Metal-resin composite molded article, method for manufacturing metal-resin composite molded article, and method for processing metallic member

Abstract

The present invention pertains to a metal-resin composite molded article in which a metallic member and a polyarylene sulfide-based resin composition member are joined, and in which, in one surface of the metallic member, the arithmetical average curvature of a peak of a surface portion joined to the polyarylene sulfide-based resin composition member is 5000-7000 (1 / mm), and the melt viscosity, specified by ISO 11433, of a polyarylene sulfide-based resin composition forming the polyarylene sulfide-based resin composition member is 20-210 Pa·s under a condition of 310°C and 1000 sec-1. The purpose of the present invention is to increase airtightness at a portion at which the metallic member and the polyarylene sulfide-based resin composition member are joined.

Description

Metal-resin composite molded product, manufacturing method of metal-resin composite molded product, and processing method of metal member

[0001] The present invention relates to a technique for joining a metal member and a polyarylene sulfide resin composition.

[0002] By combining materials with different properties, such as electrically conductive materials such as metals and electrically insulating materials such as resins, lightweight, strong, or highly functional parts are being used in a variety of fields. For example, metal-resin composite molded products, which are made by joining metal members with thermoplastic resins, are used in automobile interior components such as console boxes around instrument panels, engine-related parts, interior parts, housings, interface connections, and power terminals for electronic devices such as digital cameras and mobile phones.

[0003] Generally, bonding and screwing are known as methods for joining different materials such as metal and resin, but these methods are not desirable because they increase the number of processes and parts required. Therefore, various methods for joining metal and resin materials have been proposed.

[0004] For example, Japanese Patent No. 4020957 describes laser processing of the surface of a metal material in a certain scanning direction, followed by laser processing in another scanning direction intersecting the scanning direction, and joining a different material to this surface. Japanese Patent Application Laid-Open No. 2020-116806 describes that by forming irregularities on the surface of a metal plate and keeping the undercut rate of the irregularities within a predetermined range, the joining strength when joining a resin molded product to this surface is improved. Japanese Patent Application Laid-Open No. 2013-71312 describes a metal-resin composite molded product in which crater-shaped depressions are formed in the metal using laser light or the like, and granular spatter is formed on the ridge-like protrusions where the metal surface melts and splashes. Japanese Patent No. 6819798 describes a composite structure formed by bonding a surface-roughened metal member and a PPS resin composition member, in which, when any five points on the surface of the surface-roughened metal member are measured using a confocal microscope in accordance with ISO (International Organization for Standardization) 25178, the number average developed area ratio (Sdr) of the interface is in the range of 5 or more, and the melt viscosity of the PPS resin is in the range of 15 to 500 [Pa s].

[0005] However, conventional methods for joining metal materials and resin materials have not been able to ensure sufficient airtightness at the joint between the metal material and the resin material, and there is a need to improve this point. Therefore, the present invention aims to provide a manufacturing method for a metal-resin composite molded product in which a metal member and a polyarylene sulfide-based resin composition member are joined, which improves the airtightness at the joint, the manufactured metal-resin composite molded product, and a method for processing a metal member.

[0006] A first aspect of the present invention is a metal-resin composite molded article in which a metal member and a polyarylene sulfide-based resin composition member are bonded together. This metal-resin composite molded article uses a polyarylene sulfide-based resin composition having excellent fluidity, and the surface texture of the surface portion of one side of the metal member that is bonded to the polyarylene sulfide-based resin composition member has an arithmetic mean curvature of the apex of 5000 to 7000 (1 / mm).

[0007] A second aspect of the present invention is a method for processing a metal member for producing a metal-resin composite molded product in which the metal member and a polyarylene sulfide-based resin composition member are joined together, in which the surface of the metal member is irradiated with a high-energy beam to provide a surface texture in which the arithmetic mean curvature of the vertices of the surface is 5000 to 7000 (1 / mm).

[0008] A third aspect of the present invention is a method for producing a metal-resin composite molded article in which a metal member and a polyarylene sulfide-based resin composition member are bonded together. In this method, the surface of the metal member is irradiated with a high-energy beam to give the metal member a surface texture with an arithmetic mean curvature of the vertices of the surface of the metal member of 5000 to 7000 (1 / mm), and the metal member is then inserted into a mold and a polyarylene sulfide-based resin composition having a melt viscosity of 20 to 210 Pa s is injection molded to bond the polyarylene sulfide-based resin composition member to the surface of the metal member.

