TWI624358B - Metal resin composite formed body and manufacturing method thereof - Google Patents

Abstract

Provided are a metal-resin composite molded body having strong bonding strength between embedded metal elements and resin elements, good surface appearance, and excellent chemical resistance to acids, alkalis, and the like, and a method for producing the same.

Provided is a metal-resin composite molded body comprising an embedded metal element and a resin element, wherein the resin element is composed of a resin composition and is insert-molded on the embedded metal element; the embedded metal element is in contact with the resin element At least a part of the surface is subjected to a physical treatment and / or a chemical treatment. The aforementioned resin composition contains: (A) 100 parts by mass of a polyarylene sulfide resin; (B) 10 ~ 250 parts by mass of an inorganic filler, which is non-fibrous and has an average particle diameter of 30 μm or less and is selected from A group consisting of spherical silica and glass beads; and (C) 3 to 55 parts by mass of an epoxy compound.

Description

Metal resin composite formed body and manufacturing method thereof

The present invention relates to a metal-resin composite formed body and a method for manufacturing the same.

A metal-resin composite formed by integrating an embedded metal element composed of a metal, an alloy, or the like and a resin element composed of a thermoplastic resin composition have conventionally been used for control around an instrument panel. Parts such as interior components, engine peripheral parts, internal parts, digital cameras, mobile phones, and other electronic devices, such as cases, are connected to the outside, including power supply terminals.

As a method of integrating the embedded metal element and the resin element, there is a method of improving the adhesion between the embedded metal element and the resin element by performing a physical treatment and / or a chemical treatment on a joint surface of the embedded metal element side; using an adhesive A method of adhering to a double-sided tape; a method of installing a fixing element such as a folding sheet or a hook in a metal element and / or a resin element and using the fixing element to fix the two; and a method of bonding using a screw or the like . Among these, in terms of the degree of freedom in designing the metal-resin composite molded body, a method of performing a physical treatment and / or a chemical treatment on the joint surface embedded in the metal element side and the use of an adhesive are effective.

Especially in terms of not using expensive adhesives, It is advantageous to apply a physical treatment and / or a chemical treatment to the joint surface on the metal element side. As a method of performing a physical treatment and / or a chemical treatment on the bonding surface on the side where the metal element is embedded, for example, the method described in Patent Document 1 can be mentioned. This method is one of effective methods that can form a rough surface in a required range of the surface of a metal element, and is simple in operation. The method described in Patent Document 1 is a method of forming a rough surface on the surface using a laser.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-167475

As described above, the metal-resin composite molded body can also be used for parts that come into contact with the outside world such as electronic equipment. The metal-resin composite molded body used in such parts is required not only to have strong bonding strength between the embedded metal element and the resin element, but also to have a good surface appearance and excellent chemical resistance to acids, alkalis, and the like.

The object of the present invention is to provide a metal-resin composite molded body having strong bonding strength between embedded metal elements and resin elements, good surface appearance, and excellent chemical resistance to acids, alkalis, and the like, and a method for producing the same.

In order to solve the aforementioned problems, the present inventors and the like have repeatedly studied intensively. As a result, it was found that a resin element composed of a specific resin composition containing a polyarylene sulfide resin was used by applying physical treatment and / or chemical treatment to at least a part of the surface of the metal element that is in contact with the resin element. Able to resolve The present invention has been completed by solving the problems described above. More specifically, the present invention provides the following matters.

(1) A metal-resin composite molded body comprising an embedded metal element and a resin element, wherein the resin element is composed of a resin composition and is insert-molded on the embedded metal element; the embedded metal element and the resin element At least a part of the contacted surface is subjected to physical treatment and / or chemical treatment; the aforementioned resin composition contains: (A) 100 parts by mass of a polyarylene sulfide resin; (B) 10 ~ 250 parts by mass of an inorganic filler. Non-fibrous, with an average particle diameter of 30 μm or less, and selected from the group consisting of spherical silica and glass beads; and (C) 3 to 55 parts by mass of the epoxy group-containing olefin copolymer; and The epoxy group content is 0.01 to 0.80% by mass.

(2) The metal-resin composite molded article according to (1), wherein the epoxy group-containing olefin-based copolymer (C) contains a structural unit derived from an α-olefin; and an α, β-unsaturated source An olefin-based copolymer of a constituent unit of an acid propylene oxide ester.

(3) The metal-resin composite molded article according to (1) or (2), wherein the (C) epoxy-containing olefin-based copolymer further contains a structural unit derived from a (meth) acrylate An olefin-based copolymer.

(4) The metal-resin composite molded article according to any one of (1) to (3), further containing (D) an epoxy group-containing compound.

(5) The metal-resin composite molded body according to any one of (1) to (4), wherein an electrical and electronic machine including a housing has at least a part constituting the housing and is The exposed portion of the aforementioned electrical and electronic equipment.

