Metal component-polyarylene sulfide resin component composite and method for manufacturing the same

Abstract

To provide a metal member-polyarylene sulfide resin member composite having an excellent airtightness between a metal member and a polyarylene sulfide resin member, and a method for manufacturing the same.SOLUTION: A metal member-polyarylene sulfide resin member composite being an injection integrated molding between a metal member and a polyarylene sulfide resin member satisfies the following: (1) |(Ra1-Ra2)| / (Ra1+Ra2)≤0.2, |(Rz1-Rz2)| / (Rz1+Rz2)≤0.2, and / or |(Rq1-Rq2)| / (Rq1+Rq2)≤0.2, where Ra1: arithmetic average roughness, Rz1: maximum height roughness, Rq1: root mean square height, measured in conformity with JIS B 0601-2001 using an atomic force microscope or a confocal laser scanning microscope with a field of view of 2 μm on the surface of the metal member, and Ra2: arithmetic average roughness, Rz2: maximum height roughness, Rq2: root mean square height, measured in conformity with JIS B 0601-2001 using an atomic force microscope or a confocal laser scanning microscope with a field of view of 2 μm on the surface of the polyarylene sulfide resin member; and (2) the polyarylene sulfide resin member contains a polyarylene sulfide resin and a modified ethylenic copolymer.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a metal member - polyarylene sulfide resin member composite excellent in airtightness of the joint surface and a method for manufacturing the same. More specifically, it is excellent in impact resistance, light weight, and mass productivity, and is particularly useful for parts applications of transportation equipment such as automobiles and aircraft, or for electrical and electronic parts applications of portable devices that require waterproofing, etc. The present invention relates to a metal member - polyarylene sulfide resin member composite excellent in airtightness between a metal member and a polyarylene sulfide resin member, and a method for manufacturing the metal member - polyarylene sulfide resin member composite.

Background Art

[0002] In order to reduce the weight of parts of transportation equipment such as automobiles and aircraft, methods of replacing a part of the metal with resin have been studied. Also, as a method of integrating resin and metal, a method of inserting a metal member having a surface subjected to physical treatment and / or chemical treatment into a mold and directly integrating it by injection molding the resin (hereinafter, may be referred to as the injection insert molding method) has attracted attention from the viewpoints of good mass productivity, few part numbers, low cost, high design freedom, and low environmental load, and has been proposed in the manufacturing process of portable electronic devices such as smartphones (for example, see Patent Documents 1 to 3).

[0003] Polyarylene sulfide (hereinafter, may also be abbreviated as PAS) represented by poly(p - phenylene sulfide) (hereinafter, may also be abbreviated as PPS) has excellent mechanical properties, thermal properties, electrical properties, and chemical resistance, and is widely used in many electrical and electronic device members, automobile device members, and other OA device members.

[0004] Also, since PAS has excellent melt fluidity, it exhibits excellent bonding strength in the injection insert molding method with a metal member having a surface subjected to physical treatment and / or chemical treatment.

[0005] On the other hand, atomic force microscopes or confocal laser microscopes are commonly used as methods for measuring the surface roughness of a metal surface by surface analysis (see, for example, Patent Documents 4 and 5).

[0006] Furthermore, proposals have been made for metal-resin composite structures with excellent airtightness at the metal-resin joint surface (see, for example, Patent Document 6). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Patent No. 5701414 [Patent Document 2] Patent No. 5714193 [Patent Document 3] Patent No. 4020957 [Patent Document 4] Japanese Patent Publication No. 2014-136366 [Patent Document 5] Patent No. 6819798 [Patent Document 6] Japanese Patent Publication No. 2020-68070 [Overview of the project] [Problems that the invention aims to solve]

[0008] However, in the metal-resin composites obtained by the injection insert molding method proposed in Patent Documents 1 to 3, the adhesion of the metal-resin joint surface is quantified by the joint strength, and its superiority is judged accordingly. However, even when the joint strength was excellent, the airtightness of the metal-resin joint surface was not necessarily excellent. Furthermore, in the composite structures proposed in Patent Documents 4 and 5, no consideration was given to the airtightness of the metal-resin joint surface. Moreover, although the cooling device and battery structure proposed in Patent Document 6 have excellent airtightness, the mechanism for achieving airtightness is not clear, and there was a need for a quantitative quantification of the mechanism for achieving airtightness.

[0009] Therefore, the present invention aims to provide a metal member-polyarylene sulfide resin composite with excellent airtightness between the metal member and the polyarylene sulfide resin composite, and a method for stably producing a metal member-polyarylene sulfide resin composite with excellent airtightness. [Means for solving the problem]

[0010] As a result of diligent research to solve the above problems, the inventors have discovered that a metal member-polyarylene sulfide resin composite, comprising a polyarylene sulfide resin member made of a specific polyarylene sulfide resin and a surface-roughened metal member, wherein the difference in surface roughness between the bonding surfaces of the metal member and the polyarylene sulfide resin member is below a certain percentage, allows the bonding surface of the polyarylene sulfide resin member to transfer the fine irregularities of the surface-roughened metal member with high precision, resulting in remarkably excellent adhesion between the bonding surfaces of the metal member and the polyarylene sulfide resin member. Consequently, it provides excellent airtightness, superior reliability of airtightness, and furthermore, a component, part, or product with excellent impact resistance, lightweight properties, and mass-producibility, thus completing the present invention.

[0011] In other words, 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 it satisfies the following (1) and (2), and to a method for manufacturing the same. (1) The arithmetic mean roughness (Ra1), maximum height roughness (Rz1), and root mean square height (Rq1) measured on the surface of a metal component using an atomic force microscope or confocal laser microscope with a field of view of 2 μm, in accordance with JIS B 0601-2001, and the arithmetic mean roughness (Ra2), maximum height roughness (Rz2), and root mean square height (Rq2) measured on the surface of a polyethylene sulfide resin component using an atomic force microscope or confocal laser microscope with a field of view of 2 μm, in accordance with JIS B 0601-2001, satisfy the relationship |(Ra1-Ra2)| / (Ra1+Ra2)≦0.2, |(Rz1-Rz2)| / (Rz1+Rz2)≦0.2, and / or |(Rq1-Rq2)| / (Rq1+Rq2)≦0.2. (2) The polyarylene sulfide resin component comprises a polyarylene sulfide resin and a modified ethylene copolymer.

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

[0013] The metal member-polyarylene sulfide resin member composite of the present invention is a metal member-polyarylene sulfide resin member composite formed by directly integrating a metal member and a polyarylene sulfide resin member by injection molding.

[0014] Furthermore, the metal member surface and the polyarylene sulfide resin member surface satisfy at least one of the following relationships (1-1) to (1-3) to form a metal member-polyarylene sulfide resin member composite with excellent airtightness.

[0015] (1-1) The maximum height roughness (hereinafter sometimes referred to as Rz1) measured on the surface of the metal member using an atomic force microscope or confocal laser microscope with a field of view of 2 μm, in accordance with JIS B 0601-2001, and the maximum height roughness (hereinafter sometimes referred to as Rz2) measured on the surface of the polyarylene sulfide resin member using an atomic force microscope or confocal laser microscope with a field of view of 2 μm, in accordance with JIS B 0601-2001, satisfy the condition │(Rz1-Rz2)│ / (Rz1+Rz2)≦0.2. Note that when measuring the polyarylene sulfide resin member with an atomic force microscope or confocal laser microscope, only the metal member can be dissolved from the metal member-polyarylene sulfide resin member composite, and the polyarylene sulfide resin member remaining as an undissolved portion can be prepared, and the joint surface of this can be measured as the member surface.

