Metal member-polyarylene sulfide resin member composite and manufacturing method thereof

Abstract

To provide a metal member-polyarylene sulfide resin member complex that has excellent air-tightness between a metal member and a polyarylene sulfide resin member, and a production method therefor.SOLUTION: A metal member-polyarylene sulfide resin member complex is an integrally injection molded product of a metal member and a polyarylene sulfide member. The polyarylene sulfide member is formed of 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) 100 pts.wt. of polyarylene sulfide (A), 5-25 pts.wt. of a modified ethylene-based copolymer (B), and 10-120 pts.wt. of glass fibers (C) are contained with respect to 100 pts.wt. of a polyarylene sulfide resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a metal member-polyarylene sulfide resin member composite having excellent airtightness at the joining surface, and a method for producing the same. More specifically, the present invention relates to a metal member-polyarylene sulfide resin member composite having excellent airtightness between a metal member and a polyarylene sulfide resin member that has excellent impact resistance, light weight, and mass producibility, 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 the like that require waterproofing, and to a method for producing the metal member-polyarylene sulfide resin 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] Furthermore, as resin compositions excellent in dimensional stability, thin-wall flowability, etc., 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 4) have been proposed.

[0006] As a polyarylene sulfide resin composition for a box-shaped molded product having excellent moldability and mechanical strength, excellent flatness of the bottom surface of the box-shaped part, and reduced dimensional variation between shots, a polyarylene sulfide resin composition comprising a polyarylene sulfide resin having a specific melt viscosity and crystallization temperature, and an inorganic filler consisting of a fibrous filler and a non-fibrous filler (see, for example, Patent Document 5) has been proposed.

[0007] Furthermore, several studies have been conducted on PAS resin compositions that have good bonding properties with metals, and, 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 6), and a resin composition that combines (a) PPS, (b) a polar group-containing polyolefin, and (c) a compatibilizer (see, for example, Patent Document 7) have been proposed.

[0008] Furthermore, a metal-resin composite structure with excellent airtightness at the metal-resin joint surface has been proposed (see, for example, Patent Document 8). [Prior art documents] [Patent documents]

[0009] [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. 2011-16942 [Patent Document 5] Patent No. 4777080 [Patent Document 6] Japanese Patent Application Laid-Open No. 2010-070712 [Patent Document 7] Japanese Patent Application Laid-Open No. 2010-284899 [Patent Document 8] Japanese Patent Application Publication No. 2020-68070 Summary of the Invention [Problem to be solved by the invention]

[0010] 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 by joint strength to determine its superiority, but even when the joint strength is excellent, the airtightness of the metal-resin joint surface is not necessarily excellent. Furthermore, in the resin composition proposed in Patent Document 4, a PPS having a specific melt viscosity and crystallization temperature is used, and an insert-molded composite member composed of the resin composition and a metal member exhibits excellent mold releasability, dimensional stability, and cold and heat resistance. However, no consideration was given to the melt viscosity and crystallization temperature of the resin composition actually bonded to the metal member in the injection insert molding, resulting in the problem that the airtightness of the composite member may not be fully satisfactory. Furthermore, in the resin composition proposed in Patent Document 4, no consideration was given to the bond strength or airtightness at the joint surface when the resin composition is formed into a composite with a metal member having a surface that has been subjected to physical and / or chemical treatment, which may result in problems. With regard to the resin compositions proposed in Patent Documents 6 and 7, no consideration was given to the bonding strength or airtightness of the bonding surface when they are formed into a composite with a metal member having a surface that has been subjected to physical and / or chemical treatment, which may result in problems. Furthermore, although the cooling device and battery structure proposed in Patent Document 8 have excellent airtightness, the mechanism for achieving this airtightness is unclear, and quantitative quantification of the mechanism for achieving this airtightness has been desired.