(6) A method for manufacturing a metal-resin composite molded article, which is a method for manufacturing a metal-resin composite molded article having an integration step, the integration step It is arranged in an injection molding die, in which at least a part of the surface is subjected to physical treatment and / or chemical treatment to embed the metal element, and the resin composition is injected into the injection molding die in a molten state to insert the embedded metal element. Integrated with resin elements, where the resin composition contains: (A) 100 parts by mass of polyarylene sulfide resin; (B) 10 ~ 250 parts by mass of inorganic filler, which is non-fibrous and has an average particle size of 30 μm or less And is selected from the group consisting of spherical silica and glass beads; and (C) 3 to 55 parts by mass of the epoxy-group-containing olefin copolymer; and the epoxy group content in the resin composition is 0.01 to 0.80 mass %.

(7) The method for producing a metal-resin composite molded body according to (6), wherein the (C) epoxy-group-containing olefin-based copolymer contains a unit selected from the group consisting of an α-olefin-derived structural unit and An olefin-based copolymer of a constituent unit of a glycidyl ester of a β-unsaturated acid.

(8) The method for producing a metal-resin composite molded article according to (6) or (7), wherein the (C) epoxy-containing olefin-based copolymer further contains a (meth) acrylate-derived An olefin-based copolymer constituting a unit.

(9) The method for producing a metal-resin composite molded article according to any one of (6) to (8), further comprising (D) an epoxy group-containing compound.

According to the present invention, it is possible to provide a metal-resin composite molded body having strong bonding strength between embedded metal elements and resin elements, good surface appearance, and excellent chemical resistance to acids, alkalis, and the like, and a method for producing the same.

Fig. 1 schematically shows the metal resins used in the examples and comparative examples. (A) is an exploded perspective view, (b) is an oblique view, and (c) is a diagram showing only a metal part.

FIG. 2 is a diagram schematically showing a method for measuring the bonding strength between a resin portion and a metal portion in an example.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments.

<Embedded metal element>

The embedded metal element used in the present invention is subjected to physical treatment and / or chemical treatment on at least a part, preferably all, of the surface in contact with the resin element.

The metal material constituting the embedded metal element is not particularly limited, and examples thereof include copper, aluminum, and magnesium. The embedded metal element may be made of a metal alloy. Examples of the metal alloy include a copper alloy, an aluminum alloy, a magnesium alloy, and stainless steel. In addition, the surface of the metal material may be subjected to surface treatment such as anodizing treatment and painting.

In the present invention, an embedded metal element that is formed into a desired shape according to the application or the like is used. For example, by inserting a molten metal or the like into a mold having a desired shape, an embedded metal element having a desired shape can be obtained. In addition, in order to shape the embedded metal element into a desired shape, cutting processing by a work machine or the like may be used.

The surface of the embedded metal element obtained as described above is subjected to physical treatment and / or chemical treatment. The location where the physical and / or chemical treatment is performed, and the size of the processing range, are determined by considering the location where the resin element is formed, etc. set.

The physical treatment and chemical treatment systems are not particularly limited, and can be used. Known physical and chemical treatments. The surface of the embedded metal element can be roughened by physical treatment, and the resin composition constituting the resin element can enter the holes formed in the roughened area to produce an anchoring effect. The adhesion of the interface is easy to improve. On the other hand, by chemical treatment, a chemical bonding effect such as covalent bond, hydrogen bond, or intermolecular force can be imparted between the embedded metal element and the resin element formed by the insert. The adhesion of the interface of the component is easily improved. Because the chemical treatment can also bring about the roughening of the surface of the embedded metal element, in this case, the same anchoring effect as the physical treatment makes the adhesion of the interface between the embedded metal element and the resin element easier to improve.

Examples of the physical treatment include a laser treatment and a sandblasting treatment (Japanese Laid-Open Patent Publication No. 2001-225346). Multiple physical processes can also be performed in combination. In the laser treatment, specifically, the surface of the metal is grooved by laser irradiation and the rough surface is processed under the conditions of melting and re-solidifying.

Examples of the chemical treatment include dry treatment such as corona discharge, Treatment (refer to Japanese Patent Application Laid-Open No. 2000-218935), chemical etching (Japanese Patent Application Laid-Open No. 2001-225352), anodizing treatment (Japanese Patent Application No. 2010-64496), hydrazine treatment, and the like. In addition, when the metal material constituting the embedded metal element is aluminum, warm water treatment may be mentioned (Japanese Patent Application Laid-Open No. 8-142110). Examples of the warm water treatment include immersion in water at 100 ° C for 3 to 5 minutes. Multiple chemical treatments can also be performed in combination.

