A, etc.

[0042] As a method for producing the metal member-polyarylene sulfide member composite of the present invention, any method can be used as long as it allows for direct integration of a metal member and a polyarylene sulfide member by injection molding. Among these, injection insert molding is preferred because it allows for particularly efficient production of the composite. An example of the injection insert molding method is a method in which a metal member is placed in a mold, a molten polyarylene sulfide composition is filled into the metal member to form a polyarylene sulfide member, and a composite in which the metal member and the polyarylene sulfide member are directly integrated is produced. The melting temperature of the polyarylene sulfide composition in this case can be 280 to 340°C. As a molding machine for performing the insert molding, an injection molding machine is preferred because it has particularly excellent productivity. Furthermore, the mold temperature during insert molding is preferably 130°C or higher, particularly 140 to 160°C, because it allows for efficient production of a metal member-polyarylene sulfide member composite with excellent airtightness. The mold pressure is preferably 1 MPa or more, and more preferably 30 MPa or more and 100 MPa or less.

[0043] The metal member-polyarylene sulfide member composite of the present invention has little warping, excellent airtightness, excellent airtightness reliability, and also has excellent properties such as impact resistance, light weight, and ease of mass production, and is particularly suitable for use in parts for transportation equipment such as automobiles and aircraft, which require these properties and reliability, or for use in electrical and electronic parts for portable devices and the like, which require waterproofing. [Effects of the Invention]

[0044] According to the present invention, it is possible to provide a highly reliable metal member-polyarylene sulfide member composite and a method for producing the same, which have little warping, excellent airtightness at the bonding surface, and further excellent impact resistance, light weight, and mass producibility, and are particularly useful for use in parts for transportation equipment such as automobiles and aircraft, or in electrical and electronic parts for portable devices that require waterproofing, and which have extremely high industrial value. [Brief explanation of the drawings]

[0045] [Figure 1] Schematic diagram of a container used in the examples for evaluating airtightness. [Figure 2] ;Schematic diagram of the lid material for airtightness evaluation. [Figure 3] ;Schematic diagram of metal components for airtightness evaluation [Figure 4] ;Metal component-polyarylene sulfide resin component composite for airtightness evaluation [Example]

[0046] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples.

[0047] The polyarylene sulfide (A), modified ethylene copolymer (B), epoxy resin (C), glass fiber (D), glass flake (E), talc (F), glass beads (G), mica (H), calcium carbonate (I), and mold release agent (J) used in the examples and comparative examples are shown below.

[0048] <Polyarylene sulfide (A)> Poly(p-phenylene sulfide) (hereinafter referred to as PPS (A-1)): melt viscosity 380 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS (A-2)): melt viscosity 790 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS (A-3)): melt viscosity 370 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS (A-4)): melt viscosity 80 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS (A-5)): melt viscosity 1280 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS (A-6)): melt viscosity 2500 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS (A-7)): melt viscosity 560 poise.

[0049] <Modified ethylene copolymer (B)> Ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B-1) (hereinafter simply referred to as ethylene polymer (B-1)): SK global chemical Co., Ltd., (trade name) Bondine AX8390, ethylene residue unit: α,β-unsaturated carboxylic acid alkyl ester residue unit: maleic anhydride residue unit (weight ratio) = 69.7:29:1.3. Ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer (B-2) (hereinafter simply referred to as ethylene polymer (B-2)): SK global chemical Co., Ltd., (trade name) LOTADER AX8700, ethylene residue unit:α,β-unsaturated carboxylic acid glycidyl ester residue unit:α,β-unsaturated carboxylic acid alkyl ester residue unit (weight ratio)=67:8:25.

[0050] <Epoxy resin (C)> Epoxy resin (C-1): Mitsubishi Chemical Corporation, (trade name) 1004.

[0051] <Glass fiber (D)> Glass fiber (D-1): manufactured by Nippon Electric Glass Co., Ltd., (product name) T-760H; fiber diameter 10 μm, fiber length 3 mm. Glass fiber (D-2): Chopped strand manufactured by Nittobo Co., Ltd., (product name) CSG-3PA 830, aspect ratio of fiber cross section: 4.

[0052] <Glass Flakes (E)> Glass flakes (E-1): Nippon Sheet Glass Co., Ltd., (trade name) REFG-301; average particle size 160 μm. Glass flakes (E-2): Nippon Sheet Glass Co., Ltd., (trade name) REFG-112; average particle size 600 μm.

