JP2008173967A - Composite of metal and resin, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite of a metal and a resin which is light-weight, and is excellent in electromagnetic wave shielding property and sealability, and to provide a manufacturing method for the composite body. <P>SOLUTION: This composite body of the metal and the resin comprises two kinds or more of metal parts, and a resin composition. In this case, the two kinds or more of the metal parts are selected from a metal part made of an aluminum alloy for which a suitable surface treatment has been performed, a metal part made of a magnesium alloy for which a suitable surface treatment has been performed, and a metal part made of copper or a copper alloy for which a suitable surface treatment has been performed. The resin composition is directly bonded to the two kinds or more of the metal parts by injection-molding, and of which the main component is a polyphenylene sulfide based resin or a polybutylene terephthalate based resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composite of metal and resin used for various devices such as electronic devices, light electrical devices, medical devices, mobile component devices, and a method for manufacturing the same. More specifically, the present invention relates to a metal-resin composite for joining metal parts such as an aluminum alloy, magnesium alloy, copper alloy, etc. with a resin composition and a method for producing the same, in particular, an aluminum alloy part and a copper alloy part via a resin product part, Used for mobile electrical equipment, weak electrical product parts, medical equipment parts, etc., in which magnesium alloy parts and copper alloy parts, or aluminum alloy parts, magnesium alloy parts and copper alloy parts are firmly joined by injection molding means The present invention relates to a composite of metal and resin excellent in electromagnetic wave shielding properties and a method for producing the same.

  Mobile electronic devices and mobile electronic devices have been further improved in performance, and such high performance often causes an increase in weight and an increase in energy consumption. For this reason, it is necessary for a mobile electronic device and a mobile electronic device to proceed in parallel with weight reduction, heat resistance, heat dissipation improvement, and robustness. In addition, as many mobile electronic devices and mobile electronic devices become more sophisticated by computerization and computerization, mobile electronic devices have the ability to shield electromagnetic waves generated from them and prevent electromagnetic waves from entering from outside. Demand for mobile electronic devices is increasing.

  In terms of weight reduction, plastics were initially used as materials for cases and casings, but lighter metals such as aluminum alloys and magnesium alloys and carbon fiber reinforced plastics were used as they became more robust. It came to be. Carbon fiber reinforced plastics include those using thermoplastic resins and those using thermosetting resins. Thermosetting resins (for example, CFRP) are as strong as metals but are difficult to recycle. In addition, electronic devices are flooding the world, and it is considered that the case itself has electromagnetic wave shielding ability. In that sense, the use of light metal cases has become the mainstream these days. That is, simply speaking, a metal case blocks electromagnetic waves. When a metal case is not used, it is necessary to shield all electromagnetic wave sources inside by wrapping them with aluminum alloy, or to shield the entire interior from electromagnetic waves by attaching an aluminum alloy thin plate inside the outer case. However, it was not the best measure from the point of aiming to reduce weight in terms of process, and there was still room for improvement.

  One of the most rational methods for producing resin parts is an injection molding method. If both the aluminum alloy part and the magnesium alloy part can be firmly joined via the resin product part, it can contribute to the manufacture of lightweight mobile electrical equipment, parts for weak electrical products, parts for medical equipment, and the like. Furthermore, if aluminum alloy parts and copper alloy parts, magnesium alloy parts and copper alloy parts, or aluminum alloy parts, magnesium alloy parts and copper alloy parts, etc. can be firmly joined by injection molding via the resin product part, mobile It is possible to contribute to the advancement of the manufacturing technology of case materials and cover material components that are particularly required to be lightweight, heat dissipation, and electromagnetic wave shielding properties, such as electrical equipment, weak electrical product parts, and medical equipment parts.

On the other hand, new technologies for integrating metal and resin have been developed. Up to now, adhesive bonding and screwing with screws and nuts have been widely used. However, various rational joining methods that do not use an adhesive or screwing have been studied. For example, the present inventors have developed a method for integrating magnesium, aluminum, copper, and alloys thereof with a high-strength engineering resin without using an adhesive. That is, these metals are shaped and treated with a different kind of surface treatment, and then inserted into an injection mold, and when a certain hard thermoplastic resin is injected there, the resin molded product and the metal part are firmly joined. This is a technique for obtaining an integrated product (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3).
Also known is a manufacturing method in which a metal part that has been chemically etched in advance is inserted into a mold of an injection molding machine and a thermoplastic resin material is injected to manufacture a metal insert composite molded product (see, for example, Patent Document 4). .

Inserting a surface-treated metal shape into a mold and injecting a thermoplastic resin into the mold, that is, integrating the two together, that is, joining the resin and metal, that is, dissimilar materials using injection molding technology This technique is referred to as “injection joining”. One of the above-described injection joining techniques is to manufacture an electronic device case from an A5052 aluminum alloy plate and a resin composition containing polyphenylene sulfide resin (hereinafter referred to as PPS) as a main component. It has been adopted. Although this product is an exterior case, there are a lot of resin bosses on the inside so that the electronic circuit board can be screwed. Following the development of injection joining technology using aluminum alloy, the present inventors have developed injection joining technology of magnesium alloy, titanium alloy and resin composition, and these technologies are used in the manufacture of electronic equipment, etc. There is a great expectation that it will be used in the future.
JP 2003-200453 A WO2004 / 041532 A1 Publication JP 2006-315398 A JP 2001-225352 A

  However, in the technique described in Patent Document 4, even if insert molding is performed on a chemically etched metal part using a thermoplastic resin, an adhesion improvement effect is not recognized, but an improvement effect is found with respect to airtightness. Has been. Then, the metal surface is finely roughened by chemical etching to increase the surface area of the metal, that is, the area of the metal / resin interface increases, resulting in pressure transmission loss when gas or liquid enters the part through the interface. It is estimated that airtightness is ensured by increasing the size (see paragraph 0010). However, even if this estimation is correct, there is a problem that the length of the interface between the metal and the resin may not be reduced in order to ensure airtightness without improving the adhesion. In other words, there is a problem that it may be difficult to reduce the weight and size.

  The present inventors have studied whether it is possible to reduce the weight of an electronic device and improve the electromagnetic wave shielding property by using an injection joining technique. In other words, it is effective to use a magnesium alloy case or case for weight reduction, but with magnesium alloy parts with improved corrosion resistance, the conductivity of the chemical conversion film is poor and the conductive paste between the electronic circuit There is a problem that a connection method that is not stable, such as using a large number of connections, must be adopted. Therefore, the present inventors have studied a method that can simultaneously ensure a rationalized outer case and a current-carrying terminal for shielding electromagnetic waves, and have reached the development of the present invention.

  Currently, not only magnesium alloy cases are attracting attention as mobile electronic device cases. Although the case parts manufactured from the magnesium alloy plate material or the magnesium alloy for casting are superior in weight to the aluminum alloy case, they are inferior to the aluminum alloy case in terms of cost and rigidity. It is also important to improve the electromagnetic wave shielding property by conducting the aluminum alloy case and the internal circuit, and this is also a problem to be solved.

  An aluminum alloy part and a magnesium alloy part are injection-bonded to each other through a resin composition mainly composed of PPS or polybutylene terephthalate resin (hereinafter referred to as PBT), and the aluminum alloy part and the magnesium alloy part are joined via the resin. The present inventors are developing a technique for producing a bonded composite. In addition, the present inventors have proposed in Japanese Patent Application No. 2006-272832 (application date: October 4, 2006) a technique for injection-bonding a resin composition mainly composed of PPS or PBT and a magnesium alloy. ing. In the present invention, a resin composition that can be used in common for hard resin injection joining using aluminum alloy, hard resin injection joining using magnesium alloy parts, and hard resin injection joining using copper alloy parts is used as it is. It is also a problem that must be solved to confirm whether it is possible and whether there is a practical electromagnetic shielding property.

  Also, electronic and electrical circuits are often placed in sealed boxes for safety and durability improvement. In such a case, sealing around the lead wire drawn out from the sealed box is required. This sealability is not an explosion-proof seal, and many air and gas leaks are not allowed, and this injection joining technique is considered suitable. For example, aluminum alloys, copper, and copper alloys are used for the lead wires, and it is necessary to confirm whether or not the injection joining technique can be used. If the sealing performance can be improved by this injection joining technique, there is great expectation for contribution to technological progress.

The present invention has been made to solve the above-described problems of the prior art, and achieves the following object.
An object of the present invention is to provide a composite of a metal and a resin excellent in light weight, electromagnetic wave shielding properties, and sealing properties.

  Another object of the present invention is to provide a method for producing a metal / resin composite capable of efficiently producing a composite of a metal / resin excellent in light weight, electromagnetic wave shielding and sealing properties.

The present invention takes the following means to achieve the above-described object.
The composite of the metal and resin of the present invention 1
A metal part made of an aluminum alloy whose surface is covered with fine recesses having an average diameter of 20 to 80 nm by a step of immersing in an aqueous solution containing at least one selected from hydrazine, ammonia, and a water-soluble amine compound, and chemical etching A metal part made of a magnesium alloy mainly having a conversion film of manganese oxide, and a rough surface shape covered with a concave part having a diameter of 1 to 100 μm and a depth of 0.5 μm or more having many fine openings of 10 to 200 nm in diameter. Two or more metal parts selected from copper or copper alloy metal parts covered with a thin layer of copper oxide, and a polyphenylene sulfide resin directly joined to the two or more metal parts by injection molding Or a resin composition containing a polybutylene terephthalate resin as a main component.