[0009] According to an aspect of the present invention, it is possible to improve the airtightness of the joint portion of a metal-resin composite molded product in which a metal member and a member made of a polyarylene sulfide resin composition are joined together.

[0010] FIG. 1 is a diagram schematically illustrating a method for processing a metal member according to an embodiment. FIG. 2 is a diagram illustrating exemplary metal clusters formed in a laser irradiated portion of a metal member. FIG. 3 is a diagram illustrating a schematic diagram of the interface between a metal member and a polyarylene sulfide-based resin composition member according to the magnitude of Spc on the surface of the polyarylene sulfide-based resin composition member in a metal-resin composite molded product according to an embodiment. FIG. 4 is a diagram illustrating the shape of a test piece used in an airtightness test. FIG. 5 is a diagram illustrating a schematic configuration of a test device for an airtightness test.

[0011] A metal-resin composite molded article according to one embodiment of the present invention will be described below. The metal-resin composite molded article of one embodiment is formed by bonding a metal member to a resin composition member, particularly a polyarylene sulfide-based resin composition member. In this metal-resin composite molded article, the bonding surface of one surface of the metal member that is bonded to the polyarylene sulfide-based resin composition member has irregularities. In one embodiment, the irregularities on the bonding surface are formed by substantially spherical metal clusters. The term "substantially spherical" does not necessarily mean that the individual shapes of the metal clusters are perfect spheres, but also includes spheroids and shapes in which a portion of a sphere or spheroid is missing. These substantially spherical metal clusters can be formed, for example, by irradiating the surface of the metal member with a laser. For example, spherical metal clusters can be formed on the surface of the metal member by irradiating the surface of the metal member with a laser under specified irradiation conditions. As a result of intensive research, the inventors of the present application have found that by providing a desired surface roughness to the surface of one surface of a metal member that is bonded to a polyarylene sulfide-based resin composition member, the airtightness of the bonded surface between the metal member and the polyarylene sulfide-based resin composition member in a metal-resin composite molded product can be improved compared to conventional methods. In the following embodiment, a case will be described in which the desired surface roughness is achieved by forming substantially spherical clusters on the bonded surface between the metal member and the polyarylene sulfide-based resin composition member, but this is not limited thereto. It is sufficient to achieve the desired surface roughness on the bonded surface between the metal member and the polyarylene sulfide-based resin composition member, and the surface treatment method therefor is not limited. The shapes of the metal member, the resin composition member, and the metal-resin composite molded product are not particularly limited, and this embodiment can be applied to metal-resin composite molded products of any shape.

[0012] The metal constituting the metal member contained in the metal-resin composite molded product is not limited, but examples thereof include aluminum, copper, silver, gold, iron, titanium, nickel, magnesium, zinc, and their alloys such as carbon steel and stainless steel. The surface of the metal member may be subjected to a surface treatment such as anodizing or may be painted. From the viewpoints of light weight and strength, it is preferable to use aluminum, magnesium, copper, or titanium as the metal. For applications requiring electrical conductivity, such as terminals, it is more preferable to use aluminum or copper, with copper being particularly preferred. For applications requiring thin-walled rigidity, it is particularly preferable to use magnesium or titanium, especially titanium.

[0013] [Polyarylene sulfide resin] The polyarylene sulfide resin (hereinafter sometimes referred to as "PAS resin") used in the polyarylene sulfide resin composition is characterized by excellent mechanical properties, electrical properties, heat resistance and other physical and chemical properties, as well as good processability. Polyarylene sulfide resins are polymer compounds mainly composed of repeating units of -(Ar-S)- (Ar represents an arylene group, and Ar-S represents an arylene sulfide group), and in this embodiment, polyarylene sulfide resins with a generally known molecular structure can be used.

[0014] Examples of the arylene group include p-phenylene, m-phenylene, o-phenylene, substituted phenylene, p,p'-diphenylenesulfone, p,p'-biphenylene, p,p'-diphenylene ether, p,p'-diphenylenecarbonyl, and naphthalene. The PAS resin may be a homopolymer consisting of only the above repeating units, or a copolymer containing the following different repeating units may be preferred in terms of processability and the like.

