JP4527196B2 - Composite and production method thereof - Google Patents

Description

  The present invention relates to a metal part used for a housing of an electronic device, a housing of a household electric appliance, a structural part, a mechanical part, or the like, or a composite made of an alloy part thereof and a resin composition part, and a manufacturing method thereof. More specifically, the present invention relates to a structure in which metal parts and thermoplastic resin composition parts made by various machining processes are integrated, and a method for manufacturing the structure, various mobile electronic devices, home appliances, medical devices, vehicle structural parts, The present invention relates to a composite of a metal part and a resin composition part used for vehicle-mounted articles, parts for building materials, other structural parts, exterior parts, and the like, and a method for producing the same.

  Technology that integrates metal and resin by various fixing means such as bonding and mechanical fixing is required from a wide range of industrial fields such as parts manufacturing for automobiles, home appliances, industrial equipment, etc. Adhesives have been developed. Among these are very good adhesives. For example, there is an adhesive that exhibits a function at room temperature or by heating, and the fixing that integrates a metal and a synthetic resin is currently mainly performed by a method using an adhesive. However, more rational fixing methods that do not use an adhesive have been studied.

  An example is a fixing method in which a high-strength engineering resin is integrated with magnesium, aluminum, light metals such as alloys thereof, and iron alloys such as stainless steel without an adhesive. For example, the present inventor has proposed a method (hereinafter abbreviated as “injection joining”) in which a metal part is inserted into a mold and a resin is injected into the metal part to perform molding and fixing simultaneously. This injection joining proposes a manufacturing technology in which polybutylene terephthalate resin (hereinafter referred to as “PBT”) or polyphenylene sulfide resin (hereinafter referred to as “PPS”) is injection molded to an aluminum alloy (for example, a patent). Reference 1). In addition, there is disclosed a technique in which a large hole is formed in an anodized film of an aluminum material, and a synthetic resin body is bited into the hole and fixed by an anchor effect (see, for example, Patent Document 2).

  The method of this injection joining in the proposal of patent document 1 is as follows. The aluminum alloy is immersed in a dilute aqueous solution of a water-soluble amine compound, and the aluminum alloy is finely etched by the weak basicity of the aqueous solution. At the same time, amine compound molecules were adsorbed on the aluminum alloy surface. The aluminum alloy thus treated is inserted into an injection mold, and the molten thermoplastic resin is injected at a high pressure. At this time, when the amine compound molecules adsorbed on the surface of the thermoplastic resin and the aluminum alloy are encountered and heat is generated, the resin that has been rapidly solidified in contact with the aluminum alloy kept at a low mold temperature is kept for some time. Although it is between, cooling solidification is delayed and it will also dig into the recessed part on the surface of an ultrafine aluminum alloy. As a result, the aluminum alloy and the thermoplastic resin are firmly bonded without the resin peeling off from the aluminum alloy surface. That is, when an exothermic reaction occurs, strong injection joining can be performed. In fact, it has been confirmed that PBT and PPS capable of exothermic reaction with an amine compound can be injection-bonded with this aluminum alloy.

JP 2004-216425 A WO2004-055248 A1 publication

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

  The present inventors have developed the above-mentioned invention and studied whether the limitation of the pretreatment method imposed on the metal part can be reduced as much as possible by improving the resin composition part. As a result, the specific PPS composition The present inventors have found that a composite comprising a part and a metal part has excellent adhesion between the metal part and the PPS composition part, and has completed the present invention.

  The present invention has been made based on the above technical background and achieves the following object. An object of the present invention is to provide a composite of a metal part and a resin composition part having improved adhesion between a metal part typified by an aluminum alloy part or a magnesium alloy part and a PPS composition part, and a manufacturing technique thereof.

The present invention takes the following means in order to achieve the object.
That is, the composite of the present invention includes a metal part whose surface is covered with a recess having a number average inner diameter of 10 to 80 nm by electron microscope observation by immersing in an erodible aqueous solution or erodible suspension, and the metal part A resin composition part having a resin composition containing 70 to 99% by weight of polyphenylene sulfide and 1 to 30% by weight of a polyolefin-based resin fixed to each other by injection molding.

  The composite of the present invention 2 has a polyphenylene sulfide of 70 to 99 weights provided by injection molding on a metal part having a hole opening portion having a number average inner diameter of 10 to 80 nm on the surface as viewed with an electron microscope. % And a resin composition component having a resin composition containing 1 to 30% by weight of a polyolefin-based resin.

  The composite of the present invention 3 is the composite of the present invention 1 or 2, wherein the metal parts are selected from aluminum parts, aluminum alloy parts, magnesium parts, magnesium alloy parts, copper parts, copper alloy parts, and titanium alloy parts. It is characterized by being 1 or more types.

  The composite of the present invention 4 is the composite of the present invention 1 or 3, wherein the metal part is a magnesium or magnesium alloy part, and the metal part is a corrosive aqueous solution or a corrosive suspension of PH 3.0 to 8.0. By passing through an etching step of immersing in a turbid liquid, the number average inner diameter is 10 to 80 nm as viewed with an electron microscope.

  The composite of the present invention 5 is the composite of the present invention 1 or 3, wherein the metal component is an aluminum component or an aluminum alloy component, and the metal component is an erodible aqueous solution or erodible suspension of PH 8.5 to 11.0. It is characterized by having a concave portion on the surface having a number average inner diameter of 10 to 80 nm as viewed with an electron microscope by etching immersed in a liquid.

  The composite of the present invention 6 is the composite of the present invention 1-5, wherein the resin composition component is based on 100 parts by weight of a resin component containing 70 to 99% by weight of polyphenylene sulfide and 1 to 30% by weight of a polyolefin resin. The resin composition part is obtained by adding 0.1 to 6 parts by weight of a polyfunctional isocyanate and / or 1 to 25 parts by weight of an epoxy resin.

  The composite of the present invention 7 is the composite of the present invention 1-5, wherein the resin composition part is based on 100 parts by weight of a resin component containing 70 to 99% by weight of polyphenylene sulfide and 1 to 30% by weight of a polyolefin resin. And 1 to 200 parts by weight of a filler is added.

  The composite of the present invention 8 is the composite of the present invention 7, wherein the filler is one kind selected from glass fiber, carbon fiber, aramid fiber, calcium carbonate, magnesium carbonate, silica, talc, clay, and glass powder. It is the above.

  The composite of the present invention 9 is the composite of the first to eighth inventions, wherein the polyolefin resin is a maleic anhydride modified ethylene copolymer, a glycidyl methacrylate modified ethylene copolymer, a glycidyl ether modified ethylene copolymer. And one or more selected from ethylene alkyl acrylate copolymers.

  The composite of the present invention 10 is the composite of the present invention 1 to 8, wherein the polyolefin resin is an ethylene-acrylic acid ester-maleic anhydride terpolymer and an ethylene-glycidyl methacrylate binary copolymer. It is characterized by including one selected.