The composite of the metal and resin of the present invention 2 in the present invention 1,
The resin composition containing the polyphenylene sulfide resin as a main component contains 97 to 70 parts by mass of polyphenylene sulfide resin and 3 to 30 parts by mass of polyolefin resin with respect to 100 parts by mass of the resin content of the polyphenylene sulfide resin. It is characterized by being.

The composite of the metal and resin of the present invention 3 in the present invention 1,
The resin composition containing the polybutylene terephthalate resin as a main component has a polybutylene terephthalate resin content of 97 to 70 parts by mass, a polyethylene terephthalate resin and / or a polyolefin with respect to 100 parts by mass of the resin content of the polybutylene terephthalate resin. 3 to 30 parts by mass of a system resin is blended.

The composite of the metal and resin of the present invention 4 in the present invention 1 to 3,
The resin composition is characterized in that 10 to 200 parts by mass of the filler is blended with respect to 100 parts by mass of the total resin content.

The composite of the metal and resin of the present invention 5 in the present invention 4,
The filler is at least one selected from glass fibers, carbon fibers, aramid fibers, other reinforcing fibers, calcium carbonate, magnesium carbonate, silica, talc, clay, glass, and other powder fillers. To do.

The composite of a metal and a resin of the present invention 6 according to the present invention 2 to 5,
The polyolefin resin is at least one selected from maleic anhydride-modified ethylene copolymer, glycidyl methacrylate-modified ethylene copolymer, glycidyl ether-modified ethylene copolymer, and ethylene alkyl acrylate copolymer. It is characterized by being.

The composite of a metal and a resin according to the present invention 7 in the present invention 2 to 5,
The polyolefin resin is one or more selected from ethylene-acrylic acid ester-maleic anhydride terpolymer and ethylene-glycidyl methacrylate terpolymer.

The composite of a metal and a resin according to the present invention 8 in the present invention 1 to 7,
The composite is one type selected from a lid provided with a case, a cover, and a terminal of an electric and electronic device composed of a metal part and a resin composition.

The method for producing a composite of a metal and a resin of the present invention 9
A step of processing an aluminum alloy part into a predetermined shape from a cast or an intermediate material, and at least one kind selected from hydrazine, ammonia, and a water-soluble amine compound for the aluminum alloy part processed into the predetermined shape A step of immersing in an aqueous solution, a step of processing a copper or copper alloy part into a predetermined shape from a cast or an intermediate material, and chemical etching the copper or copper alloy part processed into the predetermined shape A step of forming a copper-based metal oxide layer on a surface layer by immersing the chemically etched copper or copper alloy component in an aqueous solution containing chlorite, the aluminum alloy component, and the copper Alternatively, insert a copper alloy part into an injection mold and have polyphenylene sulfide resin or polybutylene terephthalate resin as the main component. The resin composition was injected, the aluminum alloy part, the copper or copper alloy part, and characterized in that it includes the step of fixing the said resin composition together.

The method for producing a composite of a metal and a resin of the present invention 10
A step of processing a magnesium alloy part into a predetermined shape from a cast or an intermediate material, a step of chemical etching by immersing the magnesium alloy part processed into the predetermined shape in an acidic aqueous solution, and the magnesium subjected to chemical etching A step of immersing the alloy part in an aqueous solution containing an alkali metal permanganate to form a thin layer mainly composed of manganese oxide on the surface; and a copper or copper alloy part from a casting or an intermediate material A step of processing into a shape, a step of chemically etching the copper or copper alloy part processed into the predetermined shape, and immersing the chemically etched copper or copper alloy part in an aqueous solution containing chlorite. The step of forming a copper-based metal oxide layer on the surface layer, the magnesium alloy component, and the copper or copper alloy component are injection-molded Inserting and injecting a resin composition containing polyphenylene sulfide resin or polybutylene terephthalate resin as a main component, and fixing the magnesium alloy part, the copper or copper alloy part, and the resin molding together. And a process.

The method for producing a composite of a metal and a resin of the present invention 11
A step of processing an aluminum alloy part into a predetermined shape from a cast or an intermediate material, and the aluminum alloy part processed into the predetermined shape is immersed in an aqueous solution containing at least one of hydrazine, ammonia, and a water-soluble amine compound A step of shaping a magnesium alloy part by mechanical processing from a casting or an intermediate material, a step of chemically etching the shaped magnesium alloy part by immersing the shaped magnesium alloy part in an acidic aqueous solution, and the magnesium alloy part. , A step of forming a thin layer mainly composed of manganese oxide on the surface by dipping in an aqueous solution containing an alkali metal permanganate, and processing a copper or copper alloy part into a predetermined shape from a cast or an intermediate material A step of chemically etching the copper or copper alloy part processed into the predetermined shape, and the copper plate subjected to the chemical etching. Forming a copper-based metal oxide layer on the surface layer by immersing the copper alloy part in an aqueous solution containing chlorite, the aluminum alloy part, the magnesium alloy part, and the copper or copper alloy Inserting a part into an injection mold, injecting a polyphenylene sulfide-based resin, or a resin composition mainly comprising a polybutylene terephthalate-based resin, the aluminum alloy part, the magnesium alloy part, the copper or copper alloy part, And an adhering step of adhering the resin composition together.

The means will be described in more detail below. [Aluminum alloy parts]
As the aluminum alloy used in the present invention, all the aluminum alloys for A1000 series to 7000 series, aluminum alloys for casting such as ADC1-12, and pure aluminum, which are stipulated in JIS standards, can be used. . As the shape, as long as it is an alloy for casting or the like, a part shaped by a die casting method, or a part that is further machined to adjust its shape can be used. Moreover, in the alloy for extending | stretching, the board | plate material etc. which are intermediate materials, and the parts which shape | molded them by applying mechanical processing, such as hot press processing, can be used.

[Surface treatment / pretreatment of aluminum alloy parts]
It is preferable that the aluminum alloy component is first dipped in a degreasing tank to remove oils and finger grease adhered by machining or the like. Specifically, it is preferable to prepare an aqueous solution in which a commercially available defatted aluminum alloy degreasing material is poured into hot water at a concentration specified by the drug manufacturer, and immerse in this to wash. In an ordinary commercial product, the concentration is 5 to 10%, the liquid temperature is 50 to 80 ° C., and the aluminum alloy component is immersed for 5 to 10 minutes.

  Regarding the subsequent steps, the treatment method differs between an alloy in which the aluminum alloy contains a relatively large amount of copper and silicon and an alloy in which the aluminum alloy has a small amount of copper and silicon.

  In the case of an aluminum alloy having a small amount of copper or silicon, that is, A1050, A1100, A3003, A5052, or the like, the following steps are preferable. That is, the aluminum alloy part is immersed in an acidic aqueous solution and then washed with water to adsorb the acid component to the surface layer of the aluminum alloy part. As the acidic aqueous solution, a dilute aqueous solution having a concentration of 1% to several percent of an inexpensive mineral acid such as nitric acid, hydrochloric acid, and sulfuric acid can be used. Next, the aluminum alloy part is immersed in a basic aqueous solution, then washed with water, and alkali etching is performed. Aluminum is an amphoteric metal that is soluble in both acid-base aqueous solutions, but the basic aqueous solution is actually more soluble, and the oil and grease remaining on the surface of the aluminum alloy due to alkali etching are separated together with the surface layer of the thin aluminum alloy. Is done. For alkaline etching, it is preferable to use an aqueous caustic soda solution having a concentration of 1% to several percent. Next, the aluminum alloy part is again immersed in the acidic aqueous solution, and then washed with water to finish the pretreatment.

  On the other hand, in the case of an aluminum alloy containing a relatively large amount of copper or silicon, such as A2017, A6063, A7075, ADC10, ADC12, etc., the following steps are preferable. That is, the aluminum alloy part is immersed in an acidic aqueous solution, then washed with water, and the acid component is adsorbed on the surface layer of the aluminum alloy part. As the acidic aqueous solution, for example, a dilute aqueous solution having a concentration of 1% to several percent of an inexpensive mineral acid such as nitric acid, hydrochloric acid, and sulfuric acid can be used. Next, the aluminum alloy part is immersed in a basic aqueous solution, then washed with water, and alkali etching is performed. Next, the aluminum alloy part is immersed in a dilute aqueous solution of ammonium difluoride or hydrofluoric acid, and then washed with water to separate silicon and the like. However, until this step, copper and silicon are smut and the surface becomes dark. Next, the aluminum alloy part is immersed in a nitric acid solution having a concentration of several percent to dissolve the copper smut, and the silicon content covered with the copper content is separated from the surface. Next, an aluminum alloy from which silicon is separated is inserted into water in an aquarium equipped with an ultrasonic generator, and ultrasonic waves are generated and vibrated to physically separate silicon and copper smut. It is preferable to finish the pretreatment by such a method.

[Surface treatment of aluminum alloy parts / Main treatment]
The pretreated aluminum alloy part is immersed in an aqueous solution containing at least one of hydrazine, ammonia, and a water-soluble amine compound. When immersed in an aqueous solution of a weakly basic solution having a pH of about 9-10, particularly an aqueous solution of hydrazine, ammonia, or a water-soluble amine at an appropriate temperature for an appropriate time, the surface has an average diameter of 20-80 nm. It is covered with a fine concave shape. For injection joining, it is optimal that the diameter of the fine recess is about 20 to 40 nm. However, if the diameter is 80 nm or less, good injection joining force is exhibited. In addition, the average diameter as used in the field of this invention is what measured the unit square of a 200 nm rectangle on the electron micrograph, for example, and remove | divided it by the number of the recessed parts which measured.

