JP2007313750A - Composite of metal with resin and process for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To strongly and integrally bond (cement) a magnesium alloy or metal parts made of a magnesium alloy containing crystals of a metal oxide and the like on its surface, with a resin. <P>SOLUTION: Magnesium alloy parts having been subjected to chemical treatment can be used. On the surface layer having a crystal layer of a metal oxide, metal carbonate or metal phosphate, a resin composition containing 70-99 wt.% of polyphenylene sulfide (PPS) and 1-30 wt.% of a polyolefin resin is firmly fixed. The resin composition is superior in the bond strength by the injection bonding to polyphenylene sulfide alone. The surfaces of the magnesium alloy parts are subjected to chemical conversion treatment, these are inserted in a mold, and the above resin composition is injected and bonded to obtain the composite. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composite body made of a metal component and a resin composition used for a housing of an electronic device, a housing of a home appliance, a structural component, a mechanical component, and the like, and a method for manufacturing the same. More specifically, the present invention relates to a structure in which metal parts and thermoplastic resin compositions made by various machinings are integrated, and a method for manufacturing the same, and various electronic devices for mobile devices, home appliances, medical devices, structural components for vehicles, and vehicles. The present invention relates to a composite of a metal part and a thermoplastic resin composition used for mounting articles, parts for building materials, other structural parts and exterior parts, and a method for producing the same.

  A technique for integrating a metal and a resin is demanded from a wide range of industrial fields such as automobiles, home appliances, and industrial equipment, and for this reason, many adhesives for fixing the two have been developed. An adhesive exhibiting a function at room temperature or by heating is to interpose between a metal and a synthetic resin to integrate both, and this method is currently a common joining (fixing) technique. However, more rational joining methods that do not use an adhesive have been studied.

  One example is a method of integrating a high-strength engineering resin into a light metal such as magnesium, aluminum or an alloy thereof, or an iron alloy such as stainless steel without an adhesive. For example, as a method of joining at the same time by a method such as injection (hereinafter referred to as injection joining), the present inventors have used polybutylene terephthalate resin (hereinafter referred to as “PBT”) or polyphenylene sulfide resin (hereinafter referred to as “injection joining”) for an aluminum alloy. "PPS") has been proposed (for example, see Patent Document 1). In addition, there has been disclosed a joining technique in which a large hole is formed in an anodized film of an aluminum material, and a synthetic resin body is bitten into the hole and fixed (for example, see Patent Document 2).

  Although the principle of this injection joining in the proposal of patent document 1 is estimation, it is considered as follows. In this injection joining, as a pretreatment, a metal part made of an aluminum alloy is immersed in a dilute aqueous solution of a water-soluble amine compound. By soaking the metal part, the surface of the aluminum alloy is etched by the weakly basic aqueous solution to form ultrafine recesses, and at the same time, amine compound molecules are adsorbed on the surface of the aluminum alloy.

  The metal part subjected to the adsorption treatment is inserted into an injection mold, and the molten thermoplastic resin is injected into the mold at a high pressure. During this injection, the PBT or PPS described above and the amine compound molecules adsorbed on the surface of the aluminum alloy encounter and generate heat. At this time, the aluminum alloy is kept at a low mold temperature. However, the resin that has been rapidly solidified by this heat generation is delayed in solidification, and also enters the recesses on the surface of the ultrafine aluminum alloy. As a result, the aluminum alloy and the thermoplastic resin are firmly bonded (fixed) without the resin peeling off from the surface of the aluminum alloy. In other words, a material capable of strong injection joining by an exothermic reaction between PBT or PPS and an amine compound has been proposed. The present inventors have confirmed that PBT or PPS which can actually generate an exothermic reaction with an amine compound can be injection-bonded with the aluminum alloy.

JP 2004-216425 A WO2004-055248 A1

  The present inventors have developed a resin composition suitable for injection joining in order to make the above-described invention more effective. In other words, the technology was further developed and developed to provide innumerable fine recesses on the metal surface for adhesion. As a result, they discovered a phenomenon in which not only a simple PPS-based composition in which the linear expansion coefficient is combined with that of an aluminum alloy, but also a composition in which properties relating to crystallinity of PPS are changed is particularly effective.

  The present inventors have developed the above-described invention and studied whether or not the above-described pretreatment necessary for metal parts can be reduced by improving the resin composition. As a result, a specific PPS resin composition is obtained. The present invention has been completed by finding that a composite comprising a metal part and a metal part has excellent adhesion between the metal part and a resin composition made of PPS.

  The present invention has been made based on the above technical background and achieves the following object. An object of the present invention is to be able to be used not only for metal parts made of aluminum alloy but also for metal parts made of magnesium alloy, and it is possible to obtain bondability with a PPS composition for a magnesium alloy subjected to chemical conversion treatment. The provision of technology.

  Therefore, some characteristics of the magnesium alloy will be described. That is, a magnesium alloy has a remarkable feature that it is the lightest and most mechanically strong metal in practical metals, and has a specific gravity of 1. compared to an aluminum alloy (specific gravity 2.7) that is light and useful. It is around 7 and very light. However, on the other hand, it is more chemically active than aluminum alloys, and is therefore difficult to handle in terms of machining, surface treatment, and the like.

  That is, in a magnesium alloy, a natural oxide layer is formed immediately after forming a bare metal surface by polishing or the like, and the chemical stability and mechanical strength of the natural oxide layer on the surface are determined by the oxide layer on the surface of the aluminum alloy. It is much inferior. If an aluminum film has an oil film or a paint film as a rust inhibitor on the natural oxide layer, it will remain stable for more than 10 years when left indoors without condensation. Swells and rusts.

  The reason for this is that carbon dioxide gas and water molecules diffusing through the oil film or coating film on the surface of the magnesium alloy react with the magnesium natural oxide layer. In short, when a magnesium alloy is actually used, it is necessary to first cover it with a strong film instead of a natural oxide film. Specifically, the magnesium alloy is treated by either chemical conversion treatment or electrolytic oxidation. The present inventors first tried to establish a technique capable of injection-bonding a resin to a magnesium alloy subjected to chemical conversion treatment.

The present invention takes the following means to achieve the above object.
That is, the composite of the metal and resin of the first aspect of the present invention is a magnesium alloy or metal component made of a magnesium alloy that includes any one kind of crystal selected from metal oxide, metal carbonate, and metal phosphate in the surface layer. In
The crystal contains one or more metals selected from chromium, manganese, calcium, strontium, aluminum, zinc, zirconium, titanium, and vanadium,
A resin composition containing 70 to 99% by weight of a polyphenylene sulfide resin and 1 to 30% by weight of a polyolefin resin is fixed to the crystal.
The metal-resin composite of the present invention 2 is characterized in that, in the present invention 1, the resin composition is 80 to 97% by weight of a polyphenylene sulfide resin and 3 to 20% by weight of a polyolefin resin.

The metal-resin composite according to the third aspect of the present invention is that the surface layer of the magnesium or magnesium alloy part in the first or second aspect of the present invention has two or more plate crystals per 1 μm ² observed by an electron microscope. Features.

  The metal-resin composite according to the fourth aspect of the present invention is the first or second aspect of the present invention, wherein the surface layer of the magnesium or magnesium alloy part has a needle-like or rod-like crystal, or a needle-like or rod-like crystal hull as viewed with an electron microscope. The ratio of the area covered by the block crystal having a diameter is 30% or more.

  The metal-resin composite according to the fifth aspect of the present invention is the first to fourth aspect of the present invention, wherein the resin composition further comprises a polyfunctional isocyanate compound with respect to 100 parts by weight of the total resin content of the polyphenylene sulfide resin and the polyolefin resin. It is a resin composition formed by blending 0.1 to 6 parts by weight and / or 1 to 25 parts by weight of an epoxy resin.