[0016] (1-2) The arithmetic mean roughness (hereinafter sometimes referred to as Ra1) measured on the surface of the metal member using an atomic force microscope or confocal laser microscope with a field of view of 2 μm in accordance with JIS B 0601-2001, and the arithmetic mean roughness (hereinafter sometimes referred to as Ra2) measured on the surface of the polyarylene sulfide resin member using an atomic force microscope or confocal laser microscope with a field of view of 2 μm in accordance with JIS B 0601-2001, satisfy the condition │(Ra1-Ra2)│ / (Ra1+Ra2)≦0.2.

[0017] (1-3) The root mean square height (hereinafter sometimes referred to as Rq1) measured on the surface of the metal member using an atomic force microscope or confocal laser microscope with a field of view of 2 μm in accordance with JIS B 0601-2001, and the root mean square height (hereinafter sometimes referred to as Rq2) measured on the surface of the polyarylene sulfide resin member using an atomic force microscope or confocal laser microscope with a field of view of 2 μm in accordance with JIS B 0601-2001, satisfy the condition │(Rq1-Rq2)│ / (Rq1+Rq2)≦0.2.

[0018] Note that Rz1, Rz2, Ra1, Ra2, Rq1, and Rq2 can be measured at any three or more points and obtained as their average values. Also, as the field of view range for observation using a confocal laser microscope, it may be appropriately selected according to the shape and dimensions of the metal member - polyarylene sulfide resin member composite, the size of the irregularities on the metal surface formed by surface roughening, etc. For example, a range of 100 μm to 2000 μm is selected.

[0019] And as a method for dissolving only the metal member from the metal member - polyarylene sulfide resin member composite, any method may be used. Among them, since it is possible to efficiently dissolve only the metal member, a method of immersing the metal member - polyarylene sulfide resin member composite in an acidic liquid such as hydrochloric acid is preferable. Also, after dissolving the metal member, it is preferable to wash the polyarylene sulfide resin member with pure water, dry it, and then observe the bonding surface.

[0020] The airtightness in the present invention refers to the airtightness with respect to, 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, light oil, 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., the electrolyte of a battery, etc. at the bonding surface between the metal member and the polyarylene sulfide resin member. As a method for evaluating airtightness, it can be appropriately selected according to the use and purpose. Examples of the helium leak test include the method proposed in Japanese Patent Application Laid-Open No. 2020-68070.

[0021] The metal member constituting the metal member-polyarylene sulfide resin member composite of the present invention may be made of any material that falls under the category of metal members. 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 allow for adaptation to various applications when composited with a polyarylene sulfide resin member. In particular, aluminum members, aluminum alloy members, magnesium members, magnesium alloy members, titanium members, titanium alloy members, copper members, and copper alloy members are preferred because they offer excellent weight reduction. More preferably, aluminum members, aluminum alloy members, copper members, and copper alloy members are preferred. Furthermore, the metal member may be a wrought material represented by a plate, a cast material represented by die casting, or a forged material.

[0022] Furthermore, it is preferable that the metal member is a metal member whose surface has been physically and / or chemically treated. By applying this physical and / or chemical treatment, a metal member-polyarylene sulfide resin member composite with excellent airtightness and other properties can be obtained when directly integrated with the polyarylene sulfide resin member.

[0023] Furthermore, any method can be used to physically and / or chemically treat the surface of a metal component, as long as it results in a roughened surface. Examples of chemical treatments include anodic oxidation and chemical treatment with an aqueous solution of acid or alkali. As for anodic oxidation, for example, a method in which an electrolytic reaction is carried out in an electrolyte with the metal component as the anode to form an oxide film on its surface may be used. Methods commonly known as anodic oxidation in fields such as plating can be used. More specifically, examples include 1) DC electrolysis, in which electrolysis is carried out by applying a constant DC voltage, and 2) bipolar electrolysis, in which electrolysis is carried out by applying a voltage in which an AC component is superimposed on a DC component. Specific examples of anodic oxidation methods include the method proposed in publication WO2004 / 055248, etc. Furthermore, as a method of chemical treatment with an aqueous solution of acid or alkali, for example, a method of chemically treating the surface of a metal component by immersing it in an aqueous solution of acid or alkali, and examples of aqueous solutions of acid or alkali in this case include phosphoric acid compounds such as phosphoric acid; chromic acid compounds such as chromic acid; hydrofluoric acid compounds such as hydrofluoric acid; nitric acid compounds such as nitric acid; hydrochloric acid compounds such as hydrochloric acid; sulfuric acid compounds such as sulfuric acid; alkaline aqueous solutions such as sodium hydroxide and ammonia aqueous solution; and methods of chemical treatment using triazinethiol aqueous solution and triazinethiol derivative aqueous solution. More specific examples include the methods proposed in Japanese Patent Publication No. 2017-132243, Japanese Patent Publication No. 2019-188651, WO2008 / 133296, Japanese Patent No. 5622785, Japanese Patent Publication No. 10-096088, Japanese Patent Publication No. 10-056263, Japanese Patent Publication No. 04-032585, Japanese Patent Publication No. 04-032583, Japanese Patent Publication No. 02-298284, WO2009 / 151099, WO2011 / 104944, etc., and in particular, when the metal member has a finely surface-roughened metal member surface, a chemical treatment method is preferred.Moreover, the metal member is preferably one having a microscopically roughened surface by a method of chemically treating its surface. When measured in accordance with JIS B 0601 - 2001 using an atomic force microscope with a 2 - μm field of view of the metal member surface, it is preferable that Rz1 is 800 nm or less.

[0024] In addition, examples of physical treatment include methods such as contacting or colliding fine solid particles with the surface, and methods of irradiating high - energy electromagnetic rays. More specifically, sandblasting treatment, liquid honing treatment, laser processing treatment, etc. can be mentioned. Further, examples of abrasives used in sandblasting treatment and liquid honing treatment include sand, steel grid, steel shot, cut wire, alumina, silicon carbide, metal slag, glass beads, plastic beads, etc. In addition, examples of laser processing treatment include the methods proposed in WO2007 / 072603 and JP - A - 2015 - 142960. Particularly, when forming a surface - roughened metal member surface having relatively large holes, either chemical treatment or physical treatment of the metal surface is possible. Among them, since a more efficient treatment becomes possible, it is preferable to use a physical treatment method. And, when measured in accordance with JIS B 0601 - 2001 using a confocal laser microscope for the metal member surface, it is preferable that Rz1 exceeds 800 nm. <00,00101> The polyarylene sulfide resin member constituting the metal member-polyarylene sulfide resin member composite of the present invention comprises a polyarylene sulfide resin and a modified ethylene copolymer. The polyarylene sulfide resin may include any material belonging to the category generally referred to as polyarylene sulfide resin, such as p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, and phenylene Examples of polyarylene sulfide resins include homopolymers or copolymers composed of 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 particularly preferred because it results in a polyarylene sulfide resin component with excellent heat resistance and strength characteristics.

[0026] Furthermore, since it is possible to efficiently obtain a metal component-polyarylene sulfide resin component composite with excellent airtightness, it is preferable that the polyarylene sulfide resin has a melt viscosity of 50 to 2000 poise, as measured under the conditions of a measurement temperature of 315°C and a load of 10 kg using a high-efficiency flow tester equipped with a die of 1 mm in diameter and 2 mm in length.