  Actually, the conditions for putting the average diameter of the recesses in the range of 20 to 80 nm are surprisingly narrow. For example, when monohydric hydrazine is used, it is preferably immersed in monohydric hydrazine at a concentration of 3 to 5% at a temperature of 60 ° C. for about 1 minute. However, when the immersion time was doubled for 2 minutes, the average diameter of the recesses on the aluminum alloy surface rapidly expanded from 25 nm when immersed for 1 minute to 60 nm. Furthermore, when immersed for 4 minutes, the average diameter of the recesses was further expanded to about 200 nm, and further recesses were formed in the large recesses, and erosion started in the lateral direction. In short, when a monohydric hydrazine aqueous solution at a temperature of 60 ° C. is used, the immersion time is 1 to 2 minutes, most preferably about 1 minute, and the conditions relating to the immersion time are very narrow and severe.

  When aqueous ammonia is used, the aqueous solution cannot be heated to a high temperature, so an aqueous solution having a temperature of 20 ° C. and a concentration of 20% is used. In this case, the immersion time is 20 to 30 minutes. In any case, it is preferable that the treatment is performed under the condition that the average diameter of the recesses is 20 to 80 nm, preferably 20 to 40 nm, by observation with an electron microscope or the like. It is washed with ion-exchanged water and dried in a hot air drier at 70 ° C. or lower.

[Magnesium, magnesium alloy parts]
The magnesium or magnesium alloy used in the present invention is all magnesium or magnesium alloys that are commercially available, such as a wrought alloy such as AZ31 and a casting alloy such as AZ91. As the shape, as long as it is an alloy for casting, a part shaped by means such as die casting, thixo mold, injection molding, etc., or a part further shaped by machining it can be used. Moreover, in the alloy for extending | stretching etc., the board | plate material which is an intermediate | middle material, etc., and the parts which shape | molded them by applying mechanical processing, such as hot press processing, can be used.

[Surface treatment / pretreatment of magnesium alloy parts]
It is preferable that the magnesium alloy part is first immersed in a degreasing tank to remove oils and finger grease adhered by machining or the like. Specifically, it is preferable to prepare an aqueous solution in which a commercially available degreasing material for magnesium is added to warm water at a predetermined temperature at a concentration as specified by the drug manufacturer, and after immersion in this, it is preferably washed with water. In a normal commercial product, the concentration of the aqueous solution is 5 to 10%, the temperature is 50 to 80 ° C., and the magnesium alloy part is immersed for 5 to 10 minutes. Next, the magnesium alloy part is immersed in an acidic aqueous solution and etched, and the surface layer of the magnesium alloy part is dissolved to remove dirt and remaining oil and surfactant residues. Acidic aqueous solutions include organic carboxylic acids having a pH of 2 to 5 (for example, acetic acid, propionic acid, citric acid, malonic acid, benzoic acid, phthalic acid, etc.) and inorganic acids (for example, nitric acid, hydrochloric acid, phosphoric acid, hydrofluoric acid, etc.) A weakly acidic aqueous solution can be used. According to the results of experiments conducted by the present inventors, relatively good results were obtained with aliphatic carboxylic acids such as acetic acid, propionic acid, citric acid, and malonic acid.

  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. Aluminum and zinc are hardly dissolved in an etching process using a weakly acidic aqueous solution and are deposited on the surface as insoluble materials. A process is required to melt and clean things. This is so-called smut removal. In AZ31 and AZ91, first, a treatment to dissolve aluminum smut by immersing in a weakly basic aqueous solution (first smut treatment), and then a treatment to dissolve zinc smut by immersing in a strong basic aqueous solution (second smut treatment). ) Is a preferred method.

  However, the surface shape of the magnesium alloy desired in the present invention has, for example, irregularities with large roughness of micron order (micrometer order) with a period of 0.1 to 10 μm by chemical etching, and the surface is observed with an electron microscope. A protrusion or wall or opening having a width or diameter of 10 nm or more and a height or depth of 10 nm or more, more preferably a protrusion or wall or opening having a width or diameter of about 50 nm and a height or depth of about 50 nm. It is necessary to have. Furthermore, it is necessary that this surface is made of a metal oxide and has high hardness.

  In other words, the above-described etching process is important for finally forming such a shape, but the first smut treatment process is also an important process in the liquid treatment of AZ31B and AZ91D. It turns out. Probably, it can be judged that not only the aluminum smut is removed, but also the aluminum exposed on the surface of the magnesium alloy is dissolved to affect the obtained roughness. Usually, a degreasing agent for aluminum alloy is used in the first smut removing step of the chemical conversion treatment of magnesium alloy, but the present inventors have tried many other weakly basic aqueous solutions. As a result, it was found that various types can be used. Particularly excellent ones are shown in the examples. Next, the second smut treatment to be performed is preferably a method in which a 15 to 25% aqueous solution of caustic soda is set to 60 to 80 ° C. and the magnesium alloy part is immersed for 5 to 10 minutes.

[Surface treatment of magnesium alloy parts / main treatment]
Next, processing that can be called main processing is performed in the liquid processing. This treatment is preferably a two-stage immersion treatment, that is, a very short acid solution is immersed in a very short time for fine etching, followed by a chemical conversion treatment.
In the fine etching step, a weakly acidic aqueous solution of an organic carboxylic acid having a pH of 4 to 6 (for example, acetic acid, propionic acid, citric acid, malonic acid, etc.) can be preferably used, and the immersion time should be as short as 15 to 90 seconds. preferable. Although this fine etching process is a process that is not included in the usual magnesium alloy chemical conversion treatment, it is preferable to include it because it produces a stronger injection joining force. The chemical conversion treatment step to be performed in the present invention is an alkali metal permanganate chlorination treatment, preferably a potassium permanganate chemical conversion treatment.

  More specific description will be given. The pretreated magnesium alloy part is finely etched by dipping in a hydrated citric acid solution with a concentration of about 0.1 to 0.3% at about 40 ° C. for 15 to 60 seconds, and then washed with ion exchange water. Next, an aqueous solution containing 1.5 to 3.0% potassium permanganate, 0.7 to 1.5% acetic acid, and 0.3 to 1.0% hydrated sodium acetate is used as a chemical conversion treatment solution at 40 to 50 ° C. It is preferable to prepare, immerse the magnesium alloy part just before for 0.5 to 1 minute, and then wash with water. This chemical conversion treatment method has been improved in order to improve the injection joining force through trial and error. The magnesium alloy part washed with water is placed in a hot air dryer set at 80 to 90 ° C. for 5 to 20 minutes and dried.

[Copper or copper alloy parts]
Not only pure copper, but also copper-based, iron-containing, and other copper alloys can be used. However, since pure copper parts are mainly used in the present invention, pure copper will be described. Except for pure copper including white bronze, etc., the description is omitted here because it is described in detail in the technology etc. proposed by the present applicant in Japanese Patent Application No. 2006-281196 (filing date: October 16, 2006). To do.
As the shape, not only copper products and cast products but also parts having a copper surface by electroless copper plating or electrolytic copper plating can be used. For the copper products, plate materials, pipe materials, other deformed extruded products, and parts formed by machining such as press processing and cutting processing can be used.

[Surface treatment / pretreatment of copper parts]
The surface treatment is performed on the shaped copper part, and the contents of the surface treatment are three steps of “degreasing”, “chemical etching”, and “surface hardening”. In this description, two steps of “degreasing step” and “chemical etching step” are referred to as “pretreatment”.
The degreasing step is a processing step in which machining oil or finger grease is adhered to a copper part that has been subjected to machining or the like, so that it is immersed in an aqueous solution containing a surfactant and washed with water. There are commercially available degreasing agents for copper that contain organic acid, sulfuric acid, nitric acid, etc. in the solution and dissolve and remove the copper oxide layer at the same time, and can expose a clean copper surface. Finished products such as an electroless copper plating process that does not require degreasing have a clean copper surface, so this process can be omitted.

  The chemical etching process oxidizes copper and dissolves it in an aqueous solution as copper ions. However, since the dissolution usually proceeds through the grain interface of the metal microcrystal, a fine uneven surface can be naturally formed. The basic chemical etching agent is to use hydrogen peroxide as an oxidizing agent and to use sulfuric acid as a stabilizer for the generated copper ions. That is, it is an aqueous solution containing hydrogen peroxide and sulfuric acid, and the commercially available product is further devised so that it can be roughened stably by adding some third component. Any of these can be used in the present invention, but it is necessary to select immersion conditions. This pretreatment is a process for making a copper part into a rough surface shape having irregularities with a period of 1 to several tens of μm and a roughness difference of 0.5 μm or more.

[Surface treatment of copper parts / surface hardening treatment]
A surface hardening process is performed following the pretreatment process. In the present invention, as a specific method thereof, the copper part is immersed in an aqueous solution containing 5 to 15% of caustic soda and 1 to 10% of sodium chlorite to oxidize the copper atoms on the surface and oxidize insoluble in the basic aqueous solution. A method of forming a second copper thin layer is used.

  Under basic conditions, both copper metal and copper oxide are relatively stable and difficult to dissolve, so that copper is oxidized by chlorite. Copper ions are less likely to dissolve and are expected to form hydroxides or oxides and form a surface layer. Actually, however, if the immersion time is extended, it will turn black after turning blue and blackish brown. It can be determined that a (black) amorphous layer or an amorphous layer containing a small amount of microcrystals is generated. In the present invention, the thickness of the copper oxide layer is not critical. Even if it is thin, if the hardened layer can be formed, the purpose is achieved, so the reaction conditions do not need to be strict. Specifically, it is preferable to immerse the caustic soda having the above concentration and an aqueous solution of sodium chlorite at 50 to 80 ° C. for several minutes. Some products are sold as copper blackening treatments on the market and can be used in the same manner. When the surface of the copper product after surface hardening was observed with an electron microscope, the surface shape was covered with a concave portion having a diameter of 1 to 100 μm and a depth of 0.5 μm or more having many fine openings having a diameter of 10 to 200 nm. Was confirmed.