  The metal-resin composite according to the sixth aspect of the present invention is the first to fifth aspects of the present invention, wherein the resin composition further comprises 1 to 200 fillers relative to a total resin content of 100 parts by weight of the polyphenylene sulfide resin and the polyolefin resin. It is characterized by blending parts by weight.

  The composite of metal and resin of the present invention 7 is the composite of the present invention 6, wherein the filler is made of glass fiber, carbon fiber, aramid fiber, calcium carbonate, magnesium carbonate, silica, talc, clay, and glass powder. It is one or more types selected.

  The metal-resin composite of the present invention 8 is the composite of the present invention 1 to 7, wherein the polyolefin resin is a maleic anhydride modified ethylene copolymer, a glycidyl methacrylate modified ethylene copolymer, a glycidyl ether modified It is at least one polyolefin resin selected from an ethylene copolymer and an ethylene alkyl acrylate copolymer.

  The composite of metal and resin of the present invention 9 is the composite of the present invention 1 to 7, wherein the polyolefin resin is an ethylene-acrylic acid ester-maleic anhydride terpolymer, ethylene-glycidyl methacrylate binary copolymer. It is characterized by being at least one polyolefin resin selected from coalescence.

  The manufacturing method of the composite of the present invention 10 includes a shape processing step of forming magnesium or a magnesium alloy material into a shape part by machining from a cast or an intermediate material, and the shaped shape part is made of chromium, manganese, calcium, By immersing in an aqueous solution or aqueous suspension containing one or more metals selected from strontium, zirconium, titanium, vanadium, potassium, and sodium, a metal oxide, a metal carbonate is formed on the surface layer of the shaped part. And a liquid treatment step for forming one or more kinds of coatings selected from metal phosphorous oxides, and the shaped parts after the liquid treatment step are inserted into an injection mold to obtain 70 to 99% by weight of polyphenylene sulfide and polyolefin A resin composition having a resin composition containing 1 to 30% by weight of a resin is injected to combine the shaped part and the resin composition together. Consisting of a fixing step to stick to. Hereinafter, each element which comprises the said means is demonstrated concretely.

[Metal parts]
Magnesium or a magnesium alloy used in the present invention includes any one crystal selected from metal oxides, metal carbonates, and metal phosphates in the surface layer. The crystal contains one or more metals selected from chromium, manganese, calcium, strontium, aluminum, zinc, zirconium, titanium, and vanadium.

  This magnesium or magnesium alloy is intended for all magnesium or magnesium alloys that are standardized or commercially available, such as AZ31 and other wrought alloys defined in Japanese Industrial Standards, AZ91, AZ92 alloys, and the like. . Shaped parts made of magnesium or magnesium alloy, if it is an alloy for casting, etc., parts shaped by methods such as die casting, thixomolding, injection molding, etc., and further machining them into the desired shape Use parts. Moreover, in the alloy for extending | stretching etc., the components which shape | molded intermediate materials, such as a board | plate material, a pipe material, and a rod material, by applying mechanical processing, such as press work, cutting, and grinding, are used.

[Surface of metal parts]
Usually, the surface of a magnesium alloy is highly ionized and easily corroded even from moisture in the air, so that surface treatment is required. For this purpose, magnesium or a magnesium alloy is immersed in an aqueous solution of a salt or acid of a different metal to form a stable layer such as a metal oxide, metal carbonate, or metal phosphate containing a different metal on its surface, In general, measures are taken to protect the inner metal by the presence of the layer. In the metal industry, such immersion type surface treatment is referred to as chemical conversion treatment, but is often referred to as chemical conversion treatment including degreasing and chemical etching performed before that. In order to avoid confusion in the present invention, the chemical conversion treatment means that the treatment in a narrow sense for forming the corrosion-resistant layer is indicated, and the treatment such as degreasing and etching usually performed before that is referred to as pretreatment. Furthermore, the whole including both the pretreatment and the chemical conversion treatment will be referred to as a liquid treatment.

  Known as a chemical conversion treatment for magnesium and magnesium alloys is a chemical conversion treatment that involves immersing in an aqueous solution containing chromic acid and providing an anticorrosion layer mainly composed of chromium oxide or chromium phosphate on the surface. And is generally called chromate treatment (see, for example, US Pat. No. 2,438,877). Recently, many treatments are used which are immersed in a manganese salt or a mixed aqueous solution of manganate and phosphoric acid to provide an anticorrosion layer mainly composed of manganese oxide or manganese phosphate as a surface layer.

  These chemical conversion treatments other than chromium-based treatment are called non-chromate treatments (see, for example, JP-A-7-126858 and JP-A-2001-123274). In addition, a method of providing a composite oxide layer of aluminum, vanadium, zinc, zirconium, titanium, or the like as an anticorrosion layer on the surface (for example, see JP 2000-199077 A) is also known as non-chromate treatment. Historically, chromate treatment methods using chromium compounds have long been used as treatment methods with excellent corrosion resistance.

  However, since a chromic acid aqueous solution for chromate treatment is used, this causes a problem because it contains hexavalent chromium, which is problematic in the environment. At present, a chemical conversion treatment method using no chromium has been demanded. Therefore, a method using the aforementioned manganese and other metals has been developed. Recently, it seems that a method using a manganese compound is regarded as an alternative to the chromate treatment. The metal part used in the present invention can be used even if it is surface-treated by any of these methods.

  According to the research results of the present inventors, more preferable requirements are (1) sufficient corrosion resistance, (2) the surface layer obtained by chemical conversion treatment has irregularities, and the surface is viewed with an electron microscope. Many crystalline substances are observed. Although both (1) and (2) are necessary, the present invention pays particular attention to (2). This is because magnesium or a magnesium alloy preferably has a hard and strong surface layer of metal oxide, metal carbonate, or metal phosphate. This is because the injected crystalline thermoplastic resin generates a strong bonding force when it bites into the hard and strong uneven surface layer and crystallizes and solidifies.

If the hard and durable surface layer obtained by the chemical conversion treatment has a concavo-convex shape with a length unit of 1 μm or less, or is covered with a concave shape having a depth of about 50 to 100 nm, The resin is locked on the surface of the metal, that is, the resin is caught on the unevenness of the metal surface layer, that is, it is preferable for producing an anchor effect. Furthermore, when two or more plate crystals are observed per 1 μm ² , the needle-like or rod-like crystals cover the surface widely, or the bulk crystals having the needle-like or rod-like crystals as the outer skin are connected to cover the surface. Is preferred. When two or more plate-like crystals are observed per 1 μm ² , the plate-like crystal serves as a wall of the concavo-convex portion, and is effective for increasing the injection joining force by forming a strong convex portion wall. On the other hand, when the surface is covered with 30% or more of needle-like or rod-like crystals, it is effective for naturally producing strong irregularities and improving the engagement with the resin to increase the injection joining force. In the following, the specific implementation method of each process and its concept will be described.

[Surface treatment / pretreatment of magnesium or magnesium alloy parts]
It is preferable that metal parts made of magnesium or a magnesium alloy are first immersed in a degreasing tank to remove oils and finger grease adhered by machining. Specifically, a commercially available magnesium degreasing material is prepared with an aqueous solution in which magnesium degreasing material is poured into hot water at a concentration specified by the drug manufacturer, and after immersing metal parts in this, it is further washed with water. preferable. In an ordinary commercial product, the concentration is 5 to 10%, the liquid temperature is 50 to 80 ° C., and the immersion is performed for 5 to 10 minutes. Next, it is immersed and etched in an acidic aqueous solution to dissolve the surface layer of the magnesium alloy part and remove the dirt and the remaining oil agent or surfactant residue.

  As the working solution, a weakly acidic aqueous solution of an organic carboxylic acid having a pH of 2.0 to 5.0, such as acetic acid, propionic acid, citric acid, benzoic acid and phthalic acid can be used. Except for high-purity magnesium whose magnesium purity is close to 100%, the magnesium alloy contains dissimilar metals. For example, AZ31 and AZ91 contain about 3% to 9% aluminum and about 1% zinc. Since aluminum and zinc are hardly dissolved in this etching process using a weakly acidic aqueous solution, they are deposited on the surface as insoluble materials. A process of melting and removing the object to clean it is necessary.