[0027] The polyarylene sulfide resin can be produced by methods known for producing polyarylene sulfide resins, for example, by polymerizing an alkali metal sulfide salt and a polyhalo-aromatic compound in a polar organic solvent. Examples of polar organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexylpyrrolidone, dimethylformamide, and dimethylacetamide. Examples of alkali metal sulfide salts include anhydrous or hydrated sodium sulfide, rubidium sulfide, and lithium sulfide. Alternatively, the alkali metal sulfide salt may be obtained by reacting an alkali metal hydrosulfide salt with an alkali metal hydroxide. Examples of polyhalo-aromatic compounds include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4'-dichlorodiphenylsulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, and 4,4'-dichlorodibiphenyl.

[0028] Furthermore, examples of polyarylene sulfide resins include linear polyarylene sulfide resins, polyarylene sulfide resins in which a small amount of trihalogen or greater polyhalogen compounds are added during polymerization to introduce some crosslinking or branching structures, polyarylene sulfide resins in which part of the molecular chain and / or terminals are modified with functional groups such as carboxyl groups, carboxymetal salts, alkyl groups, alkoxy groups, amino groups, and nitro groups, and polyarylene sulfide resins that have been heat-treated in a non-oxidizing inert gas such as nitrogen. Mixtures of these polyarylene sulfide resins are also acceptable. In addition, the polyarylene sulfide resin may be obtained by reducing impurities such as sodium atoms, oligomers of polyarylene sulfide resin, sodium chloride, and sodium salt of 4-(N-methyl-chlorophenylamino)butanoate by acid washing, hot water washing, or washing with organic solvents such as acetone and methyl alcohol.

[0029] The polyarylene sulfide resin component constituting the metal component-polyarylene sulfide resin component composite of the present invention contains a modified ethylene copolymer, which has reactive functional groups such as epoxy groups, maleic anhydride groups, carboxylic acid groups, amino groups, isocyanate groups, etc., in its molecule. Examples include 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 graft-modified ethylene-α-olefin copolymer. The amount of the modified ethylene copolymer is preferably 1 to 40 parts by weight per 100 parts by weight of the polyarylene sulfide resin, as this makes it possible to create a metal component-polyarylene sulfide resin component composite with fewer defects at the bonding surface and excellent impact resistance.

[0030] As for the polyarylene sulfide resin member, it is preferable to further incorporate glass fibers, as this results in a metal member-polyarylene sulfide resin member composite with particularly excellent strength and impact resistance. Any type of glass fiber generally referred to as glass fiber may be used. Specific examples of the glass fiber include chopped strands with an average fiber diameter of 6 to 14 μm, chopped strands made of flattened glass fibers with an aspect ratio of 2 to 4, milled fibers, roving, etc.; silane fibers; aluminosilicate glass fibers; hollow glass fibers; non-enamel glass fibers, etc. Among these, it is preferable to use chopped strands with an average fiber diameter of 6 to 14 μm, or chopped strands made of flattened glass fibers with an aspect ratio of 2 to 4, as these result in a metal member-polyarylene sulfide resin member composite with fewer defects at the bonding surface and excellent impact resistance. These glass fibers can be used in combination of two or more types, and if necessary, they may be pre-surface-treated with functional compounds or polymers such as epoxy compounds, isocyanate compounds, silane compounds, or titanate compounds. The amount of glass fiber to be blended is preferably 5 to 120 parts by weight per 100 parts by weight of polyarylene sulfide resin, as this results in a metal member-polyarylene sulfide resin composite with fewer defects at the bonding surface and excellent impact resistance.

[0031] The polyarylene sulfide resin component may further contain, for example, 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, glass balloons, or glass flakes. It may also contain one or more conventional additives such as nucleating agents such as talc, kaolin, and silica; plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organophosphorus compounds; antioxidants; heat stabilizers; lubricants; UV inhibitors; and foaming agents. Furthermore, the product may be made by mixing one or more of various thermosetting resins and thermoplastic resins, such as epoxy resins, cyanate ester resins, phenolic resins, polyimides, silicone resins, polyesters, polyamides, polyphenylene oxides, polycarbonates, polysulfones, polyetherimides, polyethersulfones, polyetherketones, polyetheretherketones, polyamideimides, polyamide elastomers, polyester elastomers, and polyalkylene oxides.

[0032] Furthermore, the polyarylene sulfide resin component may contain a release agent to improve mold release properties and appearance when forming a molded product. Suitable release agents include, for example, polyethylene wax, polypropylene wax, and fatty acid amide wax. Commonly available commercially available polyethylene wax and polypropylene wax can be used. The fatty acid amide wax is a polycondensate composed of a higher aliphatic monocarboxylic acid, a polybasic acid, and a diamine, and any product belonging to this category can be used. For example, a polycondensate composed of stearic acid, sebacic acid, and ethylenediamine, such as (product name) Light Amid WH-255 (manufactured by Kyoeisha Chemical Co., Ltd.), can be cited.

[0033] As a method for manufacturing the metal member-polyarylene sulfide resin composite of the present invention, one method is to directly integrate the metal member and the polyarylene sulfide resin member by injection molding, and among these, integration by injection insert molding is particularly preferable because it allows for efficient production of the composite. As an example of the injection insert molding method, one can install a metal member in a mold, fill the metal member with molten polyarylene sulfide resin to form a polyarylene sulfide resin member, and thus form a composite in which the metal member and the polyarylene sulfide resin member are directly integrated. The melting temperature of the polyarylene sulfide resin in this case can be 280 to 340°C, and as the molding machine for performing insert molding, it is preferable to use an injection molding machine because it is particularly superior in productivity. Furthermore, since it is possible to efficiently produce a metal member-polyarylene sulfide resin composite with excellent airtightness, the mold temperature when performing insert molding is preferably 130°C or higher, and particularly preferably 140 to 160°C. Furthermore, the mold holding pressure is preferably 1 MPa or higher, and particularly preferably 30 to 100 MPa.

[0034] The metal-polyarylene sulfide resin composite of the present invention possesses excellent airtightness, reliability of that airtightness, and also exhibits superior impact resistance, lightness, and mass-producibility. It is particularly suitable for use in parts for transportation equipment such as automobiles and aircraft, where these properties and reliability are required, or in electrical and electronic components for portable devices where waterproofing is required. [Effects of the Invention]

[0035] According to the present invention, a highly reliable metal-polyarylene sulfide resin composite and a method for manufacturing the same can be provided, which are excellent in terms of airtightness of the joint surface, as well as impact resistance, light weight, and mass producibility, and are particularly useful for applications in transportation equipment such as automobiles and aircraft, or for electrical and electronic components such as portable devices that require waterproofing. Its industrial value is extremely high. [Brief explanation of the drawing]

[0036] [Figure 1] Schematic diagram of the container used for airtightness evaluation in the example. [Figure 2] Schematic diagram of a cover material used for airtightness evaluation. [Figure 3] Schematic diagram of a metal component used for airtightness evaluation. [Figure 4] Metal component-polyarylene sulfide resin component composite for airtightness evaluation. [Examples]

[0037] The present invention will be described in detail below with reference to examples, but the present invention is not limited in any way thereto.

[0038] The polyarylene sulfide resin (A), modified ethylene copolymer (B), glass fiber (C), and other resin materials used in the examples and comparative examples are shown below.

[0039] <Polyarylene sulfide resin (A)> Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-1)): Melt viscosity 210 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-2)): Melt viscosity 380 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-3)): Melt viscosity 100 poise.

[0040] <Modified ethylene copolymer (B)> Ethylene-α,β-unsaturated carboxylate alkyl ester-maleic anhydride copolymer (B-1) (hereinafter simply referred to as ethylene polymer (B-1)): Manufactured by SK global chemical, (product name) Bondine AX8390, ethylene residue units: α,β-unsaturated carboxylate alkyl ester residue units: maleic anhydride residue units (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-based polymer (B-2)): Manufactured by SK global chemical, (product name) LOTADER AX8700, ethylene residue units: α,β-unsaturated carboxylic acid glycidyl ester residue units: α,β-unsaturated carboxylic acid alkyl ester residue units (weight ratio) = 67:8:25.