[Treatment on the metal part side]
The present inventors have continued research and development on a composite made of a metal component made of a titanium alloy, stainless steel, steel, and the like and a resin composition, and have established the technology. The contents of this technique will not be described any further here, but these techniques including aluminum alloy, magnesium alloy, copper, and copper alloy are summarized as follows.

There are three conditions for processing on the metal part side.
(1) The first condition is that the surface of the metal alloy has irregularities with a period of 0.5 to 10 μm by a chemical etching method, and the height difference of the irregularities is about half of the period, that is, a roughness up to 0.25 to 5 μm. It is a surface.
However, in practice, it is difficult to cover the entire surface with the period and height difference in a chemical reaction with variations. Therefore, in fact, when viewed with a roughness meter, it is possible to draw a contour curve with irregular periodicity of 0.2 to 20 μm and an uneven height difference of 0.2 to 10 μm, or When scanning analysis is performed with a scanning probe microscope, the average period of the “roughness curve” in JIS standard (JIS B0601: 2001), that is, the average length (RSm) of the contour curve elements is 0.5 to 10 μm, and If it is a roughness surface whose maximum height roughness (Rz) is 0.2 to 5 μm, the first condition is substantially satisfied. The metal surface irregularities that substantially satisfy the first condition are referred to as “micron-order irregularities”.

(2) The second condition is that ultra-fine irregularities with a period of about 10 to 300 nm are formed on the wall surfaces of each micron-order irregularity by further adding fine etching treatment, oxidation treatment, chemical conversion treatment or the like. .
(3) The third condition is that the complex surface shape of the metal alloy is covered with a ceramic material, specifically, a metal oxide layer thicker than a natural oxide layer before chemical etching.

  The bonding principle is that the resin composition penetrates into the concave portion of the micron order irregularities, and further, the resin composition solidifies three-dimensionally from the concave portion with the resin composition also entering the concave portion of the ultra-fine irregularities on the concave wall surface. It depends on the anchor effect theory that it will not come off. Since the metal oxide layer covering the ultra-fine irregularities is higher in hardness than the metal phase, the resin composition solidified in the concaves related to the micron-order irregularities is like a spike due to the ultra-fine irregularities covered with high hardness. Hooked and fixed.

[Resin composition / PPS composition]
The resin composition constituting the present invention is a resin composition containing 70 to 97 parts by mass of PPS and 3 to 30 parts by mass of a polyolefin-based resin. A resin composition containing 80 to 95 parts by mass and 5 to 20 parts by mass of a polyolefin-based resin is preferable. Here, when PPS is less than 70 parts by mass or when it exceeds 97 parts by mass, the resulting composite is inferior in the bondability between the metal part and the resin composition part.

  Any PPS may be used as long as it belongs to the category called PPS. Among them, a high-efficiency flow 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 part. It is preferable that the measured melt viscosity is 100 to 30000 poise under the conditions of a measurement temperature of 315 ° C. and a load of 98 N (10 kgf) with a tester. 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.

  In addition, the PPS may be a linear one, a branched structure introduced, or a heat treatment performed in an inert gas. Further, PPS is obtained by reducing impurities such as ions and oligomers by performing a deionization process (such as acid cleaning or hot water cleaning) before or after heat curing or a cleaning process using 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 resin include ethylene resins and propylene resins that are generally known as polyolefin resins, and may be commercially available. Among them, since it is possible to obtain a composite having particularly excellent adhesiveness, maleic anhydride-modified ethylene copolymer, glycidyl methacrylate-modified ethylene copolymer, glycidyl ether-modified ethylene copolymer, ethylene alkyl An acrylate copolymer or the like is preferable.

  Examples of maleic anhydride-modified ethylene copolymers include “maleic anhydride graft-modified ethylene polymer”, “maleic anhydride-ethylene copolymer”, “ethylene-acrylic acid ester-maleic anhydride terpolymer”. Among them, “ethylene-acrylic acid ester-maleic anhydride terpolymer” is preferable, and “ethylene-acrylic acid ester-anhydride” is preferable. Specific examples of the “maleic acid terpolymer” include “Bondyne (manufactured by Arkema)” and the like.

  Examples of the glycidyl methacrylate-modified ethylene copolymer include “glycidyl methacrylate graft-modified ethylene polymer” and “glycidyl methacrylate-ethylene copolymer”, and among them, particularly excellent composites can be obtained. “Glycidyl methacrylate-ethylene copolymer” is preferable, and specific examples of “glycidyl methacrylate-ethylene copolymer” include “Bond First” (manufactured by Sumitomo Chemical Co., Ltd.).

  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 , “Rotril (manufactured by Arkema)” and the like.

  In the composite of the present invention, since the bondability between the metal part and the resin composition part becomes better, the resin composition part is a resin containing 70 to 97 parts by mass of PPS and 3 to 30 parts by mass of polyolefin resin. It is preferable that 0.1 to 6 parts by mass of a polyfunctional isocyanate compound and / or 1 to 25 parts by mass of an epoxy resin are further blended with respect to 100 parts by mass in total.

  As the polyfunctional isocyanate compound, commercially available non-block type and block type compounds 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. Moreover, as a polyfunctional block type isocyanate compound, it has two or more isocyanate groups in the molecule, the isocyanate group is reacted with a volatile active hydrogen compound, and inactivated at room temperature, The type of the polyfunctional blocked isocyanate compound is not particularly specified, and generally the isocyanate group is masked by a blocking agent such as alcohols, phenols, ε-caprolactam, oximes, and active methylene compounds. It has a structure. Examples of the multifunctional block type isocyanate include “Takenate (manufactured by Mitsui Takeda Chemical Co.)”.

  As the epoxy resin, an epoxy resin generally known as a bisphenol A type, a cresol novolak type, or the like can be used. Examples of the bisphenol A type epoxy resin include “Epicoat (manufactured by Japan Epoxy Resin)” and the like, and examples of the cresol novolac type epoxy resin include “Epiclon (manufactured by Dainippon Ink and Chemicals)”.

  In addition, the composite of the present invention has a PPS of 70 to 97 parts by mass and a polyolefin resin 30 for the purpose of adjusting the difference in linear expansion coefficient between the metal part and the resin composition part and improving the mechanical strength of the resin composition part. It is sufficient that the resin composition part further includes 10 to 200 parts by weight of filler, more preferably 10 to 150 parts by weight of resin composition, with respect to 100 parts by weight of the total resin content including ~ 3 parts by weight. Good parts. All or most of the filler may be carbon fiber. The resin composition itself becomes a conductor due to the presence of the carbon fibers. As fillers to be used other than carbon fibers, there are fiber fillers and powder fillers.

  Examples of the fiber filler include glass fibers and aramid fibers. Specific examples of the glass fibers include chopped strands having an average fiber diameter of 6 to 14 μm. Examples of the powder filler include calcium carbonate, mica, glass flake, glass balloon, magnesium carbonate, silica, talc, clay, pulverized carbon fiber and aramid fiber. The fiber filler is preferably treated with a silane coupling agent or a titanate coupling agent.

[Resin composition / PBT resin composition]
The PBT resin composition will be described. As the resin composition, those having a composition of 3 to 30% of PET and / or polyolefin resin and 70 to 97% of PBT are preferable. The same polyolefin resin as described in the section of the PPS resin composition can be used. When the composition ratio of PET and / or polyolefin resin is small, and when the resin composition exceeds 30%, the effect on the injection joining force becomes uncertain. Regarding injection joining, it is preferable that the resin composition of PET and / or polyolefin resin is 5 to 20% because the joining force is particularly strong and stable. In addition, when the PET component exceeds 30% of the resin component composition, the transesterification reaction may occur at a high temperature in the injection cylinder of the injection molding machine and the strength of the resin itself may be reduced. If it exceeds 30% of the composition, gas generation during injection molding increases, and the possibility of breakage of runners and the like increases, which increases the possibility of breaking the molding cycle.
In order to make the linear expansion coefficient equal to that of the magnesium alloy, mixing a large amount of filler stabilizes the injection joining force with time. This is the same as the PPS system described above.

[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 and insert the magnesium alloy part subjected to the above-mentioned surface treatment on the mold surface, insert the copper and / or copper alloy part subjected to the surface treatment, close the mold, The composite is produced by injecting and solidifying the thermoplastic resin composition, and then opening and releasing the mold.

  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, injection pressure, and injection speed are not particularly different from those of ordinary injection molding, but it is preferable to increase the injection speed and injection pressure.

  Although various proposals can be considered for the shape and structure of the composite, in this description, the case of a notebook personal computer (hereinafter referred to as a personal computer) is taken as an example. FIG. 1 is a perspective view schematically showing an exterior case of a notebook computer. Here, the metal plate 1 is made of an aluminum alloy or a magnesium alloy, and constitutes an outer case together with the resin outer peripheral portion 2. 3 is a copper energizing terminal, and 4 is a resin boss that connects the copper energizing terminal and the exterior case. The resin outer peripheral portion 2 and the resin boss portion 4 can be injection-bonded to the metal plate material 1 made of aluminum alloy or magnesium alloy and the copper energizing terminal 3 all at once.

[Corrosion resistance treatment of magnesium-containing alloy composite]
The composite produced by injection joining may be scratched by the chemical conversion film on the magnesium alloy at the portion pressed by the mold. Therefore, it is preferable to immerse the composite as it is in a commercially available chemical conversion treatment material for magnesium alloy, particularly an aqueous solution in which a silicon-based treatment agent is diluted.

