JP4927491B2 - Metal-resin composite and method for producing the same - Google Patents

Description

  The present invention relates to a composite of a metal and a resin composed of a metal 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 manufacturing method thereof. More specifically, the present invention relates to a composite body obtained by integrating and laminating a base material made of magnesium alloy produced by various machining processes and a thermoplastic resin composition, and a method for producing the same. Various electronic devices, electrical appliances, medical devices, automobiles The present invention relates to a composite of metal and resin used for structural parts and exterior parts such as railway vehicles, aircraft, vehicle-mounted products, and building materials, and a method for manufacturing the same.

  Technology for integrating metal and synthetic resin is required from a wide range of industrial fields such as automobiles, home appliances, parts manufacturing industries such as industrial equipment, and many adhesives have been developed for this purpose. Among these, very good adhesives have been proposed. For example, an adhesive that exhibits a function at room temperature or by heating is used for joining that integrates a metal and a synthetic resin, and this method is now a common joining technique.

However, more rational joining methods that do not use an adhesive have been studied. An 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, the present inventors have injected a molten resin into a metal part previously inserted in an injection mold and molded a resin portion, and at the same time, fixed (joined) the molded article and the metal part. (Hereinafter abbreviated as “injection joining”).
This invention proposes a manufacturing technique in which polybutylene terephthalate resin (hereinafter referred to as “PBT”) or polyphenylene sulfide resin (hereinafter referred to as “PPS”) is injection-bonded to an aluminum alloy (for example, a patent). Reference 1). In addition, there is disclosed a joining technique in which a large hole is provided in an anodized film of an aluminum material, and a synthetic resin body is bitten into the hole and bonded (for example, see Patent Document 2).

  The principle of this injection joining in the proposal of Patent Document 1 is as follows. The aluminum alloy is immersed in a dilute aqueous solution of a water-soluble amine compound, and the aluminum alloy is finely etched by the weak basicity of the aqueous solution. Further, it was found that the adsorption of amine compound molecules on the surface of the aluminum alloy occurs simultaneously with this immersion. The aluminum alloy thus treated is inserted into an injection mold, and the molten thermoplastic resin is injected at a high pressure.

At this time, heat is generated by encountering the thermoplastic resin and the amine compound molecules adsorbed on the aluminum alloy surface. At almost the same time as this heat generation, this thermoplastic resin is rapidly cooled in contact with the aluminum alloy maintained at a low mold temperature, so that the resin that is solidified while crystallizing is an ultrafine aluminum alloy that is delayed in solidification. It will also sink into the recess on the surface. Thus, the aluminum alloy and the thermoplastic resin are firmly bonded (fixed) without the resin being peeled off from the surface of the aluminum alloy. That is, when an exothermic reaction occurs, strong injection joining can be performed. In fact, it has been confirmed that PBT and PPS capable of exothermic reaction with an amine compound can be injection-bonded with this aluminum alloy.
JP 2004-216425 A WO2004 / 055248 A1

  The present inventors sought and 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, not only simple PBT and PPS compositions that have a linear expansion coefficient combined with an aluminum alloy are optimal, but the material properties related to crystallinity of both resins are further related to this injection joining. It has been found that. On the other hand, the present inventors also focused on the surface layer of the metal to be injection-bonded. As a result, since the characteristics of the crystallinity of PBT and PPS were understood, it was inferred that in addition to the already elucidated aluminum alloy processed by ultrafine etching, it could be joined by injection molding. Hereinafter, this reasoning will be described in detail.

  Assuming that a thermoplastic resin can be injection-bonded to a metal shape, there are two major conditions. One is a metal surface layer having an uneven shape on the micrometer level, and further, the surface itself for forming the unevenness is a hard surface and has an uneven shape on the electron microscope level (with nano-level ultrafineness). is there. PBT or PPS can penetrate even without the adsorption of amine-based molecules if the concave diameter is large at the micrometer level. Second, the resin is a crystalline resin, the crystallinity is high, the crystal part of the resin is hard, has mechanical strength, and has an appropriate size for fixing the resin. PBT or PPS. In injection molding under these two conditions, when the molten resin comes into contact with a low-temperature mold or insert metal of about 100 ° C from the melting point of the resin and is rapidly cooled, the crystallization and solidification of the resin is caused by Can happen inside. If it becomes so, strong joining (adhesion) will arise between resin and a metal.

  Furthermore, as a preferable condition (third condition) for injection joining, it can be said that if the above-described resin composition is improved, the injection joining becomes stronger. In other words, the resin composition having crystallinity is crystallized and solidified upon rapid cooling, but is an improvement of the resin composition that slows the solidification rate. In short, even if it is rapidly cooled to a temperature lower than the melting point of the resin, a seed crystal is immediately formed from the resin and does not grow and solidify. A certain minute time becomes a supercooled state and maintains the molten state. It was estimated that the supercooling time can be delayed by mixing some foreign resin into this resin.

  The minimum size of the seed crystal, that is, the resin crystal is probably about 10 nm or more. Even after the seed crystal is formed and the growth starts, it reaches the entrance of the ultra fine recess having a diameter of 20 to 80 nm. It is presumed that it is not easy to penetrate deeply. However, in the case of a resin composition in which seed crystals cannot be formed immediately upon rapid cooling and the subsequent crystal growth is somewhat slow, the resin can enter the recesses if the recess diameter is several hundred nm. Further, if the surface in the recess is rough, it is considered that the resin composition firmly crystallized and solidified in the recess is difficult to be removed, and in this case, it is considered that a stronger bond can be produced.

  Magnesium alloy is lighter than aluminum alloy, which is the biggest feature of magnesium alloy, but it is more chemically active than aluminum alloy. Even when a magnesium alloy is exposed to a bare metal surface by polishing or the like, a natural oxide layer is formed and gives some stability. However, the stability and robustness of this natural oxide layer is far inferior to the oxide film layer of aluminum alloy. For example, in the case of an aluminum alloy, if there is a rust preventive oil film or a paint film on the natural oxide layer, it will remain stable for more than a decade when left indoors without condensation, but in the case of a magnesium alloy, it will last for a year. Swelling and rusting will occur during this period. Water molecules that have diffused through oil films and coatings pass through the natural oxidation layer and oxidize magnesium. In short, when a magnesium alloy is actually used, it is indispensable to cover it with a strong film instead of a natural oxide film.

  Specifically, the magnesium alloy is processed by either chemical conversion treatment or electrolytic oxidation. Currently, chemical conversion treatment is common. The inventors of the present invention have sought to establish a technique capable of injecting and bonding a resin to a magnesium alloy subjected to chemical conversion treatment from a practical viewpoint. Fortunately, the surface of the chemically treated magnesium alloy is covered with a metal oxide, metal carbonate, or metal phosphate that is much harder than the substrate that is the metal body. This coincides with one of the two conditions required in the above-described injection joining, that is, the surface is covered with hard material irregularities.