[0041] <Glass fiber (C)> Glass fiber (C-1); manufactured by Owens Corning Japan Ltd., (product name) RES03-TP91; fiber diameter 10 μm, fiber length 3 mm. Glass fiber (C-2); chopped strand manufactured by Nitto Boseki Co., Ltd., (product name) CSG-3PA 830, fiber cross-sectional aspect ratio 4.

[0042] <Polybutylene terephthalate resin (D)> Polybutylene terephthalate resin (hereinafter simply referred to as PBT(D-1)): Manufactured by Mitsubishi Engineering Plastics Corporation, (product name) NovaDuran 5010R5L.

[0043] <Polyamide resin (E)> Polyamide 66 resin (hereinafter simply referred to as PA(E-1)): Manufactured by DuPont, (product name) Seidel 101.

[0044] <Polyethylene resin (F)> Low-density polyethylene resin (hereinafter simply referred to as PE(F-1)): Manufactured by Tosoh Corporation, (product name) Petrocene 249.

[0045] <Synthesis Example 1 (Synthesis of PPS(A-1))> In a 15-liter autoclave equipped with a stirrer, 1814 g of flake sodium sulfide (Na2S·2.9H2O), 48 g of 30% caustic soda solution (30% NaOHaq), and 3679 g of N-methyl-2-pyrrolidone were charged. The mixture was gradually heated to 200°C while stirring under a nitrogen stream, and 380 g of water was distilled off. After cooling to 190°C, 2107 g of p-dichlorobenzene and 985 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225°C over 2 hours, polymerized at 225°C for 1 hour, then heated to 250°C over 25 minutes, and polymerized further 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 reached was 170°C and the pressure was 4.7 kPa. The obtained cake was washed with 80°C hot water to a slurry concentration of 20%, and then the poly(p-phenylene sulfide) was washed again by adding hot water in the same manner and raising the temperature to 175°C for a total of two washes. The obtained polyphenylene sulfide was dried at 105°C overnight. Next, the dried polyphenylene sulfide was filled into a batch-type rotary kiln firing apparatus, heated to 240°C under a nitrogen atmosphere, and cured by holding for 1 hour to obtain PPS(A-1) with a melt viscosity of 210 poise.

[0046] <Synthesis Example 2 (Synthesis of PPS(A-2))> In a 15-liter autoclave equipped with a stirrer, 1814 g of flake sodium sulfide (Na2S·2.9H2O), 8.7 g of granular caustic soda (100% NaOH: Wako Pure Chemical Industries special grade), and 3232 g of N-methyl-2-pyrrolidone were charged. The mixture was gradually heated to 200°C while stirring under a nitrogen stream, and 340 g of water was removed by distillation. After cooling to 190°C, 2107 g of p-dichlorobenzene and 1783 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225°C over 2 hours, polymerized at 225°C for 1 hour, then heated to 250°C over 25 minutes, and polymerized at 250°C for 2 hours. Next, 509 g of distilled water was injected into the system at 250°C, and the polymerization reaction was carried out for another hour at a temperature of 255°C. After polymerization, N-methyl-2-pyrrolidone was recovered from the polymerization slurry by distillation under reduced pressure. The final temperature reached was 170°C and the pressure was 4.7 kPa. The resulting cake was washed with 80°C warm water to a slurry concentration of 20%, and then the poly(p-phenylene sulfide) was washed again by adding warm water and raising the temperature to 175°C for a total of two washes. The resulting poly(p-phenylene sulfide) was dried at 105°C overnight to obtain PPS(A-2) with a melt viscosity of 380 poise.

[0047] <Synthesis Example 3 (Synthesis of PPS(A-3))> In a 15-liter autoclave equipped with a stirrer, 1814 g of flake sodium sulfide (Na2S·2.9H2O), 8.7 g of granular caustic soda (100% NaOH: Wako Pure Chemical Industries special grade), and 3232 g of N-methyl-2-pyrrolidone were charged. The mixture was gradually heated to 200°C while stirring under a nitrogen stream, and 339 g of water was removed by distillation. After cooling to 190°C, 2085 g of p-dichlorobenzene and 1783 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225°C over 2 hours, polymerized at 225°C for 1 hour, then heated to 250°C over 25 minutes, and polymerized at 250°C for 2 hours. After polymerization, N-methyl-2-pyrrolidone was recovered from the polymerization slurry by distillation under reduced pressure. The final temperature reached was 170°C and the pressure was 4.7 kPa. The obtained cake was washed with 80°C hot water to a slurry concentration of 20%, and then the poly(p-phenylene sulfide) was washed again by adding hot water and raising the temperature to 175°C. The obtained poly(p-phenylene sulfide) was dried at 105°C overnight to obtain PPS(A-3) with a melt viscosity of 100 poise.

[0048] The evaluation and measurement methods for the obtained polyarylene sulfide resin and metal member-polyarylene sulfide resin member composite are described below.

[0049] ~Measuring the melt viscosity of polyarylene sulfide resin~ The melt viscosity was measured using a high-efficiency flow tester (manufactured by Shimadzu Corporation, product name CFT-500) equipped with a die with 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.

[0050] ~Measurement of Rz1, Ra1, and Rq1 on the surface of surface-treated metal components~ (Measurement by atomic force microscope) The surface roughness of three arbitrary points on the surface of a surface-treated metal component was measured using an atomic force microscope (Hitachi High-Tech Science Co., Ltd., product name: E-sweep) with a scanning probe (Olympus Corporation, product name: OMCL-AC200TN-R3, spring constant: 9 N / m) in dynamic force mode, in accordance with JIS B 0601-2001, within a 2 μm field of view, and the average value of the three points was determined.

[0051] (Measurement using a confocal laser microscope) The surface roughness of three arbitrary points on the surface of a surface-treated metal component was measured using a confocal laser microscope (Keyence Corporation, product name VK-X200) within a 1000 μm field of view in accordance with JIS B 0601-2001, and the average value of the three points was determined.

[0052] ~Measurement of Rz2, Ra2, and Rq2 at the bonding surface of polyarylene sulfide resin components~ (Measurement by atomic force microscope) In the metal component-polyarylene sulfide resin component composite, the metal component was immersed in a bath containing a 10% hydrochloric acid aqueous solution to dissolve only the metal component. The surface roughness of three arbitrary points on the bonding surface of the remaining polyarylene sulfide resin component was measured using an atomic force microscope (Hitachi High-Tech Science Co., Ltd., product name: E-sweep) with a scanning probe (Olympus Corporation, product name: OMCL-AC200TN-R3, spring constant: 9 N / m) in dynamic force mode in accordance with JIS B 0601-2001, within a 2 μm field of view, and the average value of the three points was determined.

[0053] (Measurement using a confocal laser microscope) In a composite of a metal component and a polyarylene sulfide resin component, the metal component was immersed in a tank containing a 10% hydrochloric acid aqueous solution to dissolve only the metal component. The surface roughness of three arbitrary points on the bonding surface of the remaining polyarylene sulfide resin component was measured using a confocal laser microscope (Keyence Corporation, product name VK-X200) in accordance with JIS B 0601-2001, within a 1000 μm field of view, and the average value of the three points was determined.