  The method for producing a composite according to the eleventh aspect of the present invention comprises a chemical immersion treatment type surface treatment step of treating a metal part so that the surface is covered with a recess or hole having a number average inner diameter of 10 to 80 nm measured by observation with an electron microscope, A metal part subjected to a surface treatment process is inserted into an injection mold, and a resin composition having a resin composition containing 70 to 99% by weight of polyphenylene sulfide and 1 to 30% by weight of a polyolefin resin is injected to form a resin composition part. A joining step of forming and injection joining to a metal part.

  In the method for producing the composite of the present invention 12, an anodizing type surface treatment step for forming a metal part covered with a hole opening having a number average inner diameter of 10 to 80 nm measured by observation with an electron microscope, and the surface treatment step are performed. The metal part is inserted into an injection mold and a resin composition having a resin composition containing 70 to 99% by weight of polyphenylene sulfide and 1 to 30% by weight of a polyolefin resin is injected to be molded as a resin composition part and the metal part And a joining step of injection joining.

The method for producing the complex of the present invention 13 includes the method for producing the complex of the present invention 11,
The surface treatment step is characterized in that the metal part made of magnesium or a magnesium alloy is immersed and etched in an erosive aqueous solution or erosive suspension having a pH of 3 to 8.

  The method for producing a composite of the present invention 14 is the method for producing a composite of the present invention 12. In the method for producing a composite of the present invention 12, in the surface treatment step, the metal part made of aluminum or an aluminum alloy is It is characterized in that it is immersed in an aqueous suspension and etched. Hereinafter, the main elements of each means will be described in detail.

[Metal parts]
There are two types of metal parts constituting the present invention in terms of the surface structure, one of which is obtained by immersing a metal in an erodible aqueous solution or erodible suspension. The shape is covered with innumerable recesses, and the number average inner diameter of the recesses is 80 nm or less. The other is obtained by an anodic oxidation method. The surface is mainly a metal oxide layer, and the surface layer is covered with an opening having an innumerable number average inner diameter of 10 to 80 nm.

  This metal part is preferably one in which a metal is processed into a predetermined shape by metal removal such as cutting, pressing, or the like, plastic processing by cutting, grinding, electric discharge processing or the like. In short, it is preferable to use a material processed into a shape required for an insert for injection molding by various processing methods. Metal parts that have been processed into the required shape should have a thick surface that should be bonded to the resin part and should not be oxidized or hydroxylated. Is preferably removed by polishing, chemical treatment or the like.

Although all types of metals that can be used in the present invention are targets, it is preferable to use a metal type having a large linear expansion coefficient. The reason is that the linear expansion coefficient of the resin composition is impossible to obtain a linear expansion coefficient equivalent to that of metal even if it is adjusted by adding a filler or the like. That is, the linear expansion coefficient of the resin composition is about 2 × 10 ⁻⁵ ° C. ⁻¹ even at the lowest. For example, since iron and the like have a linear expansion coefficient that is half of this, even if the composite is integrated by injection bonding with a long-term temperature change, there is a possibility that the adhesion force of the interface gradually decreases over time. Because. For this reason, the target metal part is preferably a metal part made of magnesium, aluminum, copper, and alloys thereof. Examples of the magnesium alloy constituting the metal part include a magnesium alloy for extension standardized by ASTM and JIS, and a magnesium alloy for casting by a die-cast method or a thixomold method. In addition, as the aluminum alloy, for example, 1000-7000 series for extension standardized by Japanese Industrial Standards (JIS) and various types of die-cast grades can be used.

[Size of recesses in metal parts]
This metal part is processed into a metal shape as described above, and after surface processing including chemical etching and anodic oxidation (hereinafter referred to as “liquid treatment”), the surface is finally observed with an electron microscope. It is made to be covered with a fine recess having a number average inner diameter of 10 to 80 nm or a hole opening by measurement.

  This is the case where the inner diameter of the recesses is less than 10 nm, but the surface covered with such ultrafine recesses is clear despite the many surface treatment experiments by chemical etching conducted by the present inventors. In the anodic oxidation performed by the present inventors, all of the holes had an inner diameter of 10 nm or more. Further, even when observation is performed using the highest model electron microscope (SEM type) sold in Japan, the observation below 10 nm is also an area where clear observation becomes difficult. From the above, it is estimated that the present invention can be applied even if the number average inner diameter of the recess is less than 10 nm, but it has not been clearly confirmed at this stage. Therefore, the present inventors explained about 10 nm or more that can be clearly observed and claimed with an electron microscope. In order to clarify this, the range of the number average inner diameter of 10 nm to 80 nm, which is the range of the size of the recessed portion that has been confirmed, is claimed in the claims.

  When a recess having a number average inner diameter exceeding 80 nm is obtained by eroding a metal with an erodible aqueous solution or an erodible suspension, the resulting composite has a significantly inferior fixing force, but the reason is as follows. Will be explained. That is, when the metal surface was eroded by immersing a metal in an erodible aqueous solution or erodible suspension, the following was found from observations by the present inventors with an optical microscope and an electron microscope. In the case of the most clear aluminum alloy A5052, when a water-soluble amine aqueous solution is adjusted to a weak basicity of about PH10 and immersed at 40 ° C., a recess having an average inner diameter of 20 to 40 nm is generated immediately and the depth is about 1 minute. Becomes the same level as the diameter. When the immersion is further continued, the depth of the concave portion becomes deeper and the edge portion that makes the concave portion is crushed, and the average inner diameter becomes larger and larger.

  When the surface of the A5052 piece dipped for about 20 minutes, washed with water and dried was observed with an electron microscope, the number average inner diameter of the recesses visible from the surface was as large as 80 to 100 nm. However, when the inside of the concave portion was observed in more detail, it was found that complicated fine concave portions and groove-like shapes were complicated as an earthworm dug a hole. According to the results of the injection bonding experiment with the PPS resin described in the present invention conducted by the present inventors, the bonding force sharply decreased when the average inner diameter of the recesses reached 80 nm. That is, in the chemical etching by immersing the A5052 aluminum alloy piece in the weakly basic aqueous solution, the joining force in the injection joining rapidly decreased with the number average inner diameter of 80 nm as a boundary.

  The present inventors consider that the complicated shape in the above-described recess is related to the reason why the bonding force rapidly decreases as the average inner diameter of the plurality of recesses increases. That is, the PPS resin according to the present invention enters the ultrafine recess formed on the metal side under the conditions of injection molding, and after entering, crystallizes and does not easily peel off. If the diameter and depth of the recess are ultrafine and this covers an infinite number of metal surfaces, the bonding force created by the resin that enters the recess and crystallizes and the metal part is supported by an infinite number of anchor effects. As a result, a very strong bonding force is generated. It is only a physical catch that is not a chemical bond, that is, an anchor effect, but if it comes to the nano order, it becomes stronger than the joining with a high performance adhesive.