The present invention has been made based on the above-described theoretical reasoning, and achieves the following objects.
An object of the present invention is to provide a metal / resin composite and a method for producing the same, in which a resin layer mainly composed of PBT or PPS can be strongly bonded to a magnesium alloy.
Another object of the present invention is a composite of a metal and a resin in which a base material made of magnesium metal having excellent corrosion resistance by chemical conversion of the surface layer and a resin composition mainly composed of PBT or PPS is integrated. A body and a method for manufacturing the same are provided.
Still another object of the present invention is to provide a metal-resin composite having high mass productivity and high productivity and a method for producing the same by molding a thermoplastic resin composition containing PBT or PPS as a main component by injection molding. provide.

In order to achieve the above object, the present invention takes the following means.
The gist of the metal-resin composite of the present invention 1 is selected from a base material made of a magnesium alloy, chromium, manganese, vanadium, calcium, zinc, calcium, strontium, zirconium, titanium, and alkali metal carbonate 1 A surface layer in which any one of a metal oxide, a metal carbonate, and a metal phosphorous oxide obtained by converting a seed or more into an aqueous solution and performing a chemical conversion treatment using the aqueous solution is formed on the surface of the magnesium alloy. And a resin composition in which the main component, which is a thermoplastic resin having crystallinity, penetrates into the concave portion of the surface layer by injection molding and is solidified, is a polybutylene terephthalate resin, and a subsidiary component is a polyethylene terephthalate resin. Consists of layers .

The gist of the metal-resin composite manufacturing method of the present invention 7 is a shaping step of forming a shaped part by machining from a cast or intermediate material made of a magnesium alloy, and a metal oxide on the surface layer of the shaped part A chemical conversion treatment step for forming one selected from a product, a metal carbonate, and a metal phosphate, and the molded component subjected to the chemical conversion treatment step is inserted into an injection mold, and the main component is polybutylene An injection step of injecting a resin composition which is a terephthalate resin and the subcomponent is a polyethylene terephthalate resin; and the shape is formed by intrusion into the concave portion of the metal oxide or the metal phosphate by the injection molding and solidifying It consists of the adhering step of adhering the part and the resin composition together.

Hereafter, each element which comprises this invention is demonstrated concretely in detail.
〔Base material〕
The base material as used in the field of this invention means the metal part which comprises a composite_body | complex. This base material is a commercially available or all known magnesium alloy including a AZ31 series wrought alloy specified by the Japanese Industrial Standards (JIS) and a AZ91 series cast alloy. If this magnesium alloy is an alloy for casting, it is a semi-finished product that has been shaped into a desired shape by molding means such as die casting, thixo mold, injection molding, etc., or a machine that is obtained by further machining it into a desired shape. Parts can be used. Further, in the wrought alloy, commercially available plates, rods, squares, pipes, etc., and parts formed by applying mechanical processing such as pressing, cutting and grinding can be used as the base material.

[Surface layer of base material (metal oxide, metal carbonate, or metal phosphate)]
The surface layer as used in the field of this invention means the metal oxide, metal carbonate, or metal phosphorus oxide formed in the surface of the base material which consists of magnesium alloys. What constitutes the surface layer is preferably one having hardness and higher mechanical strength than the base material. 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.

  On the surface of the substrate of the present invention, a layer of metal phosphate, metal carbonate, or metal oxide is formed by immersion in an aqueous solution. This is because the magnesium alloy, which has a high tendency to ionization and is easily corroded and oxidized even from moisture in the air, is immersed in an aqueous solution of a salt or acid of a different metal to dissimilar metal and / or magnesium oxide, carbonate, Alternatively, a stable layer of phosphorous oxide is formed, and internal metal corrosion is prevented by the presence of the layer. In the metal surface treatment industry, such immersion treatment is called chemical conversion treatment.

  In many cases, the chemical conversion treatment includes degreasing and chemical etching performed as a pretreatment of the chemical conversion treatment. In the present invention, in order not to confuse both, “chemical conversion treatment” means a treatment in a narrow sense for forming a corrosion-resistant layer, and treatments such as degreasing and etching performed as pretreatment of this chemical conversion treatment are “ The entire process including both the pretreatment and the chemical conversion treatment is referred to as “liquid treatment”.

  Chemical conversion treatment other than chromium-based treatment is called non-chromate treatment, and as far as the present inventors know, manganese-based treatment has been mainly used recently (for example, Japanese Patent Laid-Open No. 7-126858, Japanese Patent Laid-Open No. 7-126858). 2001-123274). In addition, a method of forming a layer made of a composite oxide such as aluminum, vanadium, zinc, zirconium, titanium, etc. as an anticorrosive layer on the surface is also known as non-chromate treatment (for example, Japan, JP 2000- 199077). 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 has a problem because it contains hexavalent chromium which is problematic in the environment, and recently, 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 substrate 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. In the present invention, both the requirement (1) and the requirement (2) are necessary. In the present invention, the requirement (2) is particularly considered and examined. 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 thermoplastic resin has a strong bonding force when it is crystallized and solidified by biting into the hard and strong uneven surface layer described above.

The hard and strong surface layer obtained by the chemical conversion treatment has a large uneven shape on the micrometer level (in other words, “having a roughness on the micron level”), and the concave surface is nano-sized. If the surface shape has a level uneven shape, the resin is caught on the surface of the metal, that is, the resin is caught by the unevenness of the metal surface layer, which is preferable for producing an anchor effect. Specifically, observation with an electron microscope is necessary, but when two or more plate-like crystals are observed per 1 μm ² , the needle-like or rod-like crystals cover the surface widely, or needle-like or rod-like The case where the lump which makes a crystal | crystallization outer shell connects and the base-material surface is covered is preferable. In addition, a large number of circular columns having a diameter of about 10 nm and a length of about 100 nm may be formed by electron microscope observation. However, this circular column is not necessarily a crystal.

When about 2 or more plate crystals are observed per 1 μm ² , the plate crystals serve as the walls of the concavo-convex portion, which is effective for increasing the fixing force as a mechanically strong fixing means. It is. On the other hand, if the surface is covered with 30% or more of needle-like or rod-like crystals, it will naturally serve as a fixing means with a rugged uneven shape, and this will improve the catching with the resin and increase the injection joining force. It is valid. In the following, the specific implementation method of each step and its concept will be described.

[Surface treatment / pretreatment of magnesium or magnesium alloy]
The pretreatment referred to in the present invention is a pretreatment for forming a surface layer made of a metal oxide, a metal carbonate, or a metal phosphate on the surface of a base material made of a magnesium alloy. The base material made of magnesium or a magnesium alloy is preferably first immersed in a degreasing tank to remove foreign substances such as oils and chips attached by machining. Specifically, a commercially available magnesium degreasing material is dissolved in warm water at a concentration specified by the drug manufacturer, the magnesium alloy is immersed in this, and then this is rinsed with clean water. Is preferred. 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. The use liquid is preferably an organic carboxylic acid having a pH of 2.0 to 5.0, and for example, a weakly acidic aqueous solution 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, in AZ31 series and AZ91 series, aluminum is contained in about 3 to 9% and zinc is about 1%. Aluminum and zinc are hardly dissolved in this etching process using a weakly acidic aqueous solution and deposited on the surface as an insoluble matter. A process for dissolving and removing these deposits is necessary.