[0011] Therefore, an object of the present invention is to provide a metal member-polyarylene sulfide resin member composite having excellent airtightness between a metal member and a polyarylene sulfide resin member, and a method for stably producing a metal member-polyarylene sulfide resin member composite having excellent airtightness. [Means for solving the problem]

[0012] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that a metal member-polyarylene sulfide resin member composite consisting of a polyarylene sulfide resin member and a metal member made of a resin composition comprising at least polyarylene sulfide resin, a modified ethylene copolymer, and glass fiber, in a specific blending ratio, and having a specific melt crystallization peak temperature and melt viscosity, has excellent airtightness at the joint surface, and have completed the present invention.

[0013] That is, the present invention relates to a metal member-polyarylene sulfide resin member composite which is an injection-molded integral body of a metal member and a polyarylene sulfide resin member, characterized in that the polyarylene sulfide resin member is an injection-molded member of a polyarylene sulfide resin 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 resin (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 ethylene-α-olefin copolymer, and 10 to 120 parts by weight of glass fiber (C).

[0014] The present invention will be described in detail below.

[0015] The metal member-polyarylene sulfide resin 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 resin member by injection molding.

[0016] The polyarylene sulfide resin composition constituting the polyarylene sulfide resin 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 resin member composite has excellent airtightness. Here, if the polyarylene sulfide resin composition has a Tc2 of less than 200°C, the mold releasability in injection insert molding is significantly reduced, resulting in poor productivity of the metal member-polyarylene sulfide resin member composite. On the other hand, if the Tc2 exceeds 230°C, the bonding between the metal member and the polyarylene sulfide resin member is poor, and the resulting metal member-polyarylene sulfide resin member composite has poor airtightness.

[0017] The metal member-polyarylene sulfide resin member composite of the present invention is a composite in which a metal member and a polyarylene sulfide resin member are firmly bonded by insert molding. A molten polyarylene sulfide resin 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 anchor effect. An important factor is that the irregularities on the metal surface are transferred accurately when the molten polyarylene sulfide resin composition solidifies. To achieve this, a polyarylene sulfide resin 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 resin member is less than 200°C, the solidification rate becomes excessively slow, significantly reducing mold releasability during composite production and resulting in poor productivity. On the other hand, if it exceeds 230°C, the solidification rate of the polyarylene sulfide resin composition becomes excessively fast, resulting in poor bonding between the metal member and the polyarylene sulfide resin member, and the resulting metal member-polyarylene sulfide resin member composite will have poor airtightness. Furthermore, since the Tc2 of the polyarylene sulfide resin member of 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 sulfide resins, it is possible to control the solidification rate from the molten state, resulting in excellent productivity and airtightness.

[0018] Furthermore, the polyarylene sulfide resin member is made of a polyarylene sulfide resin composition having a melt flow rate (hereinafter sometimes referred to as MFR) measured at 315°C in accordance with ISO 1133 of 20 g / 10 min to 150 g / 10 min, so that the resulting metal member-polyarylene sulfide resin member composite has excellent airtightness at the bonding surface. Here, if the polyarylene sulfide resin 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, resulting in poor bonding between the metal member and the polyarylene sulfide resin member, and the resulting metal member-polyarylene sulfide resin 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 resin member composite of the present invention has a specific fluidity of 20 g / 10 min or more and 150 g / 10 min or less of MFR of the polyarylene sulfide resin member, and therefore exhibits good processability during member molding and excellent airtightness.

[0019] In the present invention, airtightness refers to the airtightness of the joint surface between a metal member and a polyarylene sulfide resin 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.

[0020] The polyarylene sulfide resin member constituting the metal member-polyarylene sulfide resin member composite of the present invention contains, per 100 parts by weight of polyarylene sulfide resin (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, and 10 to 120 parts by weight of glass fiber (C). The polyarylene sulfide resin (A) may be any resin that falls into the category generally referred to as a polyarylene sulfide resin. Examples of the polyarylene sulfide resin (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 resin 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 resin member that is particularly excellent in heat resistance and strength characteristics.