[Coating complex]
Although the composite obtained in the above step can be used as it is, it is preferable to coat the surface to be the exterior part. As a paint, a resin paint and a metal part can be painted, and a baking paint for metal paint can be used. If the resin composition side is about 200 ° C., it has heat resistance that does not cause any problem, so there is no concern about using such a high-temperature baking type paint. If only the metal part is to be painted, commercially available coatings for aluminum alloy coating and magnesium alloy coating can be used. Among these commercially available paints, there are urethane paints and acrylic urethane paints, which have a baking temperature as low as 120 ° C. or less, and can be made with hot air dryers owned by many coating companies. However, it is not recommended to apply these commercially available paints on the PBT resin composition or the PPS resin composition because adhesion to the resin composition may be insufficient.

[Connection from composite to electronic circuit]
In FIG. 1, a copper wire is soldered to an energizing terminal 3 from an electronic circuit. The surface of the copper current-carrying terminal 3 is made of cupric oxide, but its thickness is, for example, 1 μm or less, so that it can be soldered as it is by rubbing with a cutter. The energization can now be made perfect.

[Action]
By applying the present invention, it is possible to contribute to weight reduction, electromagnetic wave shielding functionality improvement, and productivity improvement of mobile electronic devices, in-vehicle devices, and robots.

  As described in detail above, the resin-metal composite of the present invention is an integral part of the resin composition part and the metal part without being easily peeled off. Moreover, the composite manufactured as a thing provided with the metal cover body of an electronic device and its electricity supply terminal can be made into the thing excellent in electromagnetic wave shielding property. Furthermore, this composite can be made to be excellent in hermeticity as having an energizing terminal. That is, two or more kinds of metal parts selected from a product obtained by subjecting an aluminum alloy to a specific surface treatment, a product obtained by subjecting a magnesium alloy part to a specific surface treatment, and / or a product obtained by subjecting a copper to a specific surface treatment are injection-molded. Inserting into a mold and injecting a thermoplastic resin composition having a specific PPS resin composition or a specific PBT resin composition, it is a lightweight composite with excellent electromagnetic shielding properties, such as a mobile electronic device or an in-vehicle electronic device. An exterior case for equipment can be obtained.

  Since the metal / resin composite having excellent light weight, electromagnetic wave shielding and sealing properties is integrated by a highly productive injection joining technique, the metal / resin composite can be efficiently produced.

  Hereinafter, embodiments of the present invention will be described in place of examples. FIG. 1 is an external view showing a composite in which an exterior case of a notebook personal computer is schematically shown. 2A is an external view showing the shape of a test piece for measuring the degree of sealing for measuring the sealing property, and FIG. 2B is a diagram showing the test piece for measuring the degree of sealing in cross section. Sectional drawing which cut | disconnected 2 (a) by the AA line, FIG.2 (c) is a side view of the test piece for a sealing degree measurement. FIG. 3A is an external view showing the shape of a test piece for conductivity measurement for measuring conductivity, and FIG. 3B is a cross-sectional view of the test piece for conductivity measurement.

  FIG. 1 shows a composite M in which an exterior case of a notebook personal computer is schematically shown. The composite M includes a metal plate 1 that is a metal part, a resin outer peripheral part 2 that is formed of a resin composition, a copper current terminal 3 that is a metal part, and a resin composition that is formed of a resin composition. It is comprised from the resin boss | hub parts 4 which are physical parts. The metal plate member 1 is a metal cover body, and constitutes a main portion of the outer case with the resin outer peripheral portion 2 and can cover the outer case and shield electromagnetic waves.

  FIGS. 2A, 2B, and 2C show a test piece S1 for measuring airtightness for measuring airtightness. Resin composition for injecting and integrating a magnesium alloy piece 11 corresponding to a magnesium alloy energization terminal, an aluminum alloy piece 12 corresponding to an aluminum alloy energization terminal, and a copper piece 13 corresponding to a copper energization terminal This is a sealability measuring test piece S1 including a resin lid member (resin composition part) 14 formed of a product. This test piece S1 for measuring airtightness corresponds to a composite body in which a lid having a terminal such as a battery is schematically shown.

  The test / evaluation of the test piece S1 for hermeticity measurement may be performed as follows. The test piece S1 is fixed to one end of the tube body 16 in a sealed state. The other end of the tube 16 is sealed with a lid. The pipe body 16 is connected to a flow path for supplying the pressure fluid from the pressure fluid supply source 17 via the on-off valve 18 and is provided with a pressure gauge 19 for measuring the internal pressure of the pipe body 16. ing. When a pressurized fluid (for example, compressed air) is supplied from the pressurized fluid supply source 17 and the pressure inside the tube body 16 reaches a predetermined pressure, the on-off valve 18 is closed, and the sealing property of the test piece S1 for measuring the sealing property is increased. taking measurement. That is, the internal pressure of the tube body 16 is measured with the pressure gauge 19 corresponding to the passage of time, and the sealing performance can be measured and evaluated depending on whether or not the internal pressure of the tube body 16 changes.

  FIG. 3 shows a conductivity measurement test piece S2 for measuring conductivity, and a metal plate material (for example, a magnesium alloy plate material) 21 and a copper piece 22 corresponding to a current-carrying terminal are formed of a resin composition. It is a composite that is injection-bonded and integrated with the resin boss portion (resin composition part) 23. The resin boss 23 is injected from the pin gate 24. One surface 21a of the metal plate 21 and one end side 22a of the copper piece 22 are in contact with each other so as to be electrically connected. The conductivity can be measured and evaluated by measuring the conductivity between one surface 21a of the metal plate 21 and the other end 22b of the copper piece 22 with a tester 30 or the like.

Examples of the present invention will be described in detail below.
The composite evaluation / measurement method is shown.
[Measurement of melt viscosity of PPS]
The melt viscosity is measured under the conditions of a measurement temperature of 315 ° C. and a load of 98 N (10 kgf) with a Koka flow tester “CFT-500 (manufactured by Shimadzu Corporation)” equipped with a die having a diameter of 1 mm and a length of 2 mm. .

[Surface observation]
(A) Electron microscope observation An electron microscope was mainly used for observation of the substrate surface. This electron microscope was observed at 1-2 kV using a scanning (SEM) electron microscope “S-4800 (manufactured by Hitachi, Ltd.)” and “JSM-6700F (manufactured by JEOL Ltd.)”.

[Measurement of bonding strength of composite]
The bonding strength test was performed by a simple method. That is, when the worker applied a load, the evaluation was made based on whether or not the joined portion maintained the joined state.

[Measurement and evaluation of conductivity of composite]
For the measurement of conductivity, a test piece S2 for conductivity measurement as shown in FIG. 3 was prepared, and the conductivity was evaluated with a tester.

[Compound sealing test]
In the sealing test, a sealing test piece S1 as shown in FIG. 2 was prepared, and the sealing performance was evaluated based on the presence or absence of pressure drop.

[Test of corrosion resistance of composite]
For the corrosion resistance test, a salt spray tester “SPT-90 (manufactured by Suga Test Instruments Co., Ltd.)” was used, and 5% salt water was continuously sprayed at 35 ° C. for 24 hours, washed with ion-exchanged water, air-dried, and corrosion resistance. Evaluated.

[Preparation Example 1 (Preparation Example of PPS Composition 1)]
A 50 liter autoclave equipped with a stirrer 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 at 205 ° C. while stirring under a nitrogen stream. The temperature was raised to 1,355 g of water. After cooling the system to 140 ° C., 7,160 g of “p-dichlorobenzene” and 5,000 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 polymer was washed repeatedly with warm water and dried at 100 ° C. for a whole day and night to obtain a 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 (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 (Arkema)”, epoxy resin “Epicoat 1004 (Japan Epoxy Resin)” “0.5 kg was mixed in advance 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.)”. PPS composition (1) which was melt-kneaded and pelletized at a cylinder temperature of 300 ° C. was supplied while supplying the mass%. The obtained PPS composition (1) was dried at 175 ° C. for 5 hours.

[Preparation Example 2 (Preparation of PPS Composition 2)]
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 mass%, 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 3)]
7.2 kg of PPS (2) obtained in Preparation 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 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 mass%, 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)]
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 mass%, 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.

[Preparation Example 5 (Preparation of PBT Composition 1)]
4.5 kg of PBT resin “Torcon 1100S (manufactured by Toray Industries, Inc.)” and 0.5 kg of PET resin “TR-4550BH (manufactured by Teijin Chemicals)” were uniformly mixed in 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 30% by mass, the cylinder temperature A PBT resin composition obtained by melt-kneading at 270 ° C. and pelletized was obtained. It dried at 140 degreeC for 3 hours, and was set as the PBT composition (1).

[Preparation Example 6 (Preparation of PBT composition 2)]
4.5 kg of PBT resin “Torcon 1100S (manufactured by Toray Industries)”, 0.5 kg of PET resin “TR-4550BH (manufactured by Teijin Chemicals)”, 0.2 kg of polyolefin resin “Bondaine TX8030 (manufactured by Arkema)”, epoxy resin 0.05 kg of “Epicoat 1004 (Japan Epoxy Resin Co., Ltd.)” was 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 30% by mass, the cylinder temperature A PBT resin composition obtained by melt-kneading at 270 ° C. and pelletized was obtained. It dried at 140 degreeC for 3 hours, and was set as the PBT composition (2).