  This is a process called so-called smut removal. In the above-described AZ31B, AZ91D, etc., first, the aluminum smut is dissolved by immersing it in a weakly basic aqueous solution (first smut treatment), and then the zinc smut is dissolved away by immersing in a strongly basic aqueous solution (second smut). Processing) is normal. In the first smut treatment described above, a commercially available degreasing agent aqueous solution for aluminum alloys can be used with a weak basicity, and the present inventors have used such a commercially available degreasing agent for aluminum at a concentration of 5 to 10% in 60%. A method of immersing for several minutes as an aqueous solution of ˜80 ° C. 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 / chemical conversion treatment of magnesium or magnesium alloy]
The chemical conversion treatment referred to in the present invention is for forming a surface layer made of a metal oxide, a metal carbonate, or a metal phosphorus oxide on the surface of a base material made of a magnesium alloy. When the above-described pretreatment is completed, a chemical conversion treatment that can be called the main treatment is then performed in the liquid treatment. The chemical conversion treatment is usually a two-stage immersion treatment, that is, first, the fine chemical etching is performed by immersing in a weak acidic aqueous solution for a short time, and then the conventional chemical conversion treatment method for various magnesium alloys is improved. . 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.

  The chemical conversion treatment step used in the present invention is basically the same as the conventionally known chemical conversion treatment. That is, this chemical conversion treatment method is a publicly known technique with many patents published, and details thereof are omitted. This chemical conversion treatment is performed by, for example, immersing in an aqueous solution or aqueous suspension containing one or more metals selected from chromium, manganese, vanadium, calcium, zinc, calcium, strontium, zirconium, titanium compounds, and alkali metal carbonates. By doing this, a metal oxide, metal carbonate, or metal phosphate is formed on the surface layer to improve the corrosion resistance of the magnesium alloy. On the other hand, as far as the present inventors know, the chemical conversion treatment that is actually commercialized is immersed in a chromic acid aqueous solution to cover the surface with chromium oxide or chromium oxide containing magnesium, or phosphorous treatment. 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. The purpose of the chemical conversion treatment for the present inventors 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 results of the study by the present inventors, sufficient corrosion resistance can be obtained in any of the chemical conversion treatment of the above-mentioned patent application type, chromate treatment, and non-chromate treatment method, which are practically used. A strong injection joint was obtained. However, when the surface of the metal was observed with an electron microscope, particularly the ones with good injection joining results, clear microcrystals were observed and beautiful nano-level repetitive structures were observed. And what adjusted the fine crystal | crystallization etching process in order to adjust the thing in which many crystals and beautiful repeating structures were observed with the electron microscope is preferable.

  A specific example of the chemical conversion treatment process which is considered to be one of the most preferable ones will be shown. The magnesium alloy part that has been pretreated is again immersed in a 0.1 to 0.5% strength hydrated citric acid solution at about 40 ° C. for 15 to 60 seconds and finely etched. Wash with water. Next, as a chemical conversion treatment solution, an aqueous solution containing potassium permanganate 1-5%, acetic acid 0.5-2%, and hydrated sodium acetate 0.1-1.0% was prepared at 40-60 ° C. The magnesium alloy part is immersed in 0.5 to 2 minutes, washed with water, and placed in a hot air drier at 60 to 90 ° C. for 5 to 20 minutes for drying. A brown magnesium alloy part covered with a thin layer of manganese oxide is obtained.

  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 magnesium alloy base material after the pretreatment was again finely etched by immersion in a 0.1 to 0.5% strength hydrated citric acid aqueous solution at about 40 ° C. for 15 to 60 seconds. Wash with replacement water. Next, as a chemical conversion treatment solution, an aqueous solution of chromic anhydride (chromium trioxide) having a concentration of 15 to 20% is prepared at 60 to 80 ° C., and the finely etched magnesium component is immersed in this for 2 to 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. The surface layer is chromated and a magnesium alloy substrate having a gray surface is obtained.

[Resin layer]
The resin layer which comprises this invention is resin which has PBT which is a thermoplastic resin which has crystallinity as a main component. Although there is not a resin can not be used in the present invention in a high degree of crystalline resin polyamides, in terms of either maintain long-term bonding strength because the mechanical strength is somewhat weak and absorbent enough Te reliability odor at this stage do not use in the present invention rather than. However, it can be used depending on the application. In addition, the resin layer as used in the field of this invention is a part formed by injection molding, and although it showed with the character of the layer, it does not indicate the thin thing, it has a thickness and is a shape object.

  In the resin layer of the present invention, polymers other than PBT or PPS, fillers such as glass fibers and carbon fibers, modifiers, and the like are mixed as necessary by a conventional method in order to improve various mechanical properties. Is good. As the basic resin of PBT, various PBT synthesized for injection molding can be used. On the other hand, the basic resin of PPS may be a linear one, a one having a branched structure introduced therein, or one subjected to heat treatment in an inert gas. What introduced the branched structure and what heat-processed in inert gas are good.

[Resin layer (composition of PPS and polio les fins)
PBT is mainly used as the resin layer of the present invention, but in the case of PPS, particularly when an appropriate amount of polyolefin resin is added, the fixing strength becomes stronger. The reason for this presumption is presumed that the crystallization rate during quenching is slowed by the addition of an appropriate amount of polyolefin resin. As a result, the resin sufficiently penetrates into the recess formed by the chemical conversion treatment surface and then crystallizes and solidifies, and the molten resin flow before solidification also corresponds to the nano level unevenness on the surface of the recess to some extent. Therefore, it is understood that the fixing strength increases.

  The resin composition comprising PPS to which the polyolefin resin used in the present invention is added is preferably composed of a resin component composition containing 70 to 97% by weight of PPS and 3 to 30% by weight of the polyolefin resin. More preferably, a resin composition containing 80 to 97 wt% PPS and 3 to 20 wt% polyolefin-based resin is preferable in order to obtain a composite having excellent adhesion. Here, when PPS is less than 65% by weight, or when it exceeds 97% by weight, the composite obtained is inferior in adhesion between the substrate and the resin layer.

  Any PPS may be used as long as it belongs to a category referred to as PPS. Among them, those having a melt viscosity of 100 to 30,000 poise are preferable because they are excellent in moldability when used as a resin composition. The melt viscosity is measured using a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg. 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.

  Moreover, as PPS, even if it is a linear thing, what introduce | transduced the branched structure, what was heat-processed in inert gas can be used. 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. Can do. Among these, from the viewpoint of obtaining a particularly excellent composite, an ethylene-acrylic acid ester-maleic anhydride terpolymer is preferable, and this ethylene-acrylic acid ester-maleic anhydride terpolymer is preferable. Specific examples include “Bondaine (product name)” (Kyoto, Japan, Arkema).