  This is a removal technique called so-called smut removal. In AZ31 and AZ91, the aluminum smut is first dissolved by dissolving in a weakly basic aqueous solution (first smut treatment), and then the zinc smut is dissolved away by immersing in a strong basic aqueous solution (second smut treatment). Is normal. In the first smut treatment, a commercially available degreasing agent aqueous solution for an aluminum alloy can be used with a weak basicity, and the present inventors have used such a commercially available degreasing agent for aluminum in a concentration of 5 to 10% at a concentration of 60 to A method of immersing as an aqueous solution at 80 ° C. for several minutes was taken. Further, as the second smut treatment, a method of dipping for 5 to 10 minutes at a temperature of 70 to 80 ° C. with a caustic soda solution having a concentration of 15 to 25% was employed.

[Surface treatment of magnesium or magnesium alloy parts / main treatment]
Next, processing that can be called main processing is performed in the liquid processing. This treatment is usually a two-step dipping treatment, that is, first dipping in a weakly acidic aqueous solution for a very short time to perform fine etching, and then improving the conventional chemical conversion treatment method for various magnesium alloys. . In the fine etching process, an organic carboxylic acid having a pH of 2.0 to 6.0, for example, a weakly acidic aqueous solution such as acetic acid, propionic acid, citric acid, benzoic acid, phthalic acid, phenol, and a phenol derivative can be used, and the immersion time is also long. An extremely short time of 15 to 40 seconds is preferable.

  Further, the chemical conversion treatment step is basically the same as the conventionally known chemical conversion treatment. That is, this chemical conversion treatment method is a well-known technique for which many patents have been filed. For example, an aqueous solution containing one or more metals selected from chromium, manganese, calcium, strontium, zirconium, titanium, vanadium, potassium, and sodium. Further, it has been proposed to improve the corrosion resistance of a magnesium alloy by forming a metal oxide, metal carbonate or metal phosphate on the surface layer by immersing in an aqueous suspension. On the other hand, as far as the present inventors know, the chemical conversion treatment that is actually commercialized is either a chromate method in which the surface is covered with chromium oxide or chromium oxide containing magnesium by immersing in a chromic acid aqueous solution, or phosphorous. There seem to be two kinds of methods of immersing in manganese acid aqueous solution and covering with manganese phosphate.

  Currently, the use of hexavalent chromium is avoided from the influence on the human body, and in the surface treatment described above, the latter has become the mainstream and is changing to what is called the non-chromate method. For the present inventors, the purpose of this treatment is not only to provide corrosion resistance, but also to form a surface having high mechanical strength in terms of material mechanics when injection-bonded. According to the examination results of the present inventors, the fine etching process is omitted, and the above-mentioned patent-application type chemical conversion treatment, chromate, and non-chromate treatment methods are all provided with sufficient corrosion resistance, and the necessary degree. A strong injection-bonded product was obtained. Among them, the stronger surface shape between the metal surface and the resin, especially by injection joining, is a product with many crystals clearly observed when viewed with an electron microscope, and many crystals are observed with an electron microscope. In order to adjust the product, it is preferable to use a fine etching process.

  The magnesium alloy part that has been pretreated is again immersed in a 0.1 to 0.5% strength hydrated citric acid aqueous solution at around 40 ° C. for 15 to 60 seconds, finely etched, and washed with ion-exchanged water. Next, an aqueous solution containing potassium permanganate 1-5%, acetic acid 1-3%, and hydrated sodium acetate 0.1-1.0% was prepared as a chemical conversion treatment solution at 40-60 ° C. Immerse the alloy parts for 0.5-2 minutes and wash with water. This is put into a warm air dryer set at 60 to 90 ° C. for 5 to 20 minutes and dried.

  On the other hand, an example of a preferable method for carrying out the present invention by a chromate treatment method generally recognized as the most excellent corrosion resistance will be described. The pretreated magnesium alloy part is again immersed in a 0.1 to 0.5% strength hydrated citric acid aqueous solution at around 40 ° C. for 15 to 60 seconds, finely etched, and washed with ion exchange water. . Next, a 15-20% strength aqueous solution of chromic anhydride (chromium trioxide) is prepared as a chemical conversion treatment solution at 60-80 ° C., and the magnesium piece is immersed in this for 2-4 minutes and washed with water. This is put into a warm air dryer set at 60 to 90 ° C. for 5 to 20 minutes and dried. A magnesium alloy part with a gray surface is obtained.

(Resin composition)
The resin composition constituting the present invention is composed of a resin component composition containing 70 to 99% by weight of PPS and 1 to 30% by weight of a polyolefin-based resin. Preferably, PPS 80 to 97 is used to form a composite excellent in bondability. It is good to set it as the resin component composition containing 3% by weight and 3-20% by weight of polyolefin resin. Here, when PPS is less than 70% by weight, or when it exceeds 99% by weight, the obtained composite is inferior in bondability (adhesiveness) between the metal part and the resin composition.

  Any PPS may be used as long as it belongs to the category called PPS, and among them, a high-flow type flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm because of excellent molding processability when used as a resin composition. Therefore, it is preferable that the measured melt viscosity is 100 to 30,000 poise under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg. PPS may be substituted with an amino group, a carboxyl group or the like, or may be copolymerized with trichlorobenzene or the like during polymerization.

  Further, the PPS may be linear, introduced with a branched structure, or heat-treated in an inert gas. Furthermore, this PPS has reduced impurities such as ions and oligomers by performing deionization treatment (acid washing, hot water washing, etc.) before or after heat curing, or washing with an organic solvent such as acetone. Alternatively, it may be cured by performing a heat treatment in an oxidizing gas after completion of the polymerization reaction.

  Examples of the polyolefin-based resin include commonly known ethylene-based resins and propylene-based resins, and may be commercially available. Among these, from the viewpoint of obtaining a composite having particularly excellent adhesiveness, maleic anhydride-modified ethylene copolymer, glycidyl methacrylate-modified ethylene copolymer, glycidyl ether-modified ethylene copolymer, ethylene alkyl acrylate copolymer Etc.

  Examples of the maleic anhydride-modified ethylene copolymer include maleic anhydride graft-modified ethylene polymer, maleic anhydride-ethylene copolymer, ethylene-acrylic acid ester-maleic anhydride terpolymer. Among them, an ethylene-acrylic acid ester-maleic anhydride terpolymer is preferable because a particularly excellent composite is obtained, and this ethylene-acrylic acid ester-maleic anhydride terpolymer is preferable. Specific examples of coalescence include “Bondyne (manufactured by Arkema Inc. (Osaka City, Osaka))” and the like.

  Examples of the glycidyl methacrylate-modified ethylene-based copolymer include glycidyl methacrylate graft-modified ethylene polymer and glycidyl methacrylate-ethylene copolymer. Among them, particularly excellent composites are obtained, and therefore glycidyl methacrylate-ethylene copolymer. A polymer is preferred, and specific examples of this glycidyl methacrylate-ethylene copolymer include “Bond First” (manufactured by Sumitomo Chemical Co., Ltd. (Chuo-ku, Tokyo)).

  Examples of the glycidyl ether-modified ethylene copolymer include glycidyl ether graft-modified ethylene copolymer and glycidyl ether-ethylene copolymer. Specific examples of the ethylene alkyl acrylate copolymer include “rotoryl ( Arkema) ”and the like.

  In the composite of the present invention, since the bondability between the metal part and the resin composition becomes better, the resin composition has a total resin content including 70 to 99% by weight of PPS and 1 to 30% by weight of polyolefin resin. It is preferable that 0.1 to 6 parts by weight of a polyfunctional isocyanate compound and / or 1 to 25 parts by weight of an epoxy resin is further blended with 100 parts by weight.