[Example 1]
A 1 mm-thick AZ31B magnesium alloy (manufactured by Nippon Metals Co., Ltd.) with an average metal crystal grain size of 7 μm, which was wet buffed, was purchased and cut into a rectangular plate having a size of 250 mm × 200 mm. A commercially available magnesium alloy degreasing agent “Cleaner 160 (manufactured by Meltex)” and water were put into a tank to prepare an aqueous solution of 75 ° C. and a concentration of 10%. The magnesium alloy sheet cut into this was immersed for 5 minutes and washed thoroughly with water. Subsequently, a 1% strength hydrated citric acid aqueous solution at 40 ° C. was prepared in a separate tank, and the washed magnesium alloy sheet was immersed in it for 4 minutes, and then thoroughly washed with water. Black smut was attached. Next, an aqueous solution containing 1% sodium carbonate and 1% sodium hydrogen carbonate at 65 ° C. was prepared in another tank, and the magnesium alloy sheet was immersed for 5 minutes, and then thoroughly washed with water.

  Subsequently, a 15% aqueous solution of caustic soda at 65 ° C. was prepared in another tank, and the magnesium alloy sheet was immersed in this for 5 minutes, and then thoroughly washed with water. With this, the zinc content in the smut can be dissolved. Subsequently, the magnesium alloy plate was immersed in a 0.25% hydrated citric acid aqueous solution at 40 ° C. prepared in another tank for 1 minute, and then the magnesium alloy plate was thoroughly washed with water. Next, prepare an aqueous solution containing potassium permanganate 2%, acetic acid 1%, and hydrated sodium acetate 0.5% at 45 ° C in a separate tank. Was carried out for 15 seconds and placed in a hot air drier at 90 ° C. for 10 minutes for drying. After drying, a plurality of magnesium alloy plate materials were wrapped together with aluminum foil (aluminum foil), and further sealed in a poly bag (polyethylene bag).

  On the other hand, a commercially available plate material of tough pitch copper (C1100) having a thickness of 1.5 mm was purchased and cut into rectangular pieces having a size of 5 mm × 10 mm. About 20 of them were sandwiched with polypropylene clips at one end to prepare for the immersion treatment. An aqueous solution in which 3% of polyoxyethylene lauryl ether “Emulgen 108 (manufactured by Kao Corporation)” was dissolved in a tank was prepared at 60 ° C. for degreasing. Here, the copper piece group prepared previously was immersed for 5 minutes together with the immersion jig, degreased, and washed with water. Next, an aqueous solution containing 1.5% of caustic soda at 40 ° C. was prepared in another tank, and the copper piece group was immersed in this for 1 minute and washed with water.

  Next, in another tank, a commercially available copper etching aid “CB-5002 (made by MEC)” is mixed for 20% by mass, 30% hydrogen peroxide solution is 17.5% by mass, and the other is mixed as ion-exchanged water. An aqueous solution was prepared, and another copper piece 5 g was added thereto and allowed to stand for 15 minutes to prepare an aqueous solution for etching. This solution is basically a mixed aqueous solution containing sulfuric acid, hydrogen peroxide and some copper ions. The aqueous solution for etching was set to 40 ° C., and the copper piece group was immersed for 4.5 minutes, and then thoroughly washed with ion-exchanged water. Next, an aqueous solution containing 10% caustic soda and 5% sodium chlorite at 70 ° C. was prepared in another tank, immersed in this for 1 minute, and then thoroughly washed with ion-exchanged water. Furthermore, it put into the warm air dryer which was 90 degreeC for 15 minutes, and dried. The copper piece surface was bluish brown. Copper pieces were released from the jig on a clean aluminum foil, wrapped together, and then stored in a plastic bag.

  In order to prepare the composite M having the shape as shown in FIG. 1, the temperature of the injection mold was set to 140 ° C., and the PPS composition (1) prepared in Preparation Example 1 was prepared as a resin composition. The magnesium alloy plate material (metal plate material 1) was taken out, and the chemical conversion treatment layer was scraped lightly with sandpaper # 2000 while positioning the portion that contacts the copper piece (current-carrying terminal 3) after injection joining with pattern paper. Since the positioning by this scraping is scheduled to be performed again after that, it was not carried out at a strict level but rather a little wider. On the other hand, the surface of the copper piece (current-carrying terminal 3) in contact with the magnesium alloy sheet 1 was also rubbed lightly with the same sandpaper # 2000 to scrape off a thin layer of cupric oxide. The mold was opened, a magnesium alloy plate (metal plate 1) was inserted into the movable side plate, and a copper piece (current terminal 3) was inserted into the fixed side plate. The mold was closed and the PPS composition (1) was injected at an injection temperature of 310 ° C. The mold was opened to obtain an integrated composite M shown in FIG. On the molding day, it was annealed by placing it in a hot air dryer at 170 ° C. for 1 hour.

The composite M was immersed in an aqueous solution containing 2.5% of hydrated manganese phosphate at 2.5 ° C, 2.5% of 80% phosphoric acid and 2% of triethylamine for 3 minutes, and then washed with water. Further, the composite M was placed in a warm air dryer set to 90 ° C. for 15 minutes and dried.
Next, a paint “Omak / Black (manufactured by Ohashi Chemical Co., Ltd.)” was applied to the surface side of the composite M at a thickness of 10 μm, and then dried at 100 ° C. for 1 hour. Next, “Omak / silver metallic” was applied at a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Thus, the complex M shown in FIG. 1 was almost completed.
The exposed portion 3a of the copper piece (the current-carrying terminal 3) inside the composite M was lightly rubbed with a blade of a cutter knife, and a part of the black film was scraped off to obtain a finished part.

The composite M is evaluated. First, as an evaluation of the bonding force, the operator tried to pull out all of the inner resin boss 4 with a finger. However, the bonding strength was so strong that even if it was pulled with pliers, it could not be pulled out at a level where the magnesium alloy plate did not deform.
Subsequently, the composite M in which five scratches having a length of 20 mm were attached with a cutter knife at intervals of 2 mm on another coating film was set in a salt spray tester. Salt water spraying was performed at a temperature of 35 ° C. for 24 hours using 5% strength brine, and then washed with ion-exchanged water and dried at 70 ° C. for 15 minutes. The coating on the side surface of the scratch was hardly lifted up, and no rust spread from the scratch.

  A mold for obtaining a test piece S2 for measuring conductivity in the shape of FIG. 3 was prepared, and a copper piece 22 and a magnesium alloy plate material (metal plate material) 21 subjected to the same surface treatment as in the production of the composite M, A test piece S2 for conductivity measurement as shown in FIG. 3 was prepared. The end surface of the one end side 22a of the copper piece 22 and the contact portion of the one surface 21a of the magnesium alloy sheet 21, that is, the surface in contact with each other, are lightly rubbed with sandpaper # 2000 and a thin layer of cupric oxide is rubbed. I'm scraping. Injecting the PPS composition (1), the outer peripheral portion of one end side 22a of the copper piece 22, the inner peripheral portion of the resin boss portion 23, one surface 21a of the magnesium alloy plate 21 and the end surface 23a of the resin boss portion 23 The test piece S2 for conductivity measurement, which is an integrated product composed of the copper piece 22, the magnesium alloy plate material 21, and the resin boss 23, was prepared.

  The coating on the external surface of the copper piece 22 was scraped off with a sandpaper to a size of about 10 mm square to expose a part of the surface on the other end side 22 b of the copper piece 22. Both test terminals of the tester were pressed against both the exposed surface of the other end 22b and the one surface 21a from which the chemical conversion layer of the magnesium alloy sheet 21 was removed, and the resistance value was measured. The resistance value was 1 ohm (Ω) or less, and the conductivity was high. In addition, it may replace with test piece S2 for electrical conductivity measurement, and may perform the same electrical conductivity measurement with the composite_body | complex M.

[Example 2]
A composite M 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. Annealed at 170 ° C. for 1 hour. At this time, an evaluation test of a bonding force in which an operator pulls out all the resin bosses 4 inside the composite M with a finger was performed. The bonding force was weaker than that of Example 1, and it could not be pulled out by finger force, but could be broken if it was pulled out with pliers. Subsequent processing and processing were performed in exactly the same manner as in Example 1. The results of the evaluation test of conductivity and corrosion resistance (salt spray test) were the same as those of Example 1.

Example 3
Instead of the PPS composition (1) obtained in Preparation Example 1, the PPS composition (3) obtained in Preparation Example 3 was used. Otherwise, Composite M was produced in the same manner as in Example 1.
The evaluation test was performed in exactly the same way as in Example 1, but the results were exactly the same.

[Comparative Example 1]
Instead of the PPS composition (1) obtained in Preparation Example 1, the PPS composition (4) obtained in Preparation Example 4 was used. Otherwise, the composite M was produced in the same manner as in Example 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 injection joining, and the injection joining was interrupted.

Example 4
An AZ91D magnesium alloy sheet material (magnesium alloy sheet material) having a thickness of 1.05 mm and a size of 250 mm × 200 mm was formed by die casting. One side of this magnesium alloy plate material was scraped off with a machine for plane cutting to obtain a magnesium alloy plate material which is a metal plate material 1 having a thickness of 1 mm. The following liquid treatment was performed using this magnesium alloy sheet. That is, an aqueous solution with a temperature of 75 ° C. and a concentration of 7.5% in which a commercially available magnesium alloy degreasing agent “Cleaner 160 (Meltex)” was added to the tank was prepared, and the magnesium alloy sheet was immersed in this aqueous solution for 5 minutes. Washed well with water. Subsequently, a 1% -concentrated malonic acid aqueous solution at 40 ° C. was prepared in another tank, and the magnesium alloy sheet was immersed in this for 2 minutes, followed by washing with water. Black smut was attached. Next, an aqueous solution containing 1% sodium carbonate and 1% sodium hydrogen carbonate was prepared in another tank at 65 ° C., and the magnesium alloy sheet was immersed for 5 minutes and washed thoroughly with water.