[0054] ~Airtightness testing and evaluation~ Distilled water was placed in an open-topped aluminum container, and the container was sealed by welding a lid material, which is a composite of a metal member and a polyarylene sulfide resin member as shown in Figure 4, to create the airtightness evaluation container shown in Figure 1. The airtightness evaluation container was held at 90°C for 200 hours, then allowed to cool to room temperature, and the interface between the metal plate material and the metal lid material and the polyarylene sulfide resin member was immersed in the test liquid. The inside of the container was pressurized to 0.5 MPa and held for 1 minute to evaluate the sealing performance. ○: If no bubbles are generated from the interface immersed in the test liquid, it is judged to have excellent airtightness. ×: If bubbles are generated from the interface immersed in the test liquid, it was determined that the airtightness was poor.

[0055] Example 1 Aluminum alloy (A5052) plate material (50 mm x 10 mm x 1 mm thick) with the shape shown in Figure 3 and aluminum alloy (A5052) lid material with the shape shown in Figure 2 were immersed for 5 minutes in a degreasing tank containing an aqueous solution (60°C) with 7.5% aluminum degreasing agent, and then rinsed with deionized water. Next, they were immersed for 1 minute in a tank containing an aqueous solution (40°C) with 1.5% caustic soda, rinsed with deionized water, and then immersed for 1 minute in a tank containing a 3% nitric acid aqueous solution (40°C), and rinsed with deionized water. Next, the aluminum alloy (A5052) plates and lids were chemically treated and surface-roughened by immersion in a tank containing an aqueous solution of 3.5% hydrated hydrazine (at a temperature of 60°C) for 1 minute, then washed with deionized water, and finally dried in a hot air dryer.

[0056] To 100 parts by weight of PPS(A-2) obtained in Synthesis Example 2, 11 parts by weight of ethylene copolymer (B-1) were uniformly mixed beforehand and fed into the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX25αIII) heated to a cylinder temperature of 300°C. Meanwhile, glass fiber (C-1) was fed from the side feeder hopper of the twin-screw extruder in an amount of 25 parts by weight per 100 parts by weight of PPS(A-2), and a poly(p-phenylene sulfide) resin composition was prepared by melt-kneading and pelletizing.

[0057] The obtained aluminum alloy (A5052) sheet material and aluminum alloy (A5052) lid material were set 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) with a cylinder temperature of 310°C, a mold temperature of 150°C, and a mold holding pressure of 60 MPa. Insert molding was performed to create a lid material that is a composite of aluminum alloy (A5052) member and polyarylene sulfide resin member, as shown in Figure 4. Then, Rz1, Ra1, and Rq1 were measured using an atomic force microscope with the obtained aluminum alloy (A5052) member-polyarylene sulfide resin member composite lid material. Next, the composite was immersed in a bath containing a 10% hydrochloric acid aqueous solution to dissolve only the aluminum alloy (A5052) member, and then Rz2, Ra2, and Rq2 of the joint surface were measured using an atomic force microscope.

[0058] The calculated values ​​for │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) were all 0.2 or less. Next, the airtightness of the aluminum alloy (A5052) member-PPS resin member composite was evaluated, and no bubbles were observed, indicating excellent airtightness. The results are shown in Table 1.

[0059] Example 2 Aluminum die-cast alloy (ADC12) plate material (50 mm x 10 mm x 1 mm thick) with the shape shown in Figure 3 and aluminum die-cast alloy (ADC12) lid material with the shape shown in Figure 2 were immersed for 5 minutes in a degreasing tank containing an aqueous solution (60°C) with 7.5% aluminum degreasing agent, and then rinsed with deionized water. Next, they were immersed for 1 minute in a tank containing an aqueous solution (40°C) with 1.5% caustic soda, rinsed with deionized water, and then immersed for 4 minutes in a tank containing an aqueous solution (40°C) with 5% hydrochloric acid and 1% hydrated aluminum chloride, and rinsed with deionized water. Next, the material was immersed for 1 minute in a tank containing an aqueous solution (at 40°C) with a 2% concentration of ammonium monohydrogen difluoride and a 10% concentration of sulfuric acid, then washed with deionized water, then immersed for 4 minutes in a tank containing a 1.5% concentration of caustic soda aqueous solution (at 40°C), washed with deionized water, and further immersed for 2 minutes in a tank containing a 3% concentration of nitric acid aqueous solution (at 40°C), then washed with deionized water. Then, it was immersed for 1 minute in a tank containing a 3.5% concentration of hydrated hydrazine aqueous solution (at 60°C), washed with deionized water, and further immersed for 1 minute in a tank containing a 0.5% concentration of hydrated hydrazine aqueous solution (at 33°C), washed with deionized water, and finally dried in a hot air dryer to obtain aluminum die-cast alloy (ADC12) plates and aluminum die-cast alloy (ADC12) lids with a surface roughened surface due to chemical treatment.

[0060] To 100 parts by weight of PPS(A-3) obtained in Synthesis Example 3, 7 parts by weight of ethylene copolymer (B-1) were uniformly mixed beforehand and fed into the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX25αIII) heated to a cylinder temperature of 310°C. Meanwhile, glass fiber (C-2) was fed from the hopper of the side feeder of the twin-screw extruder in an amount of 100 parts by weight per 100 parts by weight of PPS(A-3), and a poly(p-phenylene sulfide) resin composition was prepared by melt-kneading and pelletizing.

[0061] The obtained aluminum die-cast alloy (ADC12) sheet material and aluminum die-cast alloy (ADC12) lid material were set 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) with a cylinder temperature of 310°C, a mold temperature of 150°C, and a mold holding pressure of 50 MPa. Insert molding was then performed to create a lid material that is a composite of aluminum die-cast alloy (ADC12) member and polyarylene sulfide resin member, as shown in Figure 4. Then, using the resulting aluminum die-cast alloy (ADC12) member-polyarylene sulfide resin composite lid material, Rz1, Ra1, and Rq1 were measured using an atomic force microscope. Next, the composite was immersed in a tank containing a 10% hydrochloric acid aqueous solution to dissolve only the aluminum die-cast alloy (ADC12) member, and then Rz2, Ra2, and Rq2 of the joint surface were measured using an atomic force microscope.

[0062] The values ​​of │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) were all calculated to be 0.2 or less. Next, the airtightness of the aluminum die-cast alloy (ADC12) member-PPS resin member composite was evaluated, and no bubbles were observed, indicating excellent airtightness. The results are shown in Table 1.

[0063] Example 3 Stainless steel (SUS316) plates (50 mm x 10 mm x 1 mm thick) with the shape shown in Figure 3 and stainless steel (SUS316) lids with the shape shown in Figure 2 were immersed for 5 minutes in a degreasing tank containing an aqueous solution (60°C) with 7.5% aluminum degreasing agent, and then rinsed with deionized water. Next, they were immersed for 1 minute in a tank containing an aqueous solution (40°C) with 1.5% caustic soda, rinsed with deionized water, and then immersed for 3 minutes in a tank containing a 10% sulfuric acid aqueous solution (65°C), and rinsed with deionized water. Finally, they were immersed for 3 minutes in a 3% nitric acid aqueous solution (40°C), rinsed with water, and then dried in a hot air dryer to obtain stainless steel (SUS316) plates and stainless steel (SUS316) lids with a surface roughened surface due to chemical treatment.

[0064] 100 parts by weight of PPS(A-1) obtained in Synthesis Example 1 were uniformly mixed with 8 parts by weight of ethylene copolymer (B-2) beforehand, and then fed into the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX25αIII) heated to a cylinder temperature of 310°C. Meanwhile, glass fiber (C-2) was fed from the side feeder hopper of the twin-screw extruder in an amount of 75 parts by weight per 100 parts by weight of PPS(A-1), and the mixture was melt-kneaded to produce a pelletized poly(p-phenylene sulfide) resin composition.