[0021] Furthermore, the polyarylene sulfide resin (A) is preferably a polyarylene sulfide resin having a melt viscosity of 90 to 2000 poise measured using a high-speed 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 resin member composite having excellent airtightness at the joining surface.

[0022] The polyarylene sulfide resin (A) can be produced by a method known for producing polyarylene sulfide resins, 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. The alkali metal sulfide salt may also be a product of reacting an alkali metal hydrosulfide salt with an alkali metal hydroxide. Examples of polyhaloaromatic compounds include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, and 4,4'-dichlorodibiphenyl.

[0023] The polyarylene sulfide resin (A) may be a linear one, one into which a small amount of a trihalogen or higher polyhalogen compound is added during polymerization to introduce a slight crosslinking or branched structure, one in which a part and / or end of the molecular chain of the polyarylene sulfide resin is 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 one that has been subjected to heat treatment in a non-oxidizing inert gas such as nitrogen, or a mixture of these polyarylene sulfide resins. The polyarylene sulfide resin may also be one in which impurities such as sodium atoms, polyarylene sulfide resin oligomers, table salt, and 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.

[0024] The polyarylene sulfide resin member constituting the metal member-polyarylene sulfide resin member composite of the present invention, which enables efficient production of a metal member-polyarylene sulfide resin member composite with excellent airtightness at the joining 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 polymer, and maleic anhydride-grafted ethylene-α-olefin copolymer, per 100 parts by weight of polyarylene sulfide resin (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 resin member composite will have poor airtightness at the joining surface. On the other hand, if the blending amount exceeds 25 parts by weight, the resulting metal member-polyarylene sulfide resin 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.

[0025] The polyarylene sulfide resin member constituting the metal member-polyarylene sulfide resin member composite of the present invention contains 10 to 120 parts by weight of glass fiber (C) per 100 parts by weight of polyarylene sulfide resin (A), since this allows for efficient production of a metal member-polyarylene sulfide resin member composite having excellent mechanical strength. As the glass fiber (C), any material generally known as glass fiber may be used. Specific examples of the glass fiber (C) 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 resin 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.

[0026] Here, if the amount of glass fiber (C) is less than 10 parts by weight, the resulting metal member-polyarylene sulfide resin member composite will have poor mechanical strength and impact resistance, while if the amount exceeds 120 parts by weight, the fluidity of the polyarylene sulfide resin composition will decrease, and the airtightness of the joint surface of the metal member-polyarylene sulfide resin member composite will decrease.

[0027] The polyarylene sulfide resin member may contain a mold release agent (D) to improve mold releasability and appearance when molded into a molded product. Suitable examples of the mold release agent (D) 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.

[0028] The polyarylene sulfide resin member may contain an epoxy resin (E), which allows for efficient production of a metal member-polyarylene sulfide resin member composite with excellent airtightness at the joining surface. The epoxy resin (E) may be any resin that falls within the category of epoxy resins. 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 versions of these, butanediol, ethylene glycol, erythritol, novolac, glycerin, polyoxyalkylene, or other compounds containing two or more hydroxyl groups in the molecule, and epichlorohydrin, etc. Examples of epoxy resins include glycidyl ether-based 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-based 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-based epoxy resins, such as glycidyl ether-based epoxy resins and glycidyl ester-based 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 resin member composite. Bisphenol A-based epoxy resins are even more preferred. The amount of the epoxy resin (E) to be added is preferably 1 to 15 parts by weight per 100 parts by weight of the polyarylene sulfide resin (A).

[0029] Furthermore, the polyarylene sulfide resin 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. 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, and glass balloons may also be added within the range not impairing the effects of the present invention.

[0030] Furthermore, the polyarylene sulfide resin member 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.

[0031] Furthermore, the polyarylene sulfide resin 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.