  Subsequently, a 15% strength caustic soda aqueous solution at 65 ° C. was prepared in another tank, and the magnesium alloy sheet was immersed in this for 5 minutes and then thoroughly washed with water. Next, the magnesium alloy sheet was immersed in an aqueous solution containing 0.25% hydrated citric acid at 40 ° C. for 1 minute, finely etched, and then washed with water. Next, prepare an aqueous solution containing potassium permanganate 2%, acetic acid 1%, and hydrated sodium acetate 0.5% at 45 ° C in a separate tank. After immersing the magnesium alloy sheet in this for 1 minute, wash well with water. Then, it was placed in a hot air drier at 90 ° C. for 10 minutes and dried. After drying, the magnesium alloy sheets were wrapped together with aluminum foil, which was then stored in a plastic bag.

A composite was produced in exactly the same manner as in Example 1 except that the AZ91D plate obtained above was used instead of the AZ31B plate. However, in the injection joining, the surface to be joined with the resin composition was made to be the side scraped with a cutting machine, a machine tool or the like.
The evaluation results were exactly the same as in Example 1.

Example 5
A final product was produced in the same manner as in Example 1 except that the PBT composition (1) obtained in Preparation Example 5 was used instead of the PPS composition (1) obtained in Preparation Example 1. did. However, the mold temperature at the time of injection joining was 140 ° C., and the injection temperature was 280 ° C.
The evaluation test was performed in exactly the same manner as in Example 1, but the results were exactly the same.

Example 6
A final product was manufactured in the same manner as in Example 1 except that the PBT composition (2) obtained in Preparation Example 6 was used instead of the PPS composition (1) obtained in Preparation Example 1. did. However, the mold temperature at the time of injection joining was 140 ° C., and the injection temperature was 280 ° C.
The evaluation test was performed in exactly the same manner as in Example 1, but the results were exactly the same.

[Comparative Example 2]
An experiment was performed in exactly the same manner as in Example 5 except that a PBT resin composition containing no PET component was used instead of the PPS composition (1) obtained in Preparation Example 1. The resin used is “Torcon 1101G30B (manufactured by Toray Industries, Inc.)”, which is a PBT resin composition containing 30% glass fiber and some carbon black pigment.
A composite M was prepared in exactly the same manner as in Example 1, and annealed at 170 ° C. for 1 hour. At this time, a strength test was performed in which the operator pulled out all the resin bosses 4 inside the composite M with fingers. The joining force was much weaker than that of Example 1, and when the sandwiching force was applied with pliers and tilted laterally, the plate portion of the magnesium alloy plate was slightly bent but could be broken.

Example 7
An A5052 aluminum alloy plate material (manufactured by Sumitomo Light Metal Industry Co., Ltd.) having a thickness of 1 mm was obtained and cut into a rectangular aluminum alloy plate material having a size of 250 mm × 200 mm to obtain an aluminum alloy plate material as the metal plate material 1. A commercially available aluminum degreasing agent “NE-6 (manufactured by Meltex Co.)” was dissolved in water at a concentration of 7.5% and immersed in a degreasing bath at 60 ° C. for 7 minutes, and then washed with water. Next, the aluminum alloy sheet was immersed in a 1% strength hydrochloric acid aqueous solution at 40 ° C. for 1 minute and then washed with water. Subsequently, it was immersed in a 1.5% strength aqueous sodium hydroxide solution for 1 minute and washed with water. Next, it was immersed in a 3% nitric acid aqueous solution bath at 40 ° C. for 1 minute and washed with water. Next, the jig is immersed in a treatment tank containing a 3.5% strength monohydrate hydrazine aqueous solution at 60 ° C. for 1 minute, and then placed in a bath of a 0.5% concentration monohydrate hydrazine aqueous solution at 40 ° C. It was immersed for 0.5 minutes and washed thoroughly with water. This was put into a hot air dryer at 67 ° C. for 15 minutes and dried. The obtained plate material was piled up to about 10 sheets, wrapped in aluminum foil, sealed in a large plastic bag, and stored. When one of the stored products was observed later with an electron microscope, the entire surface was covered with ultrafine recesses having a diameter of 20 to 40 nm.

  On the other hand, a commercially available plate material of tough pitch copper (C1100) having a thickness of 1.5 mm was purchased and cut into rectangular pieces having a size of 5 mm × 10 mm. About 20 of them were sandwiched with polypropylene clips at one end to prepare for the immersion treatment. An aqueous solution containing 3% of polyoxyethylene lauryl ether “Emulgen 108 (manufactured by Kao Corporation)” was prepared in a tank, and the aqueous solution was heated to 60 ° C. to obtain a degreasing solution. The copper piece group was immersed in this degreasing solution for 5 minutes and washed with water. Next, an aqueous solution containing 1.5% of caustic soda at 40 ° C. was prepared in another tank, and the copper piece group was immersed in this for 1 minute and washed with water. Next, a mixed aqueous solution of 20% by mass of a commercially available copper etching assistant “CB-5002 (made by MEC)” at 40 ° C., 17.5% by mass of 30% hydrogen peroxide, and the remainder with ion-exchanged water. Was prepared as an etching solution, the copper piece was immersed for 4.5 minutes, and then thoroughly washed with ion-exchanged water. Next, an aqueous solution containing 10% caustic soda and 5% sodium chlorite at 70 ° C. was prepared in another tank, immersed in this for 1 minute, and then thoroughly washed with ion-exchanged water. Next, the copper piece group was placed in a hot air dryer at 90 ° C. for 15 minutes and dried.

  The surface of the copper piece was bluish brown. Copper pieces were released from the jig on a clean aluminum foil, wrapped together, and then stored in a plastic bag.

  In order to obtain the composite M which is an integrated shape shown in FIG. 1, the injection mold was set to 140 ° C., and the PPS composition (1) prepared in Preparation Example 1 was prepared as a resin composition. Take out the copper piece (the current-carrying terminal 3), and lightly polish the surface (one-side surface) in contact with the aluminum alloy plate (metal plate 1) by injection bonding with sandpaper # 2000 to form a thin layer of cupric oxide. Scraped off. The mold was opened, an aluminum alloy sheet was inserted into the movable mold, and a copper piece was inserted into the fixed mold. The mold was closed and the PPS composition (1) was injected at an injection temperature of 310 ° C. The mold was opened to obtain an integrated composite M shown in FIG. On the molding day, it was annealed by placing it in a hot air dryer at 170 ° C. for 1 hour.

  Next, a coating “Omak / Black (manufactured by Ohashi Chemical Co., Ltd.)” was applied on the surface side of the composite M at a thickness of 10 μm and dried at 100 ° C. for 1 hour. Next, “Omak / Silver Metallic” was applied with a thickness of 10 μm and baked at 170 ° C. for 30 minutes. Thus, the complex M shown in FIG. 1 was almost completed.

The exposed portion 3a of the copper piece (the current-carrying terminal 3) inside the composite M was lightly rubbed with a blade of a cutter knife, and a part of the black film was scraped off to obtain a finished part.
The coating film on the outer surface of the aluminum alloy plate (metal plate 1) was scraped off with a sandpaper to a size of about 10 mm square to expose the aluminum alloy. The resistance value was measured by pressing both test terminals of the tester against both the exposed portion surface and the exposed portion (surface at the other end) 3a of the copper piece. The resistance value was 1 ohm (Ω) or less and high conductivity. Next, 5 scratches with a length of 20 mm were attached to another coating film at intervals of 2 mm with a cutter knife and set in a salt spray tester. Using 5% salt water, salt water spray was performed at 35 ° C. for 24 hours, washed with ion-exchanged water, and dried at 70 ° C. for 15 minutes. The coating on the side surface of the scratch was hardly lifted up, and no rust spread from the scratch.

Example 8
AZ31B magnesium alloy having a thickness of 1 mm, A1050 aluminum alloy, and C1100 tough pitch copper were cut into small pieces each having a size of 30 mm × 5 mm, and each of the magnesium alloy surface treatment method, the copper surface treatment method of Example 1, and The aluminum alloy was treated according to the aluminum alloy surface treatment method of Example 7, wrapped in aluminum foil and stored.

  A metal mold for obtaining a test piece S1 for measuring hermeticity having the shape shown in FIG. 2 was prepared. After the mold temperature was set to 140 ° C., three kinds of metals made of magnesium alloy, copper, and aluminum alloy were subjected to surface treatment. One piece of each of the pieces (magnesium alloy piece 11, aluminum alloy piece 12, copper piece 13) was inserted, and the PPS composition (1) was injected to obtain a test piece S1 for hermeticity measurement. This was annealed at 170 ° C. for 1 hour within the same day as the injection joining.

  The shape shown in FIG. 2 schematically shows the shape of a portion for drawing out a conducting wire from a sealed electric circuit, and the resin lid member 14 corresponds to a lid for sealing an electric and electronic circuit contained in a container. It is. The lid member 14 is, for example, a circular member having a thickness of 5 mm and a diameter of 45 mm, and the portion to be joined to the metal is formed to a thickness of 10 mm. The test piece S1 for measuring the sealing property is bonded to the tip of an aluminum pipe (tubing body) 16 having an inner diameter of 45 mm, a thickness of 1 mm, and a length of 500 mm with an epoxy adhesive “Cemedine 1000 (Cemedine)”. It was left to cure for 2 days. An air inlet port to which a pressure gauge 19 and an on-off valve 18 are connected is provided on the opposite side of the pipe 16.