[0015] As the homopolymer, a polyphenylene sulfide resin having a p-phenylene sulfide group as a repeating unit, in which a p-phenylene group is used as the arylene group, is preferably used. Furthermore, as the copolymer, a copolymer formed from a combination of two or more different arylene sulfide groups containing the above-mentioned arylene group can be used. Among these, a copolymer formed from a combination of a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferred. Among these copolymers, those containing 70 mol % or more, preferably 80 mol % or more, of p-phenylene sulfide groups are suitable from the viewpoint of physical properties such as heat resistance, moldability, and mechanical properties. Furthermore, among these polyarylene sulfide resins, a high-molecular-weight polymer having a substantially linear structure (e.g., poly-p-phenylene sulfide) obtained by condensation polymerization of a monomer mainly composed of a bifunctional halogenated aromatic compound is particularly preferred. The polyarylene sulfide resin used in this embodiment may be a mixture of two or more polyarylene sulfide resins having different molecular weights.

[0016] In addition to the linear polyarylene sulfide resin, a polymer can be used in which a small amount of a monomer such as a polyhaloaromatic compound having three or more halogen substituents is used during condensation polymerization to form a partially branched or crosslinked structure. Also used is a polymer in which a low-molecular-weight linear polymer is heated at high temperature in the presence of oxygen or the like to increase the melt viscosity through oxidative crosslinking or thermal crosslinking, thereby improving moldability. In this embodiment, the polyarylene sulfide resin composition refers to a composition containing one or more of the above-mentioned polyarylene sulfide resins and other additives that can be added as needed.

[0017] [Olefin-Based Copolymer] In this embodiment, an olefin-based copolymer may be added to the polyarylene sulfide-based resin composition to improve the bonding between a metal member and a polyarylene sulfide-based resin composition member. The olefin-based copolymer contains an α-olefin, a glycidyl ester of an α,β-unsaturated acid, and a (meth)acrylic acid ester as copolymerization components. First, the essential copolymerization components will be described.

[0018] In the present invention, the α-olefin is not particularly limited, and conventionally known α-olefins can be used. For example, ethylene, propylene, butylene, etc. are usable. Among these α-olefins, ethylene is particularly preferred. Two or more of these α-olefins can also be used in combination.

[0019] The glycidyl ester of an α,β-unsaturated acid is a component represented by the following general formula (1). (R1 in formula (1) represents hydrogen or a lower alkyl group.)

[0020] Examples of the compound represented by the general formula (1) include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, etc. In the present invention, it is preferable to use glycidyl methacrylate.

[0021] The inclusion of a glycidyl ester of an α,β-unsaturated acid as a copolymerization component improves bonding with metals. However, as the content of the copolymerization component derived from the glycidyl ester increases, the problem of mold deposits becomes more pronounced. Traditionally, mold deposits have been thought to be caused by thermal degradation of thermoplastic elastomers such as olefin copolymers at high temperatures. However, in the case of an olefin copolymer containing an α-olefin and a glycidyl ester of an α,β-unsaturated acid as copolymerization components, the problem of mold deposits can be reduced even when using an olefin copolymer by reducing the amount of glycidyl ester of an α,β-unsaturated acid used.

[0022] The acrylic acid ester that can be used in the embodiment is not particularly limited, and conventionally known acrylic acid esters can be used. Examples of acrylic acid esters that can be used include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, etc.), methacrylic acid and methacrylic acid esters (e.g., methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-octyl methacrylate, etc.). Of these acrylic acid esters, methyl acrylate is particularly preferred.

[0023] The olefin copolymer used in the embodiment may contain other copolymer components within the range that does not impair the effects of the present invention.

[0024] The olefin copolymer used in the embodiment can be produced by polymerization using a conventionally known method.

[0025] The content of the olefin copolymer contained in the composition of the present invention is not particularly limited. In an embodiment, the olefin copolymer is preferably contained in an amount of 0 to 20 parts by mass, more preferably 1% by mass or more and 15% by mass or less, relative to 100 parts by mass of the polyarylene sulfide resin.

[0026] [Inorganic Filler] The resin composition of the present invention can be blended with an inorganic filler for the purpose of improving performance such as mechanical strength, heat resistance, dimensional stability (resistance to deformation and warpage), and electrical properties. As the inorganic filler, fibrous, powdery, or plate-like fillers can be used depending on the purpose. Examples of fibrous fillers include inorganic fibrous materials such as glass fiber, asbestos fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, potassium titanate fiber, and fibrous metals such as stainless steel, aluminum, titanium, copper, and brass. Particularly representative fibrous fillers are glass fiber and carbon fiber. On the other hand, examples of powdery fillers include carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, metal oxides such as iron oxide, titanium oxide, zinc oxide, and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, silicon carbide, silicon nitride, boron nitride, and various metal powders. Examples of plate-like fillers include mica, glass flakes, and various metal foils. In an embodiment, the use of glass fiber, calcium carbonate, and glass beads, or a combination of these, is preferred. These inorganic fillers can be used alone or in combination of two or more.