[0032] The metal member constituting the metal member-polyarylene sulfide resin member composite of the present invention may be made of any material as long as it belongs to the category of metal members, and among them, 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 applications when formed into a composite with a polyarylene sulfide resin 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.

[0033] 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 resin member, a metal member-polyarylene sulfide resin 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.

[0034] 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.

[0035] As a method for producing the metal member-polyarylene sulfide resin 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 resin member by injection molding. Among these, injection insert molding is preferred because it allows for particularly efficient production of the composite. Examples of injection insert molding include a method in which a metal member is placed in a mold, a molten polyarylene sulfide resin composition is filled into the metal member to form a polyarylene sulfide resin member, and a composite in which the metal member and the polyarylene sulfide resin member are directly integrated. The melting temperature of the polyarylene sulfide resin composition in this case can be 280 to 340°C. As a molding machine for insert molding, injection insert molding is preferably performed using an injection molding machine, as this is particularly advantageous in terms of productivity. Furthermore, a mold temperature during insert molding is preferably 130°C or higher, particularly 140 to 160°C, because this allows for efficient production of a metal member-polyarylene sulfide resin 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.

[0036] The metal member-polyarylene sulfide resin member composite of the present invention has excellent airtightness and excellent airtight reliability, as well as excellent impact resistance, light weight, and mass-producibility, and is particularly suitable for use in parts for transportation equipment such as automobiles and aircraft, which require these properties and reliability, or for electrical and electronic parts for portable devices and the like, which require waterproofing. [Effects of the Invention]

[0037] According to the present invention, it is possible to provide a highly reliable metal member-polyarylene sulfide resin member composite that has excellent airtightness at the joining surface, as well as excellent impact resistance, light weight, and mass producibility, and is particularly useful for use in parts for transportation equipment such as automobiles and aircraft, or in electrical and electronic parts for portable devices and the like that require waterproofing, and a method for producing the same, and the industrial value of the composite is extremely high. [Brief explanation of the drawings]

[0038] [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 component for airtightness evaluation. [Figure 4] ;Metal component-polyarylene sulfide resin component composite for airtightness evaluation. [Example]

[0039] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples.

[0040] The polyarylene sulfide resin (A), modified ethylene copolymer (B), glass fiber (C), epoxy resin (E) and release agent (D) used in the examples and comparative examples are shown below.

[0041] <Polyarylene sulfide resin (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 2500 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS (A-6)): melt viscosity 560 poise.

[0042] <Modified ethylene copolymer (B)> Ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid butyl ester copolymer (B-1) (hereinafter simply referred to as ethylene copolymer (B-1)): SK global chemical Co., Ltd., (trade name) LOTADER AX8750, ethylene residue unit: methacrylic acid glycidyl ester residue unit: acrylic acid butyl ester residue unit (weight ratio) = 70:5:25. Ethylene-α,β-unsaturated carboxylic acid butyl ester-maleic anhydride copolymer (B-2 (hereinafter simply referred to as ethylene copolymer (B-2))): manufactured by SK global chemical Co., Ltd., (trade name) LOTADER 3410, ethylene residue unit: acrylic acid butyl ester residue unit: maleic anhydride residue unit (weight ratio) = 80:17:3. Ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid methyl ester copolymer (B-3) (hereinafter simply referred to as ethylene copolymer (B-3)): manufactured by SK global chemical Co., Ltd., (trade name) LOTADER AX9800, ethylene residue unit: methacrylic acid glycidyl ester residue unit: acrylic acid ethyl ester residue unit (weight ratio) = 68:8:24.

[0043] <Glass fiber (C)> Glass fiber (C-1): Nippon Electric Glass Co., Ltd. (product name) ECS03T-732H / PW. Glass fiber (C-2): Chopped strand manufactured by Nittobo Co., Ltd., (product name) CSG-3PA 830, aspect ratio of fiber cross section: 4.

[0044] <Epoxy resin (E)> Epoxy resin (E-1): Mitsubishi Chemical Corporation, (trade name) 1004.