  As this polyfunctional isocyanate compound, a commercially available non-block type or block type compound can be used. Examples of the polyfunctional non-blocked isocyanate compound include 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylpropane diisocyanate, toluene diisocyanate, phenylene diisocyanate, bis (4-isocyanatophenyl) sulfone, and the like. The polyfunctional block type isocyanate compound has two or more isocyanate groups in the molecule, and the isocyanate group is reacted with a volatile active hydrogen compound so as to be inactive at room temperature. The type of the polyfunctional block type isocyanate compound is not particularly specified. Generally, the isocyanate group is masked by a blocking agent such as alcohols, phenols, ε-caprolactam, oximes, and active methylene compounds. Has a structured. Examples of the polyfunctional block type isocyanate include “Takenate (manufactured by Mitsui Takeda Chemical Co.)”.

  As this epoxy resin, an epoxy resin generally known as a bisphenol A type, a cresol novolac type or the like can be used. As the bisphenol A type epoxy resin, for example, “Epicoat (manufactured by Japan Epoxy Resin Co., Ltd.)” or the like can be used. Examples of the cresol novolac type epoxy resin include “Epiclon (manufactured by Dainippon Ink and Chemicals, Chuo-ku, Tokyo)” and the like.

  In addition, the composite of the present invention has a PPS of 70 to 99% by weight and a polyolefin resin 30 to 1 for the purpose of adjusting the difference in linear expansion coefficient between the metal part and the resin composition and improving the mechanical strength of the resin composition. It is preferable that the resin composition further comprises 1 to 200 parts by weight, more preferably 10 to 150 parts by weight of the filler with respect to 100 parts by weight of the total resin content including wt%.

  Examples of this filler include fillers such as a fibrous filler, a granular filler, and a plate-like filler. Examples of the fibrous filler include glass fiber, carbon fiber, and aramid fiber. Specific examples of the glass fiber include chopped strands having an average fiber diameter of 6 to 14 μm. Examples of the plate-like and granular fillers include calcium carbonate, mica, glass flakes, glass balloons, magnesium carbonate, silica, talc, clay, pulverized products of carbon fibers and aramid fibers. The filler is preferably treated with a silane coupling agent or a titanate coupling agent.

[Production method of composite]
The method for producing a composite of the present invention is an injection molding method in which a metal part is inserted into an injection mold, and is performed as follows. Prepare an injection mold, open the mold, insert the magnesium alloy part that has been subjected to the above liquid treatment into one of the molds, close the mold, and add PPS 70 to 99 wt% and polyolefin resin 1 to 30 wt%. A composite is manufactured by injecting and solidifying a thermoplastic resin composition having a resin component composition, and then opening and releasing the mold.

  The injection conditions will be described. The mold temperature is preferably 100 ° C. or higher, and more preferably 120 ° C. or higher because it has little influence on the resin strength after solidification and is excellent in production efficiency of the composite. On the other hand, the injection temperature, the injection pressure, and the injection speed are not particularly different from those of ordinary injection molding.

[Action]
As described in detail above, by applying the bonding method of the present invention, it was possible to improve the bonding property, increase the efficiency, expand the application range, and the like. As a result, the weight of mobile electronic devices and home appliances, the weight of components for automobiles, the weight of robot arms and legs for industrial use, and other parts used in many industrial fields, It can contribute to the supply, weight reduction, and productivity of the housing.

  As described in detail above, the composite of the present invention is an integral body of the resin composition and the metal part without being easily peeled off. By using a specific chemical conversion treatment for a magnesium alloy part and using a thermoplastic resin composition having a resin composition containing 70 to 99% by weight of PPS and 1 to 30% by weight of a polyolefin resin, the bondability is maintained. However, environmental stability on the metal side increased.

  Hereinafter, embodiments of the present invention will be described by way of examples. FIG. 1 schematically shows a cross-section of an injection mold used in examples described later. FIG. 2 is an external view showing an external appearance of a metal / resin composite 7 molded by an injection mold. The injection mold 10 is a normal mold including a movable side mold plate 2, a fixed side mold plate 3, a cavity portion, a pinpoint gate 5, a runner, and the like. For forming the composite 7, the movable side mold plate 2 is opened, the aluminum alloy piece 1 is inserted into the cavity portion of the fixed side mold plate 3, and the movable side mold plate 2 is closed.

The molten resin is injected into the cavity through the pinpoint gate 5, and the resin portion 4 is molded to obtain the composite body 7. The composite 7 has a joint surface 5 between the aluminum alloy piece 1 and the resin portion 4, and the area of the joint surface 5 is 5 mm × 10 mm as will be described later. That is, the area of the joint surface is 0.5 cm ² .

Examples of the present invention will be described in detail below.
The evaluation / measurement methods for the composites obtained from the examples are shown below.
-Measurement of melt viscosity of PPS-
The melt viscosity was measured under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg with a Koka flow tester “CFT-500 (manufactured by Shimadzu Corp.)” equipped with a die having a diameter of 1 mm and a length of 2 mm.
-X-ray surface observation (XPS observation)-
An ESCA “AXIS-Nova (Kuratos / Shimadzu Corporation)” in a format that observes a surface having a diameter of several μm within a depth of several nm was used.
-Electron microscope observation-
SEM type electron microscopes “S-4800 (manufactured by Hitachi, Ltd.)” and “JSM-6700F (JEOL)” were used to observe at 1-2 KV.
-Observation with scanning probe microscope-
“SPM-9600 (manufactured by Shimadzu Corporation)” was used.
-Measurement of composite bond strength-
Using a tensile tester “Model 1323 (manufactured by Aiko Engineering Co., Ltd.)”, the shear breaking force was measured at a pulling speed of 10 mm / min.

[Preparation Example 1] (Preparation Example of PPS Composition)
This Adjustment Example 1 shows an adjustment example in which PPS and polyolefin resin are mixed. A 50 liter autoclave equipped with a stirrer was charged with 6214 g of Na ₂ S · 2.9H ₂ O and 17000 g of N-methyl-2-pyrrolidone and gradually heated to 205 ° C. with stirring under a nitrogen stream, Water was distilled off. After the system was cooled to 140 ° C., 7160 g of p-dichlorobenzene and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 2 hours, then heated to 250 ° C. over 30 minutes, and further polymerized at 250 ° C. for 3 hours.

  After completion of the polymerization, the mixture was cooled to room temperature and the polymer was isolated using a centrifuge. The solid content was repeatedly washed with warm water and dried at 100 ° C. for a whole day and night to obtain PPS having a melt viscosity of 280 poise (hereinafter referred to as PPS (1)). This PPS (1) was further cured at 250 ° C. for 3 hours under a nitrogen atmosphere to obtain PPS (hereinafter referred to as PPS (2)). The resulting PPS (2) had a melt viscosity of 400 poise.

  6.0 kg of the obtained PPS (2), 1.5 kg of ethylene-acrylic acid ester-maleic anhydride terpolymer “Bondyne TX8030 (manufactured by Arkema)”, epoxy resin “Epicoat 1004 (Japan Epoxy Resin Co., Ltd.) 0.5 kg) was previously mixed uniformly with a tumbler. Thereafter, the glass fiber “RES03-TP91 (manufactured by Nippon Sheet Glass Co., Ltd.)” having an average fiber diameter of 9 μm and a fiber length of 3 mm is added from the side feeder with a twin screw extruder “TEM-35B (manufactured by Toshiba Machine Co., Ltd.)”. While being fed so as to be 20% by weight, a PPS composition (1) which was melt-kneaded at a cylinder temperature of 300 ° C. and pelletized was obtained. The obtained PPS composition (1) was dried at 175 ° C. for 5 hours.