[0053] <Talc (F)> Talc (F-1): manufactured by Hayashi Kasei Co., Ltd., (trade name) Talc Powder PK-C; average particle size 12 μm.

[0054] <Glass beads (G)> Glass beads (G-1); Potters Barotini Co., Ltd. (product name) EGB731; average particle size 20 μm.

[0055] <Mica (H)> Mica (H-1): Yamaguchi Mica Co., Ltd., (trade name) B-112; average particle size 510 μm.

[0056] <Calcium carbonate (I)> Calcium carbonate (I-1): Shiraishi Kogyo Co., Ltd., (trade name) Whiten P-30; average particle size 6 μm.

[0057] <Release agent (J)> Release agent (J-1): Kyoeisha Chemical Co., Ltd. (trade name) Light Amide WH-255.

[0058] <Synthesis Example 1 (Synthesis of PPS (A-1))> A 50-liter autoclave equipped with a stirrer was charged with 6214 g of flake sodium sulfide (NaS·2.9H2O), 164 g of 30% caustic soda solution (30% NaOH aq), and 17,000 g of N-methyl-2-pyrrolidone. The mixture was gradually heated to 200°C while stirring under a nitrogen stream, and 1,355 g of water was distilled off. After cooling to 190°C, 6,800 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 1 hour. The temperature was then raised to 250°C over 25 minutes and polymerized at 250°C for 2 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 then hot water was added again in the same manner, raising the temperature to 175°C, and the poly(p-phenylene sulfide) was washed twice in total. The resulting poly(p-phenylene sulfide) was dried at 105°C for 24 hours. The dried polyphenylene sulfide was then loaded into a batch rotary kiln-type calciner, heated to 240°C in a nitrogen atmosphere, and held there for 4 hours to obtain PPS (A-1) with a melt viscosity of 380 poise.

[0059] <Synthesis Example 2 (Synthesis of PPS (A-2))> A 50-liter autoclave equipped with a stirrer was charged with 6214 g of flake sodium sulfide (NaS·2.9H2O), 164 g of 30% caustic soda solution (30% NaOH aq), and 17,000 g of N-methyl-2-pyrrolidone. The mixture was gradually heated to 200°C while stirring under a nitrogen stream, and 1,355 g of water was distilled off. After cooling to 190°C, 6,890 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 1 hour. The temperature was then raised to 250°C over 25 minutes and polymerized at 250°C for 2 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 then hot water was added again in the same manner, raising the temperature to 175°C, and the poly(p-phenylene sulfide) was washed twice in total. The resulting poly(p-phenylene sulfide) was dried at 105°C for 24 hours. The dried polyphenylene sulfide was then loaded into a batch rotary kiln-type calciner, heated to 240°C in a nitrogen atmosphere, and held for 5 hours to obtain PPS (A-2) with a melt viscosity of 790 poise.

[0060] <Synthesis Example 3 (Synthesis of PPS (A-3))> A 50-liter autoclave equipped with a stirrer was charged with 6214 g of flake sodium sulfide (NaS·2.9H2O), 164 g of granular 30% caustic soda solution (30% NaOH aq), and 17,000 g of N-methyl-2-pyrrolidone. The mixture was gradually heated to 200°C while stirring under a nitrogen stream, and 1,346 g of water was distilled off. After cooling to 190°C, 6,900 g of p-dichlorobenzene, 12 g of 3,5-dichloroaniline, and 5,000 g of N-methyl-2-pyrrolidone were added and sealed under a nitrogen stream. The mixture 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 further polymerized at 250°C for 5 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 by adding 80°C hot water to a slurry concentration of 20%, and hot water was added again in the same manner, raising the temperature to 175°C, and the poly(p-phenylene sulfide) was washed twice in total. The resulting polyphenylene sulfide was dried at 105°C for one day. The dried polyphenylene sulfide was then loaded into a batch-type rotary kiln-type calciner, heated to 240°C in a nitrogen atmosphere, and held for 4 hours to perform a heat treatment, yielding PPS (A-3) with a melt viscosity of 370 poise.