[0065] The obtained stainless steel (SUS316) plate material and stainless steel (SUS316) lid material were set 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) with a cylinder temperature of 310°C, a mold temperature of 155°C, and a mold holding pressure of 70 MPa. Insert molding was performed to create a lid material that is a composite of stainless steel (SUS316) material and polyarylene sulfide resin material, as shown in Figure 4. Then, Rz1, Ra1, and Rq1 were measured using an atomic force microscope with the obtained stainless steel (SUS316) material-polyarylene sulfide resin material composite lid material. Next, the composite was immersed in a bath containing a 10% hydrochloric acid aqueous solution to dissolve only the stainless steel (SUS316) material, and then Rz2, Ra2, and Rq2 of the joint surface were measured using an atomic force microscope.

[0066] The values ​​of │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) were all calculated to be 0.2 or less. Next, the airtightness of the stainless steel (SUS316) member-PPS resin member composite was evaluated, and no bubbles were observed, indicating excellent airtightness. The results are shown in Table 1.

[0067] Example 4 Copper (C1100) plates (50mm x 10mm x 1mm thick) with the shape shown in Figure 3 and copper (C1100) lids with the shape shown in Figure 2 were immersed for 5 minutes in a degreasing tank containing an aqueous solution (60°C) with 7.5% aluminum degreasing agent, and then rinsed with deionized water. Next, they were immersed for 1 minute in a tank containing an aqueous solution (40°C) with 1.5% caustic soda, and then rinsed with deionized water. Then, they were immersed for 1 minute in a tank containing a 10% nitric acid aqueous solution (40°C), rinsed with deionized water, and finally immersed for 10 minutes in a tank containing a 3% nitric acid aqueous solution (40°C), and then rinsed with deionized water. Next, the materials were immersed for 35 minutes in a tank containing an aqueous solution (at a temperature of 70°C) with 2% potassium permanganate and 3% caustic potassium, washed with deionized water, and then immersed for 10 minutes in a tank containing an aqueous solution (at a temperature of 55°C) with 5% sodium chlorite and 10% caustic soda, washed with deionized water, and finally dried in a hot air dryer to obtain copper (C1100) plates and copper (C1100) lids with a chemically treated, surface-roughened surface.

[0068] To 100 parts by weight of PPS(A-2) obtained in Synthesis Example 2, 10 parts by weight of ethylene copolymer (B-2) were uniformly mixed beforehand and fed into the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX25αIII) heated to a cylinder temperature of 300°C. Meanwhile, glass fiber (C-1) was fed from the side feeder hopper of the twin-screw extruder in an amount of 15 parts by weight per 100 parts by weight of PPS(A-2), and a poly(p-phenylene sulfide) resin composition was prepared by melt-kneading and pelletizing.

[0069] The obtained copper (C1100) plate material and copper (C1100) lid material were set 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) with a cylinder temperature of 300°C, a mold temperature of 150°C, and a mold holding pressure of 50 MPa. Insert molding was performed to create a lid material that is a copper (C1100) member-polyarylene sulfide resin member composite, as shown in Figure 4. Then, Rz1, Ra1, and Rq1 were measured using an atomic force microscope with the obtained copper (C1100) member-polyarylene sulfide resin member composite lid material. Next, the composite was immersed in a bath containing a 10% hydrochloric acid aqueous solution to dissolve only the copper (C1100) member, and then Rz2, Ra2, and Rq2 of the joint surface were measured using an atomic force microscope.

[0070] The values ​​of │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) were all calculated to be 0.2 or less. Next, the airtightness of the copper (C1100) member-PPS resin member composite was evaluated, and no bubbles were observed, indicating excellent airtightness. The results are shown in Table 1.

[0071] Example 5 To 100 parts by weight of PPS(A-2) obtained in Synthesis Example 2, 10 parts by weight of ethylene copolymer (B-1) were uniformly mixed beforehand. The mixture was then placed in the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX25αIII) heated to a cylinder temperature of 280°C, and melt-kneaded to produce a poly(p-phenylene sulfide) resin composition in pellet form.

[0072] A surface-roughened aluminum alloy (A5052) plate and aluminum alloy (A5052) lid material, obtained by the same method as in Example 1, were set in a mold. Using an injection molding machine (Sumitomo Heavy Industries, Ltd., product name SE75S) with a cylinder temperature of 285°C, a mold temperature of 150°C, and a mold holding pressure of 50 MPa, a poly(p-phenylene sulfide) resin composition was injection molded, and insert molding was performed to create the shape shown in Figure 4, thereby producing a lid material that is a composite of an aluminum alloy (A5052) member and a polyarylene sulfide resin member. Then, using the resulting aluminum alloy (A5052) member-polyarylene sulfide resin composite lid material, Rz1, Ra1, and Rq1 were measured using an atomic force microscope. Next, the composite was immersed in a tank containing a 10% hydrochloric acid aqueous solution to dissolve only the aluminum alloy (A5052) member, and then Rz2, Ra2, and Rq2 of the joint surface were measured using an atomic force microscope.

[0073] The calculated values ​​for │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) were all 0.2 or less. Next, the airtightness of the aluminum alloy (A5052) member-PPS resin member composite was evaluated, and no bubbles were observed, indicating excellent airtightness. The results are shown in Table 1.

[0074] [Table 1]

[0075] Comparative Example 1 A composite was prepared using the same method as in Example 1, with the exception that an ethylene copolymer was not mixed, using a PPS resin composition obtained by the same method as in Example 1, a chemically treated and surface-roughened aluminum alloy (A5052) plate material, and an aluminum alloy (A5052) lid material. Rz1, Ra1, Rq1, Rz2, Ra2, and Rq2 were measured using an atomic force microscope with the obtained composite.

[0076] The values ​​of │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) were all calculated to be greater than 0.2. Next, an airtightness evaluation was performed, and the formation of air bubbles was observed, indicating poor airtightness. The results are shown in Table 2.

[0077] Comparative Example 2 A composite was prepared using the same method as in Example 2, with the exception that an ethylene copolymer was not mixed in. The composite was made using a PPS resin composition obtained by the same method as in Example 2, a plate material made of aluminum die-cast alloy (ADC12) with a surface roughened surface due to chemical treatment, and a lid material made of aluminum die-cast alloy (ADC12). Rz1, Ra1, Rq1, Rz2, Ra2, and Rq2 were measured using an atomic force microscope with the obtained composite.

[0078] The calculated values ​​for │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) all exceeded 0.2. Next, an airtightness evaluation was performed, revealing the presence of bubbles and indicating poor airtightness. The results are shown in Table 2.

[0079] Comparative Examples 3-5 A composite was manufactured using the same method as in Example 3, with the mold temperature and mold holding pressure set to the conditions shown in Table 2, using a PPS resin composition obtained by the same method as in Example 3, a stainless steel (SUS316) plate material with a surface roughened by chemical treatment, and a stainless steel (SUS316) lid material. Rz1, Ra1, Rq1, Rz2, Ra2, and Rq2 were measured using an atomic force microscope with the obtained composite.

[0080] The calculated values ​​for │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) all exceeded 0.2. Next, an airtightness evaluation was performed, revealing the presence of bubbles and indicating poor airtightness. The results are shown in Table 2.

[0081] [Table 2]

[0082] Example 6 Aluminum alloy (A5052) plate material (50 mm × 10 mm × 1 mm thick) with the shape shown in Figure 3 and aluminum alloy (A5052) lid material with the shape shown in Figure 2 were immersed for 5 minutes in a degreasing tank containing an aqueous solution (60°C) with 7.5% aluminum degreasing agent, and then washed with deionized water. Next, they were immersed for 2 minutes in a tank containing an aqueous solution (30°C) mixed in the weight ratio of sulfuric acid:ferric chloride:cupric chloride:deionized water = 8.2:7.8:0.4:83.6, washed with deionized water, and then dried in a hot air dryer to obtain aluminum alloy (A5052) and aluminum alloy (A5052) lid material with a chemically treated and surface-roughened surface.