[0027] In the embodiment, the content of the inorganic filler is preferably 0 to 70 parts by mass, and more preferably 0 to 65 parts by mass, relative to 100 parts by mass of the polyarylene sulfide resin. If the content of the inorganic filler is more than 70 parts by mass, the melt viscosity of the polyarylene sulfide-based resin composition increases, and the polyarylene sulfide-based resin may not fill the metal clusters on the surface of the metal member, and airtightness between the metal member and the polyarylene sulfide-based resin composition member may not be obtained.

[0028] [Other Components] The polyarylene sulfide resin composition used in the embodiment may contain other resins as long as the effects of the present invention are not impaired. The polyarylene sulfide resin composition used in the present invention also includes compositions to which desired properties have been imparted by adding a nucleating agent, a pigment such as carbon black or an inorganic calcined pigment, an antioxidant, a stabilizer, a plasticizer, a lubricant, or a mold release agent in order to impart desired properties to a molded article.

[0029] [Polyarylene sulfide resin composition] The polyarylene sulfide resin composition of the embodiment can be prepared by a conventionally known method. For example, any of the following methods can be used: a method in which each component is mixed and then kneaded and extruded in an extruder to prepare pellets; a method in which pellets with different compositions are first prepared, a predetermined amount of the pellets are mixed and molded to obtain a molded product of the desired composition; and a method in which one or more of the components are directly charged into a molding machine. The melt viscosity of the polyarylene sulfide resin composition of the embodiment according to ISO 11433 is 310°C, 1000 sec. －１ It is preferable that the viscosity is 20 to 210 Pa·s under the above conditions.

[0030] The method for joining the metal member and the polyarylene sulfide-based resin composition member will be described in detail later, but is not particularly limited. For example, they can be joined by welding methods such as ultrasonic welding, vibration welding, and laser welding, or injection molding. For example, joining is preferably performed by insert molding using a metal material as an insert member. The metal member used in the embodiment and its processing method will be described later.

[0031] A second embodiment of the present invention is a method for processing a metal member for producing a metal-resin composite molded product in which a metal member and a polyarylene sulfide-based resin composition member are bonded. FIG. 1 schematically illustrates the second embodiment of the method for processing a metal member. As shown in FIG. 1, when a laser is irradiated onto a metal member, the metal on the surface of the metal member is melted by the high-energy laser beam, pushed out of the irradiated area, and then solidified into spherical shapes due to surface tension, thereby forming irregularities on the surface of the metal member. In one embodiment, the surface of the metal member is scanned with a laser at a fine pitch, generating spherical objects that overlap to form metal clusters. Alternatively, the metal member sublimes, and liquid metal particles scattered by the metal member solidify (re-adhere), and accumulate to form spherical metal clusters. FIG. 2 illustrates an exemplary image of a metal cluster formed in the laser-irradiated area when the metal member is irradiated with a laser. Here, when the laser output (energy per unit time) is low, the metal on the surface of the metal member does not melt, or sublimation or scattering of liquid metal particles does not occur. Therefore, the laser output for forming spherical metal clusters is appropriately determined depending on the metal material used for the metal member. Furthermore, to form the molten metal extruded outside the laser irradiation area into minute spheres, the laser scanning pitch is preferably 30 μm or less, more preferably 20 μm or less, or even 10 μm or less. The laser output and irradiation speed determine the energy imparted to the metal member surface per unit area per unit time. Therefore, in addition to the laser output, the irradiation speed is also a factor in forming spherical metal clusters. Appropriate laser output and irradiation speed cause a localized temperature rise on the metal member surface in an extremely short time, thereby forming spherical metal clusters. Using the metal member processing method of the second embodiment, substantially spherical metal clusters can be formed on the surface portion of one surface of the metal member used in the metal-resin composite molded product of the first embodiment that is bonded to the polyarylene sulfide-based resin composition member.

[0032] From the viewpoint of ensuring sufficient airtightness of the joint surface between the metal member and the polyarylene sulfide-based resin composition member, it is preferable that spherical metal clusters are formed over the entire joint surface between the metal member and the polyarylene sulfide-based resin composition member. To achieve this, it is advisable to make the laser scanning pitch smaller than the laser irradiation diameter.

[0033] In this disclosure, the term "high-energy beam" refers to a beam with energy per unit time high enough to form spherical metal clusters on the surface of a metal member. A typical high-energy beam is a laser, but is not limited to this and may also be a beam generated by an electron gun.