[0061] <Synthesis Example 4 (Synthesis of PPS (A-4))> A 50-liter autoclave equipped with a stirrer was charged with 6214 g of flake sodium sulfide (NaS·2.9H2O), 164 g of 30% caustic soda solution (30% NaOH aq), and 17,000 g of N-methyl-2-pyrrolidone. The mixture was gradually heated to 200°C with stirring under a nitrogen stream, and 1,362 g of water was distilled off. After cooling to 190°C, 6,747 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 1 hour, then heated to 250°C over 25 minutes and polymerized at 250°C for 2 hours. After polymerization, N-methyl-2-pyrrolidone was recovered from the polymerization slurry by distillation under reduced pressure. The final temperature reached 170°C and the pressure reached 4.7 kPa. The resulting cake was washed with 80°C hot water to a slurry concentration of 20%, and then similarly washed with hot water again, raising the temperature to 175°C to obtain poly(p-phenylene sulfide). The resulting poly(p-phenylene sulfide) was dried overnight at 105°C. The dried polyphenylene sulfide was then loaded into a batch-type rotary kiln-type calciner, heated to 240°C under a nitrogen atmosphere, and held there for 1 hour to obtain PPS (A-4) with a melt viscosity of 80 poise.

[0062] <Synthesis Example 5 (Synthesis of PPS (A-5))> A 50-liter autoclave equipped with a stirrer was charged with 6214 g of flake sodium sulfide (NaS·2.9H2O), 164 g of 30% caustic soda solution (30% NaOH aq), and 17,000 g of N-methyl-2-pyrrolidone. The mixture was gradually heated to 205°C while stirring under a nitrogen stream, and 1,365 g of water was distilled off. After cooling to 190°C, 6,871 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. The temperature was then raised to 250°C over 30 minutes and polymerized at 250°C for 2 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 by adding 80°C hot water to a slurry concentration of 20%, and hot water was added again in the same manner, raising the temperature to 175°C to wash the poly(p-phenylene sulfide). The resulting poly(p-phenylene sulfide) was dried overnight at 105°C. The dried polyphenylene sulfide was then loaded into a batch rotary kiln-type calciner, heated to 240°C in an air atmosphere, and held for 2 hours to perform a heat treatment, yielding PPS (A-5) with a melt viscosity of 1280 poise.

[0063] <Synthesis Example 6 (Synthesis of PPS (A-6))> A 50-liter autoclave equipped with a stirrer was charged with 6865 g of flake sodium sulfide (NaS·2.9H2O), 164 g of 30% caustic soda solution (30% NaOH aq), and 17,000 g of N-methyl-2-pyrrolidone. The mixture was gradually heated to 205°C while stirring under a nitrogen stream, and 1,365 g of water was distilled off. After cooling to 190°C, 7,192 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 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 by adding 80°C hot water to a slurry concentration of 20%, and hot water was added again in the same manner, raising the temperature to 175°C to wash the poly(p-phenylene sulfide). The resulting poly(p-phenylene sulfide) was dried overnight at 105°C. The dried polyphenylene sulfide was then loaded into a batch rotary kiln-type calciner, heated to 240°C in an air atmosphere, and held for 5 hours to perform a heat treatment, yielding PPS (A-6) with a melt viscosity of 2500 poise.

[0064] <Synthesis Example 7 (Synthesis of PPS (A-7))> The resulting cake was washed with 80°C warm water to a slurry concentration of 20%, then washed with a 1% aqueous hydrochloric acid solution, and again with warm water added in the same manner to raise the temperature to 175°C to wash the poly(p-phenylene sulfide), thereby obtaining PPS-7 in the same manner as in Synthesis Example 2. The melt viscosity of PPS (A-7) was 560 poise.

[0065] The evaluation and measurement methods for the obtained polyarylene sulfide and metal member-polyarylene sulfide member composite are shown below.

[0066] ~Melt viscosity measurement of polyarylene sulfide~ 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.

[0067] ~MFR measurement~ In accordance with ISO 1133, the MFR was measured under the conditions of a measurement temperature of 315°C, a load of 5 kg, and an inner diameter of the die of 2 mm.

[0068] ~Crystallization temperature measurement~ Using a DSC, the temperature was raised from 23°C to 330°C, held for 5 minutes, and then cooled to 150°C at a rate of 20°C / min. The peak temperature of the melt crystallization peak (melt crystallization temperature: T C 2) was measured.

[0069] ~Evaluation of adhesion to metal components and warpage~ A metal plate (127 mm x 12.7 mm x 0.5 mm thick) having a surface that had been subjected to physical and / or chemical treatment was placed in the mold of an injection molding machine with the mold temperature set to 140°C, and the polyarylene sulfide composition was poured into the hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name SE75S) heated to 300°C, and injection insert molding was carried out to obtain a metal member-polyarylene sulfide member composite measuring 127 mm x 12.7 mm x 3.2 mm thick (composite length to composite thickness ratio: 40, composite length to composite thickness ratio: 4).