[0083] To 100 parts by weight of PPS(A-1) obtained in Synthesis Example 1, 13 parts by weight of ethylene copolymer (B-1) were uniformly mixed beforehand and fed into the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX25αIII) heated to a cylinder temperature of 300°C. Meanwhile, glass fiber (C-1) was fed from the side feeder hopper of the twin-screw extruder in an amount of 23 parts by weight per 100 parts by weight of PPS(A-1), and a poly(p-phenylene sulfide) resin composition was prepared by melt-kneading and pelletizing.

[0084] The obtained aluminum alloy (A5052) sheet material and aluminum alloy (A5052) lid material were set 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) with the cylinder temperature set to 310°C, the mold temperature to 150°C, and the mold holding pressure to 50 MPa. Insert molding was then performed to create a lid material that is a composite of aluminum alloy (A5052) member and polyarylene sulfide resin member, as shown in Figure 4. Then, using the lid material which was a composite of aluminum alloy (A5052) and polyarylene sulfide resin, Rz1, Ra1, and Rq1 were measured using a confocal laser microscope. Next, the composite was immersed in a tank containing a 10% hydrochloric acid aqueous solution to dissolve only the aluminum alloy (A5052) component. After that, Rz2, Ra2, and Rq2 of the joint surface were measured using a confocal laser microscope, and the values ​​of │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) were calculated, and all were 0.2 or less. Subsequently, the airtightness of the aluminum alloy (A5052) component-PPS resin component composite was evaluated, and no bubbles were observed, indicating excellent airtightness. The results are shown in Table 3.

[0085] Example 7 Aluminum die-cast alloy (ADC12) plates (50 mm × 10 mm × 1 mm thick) with the shape shown in Figure 3 and aluminum die-cast alloy (ADC12) lids with the shape shown in Figure 2 were subjected to continuous irradiation with a single-mode fiber laser using the following conditions: output 274 W, wavelength 1070 nm, laser irradiation speed 10000 mm / sec, and line spacing 0.05 mm. This physical treatment resulted in the acquisition of surface-roughened aluminum die-cast alloy (ADC12) plates and aluminum die-cast alloy (ADC12) lids. The Rz1, Ra1, and Rq1 of the surface-roughened areas of the obtained aluminum die-cast alloy (ADC12) plates and aluminum die-cast alloy (ADC12) lids were then measured using a confocal laser microscope.

[0086] To 100 parts by weight of PPS(A-3) obtained in Synthesis Example 3, 8 parts by weight of ethylene copolymer (B-2) were uniformly mixed beforehand and fed into the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX25αIII) heated to a cylinder temperature of 310°C. Meanwhile, glass fiber (C-2) was fed from the side feeder hopper of the twin-screw extruder in an amount of 95 parts by weight per 100 parts by weight of PPS(A-3), and a poly(p-phenylene sulfide) resin composition was prepared by melt-kneading and pelletizing.

[0087] The obtained aluminum die-cast alloy (ADC12) sheet material and aluminum die-cast alloy (ADC12) lid material were set 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) with a cylinder temperature of 310°C, a mold temperature of 155°C, and a mold holding pressure of 60 MPa. Insert molding was then performed to create a lid material which is a composite of aluminum die-cast alloy (ADC12) member and polyarylene sulfide resin member, as shown in Figure 4. The resulting aluminum die-cast alloy (ADC12) member-polyarylene sulfide resin member composite was immersed in a tank containing a 10% hydrochloric acid aqueous solution to dissolve only the aluminum die-cast alloy (ADC12) member. Then, the Rz2, Ra2, and Rq2 of the joint surface were measured using a confocal laser microscope, and the values ​​of │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) were calculated, all of which were 0.2 or less. Subsequently, the airtightness of the aluminum die-cast alloy (ADC12) member-PPS resin member composite was evaluated, and no bubbles were observed, indicating excellent airtightness. The results are shown in Table 3.

[0088] Example 8 Stainless steel (SUS304) plates (50 mm x 10 mm x 1 mm thick) with the shape shown in Figure 3 and stainless steel (SUS304) lids with the shape shown in Figure 2 were immersed for 5 minutes in a degreasing tank containing an aqueous solution (at 60°C) with 7.5% aluminum degreasing agent, and then washed with deionized water. Next, the plates were immersed for 13 minutes in a tank containing an aqueous solution (at 53°C) mixed with 35% hydrochloric acid aqueous solution, 38% ferric chloride aqueous solution, manganese chloride tetrahydrate aqueous solution, 40% 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine aqueous solution, and deionized water in a weight ratio of 11:48:1:0.05:39.95, washed with deionized water, and then dried in a hot air dryer to obtain stainless steel (SUS304) plates and stainless steel (SUS304) lids with a chemically treated and surface-roughened surface.

[0089] To 100 parts by weight of PPS(A-3) obtained in Synthesis Example 3, 9 parts by weight of ethylene copolymer (B-1) were uniformly mixed beforehand and fed into the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX25αIII) heated to a cylinder temperature of 310°C. Meanwhile, glass fiber (C-2) was fed from the side feeder hopper of the twin-screw extruder in an amount of 70 parts by weight per 100 parts by weight of PPS(A-3), and a poly(p-phenylene sulfide) resin composition was prepared by melt-kneading and pelletizing.

[0090] The obtained stainless steel (SUS304) plate material and stainless steel (SUS304) lid material were set 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) with a cylinder temperature of 310°C, a mold temperature of 155°C, and a mold holding pressure of 60 MPa. Insert molding was then performed to create a lid material that is a composite of stainless steel (SUS304) material and polyarylene sulfide resin material, as shown in Figure 4. Then, using the obtained stainless steel (SUS304) member-polyarylene sulfide resin member composite lid material, Rz1, Ra1, and Rq1 were measured using a confocal laser microscope. Next, the composite was immersed in a tank containing a 10% hydrochloric acid aqueous solution to dissolve only the stainless steel (SUS304) member. After that, Rz2, Ra2, and Rq2 of the joint surface were measured using a confocal laser microscope, and the values ​​of │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) were calculated, and all were 0.2 or less. Subsequently, the airtightness of the stainless steel (SUS304) member-PPS resin member composite was evaluated, and no bubbles were observed, indicating excellent airtightness. The results are shown in Table 3.

[0091] Example 9 Copper (C1100) plates (50 mm × 10 mm × 1 mm thick) with the shape shown in Figure 3 and copper (C1100) plates with the shape shown in Figure 2 were irradiated with laser light using a fiber laser (Keyence Corporation, product name MD-F3200) as the laser oscillator, under the conditions of output 24 W, wavelength 1090 nm, pulse frequency 60 kHz, laser irradiation speed 2000 mm / sec, and line spacing 0.05 mm. This physical treatment resulted in the acquisition of surface-roughened copper (C1100) plates and copper (C1100) lids. The Rz1, Ra1, and Rq1 of the surface-roughened areas of the obtained copper (C1100) plates and copper (C1100) lids were then measured using a confocal laser microscope.

[0092] To 100 parts by weight of PPS(A-1) obtained in Synthesis Example 1, 12 parts by weight of ethylene copolymer (B-1) were uniformly mixed beforehand and fed into the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX25αIII) heated to a cylinder temperature of 300°C. Meanwhile, glass fiber (C-1) was fed from the side feeder hopper of the twin-screw extruder in an amount of 15 parts by weight per 100 parts by weight of PPS(A-1), and a poly(p-phenylene sulfide) resin composition was prepared by melt-kneading and pelletizing.