[Preparation Example 2] (Preparation of PPS composition)
PPS (1) obtained in Preparation Example 1 was cured at 250 ° C. for 3 hours in an oxygen atmosphere to obtain PPS (hereinafter referred to as PPS (3)). The melt viscosity of the obtained PPS (3) was 1800 poise. 5.98 kg of the obtained PPS (3) and 0.02 kg of polyethylene “Nipolon Hard 8300A (manufactured by Tosoh Corporation)” were uniformly mixed in advance with a tumbler. Thereafter, in the twin screw extruder “TEM-35B”, while supplying glass fiber “RES03-TP91” having an average fiber diameter of 9 μm and a fiber length of 3 mm from the side feeder so that the addition amount becomes 40% by weight, the cylinder temperature PPS composition (2) pelletized by melt-kneading at 300 ° C. was obtained. The obtained PPS composition (2) was dried at 175 ° C. for 5 hours.

[Preparation Example 3] (Preparation of PPS composition)
7.2 kg of PPS (2) obtained in Example 1 and 0.8 kg of “glycidyl methacrylate-ethylene copolymer” “Bond First E (manufactured by Sumitomo Chemical Co., Ltd.)” were uniformly mixed in advance by a tumbler. Thereafter, in the twin screw extruder “TEM-35B”, while supplying glass fiber “RES03-TP91” having an average fiber diameter of 9 μm and a fiber length of 3 mm from the side feeder so that the addition amount becomes 20% by weight, the cylinder temperature A PPS composition (3) which was melt-kneaded at 300 ° C. and pelletized was obtained. The obtained PPS composition (3) was dried at 175 ° C. for 5 hours.

[Preparation Example 4] (Preparation of PPS composition)
4.0 kg of PPS (2) obtained in Preparation Example 1 and 4.0 kg of ethylene-acrylic acid ester-maleic anhydride terpolymer “Bondyne TX8030 (manufactured by Arkema)” were uniformly mixed in advance using a tumbler. . Thereafter, in the twin screw extruder “TEM-35B”, while supplying glass fiber “RES03-TP91” having an average fiber diameter of 9 μm and a fiber length of 3 mm from the side feeder so that the addition amount becomes 20% by weight, the cylinder temperature A PPS composition (4) pelletized by melt-kneading at 300 ° C. was obtained. The obtained PPS composition (4) was dried at 175 ° C. for 5 hours.

[Example 1]
Purchase 0.8mm-thick AZ31B magnesium alloy (manufactured by Nippon Metals Co., Ltd.) with an average metal crystal grain size of 7μm by wet buffing, and make 18mm x 45mm (0.8mm thick) rectangular pieces It cut | disconnected and it was set as the magnesium alloy piece which is the metal plate 1. FIG. Drill holes at the ends of this alloy piece, pass through copper wires coated with vinyl chloride to dozens of pieces, bend and process the copper wires so that the alloy pieces do not overlap each other, so that all can be suspended at the same time did.

  A commercially available magnesium alloy degreasing agent “Cleaner 160 (manufactured by Meltex Co., Ltd.)” was poured into water to obtain an aqueous solution having a concentration of 75 ° C. and a concentration of 10%. The alloy piece was immersed in this for 5 minutes and washed thoroughly with water.

  Subsequently, a 2% acetic acid aqueous solution at 40 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 2 minutes and washed with water. Black smut was attached. Subsequently, a 7.5% aqueous solution of aluminum alloy degreasing agent “NE-6 (manufactured by Meltex Co.)” adjusted to 75 ° C. in another tank was prepared and immersed in water for 5 minutes. It was considered that the aluminum content in the smut could be dissolved due to the weak basicity of this solution. Subsequently, a 20% aqueous solution of caustic soda at 75 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 5 minutes and washed with water. It was assumed that the zinc content in the smut could be dissolved.

  Subsequently, it was immersed in a 2% nitric acid aqueous solution at 40 ° C. prepared in a separate tank for 1.5 minutes and washed with water. Next, a manganese phosphate non-chromate chemical conversion treatment liquid at 45 ° C. was prepared in another tank. That is, prepare an aqueous solution containing 2.5% manganese phosphate, 2.5% 85% phosphoric acid, and 2% triethylamine, soak it in water for 5 minutes, wash thoroughly with water and dry at 60 ° C. The machine was dried for 10 minutes. After drying, the copper wire was pulled out from the magnesium alloy piece on a clean aluminum foil, wrapped in a lump, and then stored in a plastic bag. At this time, the finger did not touch the surfaces to be joined (the end on the opposite side from where the holes were made).

Two days later, one of them was observed with an electron microscope. On the surface layer, many plate-like crystal layers were visible, and other irregular deposits were visible. This is shown in FIG. Further, the plate crystals formed voids, and the interval was 300 to 1000 nm, and many were 400 to 600 nm. This metal plate was observed with a scanning probe microscope to observe the surface irregularity and the depth of the recess. The depth of the concave portion was often 50 to 150 nm. Although 10 places were observed by electron microscope observation, ² to 5 plate crystals could be confirmed at 1 μm ² . On the same day, another one was observed by ESCA. Manganese, phosphorus and oxygen were observed in large quantities, trace amounts of magnesium, zinc and aluminum were observed, and it was confirmed that the main component was manganese phosphate.

Further, after one day, the remaining magnesium alloy piece was taken out, and the one with a hole was picked with a glove so that oil and the like would not adhere, and inserted into an injection mold set at 140 ° C. The mold was closed and the PPS composition (1) obtained in Preparation Example 1 was injected at an injection temperature of 310 ° C. The mold temperature was 140 ° C., and 20 integrated composites 7 shown in FIG. 2 were obtained. The size of the resin part was 10 mm × 45 mm × 5 mm, and the bonding surface 6 was 0.5 cm ² of 10 mm × 5 mm. When four pieces were subjected to a tensile breaking test on the day of molding, the average shear breaking force was 13 MPa. In addition, five pieces annealed by putting them in a hot air dryer at 170 ° C. for 1 hour on the day of molding were further subjected to a tensile test one day later, and the average shear breaking force was 12.8 MPa.

  The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (Ohashi Chemical Co., Ltd.)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Although sprayed with salt water at 35 ° C. for 8 hours using 5% salt water, washed with water and dried, no abnormality was observed in appearance.

[Comparative Example 1]
A magnesium alloy piece was prepared in exactly the same manner as in Example 1, except that the PPS composition (2) obtained in Preparation Example 2 was used instead of the PPS composition (1) obtained in Preparation Example 1. The composite was obtained by injection molding. The resulting composite was annealed at 170 ° C. for 1 hour. In short, it is an experiment using a PPS resin composition containing only a small amount of polyolefin polymer and PPS and filler. One day later, when these were subjected to a tensile test, the shear breaking strength was 9.0 MPa on an average of 10 pieces. It is only about 70% of the numerical value of Example 1, and the difference of the used resin material came out as a result.

[Comparative Example 2]
A magnesium alloy piece was obtained in exactly the same manner as in Example 1 except that the chemical conversion treatment was not performed. That is, an AZ31 magnesium alloy piece was made, degreased, roughly etched, desmutted, finely etched, and desmutted. In short, it was washed with water and dried without being treated with non-chromate manganese phosphate. Crystals were not observed by electron microscope observation, and the surface was a natural oxide layer of magnesium.

Two days later, the remaining magnesium alloy piece was taken out, and the one with a hole so that oil and the like would not adhere was picked with gloves and inserted into an injection mold set at 140 ° C. The mold was closed and the PPS composition (1) obtained in Preparation Example 1 was injected at an injection temperature of 310 ° C. The mold temperature was 140 ° C., and 14 integrated composites shown in FIG. 2 were obtained. The size of the resin part was 10 mm × 45 mm × 5 mm, and the bonding surface 6 was 0.5 cm ² of 10 mm × 5 mm. When four pieces were subjected to a tensile breaking test on the day of molding, the average shear breaking force was 11.3 MPa.