  Now, in the case of a surface having a large recess of 80 nm or more, the reason why the bonding force is weakened becomes clear by imagining the dynamic state of resin flow, crystallization, and solidification. That is, even when immersed in a weakly erodible chemical solution and immersed for the purpose of forming fine recesses with an average inner diameter of several tens of nanometers on the metal surface, if the immersion conditions pass and the average inner diameter of the recesses exceeds 80 nm, As described above, the three-dimensionally complicated shape is obtained such that small concave portions and holes can be formed in various directions again in the concave portions. If the metal piece eroded deeply in this way is cut vertically and its cross section is viewed, a portion having a depth of 100 to 200 nm from the surface becomes a worm-eaten layer, that is, a sponge-like layer. In short, when chemical etching is advanced so that the number average inner diameter of the recesses is increased to 80 nm, the surface layer of the metal piece becomes a sponge layer and the surface layer itself becomes weak.

  In the case of a sponge layer, the injected resin cannot enter the deepest part of the complex space on the metal surface. This is because it cools before entering the innermost part and starts to crystallize and solidify. The injected resin can bite into the surface of the sponge, but cannot go far. Therefore, when the two are integrated and then the shearing force or the resin is pulled and peeled off from the surface, that is, when it is broken by the peeling force, the metal sponge layer not previously filled with the resin is broken. For this reason, high joining force cannot be shown. Since the same tendency was recognized also in the magnesium alloy AZ31, it was judged that the smaller recessed part about 80 nm diameter or less was effective for injection joining.

  From the above, when regular irregularities are made on the metal surface by a method such as photochemical reaction using a resist and laser control, and the PPS resin of the present invention is injection-bonded thereto, the number average inner diameter of the irregularities unit and the depressions Even when the thickness exceeds 80 nm, the injection joining force is considered to be sufficiently strong. This is because the concave portion does not become a complex layer or a sponge-like layer that is generated by etching with an erodible chemical solution. However, it is a microfabrication technology for semiconductor manufacturing itself that makes undulations of several tens to several hundreds of nanometers on a metal surface using a laser or a photochemical method. It is not suitable as a technical means for manufacturing a lightweight and strong metal resin integrated product, which is the purpose of the above, in large quantities at low cost. Practicality is lost due to too much effort and cost. If the present invention is used, the aluminum alloy may be simply immersed in a weakly basic aqueous solution, and the magnesium alloy may be simply immersed in a weakly acidic to neutral aqueous solution. The PPS resin described is strongly injection bonded to the metal surface. The metal surface treatment cost according to the present invention is very low.

[Surface treatment of metal parts (liquid treatment and anodic oxidation)]
First, an outline of a liquid treatment method for producing a metal part covered with recesses having a number average inner diameter of 10 to 80 nm of a large number of recesses formed by immersion in an erodible aqueous solution or erosion suspension will be described. Liquid treatment basically consists of two treatment steps: a pretreatment step for chemically removing rust, dirt, oxides and hydroxides, and a main treatment step for fine etching. First, the etching method will be described.

  For metals in general, it is common practice to use an erosive aqueous solution or erosive suspension for the metal species. This is so-called chemical etching. Weakly acidic liquids for many metal species and weakly acidic liquids and weakly basic liquids for amphoteric metals such as aluminum are candidates. First, for aluminum and aluminum alloys, a weakly basic erodible aqueous solution or erodible suspension having a pH of 8.5 to 11.0 was suitable as the treatment liquid. In a basic solution with a pH of 11 or more, aluminum is vigorously dissolved and it is difficult to form fine recesses. On the other hand, in a weakly basic solution with a pH of 8.5 or less, the reaction is weak and it is difficult to form clear recesses. Therefore, it is estimated that the PH value of the liquid in which the recess is clearly formed and the average inner diameter of the recess becomes a desired diameter is within the PH value.

  For magnesium or a magnesium alloy, a weakly acidic to neutral erosive aqueous solution or erosive suspension having a pH of 3.0 to 8.0 was suitable as an etching solution. That is, an erodible aqueous solution having a pH of 3.0 to 8.0, such as inorganic acid, aliphatic carboxylic acid, citric acid, aromatic carboxylic acid, phenols, and neutral salt ammonium chloride can be used. In addition, with copper, it was tested that a weakly acidic aqueous solution could be used as an erodible aqueous solution. However, in a dilute hydrochloric acid aqueous solution, some of the copper ions in the solution were reduced by the hydrogen generated when copper was dissolved out as metal ions. The surface was covered with black material. Etching was possible by using both hydrogen peroxide and sulfuric acid as oxidizing agents.

  Next, the anodic oxidation method will be described. After the surface is cleaned by pretreatment or the like, innumerable fine pores are formed on the surface by electrolysis in an acid-basic aqueous solution. A well-known method is to oxidize an aluminum alloy as an anode by energizing it in an acidic aqueous solution and covering the surface with a strong and hard aluminum oxide layer. If the surface is covered with non-conducting aluminum oxide, electricity will not pass and the oxidation should end there, but in practice the energization continues and the thickness of the aluminum oxide layer reaches several tens of micrometers. This is because innumerable holes having a number average inner diameter of several tens to several tens of nanometers are opened in the aluminum oxide layer, and current is continuously passed through the holes. When the anodic oxide of aluminum or aluminum alloy having innumerable holes is immersed in an aqueous solution in which a dye is dissolved, the dye enters the hole and is dyed. This is further processed and sealed to prevent the dye from escaping, which is dyed alumite.

  The surface layer formed by the anodic oxidation method is not a metal, but is a metal oxide layer that is stronger and harder than a metal. If a fine hole is formed in this hard and strong metal oxide layer, it can be applied to a metal provided with a metal oxide formed by an anodic oxidation method according to the fixing principle of the present invention. The present invention is naturally effective. A metal oxide layer having an infinite number of fine holes formed on a metal, that is, an anodic oxide with unsealed holes, can be used satisfactorily. In addition to aluminum, magnesium, niobium, titanium, and zinc are known as metal species capable of forming an infinite number of fine apertures having an average inner diameter of several tens of nm or less by an anodic oxidation method. In normal anodization of aluminum, the inner diameter and the hole diameter of the opening are said to be 15 to 20 nm, but the number average inner diameter of the opening can be expanded under various conditions during anodization.

  Furthermore, the spark method is adopted in aluminum, magnesium, titanium, niobium, zinc, and other anodic oxidation. That is, after a non-conductive oxide layer is formed on the metal surface by anodic oxidation, a hole is formed by applying a high voltage of 100 volts or more, and anodic oxidation is further advanced through this hole to form an oxide layer of several μm. It is what. In normal anodizing, the voltage is around 10 volts and no discharge occurs, so the state of the holes and openings by the discharge method is somewhat irregular and the surface is messy. The number average inner diameter of the opening may be 50 to 80 nm because the surface of the metal oxide layer is broken. Both the unsealed alumite layer and the anodic oxide layer of various metals by the spark method are metal oxide layers, so to speak, they are ceramic and are hard and strong. Therefore, it can be strongly injection-bonded with the PPS resin according to the present invention.