[0093] The obtained copper (C1100) plate material and copper (C1100) lid material were set 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) with a cylinder temperature of 300°C, a mold temperature of 145°C, and a mold holding pressure of 55 MPa. Insert molding was then performed to create a lid material that is a copper (C1100) member-polyarylene sulfide resin member composite in the shape shown in Figure 4. The composite was then immersed in a tank containing a 10% hydrochloric acid solution to dissolve only the copper (C1100) component. After this, the Rz2, Ra2, and Rq2 of the joint surface were measured using a confocal laser microscope, and the values ​​of │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) were calculated. The results showed that all values ​​were 0.2 or less. Subsequently, the airtightness of the copper (C1100) component-PPS resin component composite was evaluated, and no bubbles were observed, indicating excellent airtightness. The results are shown in Table 3.

[0094] Example 10 To 100 parts by weight of PPS(A-2) obtained in Synthesis Example 2, 8 parts by weight of ethylene copolymer (B-1) were uniformly mixed beforehand. The mixture was then placed in the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX25αIII) heated to a cylinder temperature of 280°C, and melt-kneaded to produce a poly(p-phenylene sulfide) resin composition in pellet form.

[0095] A surface-roughened aluminum alloy (A5052) plate and aluminum alloy (A5052) lid, obtained by the same method as in Example 6, were set in a mold. Using an injection molding machine (Sumitomo Heavy Industries, Ltd., product name SE75S) with a cylinder temperature of 300°C, a mold temperature of 150°C, and a mold holding pressure of 55 MPa, a poly(p-phenylene sulfide) resin composition was injection molded, and insert molding was performed to create a lid that is a composite of an aluminum alloy (A5052) member and a polyarylene sulfide resin member, as shown in Figure 4. Then, using the lid material which was a composite of aluminum alloy (A5052) and polyarylene sulfide resin, Rz1, Ra1, and Rq1 were measured using a confocal laser microscope. Next, the composite was immersed in a tank containing a 10% hydrochloric acid aqueous solution to dissolve only the aluminum alloy (A5052) component. After that, Rz2, Ra2, and Rq2 of the joint surface were measured using a confocal laser microscope, and the values ​​of |(Rz1-Rz2)| / (Rz1+Rz2), |(Ra1-Ra2)| / (Ra1+Ra2), and |(Rq1-Rq2)| / (Rq1+Rq2) were calculated, and all were found to be 0.2 or less. Subsequently, the airtightness of the aluminum alloy (A5052) component-PPS resin component composite was evaluated, and no bubbles were observed, indicating excellent airtightness. The results are shown in Table 3.

[0096] [Table 3]

[0097] Comparative Example 6 A composite was manufactured using the same method as in Example 6, using a PPS resin composition obtained by the same method as in Example 6, a surface-roughened aluminum alloy (A5052) plate material, and an aluminum alloy (A5052) lid material, except that an ethylene copolymer was not mixed. Using the obtained composite, Rz1, Ra1, Rq1, Rz2, Ra2, and Rq2 were measured using a confocal laser microscope, and the values ​​of │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) were calculated, and all were greater than 0.2. Next, an airtightness evaluation was performed, and the generation of bubbles was observed, indicating poor airtightness. The results are shown in Table 4.

[0098] Comparative Examples 7-9 A composite was manufactured using the same method as in Example 6, except that the PPS(A-1) obtained in Synthesis Example 1 was replaced with PE(F-1), PBT(D-1), and PA(E-1), and the cylinder temperature of the twin-screw extruder, the cylinder temperature of the injection molding machine, the mold temperature, and the mold holding pressure were set to the conditions shown in Table 4. Using the resin composition obtained by the same method as in Example 6, a surface-roughened aluminum alloy (A5052) sheet material, and an aluminum alloy (A5052) lid material, a composite was manufactured by the same method as in Example 6. Using the obtained composite, Rz1, Ra1, Rq1, Rz2, Ra2, and Rq2 were measured using a confocal laser microscope, and the values ​​of │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq1-Rq2)│ / (Rq1+Rq2) were all greater than 0.2. Subsequently, an airtightness evaluation was performed, and the generation of air bubbles was observed, indicating poor airtightness. The results are shown in Table 4.

[0099] Comparative Examples 10-12 A composite was manufactured using the same method as in Example 8, with the PPS resin composition, surface-roughened stainless steel (SUS304) plate material, and stainless steel (SUS304) lid material obtained by the same method as in Example 8, except that the mold temperature and mold holding pressure were set to the conditions shown in Table 4. Rz1, Ra1, Rq1, Rz2, Ra2, and Rq2 were measured using a confocal laser microscope with the obtained composite, and the values ​​of │(Rz1-Rz2)│ / (Rz1+Rz2), │(Ra1-Ra2)│ / (Ra1+Ra2), and │(Rq-Rq2)│ / (Rq1+Rq2) were calculated, and all were greater than 0.2. Next, an airtightness evaluation was performed, and the generation of air bubbles was observed, indicating poor airtightness. The results are shown in Table 4.

[0100] [Table 4] [Industrial applicability]

[0101] The present invention provides a composite material that is free of defects such as voids at the joint surface, has excellent airtightness at the joint surface, and further excels in impact resistance, lightness, and mass producibility. It is particularly useful for applications in transportation equipment such as automobiles and aircraft, or for electrical and electronic components in portable devices where waterproofing is required. [Explanation of symbols]

[0102] 1; Metal plate material. 2; Metal plate material. 3; Metal lid material. 4; PPS resin component.

Claims

1. A metal member-polyarylene sulfide resin composite is an injection-molded integral body of a metal member and a polyarylene sulfide resin member, characterized in that it satisfies the following (1) and (2), and is an injection-molded integral body under the conditions of a mold temperature of 140 to 160°C and a mold holding pressure of 30 to 100 MPa. (1) The arithmetic mean roughness (Ra1), maximum height roughness (Rz1), and root mean square height (Rq1) measured on the surface of a metal member using an atomic force microscope or confocal laser microscope with a field of view of 2 μm in accordance with JIS B 0601-2001, and the arithmetic mean roughness (Ra2), maximum height roughness (Rz2), and root mean square height (Rq2) measured on the surface of a polyethylene sulfide resin member using an atomic force microscope or confocal laser microscope with a field of view of 2 μm in accordance with JIS B 0601-2001, satisfy the relationship between |(Ra1-Ra2)| / (Ra1+Ra2)≦0.2, |(Rz1-Rz2)| / (Rz1+Rz2)≦0.2, and / or |(Rq1-Rq2)| / (Rq1+Rq2)≦0.

2. (2) The polyarylene sulfide resin member contains at least 1 to 40 parts by weight of a modified ethylene copolymer with respect to 100 parts by weight of polyarylene sulfide resin.

2. The metal member-polyarylene sulfide resin member composite according to claim 1, characterized in that the modified ethylene copolymer is at least one modified ethylene copolymer selected from the group consisting of ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer, and maleic anhydride graft-modified ethylene-α-olefin copolymer.

3. The metal member-polyarylene sulfide resin member composite according to claim 1 or 2, characterized in that the metal member is a metal member having a chemically treated surface.

4. The metal member-polyarylene sulfide resin member composite according to claim 1 or 2, characterized in that the metal member is a metal member having a surface that has been physically treated.

5. A container characterized in that the metal member-polyarylene sulfide resin member composite described in any one of Claims 1 to 4 is used as the lid material.

6. The container according to claim 5, characterized in that it is a highly airtight container.

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