  Examples of the glycidyl methacrylate-modified ethylene copolymer include glycidyl methacrylate graft-modified ethylene polymer and glycidyl methacrylate-ethylene copolymer. Among them, particularly excellent composites can be obtained, and thus glycidyl methacrylate-ethylene copolymer. It is preferably a polymer, and specific examples of this glycidyl methacrylate-ethylene copolymer include “Bond First (product name)” (Chuo-ku, Tokyo, Japan).

  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 ( Product name) "(Kyoto, Japan, Arkema Co., Ltd.)" and the like. In the composite of the present invention, since the bondability between the base material and the resin layer becomes better, the resin composition is a total of the resin content including 70 to 97% by weight of PPS and 3 to 30% by weight of polyolefin resin. What blends 0.1-6 weight part of polyfunctional isocyanate compounds and / or 1-25 weight part of epoxy resins with respect to 100 weight part is preferable.

  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, and bis (4-isocyanatophenyl) sulfone. 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 (product name)” (Tokyo, Japan, manufactured by Mitsui Chemicals Polyurethanes).

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

[Resin layer (composition of PBT and PET mixed)]
The resin component of the resin layer of the present invention is a composition in which PBT and polyethylene terephthalate (PET) are mixed. A mixing ratio of 65 to 87 % by weight of PBT and 13 to 35% by weight of PET is suitable.

[filler]
The resin used in the resin layer of the present invention uses a polybutylene terephthalate resin or a polyphenylene sulfide resin, which is a thermoplastic resin having crystallinity, as a main pomer. For reasons such as improvement of mechanical properties, these resins are used. You may mix a filler with a polymer. The mixing ratio of the filler is 1 to 200 parts by weight of the filler with respect to 100 parts by weight of the total resin content of the polyphenylene sulfide resin and the polyolefin resin, or 100 parts by weight of the total resin of the polybutylene terephthalate resin and the polyethylene terephthalate resin. What is blended is good. Examples of the filler include fillers such as a fibrous filler, a granular filler, and a plate 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]
As a method for producing the composite of the present invention, it is preferable to produce the composite by a method in which a base material made of a magnesium alloy is inserted into an injection mold, the mold is closed, and a resin is injected, that is, an injection joining method. An example is given. An injection mold is prepared, this mold is opened, and a base material made of a magnesium alloy subjected to chemical conversion treatment obtained by the above-mentioned treatment is inserted into one of the molds, the mold is closed, and PBT or PPS is inserted. A composite is manufactured by injecting and solidifying a thermoplastic resin composition having a resin component composition, and then opening and releasing the mold.

  Next, 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 the resin is solidified 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 different from the normal injection molding conditions, but speakingly, the injection speed and the injection pressure should be high.

As described above in detail, the composite of the present invention can be integrated without easily peeling off the resin composition part and the base material made of a magnesium alloy. In addition, this composite is excellent in corrosion resistance because a metal oxide, metal carbonate, or metal phosphate is formed on the surface layer of the substrate. Furthermore, by molding a thermoplastic resin composition containing PBT as a main component and a subsidiary component as PET by injection molding, a composite body composed of a base material made of a magnesium alloy and a resin layer having high mass productivity and high productivity is made. I was able to.

Hereinafter, embodiments of the present invention will be described with reference examples and examples. FIG. 1 and FIG. 2 are used as a common view of each reference example and embodiment. FIG. 1 is a mold structure diagram schematically showing an injection mold including a movable side mold, a fixed side mold, and the like. FIG. 2 is an appearance of the composite 7 in which the base material 1 and the resin composition 4 are integrally fixed by this injection mold.

The magnesium alloy plate 1 processed into a predetermined shape is inserted between the movable side mold plate 2 and the fixed side mold plate 3, and the molten resin composition 4 is injected from the nozzle and injected into the cavity through the pin gate 5. . The resin composition 4 is fixed to the joint surface 6 having fine concave portions formed on the surface of the magnesium alloy plate 1, and the composite 7 in which both are integrated is manufactured. In each of the following reference examples and examples, the magnesium alloy plate 1 and the resin composition 4 are pulled together to measure the bonding strength of the composite body 7 produced in each reference example and example. The fixing force was confirmed by applying a shear stress and measuring the breaking strength.

Examples of the present invention , reference examples, comparative examples and elements therefor will be described in detail below. As a premise, the evaluation / measurement method and measurement equipment used for evaluation / measurement of the composites obtained from the examples described later are shown below.
[Evaluation / Measurement Method and Measurement Equipment]
(A) Measurement of melt viscosity of resin In order to measure the melt viscosity of resin, an elevated flow tester known as a measure of melt viscosity and flow performance of various thermoplastic and thermosetting plastics was used. . A Koka-type flow tester “CFT-500 (product name)” (manufactured by Shimadzu Corporation, Kyoto, Japan) equipped with a die having a diameter of 1 mm and a length of 2 mm, measuring temperature 315 ° C., load 0.98 Mpa (10 kgf) The melt viscosity was measured under the following conditions.
(B) X-ray photoelectron analyzer (XPS observation)
As one of the surface observation methods, the energy of photoelectrons emitted from the sample was analyzed by irradiating the sample with X-rays, and a photoelectron analyzer (XPS observation) for performing qualitative analysis of elements and the like was performed. This photoelectron analyzer used “AXIS-Nova (product name)” (manufactured by Kleitos Analytical Co., Ltd./Shimadzu Corporation) in the form of observing a surface having a diameter of several μm within a depth of several nanometers.
(C) Electron microscope observation An electron microscope was mainly used for observation of the substrate surface. This electron microscope is a scanning (SEM) electron microscope “S-4800 (product name)” (Tokyo, Japan, manufactured by Hitachi, Ltd.) and “JSM-6700F (product name)” (Tokyo, Japan, (Manufactured by JEOL Ltd.) and observed at 1-2 KV.
(D) Scanning probe microscope observation Further, the above microscope was used mainly for the observation of the substrate surface. This microscope is a scanning probe microscope that uses a probe with a sharp tip to move the surface of a substance so as to trace the surface state. As this scanning probe microscope, “SPM-9600 (product name)” (Kyoto, Japan, manufactured by Shimadzu Corporation) ”was used.
(E) Measurement of bonding strength of composite The tensile stress was determined by pulling the composite 7 with a tensile tester and applying a shearing force, and taking the breaking force as the shearing stress. This tensile tester used “Model 1323 (product name)” (Tokyo, Japan, manufactured by Aiko Engineering Co., Ltd.) and measured the shear force at a pulling speed of 10 mm / min.
(F) Salt spray test To test the corrosion resistance of the composite of the present invention, a salt spray test was conducted. For this test, a salt spray tester “SPT-90 (Tokyo, Japan, manufactured by Suga Test Instruments Co., Ltd.)” which is a kind of material tester for spraying salt water to test the corrosion resistance and deterioration of the material is used. It was.