[0034] A third embodiment is a method for producing a metal-resin composite molded article in which a metal member and a polyarylene sulfide-based resin composition member are bonded. The method for producing a metal-resin composite molded article of the third embodiment involves irradiating the surface of the metal member with a high-energy beam such as a laser to form irregularities on the surface of the metal member, and then melt-bonding the metal member with the irregularities formed on the surface to the polyarylene sulfide-based resin composition member. In the third embodiment, substantially spherical metal clusters are formed on the surface (bonding surface) of the metal member. By forming spherical metal clusters on the bonding surface between the metal member and the polyarylene sulfide-based resin composition member, when the metal member and the polyarylene sulfide-based resin composition member are insert-molded, the molten polyarylene sulfide-based resin composition penetrates into the spherical metal clusters, thereby improving adhesion between the metal and the polyarylene sulfide-based resin composition during the molding stage. Therefore, the produced metal-resin composite molded article achieves higher airtightness than conventional at the bonding surface between the metal member and the polyarylene sulfide-based resin composition member.

[0035] The area where spherical metal clusters are formed on the surface of the metal member is preferably the entire joint surface between the metal member and the polyarylene sulfide-based resin composition member, but is not limited to this. For example, if spherical metal clusters are formed over a large portion of the joint surface, for example, 70 to 80% or more of the joint surface, a sufficiently high level of airtightness can be ensured at the joint surface between the metal member and the polyarylene sulfide-based resin composition member. For example, when the entire joint surface between the metal member and the polyarylene sulfide-based resin composition member is irradiated with a laser, if the laser scanning pitch is larger than the laser irradiation diameter, areas of the joint surface will not be irradiated with the laser. Even in this case, if the area of ​​the joint surface that is not irradiated with the laser is relatively small, a sufficiently high level of airtightness can be ensured at the joint surface between the metal member and the polyarylene sulfide-based resin composition member.

[0036] The present inventors further focused on the shape of the spherical metal clusters formed on the surface of a metal member and conducted research into the relationship between various surface roughness parameters of the metal member surface and the airtightness of the joint surface between the metal member and a polyarylene sulfide-based resin composition member. As a result, they found that by setting the Spc (arithmetic mean curvature of the peaks) of the apexes of the spherical metal clusters within a predetermined range, the airtightness of the joint surface between the metal member and the polyarylene sulfide-based resin composition member can be significantly improved. Spc (arithmetic mean curvature of the peaks) is a surface texture parameter defined in ISO 25178 and represents the average value of the principal curvatures of the peaks formed on the surface to be evaluated. A small Spc indicates that the point (peak) that comes into contact with another object (in this embodiment, a polyarylene sulfide-based resin composition member) is rounded, while a large Spc indicates that the point that comes into contact with another object is sharp.

[0037] The reason why the airtightness of the joint surface between the metal member and the resin is improved by setting the Spc of the apex of the spherical metal cluster within a predetermined range is inferred as follows, with reference to FIG. 3 . FIG. 3 schematically shows the joint surface between the metal member and the polyarylene sulfide-based resin composition member when the Spc of the apex of the spherical metal cluster formed on the surface of the metal member is large ("large Spc"), medium ("medium Spc"), and small ("small Spc"). When the Spc on the surface of the metal member is large, the apex of the spherical metal cluster has a sharp shape. When the polyarylene sulfide-based resin composition in contact with this surface cools, sink marks (shrinkage) occur. However, if the apex of the metal cluster has a sharp shape, gaps are likely to occur between the polyarylene sulfide-based resin composition and the metal at the joint surface of the apex, which is disadvantageous in terms of achieving high airtightness. On the other hand, when the Spc on the surface of the metal member is small, the spherical metal cluster has a surface texture that changes gradually overall. The surface area of ​​the joint between the metal member and the polyarylene sulfide-based resin composition member is small, and it is difficult to improve the adhesion between the metal member and the polyarylene sulfide-based resin composition member during the molding stage of the metal-resin composite molded product. Therefore, when the Spc on the surface of the metal member is moderate, the molten polyarylene sulfide-based resin composition penetrates sufficiently into the spherical metal clusters on the surface of the metal member. Therefore, it is presumed that the adhesion between the metal member and the polyarylene sulfide-based resin composition member of the metal-resin composite molded product can be extremely improved.