[0070] The interface of the metal member-polyarylene sulfide member composite was visually inspected 24 hours after molding. ○: No delamination was observed at the interface of the metal member-polyarylene sulfide member composite. ×: Peeling was observed at the interface of the metal member-polyarylene sulfide member composite.

[0071] Furthermore, the amount of deflection occurring on the long side of the metal member-polyarylene sulfide member composite 24 hours after molding was evaluated as the amount of warpage.

[0072] ~Airtightness testing and airtightness evaluation~ Distilled water was placed in an open-top aluminum container, and the container was welded and sealed to a lid, which was a metal member-polyarylene sulfide member composite shown in Figure 4, to produce an airtightness evaluation container as shown in Figure 1. The airtightness evaluation container was subjected to a thermal cycle in which it was held at 150°C for 30 minutes, cooled to -40°C, held for 30 minutes, and then heated again to 150°C. After 2000 cycles, it was held at room temperature, and the interfaces between the metal plate and metal lid and the polyarylene sulfide member were immersed in the test liquid. The pressure inside the container was increased to 0.5 MPa and held for 1 minute to evaluate the sealing property. ◯: When no bubbles were generated from the interface immersed in the test liquid, it was determined that the airtightness was excellent. ×: When bubbles were generated from the interface immersed in the test liquid, it was judged that the airtightness was poor.

[0073] Example 1 An aluminum alloy (A5052) plate (50 mm × 10 mm × 1 mm thick) having the shape shown in Figure 3, and an aluminum alloy (A5052) lid and aluminum alloy (A5052) plate (127 mm × 12.7 mm × 0.5 mm thick) having the shape shown in Figure 2 were immersed in a degreasing tank containing an aqueous solution (liquid temperature 60°C) containing 7.5% aluminum degreasing agent for 5 minutes, and then rinsed with ion-exchanged water. Next, they were immersed in a tank containing an aqueous solution (liquid temperature 40°C) containing 1.5% caustic soda for 1 minute, rinsed with ion-exchanged water, and further immersed in a tank containing a 3% nitric acid aqueous solution (liquid temperature 40°C) for 1 minute, and then rinsed with ion-exchanged water. Next, the aluminum alloy (A5052) plate and aluminum alloy (A5052) lid material with roughened surfaces were obtained by immersing the aluminum alloy (A5052) plate and aluminum alloy (A5052) lid material in a tank containing an aqueous solution (liquid temperature: 60°C) containing 3.5% hydrazine hydrate for 1 minute, rinsing with ion-exchanged water, and then immersing the aluminum alloy (A5052) plate and aluminum alloy (A5052) lid material in a tank containing an aqueous solution (liquid temperature: 33°C) containing 0.5% hydrazine hydrate for 3 minutes, rinsing with ion-exchanged water, and then drying in a hot air dryer.

[0074] 100 parts by weight of the PPS (A-1) obtained in Synthesis Example 1, 10 parts by weight of an ethylene copolymer (B-2), 1 part by weight of an epoxy resin (C-1), and 50 parts by weight of glass flakes (E-1) were mixed uniformly in advance and charged into the hopper of a twin-screw extruder (manufactured by The Japan Steel Works, Ltd., (product name) TEX25αIII) heated to a cylinder temperature of 300°C. Meanwhile, glass fiber (D-1) was charged into the hopper of the side feeder of the twin-screw extruder so that it was 50 parts by weight per 100 parts by weight of the PPS (A-1), and melt-kneaded and pelletized to produce a poly(p-phenylene sulfide) composition. The MFR and Tc2 of the resulting poly(p-phenylene sulfide) resin composition were then measured.

[0075] The resulting aluminum alloy (A5052) plate and aluminum alloy (A5052) lid were placed in a mold, and a poly(p-phenylene sulfide) composition was injection molded using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name: SE75S) set at a cylinder temperature of 310°C, a mold temperature of 145°C, and a mold holding pressure of 50 MPa. Insert molding was performed to produce the shape shown in Figure 4, resulting in a lid that was an aluminum alloy (A5052) member-polyarylene sulfide member composite. Next, evaluation of the metal bondability and warpage of the aluminum alloy (A5052) member-PPS composition member composite revealed good metal bondability and no warpage. Evaluation of the airtightness of the aluminum alloy (A5052) member-PPS composition member composite revealed no bubbles and excellent airtightness.