<Resin element>

The resin element used in the present invention is composed of a resin composition and is The insert is formed on the embedded metal element. The above resin composition contains (A) 100 parts by mass of a polyarylene sulfide resin; (B) 10 to 250 parts by mass of an inorganic filler, which is non-fibrous, has an average particle diameter of 30 μm or less, and is selected from spherical silica and The group consisting of glass beads; and (C) 3 to 55 parts by mass of the epoxy group-containing olefin copolymer; and the epoxy group content in the resin composition is 0.01 to 0.80 mass%. Hereinafter, each component contained in the resin composition used by this invention is demonstrated.

[(A) Polyarylene sulfide resin]

The (A) polyarylene sulfide resin is not particularly limited, and a conventionally known polyarylene sulfide resin can be used. As the (A) polyarylene sulfide resin, a polyphenylene sulfide (PPS) resin can be suitably used. (A) A polyarylene sulfide resin system can be used individually by 1 type or in combination of 2 or more types.

Because inserting metal components and resin components can get better Adhesion. The melt viscosity of (A) polyarylene sulfide resin measured at 310 ° C at a shear rate of 1216 / s is 8 ~ 300Pa. s is better, 10 ~ 200Pa. s is particularly good.

[(B) Inorganic filler]

(B) The inorganic filler is not particularly limited as long as it is non-fibrous, has an average particle diameter of 30 μm or less, and is selected from the group consisting of spherical silica and glass beads. (B) The inorganic filler of a component can be used individually by 1 type or in combination of 2 or more types.

The shape of the inorganic filler of the component (B) is not particularly limited as long as it is non-fibrous, and examples thereof include a spherical shape, a granular shape, a plate shape, a scaly shape, and an irregular shape. When the shape of the inorganic filler is non-fibrous, the obtained metal-resin composite molding system tends to be excellent in surface appearance and chemical resistance.

The average particle diameter of the component (B) inorganic filler is 30 μm or less, It is preferably from 0.1 to 25 μm, more preferably from 0.1 to 10 μm, and even more preferably from 0.1 to 5 μm. The smaller the average particle diameter is, the better the surface appearance is. On the other hand, when the average particle diameter is more than 30 μm, a sufficient surface appearance may not be obtained. In addition, in this specification, the average particle diameter uses laser diffraction. The cumulative value of the particle size distribution measured by the scattering method is 50% of the particle size (50% d).

With respect to 100 parts by mass of (A) polyarylene sulfide resin, The content of the organic filler is usually 10 to 250 parts by mass, preferably 20 to 200 parts by mass. When the content is less than 10 parts by mass, the rigidity and dimensional accuracy of the material tend to be insufficient. When the content is more than 250 parts by mass, fluidity tends to deteriorate and sufficient bonding strength with the metal cannot be obtained.

[(C) Epoxy-based olefin copolymer]

(C) The epoxy group-containing olefin-based copolymer is not particularly limited. (C) An epoxy-group-containing olefin copolymer system can be used individually by 1 type or in combination of 2 or more types.

Examples of the (C) epoxy-group-containing olefin copolymer include an olefin-based copolymerization including a structural unit derived from an α-olefin and a structural unit derived from an propylene oxide of an α, β-unsaturated acid. In particular, an olefin-based copolymer containing a structural unit derived from a (meth) acrylate is further preferred because a particularly excellent metal-resin composite molded article can be obtained. Hereinafter, (meth) acrylates are also referred to as (meth) acrylates. For example, glycidyl (meth) acrylates are also referred to as glycidyl (meth) acrylates. In the present specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid, and "(meth) acrylic acid ester" means both acrylic acid and methacrylic acid ester.

The α-olefin is not particularly limited, and examples thereof include ethylene, Propylene, butene and the like are particularly preferred. The α-olefins can be used alone or in combination of two or more. Since (C) the epoxy group-containing olefin-based copolymer contains a structural unit derived from an α-olefin, flexibility can be easily imparted to the resin element. By making the resin element soft by imparting flexibility, it contributes to improving the bonding strength between the embedded metal element and the resin element, and it also contributes to improving the impact resistance.

There is no particular limitation on the propylene oxide as the α, β-unsaturated acid. Examples include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, and glycidyl methacrylate is particularly preferred. The propylene oxide ester of an α, β-unsaturated acid can be used singly or in combination of two or more kinds. (C) The epoxy-group-containing olefin-based copolymer contains constituent units derived from α, β-unsaturated acid, and the bonding strength between the metal element and the resin element is easily improved. effect.

The (meth) acrylate is not particularly limited. For example, it may be Examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, and the like; methyl methacrylate, ethyl methacrylate, Methacrylates such as n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-octyl methacrylate, and the like. Especially preferred is methyl acrylate. The (meth) acrylic acid esters can be used alone or in combination of two or more. The structural unit derived from (meth) acrylate is effective in improving the bonding strength between the embedded metal element and the resin element.