[In the case of magnesium alloy]
A specific method of surface treatment with an erodible aqueous solution or erosive suspension of a magnesium alloy will be described. In the pretreatment, in order to first wash away the oil layer, dirt, etc. on the surface remaining in the metal processing step, a commercially available aqueous solution of magnesium degreasing agent is usually immersed at 40 to 70 ° C. for several minutes. Subsequently, it is immersed in a slightly strong acidic aqueous solution and rough etched, and the surface is melted to remove dirt and rust. However, except when pure magnesium is used, there are different kinds of metals included, and these are difficult to dissolve and often deposit on the surface as insoluble matter.

  For example, AZ31 contains about 3% of aluminum and about 1% of zinc, and these are hardly dissolved by an acidic liquid and become a deposit (called smut). Considering the properties of these deposits, magnesium is not dissolved but is dissolved in a solution that dissolves them, specifically, a basic aqueous solution to dissolve them to obtain a clean surface. This is so-called smut removal. Subsequently, fine etching which is the main treatment, but an erodible aqueous solution or an erodible suspension adjusted to PH 3.0 to 8.0, preferably PH 3.5 to 7.5 can be used as a liquid for immersion. Thereafter, the smut is removed and washed with water in the same manner as described above, or the smut generated in the fine etching is small, so that the smut is not carried out and is dried as it is.

  An aqueous solution of an inorganic acid or an aliphatic carboxylic acid is preferably used for the initial rough etching, and specifically, hydrochloric acid, acetic acid, propionic acid, or the like can be preferably used. Also, the erodible aqueous solution or erodible suspension used in this treatment etching includes inorganic acids such as nitric acid, aliphatic carboxylic acids such as acetic acid, propionic acid and butyric acid, polybasic acids such as citric acid, benzoic acid and Aqueous solutions or suspensions of aromatic carboxylic acids such as phthalic acid, phenols such as carboxylic acid, and almost neutral salts such as ammonium chloride and ammonium fluoride can also be used.

  For example, the fine etching can be performed by immersing in a 0.5 to 1.0% aqueous citric acid solution at 30 to 50 ° C. for several minutes. This etched magnesium alloy, AZ31B, is clean enough to prevent smuts, but the present inventors dissolved fine aluminum deposited in a weakly basic aqueous solution and subsequently immersed in a strong basic aqueous solution to deposit finely. The standard was to add a smut removal treatment to dissolve zinc. Actually, the obtained magnesium alloy piece is observed with an electron microscope, and an appropriate immersion time in an erodible aqueous solution or an erodible suspension is preferably determined by observation with an electron microscope.

  Magnesium alloy anodization is a well-known technology that is contracted and produced on a commercial basis by specialists in Japan and abroad. In the anodic oxidation of the magnesium alloy, there is a case where the sealing treatment is performed in the same manner as the alumite, and the present inventors commissioned a standard anodic oxide which is not subjected to the sealing treatment to request the preparation. This unsealed anodic oxide was found to have an opening having a number average inner diameter of 20 to 40 nm by electron microscope observation, and the PPS composition of the present invention could be injection joined.

[In the case of aluminum alloy]
First, a surface treatment method using an erodible aqueous solution or erodible suspension of an aluminum alloy will be described. In the pretreatment of the aluminum alloy, in order to wash away the oil layer, dirt, etc. on the surface remaining in the metal processing step, a commercially available aqueous solution of a degreasing agent for aluminum is usually immersed in this at a temperature of 40 to 70 ° C. for several minutes. Subsequently, the surface of the aluminum alloy component is slightly dissolved by repeating immersion and washing in basic and acidic aqueous solutions in order to remove the oxidized layer and dirt on the surface. Up to this point, preprocessing has been performed. Subsequently, fine etching, which is the main treatment, is carried out by dissolving or suspending the following substances or the like in water at 25 to 70 ° C., preferably at pH 8.5 to 11.0, more preferably at pH 9.0 to 10.0. The erodible aqueous solution or erodible suspension is preferably used as the immersion liquid.

  The substance used is preferably hydrazine, ammonia, water-soluble amines, or alkaline earth metal hydroxides. Water-soluble amines include pyridine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, ethanolamine, allylamine, ethanolamine, diethanolamine, triethanolamine, aniline, and other amines are used. it can. Also preferred as the alkaline earth metal hydroxide is magnesium hydroxide.

  As a specific example, an aqueous solution having a concentration of 3 to 5% at 50 to 60 ° C. gives a preferable result as an erodible aqueous solution for hydrazine, and a suspension obtained by adding about 1% of magnesium hydroxide at 40 ° C. is an erodible solution. It could be preferably used as a suspension. The immersion time varies depending on the erodible aqueous solution or erodible suspension used, but is 0.5 to 2 minutes. After being immersed in these erodible aqueous solutions or erosive suspensions, they are washed with water and dried. The appropriate immersion time in the erodible aqueous solution or erodible suspension is preferably determined by observation with an electron microscope, and the number average inner diameter of the recesses is in the range of 80 nm or less, preferably 10 to 50 nm. Confirm and decide the treatment method.

  Next, the anodic oxidation method will be described. Speaking of the anodizing method used for aluminum alloys is anodization itself, which is a well-known technique and there are many books, so a detailed description is omitted. Use without staining or sealing. That is, it is used with unsealed holes.

[Resin composition parts]
The resin composition constituting the resin composition part constituting the present invention is composed of a resin component composition containing 70 to 99% by weight of PPS and 1 to 30% by weight of a polyolefin resin, and is particularly a composite having excellent bonding properties. Is preferably a resin component composition containing PPS 80 to 97% by weight and polyolefin resin 3 to 20% by weight. Here, when the PPS is less than 70% by weight or exceeds 99% by weight, the composite obtained 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.

  Further, the PPS may be a linear one, a one having a branched structure introduced therein, or one that has been heat-treated in an inert gas. Furthermore, this PPS is a product in which impurities such as ions and oligomers are reduced by performing deionization treatment (acid washing, hot water washing, etc.) before or after heat curing or washing treatment with an organic solvent such as acetone. Alternatively, it may be cured by heating 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 particularly excellent in fixation, maleic anhydride-modified ethylene copolymer, glycidyl methacrylate-modified ethylene copolymer, glycidyl ether-modified ethylene copolymer, ethylene alkyl acrylate A copolymer or the like is preferable.

  Examples of the maleic anhydride-modified ethylene copolymer include maleic anhydride graft-modified ethylene polymer, maleic anhydride-ethylene copolymer, ethylene-acrylic acid ester-maleic anhydride terpolymer. Among them, an ethylene-acrylic acid ester-maleic anhydride terpolymer is preferable because a particularly excellent composite is obtained, and this ethylene-acrylic acid ester-maleic anhydride terpolymer is preferable. As a specific example, “Bondaine (made by Arkema, France)” and the like can be mentioned.