[0076] Example 2 An aluminum die-cast alloy (ADC12) plate (50 mm × 10 mm × 1 mm thick) with the shape shown in Figure 3 and an aluminum die-cast alloy (ADC12) lid with the shape shown in Figure 2 were immersed in a degreasing tank containing a 7.5% aluminum degreaser (liquid temperature 60°C) for 5 minutes, then rinsed with ion-exchanged water. Next, they were immersed in a tank containing a 1.5% caustic soda solution (liquid temperature 40°C) for 1 minute, rinsed with ion-exchanged water, and further immersed in a tank containing a 5% hydrochloric acid and 1% aluminum chloride hydrate solution (liquid temperature 40°C) for 4 minutes, then rinsed with ion-exchanged water. Next, the aluminum die-cast alloy (ADC12) plate and aluminum die-cast alloy (ADC12) lid were obtained by immersing the aluminum die-cast alloy (ADC12) plate and aluminum die-cast alloy (ADC12) lid in a tank containing 2% ammonium hydrogen difluoride and 10% sulfuric acid (liquid temperature 40 ° C) for 1 minute, rinsing with ion-exchanged water, immersing the aluminum die-cast alloy (ADC12) plate and aluminum die-cast alloy (ADC12) lid in a tank containing 1.5% caustic soda (liquid temperature 40 ° C) for 4 minutes, rinsing with ion-exchanged water, immersing the aluminum die-cast alloy (ADC12) plate and aluminum die-cast alloy (ADC12) lid in a tank containing 3.5% hydrazine hydrate (liquid temperature 60 ° C) for 1 minute, rinsing with ion-exchanged water, immersing the aluminum die-cast alloy (ADC12) plate and aluminum die-cast alloy (ADC12) lid in a tank containing 0.5% hydrazine hydrate (liquid temperature 33 ° C) for 1 minute, rinsing with ion-exchanged water, and drying in a hot air dryer.

[0077] 100 parts by weight of the PPS (A-2) obtained in Synthesis Example 2, 10 parts by weight of an ethylene copolymer (B-1), 4 parts by weight of an epoxy resin (C-1), and 45 parts by weight of glass flakes (E-1) were uniformly mixed in advance and charged into the hopper of a twin-screw extruder (manufactured by The Japan Steel Works, Ltd., (product name) TEX25αIII) heated to a cylinder temperature of 310°C. Meanwhile, glass fiber (D-2) was charged from the hopper of the side feeder of the twin-screw extruder so that it was 55 parts by weight per 100 parts by weight of the PPS (A-2), and melt-kneaded and pelletized to produce a poly(p-phenylene sulfide) composition. The MFR and Tc2 of the resulting poly(p-phenylene sulfide) composition were then measured.

[0078] The resulting aluminum die-cast alloy (ADC12) plate and aluminum die-cast alloy (ADC12) lid were placed in a mold, and a poly(p-phenylene sulfide) composition was injection molded using an injection molding machine (Sumitomo Heavy Industries, Ltd., product name: SE75S) set at a cylinder temperature of 310°C, a mold temperature of 150°C, and a mold pressure of 60 MPa. Insert molding was performed to produce the shape shown in Figure 4, resulting in a lid that was an aluminum die-cast alloy (ADC12) member-polyarylene sulfide member composite. Next, evaluation of the metal bondability and warpage of the aluminum die-cast alloy (ADC12) member-PPS composition composite revealed good metal bondability and no warpage. Furthermore, evaluation of the airtightness of the aluminum die-cast alloy (ADC12) member-PPS composition composite revealed no bubbles and excellent airtightness.

[0079] Example 3 A stainless steel (SUS304) plate (50 mm × 10 mm × 1 mm thick) with the shape shown in Figure 3 and a stainless steel (SUS304) lid with the shape shown in Figure 2 were immersed for 5 minutes in a degreasing tank containing a 7.5% aluminum degreaser (liquid temperature: 60°C) and then rinsed with ion-exchanged water. Next, the plates were immersed for 13 minutes in a tank containing a mixture (53°C) of 35% hydrochloric acid, 38% ferric chloride, manganese chloride tetrahydrate, 40% 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, and ion-exchanged water in a weight ratio of 11:48:1:0.05:39.95. After rinsing with ion-exchanged water, the plates and lids were dried in a hot air dryer to obtain surface-roughened stainless steel (SUS304) plates and lids.