Contains constituent units derived from α-olefins and derived from α, β-unsaturation The olefin-based copolymer of the constituent unit of the acid propylene oxide and the olefin-based copolymer further containing the (meth) acrylate-derived constituent unit can be produced by copolymerization by a conventionally known method. For example, the copolymer can be obtained by copolymerization using a radical polymerization reaction that is generally known. The type of the copolymer is not particularly limited, and may be, for example, a random copolymer or a block copolymer. Also, for example, polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly 2-ethylhexyl acrylate, polystyrene, poly Acrylonitrile, acrylonitrile. Styrene copolymer, butyl acrylate. An olefin-based graft copolymer in which a branched or cross-linked structure such as a styrene copolymer is chemically bonded to the olefin-based copolymer. The type of the copolymer is preferably not an olefin-based graft copolymer, and more preferably a random copolymer and / or a block copolymer.

To the extent that the effects of the present invention are not impaired, The olefin-based copolymer used contains constituent units derived from other copolymerization components.

More specifically, as (C) an epoxy-containing olefin-based copolymer, examples Examples thereof include a glycidyl methacrylate-modified ethylene copolymer, a glycidyl ether-modified ethylene copolymer, and the like, and a glycidyl methacrylate-modified ethylene copolymer is particularly preferred.

As propylene methacrylate modified ethylene copolymer, it can Glyceryl methacrylate graft-modified ethylene polymers, ethylene-glycidyl methacrylate copolymers, and ethylene-glycidyl methacrylate-methyl acrylate copolymers are exemplified. Because it is possible to obtain particularly excellent metal-resin composite moldings, especially ethylene-methacrylate copolymers and ethylene-methacrylate epoxy A propylene-methyl acrylate copolymer is preferable, and an ethylene-glycidyl methacrylate-methyl acrylate copolymer is particularly preferable. Specific examples of the ethylene-glycidyl methacrylate copolymer and the ethylene-glycidyl methacrylate-methyl acrylate copolymer include "Bondfast" (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of the glycidyl ether-modified ethylene copolymer include a glycidyl ether graft-modified ethylene copolymer and a glycidyl ether-ethylene copolymer.

The content of (C) the epoxy group-containing olefin-based copolymer is usually 3 to 55 parts by mass, and preferably 3 to 30 parts by mass, with respect to 100 parts by mass of the (A) polyarylene sulfide resin. When the content is less than 3 parts by mass, the bonding strength between the embedded metal element and the resin element may not be sufficiently obtained. The adhesion between the embedded metal element and the resin element affects the difference in linear expansion between these elements. It is considered that the stress relaxation is achieved by the (C) epoxy-group-containing olefin copolymer, the strain is reduced, and the above-mentioned bonding strength can be improved. Toughness is effective for a stress relaxation system, and toughness can be evaluated by tensile elongation. It is considered that when the content of the epoxy group-containing olefin copolymer (C) as a function of the elastomer is small, the tensile elongation is small and a sufficient stress relaxation effect cannot be obtained. Moreover, stress relaxation also contributes to improvement of impact resistance. On the other hand, when the content is more than 55 parts by mass, the viscosity rise tends to increase due to the reaction between the (C) epoxy-containing olefin-based copolymer and (A) the polyarylene sulfide resin, so the flowability tends to deteriorate and the The bonding strength between the embedded metal element and the resin element may not be sufficiently obtained. From the viewpoint of sulfuric acid resistance, the above content is also preferable when the content is 3 to 30 parts by mass, and a relatively excellent metal-resin composite molded body is easily obtained.

The epoxy group content in the resin composition is usually 0.01 to 0.80% by mass, and preferably 0.03 to 0.60% by mass. When the above epoxy group content is 0.01 to 0.80% by mass, the bonding between the embedded metal element and the resin element The strength can be easily maintained, and the mold release property at the time of insert molding is not easily deteriorated, and the amount of gas generated can be suppressed and the frequency of mold maintenance is easily reduced, which is preferable. The epoxy group content in the resin composition is the epoxy group content in the epoxy group-containing olefin-based copolymer (C) and the epoxy group in the epoxy group-containing compound (D) described later. Total content. When the resin composition contains only (C) an epoxy-containing olefin copolymer as an epoxy-containing component, the epoxy group content in the resin composition is the same as (C) an epoxy-containing olefin. The epoxy groups in the copolymers have the same content. (C) The epoxy group content in the epoxy-containing olefin-based copolymer is preferably 0.02 to 0.60% by mass, and more preferably 0.02 to 0.50% by mass in the total composition.

[(D) Epoxy-containing compound]

The resin composition used in the present invention may contain (D) an epoxy group-containing compound. When the (D) epoxy group-containing compound is added to the resin composition used in the present invention, it is easier to improve the bonding strength between the metal element and the resin element in the obtained metal-resin composite molded article. The (D) epoxy group-containing compound system is not particularly limited as long as it contains an epoxy group-containing compound other than the (C) epoxy group-containing olefin-based copolymer. (D) The epoxy group-containing compound can be used alone or in combination of two or more.