  After the epoxy adhesive was cured, compressed air from a compressor (pressure fluid supply source) was supplied to set the pressure inside the pipe 16 to 0.2 MPa (gauge pressure), and the on-off valve 18 was closed. Even after 48 hours, the pressure inside the pipe 16 did not decrease, and it was found that the air tightness was excellent. Air does not leak from anywhere on the joint surface between the lid member 14 and each metal piece (magnesium alloy piece 11, aluminum alloy piece 12, copper piece 13) of magnesium alloy, copper, and aluminum alloy corresponding to the energizing terminal. . In other words, the joining surface of the magnesium alloy metal piece and the PPS composition (1), the joining surface of the copper metal piece and the PPS composition (1), the aluminum alloy metal piece and the PPS composition (1). Air does not leak from anywhere on the joint surface. That is, it can be evaluated that the part joined by injection joining is very excellent in hermeticity, and for example, it can be adopted as a part for drawing out the lid member and the conductive wire.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to this embodiment. Needless to say, changes can be made without departing from the scope and spirit of the present invention. For example, the metal / resin composite may be a lid provided with terminals as shown in FIGS. That is, the lid body 40 having terminals is provided between a metal lid member 41 that is a metal part, current-carrying terminals 42 and 43 that are metal parts, and between the metal lid member 41 and the current-carrying terminals 42 and 43. This is a composite composed of a lid insulating member 44 which is a resin composition part. In other words, the lid 40 seals the opening of the container body 49 such as a battery.

  The metal parts (metal lid member 41, energizing terminals 42, 43) are preferably aluminum alloy parts, copper parts, copper alloy parts, magnesium alloy parts, and the like. For example, the metal lid member 41 may be an aluminum alloy part, a magnesium alloy part, or the like, and the energizing terminals 42 and 43 may be a copper part, a copper alloy part, an aluminum alloy part, or the like. The resin composition is preferably a PPS resin composition, a PBT resin composition, or the like. Furthermore, the metal lid member 41 is preferably plate-shaped.

  The metal lid member 41 and the current-carrying terminals 42 and 43 are inserted into the lid manufacturing die after the surface treatment as described above. The resin composition is injected into the cavity formed in the mold, and the lid body 40 in which the metal lid member 41, the current terminals 42 and 43, and the lid insulating member 44 are joined and integrated is manufactured. By doing in this way, the lid body 40 in which only the vicinity of the energization terminals 42 and 43 is insulated can be manufactured with high productivity. The lid 40 is mostly a plate-like metal lid member 41, and the overall rigidity of the lid 40 can be improved. Moreover, it can also be excellent in the airtightness.

  Further, the composite of metal and resin may be a cover of an electric / electronic device that is lightweight and has excellent electromagnetic shielding properties. In other words, the composite of metal and resin is composed of two or more metal parts selected from metal parts such as aluminum alloy, magnesium alloy, copper, and copper alloy, and polyphenylene sulfide-based resin or polybutylene terephthalate-based. What is necessary is just to be comprised from the resin composition which has resin as a main component.

FIG. 1 is an external view showing a composite body schematically showing an exterior case of a notebook personal computer. FIG. 2A is an external view showing the shape of a sealing degree measurement test piece for measuring the sealing property, and FIG. 2B is a cross-sectional view of the sealing degree measurement test piece of FIG. Sectional drawing cut | disconnected by the line, FIG.2 (c) is a side view of the test piece for a sealing degree measurement. FIG. 3A is an external view showing the shape of a test piece for conductivity measurement for measuring conductivity, and FIG. 3B is a cross-sectional view of the test piece for conductivity measurement. FIG. 4 is a cross-sectional view of a composite body in which a lid provided with terminals is schematically shown. FIG. 5 is a plan view of a composite body in which a lid body provided with terminals is schematically shown.

Explanation of symbols

1: Metal plate material 2: Resin outer peripheral portion 3: Copper energizing terminal 4: Resin boss portion 11: Magnesium alloy piece 12: Aluminum alloy piece 13: Copper piece 14: Resin lid member 21: Metal plate material 22 : Copper piece 23: Resin boss 24: Pin gate 40: Lid

Claims (11)

A metal part made of an aluminum alloy whose surface is covered with fine recesses having an average diameter of 20 to 80 nm by a step of immersing in an aqueous solution containing at least one selected from hydrazine, ammonia, and a water-soluble amine compound, and chemical etching A metal part made of a magnesium alloy mainly having a conversion film of manganese oxide, and a rough surface shape covered with a concave part having a diameter of 1 to 100 μm and a depth of 0.5 μm or more having many fine openings of 10 to 200 nm in diameter. Two or more metal parts selected from copper or copper alloy metal parts covered with a thin layer of copper oxide;
A metal / resin composite comprising a resin composition comprising a polyphenylene sulfide-based resin or a polybutylene terephthalate-based resin as a main component, which is directly joined to the two or more metal parts by injection molding. In the composite of a metal and a resin according to claim 1,
The resin composition mainly composed of the polyphenylene sulfide resin is
97 to 70 parts by mass of polyphenylene sulfide resin and 3 to 30 parts by mass of polyolefin resin are blended with respect to 100 parts by mass of the resin content of the polyphenylene sulfide resin. Complex. In the composite of a metal and a resin according to claim 1,
The resin composition mainly comprising the polybutylene terephthalate resin is
97 to 70 parts by mass of polybutylene terephthalate resin, 3 to 30 parts by mass of polyethylene terephthalate resin and / or polyolefin resin are blended with respect to 100 parts by mass of the resin content of the polybutylene terephthalate resin. A composite of metal and resin. In the composite of a metal and a resin according to any one of claims 1 to 3,
The resin composition is a composite of a metal and a resin, wherein the total amount of the resin is 100 parts by mass and the total amount of the filler is 10 to 200 parts by mass. In the composite of a metal and a resin according to claim 4,
The filler is at least one selected from glass fiber, carbon fiber, aramid fiber, other reinforcing fiber, calcium carbonate, magnesium carbonate, silica, talc, clay, glass, and other powder fillers. A composite of metal and resin. In the composite of a metal and a resin according to any one of claims 2 to 5,
The polyolefin resin is one or more selected from a maleic anhydride-modified ethylene copolymer, a glycidyl methacrylate-modified ethylene copolymer, a glycidyl ether-modified ethylene copolymer, and an ethylene alkyl acrylate copolymer. A composite of metal and resin, characterized by being. In the composite of a metal and a resin according to any one of claims 2 to 5,
The polyolefin-based resin is one or more selected from ethylene-acrylic acid ester-maleic anhydride terpolymer and ethylene-glycidyl methacrylate terpolymer. Complex. In the composite of a metal and a resin according to any one of claims 1 to 7,
The composite is a metal / resin composite characterized in that the composite is one selected from a lid provided with a case, a cover, and a terminal of an electric / electronic device composed of a metal part and a resin composition. A process of processing an aluminum alloy part into a predetermined shape from a cast or an intermediate material;
Immersing the aluminum alloy part processed into the predetermined shape in an aqueous solution in which at least one member selected from hydrazine, ammonia, and a water-soluble amine compound is dissolved;
A step of processing a copper or copper alloy part into a predetermined shape from a cast or an intermediate material;
Chemically etching the copper or copper alloy part processed into the predetermined shape;
Forming the copper-based metal oxide layer on the surface layer by immersing the chemically etched copper or copper alloy component in an aqueous solution containing chlorite;
Inserting the aluminum alloy part and the copper or copper alloy part into an injection mold, injecting a resin composition mainly composed of polyphenylene sulfide resin or polybutylene terephthalate resin, the aluminum alloy part, A process for producing a composite of a metal and a resin, comprising a step of integrally bonding a copper or copper alloy part and the resin composition. Processing a magnesium alloy part into a predetermined shape from a cast or intermediate material;
A step of chemical etching by immersing the magnesium alloy component processed into the predetermined shape in an acidic aqueous solution;
Immersing the chemically etched magnesium alloy part in an aqueous solution containing an alkali metal permanganate to form a thin layer mainly composed of manganese oxide on the surface;
A step of processing a copper or copper alloy part into a predetermined shape from a cast or an intermediate material;
Chemically etching the copper or copper alloy part processed into the predetermined shape;
Forming the copper-based metal oxide layer on the surface layer by immersing the chemically etched copper or copper alloy component in an aqueous solution containing chlorite;
Inserting the magnesium alloy part and the copper or copper alloy part into an injection mold, injecting a polyphenylene sulfide-based resin, or a resin composition mainly comprising a polybutylene terephthalate-based resin, the magnesium alloy part, A method for producing a composite of a metal and a resin, comprising a step of integrally fixing the copper or copper alloy part and the resin molding. A process of processing an aluminum alloy part into a predetermined shape from a cast or an intermediate material;
Immersing the aluminum alloy part processed into the predetermined shape in an aqueous solution containing at least one of hydrazine, ammonia, and a water-soluble amine compound;
The process of shaping magnesium alloy parts by mechanical processing etc. from castings and intermediate materials,
Immersing the shaped magnesium alloy part in an acidic aqueous solution and chemically etching; and
Immersing the magnesium alloy part in an aqueous solution containing an alkali metal permanganate to form a thin layer mainly composed of manganese oxide on the surface;
Processing copper and copper alloy parts from castings and intermediate materials into a predetermined shape;
Chemically etching the copper or copper alloy part processed into the predetermined shape;
Forming the copper-based metal oxide layer on the surface layer by immersing the chemically etched copper or copper alloy component in an aqueous solution containing chlorite;
Inserting the aluminum alloy part, the magnesium alloy part, and the copper or copper alloy part into an injection mold, injecting a polyphenylene sulfide-based resin, or a resin composition mainly composed of a polybutylene terephthalate-based resin, A metal-resin composite comprising the aluminum alloy part, the magnesium alloy part, the copper or copper alloy part, and a fixing step for fixing the resin composition together. Method.

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