[0038] Specifically, the Spc of the apex of the spherical metal cluster on the surface of the metal member is preferably in the range of 5000 to 7000 (1 / mm), and more preferably in the range of 5500 to 6500 (1 / mm). To adjust this Spc to fall within the desired range, the energy applied by laser irradiation to the surface that will become the joining surface between the metal member and the polyarylene sulfide-based resin composition member is controlled. When a pulsed laser is used as the laser, the energy E per pulse is expressed as P / f, where P is the average output and f is the frequency. Therefore, by adjusting the average output P (so-called laser output) and / or the frequency f, the energy applied to the surface that will become the joining surface between the metal member and the polyarylene sulfide-based resin composition member can be controlled. For example, increasing the frequency of the pulsed laser reduces the amount of energy per pulse applied to the surface of the metal member, thereby tending to decrease the Spc. Conversely, decreasing the frequency of the pulsed laser increases the amount of energy per pulse applied to the surface of the metal member, tending to increase the Spc, but once the amount of energy becomes sufficiently large, the Spc saturates. Furthermore, since Spc may change depending on environmental conditions (for example, Spc may decrease if the environmental temperature is low), it is checked whether Spc is within a desired range after laser irradiation.

[0039] The particle size of the particles constituting the metal clusters is preferably 1 to 500 μm, more preferably 5 to 300 μm, and particularly preferably 10 to 200 μm. If the particle size is less than 1 μm, the polyarylene sulfide resin may not fill the gaps between the particles constituting the resin clusters, resulting in poor adhesion. If the particle size exceeds 500 μm, shrinkage of the polyarylene sulfide resin after molding may cause gaps between the resin and the metal member, resulting in poor airtightness.

[0040] The method for joining a metal member and a polyarylene sulfide-based resin composition member is not limited, and they can be joined by welding methods such as ultrasonic welding, vibration welding, and laser welding, or by injection molding. For example, they can be joined by insert molding using a metal material as an insert member. That is, a metal member having spherical metal clusters formed on its surface as described above is inserted into a mold, and a polyarylene sulfide-based resin composition is injected into the mold, and these are molded together to join the polyarylene sulfide-based resin composition member to the surface of the metal member.

[0041] The manufacture of a metal-resin composite molded product will be specifically described below. In the examples, a metal-resin composite molded product 10 (hereinafter referred to as "test piece 10") having the shape shown in FIG. 4 was prepared as a test piece. As shown in FIG. 4, the test piece 10 consisted of a circular metal member 11 having an inner hole in the center and a resin molded product 12 placed in the inner hole of the metal member 11. The metal member 11 had an outer diameter of φ50 mm, an inner hole diameter of φ20 mm, and a thickness of 1 mm. The resin molded product 12 had an outer diameter of φ30 mm and a thickness of 3 mm.

[0042] The components used in the materials constituting the metal member 11 and the resin molded article 12 are as follows: Metal member: aluminum A5052, copper C1100 Polyarylene sulfide resin composition: Polyarylene sulfide resin 1: Fortron KPS (melt viscosity: 20 Pa·s (shear rate: 1200 sec)) manufactured by Kureha Corporation －１ , 310°C)) Polyarylene sulfide resin 2: Fortron KPS manufactured by Kureha Corporation (melt viscosity: 28 Pa·s (shear rate: 1200 sec) －１, 310°C) Polybutylene terephthalate resin: "300FP" manufactured by Polyplastics Co., Ltd. Polyethylene terephthalate resin: "PET II" manufactured by Takayasu Co., Ltd. Olefin copolymer 1: "Bondfast 7L" manufactured by Sumitomo Chemical Co., Ltd. Olefin copolymer 2: "Bondfast 7M" manufactured by Sumitomo Chemical Co., Ltd. Glass fiber 1: "ECS03T747" manufactured by Nippon Electric Glass Co., Ltd. Glass fiber 2: "ECS03T187" manufactured by Nippon Electric Glass Co., Ltd. Calcium carbonate: "MC-35W" manufactured by Asahi Komatsu Co., Ltd. Carbon black: "MA600B" manufactured by Mitsubishi Chemical Corporation Pentaerythritol stearate: LOXYOL VPG861 manufactured by Emery Oleochemicals Japan Antioxidant: "Irganox 1010" manufactured by BASF Japan Ltd. Phosphorus-based stabilizer: monocalcium phosphate manufactured by Taihei Chemical Industry Co., Ltd. Table 1 shows the ratio of components of the polyarylene sulfide resin composition used as the material for the resin molded article. The melt viscosity of the polyarylene sulfide resin composition shown in Table 1 was measured in accordance with ISO 11433 as follows: A Capillograph manufactured by Toyo Seiki Seisakusho Co., Ltd. was used, and a flat die with a diameter of 1 mm and a length of 20 mm was used as a capillary. The barrel temperature was 310°C, and the shear rate was 1000 sec. －１ The melt viscosity was measured under the following conditions.