(D) The epoxy group-containing compound may be a compound containing one epoxy group in one molecule, or a compound containing two or more epoxy groups in one molecule. Examples of the epoxy-group-containing compound (D) include bisphenol-type epoxy compounds obtained by reacting bisphenol A with epichlorohydrin; and novolac-type compounds obtained by reacting novolac resin with epichlorohydrin. Epoxy resins; polypropylene oxides obtained by reacting polycarboxylic acids with epichlorohydrin; alicyclics obtained from alicyclic compounds Epoxy compounds; epoxy-propyl ethers obtained by reacting an aliphatic compound having a phenolic hydroxyl group with epichlorohydrin; and reacting a compound having epoxidized butadiene and a double bond with a peroxide and The obtained epoxy compound. Specific examples include bisphenol A epoxy compounds, methylglycidyl ether, phenylglycidyl ether, various fatty acid glycidyl esters, ethylene glycol diglycidyl ether, and phthalic acid. Acid propylene oxide, propylene glycol hexahydrophthalate, epoxidized polybutadiene, epoxidized SBS, etc. Particularly, a bisphenol-type epoxy compound such as a bisphenol A-type epoxy compound is preferred.

(D) Epoxy-containing group with respect to 100 parts by mass of (A) polyarylene sulfide resin The content of the compound is preferably 0.01 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass. When the content is 0.01 to 10 parts by mass, the joint strength between the embedded metal element and the resin element is more easily improved.

The epoxy group content in (D) the epoxy group-containing compound is as described above. The total content of the epoxy group in the epoxy group-containing olefin copolymer (C) and the epoxy group content in the epoxy group-containing compound (D) is 0.01 to 0.80 mass in the total composition. (D) The epoxy group content in the epoxy group-containing compound is preferably 0.5% by mass or less (for example, greater than 0% by mass and 0.5% by mass) or less in the total composition. 0.35 mass% or less (for example, more than 0 mass% and 0.35 mass% or less) is preferable. When the epoxy group content is 0.5% by mass or less in the total composition, the peel resistance between the metal element and the resin element is not easily lowered. In particular, at the time of insert molding, even at the flowing end of the resin composition in a molten state, interfacial peeling does not easily occur. In addition, since the mold release property is not easily deteriorated during insert molding, it is preferable in terms of easily obtaining a target molded product and in terms of productivity not being easily lowered.

[Other ingredients]

The resin composition used in the present invention may contain, in addition to the above-mentioned components, inorganic fillers, organic fillers, Additives such as flame retardants, ultraviolet absorbers, heat stabilizers, light stabilizers, colorants, carbon black, release agents, plasticizers, etc.

[Manufacturing method of resin composition]

The method for producing the resin composition used in the present invention is not particularly limited as long as the components in the resin composition can be uniformly mixed, and can be appropriately selected from the conventionally known methods for producing resin compositions. For example, a melt-kneading device such as a uniaxial or biaxial extruder is used to melt-knead each component and extrude, and then the obtained resin composition is processed into powder, chips, pellets, and the like. The required form method.

<Metal Resin Composite Molded Body>

The metal-resin composite molding system of the present invention includes: an embedded metal element; and a resin element, which is composed of the resin composition and is insert-molded on the embedded metal element. At least a part of the surface of the embedded metal element that is in contact with the resin element is subjected to physical treatment and / or chemical treatment. Since the metal-resin composite molding system of the present invention uses a resin composition containing (C) an epoxy-containing olefin-based copolymer and adjusting the epoxy group content to a predetermined range, the bonding strength between the embedded metal element and the resin element Strong. In addition, the inorganic filler containing the component (B) has a good surface appearance and excellent chemical resistance to acids, alkalis, and the like.

The metal resin of the present invention has the characteristics as described above. The composite molded body can be suitably used in applications that are required not only to have strong bonding strength between the embedded metal element and the resin element, but also to have a good surface appearance and to have excellent chemical resistance to acids and alkalis. For example, the metal-resin composite molded article of the present invention is suitable as a metal-resin composite molded article that includes electrical and electronic parts and the like which are easily affected by humidity and moisture. In particular, it is suitable for parts intended for use in motors or electronic equipment that are related to failure due to intrusion of moisture and moisture, such as rivers, ponds, ski resorts, and bathrooms. The metal-resin composite molded article of the present invention is also useful, for example, as at least a part of a housing for an electric machine or an electronic device. The above-mentioned housing for an electrical and electronic device may include a resin boss, a holding element, and the like inside. Here, examples of the housings for electrical and electronic devices include mobile phones, and housings for electronic devices that carry images, such as cameras, camcorders, and digital cameras; notebook personal computers, pocket computers, and electronic desks. Housings of portable information or communication terminal equipment such as computers, electronic notebooks, PDC, PHS, mobile phones; housings of portable audio electronic equipment such as MD, cassette stereo headphones, radios; and LCD TVs. Housings for household electrical appliances such as monitors, telephones, fax machines, handheld scanners, etc.