  Examples of the glycidyl methacrylate-modified ethylene-based copolymer include glycidyl methacrylate graft-modified ethylene polymer and glycidyl methacrylate-ethylene copolymer. Among them, particularly excellent composites are obtained, and therefore glycidyl methacrylate-ethylene copolymer. A polymer is preferred, and specific examples of the glycidyl methacrylate-ethylene copolymer include “Bond First” (manufactured by Sumitomo Chemical Co., Ltd., Japan). Examples of the glycidyl ether-modified ethylene copolymer include glycidyl ether graft-modified ethylene copolymer and glycidyl ether-ethylene copolymer. Specific examples of the ethylene alkyl acrylate copolymer include “rotoryl ( Arkema) ”and the like.

[Addition of polyfunctional isocyanate compound and epoxy resin]
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 99% by weight of PPS and 1 to 30% by weight of polyolefin resin. It is preferable that 0.1 to 6 parts by weight of a polyfunctional isocyanate compound and / or 1 to 25 parts by weight of an epoxy resin is further blended with respect to 100 parts by weight in total.

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

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

[Addition of filler to resin component]
Further, the composite of the present invention has a PPS of 70 to 99% by weight 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 preferable that the resin composition part further comprises 1 to 200 parts by weight, more preferably 10 to 150 parts by weight of filler relative to 100 parts by weight of the total resin content including ˜1% by weight.

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

[Insert and injection molding]
As a method for producing the composite of the present invention, any production method can be used as long as the composite can be produced. Among them, the productivity and reliability of the composite are particularly excellent, What is manufactured by the injection molding method which inserted the metal part is good, and the implementation method is disclosed below. Prepare an injection mold, open the mold, insert a metal part obtained by the above-mentioned treatment into one of the molds, close the mold, PPS 70 to 99 wt% and polyolefin resin 1 to 30 wt% The composite is produced by injecting a thermoplastic resin composition having a resin composition containing% and solidifying the mold and then releasing the mold.

  The injection conditions will be described. Considering from the theoretical aspect of the fixing principle of the present invention described above, the basis of the molding condition is that the molten resin comes into contact with the metal part inserted at high temperature and high pressure. In that sense, there are some differences from general injection molding. The main point is to make the mold temperature slightly higher. Specifically, it is preferably 100 ° C. or higher, more preferably 120 ° C. or higher. On the other hand, the injection temperature, injection pressure, and injection speed are not particularly different from ordinary injection molding.

  As described in detail above, the composite of the present invention is an integral body of the resin composition part and the metal part without being easily peeled off. A metal part covered with a recess having a number average inner diameter of 10 to 80 nm or an opening of a hole, measured with an electron microscope on the surface of the metal part, and 70 to 99% by weight of PPS and 1 to 30% by weight of a polyolefin resin. Bondability was enhanced by using a thermoplastic resin composition having a resin component composition.

FIG. 1 is a mold configuration diagram schematically showing a process of manufacturing a composite 4 of a metal plate and a resin composition. FIG. 2 is an external view of a single body schematically showing a composite of a metal plate and a resin composition. FIG. 3 is a surface photograph of an A5052 aluminum alloy obtained by ultrafine etching using a magnesium hydroxide suspension. FIG. 4 is a surface photograph of an A5052 aluminum alloy obtained by ultrafine etching using a hydrated hydrazine aqueous solution.

  Hereinafter, embodiments of the present invention will be described by way of examples. 1 and 2 are used as a common diagram of the respective embodiments. FIG. 1 shows that a metal part 1 processed into a predetermined shape is inserted into injection molds 2 and 3, a PPS composition 4 is injected through a pin gate 5, and is integrated with the metal part 1 by a joining surface 6 having fine recesses. It is the metal mold | die structure figure which showed typically the process which manufactures the conjugated complex. FIG. 2 is an external view showing the composite 7 after joining. In the following examples, various joint strengths produced in connection with the present invention are shown by measured values of shear fracture strength, and the effectiveness of the present invention is confirmed.

Examples of the present invention will be described in detail below.
The evaluation / measurement methods for the composites obtained from the examples are shown below.

~ Measurement of melt viscosity of PPS ~
The melt viscosity was measured under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg using a Koka-type flow tester “CFT-500 (manufactured by Shimadzu Corporation)” equipped with a die having a diameter of 1 mm and a length of 2 mm.

-Electron microscope observation of metal parts-
An SEM type electron microscope “S-4800 (manufactured by Hitachi, Ltd.)” was used and observed at 1.0 KV.

-Definition of number average inner diameter of recess-
Using the above-mentioned observation photograph with an electron microscope, the inner diameters of all the concave portions recognized in a square having a side of 200 or 300 nm are measured. For non-circular ones, the inner diameter is assumed as a circle with the same area. The total number including the assumed inner diameter and dividing by the number is taken as the number average inner diameter.

-Measurement of composite bond strength-
Using a tensile tester “Model 1323 (manufactured by Aiko Engineering Co., Ltd.)”, the shear breaking force was measured at a pulling speed of 10 mm / min.

[Preparation Example 1 (Preparation Example of PPS Composition)]
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 heated to 205 ° C. while stirring under a nitrogen stream. 1,355 g of water was distilled off. After cooling this 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 solid content was repeatedly washed with warm water and dried at 100 ° C. for a whole day and night to obtain PPS having a melt viscosity of 280 poise (hereinafter referred to as PPS (1)). This PPS (1) was further cured at 250 ° C. for 3 hours under a nitrogen atmosphere to obtain PPS (hereinafter referred to as PPS (2)).

The resulting PPS (2) had a melt viscosity of 400 poise.
6.0 kg of the obtained PPS (2) and 1.5 kg of ethylene-acrylic acid ester-maleic anhydride terpolymer “Bondyne TX8030 (manufactured by Arkema)”, epoxy resin “Epicoat 1004 (manufactured by 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 at a cylinder temperature of 300 ° C. and pelletized while being fed at a weight percent was obtained. The obtained PPS composition (1) was dried at 175 ° C. for 5 hours.

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

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

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

[Example 1]
A commercially available 1.6 mm thick A5052 aluminum alloy was purchased and cut into a large number of 18 mm × 45 mm rectangular pieces to obtain an aluminum alloy plate as the metal plate 1. When the aluminum alloy plate was observed with an electron microscope, it was not observed that the surface was covered with a recess having a number average inner diameter of 80 nm or less. A hole is made in the end of this aluminum alloy plate, and a copper wire coated with vinyl chloride is passed to dozens, and the copper wire is bent and processed so that the aluminum alloy plates do not overlap each other, and all can be hung at the same time. I did it.

  After putting 7.5% of commercially available degreasing agent “NE-6 (manufactured by Meltex Co.)” for aluminum alloy into water in a tank, heat and dissolve it at 75 ° C., soak the aluminum alloy plate for 5 minutes, Washed with water. Subsequently, a 1% hydrochloric acid aqueous solution at 40 ° C. was prepared in another tank, and the aluminum alloy plate was immersed in this for 1 minute and washed with water. Subsequently, a 1% aqueous solution of caustic soda at 40 ° C. was prepared in another tank, immersed for 1 minute and washed with water. Subsequently, a 1% hydrochloric acid aqueous solution at 40 ° C. was prepared in another tank, and the aluminum alloy plate was immersed in this for 1 minute and washed with water. Up to now, it is a pretreatment step in the liquid treatment.