[Preparation Example 1 of PPS Composition]
This PPS adjustment example 1 shows an adjustment example in which PPS and polyolefin resin are mixed. An autoclave equipped with a stirrer and having a capacity of 50 liters was charged with 6,214 g of Na ₂ S · 2.9H ₂ O and 17,000 g of N-methyl-2-pyrrolidone and gradually stirred while stirring under a nitrogen stream. The temperature was raised to 0 ° C., and 1355 g of 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) and 1.5 kg of ethylene-acrylic acid ester-maleic anhydride terpolymer "Bondyne TX8030 (product name)" (Kyoto, Japan, Arkema Co., Ltd.) ”, 0.5 kg of epoxy resin“ Epicoat 1004 (product name) ”(Tokyo, Japan, manufactured by Japan Epoxy Resin Co., Ltd.) was previously mixed uniformly with a tumbler. Thereafter, glass fiber “RES03-TP91 (product name)” having an average fiber diameter of 9 μm and a fiber length of 3 mm in a twin screw extruder “TEM-35B (product name)” (manufactured by Toshiba Machine Co., Ltd., Shizuoka, Japan). (Tokyo, Japan, manufactured by Nippon Sheet Glass Co., Ltd.) was fed from the side feeder so that the addition amount was 20% by weight, and the PPS composition (1) pelletized by melt kneading at a cylinder temperature of 300 ° C. Obtained. This PPS composition (1) is a resin composition in which the polyolefin resin occupies 20% of the total resin content, and the epoxy resin content occupies 7 parts with the total resin content being 100 parts. The obtained PPS composition (1) was dried at 175 ° C. for 5 hours.

[Preparation Example 2 of PPS Composition]
The PPS composition (1) obtained in Preparation Example 1 of the PPS composition was cured at 250 ° C. for 3 hours in an oxygen atmosphere to obtain PPS (hereinafter referred to as PPS (3)). The resulting PPS (3) had a melt viscosity of 1800 poise. 5.98 kg of the obtained PPS (3) and 0.02 kg of polyethylene “Nipolon Hard 8300A (product name)” (manufactured by Tosoh Corporation, Tokyo, Japan) were uniformly mixed in advance with a tumbler. Thereafter, the glass fiber “RES03-TP91” having an average fiber diameter of 9 μm and a fiber length of 3 mm is added from the side feeder in the above-described twin-screw extruder “TEM-35B” (described above) so that the addition amount becomes 40% by weight. While being supplied, a PPS composition (2) was obtained which was melt-kneaded and pelletized at a cylinder temperature of 300 ° C. This composition is a resin composition in which the polyolefin resin occupies 0.3% of the total resin content. The obtained PPS composition (2) was dried at 175 ° C. for 5 hours.

[Preparation Example 3 of PPS Composition]
7.2 kg of PPS (2) obtained in Preparation Example 1 of PPS composition and 0.8 kg of glycidyl methacrylate-ethylene copolymer “Bond First E (manufactured by Sumitomo Chemical Co., Ltd.)” were previously mixed uniformly with a tumbler. did. Thereafter, glass fiber “RES03-TP91” having an average fiber diameter of 9 μm and a fiber length of 3 mm is supplied from the side feeder with a twin screw extruder “TEM-35B” (described above) so that the addition amount is 20% by weight. Then, the PPS composition (3) which was melt-kneaded and pelletized at a cylinder temperature of 300 ° C. was obtained. This composition is a resin composition in which the polyolefin resin occupies 10% of the total resin content. The obtained PPS composition (3) was dried at 175 ° C. for 5 hours.

[Preparation Example 4 for PPS Composition]
4.0 kg of PPS (2) obtained in Preparation Example 1 of PPS composition and 4.0 kg of ethylene-acrylic acid ester-maleic anhydride terpolymer "Bondyne TX8030 (product name)" (Kyoto, Kyoto, Japan) City, Arkema) ”was previously mixed uniformly with a tumbler. Thereafter, glass fiber “RES03-TP91” having an average fiber diameter of 9 μm and a fiber length of 3 mm is supplied from the side feeder with a twin screw extruder “TEM-35B” (described above) so that the addition amount is 20% by weight. Then, the PPS composition (4) which was melt-kneaded and pelletized at a cylinder temperature of 300 ° C. was obtained. This composition is a resin composition in which the polyolefin resin occupies 50% of the total resin content. The obtained PPS composition (4) was dried at 175 ° C. for 5 hours.

[PBT Composition Preparation Example 5]
PBT containing 47% PBT and 38% glass fiber using commercially available PBT resin “Torcon 1101G45 (Tokyo, Japan, Toray Industries, Inc.)” and PET resin using a twin screw extruder “TEM-35B” (supra) A composition (1) was obtained. This PBT composition (1) is a resin composition in which PET accounts for 24% of the total resin content. The resulting composition was dried at 130 ° C. for 5 hours.

[ Reference Example 1]
The final surface treatment was wet buffing, and a 0.8 mm thick AZ31B magnesium alloy (Tokyo, Japan, manufactured by Nippon Metal Industry Co., Ltd.) having an average metal crystal grain size of 7 μm on its surface was used. This magnesium alloy plate was cut into 18 mm × 45 mm (0.8 mm thickness) rectangular pieces to obtain a magnesium alloy plate 1. Opening a through-hole at the end of the magnesium alloy plate 1 and passing ten copper wires coated with vinyl chloride, bending and processing the copper wire so that the plurality of magnesium alloy plates 1 do not overlap each other, All can be hung at the same time.

  A commercially available magnesium alloy degreasing agent “Cleaner 160 (product name)” (manufactured by Meltex Inc., Tokyo, Japan) was added to water in a degreasing tank to obtain an aqueous solution at 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 a degreasing agent for aluminum alloy “NE-6 (product name)” (manufactured by Meltex Inc., Tokyo, Japan) adjusted to 75 ° C. in another tank is prepared and immersed for 5 minutes. Washed well with water. 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 is estimated 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 another 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 plate on a clean aluminum foil, placed together, wrapped in a plastic bag and sealed and stored. At this time, a finger or the like was prevented from coming into contact with the surfaces to be joined (the end on the opposite side from where the through hole was formed).

Two days later, one of them was observed with an electron microscope. Many plate crystals were seen on the surface, and other irregular shapes were seen. The major axis of the void formed by the plate crystals was 600 to 400 nm and the depth was 500 nm or more. The number of plate-like crystals that can be confirmed per 1 μm square was 1 to 5, although it varied depending on the location. The surface image is shown in an electron micrograph (see FIG. 3). Further, after one day, the remaining magnesium alloy plate 1 was taken out, and the one with a through hole was picked with gloves so as to prevent oil and the like from adhering, and inserted into an injection mold set at 140 ° C. A PBT resin composition “Tuffpet G1030 (product name)” (manufactured by Mitsubishi Rayon Co., Ltd., Tokyo, Japan) containing 30% glass fiber was injected at an injection temperature of 260 ° C. The mold temperature was 140 ° C., and 20 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 break test on the day of molding, the average shear force was 11.8 Mpa. In addition, five pieces annealed by putting them in a hot air dryer at 150 ° C. for 1 hour on the molding day were further subjected to a tensile test one day later, and the average shear breaking stress was 11.9 MPa. The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (product name)” (manufactured by Ohashi Chemical Industries, Osaka, Japan) at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. After spraying with salt water for 8 hours at room temperature using 1% salt water, it was washed with water and dried, but no abnormality was observed in appearance.