<Method for Manufacturing Metal Resin Composite Molded Body>

The specific steps of the manufacturing method of the metal-resin composite molded body are not particularly limited, as long as the embedded metal element and the resin element are made to adhere to each other through at least a part of the surface of the embedded metal element that has undergone physical and / or chemical treatment , And the resin element and the embedded metal element can be integrated.

For example, an embedded metal element having at least a part of its surface subjected to physical treatment and / or chemical treatment may be arranged in a mold for injection molding, and A method of injecting a resin composition used in the present invention into a mold for injection molding in a molten state to produce a metal-resin composite formed body in which a resin element and an embedded metal element are integrated. The conditions of the injection molding are not particularly limited, and preferable conditions can be appropriately set in accordance with the physical properties of the polyarylene sulfide resin and the like. In addition, methods such as transfer molding and compression molding are also effective methods for forming a metal-resin composite molded body in which a resin element and an embedded metal element are integrated. In these methods, at least a part, preferably all, of the surface of the embedded metal element that is in contact with the resin element is subjected to a physical treatment and / or a chemical treatment.

As another example, an injection molding method or the like may be used in advance. Resin elements are manufactured by a conventional molding method. The physically and / or chemically treated embedded metal elements and the resin elements are brought into contact with each other at a desired joining position, and heat is supplied to the abutment surface so that the resin element is near the abutment surface. A method of melting and manufacturing a metal-resin composite formed body in which a resin element and an embedded metal element are integrated. In this method, at least a part, preferably all, of the surface of the embedded metal element that is in contact with the resin element is subjected to a physical treatment and / or a chemical treatment.

[Example]

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

The schematic diagram of the metal-resin composite molding used in an Example and a comparative example is shown in FIG. (a) is an exploded perspective view, (b) is an oblique view, and (c) is a view showing only a metal part. This metal-resin composite molded body was manufactured by the following method. The unit of dimension in the figure is mm.

<Preparation of resin composition>

After the following raw material components were dry-blended, they were charged into a biaxial extruder with a cylinder temperature of 320 ° C and melt-kneaded to obtain pelletized thermoplastic resin compositions. The blending amount (parts by mass) of each component is shown in Tables 1 to 3.

． Polyphenylene sulfide resin

A-1: (stock) made by KUREHA, Fortron KPS W202A (product name), melt viscosity: 20Pa. s (shear speed: 1216sec ^-1 , temperature: 310 ° C)

A-2: (stock) made by KUREHA, Fortron KPS W214A (product name), melt viscosity: 130Pa. s (shear speed: 1216sec ^-1 , temperature: 310 ° C)

． Inorganic filler

B-1: Glass beads (Made by Potters-Ballotini, EMB-10 (average particle size: 5 μm))

B-2: Glass beads (manufactured by Potters-Ballotini, GL-BS (average particle size: 20 μm))

B-3: Spherical silica (manufactured by ADMATECHS, SO-C2 (average particle size: 0.55 μm))

B-4: Spherical silica (manufactured by ADMATECHS, SO-C6 (average particle size: 2.2 μm))

B-5: Calcium carbonate (manufactured by Shiraishi Industry Co., Ltd., Brilliant-1500 (average particle size 50% d: 0.7 μm))

B-6: Glass shards (manufactured by Nippon Plate Glass Co., Ltd., REFG-401 (average particle size: 300 μm, average thickness: 5 μm))

B-7: Glass fiber (manufactured by Owens Corning Co., Ltd., 03DE-FT798 (fiber diameter 6 μm, fiber length 3 mm))

． Epoxy-based olefin copolymer

C-1: ethylene-glycidyl methacrylate-methyl acrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Bondfast7L)

C-2: ethylene-glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., BondfastE)

C-3: Ethylene Ethyl Acrylate Copolymer (manufactured by UNICAR of Japan, NUC-6570)

． Epoxy-containing compound

D-1: Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation), jER (formerly "EPICOAT", any of which is a registered trademark) 1004K (product name)), epoxy content: 4.6% by mass, Epoxy equivalent 925, molecular weight: 1650

The method for measuring the melt viscosity is as follows.

[Melting viscosity]

The melt viscosity at a barrel temperature of 310 ° C. and a shear rate of 1216 / sec was measured using a CAPIROGRAPH manufactured by Toyo Seiki Co., Ltd. and using a 1 mmψ × 20 mmL / flat die as a capillary tube.

<Physical or chemical treatment of embedded metal elements>

As the embedded metal element, a plate made of copper (C-1100P, thickness 2mm) or aluminum (A5052, thickness 2mm) and subjected to physical or chemical treatment as described below is used. These plate-shaped embedded metal elements have a joint surface at a portion shown by the oblique line in FIG. 1 (a). In Tables 1 to 3, "physical", "chemical 1", and "chemical 2" each refer to the following physical treatment, chemical treatment 1, and chemical treatment 2.