[0045] <Release agent (D)> Release agent (D-1): Kyoeisha Chemical Co., Ltd. (trade name) Light Amide WH-255.

[0046] <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.

[0047] <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.

[0048] <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.

[0049] <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.

[0050] <Synthesis Example 5 (Synthesis of PPS (A-5))> 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-5) with a melt viscosity of 2500 poise.

[0051] <Synthesis Example 6 (Synthesis of PPS (A-6))> The resulting cake was washed with 80°C hot water to a slurry concentration of 20%, then washed with a 1% aqueous hydrochloric acid solution, and again with hot water added in the same manner to raise the temperature to 175°C to wash the poly(p-phenylene sulfide), thereby obtaining PPS (A-6) in the same manner as in Synthesis Example 2. The melt viscosity of PPS (A-6) was 560 poise.

[0052] The evaluation and measurement methods for the obtained polyarylene sulfide resin and metal member-polyarylene sulfide resin member composite are shown below.

[0053] ~Melt viscosity measurement of polyarylene sulfide resin~ 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.

[0054] ~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.

[0055] ~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.

[0056] ~Evaluation of the bondability between resin and metal components~ A metal plate having a surface that has been subjected to physical and / or chemical treatment is placed in the mold of an injection molding machine, and a polyarylene sulfide resin composition is poured into the hopper of the injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name SE75S), and injection insert molding is performed to form a bonded area of ​​50 mm 2 Shear tensile test pieces were obtained. Next, the bond strength of the bonded surface was measured using the shear tensile test pieces in accordance with ISO 19095, and the bond strength was evaluated. Bonds with a bond strength of 30 MPa or more were determined to have excellent bondability.

[0057] ~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 resin 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 cooling-heating cycle in which it was held at 150°C for 30 minutes, cooled to -40°C, held there 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 resin member were immersed in the test liquid. The pressure inside the container was increased to 0.5 MPa and held there 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.

[0058] Example 1 Aluminum alloy (A5052) plate material (50 mm × 10 mm × 1 mm thick) with the shape shown in Figure 3, aluminum alloy (A5052) lid material with the shape shown in Figure 2, and aluminum alloy (A5052) plate material (45 mm × 18 mm × 1.5 mm thick) for shear tensile tests were immersed in a degreasing bath containing an aqueous solution (liquid temperature: 60 °C) containing 7.5% aluminum degreasing agent for 5 minutes, then rinsed with ion-exchanged water. Next, they were immersed in a bath containing an aqueous solution (30 °C) of sulfuric acid:ferric chloride:cupric chloride:ion-exchanged water in a weight ratio of 8.2:7.8:0.4:83.6 for 2 minutes, rinsed with ion-exchanged water, and dried in a warm-air dryer to obtain surface-roughened aluminum alloy (A5052) and aluminum alloy (A5052) lid material.

[0059] 100 parts by weight of the PPS (A-1) obtained in Synthesis Example 1 and 12 parts by weight of an ethylene copolymer (B-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 (C-1) was charged into the hopper of the side feeder of the twin-screw extruder so that 30 parts by weight of glass fiber (C-1) was added to 100 parts by weight of the PPS (A-1), and the mixture was melt-kneaded and pelletized to produce a poly(p-phenylene sulfide) resin composition. The MFR and crystallization temperature of the resulting poly(p-phenylene sulfide) resin composition were then measured.

[0060] The resulting aluminum alloy (A5052) plate, aluminum alloy (A5052) lid, and aluminum alloy (A5052) plate for shear tensile testing were placed in a mold. 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 140 °C, and a mold pressure of 50 MPa. Insert molding was performed to produce a lid and shear tensile test specimen, which is an aluminum alloy (A5052) member-PPS resin member composite with the shape shown in Figure 4. The bonding between the resin member and the metal member of the aluminum alloy (A5052) member-PPS resin composition composite was evaluated, and the bonding was found to be excellent. Furthermore, the airtightness of the aluminum alloy (A5052) member-PPS resin composition composite was evaluated, showing no bubbles and excellent airtightness.