  Subsequently, an erodible suspension in which 2% magnesium hydroxide at 40 ° C. was dissolved was prepared in another tank, immersed for 3 minutes, washed with water, 15 minutes at 40 ° C., and 5 minutes at 60 ° C., It dried with the warm air dryer. The copper wire was pulled out from the aluminum alloy plate on a clean aluminum foil and wrapped together. At this time, the finger is not touching the surfaces to be joined (the end portion on the opposite side from where the holes are made). One day later, one of them was observed with an electron microscope, and it was confirmed that fine concave portions having an average inner diameter of 55 nm covered the surface. This is shown in FIG.

Two days later, the remaining aluminum alloy plate was taken out, and the one with a hole so that oil and the like would not adhere was picked with gloves and inserted into an injection mold set at 140 ° C. The mold was closed and the PPS composition (1) obtained in Preparation Example 1 was injected at an injection temperature of 300 ° C. The mold temperature was 140 ° C., and 12 integrated composites shown in FIG. 2 were obtained. The size of the resin part 4 was 10 mm × 45 mm × 5 mm, and the joint surface 6 was 0.5 cm ² of 10 mm × 5 mm. This was annealed at 170 ° C. for 1 hour, and one day later, they were tensile tested. The average shear breaking force of 12 pieces was 5.9 Mpa (60.5 kgf / cm ² ).

[Comparative Example 1]
A composite was obtained in 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. One day later, they tried to pull test them. However, half of the 10 molded pieces were broken by the handling before applying to the tensile tester. The average shear breaking force of the remaining 5 pieces was 2.0 Mpa (20.5 kgf / cm ² ).

[Example 2]
A commercially available 1.6 mm thick A1100 aluminum alloy plate was purchased and cut into a large number of 18 mm × 45 mm rectangular pieces to obtain an aluminum alloy plate as the metal plate 1. A hole is made in the end of this aluminum alloy plate 1 and a copper wire coated with vinyl chloride is passed through the hole for dozens, and the copper wire is bent and processed so that the aluminum alloy plates do not overlap each other. Can be hung at the same time.

  A commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex Co.)” 7.5% was dissolved in water and heated to 75 ° C., and the aluminum alloy plate was immersed for 5 minutes and washed thoroughly with water. Subsequently, a 1% hydrochloric acid aqueous solution at 40 ° C. was prepared in another tank, and the aluminum alloy plate was immersed in the tank for 1 minute and washed with water. Subsequently, a 1% aqueous solution of caustic soda at 40 ° C. was prepared in another tank, immersed for 1 minute and washed with water. Subsequently, a 1% hydrochloric acid aqueous solution having a temperature of 40 ° C. was prepared in another tank, which was immersed for 1 minute and washed with water. This is the preprocessing.

  Subsequently, a 5% monohydric hydrazine aqueous solution at 60 ° C. was prepared in a separate tank, immersed for 1 minute and sufficiently washed with water. This was put into a warm air dryer at 40 ° C. for 15 minutes and at 60 ° C. for 5 minutes and dried. The aluminum alloy plate was placed on a clean aluminum foil with the copper wire removed and wrapped together. At this time, the finger is not touching the surfaces to be joined (the end portion on the opposite side from where the holes are made).

  One day later, one was observed with an electron microscope, and the surface was covered with a recess having a number average inner diameter of 23 nm. This is shown in FIG. Further, when another atom was subjected to XPS observation to analyze the atomic composition existing on the surface, nitrogen atoms were clearly observed. This indicates that the hydrazine used in the liquid treatment remains after drying, probably chemisorbed and remains on the aluminum alloy surface.

Two days later, the remaining aluminum alloy plate was taken out, and the one with a hole so that oil and the like would not adhere was picked with gloves and inserted into an injection mold set at 140 ° C. The mold was closed, the PPS composition (1) obtained in Preparation Example 1 was injected at an injection temperature of 300 ° C., and the integrated composite shown in FIG. It was. When this composite was measured for shear breaking strength with a tensile tester, the average was 27.5 MPa (280 kgf / cm ² ).

[Example 3]
The liquid treatment of the A1100 aluminum alloy plate proceeded in exactly the same manner as in Example 2, but after immersing it in a 5% monohydric hydrazine aqueous solution bath at 60 ° C. and washing it with water, it was prepared in another bath. The difference is that it was immersed in a 1% nitric acid aqueous solution at 40 ° C. for 30 seconds and washed with water. Then, it put into a warm air dryer for 15 minutes at 40 degreeC, and 5 minutes at 60 degreeC, and dried. The aluminum alloy plate was placed on a clean aluminum foil with the copper wire pulled out, wrapped and stored together. At this time, the finger is not touching the surfaces to be joined (the end portion on the opposite side from where the holes are made).

  One day later, one was observed with an electron microscope, and it was confirmed that a recess having a number average inner diameter of 25 nm covered the surface. Further, when XPS observation was performed using the other one, nitrogen atoms could not be observed. From this, it is considered that the amine compound, that is, hydrazine is not adsorbed on the aluminum alloy plate, and the adsorbed hydrazine is desorbed by immersing in an acidic solution and washing with water at the end of the liquid treatment.

Two days later, the remaining aluminum alloy plate was taken out, and the one with a hole so that oil and the like would not adhere was picked with gloves and inserted into an injection mold set at 140 ° C. The mold was closed, the PPS composition (1) obtained in Preparation Example 1 was injected at an injection temperature of 300 ° C., and the integrated composite shown in FIG. It was. When this composite was measured for shear breaking strength with a tensile tester, it was 9.7 Mpa (99 kgf / cm ² ) on average.

  The aluminum alloy plate according to the previous example (Example 2) is also based on the invention previously made by the present inventors (Japanese Patent Application No. 2002-325244), and it is confirmed by XPS that the amine compound is adsorbed on the surface of the aluminum alloy. System. In such systems, it has been known that strong injection joining occurs when PPS or PBT resin is used. This example is covered with almost the same recess as in Example 2, but in this example, no amine compound is adsorbed (nitrogen is not confirmed by XPS), whereas in Example 2, nitrogen atoms are recognized by XPS. Adsorption of amine compounds is assumed.

If there is an adsorbed amine compound (adsorbed hydrazine in Example 2) on the surface, it is considered that the reaction between the PPS molecule terminal chlorine and the amine compound occurs when contacted with the molten PPS resin, and heat is generated. It is done. If heat is generated, the melted PPS is delayed in crystallization and solidification, and tends to enter the recesses on the surface of the aluminum alloy. This would have produced a strong injection joining force in Example 2. However, in this example, a strong bond was generated despite the absence of an exothermic reaction on the aluminum alloy plate surface. If it is assumed from Example 2 that the used PPS resin has entered all of the recesses and the shear breaking force is 300 kgf / cm ² (29.4 Mpa) in this case, in this example, about 100 kgf / cm ² (9. Since the shear breaking force is 8 Mpa), it is calculated that the resin has entered about 1/3 of the recess.