[0043] Before joining with the resin molded product 12, a laser processing machine (ML-7350DL manufactured by Amada Weld Tech) was used to perform concentric laser processing on the surface of the metal member 11 in a range of φ20 mm to φ26 mm (the joining surface with the resin molded product 12). Table 2 below shows the laser irradiation conditions for Examples 1 and 2. Tables 3 and 4 below show the laser irradiation conditions for Comparative Examples 1 to 11. Although not shown in the tables, the laser irradiation pitch was 10 μm and the irradiation diameter was 58 μm for all Examples and Comparative Examples. The pitch is the distance between the concentric circles scanned by the laser. Because the pitch was smaller than the irradiation diameter, the entire joining surface between the metal member 11 and the resin molded product 12 was irradiated with the laser.

[0044] In all examples and comparative examples, the surface of the metal member 11 was observed with a scanning electron microscope (SEM), and it was confirmed that spherical metal clusters were formed all over the surface. Furthermore, the Spc of the apex of the spherical metal clusters formed on the surface of the metal member 11 was measured using a Keyence VK-X3000 laser microscope (see Tables 2 to 4).

[0045] After laser treatment of the metal member 11, insert molding was performed under the following conditions using the metal member 11 as an insert member and each material listed in Table 1 as a resin composition, and the metal member 11 and the resin molded product 12 were joined to form a test piece 10 of a metal resin composite molded product shown in Figure 4. The insert molding conditions were as follows: Injection molding machine: Sodick TR100EH Cylinder temperature: 320°C (Examples 1 and 2, Comparative Examples 1 to 11), 260°C (Comparative Examples 12 to 15) Mold temperature: 150°C (Examples 1 and 2, Comparative Examples 1 to 11), 80°C (Comparative Examples 12 to 15) Injection speed: 15 mm / s Holding pressure: 50 MPa

[0046] Next, an airtightness test was performed on the bonded surface between the metal member 11 and the resin molded article 12 for the test specimens 10 molded as examples and comparative examples. The configuration of the test apparatus for the airtightness test (helium leak test, vacuum method) is shown in FIG. 5 . As shown in FIG. 5 , a jig 2 and a test specimen 10 were placed in a chamber 3 sealed from the outside. The jig 2 had a bottomed rectangular parallelepiped shape, and by placing the test specimen 10 on top, the interior of the jig 2 was sealed from the rest of the chamber 3. With the valve 6 open, a vacuum was created inside the jig 2 using a vacuum pump 5. Then, with the valve 6 closed, the chamber 3 was filled with helium gas using a helium cylinder 4. Helium gas leaking from the bonded portion of the test specimen 10 in the chamber 3 was detected by a helium detector 7. A control device 8 displayed the helium gas detection results. A G-FINE Helium Leak Tester manufactured by Cosmo Instruments Co., Ltd. and an L300i Helium Leak Tester manufactured by Inficon Co., Ltd. were used as the helium detector 7.

[0047] The helium pressure in the chamber 3 was set to 400 kPa, and the vacuum pressure in the jig 2 was set to 100 kPa. If the airtightness of the joint between the metal member 11 and the resin molded product 12 of the test piece 10 is low, the helium gas in the chamber 3 will flow into the jig 2 and be detected by the helium detector 7. In this test, the helium pressure (detected pressure) detected by the helium detector 7 was 1.0 × 10 －７ (In the table, this is shown as "1.0E-7") Pa·m ３ / s or more is judged to be poor airtightness, and 1.0 x 10 －７ (1.0E-7) Pa・m ３ With respect to the detected pressure of the airtightness test on the test specimens, Table 2 shows the results of Examples 1 and 2, and Tables 3 and 5 show the results of Comparative Examples 1 to 15.

[0048]

[0049] According to Tables 2 to 5, when the melt viscosity of the polyarylene sulfide-based resin composition is 210 Pa s or less and the SPC of the apex of the metal cluster of the metal member is 5000 to 7000 (1 / mm), it was confirmed that the airtightness of the joint between the metal member and the polyarylene sulfide-based resin composition member is high (i.e., the detected pressure is low). As shown in Comparative Examples 1 and 2, even if the melt viscosity of the polyarylene sulfide-based resin composition is 210 Pa s or less, good airtightness could not be obtained when the SPC of the metal member is outside the above range. Furthermore, as shown in Comparative Examples 4, 5, and 7 to 10, even if the SPC of the metal member is within the above range, good airtightness could not be obtained at the joint between the metal member and the polyarylene sulfide-based resin composition member when the melt viscosity of the polyarylene sulfide-based resin composition exceeds 210 Pa s. Furthermore, as shown in Comparative Examples 13 and 14, when a resin composition other than a polyarylene sulfide-based resin composition was used, good airtightness could not be obtained at the joint between the metal member and the polyarylene sulfide-based resin composition member, even when the Spc of the metal member was 5000 to 7000 (1 / mm) and the viscosity of the resin composition was 210 Pa·s or less.