[0061] Example 2 Aluminum die-cast alloy (ADC12) plate material (50 mm × 10 mm × 1 mm thick) with the shape shown in Figure 3, aluminum die-cast alloy (ADC12) lid material with the shape shown in Figure 2, and aluminum die-cast alloy (ADC12) plate material for shear tensile tests (45 mm × 18 mm × 1.5 mm thick) were immersed in a degreasing bath containing a 7.5% aluminum degreaser solution (liquid temperature: 60°C) for 5 minutes, then rinsed with ion-exchanged water. Next, they were immersed in a bath containing a 1.5% caustic soda solution (liquid temperature: 40°C) for 1 minute, rinsed with ion-exchanged water, and further immersed in a bath 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.

[0062] 100 parts by weight of the PPS (A-2) obtained in Synthesis Example 2 and 10 parts by weight of an ethylene copolymer (B-2) were uniformly mixed in advance, and the mixture was charged into the hopper of a twin-screw extruder (trade name: TEX25αIII, manufactured by The Japan Steel Works, Ltd.) heated to a cylinder temperature of 300°C. Meanwhile, glass fiber (C-2) was charged from the hopper of a side feeder of the twin-screw extruder in an amount of 30 parts by weight per 100 parts by weight of the PPS (A-2), and the mixture was melt-kneaded and pelletized to prepare a poly(p-phenylene sulfide) resin composition. The MFR and crystallization temperature of the obtained poly(p-phenylene sulfide) resin composition were then measured.

[0063] The resulting aluminum die-cast alloy (ADC12) plate, aluminum die-cast alloy (ADC12) lid, and aluminum die-cast alloy (ADC12) plate for shear tensile testing were placed in a mold. 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 310 °C, a mold temperature of 145 °C, and a mold holding pressure of 45 MPa. Insert molding was performed to produce a lid and shear tensile test specimen, which was an aluminum die-cast alloy (ADC12) member-PPS resin member composite with the shape shown in Figure 4. The bondability between the resin member and the metal member of the aluminum die-cast alloy (ADC12) member-PPS resin composition composite was then evaluated, and the bondability was found to be excellent. Furthermore, the airtightness of the aluminum die-cast alloy (ADC12) member-PPS resin composition composite was evaluated, showing no bubbles and excellent airtightness.

[0064] Example 3 Stainless steel (SUS316) plates (50 mm × 10 mm × 1 mm thick) with the shape shown in Figure 3, stainless steel (SUS316) lids with the shape shown in Figure 2, and stainless steel (SUS316) plates (45 mm × 18 mm × 1.5 mm thick) for shear and tensile tests were immersed in a degreasing bath containing a 7.5% aluminum degreaser (liquid temperature: 60°C) for 5 minutes and then rinsed with ion-exchanged water. Next, they were immersed in a bath containing a 1.5% aqueous solution of caustic soda (liquid temperature: 40°C) for 1 minute, rinsed with ion-exchanged water, and further immersed in a bath containing a 10% sulfuric acid solution (liquid temperature: 65°C) for 3 minutes and rinsed with ion-exchanged water. Next, they were immersed in a 3% aqueous nitric acid solution (liquid temperature: 40°C) for 3 minutes, rinsed, and then dried in a hot air dryer to obtain surface-roughened stainless steel (SUS316) plates and stainless steel (SUS316) lids.

[0065] 100 parts by weight of the PPS (A-3) obtained in Synthesis Example 3 and 12 parts by weight of the ethylene copolymer (B-3) 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 (C-1) was charged into the hopper of the side feeder of the twin-screw extruder so that 30 parts by weight of glass fiber (C-1) was added to 100 parts by weight of the PPS (A-3), and the mixture was melt-kneaded and pelletized to produce a poly(p-phenylene sulfide) resin composition. The MFR and crystallization temperature of the resulting poly(p-phenylene sulfide) resin composition were then measured.