[0080] 100 parts by weight of the PPS (A-3) obtained in Synthesis Example 3, 10 parts by weight of an ethylene copolymer (B-1), 3 parts by weight of an epoxy resin (C-1), and 45 parts by weight of glass flakes (E-1) were uniformly mixed in advance and charged into the hopper of a twin-screw extruder (manufactured by The Japan Steel Works, Ltd., (trade name) TEX25αIII) heated to a cylinder temperature of 300 ° C. Meanwhile, glass fiber (D-1) was charged from the hopper of the side feeder of the twin-screw extruder so that it was 55 parts by weight per 100 parts by weight of the PPS (A-3), and melt-kneaded and pelletized to produce a poly(p-phenylene sulfide) composition. The MFR and Tc2 of the resulting poly(p-phenylene sulfide) composition were then measured.

[0081] The resulting stainless steel (SUS304) plate and stainless steel (SUS304) lid were placed in a mold, and a poly(p-phenylene sulfide) resin composition was injection molded using an injection molding machine (Sumitomo Heavy Industries, Ltd., product name: SE75S) set at a cylinder temperature of 300°C, a mold temperature of 145°C, and a mold pressure of 50 MPa. Insert molding was performed to produce the shape shown in Figure 4, resulting in a lid that was a stainless steel (SUS304) member-polyarylene sulfide member composite. Next, evaluation of the metal bondability and warpage of the stainless steel (SUS304) member-PPS composition composite revealed good metal bondability and no warpage. Evaluation of the airtightness of the stainless steel (SUS304) member-PPS composition composite revealed no bubbles and excellent airtightness.

[0082] Example 4 Copper (C1100) plate material (50 mm x 10 mm x 1 mm thick) having the shape shown in Figure 3 and copper (C1100) plate material having the shape shown in Figure 2 were irradiated with laser light using a fiber laser (manufactured by Keyence Corporation, product name MD-F3200) as the laser oscillator under conditions of output power of 24 W, wavelength of 1090 nm, pulse frequency of 60 kHz, laser irradiation speed of 2000 mm / sec, and line spacing of 0.05 mm, to obtain surface-roughened copper (C1100) plate material and copper (C1100) lid material.

[0083] 100 parts by weight of the PPS (A-1) obtained in Synthesis Example 1, 20 parts by weight of an ethylene copolymer (B-1), 6 parts by weight of an epoxy resin (C-1), and 40 parts by weight of glass flakes (E-2) were uniformly mixed in advance and charged into the hopper of a twin-screw extruder (manufactured by The Japan Steel Works, Ltd., (product name) TEX25αIII) heated to a cylinder temperature of 300 ° C. Meanwhile, glass fiber (D-1) was charged from the hopper of the side feeder of the twin-screw extruder so that it was 60 parts by weight per 100 parts by weight of the PPS (A-1), and melt-kneaded and pelletized to produce a poly(p-phenylene sulfide) composition. The MFR and Tc2 of the resulting poly(p-phenylene sulfide) composition were then measured.

[0084] A poly(p-phenylene sulfide) composition was prepared by melt-kneading and pelletizing.

[0085] The obtained copper (C1100) plate and copper (C1100) lid were placed in a mold, and a poly(p-phenylene sulfide) resin composition was injection molded using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name: SE75S) set at a cylinder temperature of 300°C, a mold temperature of 145°C, and a mold holding pressure of 55 MPa. Insert molding was performed into the shape shown in Figure 4 to produce a lid, which was a copper (C1100) member-polyarylene sulfide member composite. Next, evaluation of the metal bonding and warpage of the copper (C1100) member-PPS composition member composite revealed good metal bonding and no warpage. Evaluation of the airtightness of the copper (C1100) member-PPS composition member composite revealed no bubbles and excellent airtightness.

[0086] Example 5 A copper (C1100) plate (50 mm × 10 mm × 1 mm thick) having the shape shown in FIG. 3 and a copper (C1100) lid having the shape shown in FIG. 2 were immersed in a degreasing tank containing a 7.5% aluminum degreaser (liquid temperature: 60°C) for 5 minutes, then rinsed with ion-exchanged water. Next, they were immersed in a tank containing a 1.5% caustic soda solution (liquid temperature: 40°C) for 1 minute, then rinsed with ion-exchanged water. Next, they were immersed in a tank containing a 10% nitric acid solution (liquid temperature: 40°C) for 1 minute, then rinsed with ion-exchanged water, and further immersed in a tank containing a 3% nitric acid solution (liquid temperature: 40°C) for 10 minutes, then rinsed with ion-exchanged water. Next, the copper (C1100) plate and copper (C1100) lid were obtained by drying in a hot air dryer after immersing them in a tank containing an aqueous solution (liquid temperature 70°C) containing 2% potassium permanganate and 3% potassium hydroxide for 35 minutes, rinsing them with ion-exchanged water, and further immersing them in a tank containing an aqueous solution (liquid temperature 55°C) containing 5% sodium chlorite and 10% sodium hydroxide for 10 minutes, rinsing them with ion-exchanged water, and then drying them in a hot air dryer to obtain copper (C1100) plate and copper (C1100) lid with roughened surfaces.