[ Reference Example 2]
An AZ31B alloy plate having a thickness of 0.8 mm and an average metal crystal grain size of 7 μm was obtained. 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 another tank, and the magnesium alloy plate 1 was immersed in this for 2 minutes and washed with water. Black smut was attached. Subsequently, a 7.5% aqueous solution of a degreasing agent for aluminum alloy “NE-6 (product name)” (manufactured by Meltex Inc., Tokyo, Japan) adjusted to 75 ° C. in another tank is prepared and immersed for 5 minutes. Washed well with water. Subsequently, a 20% caustic soda aqueous solution at 75 ° C. was prepared in another tank, and the magnesium alloy plate group 1 was immersed in this for 5 minutes and washed with water. This is the pretreatment, and the treatment method was the same as in Reference Example 1.

  Subsequently, it was immersed in a 0.5% strength aqueous 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 sodium acetate 0.5% was prepared at 45 ° C., immersed for 1 minute, and thoroughly washed with water. It was brown and seemed to be covered with manganese dioxide. 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 plate 1 and placed 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 through hole).

Two days later, one of them was observed with an electron microscope. As a result, spherical objects with a diameter of 80 to 120 nm with fine needle crystals gathered, and these gathered and joined together to form irregularities with a large period. The period was 0.5-1 μm and the depth of the recess was 0.3-1 μm. There were 90 to 120 spheres counted per 1 μm square. A photograph is shown in FIG. Further, after 1 day, the remaining magnesium alloy plate 1 was taken out, and the one with a through hole was picked with gloves so as to prevent oil or the like from adhering, and inserted into an injection mold set at 140 ° C. Ten integrated composites shown in FIG. 2 were obtained in exactly the same manner as in Reference Example 1. On the day of molding, the sample was put into a 150 ° C. hot air dryer for 1 hour for annealing, and a tensile test was conducted one day later. The average shear force was 11.6 MPa.

[ Reference Example 3]
An AZ31 alloy plate having a thickness of 0.8 mm with an average metal crystal grain size of 7 μm was obtained. 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 another tank, and the magnesium alloy plate 1 was immersed in this for 2 minutes and washed with water. Black smut was attached. Subsequently, a 7.5% aqueous solution of an aluminum alloy degreasing agent “NE-6 (product name)” adjusted to 75 ° C. in a separate tank was prepared and immersed in water for 5 minutes. Subsequently, a 20% caustic soda aqueous solution at 75 ° C. was prepared in another tank, and the magnesium alloy plate group 1 was immersed in this for 5 minutes and washed with water. This is the pretreatment, and the treatment method was the same as in Reference Example 1.

  Subsequently, it was immersed in a 0.5% strength aqueous citric acid solution at 40 ° C. prepared in a separate tank for 15 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 plate 1 and placed 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 through hole).

Further, after one day, the remaining magnesium alloy plate 1 was taken out, and the one with a through hole was picked with gloves so as to prevent oil and the like from adhering, and inserted into an injection mold set at 140 ° C. Ten integrated composites shown in FIG. 2 were obtained in exactly the same manner as in Reference Example 1. On the day of molding, the sample was annealed for 1 hour in a hot air dryer at 150 ° C., and a tensile test was conducted one day later. The average shear force was 7.7 MPa (78 kgf / cm 2).

[ Reference Example 4]
An AZ31 alloy plate having a thickness of 0.8 mm with an average metal crystal grain size of 7 μm was obtained. A rectangular piece was cut in the same manner as in Reference 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 another tank, and the magnesium alloy plate 1 described above was immersed in this for 2 minutes and washed with water. Black smut was attached. Subsequently, a 7.5% aqueous solution of an aluminum alloy degreasing agent “NE-6 (product name)” adjusted to 75 ° C. in a separate tank was prepared and immersed in water for 5 minutes. Subsequently, a 20% caustic soda aqueous solution at 75 ° C. was prepared in another tank, and the magnesium alloy plate group 1 was immersed in this for 5 minutes and washed with water. This is the pretreatment, and the treatment method was the same as in Reference Example 1.

  Subsequently, it was immersed in a 0.5% strength aqueous citric acid solution at 40 ° C. prepared in a separate tank for 15 seconds and washed with water. Next, it was immersed for 5 seconds in a 70 ° C. aqueous solution containing 1% zinc acetylacetonate 2%, titanium sulfate 24% aqueous solution and 0.1% diammonium dizirconate 0.1%, 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 plate 1 and placed 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 through hole).

Further, after 1 day, the remaining magnesium alloy plate 1 was taken out, and the one with a through hole was picked with gloves so as to prevent oil or the like from adhering, and inserted into an injection mold set at 140 ° C. Ten integrated composites shown in FIG. 2 were obtained in exactly the same manner as in Reference 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 force was 6.9 MPa.

[ Reference Example 5]
An AZ31B alloy plate having a thickness of 0.8 mm and an average metal crystal grain size of 7 μm was obtained. It cut | disconnected similarly to the reference example 1 and made it the rectangular piece, and the pre-processing including degreasing was performed. The pretreatment method was the same as in Reference Examples 1 to 4. 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 pieces were immersed in an aqueous solution containing 20% chromic acid 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 other end opposite to the end where the through hole was opened).

One day later, one was observed with ESCA. A large amount of chromium and oxygen was observed. The main component appeared to be a composite of trivalent chromium oxide or chromium hydroxide. Further, one day later, the magnesium alloy piece was taken out, and the one with a through hole was picked with a glove so as to prevent oil or the like from adhering, 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 Reference Example 1. As it was put in a hot air dryer at 150 ° C. for 1 hour and annealed, and a tensile test was conducted one day later, the average shearing force was 6.6 MPa. The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (product name)” 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.

[ Reference Example 6]
Metal crystal grain size of the average final processing of wet buffing is, 7 [mu] m or less is 0.8mm thick AZ31B magnesium alloy (Tokyo, Japan, Nippon Metal Industry Co., Ltd.) cut to the same shape as in Reference Example 1 A rectangular piece was prepared and pretreatment including degreasing was performed. The pretreatment method was the same as in Reference Examples 1-5. 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 through hole).

One day later, one was observed with an electron microscope. The result is shown in the photograph of FIG. The crossed rod-like crystals were beautiful with a mesh pattern. On the other hand, in the analysis by ESCA, trace amounts of aluminum, zinc and silicon were recognized in addition to magnesium, oxygen and carbon. Since carbon which was not a trace amount was confirmed, it was estimated that magnesium carbonate was the main component of the surface layer. Further, after one day, the remaining magnesium alloy piece was taken out, and the one with a through hole was picked with a glove so as to prevent oil or the like from adhering, and inserted into an injection mold set at 140 ° C. Injection molding was performed in exactly the same manner as in Reference Example 1 to obtain 20 integrated composites 7 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 shearing force was 7.0 MPa.