[0066] The resulting stainless steel (SUS316) plate, stainless steel (SUS316) lid, and stainless steel (SUS316) plate for shear tensile testing were placed in a mold. 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 140°C, and a mold pressure of 50 MPa. Insert molding was performed to produce a lid and shear tensile test specimen, which was a stainless steel (SUS316)-PPS resin composite with the shape shown in Figure 4. The bondability of the stainless steel (SUS316)-PPS resin composition composite between the resin and metal components was evaluated, and the bondability was found to be excellent. Furthermore, the airtightness of the stainless steel (SUS316)-PPS resin composition composite was evaluated, showing no bubbles and excellent airtightness.

[0067] Example 4 Copper (C1100) plates (50 mm × 10 mm × 1 mm thick) with the shape shown in Figure 3, copper (C1100) lids with the shape shown in Figure 2, and copper (C1100) plates (45 mm × 18 mm × 1.5 mm thick) for shear tensile tests were immersed in a degreasing bath containing a 7.5% aluminum degreaser (liquid temperature: 60°C) for 5 minutes and then rinsed with ion-exchanged water. Next, they were immersed in a bath containing a 1.5% caustic soda solution (liquid temperature: 40°C) for 1 minute and then rinsed with ion-exchanged water. Next, they were immersed in a bath containing a 10% nitric acid solution (liquid temperature: 40°C) for 1 minute and then rinsed with ion-exchanged water. They were then immersed in a bath containing a 3% nitric acid solution (liquid temperature: 40°C) for 10 minutes and 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.

[0068] 100 parts by weight of the PPS (A-1) obtained in Synthesis Example 1 and 15 parts by weight of an ethylene copolymer (B-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 (C-2) was charged into the hopper of the side feeder of the twin-screw extruder so that the amount was 45 parts by weight per 100 parts by weight of the PPS (A-1), and the mixture was melt-kneaded and pelletized to produce a poly(p-phenylene sulfide) resin composition. The MFR and crystallization temperature of the resulting poly(p-phenylene sulfide) resin composition were then measured.

[0069] The obtained copper (C1100) plate, copper (C1100) lid, and copper (C1100) plate for shear tensile testing 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 to produce a copper (C1100) member-PPS resin member composite lid and shear tensile test specimens with the shape shown in Figure 4. The bonding between the resin member and the metal member of the copper (C1100) member-PPS resin composition composite was evaluated, and the bonding was found to be good. Furthermore, the airtightness of the copper (C1100) member-PPS resin composition composite was evaluated, showing no bubbles and excellent airtightness.

[0070] Examples 5 to 10 A pellet-shaped polyarylene sulfide resin composition was prepared in the same manner as in Example 1, with the blending ratios of the polyarylene sulfide resin (A), ethylene copolymer, glass fiber (C), mold release agent (D), and epoxy resin (E) set as shown in Table 1. The MFR and crystallization temperature of the obtained poly(p-phenylene sulfide) resin composition were measured.

[0071] The surface-roughened aluminum alloy (A5052) plate obtained by the same method as in Example 1, an aluminum alloy (A5052) lid, and an aluminum alloy (A5052) plate for shear tensile testing were set in a mold, and insert molding was performed in the same manner as in Example 1 under the injection molding conditions shown in Table 1 to produce a lid and shear tensile test specimen, which was an aluminum alloy (A5052) member-PPS resin member composite. Next, evaluation of the resin member and metal member of the aluminum alloy (A5052) member-PPS resin composition member composite revealed good bonding in both cases. Furthermore, evaluation of the airtightness of the aluminum alloy (A5052) member-PPS resin composition member composite revealed no air bubbles and excellent airtightness in all cases.