[0087] 100 parts by weight of the PPS (A-3) obtained in Synthesis Example 3, 15 parts by weight of the ethylene copolymer (B-2), 1 part by weight of the epoxy resin (C-1), and 60 parts by weight of the glass flakes (E-1) were uniformly mixed in advance and charged into the hopper of a twin-screw extruder (manufactured by The Japan Steel Works, Ltd., (product name) TEX25αIII) heated to a cylinder temperature of 300 ° C. Meanwhile, glass fiber (D-2) was charged from the hopper of the side feeder of the twin-screw extruder so that it was 40 parts by weight per 100 parts by weight of the PPS (A-3), and melt-kneaded and pelletized to produce a poly(p-phenylene sulfide) composition. The MFR and Tc2 of the resulting poly(p-phenylene sulfide) composition were then measured.

[0088] The obtained copper (C1100) plate and copper (C1100) lid were placed in a mold, and a poly(p-phenylene sulfide) composition was injection molded using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name: SE75S) set at a cylinder temperature of 300°C, a mold temperature of 150°C, and a mold holding pressure of 60 MPa. Insert molding was performed into the shape shown in Figure 4 to produce a lid, which was a copper (C1100) member-polyarylene sulfide member composite. Next, evaluation of the metal bondability and warpage of the copper (C1100) member-PPS composition composite revealed good metal bondability and no warpage. Evaluation of the airtightness of the copper (C1100) member-PPS composition composite revealed no bubbles and excellent airtightness.

[0089] Examples 6 to 10 A pellet-shaped polyarylene sulfide composition was prepared in the same manner as in Example 1, with the blending ratios of the polyarylene sulfide resin (A), ethylene copolymer (B), epoxy resin (C), glass fiber (D), and glass flake (E) set as shown in Table 1. The MFR and Tc2 of the obtained poly(p-phenylene sulfide) composition were measured.

[0090] The surface-roughened aluminum alloy (A5052) plate obtained by the same method as in Example 1 and an aluminum alloy (A5052) lid were set in a mold, and insert molding was performed by the same method as in Example 1 under the injection molding conditions shown in Table 1 to produce a lid that was an aluminum alloy (A5052) member-polyarylene sulfide member composite. Next, the metal bondability and warpage of the aluminum alloy (A5052) member-PPS composition member composite were evaluated, and the metal bondability was good and no warpage was observed. Furthermore, the airtightness of the aluminum alloy (A5052) member-PPS composition member composite was evaluated, and no air bubbles were observed, indicating excellent airtightness.

[0091] [Table 1]

[0092] Comparative Examples 1 to 6 A pellet-shaped polyarylene sulfide composition was prepared in the same manner as in Example 1, with the blending ratios of the polyarylene sulfide resin (A), ethylene copolymer (B), epoxy resin (C), glass fiber (D), and glass flake (E) set as shown in Table 1. The MFR and Tc2 of the obtained poly(p-phenylene sulfide) composition were measured.

[0093] The surface-roughened aluminum alloy (A5052) plate material obtained by the same method as in Example 1 and the aluminum alloy (A5052) lid material were set in a mold, and insert molding was performed by the same method as in Example 1 under the injection molding conditions shown in Table 1 to produce a lid material that was an aluminum alloy (A5052) member-polyarylene sulfide member composite.

[0094] The aluminum alloy (A5052) component-polyarylene sulfide component composites obtained in Comparative Examples 1, 2, 3, and 5 had poor metal bonding and airtightness, and the aluminum alloy (A5052) component-polyarylene sulfide component composites obtained in Comparative Examples 4 and 6 had large amounts of warping.

[0095] Comparative Example 7 A pellet-shaped polyarylene sulfide composition was prepared in the same manner as in Example 1, with the blending ratios of the polyarylene sulfide resin (A), ethylene copolymer (B), epoxy resin (C), glass fiber (D), and glass flake (E) set as shown in Table 2. The MFR and Tc2 of the obtained poly(p-phenylene sulfide) composition were measured.