[ Reference Example 7]
In exactly the same manner as in Reference Example 1, 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 or less. 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% phosphorus, and washed well 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 other end opposite to the one end where the through hole was opened). One day later, one was observed with ESCA.

Large amounts of magnesium, calcium, strontium and oxygen and very small amounts of zinc, aluminum, carbon and silicon were observed. The main components were seen as oxides of magnesium, calcium and strontium. Whether it was a single composition or multiple compositions was not known by the analyzer used. Further, after one day, the remaining magnesium alloy piece was taken out, and the one with a through hole was picked with a glove so as to prevent oil or the like from adhering, and inserted into an injection mold set at 140 ° C. Injection molding was performed in exactly the same manner as in Reference 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 shearing force was 7.3 MPa.

[ Reference Example 8]
In exactly the same manner as in Reference Example 1, pretreatment was performed using 0.8 mm-thick AZ31B magnesium alloy pieces having an average metal crystal grain size of 7 μm or less. 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 through 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 through hole was picked with a glove so as to prevent oil or the like from adhering, and inserted into an injection mold set at 140 ° C. Injection molding was performed in exactly the same manner as in Reference Example 1 to obtain 20 integrated composites 7 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 shearing force was 7.0 MPa. The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (product name)” 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.

[ Reference Example 9]
Reference Example 9 is for confirming the effect of the PPS resin. As a resin to be injected, “Sustile GS-30 (product name)” (manufactured by Tosoh Corporation, Tokyo, Japan), which is a PPS resin containing 30% glass fiber, was used. The injection conditions during molding were injection at an injection temperature of 310 ° C. and a mold temperature of 140 ° C. Except for this injection molding condition, the conditions are exactly the same as in Reference Example 1. When four pieces were subjected to a tensile fracture test on the same day of molding, the average shearing force was 8.8 MPa (90 kgf / cm @ 2). In addition, five samples annealed by putting them in a hot air dryer at 170 ° C. for 1 hour on the molding day were further subjected to a tensile test one day later, and the average shear force was 9.3 MPa.

  The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (product name)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Although sprayed with salt water at room temperature for 8 hours using 1% salt water, washed with water and dried, no abnormality was observed in appearance.

[ Reference Example 10]
Reference Example 10 is for confirming the effect of the PPS resin. Processing of magnesium alloys piece, Reference Example 9 and substantially performs the same processing, injection joining was also performed in the same manner as in Reference Example 9. However, the synthetic resin used was the PPS composition (1) according to Preparation Example 1 of the PPS composition, instead of “Sustile GS-30” used in Reference Example 9. Thus, 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 joining surface 6 was 0.5 cm 2 of 10 mm × 5 mm.

  When four pieces were subjected to a tensile break test on the day of molding, the average shear force was 13.0 MPa. Further, five samples annealed by putting them in a hot air dryer at 170 ° C. for 1 hour on the day of molding were subjected to a tensile test one day later, and the average shear force was 12.8 MPa. The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (product name)” 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.

[ Reference Example 11]
Except for using the PPS composition (3) obtained in Preparation Example 3 instead of the PPS composition (1) obtained in Preparation Example 1 of the PPS composition, the same method as in Example 10 was used. A complex was obtained. The composite was annealed at 170 ° C. for 1 hour on the day of molding, and two days later, the composite was measured for shearing force 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 (product name)” (manufactured by Ohashi Chemical Industries, Osaka, Japan) 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.

[ Reference Example 12]
A magnesium alloy piece was prepared in exactly the same manner as in Reference Example 10 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, these were subjected to a tensile test, and the shear force was 9.0 MPa on an average of 10 pieces. This is only about 70% of the numerical value of Reference Example 1, resulting in a difference in the resin material used.

[ Reference Example 13]
A 0.8 mm thick AZ31B alloy plate having an average metal crystal grain size of 7 μm was used. A rectangular piece was cut in the same manner as in Reference 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 an aluminum alloy degreasing agent “NE-6 (product name)” adjusted to 75 ° C. in a separate 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. This is the pretreatment, and the treatment method was the same as in Reference 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 through hole).

Two days later, one was observed by ESCA, a large amount of manganese and oxygen was 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 through hole was picked with gloves so as not to allow oil or the like to 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 Reference Example 1.

  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 force was 15.1 MPa. The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (product name)” 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 14]
An AZ31B alloy piece was pretreated in exactly the same manner as in Example 13. Next, it was immersed in a 0.25% strength hydrated citric acid aqueous solution at 40 ° C. prepared in another tank for 1 minute 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., immersed for 1 minute and washed with water. It put into the warm air dryer which was 60 degreeC for 15 minutes, and dried. The copper wire was pulled out from the magnesium alloy piece and placed on a clean aluminum bed, wrapped together, and then put in a plastic bag, which was sealed and stored.

Two days later, this was taken out and inserted into an injection mold set at 140 ° C. to inject the PBT composition (1). The injection molding conditions were the same as in Example 1. An integrated product shown in FIG. 2 was obtained, which was put into a hot air dryer at 150 ° C. for 1 hour and annealed within the same day, and then a tensile test was conducted one day later. The average shear force was 15.8 MPa. It was.
The remaining 10 integrated products were coated with the paint “Omak / Silver Metallic (product name)” 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]
Comparative Example 1 was performed in order to confirm the effect of the chemical conversion treatment of Reference Example 1. A magnesium alloy plate 1 was obtained in exactly the same manner as in Reference Example 1 except that no chemical conversion treatment was performed. That is, the AZ31B magnesium alloy plate 1 was made, degreased, roughly etched, desmutted, finely etched, and desmutted. In short, it was washed with water and dried without performing only the manganese phosphate nonchromate treatment. Two days later, the remaining magnesium alloy plate 1 was taken out, and the one with a through hole was picked with gloves so as not to allow oil or the like to adhere thereto, and inserted at 140 ° C. into an injection mold.

The injection mold was closed and the same PBT resin as in Reference Example 1 was injected at an injection temperature of 260 ° 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 joining surface 6 was 0.5 cm 2 of 10 mm × 5 mm. When annealing was performed at 150 ° C. for 1 hour on the day of molding and four pieces were subjected to a break test, the average shear force was 7.4 MPa.

The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (product name)” at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. The next day, the coated product was sprayed with salt water at room temperature for 8 hours using 1% salt water, washed with water, and dried. As a result, fine coating swelling was observed in all the integrated products. When all of the ten pieces were subjected to a tensile fracture test, the average shear force was 4.9 MPa (50 kgf / cm ² ). 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.