  The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (Ohashi Chemical Co., Ltd.)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. The next day, this coated product was sprayed with salt water for 8 hours at 35 ° C. using 5% salt water, washed with water and dried. As a result, fine film swelling was observed in all the integrated products. When all 10 pieces were subjected to a tensile breaking test, the shear breaking strength was 7.0 MPa on average. A brittle oxide film also penetrated the fractured surface, and it was confirmed that if it was not chemically treated, it could not withstand actual use only by painting.

[Example 2]
A composite was obtained in the same manner as in Example 1, except that the PPS composition (3) obtained in Preparation Example 3 was used instead of the PPS composition (1) obtained in Preparation Example 1. It was. The composite was annealed at 170 ° C. for 1 hour on the day of molding, and two days later, the composite was measured for shear breaking strength with a tensile tester. As a result, the average was 12.5 MPa. The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (Ohashi Chemical Co., Ltd.)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Although sprayed with salt water at 35 ° C. for 8 hours using 5% salt water, washed with water and dried, no abnormality was observed in appearance.

[Comparative Example 3]
A composite was produced in the same manner as in Example 1, except that the PPS composition (4) obtained in Preparation Example 4 was used instead of the PPS composition (1). In short, this is an experiment using a PPS resin composition containing a very large amount of polyolefin polymer. However, a large amount of gas was generated during molding and the molding was interrupted.

[Example 3]
Example 1 with the exception that a 0.8 mm thick AZ31B magnesium alloy plate having a surface finish of wet buffing and an average metal crystal grain size of 16 μm was obtained and the liquid recipe in the chemical conversion treatment was changed to the following: In exactly the same manner, it was cut into rectangular pieces and treated with liquid. In other words, the liquid treatment does not require fine etching, and chemical conversion treatment is performed by immersing in a 45 ° C. aqueous solution containing 2.5% manganese phosphate, 2.5% 85% phosphoric acid, and 2% triethylamine for 1 minute. did.

Two days after drying, one of the treated pieces was observed with an electron microscope. The photograph is shown in FIG. 4, and the number of plate crystals was much smaller than that in FIG. 3, and 0 to 1 per 1 μm ² . As can be seen in the photo, many irregular deposits were visible. On the same day, another one was observed with ESCA, a large amount of manganese, phosphorus, carbon, and oxygen were observed, trace amounts of magnesium, zinc, aluminum, and silicon were observed, and it was confirmed that the main component was manganese phosphate. It was done. Further, after one day, the remaining magnesium alloy piece was taken out and insert injection molded in exactly the same manner as in Example 1.

  On the day of molding, the sample was put into a hot air dryer at 150 ° C. for 1 hour for annealing, and a tensile test was conducted one day later. The average shear breaking strength was 10.0 MPa. Although it was joined, it could not be said that the joining force was sufficiently high. It was considered that the surface crystal state after the liquid treatment in Example 1 was changed due to the difference in the crystal grain size of the material AZ31B alloy and the difference in the liquid treatment method.

  The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (Ohashi Chemical Co., Ltd.)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Although sprayed with salt water at 35 ° C. for 8 hours using 5% salt water, washed with water and dried, no abnormality was observed in appearance.

[Example 4]
An AZ31 alloy plate having a thickness of 0.8 mm and an average metal crystal grain size of 7 μm was used. A rectangular piece was cut in the same manner as in Example 1, and this was immersed in a 10% strength aqueous solution of the degreasing agent “Cleaner 160” at 75 ° C. for 5 minutes and washed thoroughly with water. Subsequently, a 2% aqueous solution of acetic acid at 40 ° C. was prepared in a separate tank, and the alloy pieces were immersed in this for 2 minutes and washed with water. Black smut was attached. Subsequently, a 7.5% aqueous solution of aluminum alloy degreasing agent “NE-6 (manufactured by Meltex Co.)” adjusted to 75 ° C. in another tank was prepared and immersed in water for 5 minutes. Subsequently, a 20% sodium hydroxide aqueous solution at 75 ° C. was prepared in another tank, and the alloy piece group was immersed in this for 5 minutes and washed with water. Up to here is the pretreatment, and the treatment method was the same as in Example 1.

  Subsequently, it was immersed in a 0.5% strength aqueous hydrated citric acid solution at 40 ° C. prepared in a separate tank for 15 seconds and washed with water. Next, an aqueous solution containing potassium permanganate 3%, acetic acid 1% and hydrated sodium acetate 0.5% was prepared at 45 ° C., immersed for 1 minute, and thoroughly washed with water. It was brown. It put into the warm air dryer which was 60 degreeC for 10 minutes, and dried. The copper wire was pulled out from the magnesium alloy piece on a clean aluminum foil, wrapped together, and then stored in a plastic bag. In this operation, the finger did not touch the surface to be joined (the end opposite to the hole).

Two days later, one of them was observed with an electron microscope and a scanning probe microscope. As a result, spherical crystals having a number average diameter of 100 nm were observed, and these spherical crystals were connected to form the entire surface layer. . The result of electron microscope observation is shown in FIG. On the same day, another one was observed with ESCA, a large amount of manganese and oxygen were observed, and trace amounts of magnesium, zinc, aluminum, carbon and silicon were also observed. The main component was considered to be manganese oxide mainly composed of manganese dioxide. The color tone was also brown, confirming this.
Further, after one day, the remaining magnesium alloy piece was taken out, and the one with a hole was picked with a glove so that oil and the like would not adhere, and inserted into an injection mold set at 140 ° C. Twenty integrated composites 7 shown in FIG. 2 were obtained in exactly the same manner as in Example 1. On the day of molding, the sample was annealed for 1 hour in a hot air dryer at 170 ° C., and a tensile test was conducted one day later. The average shear breaking strength was 15.1 MPa.

  The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (Ohashi Chemical Co., Ltd.)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Although sprayed with salt water at 35 ° C. for 8 hours using 5% salt water, washed with water and dried, no abnormality was observed in appearance.

[Comparative Example 4]
A composite was obtained in the same manner as in Example 4 except that the PPS composition (2) obtained in Preparation Example 2 was used instead of the PPS composition (1) obtained in Preparation Example 1. . The composite was annealed at 170 ° C. for 1 hour on the day of molding, and two days later, the composite was measured for shear breaking strength with a tensile tester. As a result, the average was 8.0 MPa. This was about 66% of Example 4.

[Example 5]
An AZ31 alloy plate having a thickness of 0.8 mm with an average metal crystal grain size of 7 μm was obtained. Cut in the same manner as in Example 1 into a rectangular piece, and pretreated. The pretreatment method was the same as in Example 1. Subsequently, it was immersed in a 0.25% strength aqueous hydrated citric acid solution at 40 ° C. prepared in a separate tank for 30 seconds and washed with water. Next, the magnesium piece was immersed in an aqueous solution containing 20% chromium trioxide at 75 ° C. for 5 minutes and washed thoroughly with water. Then, it was put into a warm air dryer set to 60 ° C. for 10 minutes and dried. The copper wire was pulled out from the magnesium alloy piece on a clean aluminum foil, wrapped together, and then stored in a plastic bag. In this operation, the finger did not touch the surface to be joined (the end opposite to the hole).

One day later, one was observed with ESCA. A large amount of chromium and oxygen was observed.
Further, one day later, the magnesium alloy piece was taken out, and the one with a hole so that oil and the like would not adhere was picked with gloves and inserted into an injection mold set at 140 ° C. In the same manner as in Example 1, 20 integrated composites shown in FIG. 2 were obtained. As it was, it was annealed by putting it in a hot air dryer at 170 ° C. for 1 hour, and then a tensile test was conducted one day later. The average shear breaking strength was 13 MPa.

  The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (Ohashi Chemical Co., Ltd.)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Although sprayed with salt water at 35 ° C. for 8 hours using 5% salt water, washed with water and dried, no abnormality was observed in appearance.

[Comparative Example 5]
A composite was obtained in the same manner as in Example 5 except that the PPS composition (2) obtained in Preparation Example 2 was used instead of the PPS composition (1) obtained in Preparation Example 1. The composite was annealed at 170 ° C. for 1 hour on the day of molding, and two days later, the composite was measured for shear breaking strength with a tensile tester. The average was 5.8 MPa. This was about 50% of Example 5.