[Physical Processing]

Using a commercially available liquid honing device, an alumina abrasive having a particle size of # 1000 (central particle size: 14.5 to 18 μm) was applied to an aluminum embedded metal element at a concentration of 20% and a gauge pressure of 0.4 MPa. Blown and roughened.

[Chemical treatment 1]

The surface of the copper-embedded metal element was immersed in an etching solution A (aqueous solution) of the following composition for 1 minute to remove the rust-preventive coating film, and then immersed in an etching solution B (aqueous solution) of the following composition for 5 minutes to etch the surface of the metal part .

． Etching liquid A (temperature 20 ° C)

． Etching liquid B (temperature 25 ° C)

[Chemical treatment 2]

The surface of the aluminum-embedded metal element was immersed in an alkaline degreasing solution (aqueous solution) of the following composition for 5 minutes to perform a degreasing treatment. Next, the surface of the metal part was etched by being immersed in an etching solution A (aqueous solution) of the following composition for 3 minutes. .

． Alkali degreasing solution (temperature 40 ℃)

AS-165F (manufactured by EBARA UDYLITE) 50ml / L

． Etching liquid A (temperature 40 ° C)

OF-901 (manufactured by EBARA UDYLITE) 12g / L

Magnesium hydroxide 25g / L

<Manufacture of Metal Resin Composite Molded Body>

A physically or chemically treated embedded metal element is placed in a mold, and the embedded metal element and a polyphenylene sulfide resin composition prepared in any of Examples 1 to 19 and Comparative Examples 1 to 12 are performed. Integration of resin components Bodyification steps. The molding conditions are as follows. The shape of the metal-resin composite molded body is shown in FIG. 1.

[Forming conditions]

Forming machine: SODICK TR-40VR (vertical injection molding machine)

Cylinder temperature: 320 ℃

Mold temperature: 150 ° C

Injection speed: 100mm / s

Holding pressure: 49MPa × 5 seconds

<Evaluation of Metal Resin Composite Molded Body>

The metal-resin composite molded body produced by the above method was evaluated for the joint strength of the joint portion, the fracture form after peeling, and peel resistance. The specific evaluation method is as follows.

[Joint Strength]

The metal-resin composite molded body having the shape shown in FIG. 1 is arranged on a base (jig) as shown in FIG. 2, and the jig is moved at a speed of 1 mm / minute so that the resin element is in an arrow direction. Push away from embedded metal elements. The strength at the time when the resin element was peeled off from the embedded metal element was measured and set as the joint strength. As a measuring device, TENSILON UTA-50kN (manufactured by ORIENTEC) was used. The measurement results are shown in Tables 1 to 3 (the values are the average of three tests).

[Destruction pattern]

After the joint strength measurement, the joint area was visually observed and evaluated. The failure occurred at the interface between the embedded metal element and the resin element (interface peeling, (Represented by x) are those generated in the embedded metal element or resin element (aggregation failure, indicated by ○). The results are shown in Tables 1 to 3.

[Peel resistance]

After the bonding strength was measured, the embedded metal element side of the bonded region was visually observed, and the ratio of the area occupied by the resin element attached to the embedded metal element to the area of the entire bonded region was determined and evaluated in accordance with the following criteria. The results are shown in Tables 1 to 3.

：: The above ratio is 50% or more, and the peel resistance is very good.

(Circle): The said ratio is 20% or more and less than 50%, and peeling resistance is favorable.

△: The above ratio is more than 0% and less than 20%, and the peel resistance is poor.

×: The above ratio was 0%, and the peel resistance was very poor.

<Other evaluation> [Surface appearance]

Using injection molding, a dumbbell-shaped test piece having a thickness of 4 mmt was produced at a cylinder temperature of 320 ° C and a mold temperature of 150 ° C, and the surface appearance was visually observed. The results of the surface appearance according to the following evaluation criteria are shown in Tables 1 to 3. When any of the evaluation systems is 5 to 3, it can be used as a product without problems, and when the evaluation is 2 or 1, it is not as good as a product.

5: Rough surface, turbidity, and gloss due to the added inorganic filler cannot be observed.

4: Roughness of the surface derived from the added inorganic filler cannot be observed, and a little turbidity can be observed, but it has gloss as a whole.

3: The surface roughness derived from the added inorganic filler cannot be observed, but a slight cloudiness can be observed.

2: Relative to the whole surface, about 1/3 of the surface roughness derived from the added inorganic filler can be observed.

1: Roughness of the surface originating from the added inorganic filler can be observed almost completely.

[Sulfuric acid resistance]

A dumbbell-shaped test piece prepared in the same manner as the user observing the surface appearance was immersed in a 10% by mass sulfuric acid aqueous solution at room temperature for 1 hour, and then washed with water, dried, and visually observed the surface appearance. The results of the sulfuric acid resistance evaluated in accordance with the following evaluation criteria are shown in Tables 1 to 3.