[Example 4]
A commercially available 1.5 mm thick AZ31B magnesium alloy plate (manufactured by Nippon Metals Co., Ltd., Japan) was purchased and cut into 18 mm × 45 mm rectangular pieces to obtain a magnesium alloy plate as the metal part 2. A hole is made in the end of this magnesium alloy plate, and copper wires coated with dozens of pieces are coated with vinyl chloride. The copper wires are bent and processed so that the magnesium alloy plates do not overlap each other, so that all can be hung at the same time. I made it. A commercially available degreased material for magnesium alloy “Cleaner 160 (manufactured by Meltex, Japan)” 10% was dissolved in water and heated to 75 ° C. for 5 minutes and washed in water.

  Next, the magnesium alloy plate was immersed in a 1% aqueous acetic acid solution at 40 ° C. for 2 minutes for rough etching, and thoroughly washed with water. Subsequently, a 7.5% aqueous solution of aluminum alloy degreasing agent “NE-6 (manufactured by Meltex Co., Ltd.)” at 75 ° C. in a separate tank is prepared and immersed for 5 minutes to make aluminum out of the smut (dirt). The minutes were dissolved. Subsequently, a 20% strength aqueous solution of caustic soda at 75 ° C. was prepared in another tank and immersed for 5 minutes to dissolve the zinc content of the smut. This removed the dirt and rust on the surface. Subsequently, it was immersed in a 2% nitric acid aqueous solution at 40 ° C. for 1.5 minutes in another tank and finely etched and washed with water. This was placed in a hot air dryer at 60 ° C. for 10 minutes and dried. They were then stored in a desiccator with a desiccant.

Two days later, one of them was observed with an electron microscope, and it was confirmed that the surface was covered with a recess having a number average inner diameter of 35 nm. Further, one day later, this magnesium alloy plate was inserted into a mold and the PPS composition (1) was injected. This process was performed in the same manner as in the other examples and reference examples. However, the shape of the metal part is different in an integrated composite product. That is, in FIG. 2, the metal portion 1 was 1.5 mm × 18 mm × 45 mm, the resin portion 4 was 10 mm × 45 mm × 5 mm, and the joint portion was 10 mm × 5 mm (0.5 cm ² ). The magnesium alloy plate was injection-bonded with the thermoplastic resin composition and subjected to a tensile test. As a result, the average shear breaking force was 11.8 Mpa (120.2 kgf / cm ² ).

[Comparative Example 2]
A composite was obtained in the same manner as in Example 4 except that the PPS composition (2) obtained in Preparation Example 2 was used instead of the PPS composition (1). One day later, they tried to pull test them. However, more than half of the dozen molded parts were broken by handling prior to applying to the tensile tester. The average shear breaking force of the remaining five pieces was 1.0 Mpa (10.5 kgf / cm ² ).

[Example 5]
A commercially available 1.5 mm thick AZ31B magnesium alloy plate (manufactured by Nippon Metal Co., Ltd.) was purchased and cut into 18 mm × 45 mm rectangular pieces to obtain a magnesium alloy plate as the metal part 2. A hole is made in the end of this magnesium alloy plate, and copper wires coated with dozens of pieces are coated with vinyl chloride. The copper wires are bent and processed so that the magnesium alloy plates do not overlap each other, so that all can be hung at the same time. I made it. 10% of a commercially available magnesium alloy degreasing material “Cleaner 160” was dissolved in water and heated to 75 ° C. for 5 minutes and washed in water.

  Next, the magnesium alloy plate was immersed in a 1% aqueous acetic acid solution at 40 ° C. for 2 minutes for rough etching, and thoroughly washed with water. Subsequently, a 7.5% strength aqueous solution of a degreasing agent “NE-6” for aluminum alloy at 75 ° C. was prepared in another tank and immersed for 5 minutes to dissolve the aluminum content in the smut. Subsequently, a 20% strength aqueous solution of caustic soda at 75 ° C. was prepared in another tank and immersed for 5 minutes to dissolve the zinc content of the smut. Subsequently, it was immersed in a 1% aqueous citric acid solution at 40 ° C. for 2 minutes in another tank, finely etched and washed with water. This was placed in a hot air dryer at 60 ° C. for 10 minutes and dried. They were then stored in a desiccator with a desiccant.

Two days later, one of them was observed with an electron microscope, and it was confirmed that the surface was covered with a recess having a number average inner diameter of 30 nm. Further, this magnesium alloy plate was inserted into a mold one day later, and the PPS composition (1) was injected in the same manner as in Example 4. The magnesium alloy plate was injection-bonded with the thermoplastic resin composition and subjected to a tensile test. As a result, the shear breaking force averaged 12.7 Mpa (130 kgf / cm ² ).

[Example 6]
A composite was obtained in the same manner as in Example 2, except that the PPS composition (3) obtained in Preparation Example 3 was used instead of the PPS composition (1) obtained in Preparation Example 1. When this composite was measured for shear breaking strength with a tensile tester, it was 21.6 Mpa (220 kgf / cm ² ) on average.

[Comparative Example 3]
An attempt was made to produce a composite by the same method as in Example 1 except that the PPS composition (4) obtained in Preparation Example 4 was used instead of the PPS composition (1). Occurred and the molding was interrupted.

[Comparative Example 4]
A commercially available 1.6 mm thick A5052 aluminum alloy plate was purchased and cut into a number of 18 mm × 45 mm rectangular pieces to obtain an aluminum alloy plate as the metal plate 1. A hole is made in the end portion of the aluminum alloy plate 1 and a copper wire coated with vinyl chloride is passed through the five holes. The copper wire is bent and processed so that the aluminum alloy plates do not overlap each other. I was able to hang at the same time.

500 cc of acetone was put into a 1 liter beaker, the aluminum alloy plate was immersed for 15 minutes, then thoroughly washed with water, and then placed in a warm air dryer at 40 ° C. for 20 minutes to dry. When one piece was observed with an electron microscope, no concave portion whose size could be defined was found. For each of the remaining four, an injection joining experiment was conducted using the PPS composition exactly as in Example 1. However, when the mold was opened, the resin part and the aluminum alloy part were peeled off and could not be obtained as an integrated product.
[Comparative Example 5]
A commercially available 1.6 mm thick A5052 aluminum alloy was purchased and cut into 18 mm × 45 mm rectangular pieces to obtain an aluminum alloy plate as the metal plate 1. A hole is made in the end of this aluminum alloy plate, and a copper wire coated with vinyl chloride is passed to dozens, and the copper wire is bent and processed so that the aluminum alloy plates do not overlap each other, and all can be hung at the same time. I did it. After putting 7.5% of commercially available degreasing agent “NE-6 (manufactured by Meltex Co.)” for aluminum alloy into water in a tank, heat and dissolve it at 75 ° C., soak the aluminum alloy plate for 5 minutes, Washed with water.