[Example 6]
The final treatment is a wet buffing, 0.8 mm thick AZ31B magnesium alloy (manufactured by Nippon Metal Co., Ltd.) with an average metal crystal grain size of 7 μm is cut into rectangular pieces of the same shape as in Example 1, and the pretreatment is performed went. The pretreatment method was the same as in Example 5. Subsequently, it was immersed in a 0.25% strength aqueous hydrated citric acid solution at 40 ° C. prepared in a separate tank for 30 seconds and washed with water. Next, it was immersed in a 60 ° C. aqueous solution containing 0.12% zircon acetylacetonate and 0.05% 40% aqueous solution of fluorotitanic acid for 2 minutes and washed thoroughly with water.

  It put into the warm air dryer which was 60 degreeC for 10 minutes, and dried. The copper wire was pulled out from the magnesium alloy piece on a clean aluminum foil, wrapped together, and then stored in a plastic bag. In this operation, the finger did not touch the surface to be joined (the end opposite to the hole). One day later, one was observed with ESCA. Large amounts of zirconium, titanium and oxygen, and small amounts of magnesium were observed. The main components were seen as oxides of zirconium and titanium.

  Further, after one day, the remaining magnesium alloy piece was taken out, and the one with a hole was picked with a glove so that oil and the like would not adhere to it, and was inserted into an injection mold set at 140 ° C. Injection molding was performed in exactly the same manner as in Example 1 to obtain 20 integrated composites shown in FIG. On the day of molding, the sample was put into a hot air drier at 170 ° C. for 1 hour for annealing, and a tensile test was conducted one day later. The average shear breaking strength was 11.2 MPa.

  The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (Ohashi Chemical Co., Ltd.)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Although sprayed with salt water at 35 ° C. for 8 hours using 5% salt water, washed with water and dried, no abnormality was observed in appearance.

[Comparative Example 6]
A composite was obtained in the same manner as in Example 6 except that the PPS composition (2) obtained in Preparation Example 2 was used instead of the PPS composition (1) obtained in Preparation Example 1. The composite was annealed at 170 ° C. for 1 hour on the day of molding, and two days later, the composite was measured for shear breaking strength with a tensile tester. As a result, the average was 6.8 MPa. This was about 60% of Example 6.

[Example 7]
The final treatment is a wet buffing, 0.8 mm thick AZ31B magnesium alloy (manufactured by Nippon Metal Co., Ltd.) with an average metal crystal grain size of 7 μm is cut into rectangular pieces of the same shape as in Example 1, and the pretreatment is performed went. The pretreatment method was the same as in Example 6. Subsequently, it was immersed in a 0.25% strength aqueous citric acid solution at 40 ° C. prepared in a separate tank for 30 seconds and washed with water. Subsequently, it was immersed in the 70 degreeC aqueous solution containing 1% of potassium carbonate for 5 minutes, and washed with water well.

  It put into the warm air dryer which was 60 degreeC for 10 minutes, and dried. The copper wire was pulled out from the magnesium alloy piece on a clean aluminum foil, wrapped together, and then stored in a plastic bag. In this operation, the finger did not touch the surface to be joined (the end opposite to the hole). One day later, one was observed with an electron microscope. The result is shown in FIG. The crystal structure was fine with a fine mesh pattern. On the other hand, ESCA analysis revealed magnesium, oxygen, carbon, and trace amounts of zinc, aluminum, and silicon. From the chemicals used, it was estimated that magnesium oxide and magnesium carbonate, or complex compounds thereof, were the main components and formed the surface layer.

  Further, after one day, the remaining magnesium alloy piece was taken out, and the one with a hole was picked with a glove so that oil and the like would not adhere to it, and was inserted into an injection mold set at 140 ° C. Injection molding was performed in exactly the same manner as in Example 1 to obtain 20 integrated composites shown in FIG. On the day of molding, the sample was put into a hot air dryer at 170 ° C. for 1 hour for annealing, and a tensile test was conducted one day later. The average shear breaking strength was 10.1 MPa. The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (Ohashi Chemical Co., Ltd.)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Although sprayed with salt water at 35 ° C. for 8 hours using 5% salt water, washed with water and dried, no abnormality was observed in appearance.

[Comparative Example 7]
A composite was obtained in the same manner as in Example 7 except that the PPS composition (2) obtained in Preparation Example 2 was used instead of the PPS composition (1) obtained in Preparation Example 1. . The composite was annealed at 170 ° C. for 1 hour on the day of molding, and two days later, the composite was measured for shear breaking strength with a tensile tester. As a result, the average was 6.0 MPa. This was about 60% of Example 7.

[Example 8]
In exactly the same manner as in Example 7, pretreatment was performed using a 0.8 mm-thick AZ31B magnesium alloy (manufactured by Nippon Metal Co., Ltd.) piece having an average metal crystal grain size of 7 μm. Subsequently, it was immersed in a 0.25% strength aqueous citric acid solution at 40 ° C. prepared in a separate tank for 30 seconds and washed with water. Subsequently, it was immersed for 10 minutes in 65 degreeC aqueous solution which contains 0.95% of hydrated calcium nitrate 1%, hydrated strontium nitrate 1%, sodium chlorination 0.05%, and 80% phosphoric acid, and washed with water well. It put into the warm air dryer which was 60 degreeC for 10 minutes, and dried.

  The copper wire was pulled out from the magnesium alloy piece on a clean aluminum foil, wrapped together, and then stored in a plastic bag. In this operation, the finger did not touch the surface to be joined (the end opposite to the hole). One day later, one was observed with ESCA. Large amounts of magnesium, calcium, strontium, and oxygen were observed, as well as small amounts of phosphorus, trace amounts of zinc, aluminum, carbon, and silicon. The main components were found to be magnesium, calcium and strontium oxides or phosphorus oxides or their complex compounds.

  Further, after one day, the remaining magnesium alloy piece was taken out, and the one with a hole was picked with a glove so that oil and the like would not adhere to it, and was inserted into an injection mold set at 140 ° C. Injection molding was performed in exactly the same manner as in Example 1 to obtain 20 integrated composites shown in FIG. On the day of molding, the sample was put into a hot air dryer at 170 ° C. for 1 hour for annealing, and a tensile test was conducted one day later. The average shear breaking strength was 10.0 MPa. The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (Ohashi Chemical Co., Ltd.)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Although sprayed with salt water at 35 ° C. for 8 hours using 5% salt water, washed with water and dried, no abnormality was observed in appearance.

[Comparative Example 8]
A composite was obtained in the same manner as in Example 8, except that the PPS composition (2) obtained in Preparation Example 2 was used instead of the PPS composition (1) obtained in Preparation Example 1. . The composite was annealed at 170 ° C. for 1 hour on the day of molding, and two days later, the composite was measured for shear breaking strength with a tensile tester. The average was 4.8 MPa. This was about 50% of Example 8.

[Example 9]
In exactly the same manner as in Example 8, a 0.8 mm-thick AZ31B magnesium alloy (manufactured by Nippon Metals Co., Ltd.) piece having an average metal crystal grain size of 7 μm was used for pretreatment. Subsequently, it was immersed in a 0.25% strength aqueous citric acid solution at 40 ° C. prepared in a separate tank for 30 seconds and washed with water. Then, it was immersed in an aqueous solution containing 45% vanadium trichloride at 45 ° C. for 2 minutes and washed thoroughly with water. It put into the warm air dryer which was 60 degreeC for 10 minutes, and dried. The copper wire was pulled out from the magnesium alloy piece on a clean aluminum foil, wrapped together, and then stored in a plastic bag.

