CN102652058A - Aluminium/resin composite exhibiting excellent weather resistance and manufacturing method for the same - Google Patents

Aluminium/resin composite exhibiting excellent weather resistance and manufacturing method for the same Download PDF

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Publication number
CN102652058A
CN102652058A CN2010800555912A CN201080055591A CN102652058A CN 102652058 A CN102652058 A CN 102652058A CN 2010800555912 A CN2010800555912 A CN 2010800555912A CN 201080055591 A CN201080055591 A CN 201080055591A CN 102652058 A CN102652058 A CN 102652058A
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Prior art keywords
aluminium
resin
formed body
concavity portion
film
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Granted
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CN2010800555912A
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CN102652058B (en
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远藤正宪
饭野诚己
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Nippon Light Metal Co Ltd
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Nippon Light Metal Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B29K2705/02—Aluminium

Abstract

Disclosed is an aluminium/resin composite which: exhibits extremely high interfacial adhesion strength and air tightness between an integrally-bonded, shaped aluminium article made from an aluminium alloy, and a molded resin article; retains the excellent adhesion strength and air tightness of the aluminium/resin bond surface in harsh environments such as those caused by temperature, humidity, dust, and corrosive materials; and is corrosion resistant, heat resistant, weather resistant, durable, and exhibits excellent peel strength on the aluminium/resin interfacial surface. Also disclosed is a manufacturing method for the aluminium/resin composite. The aluminium/resin composite contains a shaped aluminium article having undulations on the surface, and a molded resin article which is bonded to the shaped aluminium article when the resin is butted thereto. A plurality of concave sections are formed due to the undulations, and an aluminium coating film is formed on the outermost surface of the undulations. Fitting sections are formed on the molded resin article where the resin enters the concave sections and hardens. The components of the aluminium/resin composite which exhibits excellent weather resistance are engaged by the concave sections and the fitting sections.

Description

Aluminium-resin complexes that weatherability is good and manufacturing approach thereof
Technical field
The present invention relates to have aluminium alloy system aluminium formed body and on said aluminium formed body surface integrated setting the aluminium-resin complexes and the manufacturing approach thereof of resin molded body; Not only the dhering strength and the air-tightness of aluminium-resin-bonded face are good; And the hot strength of corrosion resistance and weatherability and then aluminium-resin-bonded face is also good, can be used for (but being not limited to) and use the wide spectrum as representative such as the various switch blocks of various sensor elements, household electrical appliance, the capacitor part of various industrial equipments with automobile.
Background technology
At automobile with various sensor elements, household electrical appliance with various switch blocks, various industrial equipment with fields such as capacitor parts; Particularly automobile with fields such as parts in; Usually can be or have harsh environment uses down such as corrosive substances such as sea salt ion that blow from the sea on the acid rain that is derived from sulfur dioxide and nitrogen oxide etc., the coastline in temperature and humidity, dust; For these sensor elements, switch block, capacitor part etc., the corrosion resistance and weatherability, durability and hear resistance and the air-tightness etc. that improve under harsh and unforgiving environments like this are just becoming important problem.
All the time; Joining technique as metal and resin; The known method that has as the use bonding agent of routine techniques; But from operating efficiency, reduce part man-hour, the viewpoint of the simple simplicityization of shape of product, durability etc.; As being more suitable in industrialized joint method, can give an example is arranged on injection molded with mould, with the molten resin injection and be filled in this mould, make resin be bonded to the method etc. of the insert molding injection molded (insert molding) of metal parts with metal parts.And, in order to carry out the joint between these metal parts and the resin, further improve engaging force, also known surface-treated method to stipulating with the surface of the metal parts of resin-bonded with cheaper price.
For example; Proposed a species complex in the patent documentation 1, this complex is that the thermoplastic resin composition of regulation that 5 μ m～50 μ m and surface have the aluminium alloy formed body of fine recess or protuberance below the 1 μ m and invade recess or the protuberance and the set of this aluminium alloy formed body constitutes by surface roughness.
In addition; A kind of metal-resin composite has been proposed in the patent documentation 2; This metal-resin composite constitutes by aluminium alloy part and through the thermoplasticity compound resin composition parts that injection molded is bonded to this aluminium alloy part surface; Said aluminium alloy part be impregnated in the aqueous solution more than a kind that is selected from ammonia, hydrazine and water-soluble amine compound and parts, its surface is formed with the atomic thin recess that the number average internal diameter is 10～80nm.
In addition; Proposed a kind of formed body in the patent documentation 3, this formed body has realized that by the metallic plate of any base treatment of having implemented to be selected from pellumina processing, not sealing of hole pellumina processing, acid etching processing, zinc-plated chromatings and blasting treatment and through insert molding injection molded method incorporate thermoplastic constitutes under the situation of not using bonding agent.
In addition, proposed a kind of method in the patent documentation 4, this method is provided with fine coarse surface layer through chemical method for etching or electrolytic etching method on aluminium sheet, and then the injection moulding organic siliconresin is made organic siliconresin-composite metal.
Also have, proposed a kind of method in the patent documentation 5, this method is that metal part surface is carried out chemical etching, then carries out injection molded with thermoplastic resin material, makes the method for metal clip thing mold pressing resin combined shaping article by this.
In addition; A kind of manufacturing approach of metal clip thing mold pressing resin combined shaping article has been proposed in the patent documentation 6; This method is through handling the surface of metal parts such as aluminum or aluminum alloy with warm water; Form the film that contains hydroxyl on its surface, then use the thermoplastic resin material injection mo(u)lding, can realize sufficient joint strength between metal material and the thermoplastic resin thus.
And then; Patent documentation 7 has proposed aluminium core metal paper tinsel plywood; Through in surface roughness (Rmax) be the aluminum or aluminum alloy intermediary of about 8～18 μ m by organic resin or organic and inorganic compoite resin adhesive metal forming, can realize adaptation good between insulative resin and the aluminium sheet.
But all there be dhering strength and the not necessarily sufficient problem of air-tightness that is exposed to harsh environment metal-resin of following time interface in above-mentioned arbitrary technical scheme.In addition; In the patent documentation 1,2,4,5; Surface after the etching is exactly material itself basically, so corrosion resistance is also insufficient, so; Dhering strength and the air-tightness of seeking to develop metal-resin composition surface not only are more excellent, and the also excellent metal-resin complex of the hot strength on metal-resin composition surface.
Therefore; The inventor at first is conceived to aluminium alloy as metal material; Studied in the dhering strength and the air-tightness at the aluminium formed body of said aluminium alloy system and the interface between the resin molded body in its surperficial integrated setting high, even under harsh environment, also can bring into play good dhering strength and air-tightness and good durability and stable on heating aluminium-resin complexes.The result finds; Through forming the jog that comprises the concavity portion that possesses certain predetermined surface shape on aluminium formed body surface; Adaptation and air-tightness between aluminium formed body and the resin molded body significantly improve; Be willing to 2008-153 for the gained achievement with Japanese Patent Laid,, proposed patent application No. 806 No. 805 and special be willing to 2008-153.
The prior art document
Patent documentation
Patent documentation 1:WO2004/041, No. 533 communiques
Patent documentation 2: Japanese Patent Laid is opened 2007-182, No. 071 communique
Patent documentation 3: Japanese Patent Laid is opened 2000-127, No. 199 communiques
Patent documentation 4: Japanese Patent Laid is opened 2000-176, No. 962 communiques
Patent documentation 5: Japanese Patent Laid the 3rd, 467, No. 471 communiques
Patent documentation 6: Japanese Patent Laid is opened 2008-162, No. 115 communiques
Patent documentation 7: japanese patent laid-open 1-275, No. 036 communique
Summary of the invention
Invent technical problem to be solved
The inventor is on above-mentioned achievement; Further to the dhering strength and the air-tightness that under harsh environment such as temperature and humidity, dust, corrosive substance, also can keep good aluminium-resin-bonded face; In addition; Not only can keep superior corrosion resistance, also can bring into play the manufacturing and providing of the aluminium-resin complexes of premium properties at the aspects such as hot strength of weatherability and aluminium-resin-bonded face and further investigate, the result finds; Form the jog that possesses concavity portion through being etched in aluminium formed body surface with predetermined surface shape; Simultaneously, form the aluminium film that contains aluminium compound in the outmost surface of said jog, said aluminium compound is selected from the aluminium film and forms the Al (OH) that handles usefulness 3, AlO (OH), Al 2O 3, Al (PO 4), Al 2(HPO 4) 3, Al (H 2PO 4) 3And AlOSiO 2In any one more than, thus, not only can improve adaptation, air-tightness and corrosion resistance between aluminium formed body and the resin molded body, and can significantly improve the hot strength of weatherability and aluminium-resin-bonded face, thereby accomplish the present invention.
Therefore; The purpose of this invention is to provide aluminium-resin complexes; Said aluminium-resin complexes is high in the dhering strength and the air-tightness at the aluminium alloy system aluminium formed body of integrated joint and the interface between the resin molded body; Under harsh environment such as temperature and humidity, dust, corrosive substance, keep the good aluminium and the dhering strength and the air-tightness of resin-bonded face; In addition, not only corrosion resistance, durability, excellent heat resistance, and also can bring into play excellent performance aspect the hot strength of weatherability and aluminium and resin-bonded face.
In addition; Another object of the present invention is to provide the manufacturing approach that to make above-mentioned aluminium-resin complexes; The aluminium formed body of said aluminium-resin complexes and the dhering strength and the air-tightness at the interface between the resin molded body are high, under harsh environment, keep the good aluminium and the dhering strength and the air-tightness of resin-bonded face, in addition; Not only corrosion resistance, durability, excellent heat resistance, and also can bring into play excellent performance aspect the hot strength of weatherability and aluminium and resin-bonded face.
The technical scheme that the technical solution problem is adopted
Promptly; The present invention is the good aluminium-resin complexes of a kind of weatherability, it is characterized in that, it is to contain on part or all of surface to have the aluminium alloy system aluminium formed body of jog and resin is combined in a lip-deep resin molded body of said aluminium formed body with mated condition aluminium-resin complexes; On said aluminium formed body surface; When the outmost surface of said jog is formed with the aluminium film, formed a plurality of concavity portion that causes because of said jog, in addition; Be formed with in the said resin molded body said resin get in the said a plurality of concavity portion and solidify and a plurality of Embedded Divisions; The engaging each other through said concavity portion and said Embedded Division of aluminium formed body and resin molded body, wherein, said aluminium film contains and is selected from the aluminium film and forms the Al (OH) that handles usefulness 3, AlO (OH), Al 2O 3, Al (PO 4), Al 2(HPO 4) 3, Al (H 2PO 4) 3And AlOSiO 2In any one above aluminium compound.
In addition, the present invention is the good aluminium-resin complexes of a kind of weatherability, it is characterized in that, it is the compound that contains aluminium alloy system aluminium formed body that has jog on part or all of surface and the resin molded body that is arranged on said aluminium formed body surface,
On said aluminium formed body surface, when the outmost surface of said jog is formed with the aluminium film, formed a plurality of concavity portion that causes because of said jog, wherein, said aluminium film contains and is selected from the aluminium film and forms the Al (OH) that handles usefulness 3, AlO (OH), Al 2O 3, Al (PO 4), Al 2(HPO 4) 3, Al (H 2PO 4) 3And AlOSiO 2In any one above aluminium compound,
Said each concavity portion intersects vertically with said thickness direction on the thickness direction cross section of aluminium formed body; And through the medium line place between the treble top line of jog and the bottom line of passing through deep; The A/F of observe being measured by scanning electron microscope is of a size of more than the 0.1 μ m below the 30 μ m; Its degree of depth is of a size of below the above 30 μ m of 0.1 μ m, in addition
In said resin molded body, be formed with said resin get in the said a plurality of concavity portion and solidify and a plurality of Embedded Divisions,
The engaging each other of aluminium formed body and resin molded body through said concavity portion and said Embedded Division.
In addition; The present invention is the manufacturing approach of the good aluminium-resin complexes of a kind of weatherability; Said compound contains aluminium alloy system aluminium formed body and is positioned at the lip-deep resin molded body of said aluminium formed body; The manufacturing approach of said aluminium-resin complexes is characterised in that, etch processes aluminum alloy materials and be formed on the aluminum alloy materials that part or all of surface has a plurality of concavity portion that causes because of jog, then; Implement the aluminium film on the jog at least of said aluminum alloy materials surface and form and handle, form to contain in the outmost surface of said jog and be selected from the aluminium film and form the Al (OH) that handles usefulness 3, AlO (OH), Al 2O 3, Al (PO 4), Al 2(HPO 4) 3, Al (H 2PO 4) 3And AlOSiO 2In the aluminium film of any one above aluminium compound; Form the aluminium formed body of aluminium alloy system thus; In addition, when resin molded body was shaped, resin got into each concavity portion of aluminium formed body and solidifies; Form the Embedded Division of resin molded body, thereby the Embedded Division of the concavity portion of aluminium formed body and resin molded body engages aluminium formed body and the integrated combination of resin molded body each other.
[about aluminium-resin complexes]
Among the present invention; As the aluminum alloy materials that is used to form the aluminium formed body; Specifically can give an example with by 1000 of pure Al system be, Al-Cu system 2000 be, Al-Mn system 3000 be, Al-Si system 4000 be, Al-Mg system 5000 be, ADC5 and ADC6, Al-Mg-Si system 6000 be, Al-Zn-Mg system 7000 be, Al-Fe system 8000 be, material that the materials such as ADC14 of ADC10, ADC10Z, ADC12 and the ADC12Z of the ADC3 of Al-Si-Mg system, Al-Si-Cu system, Al-Si-Cu-Mg system constitute suitably be processed into desired shape and rapidoprint, and with these rapidoprints suitably make up and combined material etc.
In addition; Among the present invention; The a plurality of concavity portion that is formed at this aluminium formed body surface because of the jog on aluminium formed body surface both can be that its opening edge portion is the hole shape of circumference for no reason or poroid concavity portion (having the concavity portion of opening edge portion for no reason); Also can be that opening edge portion has the slit-shaped at both ends or the concavity portion of ditch shape (having the concavity portion that end opening edge portion is arranged), can also to be these hole shape or poroid concavity portions with opening edge portion for no reason with the concavity portion with slit-shaped that end opening edge portion is arranged or ditch dress mix exists.
In addition; A plurality of concavity portion for the aluminium formed body; Be preferably and in part or all of concavity portion, be formed with from the part of concavity portion or whole opening edge portion towards A/F direction center with the outstanding protuberance of cornice shape; Thus; The A/F of concavity portion is less than the inner width dimensions of concavity portion, gets into such concavity portion in and the Embedded Division of the resin molded body that curing forms and concavity portion between the formation snap-in structure that can't break away from each other, have any side to be destroyed in the Embedded Division so long as not the concavity portion of aluminium formed body and resin molded body or both are destroyed simultaneously; Then can not break away from, dhering strength and air-tightness between aluminium formed body and the resin molded body further improve.
Also have; If the part or all of opening edge portion in a plurality of concavity portion of aluminium formed body is formed with the protuberance of above-mentioned cornice shape as stated; Then in these concavity portions; The Embedded Division of resin molded body may not be chimeric with closed state; For example, even cause between these aluminium formed bodies and resin molded body, producing inevitably atomic little gap, also can keep good dhering strength and air-tightness between these aluminium formed bodies and the resin molded body because of the influence of the difference of the thermal coefficient of expansion between aluminium formed body and the resin molded body and environment temperature.
And then, among the present invention, forming the aluminium film that contains aluminium compound in the outmost surface of the jog of above-mentioned aluminium formed body, said aluminium compound is selected from the aluminium film and forms the Al (OH) that handles usefulness 3, AlO (OH), Al 2O 3, Al (PO 4), Al 2(HPO 4) 3, Al (H 2PO 4) 3And AlOSiO 2In any one more than; Because said aluminium film; On the outmost surface of a plurality of concavity portion that forms because of jog, form the pellumina that has the functional group that makes a concerted effort with the chemical bond of resin or have the micro concavo-convex shape; Therefore; Entering has in the concavity portion of such predetermined surface shape and between the Embedded Division of the resin molded body that solidifies and the concavity portion and not only forms strong physics snap-in structure, also forms the chemical bonding that can't break away from each other, has any side to be destroyed in the Embedded Division so long as not the concavity portion of aluminium formed body and resin molded body or both are destroyed simultaneously; Then can not break away from, dhering strength and air-tightness between aluminium formed body and the resin molded body further improve.
In addition; The aluminium formed body that on the outmost surface of jog (especially concavity portion), has the aluminium film when having above-mentioned predetermined surface shape; Compare with the situation that only has the predetermined surface shape that is caused by etch processes, not only corrosion resistance significantly improves, and the hot strength of weatherability and aluminium-resin-bonded face significantly improves; Therefore; Even such aluminium formed body is placed under the very harsh environment, make resin get in the concavity portion and curing then, between aluminium formed body and resin molded body, still can keep good dhering strength and air-tightness.
And then; Have the aluminium formed body of above-mentioned surface configuration and the aluminium-resin complexes of the integrated combination of resin molded body; With only compare with the aluminium-resin complexes of the integrated combination of resin molded body through the aluminium formed body of etch processes; Not only dhering strength, air-tightness raising can be made, and the aluminium-resin complexes of significant corrosion resistance can be brought into play.
Among the present invention; The a plurality of concavity portion that forms for jog because of aluminium formed body surface; If the Fig. 1 in the cross section of this aluminium formed body of reference patternization ground expression describes; Then itself and this thickness direction intersects vertically on the thickness direction cross section of aluminium formed body 1; And locate through the medium line (HL) between the bottom line (BL) in deep through the treble top line (TL) of jog with at formed body; Observe through scanning electron microscope the concavity portion record A/F (d) size more than the 0.1 μ m and below the 30 μ m, better be more than the 0.5 μ m and below the 20 μ m, be more preferably more than the 1 μ m and below 10 μ m, the size of the degree of depth more than the 0.1 μ m and below the 30 μ m, better be more than the 0.5 μ m and below 20 μ m.The A/F of this concavity portion (d) is if less than 0.1 μ m, and then molten resin is difficult to get into during injection molded, produces small space on the interface of aluminium formed body 1 and resin molded body, is difficult to obtain good dhering strength and air-tightness; Otherwise if greater than 30 μ m, then when the surface treatment (etch processes) of aluminium formed body 1, solubilizing reaction excessively carries out, and the problem that the defective of generation material surface or the thickness of slab reduction of material increase produces the not enough product of the strength of materials, causes productivity ratio to reduce.In addition, if the degree of depth less than 0.1 μ m, then is difficult to obtain the Embedded Division of enough resin molded bodies 2; Otherwise if greater than 30 μ m, then when the surface treatment (etch processes) of aluminium formed body 1, solubilizing reaction excessively carries out, the problem that the defective of generation material surface or the thickness of slab reduction of material increase.
Among the present invention; The density of a plurality of concavity portion that forms about jog because of aluminium formed body surface; In the square zone of 0.1mm, A/F is in the scope of 0.5 μ m～20 μ m and in the scope of number about 5～200 of the concavity portion of the size more than a kind or 2 kinds of the degree of depth in the scope of 0.5 μ m～20 μ m.
In addition; In the aluminium formed body of the present invention; The protuberance that is formed at the cornice shape of this concavity portion better is to satisfy following condition: on the thickness direction cross section of the integrally formed article of aluminium-resin; Draw from this resin molded body side direction aluminium shaping side when many observation lines that thickness direction extends with the interval of 0.1 μ m each other; On 1 observation line, be formed with the laminated section more than at least 1 that constitutes by resin-aluminium-resin, and the thickness of the aluminium formed body of this laminated section part is more than 0.1 μ m in the scope below the 30 μ m; In the integrally formed article of aluminium-resin, better be the protuberance that in the scope of 1000 observation lines, has the such cornice shape more than 1.
In addition; The a plurality of concavity portion of aluminium formed body partly or entirely in; The dual concavity portion structure that both can have the inside concavity portion that on the wall of inside, is formed with more than at least 1; Also can have the inside concaveconvex structure that on the wall of inside, is formed with the inner projection portion more than at least 1, can also have these dual concavity portion's structure and inner concaveconvex structures simultaneously.The a plurality of concavity portion of aluminium formed body partly or entirely in; Through having such dual concavity portion's structure or inner concaveconvex structure; The concavity portion of aluminium formed body and the Embedded Division of resin molded body combine each other securely, can bring into play better dhering strength and air-tightness between aluminium formed body and the resin molded body.
Among the present invention; For the good performance of performance on the hot strength of weatherability and aluminium-resin-bonded face; The thickness of the aluminium film that forms in the outmost surface of the jog on aluminium formed body surface is more than 0.001 μ m in the scope below the 30 μ m; Be preferably below 8 μ m more than the 0.003 μ m, be more preferably below 5 μ m more than the 0.006 μ m.But, when the aluminium film is pellumina (Al 2O 3) time, its thickness is preferably more than the 0.1 μ m.If the thickness less than 0.01 μ m (pellumina (Al of aluminium film 2O 3) situation under, less than 0.1 μ m), can not give full play to the effect of weatherability, if thickness surpasses 30 μ m, produce the problem that the jog tunicle on the surface of aluminium formed body buries, the hot strength on composition surface and air-tightness reduction.
[about the manufacturing approach of aluminium-resin complexes]
Among the present invention; When making above-mentioned aluminium-resin complexes; At first form the aluminium formed body that the surface has above-mentioned a plurality of desired concavity portion; As its method, for example can give an example aluminum alloy materials is implemented etch processes and on part surface or whole surface, formed jog, utilizes this jog to form to have the method for the aluminium formed body of a plurality of concavity portion.
In addition; The etching solution that uses in the etch processes as this aluminum alloy materials; The etching solution that can give an example and form by for example aqueous acids such as hydrochloric acid, phosphoric acid, sulfuric acid, acetate, oxalic acid, ascorbic acid, benzoic acid, butyric acid, citric acid, formic acid, lactic acid, isobutyric acid, malic acid, propionic acid, tartaric acid; In order to form a plurality of concavity portions that the A/F and the degree of depth are desired size or to form the protuberance etc. of the cornice shape outstanding in the part or all of opening edge portion of concavity portion towards A/F direction center; Promptly be controlled to be desired shape and size for the concavity portion that will be formed at the surface; Need to use the more weak aqueous acid of oxidability as aqueous acid; In addition, for the oxide scale film that will be formed at aluminum alloy material surface is dissolved in the more weak aqueous acid of above-mentioned oxidability, need to use the etching solution that contains halide ion with the concentration of regulation.
That is,, can use in the more weak aqueous acid of oxidability concentration range with regulation to contain and be selected from chlorion (Cl as etching solution -), fluorine ion (F -) and iodide ion (I -) the etching solution of any halide ion more than a kind or 2 kinds.In addition; If use the more weak aqueous acid of the oxidability of above-mentioned halogen-containing ion, aluminum alloy materials impregnated in this etching solution, then at first the halide ion in the etching solution with the oxide scale film dissolving of aluminum alloy material surface; Aluminium alloy with inside dissolves then; Again further to the aluminum alloy materials internal corrosion, at this moment, because the oxide scale film of inner aluminium alloy specific surface is etched (dissolving easily) more easily; So through the composition of setting etching solution and the condition of etch processes etc.; Concavity portion for producing because of the jog that is formed at the surface can be controlled to be desired size with its A/F and the degree of depth etc., forms the protuberance of the cornice shape outstanding towards A/F direction center in the opening edge portion of part or all of concavity portion.
As the etching solution that uses in order to realize this purpose, specifically can give an example as the acid concentration of aqueous acid more than the 0.1 weight % and below the 80 weight %, better be more than the 0.5 weight % and the aqueous hydrochloric acid solution below the 50 weight %, phosphate aqueous solution, dilute sulfuric acid aqueous solution, acetic acid aqueous solution etc. and acid concentration more than the 5 weight % and below the 30 weight %, better be more than the 10 weight % and the oxalic acid aqueous solution below 20 weight % etc.; In addition, as the halide that adds in order in these aqueous acids, to import halide ion, the for example chlorides such as sodium chloride, potassium chloride, magnesium chloride, aluminium chloride of can giving an example; Fluorides such as calcirm-fluoride; Bromides such as KBr etc. are considered security etc., preferred chloride.In addition, the halogen ion concentration in this etching solution more than 0.5 grams per liter (g/L) and below 300g/L, better is more than the 1g/L and below 100g/L usually; If be lower than 0.5g/L; Then the effect of halide ion is little; Therefore can produce and to form the problem of concavity portion that opening edge portion has the protuberance of cornice shape; When being higher than 300g/L, because solubilizing reaction sharply carries out when the surface treatment (etch processes) of aluminium formed body, so can produce the problem of the control that is difficult to carry out concavity portion.
Among the present invention, as the etching solution that is used for forming on aluminium formed body surface desired concavity portion, nitric acid and concentration are higher than the stronger aqueous acid of oxidability such as the concentrated sulfuric acid of 80 weight % and the aqueous solution of alkali such as NaOH and potassium hydroxide is inappropriate.For aluminium alloy, the aqueous acid that oxidability is stronger has the epithelium generative capacity, can form firm oxide scale film on aluminium formed body surface on the contrary, is difficult to utilize halide ion to come the dissolved oxygen epithelium.In addition, aqueous alkalis such as NaOH and potassium hydroxide are comprehensive lysotypes to the dissolution mechanism of aluminium alloy, even under the situation of having added halide ion, this tendency can not change yet, and are difficult to form the concavity portion with desired shape and size.
Among the present invention, the treatment conditions when with above-mentioned etching solution etch processes is carried out on the surface of aluminum alloy materials are according to the quantity of the desired a plurality of concavity portion of the kind of employed etching solution, acid concentration, halogen ion concentration etc. and aluminium formed body and size etc. and different, usually; During for aqueous hydrochloric acid solution; Treatment conditions are for bathing 20～80 ℃ of temperature, dip time 1～30 minute, and during for phosphate aqueous solution, treatment conditions are for bathing 30～80 ℃ of temperature, dip time 1～5 minute; During for aqueous sulfuric acid; Treatment conditions are for bathing 40～80 ℃ of temperature, dip time 2～8 minutes, and during for oxalic acid aqueous solution, treatment conditions are for bathing 50～80 ℃ of temperature, dip time 1～3 minute; During for acetic acid aqueous solution, treatment conditions are for bathing 50～80 ℃ of temperature, dip time 1～3 minute.The acid concentration of employed etching solution and bath Wen Yuegao, the effect of etch processes is remarkable more, can realize the short time processing; Be lower than 20 ℃ if bathe temperature, then dissolution velocity is slow, and generating the concavity portion with enough sizes (A/F and the degree of depth) needs the long period, is higher than 80 ℃ if bathe temperature, and then solubilizing reaction sharply carries out, and is difficult to carry out the A/F of concavity portion and the control of the degree of depth; If dip time less than 1 minute then is difficult to carry out the A/F of concavity portion and the control of the degree of depth, otherwise, if dip time surpasses 30 minutes, then cause productivity ratio to reduce.
Among the present invention; When forming aluminium formed body with concavity portion as stated aluminum alloy materials being implemented etch processes; For carry out degreasing with surface adjustment, remove surface attachments, pollutant etc., can be as required the surface of the aluminum alloy materials before this etch processes be implemented by the acid treatment of adopting aqueous acid and/or the preliminary treatment of adopting the alkali treatment of aqueous slkali to constitute.
Here; As aqueous acid used in this preliminary treatment, for example can use with the aqueous acid of commercially available acid degreasing agent modulation or with organic acid such as inorganic acid such as sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid or acetate, citric acid or with these acid mix and the aqueous acid modulated of sour reagent such as mixed acid etc.; As aqueous alkali, for example can use with the aqueous alkali of commercially available alkaline defatting agent modulation, with the aqueous alkali of base reagents such as caustic soda modulation or the aqueous alkali that its mixing is modulated into etc.
The pretreated method of operating of using above-mentioned aqueous acid and/or aqueous alkali to carry out can be identical with the pretreated method of operating and the treatment conditions of carrying out with this aqueous acid or aqueous alkali in the past with treatment conditions, can carry out through for example method such as infusion process, spray-on process.
After such etch processes finishes, among the present invention, on the outmost surface of the jog that forms through etch processes, implement to be selected from Al (OH) in order to form to contain 3, AlO (OH), Al 2O 3, Al (PO 4), Al 2(HPO 4) 3, Al (H 2PO 4) 3And AlOSiO 2In the aluminium film of aluminium film of any one above aluminium compound form and handle.Form the used Treatment Solution of processing as said aluminium film; The aluminium film that contains such aluminium compound is just not special to be limited so long as can form; For example, can give an example ion exchange water, distilled water, silane coupler, ammonium hydrogen phosphate solution, ammonium dihydrogen phosphate, phosphoric acid solution etc.
Implement above-mentioned aluminium film and form after the processing, can wash processing as required, this washing is handled can use water for industrial use, underground water, running water, ion exchange water etc., can suitably select according to the aluminium formed body of manufacturing.Also can carry out dried to implementing aluminium film formation aluminium alloy treated material as required, this dried can be the air dry that is positioned over room temperature, also can be the force drying of carrying out with air blast, drying machine, baking oven etc.
It is different according to the Treatment Solution of using that the aluminium film forms the treatment conditions of handling; Particularly, when Treatment Solution is ion exchange water or distilled water, carry out the impregnation process of dipping more than 60 seconds in the warm water more than 50 ℃; Perhaps depress steam treatment more than 1 minute in adding more than the 0.1MPa; When Treatment Solution is a ratio with 0.1～100g/L when containing the phosphate aqueous solution class solution of the phosphate radical class more than in phosphate radical, hydrogen phosphate, the dihydrogen phosphate any one, it is desirable in Treatment Solution dipping after 30 seconds～30 minutes, with 80～400 ℃ heated-air dryings 30 seconds～30 minutes; In addition; When Treatment Solution is a ratio with 0.1～100g/L when containing the solution of silane coupler, it is desirable in Treatment Solution dipping after 30 seconds～30 minutes, with 80～400 ℃ heated-air dryings 30 seconds～30 minutes.
By the etching process and the aluminum film formation process or by pre-treatment, etching treatment and the aluminum film obtained by treating aluminum to form the molded surface due to uneven portion formed by an etching process, the surface of the 60 ° surface gloss (using Suga Test Machine Corporation (Club Suga Testing Machine) system portable gloss meter measurement) is preferably below 60.This surface gloss surpasses under 60 the situation, and when the injection molded of thermoplastic resin, molten resin can't fully get in the concavity portion of aluminium formed body, can't obtain the enough bond strengths between aluminium formed body and the resin molded body.
In addition; Carry out cross-section with 1000 times multiple to forming through above-mentioned etch processes and aluminium film to handle or form the surface of handling the aluminium formed body that obtains with SEM or light microscope through preliminary treatment, etch processes and aluminium film; For resulting cross-section photo, the surface area that is preferably the aluminium formed body is more than 1.2 times below 10 times of surface area that form the aluminum alloy materials before the jog through etch processes.This surface area increment rate is lower than 1.2 times or be higher than under 10 the situation, and resin can't fully get in the concavity portion of aluminium formed body, can't obtain the enough bond strengths between aluminium formed body and the resin molded body.
Then; In order to obtain aluminium-resin complexes of the present invention; Obtaining making metal or resin-bonded behind the surface coated binding agent of aluminium formed body as stated, perhaps between aluminium formed body that obtains and metal, insert resin, through hot press apply heat with pressure make their joint; Also maybe the aluminium formed body that obtains is put into the use in injection molding metal die; The thermoplastic resin of the regulation of fusion is injected in the said metal die and it is solidified, compoundization of promptly so-called resin through having used the aluminium formed body, manufacturing objective thing aluminium formed body.
Here; About being used to make the resin of aluminium-resin complexes of the present invention; Can use various thermoplastic resins separately; Consider the desired physical property of aluminium-resin complexes of the present invention, purposes, environment for use etc.; As thermoplastic resin; Desirable example is the mixture of acrylic resin, polyvinyl resin, acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate resin, polyamide, polyphenylene sulfide polyarylene sulfide resins such as (PPS), polyacetal resin, liquid crystal liquid crystal property resin, PETG (PET) and polybutylene terephthalate (PBT) polyester resins such as (PBT), acetal resin, polyimide resin, syndiotactic polytyrene resin etc. or the said thermoplastic resin more than 2 kinds for example; In addition; In order to improve performances such as adaptation between aluminium formed body and the resin molded body, mechanical strength, hear resistance, dimensional stability (anti-distortion, bending etc.), electrical properties better, better is adds fibrous, powder shape, filler, various elastomer composition such as tabular in these thermoplastic resins.
In addition; As the filler that is added in the thermoplastic resin; The inorganic fibre fillers such as glass fibre, carbon fiber, metallic fiber, asbestos fibre, boron fibre of can giving an example; The organic fiber filling agent of high-melting-points such as polyamide, fluororesin, acrylic resin is the powdered fillers such as inorganic particle class of representative with quartz powder, bead, glass dust, calcium carbonate, tabular fillers such as silicates such as sheet glass, talcum, mica etc.; With respect to 100 weight portion thermoplastic resins; The addition of filler better is more than 20 weight portions and below 220 weight portions below 250 weight portions, is more preferably and is adding more than 30 weight portions and in the scope below 100 weight portions.If the addition of this filler surpasses 250 weight portions, the problem that then can produce the mobile recess that descends, is difficult to get into the aluminium formed body, can't obtain good dhering strength, cause mechanical property to descend.
In addition; As the elastomer composition that is added in the thermoplastic resin; The elastomers such as polyurethanes, hud typed, olefines, polyesters, amide-type, phenylethylene of can giving an example, the melt temperature of the thermoplastic resin in the time of can considering injection molded waits to be selected, with respect to 100 weight portion thermoplastic resins; The addition of elastomer composition better is 3～25 weight portions below 30 weight portions.If the addition of this elastomer composition surpasses 30 weight portions, then can't observe the effect of further raising dhering strength, can produce degradation problem under the mechanical property.The fiting effect of this elastomer composition shows significantly especially when using polyester resin as thermoplastic resin.
Also can be used for making the known additive that the suitable interpolation of aluminium-resin complexes of the present invention makes an addition to thermoplastic resin usually, i.e. stabilizing agents such as colouring agents such as fire retardant, dyestuff or pigment, anti-oxidant or ultra-violet absorber, plasticizer, lubricant, lubriation material, releasing agent, crystallization promoter, nucleator etc. according to desired performance.
Among the present invention; About the aluminium formed body being arranged at the injection molded of injection molded with the thermoplastic resin that carries out in the mould; Can adopt the molding condition of the used desired routine of thermoplastic resin; But positively to get in the concavity portion of aluminium formed body and solidify this point be very important to the thermoplastic resin of fusion when injection molded; Better be mold temperature or material cylinder temperature are set at thermoplastic resin kind with rerum natura and be shaped circulate the higher temperature in the receptible scope; Particularly for mold temperature; The lower limit of temperature must better be more than 130 ℃ more than 90 ℃, and the upper limit can be according to the kind of employed thermoplastic resin in 100 ℃～scope than the temperature of low about 20 ℃ of the fusing point of this thermoplastic resin or softening point (being a side higher in fusing point and the softening point when being added with the elastomer composition).In addition, the lower limit of mold temperature better is to be set to compare the temperature that can not hang down more than 140 ℃ with the fusing point of thermoplastic resin.
In addition, be used to make the resin of aluminium-resin complexes of the present invention, except above-mentioned thermoplastic resin, also can use heat-curing resin, normal temperature cure property resin, various binding agents etc.The heat-curing resin epoxy resin etc. of can giving an example, in addition, the normal temperature cure property resin polyester resin etc. of can giving an example.In addition, can give an example nitrile rubber class, synthetic rubber class, epoxies, alpha-cyanoacrylate class, polyvinyl chloride-base, plastics class, thermometal class etc. of binding agent.
The effect of invention
Aluminium-resin complexes of the present invention is compared with the situation of only carrying out etch processes; The dhering strength and the air-tightness at the interface between aluminium formed body and the resin molded body (aluminium/resin boundary surface) are higher; Even and be exposed to harsh corrosive atmosphere and also can keep good dhering strength, air-tightness and corrosion resistance; And the cosmetic variation that can keep the corrosion because of aluminium to cause for a long time, be can the long term maintenance high reliability aluminium-resin complexes.Therefore; Aluminium-resin complexes of the present invention is suitable as the various sensor elements that use with for example automobile, the various switch blocks that household electrical appliance use, the capacitor part that various industrial equipment uses etc. and is the integrally formed parts of the metal-resin in the extensive fields of representative, is especially suitable for use as resin molded body gave prominence to and required high bond strength with mated condition from the part surface of aluminium formed body the integrally formed parts of metal-resin.
In addition; Manufacturing approach according to aluminium-resin complexes of the present invention; Through surface gloss or the surface roughness of measuring the aluminium formed body during fabrication; The dhering strength of measurable products obtained therefrom not only carries out the qualitative control of product when making easily, and can make the high product of reliability of the deviation that does not almost have dhering strength between each product.
Description of drawings
Fig. 1 duplicates and the cross section copy pattern that is used for concavity portion is described the thickness direction cross section of the aluminium formed body of embodiment 1.
Fig. 2 is the cross-sectional illustration figure of the exemplary of the expression shape of carrying out the concavity portion after the abstract according to Fig. 1.
Fig. 3 pulls front view and the side view that method adhesive force is measured the aluminium-binding agent-aluminium test film of (posiTEST) test (estimate and use trial target) with aluminium test film (aluminium formed body) being used to of processing.
Fig. 4 is the front view and the side view of the aluminium-resin that is used to pull method adhesive force determination test-aluminium test film (estimate and use trial target) of processing with aluminium test film (aluminium formed body).
Fig. 5 is the front view and the side view of the aluminium that is used to pull method adhesive force determination test-resin test film (estimate and use trial target) of processing with aluminium test film (aluminium formed body).
Fig. 6 is illustrated in to estimate the cross-sectional illustration figure that is arranged at the state of the transmission device portion that pulls method adhesive force determination test device with trial target when pulling method adhesive force determination test.
Fig. 7 is used to explain the cross-sectional illustration figure of evaluation with the observation evaluation method of the laminate part of the resin-aluminium-resin of trial target.
The explanation of symbol
1 ... Aluminium formed body (aluminium test film), TL ... Top line, BL ... Bottom line, HL ... Medium line, d ... A/F, OL ... Observation line, 2 ... Resin molded body, 3 ... Concavity portion, 4 ... Binding agent, 5,7 ... De リ one), 8 dolly (pad stake) (Japanese: ... Transmission device, 9 ... Dolly (De リ one) is fixedly used instrument
The specific embodiment
Below based on embodiment and comparative example preferred implementation of the present invention is specified.The present invention is not limited to following example.
[embodiment 1]
[preparation of aluminium formed body]
Cut big or small 3 of the aluminium flakes of 50mm * 50mm (aluminum alloy materials) that are from aluminium alloy (JISA 1050-H24) plate of thick 1mm; These aluminium flakes are implemented preliminary treatment; That is: at first in 30 weight % aqueous solution of nitric acid under the normal temperature dipping 5 minutes after; Fully wash with ion exchange water, then in 5 weight % sodium hydroxide solutions in 1 minute after washing of 50 ℃ of dippings, in 30 weight % aqueous solution of nitric acid, in normal temperature under, flood 3 minutes after washings again.
Then, above-mentioned pretreated aluminium flake is implemented etch processes, that is: in the aqueous hydrochloric acid solution of 2.5 weight %, add the aluminum chloride hexahydrate (AlCl of 54g/L 36H 2O) as water-soluble inorganic halide, be mixed with etching solution (chlorine ion concentration: 48g/L), under 66 ℃ in said etching solution 4 minutes after washings of dipping.
Next; In the aqueous solution of nitric acid of 30 weight %, flood 3 minutes after washings under the normal temperature; Be implemented in dipping 20 minutes water and processing in 80 ℃ the hot water; Thus, the outmost surface that is implemented in the jog on the aluminium flake surface that forms through above-mentioned etch processes forms the aluminium film formation processing of aluminium film (AlO (OH)), makes 3 aluminium test films (aluminium formed body).
[the concavity portion on the surface of aluminium test film (aluminium formed body) is observed]
Each aluminium test film for gained; With scanning electron microscope (the system FE-SEM of Hitachi, Ltd; The S-4500 type) observes certain regional cross section in its thickness direction cross section; At first confirm on the thickness direction cross section of aluminium formed body to intersect vertically and the treble top line (TL) through jog with this thickness direction; Then confirm likewise roughly that the thickness direction with the aluminium formed body intersects vertically and the bottom line in deep through jog with above-mentioned; Again from top line (TL) to bottom line (BL) line segment that vertically draws; Pars intermedia that will be through this line segment and and the medium line (HL) that draws abreast of top line (TL) (or bottom line (BL)) on the distance note that is present in the space between aluminium formed body and the aluminium formed body make the A/F (d) of concavity portion, observe and measure the shape and the size (A/F and the degree of depth) of the concavity portion that forms because of jog on aluminium test film surface, and measure.
On certain regional cross section of observed each aluminium test film (aluminium formed body); The exemplary of shape of for example carrying out the concavity portion 3 after the abstract shown in the cross section copy pattern of the aluminium formed body of Fig. 1 or according to this Fig. 1 is as shown in Figure 2; Be have a part from opening edge portion towards A/F direction center with the concavity portion (shape a :) of the outstanding protuberance of cornice shape with reference to Fig. 2 (a), have from whole opening edge portion towards A/F direction center with the concavity portion (shape b :) of the outstanding protuberance of cornice shape, have the concavity portion (shape c :) of the inner dual concavity portion structure that also is formed with concavity portion and have the concavity portion (shape d :) that wall in inside is formed with the inside concaveconvex structure of inner projection portion with reference to Fig. 2 (d) with reference to Fig. 2 (c) with reference to Fig. 2 (b), observed the concavity portion of all shape a～d among this embodiment 1.In addition, about the shape of such concavity portion 3, each aluminium test film is identical, in addition, even it is also still identical to change the observation place of each aluminium test film.
Here, about the evaluation of the shape of observed concavity portion, any note more than 1 or 2 that will have among above-mentioned shape a～d is done good (zero), in addition, and with not existing any 1 note among shape a～d to do bad (*).Shape for concavity portion observed in following examples 2～18 and the comparative example 1～3 is also estimated with same standard.
The size (A/F and the degree of depth) of observed concavity portion on certain regional cross section of each aluminium test film of being measured with and ratio be: in the square zone of 0.1mm, A/F 0.1 μ m～1
The concavity portion of μ m has 10～100, and the concavity portion of A/F 1 μ m～10 μ m has 1～10, and the concavity portion of A/F 11 μ m～30 μ m has 1～3, and the degree of depth is in the scope of 0.1 μ m～30 μ m.In addition; Form dual concavity portion structure inside concavity portion size (A/F and the degree of depth) with and ratio roughly the same; In the square zone of 0.1mm, the concavity portion of A/F 0.1 μ m～1 μ m has 10～50, and the concavity portion of A/F 1 μ m～10 μ m has 1～50; The concavity portion of A/F 11 μ m～30 μ m has 1～2, and the degree of depth is in the scope of 0.1 μ m～20 μ m.Size about said concavity portion also is that each aluminium test film is all identical, in addition, does not also change basically even change the observation place of each aluminium test film.
Here, about the evaluation of the size of observed concavity portion, with A/F in the scope of 0.1～30 μ m and the note of the degree of depth in the scope of 0.1～30 μ m do good (zero), the note that does not satisfy this condition is done bad (*).Shape for concavity portion observed in following examples 2～18 and the comparative example 1～3 is also estimated with same standard.
[the surface gloss evaluation of aluminium test film (aluminium formed body)]
Use portable gloss meter (must congratulate testing machine Co., Ltd. system) to measure the 60 degree glossiness on the surface of 3 aluminium test films that obtain respectively, the mean value of calculating 3 values of mensuration is as 60 degree glossiness of aluminium test film.The result is 26.
[evaluation of the surface area increment rate of aluminium test film (aluminium formed body)]
For 3 aluminium test films that obtain, carry out cross-section with SEM or light microscope respectively with 1000 times multiple, for the cross-section photo that obtains, measure the surface area on aluminium formed body surface with image processing software (ImageJ).For untreated aluminum alloy materials, the surface area of obtaining each aluminium test film surface that obtains respectively increases ratio, and the mean value of calculating 3 values that obtain is defined as the surface area increment rate.The result is 3.48 times.
[mensuration of the average film thickness of the outmost surface of aluminium test film (aluminium formed body)]
For 3 aluminium test films that obtain; Carry out cross-section with TEM (FEI system TECNAI G2F20S-TWIN) respectively with 100,000 times～300,000 times multiples; Measure the thickness of the surperficial film that forms of aluminium test film by the cross-section photo that obtains; Calculate the mean value of 3 values that record, with it as average film thickness.The result is 0.3 μ m.
[evaluation is with the observation evaluation of the laminate part of the method that pulls adhesive force determination test, atmospheric exposure test (salt spraytest) and the resin-aluminium-resin of trial target]
1. estimate preparation with trial target
(1) the trial target configuration is with the making of dolly
For the method that the pulls adhesive force determination test of aluminum with dolly (De Falusike Co., Ltd. (デ Off ェ Le ス コ society) system; Size: 20mm φ; JISA 1100); Same with above-mentioned aluminium test film (aluminium formed body); Enforcement preliminary treatment, etch processes and aluminium film form to be handled, and the making of making trial target is used dolly, said dolly to be used for being produced on the following evaluation that pulls method adhesive force determination test and atmospheric exposure test (salt spraytest) use and used trial target.
(2) evaluation is with the making of trial target [adopting the joint of the resin (binding agent) of binding agent]
As shown in Figure 3; (Hensel steps Advantest Ma Telialuzi company (Ha Application Star マ Application ア De バ Application テ ス ト マ テ リ ア Le ズ) system through two liquid mixed type epoxies snap cure binding agents with dolly 5 with the trial target making with the above-mentioned aluminium test film that obtains (aluminium formed body) 1; Trade name: ア ラ Le ダ イ ト ラ ピ ッ De) behind 4 joints; With hot press (the system AH-2003 of Ya Suwang Co., Ltd. (ア ズ ワ Application)) normal temperature pressurization under squeeze pressure 0.1MPa, kept 24 hours under the previous status, make its crimping; Then; After adhesive cures, the unnecessary binding agent 4 usefulness scrapers that will extrude from the composition surface between aluminium test film 1 and the dolly 5 separate from the composition surface, and the composition surface is adjusted into 3.14cm 2, make aluminium-binding agent-aluminium test film (estimate and use trial target).
(3) estimate with the trial target making of [employing adds the joint of the resin of thermo-compressed]
As shown in Figure 4, on the above-mentioned aluminium test film that obtains (aluminium formed body) 1, carry the particle (resin) 6 of polyphenylene sulfide (Dongli Ltd. (eastern レ) system), be 0.04g/cm 2, trial target is set thereon makes of dolly 5, in squeeze pressure 0.1MPa, 300 ℃ of following thermo-compressed of plate temperature, preparing resin is with 3.14cm with hot press (the system AH-2003 of Ya Suwang Co., Ltd.) 2The aluminium-binding agent-aluminium test film (estimate and use trial target) of the fixing bonding of bonding area.
(4) evaluation is with the making of trial target [adopting the joint of the resin of injection molded]
As shown in Figure 5; The above-mentioned aluminium test film that obtains (aluminium formed body) 1 is placed in the metal die of the outer injection molding machine of diagram (the system ST10R2V of Nisei Co., Ltd. (NISSEI)), uses polyphenylene sulfide (Dongli Ltd.'s system) as thermoplastic resin, 5 seconds injection times; Injection moulding speed 80 mm/second; The 100MPa that keep-ups pressure, 320 ℃ of forming temperatures, injection molded under the condition that the metal die temperature is 160 ℃; At the upper surface integral forming resin round forging die 7 of aluminium test film 1, preparing resin round forging die 7 is 3.14cm with respect to the bonding area of the upper surface of aluminium test film 1 2Aluminium-resin test film (estimate use trial target).
2. atmospheric exposure test (salt spraytest; SST 1000 hours)
About 3 kinds of evaluations of above-mentioned making with trial target, aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film; Each is estimated with in the trial target importing salt spraytest machine (must congratulate the system CASSER-23L-ISO of testing machine Co., Ltd.); After 1000 hours; From testing machine, take out to estimate and use trial target, carry out outward appearance and observe.Observe about said outward appearance, estimate the white rust generation number on the surface of the test film side at position except that the junction surface, the result in any one estimates with trial target, is zero (0).In addition, the appearance of surface discolouration is with zero: do not have variation, △: change slightly, *: the three phases evaluation that has significant change, the result, any one ocular estimate of estimating with trial target is zero.
3. adopt the composition surface hot strength evaluation that pulls method adhesive force determination test machine
Employing pulls method adhesive force determination test machine (De Falusike Co., Ltd. (デ Off ェ Le ス コ society) system); According to ASTM D4541 (ISO 4624) test method(s); Measure after the above-mentioned atmospheric exposure test each estimate hot strength with the aluminium-resin-bonded face of trial target (dolly size: 20mm φ, resolution: ± 0.01MPa, precision: ± 1% and, measurement range: 0～20MPa).Measure about the said method adhesive force that pulls; As shown in Figure 6; Partly be connected through the fixing dolly 5 (or 7) that will estimate with trial target with instrument 9 of dolly with the transmission device 8 that pulls method adhesive force determination test machine, then, with the pump loading (disengaging loading) of mensuration dolly 5 (or 7) till partly peeling off of exerting pressure from aluminium test film (aluminium formed body) 1; In addition, the state at the junction surface of back aluminium test film 1 is peeled off in investigation.
Estimating the loading of peeling off with trial target, is 6.3MPA under the situation of aluminium-binding agent-aluminium test film, under the situation of aluminium-resin-aluminium test film, is 5.7MPA, in addition, is 5.5MPA under the situation of aluminium-resin test film.In addition; About the observed state of peeling off, binding agent or resin are good (zero) when remaining on the entire bonding face of aluminium test film, in addition; When an aluminium test film side part is remaining, be part good (△) only; When aluminium test film side does not have remaining (interface peel), be bad (*), evaluation result is good (zero).
4. the observation evaluation of the laminate part of resin-aluminium-resin
In addition; As shown in Figure 7; Cut off along thickness direction towards range upon range of resin (binding agent) on it from the aluminium test film respectively; Observe the thickness direction cross section of above 3 kinds of evaluations making through SEM or light microscope with 1000 times multiplying power with trial target, aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film; Cross-section photo for gained; Draw from resin molded body 2 side direction aluminium formed bodies 1 side when many observation lines (OL) that thickness direction extends with the interval of 0.1 μ m each other, on 1 observation line, have the laminated section more than at least 1 that constitutes by resin (binding agent)-aluminium-resin (binding agent), and the thickness of the aluminium formed body of this laminated section part is more than 0.1 μ m in the scope below the 30 μ m; To in the scope of 1000 observation lines (OL), exist the situation note of the such laminated section more than 1 to do good (zero), such laminated section 1 all non-existent situation in the scope of 1000 observation lines (OL) is remembered that doing bad (*) estimates that the result is well (zero).Also estimate for following examples 2～18 and comparative example 1～3 with same standard.
(embodiment 2～5)
Except the treatment fluid shown in the use below table 1 replaces the water and the processing of 80 ℃, 20 minutes the Hot water immersion of embodiment 1 to form the processing as the aluminium film with making aluminium test film (aluminium formed body) of the treatment conditions shown in the below table 1 and test system effect dolly; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with embodiment 1; In addition, the laminated section that likewise implement atmospheric exposure test (salt spraytest) with the foregoing description 1, pulls method adhesive force determination test and resin-aluminium-resin observe to be estimated.
The result is shown in table 2 with the result of embodiment 1.
[table 1]
Figure BDA00001738097200201
(notes) silane coupler: β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane
(siloxanes Co., Ltd. of SHIN-ETSU HANTOTAI (the シ リ コ of SHIN-ETSU HANTOTAI-Application society) system: KBM303)
[embodiment 6]
Except using JISA5052-H34 as the aluminium alloy plate of making aluminium flake, same with the foregoing description 1, when making aluminium test film (aluminium formed body), make dolly.Then; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with the foregoing description 1; In addition; The same with the situation of embodiment 1, implement atmospheric exposure test (salt spraytest), pull the observation evaluation of the laminated section of method adhesive force determination test and resin-aluminium-resin.
The result is shown in table 2 with the result of embodiment 1.
[embodiment 7]
Except using JIS A3003-H24 as the aluminium alloy plate of making aluminium flake, same with the foregoing description 1, when making aluminium test film (aluminium formed body), make dolly.Then; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with the foregoing description 1; In addition; The same with the situation of embodiment 1, implement atmospheric exposure test (salt spraytest), pull the observation evaluation of the laminated section of method adhesive force determination test and resin-aluminium-resin.
The result is shown in table 2 with the result of embodiment 1.
[embodiment 8]
With the foregoing description 1 likewise; When making the aluminium test film, make dolly, then, likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with the foregoing description 1; Do not implement atmospheric exposure test (salt spraytest); Likewise implement to pull method adhesive force determination test with the foregoing description 1, and then, the observation evaluation of the laminated section of resin-aluminium-resin implemented.
The result is shown in table 2 with the result of embodiment 1.
The result of the test of result of the test of comparative studies the foregoing description 1 and said embodiment 8 can be known; Even aluminium-resin complexes of the present invention is exposed to as after under the condition of atmospheric exposure test; Still with expose under the described conditions before the same, keep the hot strength of good aluminium-resin-bonded face.
[embodiment 9]
Likewise make aluminium test film (aluminium formed body) with the foregoing description 1, in addition, make dolly.Then; Aluminium test film to making is implemented atmospheric exposure test (salt spraytest); Then; After washing,, then, likewise makes evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with embodiment 1 with 100 ℃ heated-air drying 5 minutes.
Likewise the evaluation of such making is implemented to pull method adhesive force determination test and estimate with trial target with the foregoing description 1; Result with above-mentioned atmospheric exposure test (salt spraytest) estimates; Simultaneously; With the foregoing description 1 likewise, implement the observation evaluation of the laminated section of resin-aluminium-resin.
The result is shown in table 2 with the result of embodiment 1.
The result of the test of the said embodiment 9 of comparative studies and each result of the test of the foregoing description 1 can be known; Among the present invention; Carried out the good weatherability of aluminium formed body (aluminium test film) itself demonstration that the aluminium film is handled after the etch processes; Even before being processed into aluminium-resin complexes, be exposed to the hot strength that still can access good aluminium-resin-bonded face under the harsh environment for a long time, operability is good.
[embodiment 10]
Likewise carry out preliminary treatment and etch processes with embodiment 1, and then, in the aqueous solution of nitric acid of 30 weight %, flooded 3 minutes under the normal temperature; Then, washing, then; Be implemented in dipping 1 minute water and processing in 100 ℃ the hot water, thus, implement the aluminium film and form and handle; Likewise make aluminium test film (aluminium formed body) with the foregoing description 1, simultaneously, likewise make dolly with the situation of embodiment 1.
Then; Aluminium test film and dolly that use obtains; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with the foregoing description 1; In addition, the same with the situation of embodiment 1, enforcement pulls the observation evaluation of the laminated section of method adhesive force determination test, atmospheric exposure test (salt spraytest) and resin-aluminium-resin.
Then table 2 is shown in table 3 with the result.
[embodiment 11]
Likewise carry out preliminary treatment and etch processes with embodiment 1; And then, in the aqueous solution of nitric acid of 30 weight %, flooded 3 minutes under the normal temperature, then; Fully washing; Then, be implemented in the solution of sulfuric acid concentration 160g/L the anodized (the aluminium film forms and handles) under 18 ℃ of solution temperatures and DC voltage 20V condition, form thickness 5 μ m and hole count 10 16Individual/m 2Anode oxide film (Al 2O 3The aluminium film), then, washing, with 120 ℃ heated-air dryings 5 minutes, making aluminium test film (aluminium formed body) in addition, was likewise made dolly.
Then; Aluminium test film and dolly that use obtains; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with the foregoing description 1; In addition, the same with the situation of the foregoing description 1, enforcement pulls the observation evaluation of the laminated section of method adhesive force determination test, atmospheric exposure test (salt spraytest) and resin-aluminium-resin.
Then table 2 is shown in table 3 with the result.
[embodiment 12]
Likewise carry out preliminary treatment and etch processes with embodiment 1, and then, in the aqueous solution of nitric acid of 30 weight %, flooded 3 minutes under the normal temperature; Then, washing, then; Add at 0.5MPa and to depress steam treatment 20 minutes (the aluminium film forms and handles), form the aluminium film of fine and close AlO (OH) thus, make aluminium test film (aluminium formed body); Simultaneously, likewise make dolly.
Then; Aluminium test film and dolly that use obtains; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with the foregoing description 1; In addition, the same with the situation of the foregoing description 1, enforcement pulls the observation evaluation of the laminated section of method adhesive force determination test, atmospheric exposure test (salt spraytest) and resin-aluminium-resin.
Then table 2 is shown in table 3 with the result.
[embodiment 13]
Except using polybutylene terephthalate (PBT) resin (Dongli Ltd. (eastern レ) system) as the thermoplastic resin; Likewise make aluminium test film and dolly with the foregoing description 1; In addition; Make aluminium-resin test film (estimate and use trial target), do not implement salt spraytest for the evaluation that obtains with trial target, enforcement pulls the observation evaluation of the laminated section of method adhesive force determination test and resin-aluminium-resin.
Then table 2 is shown in table 3 with the result.
[embodiment 14]
After likewise carrying out preliminary treatment with embodiment 1, use the formulated etching solution (chlorine ion concentration: 30g/L), under 66 ℃, 4 minutes condition, in said etching solution, flood of sodium chloride that in 50 weight % phosphate aqueous solutions, adds 50g/L; Carry out etch processes, and then, washing; Then, in the aqueous solution of nitric acid of 30 weight %, flood after 3 minutes washing once more under the normal temperature; Then, dipping is 1 minute in 100 ℃ hot water, implements water and processing (the aluminium film forms and handles); Likewise make aluminium test film (aluminium formed body) with the foregoing description 1, simultaneously, likewise make dolly with embodiment 1.
Then; Aluminium test film and dolly that use obtains; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with the foregoing description 1; In addition, the same with the situation of embodiment 1, enforcement pulls the observation evaluation of the laminated section of method adhesive force determination test, atmospheric exposure test (salt spraytest) and resin-aluminium-resin.
Then table 2 is shown in table 3 with the result.
[embodiment 15]
After likewise carrying out preliminary treatment with embodiment 1, use the formulated etching solution (chlorine ion concentration: 30g/L), under 66 ℃, 4 minutes condition, in said etching solution, flood of sodium chloride that in 10 weight % aqueous sulfuric acids, adds 50g/L; Carry out etch processes, and then, washing; Then, in the aqueous solution of nitric acid of 30 weight %, flood after 3 minutes washing once more under the normal temperature; Then, dipping is 1 minute in 100 ℃ hot water, implements water and processing (the aluminium film forms and handles); Likewise make aluminium test film (aluminium formed body) with the foregoing description 1, simultaneously, likewise make dolly with embodiment 1.
Then; Aluminium test film and dolly that use obtains; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with the foregoing description 1; In addition, the same with the situation of embodiment 1, enforcement pulls the observation evaluation of the laminated section of method adhesive force determination test, atmospheric exposure test (salt spraytest) and resin-aluminium-resin.
Then table 2 is shown in table 3 with the result.
[embodiment 16]
After likewise carrying out preliminary treatment with embodiment 1, use the formulated etching solution (chlorine ion concentration: 30g/L), under 66 ℃, 4 minutes condition, in said etching solution, flood of sodium chloride that in 30 weight % oxalic acid aqueous solutions, adds 50g/L; Carry out etch processes, and then, washing; Then, in the aqueous solution of nitric acid of 30 weight %, flood after 3 minutes washing under the normal temperature; Then, dipping is 1 minute in 100 ℃ hot water, implements water and processing (the aluminium film forms and handles); Likewise make aluminium test film (aluminium formed body) with the foregoing description 1, simultaneously, likewise make dolly with embodiment 1.
Then; Aluminium test film and dolly that use obtains; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with the foregoing description 1; In addition, the same with the situation of embodiment 1, enforcement pulls the observation evaluation of the laminated section of method adhesive force determination test, atmospheric exposure test (salt spraytest) and resin-aluminium-resin.
Then table 2 is shown in table 3 with the result.
[embodiment 17]
After likewise carrying out preliminary treatment with embodiment 1, use the formulated etching solution (chlorine ion concentration: 54g/L), under 66 ℃, 4 minutes condition, in said etching solution, flood of sodium chloride (NaCl) that in 2.5 weight % aqueous hydrochloric acid solutions, adds 50g/L; Carry out etch processes, and then, washing; Then, in the aqueous solution of nitric acid of 30 weight %, flood after 3 minutes washing under the normal temperature; Then, dipping is 1 minute in 100 ℃ hot water, implements water and processing (the aluminium film forms and handles); Likewise make aluminium test film (aluminium formed body) with the foregoing description 1, simultaneously, likewise make dolly with embodiment 1.
Then; Aluminium test film and dolly that use obtains; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with the foregoing description 1; In addition, the same with the situation of embodiment 1, enforcement pulls the observation evaluation of the laminated section of method adhesive force determination test, atmospheric exposure test (salt spraytest) and resin-aluminium-resin.
Then table 2 is shown in table 3 with the result.
[embodiment 18]
Likewise carry out preliminary treatment and etch processes with embodiment 1; And then, in the aqueous solution of nitric acid of 30 weight %, flooded 3 minutes under the normal temperature, then; Fully washing; Then, in the solution of sulfuric acid concentration 160g/L, under the condition of 18 ℃ of solution temperatures and DC voltage 20V, implement anodized (the aluminium film forms and handles), form thickness 1 μ m and hole count 10 16Individual/m 2Anode oxide film (Al 2O 3The aluminium film), then, washing, with 120 ℃ heated-air dryings 5 minutes, making aluminium test film (aluminium formed body) in addition, was likewise made dolly.
Then; Aluminium test film and dolly that use obtains; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with the foregoing description 1; In addition, the same with the situation of the foregoing description 1, enforcement pulls the observation evaluation of the laminated section of method adhesive force determination test, atmospheric exposure test (salt spraytest) and resin-aluminium-resin.
Then table 2 is shown in table 3 with the result.
[table 2]
Figure BDA00001738097200261
[table 3]
Figure BDA00001738097200271
[comparative example 1]
After embodiment 1 preliminary treatment likewise, do not carry out etch processes, implement to form processing with the embodiment 1 same aluminium film that utilizes water and processing, make aluminium test film (aluminium formed body), simultaneously, likewise make dolly with embodiment 1.
Then; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film, aluminium-resin test film) with the foregoing description 1, pull the observation evaluation of the laminated section of method adhesive force determination test and resin-aluminium-resin for the evaluation that obtains with trial target enforcement.
The result is shown in table 4.
[comparative example 2]
After carrying out preliminary treatment and etch processes similarly to Example 1, in the aqueous solution of nitric acid of 30 weight %, flood after 3 minutes washing under the normal temperature; Then; Do not carry out the aluminium film and form processing, drying is 5 minutes under 100 ℃ hot blast, makes aluminium test film (aluminium formed body); Simultaneously, make dolly similarly to Example 1.
Then; Likewise make evaluation with trial target (aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film and aluminium-resin test film) with the foregoing description 1; In addition; The same with the situation of embodiment 1, implement atmospheric exposure test (salt spraytest), pull the observation evaluation of the laminated section of method adhesive force determination test and resin-aluminium-resin.
The result is shown in table 4 with the result of comparative example 1.
[comparative example 3]
Finish after the preliminary treatment of embodiment 1, in 2.5 weight % aqueous hydrochloric acid solutions, flooding 4 minutes washing under 66 ℃; In in 30 weight % aqueous solution of nitric acid, flooding 3 minutes after washings under the normal temperature, after 5 minutes, import in the salt spraytest machine again with 100 ℃ heated-air dryings; After 1000 hours, from testing machine, take out test film; After the washing,, make aluminium test film (aluminium formed body) with 100 ℃ heated-air dryings 5 minutes.In addition, likewise make dolly, make aluminium-binding agent-aluminium test film, aluminium-resin-aluminium test film, aluminium-resin test film (estimate and use trial target) respectively with embodiment 1.Likewise the evaluation of such making is implemented to pull method adhesive force determination test and estimate with trial target with the foregoing description 1; Result with above-mentioned atmospheric exposure test (salt spraytest) estimates; Simultaneously; With the foregoing description 1 likewise, implement the observation evaluation of the laminated section of resin-aluminium-resin.
The result is shown in table 4 with the result of comparative example 1.
[table 4]
Figure BDA00001738097200291

Claims (10)

1. aluminium-resin complexes that weatherability is good; It is characterized in that; It is to contain on part or all of surface to have the aluminium alloy system aluminium formed body of jog and resin is combined in a lip-deep resin molded body of said aluminium formed body with mated condition aluminium-resin complexes
On said aluminium formed body surface; When the outmost surface of said jog is formed with the aluminium film; Formed a plurality of concavity portion that causes because of said jog, be formed with in the said resin molded body said resin get in the said a plurality of concavity portion and solidify and a plurality of Embedded Divisions, aluminium formed body and resin molded body engage through said concavity portion and said Embedded Division each other; Wherein, said aluminium film contains the Al (OH) that is selected from aluminium film formation processing usefulness 3, AlO (OH), Al 2O 3, Al (PO 4), Al 2(HPO 4) 3, Al (H 2PO 4) 3And AlOSiO 2In any one above aluminium compound.
2. aluminium-the resin complexes that weatherability is good is characterized in that, it is to contain on part or all of surface to have the aluminium alloy system aluminium formed body of jog and be arranged on the compound at the lip-deep resin molded body of said aluminium formed body,
On said aluminium formed body surface, when the outmost surface of said jog is formed with the aluminium film, formed a plurality of concavity portion that causes because of said jog, wherein, said aluminium film contains and is selected from the aluminium film and forms the Al (OH) that handles usefulness 3, AlO (OH), Al 2O 3, Al (PO 4), Al 2(HPO 4) 3, Al (H 2PO 4) 3And AlOSiO 2In any one above aluminium compound,
Said each concavity portion intersects vertically with said thickness direction on the thickness direction cross section of aluminium formed body; And through the medium line place between the treble top line of jog and the bottom line of passing through deep; The A/F of observe being measured by scanning electron microscope is of a size of more than the 0.1 μ m below the 30 μ m; Its degree of depth is of a size of below the above 30 μ m of 0.1 μ m
In said resin molded body, be formed with said resin get in the said a plurality of concavity portion and solidify and a plurality of Embedded Divisions,
The engaging each other of aluminium formed body and resin molded body through said concavity portion and said Embedded Division.
3. according to claim 1 or claim 2 the good aluminium-resin complexes of weatherability; In the said aluminium formed body; In part or all of said a plurality of concavity portion; Be formed with from the part of concavity portion or whole opening edge portion towards A/F direction center with the outstanding protuberance of cornice shape, by this protuberance, the concavity portion of the aluminium formed body snap-in structure that formation can't break away from each other with the Embedded Division of resin molded body.
4. the good aluminium-resin complexes of weatherability as claimed in claim 3; It is characterized in that; On the thickness direction cross section of the integrally formed article of aluminium-resin; Draw from said resin molded body side direction aluminium shaping side when many observation lines that thickness direction extends with the interval of 0.1 μ m each other; There is the laminated section more than at least 1 that is made up of resin-aluminium-resin in cornice shape protuberance on 1 observation line, and in the scope below the 30 μ m, there is 1 the above cornice shape protuberance in the thickness of the aluminium formed body of said laminated section part in the scope of 1000 observation lines more than 0.1 μ m.
5. like the good aluminium-resin complexes of each described weatherability in the claim 1～4, the dual concavity portion structure of the inside concavity portion that partly or entirely the having of a plurality of concavity portion of aluminium formed body is formed with on the wall of inside more than 1 at least.
6. like the good aluminium-resin complexes of each described weatherability in the claim 1～4, partly or entirely the having of a plurality of concavity portion of aluminium formed body is formed with the inside concaveconvex structure of at least 1 above inner projection portion on the wall of inside.
7. like the good aluminium-resin complexes of each described weatherability in the claim 1～6,60 degree mirror surface lusters of aluminium formed body are below 60.
8. like the good aluminium-resin complexes of each described weatherability in the claim 1～7, the surface area of aluminium formed body is more than 1.2 times below 10 times of surface area that form the aluminum alloy materials before the jog.
9. the manufacturing approach of aluminium-resin complexes that a weatherability is good; Said compound contains aluminium alloy system aluminium formed body and is positioned at the lip-deep resin molded body of said aluminium formed body; The manufacturing approach of said aluminium-resin complexes is characterised in that; Etch processes aluminum alloy materials and be formed on the aluminum alloy materials that part or all of surface has a plurality of concavity portion that causes because of jog; Then, implement the aluminium film on the jog at least of said aluminum alloy materials surface and form and handle, form to contain in the outmost surface of said jog and be selected from Al (OH) 3, AlO (OH), Al 2O 3, Al (PO 4), Al 2(HPO 4) 3, Al (H 2PO 4) 3And AlOSiO 2In the aluminium film of any one above aluminium compound; Form the aluminium formed body of aluminium alloy system thus; In addition; When resin molded body was shaped, resin got into each concavity portion of aluminium formed body and is solidified to form the Embedded Division of resin molded body, thereby the Embedded Division of the concavity portion of aluminium formed body and resin molded body engages aluminium formed body and the integrated combination of resin molded body each other.
10. the manufacturing approach of aluminium-resin complexes that weatherability as claimed in claim 9 is good, the aluminium film of aluminium formed body form to handle forms through being selected from following any one aluminium film: dipping is more than 60 seconds in the warm water more than 50 ℃; 0.1MPa above adding depressed, steam treatment is more than 1 minute; Dipping is after 30 seconds～30 minutes, with 80～400 ℃ heated-air dryings 30 seconds～30 minutes in the phosphoric acid class aqueous solution of 0.1～100g/L of the phosphate radical class more than any one in containing phosphate radical, hydrogen phosphate, dihydrogen phosphate; With dipping in the solution of the silane coupler that contains 0.1～100g/L after 30 seconds～30 minutes with 80～400 ℃ heated-air drying 30 seconds～30 minutes.
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CN111571916A (en) * 2019-02-15 2020-08-25 国立大学法人东京大学 Method for producing composite component and composite component
CN110588104A (en) * 2019-08-13 2019-12-20 安徽凤杰金属资源有限公司 Flame-retardant recycled plastic particles
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