  Subsequently, a 1% hydrochloric acid aqueous solution at 40 ° C. was prepared in another tank, and the aluminum alloy plate was immersed in this for 1 minute and washed with water. Subsequently, a 1% aqueous solution of caustic soda at 40 ° C. was prepared in another tank, immersed for 1 minute, and sufficiently washed with running ion-exchanged water. Compared with Example 1, this is like pretreatment as a liquid treatment of an aluminum alloy. The copper wire was pulled out of the aluminum alloy plate on a clean aluminum foil and wrapped together. At this time, the finger is not touching the surfaces to be joined (the end portion on the opposite side from where the holes are made).

One day later, one of them was observed with an electron microscope, but it was a hilly shape with irregularities of 100 to 200 nm units rather than being covered with fine concave portions.
Two days later, the remaining aluminum alloy plate was taken out, and the one with a hole so that oil and the like would not adhere was picked with gloves and inserted into an injection mold set at 140 ° C. The mold was closed and the PPS composition (1) obtained in Preparation Example 1 was injected at an injection temperature of 300 ° C. The mold temperature was 140 ° C. Although 12 integrated composites shown in FIG. 2 were obtained, they were all broken while they were touched to stand for one day and to be put on a tensile tester.

[Example 7]
A commercially available 1.6 mm thick A5052 aluminum alloy was purchased and cut into 18 mm × 45 mm rectangular pieces to obtain an aluminum alloy plate as the metal plate 1. A hole is made in the end of this aluminum alloy plate, and a copper wire coated with vinyl chloride is passed to dozens, and the copper wire is bent and processed so that the aluminum alloy plates do not overlap each other, and all can be hung at the same time. I did it.

A commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex)” 7.5% was poured into water and then melted at 75 ° C., and the aluminum alloy plate was immersed for 5 minutes and purified for 5 minutes. It was washed with running water, placed in a warm air dryer set at 40 ° C. for 15 minutes, and then placed in a warm air dryer set at 60 ° C. for 5 minutes for drying. This was wrapped in aluminum foil and stored.
One day later, 10 pieces were taken out and the PPS composition (1) obtained in Preparation Example 1 was injected at an injection temperature of 300 ° C. in the same manner as in Example 1. The mold temperature was 140 ° C. Ten integrated composites shown in FIG. 2 were obtained, and left to stand for one day, and when subjected to a tensile test, they were broken at an average of 7.4 Mpa (75 kgf / cm ² ). When the aluminum alloy portion was observed with an electron microscope, it was almost covered with a recess having a number average inner diameter of 48 nm. It was found that the degreasing solution was weakly basic with a pH of 9.0 and was finely etched by itself.

[Example 8]
A commercially available 1.6 mm thick A5052 aluminum alloy was purchased and cut into a large number of 18 mm × 45 mm rectangular pieces to obtain an aluminum alloy plate as the metal plate 1. A hole is made in the end of this aluminum alloy plate, and a copper wire coated with vinyl chloride is passed to dozens, and the copper wire is bent and processed so that the aluminum alloy plates do not overlap each other, and all can be hung at the same time. I did it.

  After putting 7.5% of commercially available degreasing agent “NE-6 (manufactured by Meltex Co.)” for aluminum alloy into water in a tank, heat and dissolve it at 75 ° C., soak the aluminum alloy plate for 5 minutes, Washed with water. Subsequently, a 10% aqueous solution of caustic soda at 50 ° C. was prepared in another tank, and the aluminum alloy plate was immersed in this for 0.5 minutes and washed with water.

Subsequently, a 60% nitric acid solution having a temperature of 90 ° C. was prepared in another tank, which was immersed for 15 seconds and washed with water. Subsequently, a 5% sulfuric acid aqueous solution at 20 ° C. is prepared in another tank, and the anode of the DC power supply “ASR3SD-150-500 (manufactured by Chuo Seisakusho)” is connected to the hole of the aluminum alloy, and the cathode is the tank. The lead plate was connected to a lead plate and anodized by constant current control to obtain a current density of 5 A / dm ² . It was anodized for 40 minutes, washed with water, and placed in a hot air drier at 60 ° C. for 1 hour for drying. One day later, one of them was observed with an electron microscope, and it was confirmed that a fine opening having a number average inner diameter of 17 nm covered the surface.

Two days later, the remaining aluminum alloy plate was taken out, and the one with a hole so that oil and the like would not adhere was picked with gloves and inserted into an injection mold set at 140 ° C. The mold was closed and the PPS composition (1) obtained in Preparation Example 1 was injected at an injection temperature of 300 ° C. The mold temperature was 140 ° C., and 12 integrated composites shown in FIG. 2 were obtained. The size of the resin part was 10 mm × 45 mm × 5 mm, and the bonding surface 6 was 0.5 cm ² of 10 mm × 5 mm. One day later, they were tensile tested. The average shear breaking strength of 12 pieces was 15.8 Mpa (161 kgf / cm ² ).

  By applying the present invention, that is, by improving the bondability, improving efficiency, expanding the application range, etc., it is possible to reduce the weight of mobile electronic devices and home appliances, reduce the weight of in-vehicle devices and parts, and improve the arm of the robot. It can contribute to the supply of parts and housing, weight reduction, and productivity in many other fields.

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

Claims (7)

An aluminum alloy part whose surface is covered with an opening of a hole having a number average inner diameter of 10 to 80 nm formed by an anodic oxidation method ;
A resin composition component comprising 70 to 99% by weight of polyphenylene sulfide and 1 to 30% by weight of a polyolefin resin fixed to the aluminum alloy component by injection molding, and a part of the resin composition component is A composite that has penetrated into the holes . The complex according to claim 1,
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. A composite characterized by that. The complex of claim 2,
The polyolefin resin is at least one selected from ethylene-acrylic acid ester-maleic anhydride terpolymer and ethylene-glycidyl methacrylate binary copolymer. In the complex according to claim 2 or 3,
The resin composition component may further include 0.1 to 6 parts by weight of a polyfunctional isocyanate compound with respect to 100 parts by weight of the total resin content including 70 to 99% by weight of the polyphenylene sulfide and 1 to 30% by weight of the polyolefin resin. Or the composite_body | complex characterized by mix | blending 1-25 weight part of epoxy resins. The composite according to claim 4,
The resin composition part is formed by further blending 1 to 200 parts by weight of a filler with respect to 100 parts by weight of the total resin content including 70 to 99% by weight of the polyphenylene sulfide and 1 to 30% by weight of the polyolefin resin. A composite characterized by that. The composite according to claim 5,
The composite is characterized in that the filler is at least one selected from glass fiber, carbon fiber, aramid fiber, calcium carbonate, magnesium carbonate, silica, talc, clay, and glass powder. A number average inner diameter 10~80nm pore opening surface treatment of the anodic oxidized to covered aluminum alloy part in section step, inserts were polyphenylene sulfide 70 an aluminum alloy component surface treatment step is made in an injection mold A joining step in which a resin composition having a resin composition containing 99% by weight and 1% to 30% by weight of a polyolefin-based resin is injected to be molded as a resin composition part and injection-bonded to the aluminum alloy part;
A method for producing a composite comprising:

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