：: No change from before immersion.

○: The surface is slightly turbid, but the surface smoothness is not changed.

×: Surface whitening was observed and the surface smoothness was deteriorated.

[Releasability]

When producing a dumbbell-shaped body test piece for observing the surface appearance, the mold release property from the mold was evaluated in accordance with the following criteria. The results are shown in Tables 1 to 3.

○: The mold can be released from the mold without any problem, and the mold release property is good.

×: It was difficult to release the mold from the mold, and the release property was poor. Unable to evaluate surface appearance.

As shown in Table 1 and Table 2, (B) spherical silica and / or glass Examples 1 to 19 in which beads and (C) epoxy-group-containing olefin copolymers were used in combination and the content of each component was adjusted to a predetermined range, it was possible to confirm that the Strong bonding strength and excellent surface appearance and sulfuric acid resistance. In addition, (C) an epoxy-group-containing olefin copolymer and (D) an epoxy-group-containing compound are used in combination, and an epoxy group in each of these components is contained The metal-resin composite molded bodies of Examples 15 to 18 in which the amount was adjusted to a predetermined range have strong bonding strength between the embedded metal element and the resin element and have excellent peel resistance.

In addition, it was confirmed that when only spherical silica and / or glass beads having an average particle diameter of 10 μm or less were used, the surface appearance was excellent.

In contrast, as shown in Table 3, compared to Examples 1 to 19, Comparative Examples 1 and 6 using calcium carbonate instead of (B) spherical silica and / or glass beads were inferior in sulfuric acid resistance. In addition, compared with Examples 1 to 19, Comparative Examples 2 to 4 and 7 in which glass fragments or glass fibers were used instead of (B) spherical silica and / or glass beads had a poor surface appearance.

In addition, although (C) an epoxy-group-containing olefin copolymer and (D) an epoxy-group-containing compound are used in combination, the total epoxy group content in each of these components is greater than 0.80 mass in the total composition % Of Comparative Example 9 was inferior in mold release property.

Claims (7)

A metal-resin composite molded body includes an embedded metal element and a resin element, wherein the resin element is composed of a resin composition and is insert-molded on the embedded metal element; a surface of the embedded metal element in contact with the resin element At least a part of it is subjected to physical treatment and / or chemical treatment; the aforementioned resin composition contains: (A) 100 parts by mass of polyarylene sulfide resin; (B) 10 ~ 111 parts by mass of inorganic filler, which is non-fibrous , The average particle diameter is 30 μm or less, and is selected from the group consisting of spherical silica and glass beads; and (C) an epoxy group-containing olefin-based copolymer of 3 to 55 parts by mass; wherein (C) the epoxy group contains an epoxy group The olefin-based copolymer contains a structural unit derived from a (meth) acrylate; and the epoxy group content in the resin composition is 0.01 to 0.80% by mass. The metal-resin composite molded article according to item 1 of the scope of patent application, wherein the (C) epoxy-containing olefin-based copolymer contains α-olefin-derived constituent units and α, β-unsaturation An olefin-based copolymer of a constituent unit of an acid propylene oxide ester. The metal-resin composite molded article according to item 1 or 2 of the patent application scope, further comprising (D) an epoxy group-containing compound. The metal-resin composite molded body according to item 1 or 2 of the scope of patent application, wherein the electrical and electronic machine including the housing has at least a part constituting the housing and is exposed outside the electrical and electronic machine Part of it. A method for manufacturing a metal-resin composite molded article is a method for manufacturing a metal-resin composite molded article having an integration step. The integration step is performed in an injection molding mold, and at least a portion of a surface is subjected to physical treatment and / or chemical treatment. The embedded metal element is treated, and the resin composition is injected into the injection molding mold in a molten state to integrate the embedded metal element and the resin element, wherein the resin composition contains: (A) polyarylene sulfide 100 parts by mass of resin; (B) 10 ~ 111 parts by mass of inorganic filler, which is non-fibrous, has an average particle diameter of 30 μm or less, and is selected from the group consisting of spherical silica and glass beads; and (C) ring-containing 3 to 55 parts by mass of an oxy-based olefin copolymer; wherein the (C) epoxy-containing olefin-based copolymer contains a structural unit derived from a (meth) acrylate; and the epoxy in the resin composition The base content is 0.01 to 0.80% by mass. The method for producing a metal-resin composite molded article according to item 5 of the scope of the patent application, wherein the (C) epoxy-group-containing olefin-based copolymer contains a structural unit derived from an α-olefin, and α An olefin-based copolymer of a constituent unit of a glycidyl ester of a β-unsaturated acid. The method for producing a metal-resin composite molded article according to item 5 or 6 of the scope of patent application, further comprising (D) an epoxy-containing compound.