  In this operation, the finger did not touch the surface to be joined (the end opposite to the hole). One day later, one was observed with ESCA. A large amount of vanadium, oxygen, a small amount of magnesium, and a very small amount of zinc, aluminum, and silicon were observed. The main component was seen as vanadium oxide or oxide of vanadium and magnesium.

  Further, after one day, the remaining magnesium alloy piece was taken out, and the one with a hole was picked with a glove so that oil and the like would not adhere to it, and was inserted into an injection mold set at 140 ° C. Injection molding was performed in exactly the same manner as in Example 1 to obtain 20 integrated composites shown in FIG. On the day of molding, the sample was put into a hot air dryer at 150 ° C. for 1 hour for annealing, and a tensile test was conducted one day later. The average shear breaking strength was 11.0 MPa.

  The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (Ohashi Chemical Co., Ltd.)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Although sprayed with salt water at 35 ° C. for 8 hours using 5% salt water, washed with water and dried, no abnormality was observed in appearance.

[Comparative Example 9]
A composite was obtained in the same manner as in Example 9, except that the PPS composition (2) obtained in Preparation Example 2 was used instead of the PPS composition (1) obtained in Preparation Example 1. . The composite was annealed at 170 ° C. for 1 hour on the day of molding, and two days later, the composite was measured for shear breaking strength with a tensile tester. As a result, the average was 8.0 MPa. This was about 70% of Example 9.

[Example 10]
In exactly the same manner as in Example 9, a 0.8 mm-thick AZ31B magnesium alloy (manufactured by Nippon Metal Co., Ltd.) piece having an average metal crystal grain size of 7 μm was used for pretreatment. Subsequently, it was immersed in a 0.25% strength aqueous hydrated citric acid solution at 40 ° C. prepared in a separate tank for 30 seconds and washed with water. Next, an aqueous solution containing potassium permanganate 2%, acetic acid 1%, and hydrated sodium acetate 0.5% was prepared at 45 ° C. and immersed for 30 seconds.

  Next, an aqueous solution containing potassium permanganate 2%, acetic acid 1%, and hydrated sodium acetate 0.5% was prepared at 10 ° C. and immersed for 5 minutes. It was brown. It put into the warm air dryer which was 60 degreeC for 10 minutes, and dried. The copper wire was pulled out from the magnesium alloy piece on a clean aluminum foil, wrapped together, and then stored in a plastic bag. In this operation, the finger did not touch the surface to be joined (the end opposite to the hole).

  Three days later, this magnesium alloy piece was taken out, and the one with a hole so that oil and the like would not adhere was picked with gloves and inserted into an injection mold set at 140 ° C. In the same manner as in Example 1, 20 integrated composites shown in FIG. 2 were obtained. On the same day, the sample was put into a hot air dryer at 170 ° C. for 1 hour for annealing, and a tensile test was conducted one day later. The average shear breaking strength was 18.0 MPa.

  The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (Ohashi Chemical Co., Ltd.)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Although sprayed with salt water at 35 ° C. for 8 hours using 5% salt water, washed with water and dried, no abnormality was observed in appearance. Since the result of Example 4 was good, this experiment was carried out by slightly modifying the temperature conditions for the chemical conversion treatment.

FIG. 1 is a mold configuration diagram schematically showing a process of manufacturing a composite of a magnesium plate piece and a resin composition. FIG. 2 is an external view of a single body schematically showing a composite of a magnesium plate piece and a resin composition. FIG. 3 is a surface photograph of an AZ31B magnesium alloy having an average particle diameter of 7 μm obtained by chemical conversion treatment using an aqueous acetic acid solution as a rough etching agent, dilute nitric acid as a fine etching agent, and manganese phosphate. It is. FIG. 4 shows a surface photograph of an AZ31B magnesium alloy having a metal crystal average particle size of 16 μm obtained by using an aqueous acetic acid solution as a rough etching agent, using dilute nitric acid as a fine etching agent, and further subjecting it to chemical conversion treatment of manganese phosphate. It is. FIG. 5 is a surface photograph of an AZ31B magnesium alloy having a metal crystal grain size of 7 μm obtained by using an acetic acid aqueous solution as a rough etching agent, citric acid as a fine etching agent, and further subjected to a potassium permanganate chemical conversion treatment. It is. FIG. 6 is a surface photograph of an AZ31B magnesium alloy having a metal crystal grain size of 7 μm obtained by using an acetic acid aqueous solution as a rough etching agent, citric acid as a fine etching agent, and further subjected to a potassium carbonate-based chemical conversion treatment. .

Explanation of symbols

1: Metal plate 2, 3: Mold 4: Resin composition 5: Pinpoint gate 6: Bonding surface 7: Composite

Claims (10)

In the metal part made of magnesium alloy or magnesium alloy containing any one kind of crystal selected from metal oxide, metal carbonate, and metal phosphate in the surface layer,
The crystal contains one or more metals selected from chromium, manganese, calcium, strontium, aluminum, zinc, zirconium, titanium, and vanadium,
A metal-resin composite characterized in that a resin composition containing 70 to 99% by weight of a polyphenylene sulfide resin and 1 to 30% by weight of a polyolefin resin is fixed to the crystal. The metal / resin composite according to claim 1,
The resin composition is a polyphenylene sulfide resin of 80 to 97% by weight and a polyolefin resin of 3 to 20% by weight. In the composite of the metal and resin according to claim 1 or 2,
^2. A metal / resin composite characterized in that two or more plate crystals per 1 μm ² are observed on the surface layer of the magnesium or magnesium alloy part by electron microscope observation. In the composite of the metal and resin according to claim 1 or 2,
The surface layer of the magnesium or magnesium alloy part is characterized in that the ratio of the area covered with acicular or rod-like crystals or massive crystals having acicular or rod-like crystal shells as viewed with an electron microscope is 30% or more. A composite of metal and resin. The metal / resin composite according to claim 1 selected from claims 1 to 4.
The resin composition further comprises 0.1 to 6 parts by weight of a polyfunctional isocyanate compound and / or 1 to 25 parts by weight of an epoxy resin with respect to 100 parts by weight of the total resin content of the polyphenylene sulfide resin and the polyolefin resin. A composite of metal and resin characterized by blending. In the metal-resin composite according to claim 1 selected from claims 1 to 5,
The resin composition is obtained by further blending 1 to 200 parts by weight of a filler with respect to 100 parts by weight of the total resin content of the polyphenylene sulfide resin and the polyolefin resin. Complex. In the composite of the metal and resin according to claim 6,
The filler is at least one selected from glass fiber, carbon fiber, aramid fiber, calcium carbonate, magnesium carbonate, silica, talc, clay, and glass powder. The metal / resin composite according to claim 1 selected from claims 1 to 7,
The polyolefin resin is at least one polyolefin selected from maleic anhydride-modified ethylene copolymer, glycidyl methacrylate-modified ethylene copolymer, glycidyl ether-modified ethylene copolymer, and ethylene alkyl acrylate copolymer. A composite of a metal and a resin, characterized in that it is a resin. The metal / resin composite according to claim 1 selected from claims 1 to 7,
Metal and resin characterized in that the polyolefin resin is at least one polyolefin resin selected from ethylene-acrylic acid ester-maleic anhydride terpolymer and ethylene-glycidyl methacrylate binary copolymer Complex. A shape processing step for converting magnesium or a magnesium alloy material into a shape part by machining from a cast or an intermediate material;
By immersing the shaped part into an aqueous solution or suspension containing one or more metals selected from chromium, manganese, calcium, strontium, zirconium, titanium, vanadium, potassium, and sodium, A liquid treatment step of forming one or more kinds of coatings selected from metal oxides, metal carbonates, and metal phosphates on the surface of the shaped part;
The shaped part after the liquid treatment step is inserted into an injection mold, and a resin composition having a resin component composition containing 70 to 99% by weight of polyphenylene sulfide and 1 to 30% by weight of a polyolefin resin is injected with the shaped part and An adhering step for adhering the resin composition together;
A method for producing a composite of a metal and a resin comprising: