JP5124129B2 - Aluminum alloy-resin composite and method for producing the same - Google Patents

Description

  The present invention relates to a composite of an aluminum alloy and a high-strength resin used for a housing of an electronic device, a housing of a home appliance, a structural component, a mechanical component, and the like, and a method for manufacturing the same. More specifically, it relates to a structure in which a light metal alloy shape and thermoplastic synthetic resin made by various types of machining are integrated, and various electronic equipment, home appliances, medical equipment, structural parts for vehicles, on-vehicle supplies, and building materials. The present invention relates to a composite of light metal alloy and resin used for parts, other structural parts, exterior parts, and the like, and a method for producing the same.

  Technology that integrates dissimilar metals and synthetic resins with adhesives is required by a wide range of industries and technical fields such as automobiles, home appliances, and industrial equipment. For this reason, many adhesives have been developed. ing. Among these, very good adhesives have been proposed. Adhesives that function at room temperature or when heated are used for joining metal and synthetic resin together, and this method is now a common technique.

  However, it has been studied conventionally whether there is a more rational joining method without using an adhesive. There has been proposed a method for integrating a high-strength engineering resin without using an adhesive with respect to magnesium, aluminum and light metal alloys such as aluminum, and iron alloys such as stainless steel. Among these, for example, a method of inserting an aluminum alloy part into an injection mold and injecting a resin component to the aluminum mold (hereinafter referred to as “injection bonding”) is currently made of aluminum alloy and polybutylene terephthalate. A combination of a resin (hereinafter referred to as “PBT”) and a polyphenylene sulfide resin (hereinafter referred to as “PPS”) has just been put into practical use by the present applicant.

  The present invention is the first invention as far as the present inventors know that the combination of this metal and the synthetic resin is capable of injection joining. The present inventors immerse an aluminum alloy shaped article in an aqueous solution of a water-soluble amine compound, wash it with water, dry it, insert it into an injection mold, and then add a thermoplastic synthetic resin composition mainly composed of PBT or the like. It has been found that the bonding force (also referred to as “fixing force” in the present invention) increases specifically when injected (see Patent Documents 1, 2, and 3). After that, it was found that the preferred surface treatment can be stably performed by gaining experience in the liquid treatment to the metal treatment method, and as a result, the polyamide resin can be injection-bonded to the aluminum alloy. This invention was proposed in Japanese Patent Application No. 2006-111137.

  The present inventors have continued to develop whether there is an appropriate resin composition for injection joining with respect to the polyamide-based resin to be used. As a result, the present invention has been clarified that a characteristic polyamide resin compound is suitable for injection joining.

JP 2003-200453 A JP 2004-268936 A WO2004 / 041532

  As described above, an aluminum alloy shape covered with ultra-fine recesses is prepared, inserted into an injection mold, and a polyamide resin composition is injected there. It has been found that an integrated object can be obtained. We tried to increase the bonding strength between the resin part and the aluminum alloy part by using polyamide resin compound and other devices.

The present invention has been made based on the technical background as described above, and achieves the following object.
An object of the present invention is to provide a composite of an aluminum alloy and a resin and a method for producing the same, in which the bonding strength between the aluminum alloy and the thermoplastic synthetic resin composition whose main component is a polyamide resin is increased.

  Another object of the present invention is to provide a composite of an aluminum alloy and a resin, and a method for producing the same, which has high productivity when the aluminum alloy and the main component are joined to a thermoplastic synthetic resin composition of polyamide resin. is there.

In order to achieve the above object, the present invention employs the following means.
The metal resin composite of the present invention 1 is covered with a concave portion having a number average inner diameter of 10 to 80 nm by observation with an electron microscope through a step of immersing in one or more aqueous solutions selected from ammonia, hydrazine, and a water-soluble amine compound. With broken aluminum alloy parts,
The fixed aluminum alloy part the invaded by injection molding in the recess, the auxiliary component is composed of a thermoplastic synthetic resin composition component of the resin component composition is an impact improver main component a polyamide resin.

The metal resin composite of the present invention 2 is covered with a recess having a number average inner diameter of 10 to 80 nm by electron microscope observation through a step of immersing in one or more aqueous solutions selected from ammonia, hydrazine, and a water-soluble amine compound. With broken aluminum alloy parts,
Intruded and fixed in the concave portion of the aluminum alloy part by injection molding, and a simple mixture of an aliphatic polyamide resin and an aromatic polyamide resin, and / or the aliphatic polyamide resin and the aromatic polyamide resin are molecules It is composed of a thermoplastic synthetic resin composition part having a main resin component composition.

The metal resin composite of the present invention 3 is the present invention 2,
The resin component composition is a terpolymer comprising a hexamethylene adipamide component, a hexamethylene isophthalamide component, and a caproamide component.

The metal resin composite of the present invention 4 is an aluminum alloy part whose surface is covered with a recess having a number average inner diameter of 10 to 80 nm by electron microscope observation through a step of immersing in an aqueous solution of ammonia, hydrazine, or a water-soluble amine compound,
Thermoplastic synthetic resin composition which is a resin component composition mainly composed of two or more kinds of aromatic polyamides selected from the group of different kinds of aromatic polyamides, which are fixed to the aluminum alloy parts by injection molding. It consists of material parts.

The metal resin composite of the present invention 5 is an anodized aluminum alloy part covered with a surface having holes having a number average inner diameter of 10 to 80 nm as measured by electron microscope observation,
The fixed aluminum alloy part the invaded by injection molding into the hole of one aliphatic polyamide resin and an aromatic polyamide resin is simply mixed, or, the aromatic polyamide resin and the aliphatic polyamide resin is molecularly It is composed of a thermoplastic synthetic resin composition part in which the bonded one is the main resin composition.

The metal resin composite of the present invention 6 is formed by an anodic oxidation method, and an aluminum alloy part covered with a surface having a hole having a number average inner diameter of 10 to 80 nm as measured by an electron microscope,
Thermoplastic synthetic resin composition which is a resin component composition mainly composed of two or more kinds of aromatic polyamides selected from the group of different aromatic polyamides, which are intruded and fixed in the holes of the aluminum alloy parts by injection molding. It consists of material parts.

The metal resin composite of the present invention 7 is the metal resin composite of the present invention 2 or 5,
The aliphatic polyamide resin is nylon 6 or nylon 66, and the aromatic polyamide resin is an aromatic nylon synthesized from phthalic acids and an aliphatic diamine.

The metal resin composite of the present invention 8 is the metal resin composite of the present invention 4 or 6,
The group of different kinds of aromatic polyamides is a group of polyamides from phthalic acid and hexamethylene diamine, polyamides from isophthalic acid and hexamethylene diamine, and polyamides from terephthalic acid and hexamethylene diamine.

The metal resin composite of the present invention 9 is the metal resin composite of the present invention 1-8,
The thermoplastic synthetic resin composition is characterized in that 1 to 200 parts by mass of a filler is contained with respect to 100 parts by mass of the resin composition.

The metal resin composite of the present invention 10 is the metal resin composite of the present invention 9,
The filler is one or more fillers selected from glass fiber, carbon fiber, aramid fiber, calcium carbonate, magnesium carbonate, silica, talc, clay, and glass powder.

The method for producing a metal resin composite of the present invention 11 is one or more selected from ammonia, hydrazine, and a water-soluble amine for forming the surface of an aluminum alloy part covered with a recess having a number average inner diameter of 10 to 80 nm. An immersion treatment step in an aqueous solution of
The aluminum alloy part subjected to the dipping process is inserted into an injection mold, and a thermoplastic synthetic resin composition having a resin composition in which the main component is a polyamide resin and the subcomponent is an impact resistance improving material is injected. Forming a resin composition part and intruding the resin composition part into the concave portion of the aluminum alloy part.

The method for producing a metal resin composite of the present invention 12 is one or more selected from ammonia, hydrazine, and a water-soluble amine for forming the surface of an aluminum alloy part covered with a recess having a number average inner diameter of 10 to 80 nm. An immersion treatment step in an aqueous solution of
The aluminum alloy part subjected to the immersion treatment process is inserted into an injection mold, and a terpolymer comprising a hexamethylene adipamide component, a hexamethylene isophthalamide component and a caproamide component is the main resin component composition And injecting the thermoplastic synthetic resin composition as a resin composition part and intruding the resin composition part into the recess of the aluminum alloy part.

The method for producing a metal resin composite of the present invention 13 is one or more selected from ammonia, hydrazine, and a water-soluble amine for forming the surface of an aluminum alloy part covered with a recess having a number average inner diameter of 10 to 80 nm. An immersion treatment step in an aqueous solution of
The aluminum alloy part subjected to the immersion treatment step is inserted into an injection mold, polyamide from phthalic acid and hexamethylene diamine, polyamide from isophthalic acid and hexamethylene diamine, and from terephthalic acid and hexamethylene diamine. A thermoplastic synthetic resin composition having a resin composition composed mainly of two or more kinds of polyamides selected from the group of polyamides is injected and molded as a resin composition part, and this is formed in the recess of the aluminum alloy part. And intruding and joining.

Production method of the present invention 1 4 metal resin composite, the anodic oxidation process a number average inner diameter of the opening is to covered aluminum alloy part surface with holes is 10 to 80 nm,
The aluminum alloy part subjected to the anodic oxidation process is inserted into an injection mold, polyamide from phthalic acid and hexamethylene diamine, polyamide from isophthalic acid and hexamethylene diamine, and from terephthalic acid and hexamethylene diamine. A thermoplastic synthetic resin composition having a resin composition composed mainly of two or more kinds of polyamides selected from the group of polyamides is injected and molded as a resin composition part, and this is molded into the hole of the aluminum alloy part. And intruding and joining.

Hereafter, each element which comprises each invention mentioned above is demonstrated in detail.
[Aluminum alloy parts]
The material of the aluminum alloy part used in the present invention is an aluminum alloy. Aluminum alloy parts are made from aluminum alloy materials by machining. Aluminum alloys are roughly classified into wrought alloys and foundry alloys. On the other hand, it can be broadly classified into a non-heat treatment type alloy that increases hardness and tensile strength only by work hardening and a heat treatment alloy that improves mechanical properties by heat treatment. Examples of the aluminum alloy belonging to the non-heat treatment type alloy include an Al—Mg alloy, an Al—Mn alloy, and an Al—Mg—Mn alloy. Examples of the aluminum alloy belonging to the heat treatment type alloy include an Al—Cu—Mg alloy, an Al—Zn—Mg alloy, an Al—Mg—Si alloy, and a heat-resistant aluminum alloy. Casting alloys are further divided into molds, sand molds, shell castings, die castings, and the like.

  Thus, many types of aluminum alloys used in the present invention are known, and are standardized as A1000 to A7000 series of JIS (Japanese Industrial Standards). In principle, these known aluminum alloys are used for the aluminum alloy parts used in the present invention. As an aluminum alloy part used in the present invention, as a raw material shape before processing, an intermediate aluminum material such as a plate-like product, a rod-like product, or a pipe-like extruded product, or a cast product is used. To obtain aluminum alloy parts from these materials, machining such as cutting, cutting, bending, drawing, etc., that is, machining such as sawing, milling, electric discharge machining, drilling, pressing, grinding, polishing, etc. Then, it is processed into a desired shape and structure. By these machining, it is processed into a metal shape that constitutes a part of the part, and this metal shape becomes an insert product in the injection molding, and constitutes a part of the shape and structure necessary for the part.

  Aluminum alloy parts that have been processed into the required shape and structure must have no thick oxide film or hydroxide film formed on the surface to be bonded. Obviously, it is necessary to remove the surface by polishing, blasting or the like. Dirts other than rust, that is, oil layers on the surface attached in the metal processing step, finger grease attached on carrying, etc. are removed in the degreasing step described below.

[Pretreatment process]
The surface of aluminum alloy parts has processing oil, finger grease, chips, etc., and fine oil droplets and dirt are attached after processing by sandblasting etc., so it should be degreased and cleaned. It is. Usually, the processed aluminum alloy part is put into a known solvent degreasing machine for degreasing treatment. Alternatively, when the adhesion of the oil agent is light, a degreasing treatment is performed first by immersing in an aqueous solution in which a commercially available degreasing agent for aluminum alloys, which is a conventional method, is dissolved, and washing with water for several minutes. Further, in order to chemically scrape the surface to obtain a clean aluminum surface, a thin caustic soda aqueous solution tank having a concentration of several percent at about 40 ° C. is prepared, and the aluminum alloy component is immersed in the caustic soda aqueous solution tank.

  Further, an acid aqueous solution such as a hydrochloric acid aqueous solution having a concentration of several percent, a nitric acid aqueous solution, or an aqueous hydrogen difluoride ammonium solution is prepared at about 40 ° C. in another tank. The acid solution to be used differs depending on the type of aluminum alloy, but different aluminum alloys can be handled by preparing several types of these solutions. The aluminum alloy shaped article immersed in an aqueous caustic soda solution and washed with water is immersed in these acid solutions and further washed with water to finish the pretreatment step.

[Immersion treatment of water-soluble amine compound in aqueous solution]
The aluminum alloy component that has been subjected to the pretreatment step described above is immersed in an aqueous solution of a water-soluble amine compound. In this immersion treatment, the surface of the aluminum alloy component is etched to form ultra-fine irregularities by being immersed in one or more aqueous solutions selected from ammonia, hydrazine, and a water-soluble amine compound. Examples of the water-soluble amine compound include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, ethanolamine, allylamine, ethanolamine, diethanolamine, triethanolamine, and aniline.

  These aqueous solutions are preferably adjusted to a weak basicity of PH 9-10, and the aluminum alloy immersed for an appropriate time is etched into ultra-fine irregularities and covered with irregularities having a diameter of 10 to 100 nm when observed with an electron microscope. It will be a situation. In the case of using an aqueous solution of a water-soluble amine or hydrazine, the aqueous solution having a concentration of 1% to 30% can be used at normal temperature to 70 ° C. for 0.5 minutes to several tens of minutes. When ammonia water is used, it can be used at a concentration of about 20% and a dipping time of ten to several tens of minutes at room temperature. After immersion, wash with water and dry with warm air. The aluminum alloy is made such that the surface is covered with fine recesses having an average inner diameter of 10 to 80 nm as measured by electron microscope observation by the above-described immersion treatment, and details of the size of the recess inner diameter will be described. The number average inner diameter referred to in the present invention means that, for example, a 200 nm rectangular unit square is defined on the electron micrograph, and all the diameters of the recesses observed therein are measured on the photo. The total is divided by the number of measured recesses.

  This is a case where the inner diameter of the recess is less than 10 nm, but the surface is covered with such ultra-fine recesses despite a number of etching experiments with aqueous solutions of water-soluble amine compounds conducted by the present inventors. I couldn't find it. In the experiments conducted by the present inventors also in anodic oxidation described later, all bore opening portion inner diameters were 10 nm or more. In addition, even when observing the surface using a model of electron microscope (SEM type) with the highest level of resolution sold in Japan, the resolution below 5 nm is difficult to observe clearly due to the surrounding vibration. But there is. In short, it is presumed that the present invention can be applied even if the inner diameter of the concave portion or the opening inner diameter of the hole by anodization is less than 10 nm, but it has not been clearly confirmed at this stage. Therefore, the inventors of the present invention will explain the recesses of 10 nm or more that can be clearly observed with an electron microscope, and will be within the scope of the present invention.

  In addition, when a recess having a number average inner diameter of the recess exceeding 80 nm is formed by immersing the aluminum alloy part in an aqueous solution of a water-soluble amine compound, the adhesion strength of the manufactured metal resin composite of the present invention is the result. Explain why. That is, when an aluminum alloy part was immersed in these erodible aqueous solutions and the surface was eroded, the following was found from observations by the inventors using an electron microscope.

  In the case of A5052 (JIS standard) of the aluminum alloy with the clearest phenomenon, when the aqueous amine aqueous solution is adjusted to a weak basicity of about PH10 and immersed at a temperature of about 50 ° C., the inner diameter is 20 to 40 nm immediately. And the depth of the recess becomes the same level as the inner diameter in about 1 minute. When the immersion is further continued, the depth of the concave portion is corroded and deepened, and the edge portion which is the outer periphery forming the concave portion is also corroded by this corrosion, and the inner diameter of the concave portion is further increased on average.

  After immersing the A5052 piece for about 20 minutes, it was washed with water and dried, and when this surface was observed with an electron microscope, the inner diameter of the concave portion visible from the surface was as large as about 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 joining experiment with the polyamide-based resin used in the present invention conducted by the present inventors, the joining force with the average concave inner diameter of 80 nm as a boundary (also referred to as “fixing force” in the present invention). Suddenly decreased.

  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 an average inner diameter of 80 nm as a boundary. As the reason why the bonding force rapidly decreases as the recess diameter increases, the present inventors consider that the complicated shape in the recess described above is related.

  That is, the polyamide resin used in the present invention penetrates into an ultrafine recess formed on the metal side under molding conditions for injection molding, and the melted polyamide resin crystallizes after entering. In other words, the composition added to the polyamide resin, the size of the ultrafine recesses, the injection molding conditions, and the like are adjusted and set so that the infiltrated molten polyamide resin is crystallized.

  If the diameter and depth of the recess is ultrafine and it covers an infinite number of metal surfaces, the polyamide resin and the metal part crystallized after entering the recess will be supported by an infinite number of anchor effects, It is considered that a very strong bonding force is generated. 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 for the purpose of forming a fine recess having a diameter of several tens of nanometers on the surface of the aluminum alloy, if the immersion time is too long and the recess diameter exceeds 80 nm, a small recess hole is again formed in the recess as described above. In other words, a three-dimensionally complicated shape is formed such that the through holes are formed in multiple layers in various directions.

If such a deeply eroded aluminum alloy piece is cut vertically and its cross section is viewed, a layer having a shape as if a part having a depth of 100 to 200 nm from the surface is eaten away, so to speak, is a hole. Alternatively, a sponge-like layer in which the through holes communicate with each other is formed. In short, when etching is performed so that the diameter of the concave portion increases to a diameter of 80 nm, the surface layer of the aluminum alloy piece becomes like a sponge layer and the mechanical strength of the surface layer itself becomes weak. Further, when the surface is formed in a sponge layer shape, it is impossible for the injected resin to enter the innermost part of the space formed by complicated holes or through holes on the metal surface.
This is because crystallization and solidification will start before cooling to the end. The injected resin can bite into the surface of the sponge, but cannot go far. Therefore, if the aluminum alloy and the resin are integrated and then destroyed by applying a shearing force or a load in the direction of peeling the resin from the aluminium alloy, the resin portion that is weak to mechanical stress is not broken and the resin is filled first. The sponge layer on the surface of the non-aluminum alloy breaks. For this reason, high joining force cannot be shown.

[Aluminum alloy / anodizing treatment]
The case where the surface treatment is performed on the shaped aluminum alloy part by the anodic oxidation method will be described. Use a commercially available aluminum degreasing agent, degrease and wash with water to remove machining oils and oils, clean the surface with pretreatment such as alkaline etching, chemical polishing, etc. This is a method of forming an aluminum oxide layer having countless fine holes. The standard alkali etching method is a method in which a 10 to 20% strength aqueous caustic soda solution is brought to 50 to 90 ° C. and immersed in this for 10 seconds to several tens of seconds to dissolve the alloy surface. Usually, it is washed with water and then chemically polished. Chemical polishing is a method in which a high-concentration aqueous solution of an acid such as nitric acid, phosphoric acid, sulfuric acid or the like is set at 80 to 100 ° C. and is immersed therein for several seconds to tens of seconds.

  The surface of the aluminum alloy is shaved by several μm or more in both steps. Subsequently, anodic oxidation is well known, and aluminum is oxidized by applying an electric current in an aqueous solution of sulfuric acid having a concentration of about 10% with an aluminum alloy as an anode at 10 to 20 ° C., and the surface is strong and hard. This is a method of covering with an aluminum layer. If the surface is covered with non-conducting aluminum oxide, electricity will not pass and the oxidation should end there, but in reality, the energization continues and the thickness of the aluminum oxide layer reaches 20 μm. This is because innumerable holes having a diameter of 10 to several tens of nm are opened on the surface of the aluminum oxide layer, and current is continuously passed through the holes. This can also be explained by the fact that when the anodic oxide of aluminum or aluminum alloy having innumerable pores is immersed in an aqueous solution in which a dye is dissolved, the dye enters the pores and is dyed.

  This is further processed and sealed to prevent the dye from escaping, which is dyed alumite. The portion where the recess and the hole are opened is not a metal, but the present invention is naturally effective from the viewpoint of the principle as long as the metal oxide is stronger and harder than the metal. That is, in the present invention, dyeing and sealing are not performed. Also, when the anodic oxidation is completed and the washed water is dried, it is performed at a low temperature. If the temperature at the time of drying is raised too much, aluminum oxide in the opening may react with water to form a hydroxide, deforming the opening and sealing the hole. The drying temperature is preferably 60 to 70 ° C.

[Thermoplastic synthetic resin composition / resin composition / part 1]
Hereinafter, the thermoplastic synthetic resin composition to be used will be described. The polyamide resin used in the present invention is a polyamide mainly composed of amino acids, lactams, or diamines and dicarboxylic acids. Representative examples of the main constituents include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine , Hexamethylenediamine, 1,5-pentanediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3, 5,5-trimethylcyclohexa , Bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, etc. , Cycloaliphatic, aromatic diamine, and adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid Examples include aliphatic, alicyclic and aromatic dicarboxylic acids such as acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid and hexahydroisophthalic acid. Nylon homopolymers or copolymers derived from It can be used in the form of mixtures.

  In the present invention, a particularly useful polyamide resin is a polyamide resin having a melting point of 150 ° C. or more and excellent in heat resistance and strength. Specific examples include polycaproamide (nylon 6), polyhexamethylene adipamide. (Nylon 66), polypentamethylene adipamide (nylon 56), polytetramethylene adipamide (nylon 46), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecane Amide (nylon 11), polydodecanamide (nylon 12), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), poly Hexamethylene adipamide / poly Xamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), polyhexa Methylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I / 6) ), Polymetaxylylene adipamide (nylon MXD6), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (Niro) 6T / M5T), poly nonamethylene terephthalamide (nylon 9T), and mixtures thereof.

  As the polyamide resin, both aliphatic nylon and aromatic nylon can be used. Nylon 66 and nylon 6 are preferred as the aliphatic nylon. The aromatic nylon is preferably synthesized from phthalic acids and hexamethylenediamine. Furthermore, it is also practically suitable to use these polyamide resins as a copolymer / mixture according to necessary properties such as moldability and compatibility. The thermoplastic synthetic resin compositions used for injection joining were classified into three types. One of them is to use a compound containing a polyamide resin as a main component and an impact resistance improving material as a subsidiary component. It is preferable that 70 to 95 parts by mass of the polyamide resin and 5 to 20 parts by mass of the impact resistance improving material are included with the total resin content being 100 parts by mass. By using the impact resistance improving material, the bonding strength necessary for the metal resin composite can be obtained. The impact resistance improver refers to a component that improves impact resistance when alloyed with a polyamide resin, and examples thereof include (co) polymers obtained by polymerizing olefinic compounds and / or conjugated diene compounds. It is done.

  Examples of the (co) polymer include an ethylene copolymer, a conjugated diene polymer, and a conjugated diene-aromatic vinyl hydrocarbon copolymer. Here, the ethylene-based copolymer refers to a copolymer of ethylene and another monomer and a multi-component copolymer, and the other monomer copolymerized with ethylene has 3 or more carbon atoms. It can be selected from α-olefins, non-conjugated dienes, vinyl acetate, vinyl alcohol, α, β-unsaturated carboxylic acids and derivatives thereof.

  Examples of the α-olefin having 3 or more carbon atoms include propylene, butene-1, pentene-1, 3-methylpentene-1, octene-1, and the like, and propylene and butene-1 can be preferably used. Non-conjugated dienes include 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-norbornene, 5-propenyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-crotyl-2 -Norbornene compounds such as norbornene, 5- (2-methyl-2-butenyl) -2-norbornene, 5- (2-methyl-2-butenyl) -2-norbornene, 5-methyl-5-vinylnorbornene, dicyclo Examples include pentadiene, methyltetrahydroindene, 4,7,8,9-tetrahydroindene, 1,5-cyclooctadiene, 1,4-hexadiene, isoprene, 6-methyl-1,5-heptadiene, 11-tridecadiene, and the like. , Preferably 5-methylidene-2-norbornene, 5-ethylidene-2-no Bornene, dicyclopentadiene, 1,4-hexadiene and the like. Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, butenedicarboxylic acid, and the derivatives include alkyl esters, Examples include aryl esters, glycidyl esters, acid anhydrides, and imides.

  The conjugated diene polymer is a polymer containing at least one conjugated diene as a constituent component. For example, a homopolymer such as 1,3-butadiene, 1,3-butadiene, isoprene (2-methyl- 1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and copolymers of one or more monomers selected from 1,3-pentadiene. Those in which some or all of the unsaturated bonds of these polymers are reduced by hydrogenation can also be preferably used.

  The conjugated diene-aromatic vinyl hydrocarbon copolymer is a block copolymer or a random copolymer composed of a conjugated diene and an aromatic vinyl hydrocarbon, and examples of the conjugated diene constituting the conjugated diene include And 1,3-butadiene and isoprene are particularly preferable. Examples of aromatic vinyl hydrocarbons include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, 1,3-dimethyl styrene, vinyl naphthalene, and among them, styrene is preferably used. Moreover, what reduced part or all of unsaturated bonds other than double bonds other than an aromatic ring of a conjugated diene-aromatic vinyl hydrocarbon type copolymer by hydrogenation can also be used preferably.

  Further, in order to finely control the dispersed particle size of the impact resistance improving material in the resin composition, various unsaturated carboxylic acids and / or derivatives or vinyl monomers are further subjected to graft reaction or copolymerization. The obtained (co) polymer can also be preferably used. The amount of unsaturated carboxylic acid and / or its derivative and vinyl monomer which are graft-reacted or copolymerized with respect to the impact resistance improving material is preferably 0.01 to 20.00% by mass. Examples of the unsaturated carboxylic acid used in the graft reaction or copolymerization include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and butenedicarboxylic acid.

  In addition, examples of the derivatives include alkyl esters, glycidyl esters, esters having a di- or tri-alkoxysilyl group, acid anhydrides, imides, and the like. Among them, glycidyl ester, di- or tri-alkoxysilyl groups may be used. The unsaturated carboxylic acid ester, acid anhydride, and imide are preferable.

  Preferred examples of unsaturated carboxylic acids or derivatives thereof include maleic acid, fumaric acid, glycidyl acrylate, glycidyl methacrylate, diglycidyl itaconate, diglycidyl citraconic acid, diglycidyl butene dicarboxylic acid, butene dicarboxylic acid mono Glycidyl ester, maleic anhydride, itaconic anhydride, citraconic anhydride, maleic imide, itaconic imide, citraconic imide, etc., and particularly glycidyl methacrylate, maleic anhydride, itaconic anhydride, maleic imide can be preferably used. .

  Examples of vinyl monomers include aromatic vinyl compounds such as styrene, vinyl cyanide compounds such as acrylonitrile, vinylsilane compounds such as vinyltrimethoxysilane, and these unsaturated carboxylic acids or their derivatives or Two or more vinyl monomers may be used in combination. In addition, about the method of grafting these unsaturated carboxylic acid, its derivative (s), or a vinyl monomer, a well-known method can be used.

  Moreover, a polyamide-type elastomer and a polyester-type elastomer can be used. Two or more of these impact resistance improving materials can be used in combination. Specific examples of such impact resistance improving materials include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2. -Norbornene copolymer, unhydrogenated or hydrogenated styrene / isoprene / styrene triblock copolymer, unhydrogenated or hydrogenated styrene / butadiene / styrene triblock copolymer, ethylene / methacrylic acid copolymer, and these A part or all of the carboxylic acid moiety in the copolymer is a salt with sodium, lithium, potassium, zinc, calcium, ethylene / methyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / Ethyl methacrylate copolymer, ethylene / ethyl acrylate-g-maleic anhydride copolymer ("G" represents a graft, the same applies hereinafter), ethylene / methyl methacrylate-g-maleic anhydride copolymer, ethylene / ethyl acrylate-g-maleimide copolymer, ethylene / ethyl acrylate-g-N -Phenylmaleimide copolymers, partially saponified products of these copolymers, ethylene / glycidyl methacrylate copolymers, ethylene / vinyl acetate / glycidyl methacrylate copolymers, ethylene / methyl methacrylate / glycidyl methacrylate copolymers, ethylene / Glycidyl acrylate copolymer, ethylene / vinyl acetate / glycidyl acrylate copolymer, ethylene / glycidyl ether copolymer, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g-maleic anhydride copolymer Polymer, ethylene Propylene / 1,4-hexadiene-g-maleic anhydride copolymer, ethylene / propylene / dicyclopentadiene-g-maleic anhydride copolymer, ethylene / propylene / 2,5-norbornadiene-g-maleic anhydride copolymer Polymer, ethylene / propylene-gN-phenylmaleimide copolymer, ethylene / butene-1-gN-phenylmaleimide copolymer, hydrogenated styrene / butadiene / styrene-g-maleic anhydride copolymer, Hydrogenated styrene / isoprene / styrene-g-maleic anhydride copolymer, ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene / propylene / 1,4-hexadiene-g-glycidyl methacrylate copolymer , Ethylene / propylene / dicyclopentadiene-g-glycidyl methacrylate copolymer Polymer, hydrogenated styrene / butadiene / styrene-g-glycidyl methacrylate copolymer, nylon 12 / polytetramethylene glycol copolymer, nylon 12 / polytrimethylene glycol copolymer, polybutylene terephthalate / polytetramethylene glycol copolymer Examples thereof include a polymer and a polybutylene terephthalate / polytrimethyl glycol copolymer.

  Among these, ethylene / methacrylic acid copolymers, and those in which part or all of the carboxylic acid portion of these copolymers is made into a salt with sodium, lithium, potassium, zinc, calcium, ethylene / propylene-g-anhydrous Maleic acid copolymers, ethylene / butene-1-g-maleic anhydride copolymers, hydrogenated styrene / butadiene / styrene-g-maleic anhydride copolymers are more preferred, ethylene / methacrylic acid copolymers and these What made a part or all of the carboxylic acid part in the copolymer a salt with sodium, lithium, potassium, zinc, calcium, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1- A g-maleic anhydride copolymer is particularly preferred.

  The addition of a polyfunctional isocyanate compound or an epoxy resin in addition to the impact resistance improver often increases the injection joining force, and these are considered to be compatible with each other. That is, it is preferable that 0.1 to 6.0 parts by mass of a polyfunctional isocyanate compound and / or 1 to 25 parts by mass of an epoxy resin is further blended with respect to 100 parts by mass of the total resin content.

  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, and bis (4-isocyanatophenyl) sulfone.

  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 so as to be inactive at room temperature. The type of the polyfunctional block type isocyanate compound is not particularly specified. Generally, the isocyanate group is masked by a blocking agent such as alcohols, phenols, ε-caprolactam, oximes, and active methylene compounds. Has a structured. As this polyfunctional block type isocyanate, for example, “Takenate (Tokyo, Japan; manufactured by Mitsui Chemicals Polyurethane Co., Ltd.)” and the like can be mentioned.

  As the 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 (manufactured by Japan Epoxy Resin Co., Ltd.)” or the like Examples of the cresol novolac type epoxy resin include “Epiclon (Tokyo, Japan; manufactured by Dainippon Ink & Chemicals, Inc.)” and the like.

[Thermoplastic synthetic resin composition / resin composition / part 2]
As the polyamide resin, when the main resin component composition is a simple mixture of an aliphatic polyamide resin and an aromatic polyamide resin, the total amount of the resin is 100 parts by mass, the aliphatic polyamide resin is 10 to 90 parts by mass, The aromatic polyamide resin is preferably 90 to 10 parts by mass. More preferably, the aliphatic polyamide resin is 70 to 90 parts by mass, and the aromatic polyamide resin is 30 to 10 parts by mass. Although both have high crystallinity, it is considered that the entire crystallization speed is reduced by mixing foreign substances. As aliphatic polyamide resins, polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polypentamethylene adipamide (nylon 56), polytetramethylene adipamide (nylon 46), polyhexamethylene Examples include sebacamide (nylon 610), polyhexamethylene dodecane (nylon 612), polyundecanamide (nylon 11), polydodecanamide (nylon 12), and mixtures thereof.

  As aromatic polyamide resin, aromatic nylon synthesized from isophthalic acid and hexamethylenediamine (nylon 6I), aromatic nylon synthesized from terephthalic acid and hexamethylenediamine (nylon 6T), polymetaxylylene adipamide (nylon MXD6) , Polynonamethylene terephthalamide (nylon 9T), and mixtures thereof. These aliphatic polyamide resins and aromatic polyamide resins can be mixed and melt-kneaded for use in the above ratio, or pellets made of the respective resins can be dry blended.

  In the case where the main composition of the resin is a composition in which an aliphatic polyamide resin and an aromatic polyamide resin are molecularly bonded, a block polymer of an aliphatic polyamide resin component and an aromatic polyamide resin component, generally copolymerized nylon ( Copolymers) are used. As the aliphatic polyamide resin component to be copolymerized, a component comprising the above aliphatic polyamide resin can be used, preferably nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, nylon 12. More preferably, nylon 6 and nylon 66 are used. As the aromatic polyamide resin component to be copolymerized, a component comprising the above aromatic polyamide resin can be used.

  Preferred copolymer nylons include polycaproamide / polyhexamethylene isophthalamide copolymer (nylon 6 / 6I), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexa Methylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), polyhexa Methylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene adipamide / polyhexame Isophthalamide / polycaproamide copolymers (nylon 66 / 6I / 6) and the like.

  A preferred copolymer nylon contains a 6I nylon component, and particularly preferred copolymer nylons include a hexamethylene adipamide component (nylon 66 component), a hexamethylene isophthalamide component (nylon 6I component), and a caproamide component ( Nylon 6 component) is a terpolymer (nylon 66 / 6I / 6 resin) that polymerizes equimolar salts of hexamethylenediamine and adipic acid, equimolar salts of hexamethylenediamine and isophthalic acid, and ε-caprolactam Obtained by heating and polymerizing in a can. The copolymerization ratio is the ratio of the blended raw materials. The preferred copolymerization ratio of each repeating structural unit is 65 to 90% by mass of nylon 66 component, 5 to 30% by mass of nylon 6I component, 1 to 14% by mass of nylon 6 component, more preferably 2 to 12% by mass. It is preferable that the nylon 6I component / nylon 6 component copolymerization ratio of 1.0 or more is simultaneously satisfied. These copolymerization ratios are achieved by adjusting the ratio of the raw materials when producing the copolymer.

  Further, a terpolymer (nylon 66 / 6T) comprising a hexamethylene adipamide component (nylon 66 component), a hexamethylene terephthalamide component (nylon 6T component), and a hexamethylene isophthalamide component (nylon 6I component). / 6I resin) can be preferably used, and an equimolar salt of hexamethylene diamine and adipic acid, an equimolar salt of hexamethylene diamine and terephthalic acid, and an equimolar salt of hexamethylene diamine and isophthalic acid in a polymerization can. Obtained by heating and polymerization. The copolymerization ratio is the ratio of the blended raw materials. The copolymerization ratio of each repeating structural unit is preferably 5 to 15% by mass for the nylon 66 component, 55 to 65% by mass for the nylon 6T component, and 20 to 30% by mass for the nylon 6I component.

  Further, a terpolymer (nylon 6 / 6T / 6I resin) comprising a caproamide component (nylon 6 component), a hexamethylene terephthalamide component (nylon 6T component), and a hexamethylene isophthalamide component (nylon 6I component). The equimolar salt of ε-caprolactam and benzoic acid, the equimolar salt of hexamethylenediamine and terephthalic acid, and the equimolar salt of hexamethylenediamine and isophthalic acid are heated and polymerized in a polymerization vessel. Can be obtained. The copolymerization ratio is the ratio of the blended raw materials. The copolymerization ratio of each repeating structural unit is preferably 5 to 15% by mass for the nylon 6 component, 55 to 65% by mass for the nylon 6T component, and 20 to 30% by mass for the nylon 6I component.

  By using the copolymer nylon having such a copolymerization ratio, it is possible to obtain solidification characteristics suitable for adhesion to Al without impairing mechanical characteristics and heat resistance characteristics. Nylon 6 is preferably 1 to 10 parts by mass, and more preferably 3 to 8 parts by mass, and can suppress deterioration of mechanical properties during moisture absorption. Furthermore, by setting the copolymerization ratio of nylon 6I and nylon 6 to 1.0 or more, it is possible to suppress deterioration of mechanical properties during moisture absorption. Further, the copolymer nylon used in the present invention preferably has a viscosity number value measured according to ISO 307 of 70 to 130 ml / g, more preferably 75 to 110 ml / g. By using copolymer nylon in this range, a thermoplastic synthetic resin composition suitable for the present invention having good adhesion to aluminum can be obtained without impairing mechanical properties.

[Thermoplastic synthetic resin composition / resin composition / part 3]
Furthermore, in this invention, the thermoplastic synthetic resin composition of the resin part composition which has as a main component 2 or more types of aromatic polyamide selected from the group of a different kind of aromatic polyamide resin can be used. In this case, the two or more kinds of aromatic polyamides may be simply mixed or molecularly bonded. When a simple mixture is used, two or more kinds of the above-mentioned aromatic polyamide resins can be the main component, preferably a polyamide resin from phthalic acid and hexamethylenediamine, isophthalic acid and hexamethylenediamine. 2 or more selected from the group consisting of polyamide resin (nylon 6T) from terephthalic acid and hexamethylene diamine, more preferably nylon 6T, nylon 6I, It is a combination.

  In this case, it is preferable that 10 to 90 parts by mass of nylon 6T and 10 to 90 parts by mass of nylon 6I are used, with the total resin content being 100 parts by mass. More preferably, nylon 6T is 50 to 80 parts by mass and nylon 6I is 20 to 50 parts by mass. By setting it as such a range, it can be set as the thermoplastic synthetic resin composition which has the outstanding heat-resistant characteristic and was suitable for adhesiveness with aluminum. Even when two or more kinds of aromatic polyamides are molecularly bonded, it is preferable to use copolymer nylon in the same ratio as in the case of simple mixing.

[Thermoplastic synthetic resin composition / filler]
In addition, the composite of the present invention has a resin content of 100 parts by mass for the purpose of adjusting the linear expansion coefficient difference between the aluminum alloy part and the resin composition part and improving the mechanical strength of the resin composition part. Furthermore, it is preferable that the resin composition part comprises 1 to 200 parts by mass of a filler, more preferably 10 to 150 parts by mass.

  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 fillers include calcium carbonate, mica, glass flakes, glass balloons, magnesium carbonate, silica, talc, clay, pulverized products of carbon fibers and aramid fibers.

Even when a filler is not included, a very strong force is required to firmly bond and remove the resin molding bonded to the metal. However, when the molded composite is subjected to a temperature cycle test, in a resin system that does not contain a filler, the adhesive strength is rapidly lowered by repeated cycles. There are two causes for this. One is that there is a large difference between the metal shape and the thermoplastic synthetic resin composition in terms of linear expansion coefficient. For example, the linear expansion coefficient of an aluminum alloy is the larger of metals, but is still much smaller than that of a thermoplastic synthetic resin. The presence of the filler lowers the linear expansion coefficient of the thermoplastic synthetic resin composition and approaches the linear expansion coefficient of the aluminum alloy, approximately 2.5 × 10 ⁻⁵ ° C. ⁻¹ .

If the type and content of the filler are selected, the linear expansion coefficient of the resin can be close to that of an aluminum alloy. For example, when 40 to 50% glass fiber is included in nylon 66, the linear expansion coefficient is 2 to 3 × 10 ^{−. Decrease} to ⁵ ° C ^-1 . The other is the relationship between the cooling shrinkage of the metal shape after insert molding and the molding shrinkage of the thermoplastic synthetic resin composition. Nylon 66 containing no filler has a molding shrinkage of 0.6 to 2.5%. On the other hand, if the aluminum alloy is cooled and contracted, for example, about 100 ° C. is cooled from the time of injection to room temperature, about 0.2% is much smaller than the molding shrinkage of the resin. If the resin shrinks over time after being released from the injection mold, internal distortion occurs at the interface, and the interface breaks with a slight impact and peels off. When 40 to 50% of glass fiber is mixed with nylon 66, the molding shrinkage decreases to about 0.4 to 0.6%. Even this is considerably larger than the shrinkage of the aluminum alloy, and even when joined, a large internal strain remains on the joint surface.

  Therefore, the inclusion of such a large amount of filler does not give a satisfactory degree of molding shrinkage. Therefore, it is first necessary as a design to perform injection joining of an aluminum alloy and a polyamide composition in such a way that large internal strain does not easily remain on the joint surfaces. However, there is a need for a method of specifically confirming whether the design result is worth using as a product. The method is surprisingly simple. That is, when the injection joint is left to stand for several days and then shows a sufficient strength to break, it can be said that the joint strength is better than the force to cause a fracture due to internal strain. Such an integrated product is heated (annealed) at 150 to 170 ° C. for about 1 hour within a few days after injection joining to soften the resin and eliminate internal strain. When the integrated strength after annealing is subjected to a destructive test and the expected strength is obtained, the design is successful, and the strength lasts long unless there is swelling due to water absorption of the polyamide and swelling of the resin part.

[Molding / Injection molding]
Prepare an injection mold, open the movable mold, insert the aluminum alloy shape material on the one side, close the movable mold, inject the thermoplastic synthetic resin composition described above, and open the movable mold It is a method of releasing. The injection conditions of this thermoplastic synthetic resin composition when molding will be described. The higher the mold temperature and injection temperature, the better results will be obtained, but it will not be raised excessively, and sufficient bonding effect will be exhibited under almost the same conditions as normal injection molding using the above thermoplastic synthetic resin composition it can. In order to increase the bonding force, it is rather effective to raise the mold temperature slightly compared to the case of molding only ordinary resin. According to the experience of the present inventors, when the mold temperature is 140 to 160 ° C., the bonding force is high and stable. Therefore, the injection mold should be made on the assumption that it is used at such a high temperature.

[Action]
ADVANTAGE OF THE INVENTION According to this invention, an aluminum alloy shape thing and a polyamide-type resin composition can be firmly adhere | attached by the method by the injection molding using an insert. The reason why this has become possible is that the metal shape is treated by various methods to form a shape in which the surface is covered with ultra-fine concave portions and hole openings, and a polyamide resin is used as a compound means. This is a specialization of the physical properties. By both of these measures, the metal alloy shaped product that has been surface-treated is inserted into an injection mold, and the polyamide resin composition is injected here so that the metal and the resin molded part can be joined. became. By using the present invention, it is considered useful for supplying parts and housings in various fields such as weight reduction of electronic devices and home electric appliances, weight reduction of in-vehicle devices and components, and so on.

  As described above in detail, if the present invention is used, the polyamide-based resin composition and the aluminum alloy shaped product can be strongly injection-bonded, and the obtained integrated product is not easily peeled off. Therefore, it is possible to make housings, parts, structures, and the like of various devices with many degrees of freedom in terms of shape, structure, and mechanical strength. The housing, parts, and structures manufactured by the present invention are useful for reducing the weight and simplifying the device manufacturing process.

Examples of the present invention will be described in detail below instead of experimental examples. The production method of the copolymerized polyamide (block polymer) used in the examples and the measurement method of the viscosity number are as follows.
[Reference Example 1 Production Method of Copolymerized Polyamide (Block Polymer)]
Raw materials such as equimolar salts of diamine and acid, which are raw materials of each copolymerized polyamide, are charged into the reactor at respective mass ratios, and the same amount of pure water as the total amount of the charged resin is added. After the replacement with ₂ , the heating was started while stirring, and the final attainment temperature was set to 270 ° C. while the internal pressure of the can was adjusted to 20 kg / cm ² at maximum. The polymer discharged into the water bath was pelletized with a strand cutter. The obtained pellets were treated in hot water at 95 ° C. for 20 hours to extract and remove unreacted monomers and low polymer. The pellet after extraction was dried at 80 ° C. for 50 hours or more.
[Reference Example 2 Method for Measuring Viscosity Number]
Viscosity number measurements with 96% sulfuric acid were performed according to ISO 307 standard method.

[Example 1]
A 1.6 mm thick A5052 aluminum alloy plate was purchased. A large number of rectangular pieces of 18 mm × 45 mm were cut. A hole with a diameter of 2 mmφ was made in the end of the aluminum alloy piece with a press. A copper wire with a vinyl chloride resin cover was prepared. The middle of the alloy piece was bent while passing the copper wire through 10 holes, and the 10 pieces could be hung while keeping the pieces from contacting each other. A tank containing 15% of an aluminum degreasing material “NE-6 (manufactured by Meltex Co., Ltd., Tokyo, Japan)” was prepared, and the liquid temperature was 75 ° C. It was immersed in this degreasing material aqueous solution for 5 minutes and washed with water. Subsequently, a 1% hydrochloric acid aqueous solution was prepared in another tank, and the liquid temperature was set to 40 ° C. The aluminum alloy piece just before was immersed here for 1 minute and washed with water.

  Subsequently, a 1% sodium hydroxide aqueous solution was prepared in another tank, and the liquid temperature was set to 40 ° C. Here, the alloy piece just before was immersed for 1 minute and washed with water. Subsequently, a 1% hydrochloric acid aqueous solution was prepared in another tank, and the liquid temperature was set to 40 ° C. The above alloy piece was dipped for 1 minute and recommended. Subsequently, the alloy piece was immersed in a 3.5% monohydric hydrazine aqueous solution at 60 ° C. for 1 minute, washed with water, and dried with a hot air dryer at 60 ° C. for 20 minutes. The aluminum alloy piece was removed from the copper wire and wrapped with aluminum foil, which was then sealed in a polyethylene bag. The next day, when observed with an electron microscope "S-4800 (Tokyo, Japan, manufactured by Hitachi, Ltd.)" at a magnification of 100,000, the entire surface is covered with a recess having a diameter of 20 to 40 nm and a number average inner diameter of 25 nm. It was confirmed.

  On the other hand, a block polymer comprising 77% by mass as a nylon 66 component from adipic acid and hexamethylene diamine, 17% by mass as a 6I nylon component and 6% by mass as a nylon 6 component from isophthalic acid and hexamethylene diamine. Synthesized by the method. The viscosity number of the obtained synthetic resin measured by the method described in Reference Example 2 is 85 ml / g, and the melt viscosity is the temperature at the flow tester “CFT-500 (Kyoto, Japan, Shimadzu Corporation)”. It was 380 poise under the conditions of 270 ° C. and a load of 98.1 N (10 kgf) In a twin-screw extruder “TEM-35B (manufactured by Toshiba Machine Co., Ltd.)”, glass fiber “RES03-TP91 (Nippon Sheet Glass Co., Ltd.) Was supplied from the side feeder so that the addition amount was 50% by mass, and a polyamide-based resin composition was obtained which was melt-kneaded and pelletized at a cylinder temperature of 280 ° C.

Two days after storing the aluminum alloy piece, the alloy piece was taken out, picked up with gloves so as not to adhere oil, etc., and inserted into an injection mold. The structure of the injection mold is shown in FIG. 1. In the figure, 1 is an aluminum alloy piece, 2 is a movable side mold plate, 3 is a fixed side mold plate, 4 is a cavity portion where resin is injected, 5 Indicates a pinpoint gate, and 6 indicates a joint surface. When injection joining is performed, an integrated product shown in FIG. 2 is obtained. In FIG. 2, 1 is an aluminum alloy piece (1.6 mm × 45.0 mm × 18.0 mm), 4 is a resin part (3 mm × 50 mm × 10 mm), 5 is a pinpoint gate, and 6 is a joint surface (5 mm × 10 mm). is there. The area of the joint surface was 0.5 cm ² . The mold was closed, and the nylon resin composition containing 50% glass fiber was injected to obtain an integrated product shown in FIG.

The injection temperature was 260 ° C and the mold temperature was 140 ° C. About 2 hours after injection joining, it was placed in a hot air dryer set at 150 ° C. for 1 hour and allowed to cool. Two days later, all ten samples were subjected to a tensile breaking test using a tensile tester. This test can measure the shear breaking force. As a result, the average shear breaking strength was 26.0 MPa (265 kgf / cm ² ).

[Comparative Example 1]
The experiment was carried out in exactly the same manner as in Example 1 except that “Amilan CM3001G45 (Tokyo, Japan, manufactured by Toray Industries, Inc.)”, which is nylon 66 containing 45% glass fiber, was used as the resin composition. The shear fracture strength of the obtained integrated product of the aluminum alloy piece and the nylon 66 resin was 18.9 MPa (193 kgf / cm ² ) on average, which was lower than that of Example 1.

[Example 2]
63% by mass of nylon 6 “CM1010 (manufactured by Toray Industries, Inc.)” and 7% by mass of an ionomer of ethylene-methacrylic acid copolymer “Himiran 1706 (manufactured by Mitsui DuPont Polychemical Co., Ltd., Japan)” were previously blended. After that, the glass fiber “RES03-TP91 (manufactured by Nippon Sheet Glass Co., Ltd.)” is added from the side feeder with a twin screw extruder “TEM-35 (Shizuoka, Japan, manufactured by Toshiba Machine Co., Ltd.)” and the addition amount is 30% by mass. While being supplied, a polyamide / elastomer resin composition was obtained by melt-kneading at a cylinder temperature of 250 ° C. and pelletizing. The obtained polyamide / elastomer compound resin composition was dried at 175 ° C. for 2 hours. An experiment was conducted in the same manner as in Example 1 except that this resin composition was used. When an integrated sample with an aluminum alloy piece was obtained, and a shear fracture strength was measured by a tensile fracture test, the average of 10 pieces was 24.6 MPa (251 kgf / cm ² ).

[Comparative Example 2]
The experiment was carried out in the same manner as in Example 2 except that “Amilan CM1011G30 (manufactured by Toray Industries, Inc.)”, which is nylon 6 containing 30% glass fiber, was used as the resin composition. The shear fracture strength of the obtained integrated body of aluminum alloy pieces and nylon 6 resin was 20.1 MPa (205 kgf / cm ² ) on average, which was significantly lower than that of Example 2.

[Example 3]
Nylon 66 composed of adipic acid and hexamethylene diamine 12% by mass, nylon 6T component composed of terephthalic acid and hexamethylene diamine 62% by mass, nylon 6I component composed of isophthalic acid and hexamethylene diamine 26% by mass The polymer was synthesized by the method of Reference Example 1. The viscosity of the resulting synthetic resin measured by the method described in Reference Example 2 is 85 ml / g, and the melt viscosity is a temperature of 300 ° C. under a flow tester “CFT-500 (manufactured by Shimadzu Corporation)”, load It was 360 poise under the condition of 10 kg. In the twin screw extruder “TEM-35B (manufactured by Toshiba Machine Co., Ltd.)”, the glass fiber “RES03-TP91 (Tokyo, Japan, manufactured by Nippon Sheet Glass Co., Ltd.)” is added by 30% by mass from the side feeder. Thus, a polyamide resin composition was obtained which was melt-kneaded at a cylinder temperature of 300 ° C. and pelletized.

An experiment was conducted in the same manner as in Example 1 except that this aromatic nylon resin composition was used and the injection temperature was 280 ° C. When an integrated sample with an aluminum alloy piece was obtained and a shear fracture strength was measured by a tensile fracture test, the average of 10 pieces was 25.5 MPa (260 kgf / cm ² ).

[Example 4]
A polymer comprising 70% by mass as a nylon 6T component comprising terephthalic acid and hexamethylenediamine and 30% by mass as a nylon 6I component comprising isophthalic acid and hexamethylenediamine was synthesized by the method of Reference Example 1. The viscosity of the resulting synthetic resin measured by the method described in Reference Example 2 was 90 ml / g, and the melt viscosity was a temperature of 300 ° C. under a flow tester “CFT-500 (manufactured by Shimadzu Corporation)”, load It was 380 poise under the condition of 10 kg. While feeding the glass fiber “RES03-TP91 (manufactured by Nippon Sheet Glass Co., Ltd.)” from the side feeder with a twin screw extruder “TEM-35B (manufactured by Toshiba Machine Co., Ltd.)”, the addition amount is 30% by mass. A polyamide resin composition that was melt-kneaded and pelletized at a cylinder temperature of 300 ° C. was obtained.

An experiment was performed in the same manner as in Example 1 except that this wholly aromatic nylon resin composition was used and the injection temperature was 290 ° C. When an integrated sample with an aluminum alloy piece was obtained, and a shear fracture strength was measured by a tensile fracture test, the average of 10 pieces was 24.0 MPa (245 kgf / cm ² ).

[Example 5]
A commercially available 1.6 mm thick A5052 aluminum alloy was 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 for aluminum alloy “NE-6 (manufactured by Meltex Co.)” into water in a tank, it is heated and dissolved at 75 ° C., and the aluminum alloy plate is immersed for 5 minutes, Washed well 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 pore 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 same aromatic nylon resin composition as that used in Example 3 was closed at the injection temperature of 280 ° C. with the mold closed. The mold temperature was 140 ° C., and 12 integrated composites shown in FIG. 2 were obtained. One day later, they were tensile tested. The average shear breaking force of 10 pieces was 25.5 MPa (260 kgf / cm ² ).

FIG. 1 is a cross-sectional view of an injection mold schematically showing the production of a composite of an aluminum alloy part and a thermoplastic synthetic resin composition part mainly composed of a polyamide resin. FIG. 2 is an external view of a single body schematically showing a composite of an aluminum alloy part and a thermoplastic synthetic resin composition part mainly composed of a polyamide resin.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Aluminum alloy component 2 ... Movable side template 3 ... Fixed side template 4 ... Thermoplastic synthetic resin composition component 5 ... Pinpoint gate 6 ... Joining surface 7 ... Composite

Claims (14)

An aluminum alloy part whose surface is covered with a recess having a number average inner diameter of 10 to 80 nm by electron microscope observation through a step of immersing in one or more aqueous solutions selected from ammonia, hydrazine, and a water-soluble amine compound;
A metal-resin composite comprising a thermoplastic synthetic resin composition part having a resin composition in which the main component is a polyamide resin and the subcomponent is an impact resistance improving material, which is intruded and fixed to the concave portion of the aluminum alloy part by injection molding. body. An aluminum alloy part whose surface is covered with a recess having a number average inner diameter of 10 to 80 nm by electron microscope observation through a step of immersing in one or more aqueous solutions selected from ammonia, hydrazine, and a water-soluble amine compound;
Intruded and fixed in the concave portion of the aluminum alloy part by injection molding, and a simple mixture of an aliphatic polyamide resin and an aromatic polyamide resin, and / or the aliphatic polyamide resin and the aromatic polyamide resin are molecules Resin composite body comprising a thermoplastic synthetic resin composition part whose main resin component is a structurally bonded one. In claim 2,
The resin component composition is a ternary copolymer composed of a hexamethylene adipamide component, a hexamethylene isophthalamide component, and a caproamide component. An aluminum alloy part whose surface is covered with a recess having a number average inner diameter of 10 to 80 nm by observation with an electron microscope after being immersed in an aqueous solution of ammonia, hydrazine, or a water-soluble amine compound;
The fixed by injection molding to the aluminum alloy part to penetrate into the recess, a thermoplastic synthetic resin composition is a resin fraction composition composed mainly of two or more aromatic polyamides selected from the aromatic group of the polyamide heterologous Metal-resin composite consisting of physical parts. An aluminum alloy part formed by anodization and covered with a surface having holes with a number average inner diameter of 10 to 80 nm as measured by electron microscope observation;
The fixed aluminum alloy part the invaded by injection molding into the hole of one aliphatic polyamide resin and an aromatic polyamide resin is simply mixed, or, the aromatic polyamide resin and the aliphatic polyamide resin is molecularly A metal-resin composite comprising a thermoplastic synthetic resin composition part in which the combined resin is the main resin component composition. An aluminum alloy part formed by anodization and covered with a surface having holes with a number average inner diameter of 10 to 80 nm as measured by electron microscope observation;
Thermoplastic synthetic resin composition which is a resin component composition mainly composed of two or more kinds of aromatic polyamides selected from the group of different aromatic polyamides, which are intruded and fixed in the holes of the aluminum alloy parts by injection molding. Metal-resin composite consisting of physical parts. In the metal resin composite according to claim 2 or 5,
A metal resin composite characterized in that the aliphatic polyamide resin is nylon 6 or nylon 66, and the aromatic polyamide resin is an aromatic nylon synthesized from phthalic acids and an aliphatic diamine. In the metal resin composite according to claim 4 or 6,
Metals characterized in that the group of different kinds of aromatic polyamides is a group of polyamides from phthalic acid and hexamethylenediamine, polyamides from isophthalic acid and hexamethylenediamine, and polyamides from terephthalic acid and hexamethylenediamine Resin composite. In the metal resin composite according to claim 1 selected from claims 1 to 8,
The said thermoplastic synthetic resin composition contains 1-200 mass parts of fillers with respect to 100 mass parts of resin component composition, The metal resin composite characterized by the above-mentioned. In the metal resin composite according to claim 9,
The metal resin composite, wherein the filler is one or more fillers selected from glass fiber, carbon fiber, aramid fiber, calcium carbonate, magnesium carbonate, silica, talc, clay, and glass powder. An immersion treatment step in one or more aqueous solutions selected from ammonia, hydrazine, and a water-soluble amine to form a surface of an aluminum alloy part covered with a recess having a number average inner diameter of 10 to 80 nm;
The aluminum alloy part subjected to the dipping process is inserted into an injection mold, and a thermoplastic synthetic resin composition having a resin composition in which the main component is a polyamide resin and the subcomponent is an impact resistance improving material is injected. Forming a resin composition part and intruding the resin composition part into the recess of the aluminum alloy part and joining the resin composition part. An immersion treatment step in one or more aqueous solutions selected from ammonia, hydrazine, and a water-soluble amine to form a surface of an aluminum alloy part covered with a recess having a number average inner diameter of 10 to 80 nm;
The aluminum alloy part subjected to the immersion treatment process is inserted into an injection mold, and a terpolymer comprising a hexamethylene adipamide component, a hexamethylene isophthalamide component and a caproamide component is the main resin component composition method for producing a metal-resin composite comprising the step of joining it to penetrate into the recess of the aluminum alloy part with a thermoplastic synthetic resin composition injected to be molded as a resin composition component is. An immersion treatment step in one or more aqueous solutions selected from ammonia, hydrazine, and a water-soluble amine to form a surface of an aluminum alloy part covered with a recess having a number average inner diameter of 10 to 80 nm;
The aluminum alloy part subjected to the immersion treatment step is inserted into an injection mold, polyamide from phthalic acid and hexamethylene diamine, polyamide from isophthalic acid and hexamethylene diamine, and from terephthalic acid and hexamethylene diamine. A thermoplastic synthetic resin composition having a resin composition composed mainly of two or more kinds of polyamides selected from the group of polyamides is injected and molded as a resin composition part, and this is formed in the recess of the aluminum alloy part. A method for producing a metal resin composite comprising a step of entering and joining. An anodizing step for forming an aluminum alloy component surface covered with holes having a number average inner diameter of 10 to 80 nm of openings;
The aluminum alloy part subjected to the anodic oxidation process is inserted into an injection mold, polyamide from phthalic acid and hexamethylene diamine, polyamide from isophthalic acid and hexamethylene diamine, and from terephthalic acid and hexamethylene diamine. A thermoplastic synthetic resin composition having a resin composition composed mainly of two or more kinds of polyamides selected from the group of polyamides is injected and molded as a resin composition part, and this is molded into the hole of the aluminum alloy part. A method for producing a metal resin composite comprising a step of entering and joining.

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