[0050] Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments. Furthermore, the above-described embodiments can be improved or modified in various ways without departing from the spirit of the present invention.

[0051] Reference Signs List 2: Jig 3: Chamber 4: Helium cylinder 5: Vacuum pump 6: Valve 7: Helium detector 8: Control device 10: Metal-resin composite molded product 11: Metal member 12: Resin molded product

Claims

1. A metal-resin composite molded product in which a metal member and a polyarylene sulfide-based resin composition member are joined together, The arithmetic mean curvature of the vertex of the surface portion of one side of the metal member that is joined to the polyarylene sulfide resin composition member is 5000 to 7000 (1 / mm). The melt viscosity of the polyarylene sulfide resin composition constituting the aforementioned polyarylene sulfide resin composition member, according to ISO 11433, is 310°C and 1000 sec. －１ A metal-resin composite molded product having a pressure of 20 to 210 Pa·s under the specified conditions.

2. Substantially spherical metal clusters are formed on the surface portion. The metal-resin composite molded article according to claim 1, wherein the arithmetic mean curvature of the vertices of the metal cluster is 5000 to 7000 (1 / mm).

3. The polyarylene sulfide resin composition comprises an olefin copolymer, The metal resin composite molded article according to claim 1, wherein the copolymerization component of the olefin copolymer comprises an α-olefin, a glycidyl ester of an α,β-unsaturated acid, and an acrylic acid ester.

4. The metal-resin composite molded article according to claim 1, wherein the arithmetic mean curvature of the vertices of the surface portion is 5500 to 6500 (1 / mm).

5. A method for manufacturing a metal-resin composite molded product in which a metal member and a polyarylene sulfide-based resin composition member are joined together, By irradiating the surface of the metal member with a high-energy beam, the metal member, whose arithmetic mean curvature at the vertices of the surface is set to 2500 to 7000 (1 / mm), is inserted into a mold, and the polyarylene sulfide resin composition is injection molded to bond the polyarylene sulfide resin composition member to the surface of the metal member. A method for manufacturing metal-resin composite molded products.

6. A method for manufacturing a metal-resin composite molded product in which a metal member and a polyarylene sulfide-based resin composition member are joined together, A high-energy beam is irradiated onto the surface of the metal member to form a substantially spherical metal cluster on the surface, wherein the arithmetic mean curvature of the vertices is 2500 to 7000 (1 / mm). A metal member having substantially spherical metal clusters formed on its surface is inserted into a mold, and the polyarylene sulfide resin composition is injection molded to bond the polyarylene sulfide resin composition member to the surface of the metal member. A method for manufacturing metal-resin composite molded products.

7. The method for manufacturing a metal-resin composite molded article according to claim 5, wherein the arithmetic mean curvature of the vertices of the metal cluster is 5000 to 7000 (1 / mm).

8. The method for manufacturing a metal-resin composite molded article according to claim 5, wherein the arithmetic mean curvature of the vertices of the metal cluster is 5500 to 6500 (1 / mm).

9. A method for processing a metal component for a metal-resin composite molded product in which a metal component and a polyarylene sulfide-based resin composition component are joined, A method for processing a metal member, comprising irradiating the surface of the metal member with a high-energy beam to make the arithmetic mean curvature of the vertices of the surface 2500 to 7000 (1 / mm).

10. A method for processing a metal component for a metal-resin composite molded product in which a metal component and a polyarylene sulfide-based resin composition component are joined, A method for processing a metal member, comprising irradiating the surface of the metal member with a high-energy beam to form substantially spherical metal clusters on the surface, wherein the arithmetic mean curvature of the vertices is 2500 to 7000 (1 / mm).

11. The method for processing a metal member according to claim 9, wherein the arithmetic mean curvature of the vertices of the surface is 5000 to 7000 (1 / mm).

12. The method for processing a metal member according to claim 9, wherein the arithmetic mean curvature of the vertices of the surface is 5500 to 6500 (1 / mm).