[0096] The surface-roughened aluminum alloy (A5052) plate material obtained by the same method as in Example 1 and the aluminum alloy (A5052) lid material were set in a mold, and insert molding was performed by the same method as in Example 1 under the injection molding conditions shown in Table 2. However, severe drooling made molding difficult, and it was not possible to obtain an aluminum alloy (A5052) member-PPS composition member composite.

[0097] Comparative Examples 8 to 16 A pellet-shaped polyarylene sulfide composition was prepared in the same manner as in Example 1, with the blending ratios of polyarylene sulfide resin (A), ethylene copolymer (B), epoxy resin (C), glass fiber (D), glass flake (E), talc (F), glass beads (G), mica (H), and calcium carbonate (I) set as shown in Table 2 or Table 3. The MFR and Tc2 of the obtained poly(p-phenylene sulfide) composition were then measured.

[0098] The surface-roughened copper (C1100) plate material and copper (C1100) lid material obtained by a method similar to that of Example 5 were set in a mold, and insert molding was performed by a method similar to that of Example 5, using the injection molding conditions shown in Table 2 or 3, to produce a lid material that was a copper (C1100) member-polyarylene sulfide member composite.

[0099] The copper (C1100) member-polyarylene sulfide member composites obtained in Comparative Examples 8 to 10 and 15 were inferior in metal bonding property and airtightness, and the copper (C1100) member-polyarylene sulfide member composites obtained in Comparative Examples 11 to 15 had a large amount of warpage. Furthermore, in Comparative Example 16, severe drooling occurred, making molding difficult, and a copper (C1100) member-PPS composition member composite could not be obtained.

[0100] [Table 2]

[0101] [Table 3] [Industrial Applicability]

[0102] The present invention provides a metal member-polyarylene sulfide member composite that exhibits minimal warping and excellent airtightness at the bonding surface, and is particularly useful for use in parts for transportation equipment such as automobiles and aircraft, or for electrical and electronic parts such as portable devices that require waterproofing. [Explanation of symbols]

[0103] 1; Metal plate material. 2; Metal plate material. 3;Metal lid material. 4;PPS material.

Claims

1. A metal member-polyarylene sulfide member composite which is an injection-molded integral body of a metal member and a polyarylene sulfide member, characterized in that the polyarylene sulfide member is an injection-molded member of a polyarylene sulfide composition which satisfies all of the following (1) to (3): (1): When a differential scanning calorimeter (DSC) is used, the temperature is raised from 23°C to 330°C, held for 5 minutes, and then cooled to 150°C at a rate of 20°C / min. The peak temperature of the melt crystallization peak obtained when the temperature is raised from 23°C to 330°C, held for 5 minutes, and then cooled to 150°C at a rate of 20°C / min is 200°C or higher and 230°C or lower. (2) The melt flow rate (MFR) measured at 315°C in accordance with ISO 1133 is 20 g / 10 min or more and 150 g / 10 min or less. (3): Per 100 parts by weight of polyarylene sulfide (A), 5 to 25 parts by weight of at least one modified ethylene copolymer (B) selected from the group consisting of ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer, and maleic anhydride-grafted modified ethylene-α-olefin copolymer; 1 to 15 parts by weight of epoxy resin (C); glass fiber (D); and glass flake (E), wherein the weight ratio of glass fiber (D) / glass flake (E) is 1 / 4 to 4 / 1, and the total amount of glass fiber (D) and glass flake (E) is 40 to 150 parts by weight per 100 parts by weight of polyarylene sulfide (A).

2. The metal member-polyarylene sulfide member composite according to claim 1, characterized in that the polyarylene sulfide composition further contains at least one release agent (J) selected from the group consisting of polyethylene wax, polypropylene wax, and fatty acid amide wax per 100 parts by weight of the polyarylene sulfide (A).

3. 3. The metal member-polyarylene sulfide member composite according to claim 1, wherein the metal member has a surface that has been subjected to a chemical or physical treatment.

4. 4. A method for producing a metal member-polyarylene sulfide member composite, in which a metal member and a polyarylene sulfide member are directly integrated by injection molding, characterized in that the metal member is placed in a mold having a mold temperature of 130°C or higher, the mold holding pressure is set to 1 MPa or higher, and a molten polyarylene sulfide composition is injected and filled into the mold to form an injection insert composite in which the metal member and the polyarylene sulfide member are directly integrated.

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