[Comparative Example 2]
A magnesium alloy piece was obtained in exactly the same manner as in Reference Example 1 except that the chemical conversion treatment was not performed. That is, an AZ31B 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. Crystalline objects 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 through hole was picked with a glove so as not to allow oil or the like to adhere, and inserted into an injection mold set at 140 ° C. The mold was closed and PPS (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 pulled and subjected to a fracture test on the same day of molding, the average shear force was 11.3 MPa.

  The remaining 10 integrated products were coated with a paint “Omak / Silver Metallic (product name)” 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 fracture test, the shearing force 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.

[Comparative Example 3]
A composite was produced in the same manner as in Example 10, except that the PPS composition (4) in Preparation Example 4 of the PPS composition was used instead of the PPS composition (1) in Preparation Example 1 of the PPS composition. Tried. In short, this is an experiment using a PPS resin composition containing a very large amount of polyolefin polymer. This resin material should be a polyolefin material rather than a PPS material. A large amount of gas was generated during molding, and the operation was stopped due to difficulty in injection molding.

[Comparative Example 4]
The final surface treatment was wet buffing, and a 0.8 mm thick AZ31B magnesium alloy (Tokyo, Japan, manufactured by Nippon Metal Industry Co., Ltd.) having an average metal crystal grain size of 7 μm on its surface was used. This is cut into 18 mm x 45 mm pieces, through holes are made in the ends of the pieces, a copper wire coated with vinyl chloride is passed through, and the copper wires are bent and processed so as not to overlap each other. 10 can be hung at the same time.

In a degreasing tank, a commercially available magnesium alloy degreasing agent “Cleaner 160” was poured into hot water having a 10% concentration of 65 ° C. and dissolved. The alloy piece was immersed in this for 5 minutes, washed thoroughly with water, and dried at 67 ° C. for 15 minutes. In short, this is a test for confirming the bonding strength of an alloy that has been subjected only to the degreasing treatment. Three days later, one of them was photographed with an electron microscope. The photograph is shown in FIG. After a further day, the alloy piece was inserted into an injection mold set at 140 ° C., and the PPS composition (1) was injected. The injection molding conditions were the same as in Reference Example 10. However, when the injection mold was opened, it was not an integrated product.

[Comparative Example 5]
Except that the resin used was changed from the PPS composition (1) to the PBT composition (1) and the injection molded nourishment ticket was matched to Example 1, the same experiment as Comparative Example 4 was performed. Also in this case, when the injection mold was opened, the resin molded product and the magnesium alloy piece could not be obtained integrally.

The following table is a list showing an outline of the above-described examples and comparative examples.

  The metal / resin composite and the method for producing the same according to the present invention can be used for a casing of an electronic device, a casing of a household electrical appliance, a structural component, a mechanical component, and the like. In particular, a magnesium alloy has a higher strength per unit weight and flexural modulus than an aluminum alloy or steel, and therefore has a wide range of uses as a structural material or component. Utilizing this characteristic, its application is expected to mobile electronic devices, aircraft fuselage parts, automobile parts, and the like that are required to be reduced in weight.

FIG. 1 is a configuration diagram of an injection mold 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 shows the surface of an AZ31B magnesium alloy having an average crystal grain size of 7 μm or less 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 with manganese phosphate. It is a photograph. FIG. 4 shows the surface of an AZ31B magnesium alloy having a metal crystal grain size of 7 μm or less, 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 a photograph. FIG. 5 is a surface photograph of an AZ31B magnesium alloy having an average particle diameter of 7 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 with potassium carbonate. is there. FIG. 6 is a surface photograph of an AZ31B magnesium alloy (manufactured by Nippon Metal Industry Co., Ltd., Tokyo, Japan) having a metal crystal average particle diameter of 7 μm that has been subjected to only degreasing treatment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Magnesium alloy plate 2 ... Movable side die plate 3 ... Fixed side die plate 4 ... Resin composition 5 ... Pinpoint gate 6 ... Joining surface 7 ... Composite

Claims (11)

A base material made of a magnesium alloy;
Metal oxidation obtained by converting one or more selected from chromium, manganese, vanadium, calcium, zinc, calcium, strontium, zirconium, titanium, and alkali metal carbonate into an aqueous solution, and performing chemical conversion treatment using this aqueous solution Any one of a material, a metal carbonate, and a metal phosphate is formed on the surface of the magnesium alloy;
A resin composition layer in which the main component, which is a thermoplastic resin having crystallinity, penetrates into the concave portion of the surface layer by injection molding, is solidified, and is a polybutylene terephthalate resin, and a subsidiary component is a polyethylene terephthalate resin; A composite of metal and resin. The metal / resin composite according to claim 1,
A composite of a metal and a resin, wherein two or more plate crystals are observed per square area of 1 μm square on the surface layer by observation with an electron microscope. The metal / resin composite according to claim 1,
A composite of metal and resin, characterized in that the surface layer is covered with a lump with needle-like crystals as observed with an electron microscope. The metal / resin composite according to claim 1,
A composite of metal and resin, wherein a large number of circular columns having a diameter of about 10 nm and a length of about 100 nm are formed on the surface layer by electron microscope observation. The metal / resin composite according to claim 1,
The polybutylene terephthalate is 65 to 87 % by weight, and the polyethylene terephthalate is 13 to 35% by weight. A metal-resin composite. In one selected from the metal-resin composite of claim 1-5.
The resin layer is formed by further blending 1 to 200 parts by weight of a filler with respect to 100 parts by weight of the total resin of the polybutylene terephthalate resin and the polyethylene terephthalate resin. Complex. A shaping step of forming a shaped part by machining from a cast or intermediate material made of a magnesium alloy;
A chemical conversion treatment step of forming one type selected from a metal oxide, a metal carbonate, and a metal phosphate on the surface layer of the shaped part;
An injection step of injecting a resin composition in which the main component is a polybutylene terephthalate resin and a secondary component is a polyethylene terephthalate resin, by inserting the shaped part subjected to the chemical conversion treatment step into an injection mold; and
A metal / resin composite comprising: a fixing step in which the shaped part and the resin composition are integrally fixed by intrusion into the concave portion of the metal oxide or the metal phosphor oxide by the injection molding and solidifying. Manufacturing method. In the manufacturing method of the composite of the metal and resin of Claim 7,
The chemical conversion treatment step is a chemical conversion treatment using one or more aqueous solutions selected from chromium, manganese, vanadium, calcium, zinc, calcium, strontium, zirconium, titanium compounds, and alkali metal carbonates. To produce a composite of metal and resin. In the manufacturing method of the composite of the metal and resin of Claim 7,
2. The method for producing a composite of metal and resin, wherein two or more plate crystals are observed per square area of 1 μm square on the surface layer by observation with an electron microscope. In the manufacturing method of the composite of the metal and resin of Claim 7,
The method for producing a composite of a metal and a resin, characterized in that the surface layer is covered with a lump with needle-like crystals observed by an electron microscope. In the manufacturing method of the composite of the metal and resin of Claim 7,
A method for producing a composite of a metal and a resin, wherein a number of circular columns having a diameter of about 10 nm and a length of about 100 nm are formed on the surface layer by electron microscope observation.