[0072] [Table 1]

[0073] Comparative Examples 1 to 4 A pellet-shaped polyarylene sulfide resin composition was prepared in the same manner as in Example 1, with the blending ratios of the polyarylene sulfide resin (A), the ethylene copolymer (B), the glass fiber (C), and the epoxy resin (E) set forth in Table 2. The MFR and crystallization temperature of the obtained poly(p-phenylene sulfide) resin composition were measured.

[0074] The surface-roughened aluminum alloy (A5052) plate obtained by the same method as in Example 1, the aluminum alloy (A5052) lid material, and the aluminum alloy (A5052) plate material for shear tensile testing 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 to produce a lid material and shear tensile test specimen that were an aluminum alloy (A5052) member-polyarylene sulfide resin member composite.

[0075] The obtained aluminum alloy (A5052) member-polyarylene sulfide resin member composites all had poor adhesiveness between the resin member and the metal member, and poor airtightness.

[0076] Comparative Example 5 A pellet-shaped polyarylene sulfide resin composition was prepared in the same manner as in Example 1, with the blending ratios of the polyarylene sulfide resin (A), the ethylene copolymer (B), and the glass fiber (C) set as shown in Table 2. The MFR and crystallization temperature of the obtained poly(p-phenylene sulfide) resin composition were measured.

[0077] The surface-roughened aluminum alloy (A5052) plate obtained by the same method as in Example 1, the aluminum alloy (A5052) lid material, and the aluminum alloy (A5052) plate material for shear tensile testing 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 resin composition member composite.

[0078] Comparative Examples 6 and 7 A pellet-shaped polyarylene sulfide resin composition was prepared in the same manner as in Example 1, with the blending ratios of polyarylene sulfide resin (A), ethylene copolymer (B), and glass fiber (C) set forth in Table 2. The MFR and crystallization temperature of the resulting poly(p-phenylene sulfide) resin composition were measured.

[0079] The surface-roughened aluminum die-cast alloy (ADC12) plate material obtained by the same method as in Example 2, the aluminum die-cast alloy (ADC12) lid material, and the aluminum die-cast alloy (ADC12) plate material for shear tensile tests were set in a mold, and insert molding was performed by the same method as in Example 2 under the injection molding conditions shown in Table 2 to produce a lid material and shear tensile test specimens that were aluminum die-cast alloy (ADC12) member-polyarylene sulfide resin member composites.

[0080] The obtained aluminum die-cast alloy (ADC12) member-polyarylene sulfide resin member composites all had poor adhesiveness between the resin member and the metal member, and poor airtightness.

[0081] [Table 2] [Industrial Applicability]

[0082] The composite of the present invention provides a metal member-polyarylene sulfide resin member composite having excellent airtightness at the joining 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 the like that require waterproofing. [Explanation of symbols]

[0083] 1; Metal plate material. 2; Metal plate material. 3;Metal lid material. 4; PPS resin component.

Claims

1. A metal member-polyarylene sulfide resin member composite, which is an injection-molded integral body of a metal member and a polyarylene sulfide resin member, characterized in that the polyarylene sulfide resin member is an injection-molded member of a polyarylene sulfide resin composition that 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 resin (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 ethylene-α-olefin copolymer, and 10 to 120 parts by weight of glass fiber (C).

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

3. 3. The metal member-polyarylene sulfide resin member composite according to claim 1, wherein the polyarylene sulfide resin composition further contains an epoxy resin (E).

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

5. 5. A method for producing a metal member-polyarylene sulfide resin member composite, in which a metal member and a polyarylene sulfide resin member are directly integrated by injection molding, comprising: placing a metal member in a mold having a mold temperature of 130°C or higher; setting the mold holding pressure to 1 MPa or higher; and injecting and filling a molten polyarylene sulfide resin composition into the mold; and forming an injection insert composite in which the metal member and the polyarylene sulfide resin member are directly integrated.

Images