CN105196652B - A kind of metal-resin composite and preparation method thereof - Google Patents

A kind of metal-resin composite and preparation method thereof Download PDF

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Publication number
CN105196652B
CN105196652B CN201410305849.XA CN201410305849A CN105196652B CN 105196652 B CN105196652 B CN 105196652B CN 201410305849 A CN201410305849 A CN 201410305849A CN 105196652 B CN105196652 B CN 105196652B
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resin
metal
etch pit
metal base
weight
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CN105196652A (en
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孙剑
吴彦琴
张云侠
陈梁
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BYD Co Ltd
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BYD Co Ltd
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Priority to PCT/CN2015/082541 priority patent/WO2016000574A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/542—Shear strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

A kind of metal-resin composite and preparation method thereof.The invention discloses a kind of copper or copper alloy resin composite body and preparation method thereof, the preparation method includes：The metal base of the oxide membranous layer at least part surface for including metallic base layer and being attached to metallic base layer is provided；Metal base is subjected to chemical etching, in oxidation film layer surface formation etch pit, to obtain surface treated metal base；Resiniferous composition is injected to the surface of surface treated metal base, and fraction compositions is filled in etch pit, resin bed is formed after shaping.In the metal-resin composite of the present invention, the bond strength between resin and metal base is high, and resin bed is difficult to come off from metallic substrate surface, thus with higher structural stability, disclosure satisfy that the requirement for requiring structural stability higher use occasion.The applicability for the preparation method that the present invention is provided is good, can be used for being combined various kinds of resin with metal base, so as to meet the requirement of a variety of use occasions.

Description

A kind of metal-resin complex and preparation method thereof
Technical field
The present invention relates to a kind of metal-resin complex and preparation method thereof, more particularly it relates to a kind of copper or Copper alloy-resin composite body and preparation method thereof.
Background technology
, it is necessary to which metal and resin are integrally melted into the part manufacture field of automobile, household electrical appliance product, industrial machine etc. Type technology.
The conventional method for being combined metal and resin is bonding technique at present.This method is by chemical adhesive by gold Category obtains complex together with molded resin-bonded.But, in the complex obtained by this method, the knot of metal and resin Close intensity poor, and adhesive binder course not acid and alkali-resistance, influence the use occasion of complex.Further, since adhesive binder course With certain thickness, thus the size of final products can be influenceed.
For adhesive method above shortcomings, researcher develops a variety of be used for the side of metal and resin-bonded Method.
CN101528437B discloses the complex of a kind of metal and resin, by copper or the base material and the first resin of copper alloy Composition or the second resin combination are formed, and the base material of the copper or copper alloy is formed in the following way：Add using machinery Work and be processed into after regulation shape, in order to by surface dissolve and carry out chemical etching, and the surface by under strong basicity lead to Peroxidating dosage form into Cu oxide thin layer covering；First resin combination or second resin combination utilize injection Shaping and directly engaged with the surface, first resin combination is using polyphenylene sulfide as principal component, described the Two resin combinations are using polybutylene terephthalate (PBT) as principal component, and the surface has following ultra tiny male and fomale(M＆F) simultaneously And there is the face being made up of following roughness face simultaneously, wherein, the ultra tiny male and fomale(M＆F) refers to that by gap periods be 10- The ultra tiny male and fomale(M＆F) that 500nm, a diameter of 10-150nm and depth or height cover for 10-500nm recess or convex portion, institute State roughness face and refer to that the big concavo-convex cycle of the male and fomale(M＆F) is 0.5-10 μm of RSm i.e. mountain valley average period, and this is coarse The concavo-convex difference of height in face be 0.2-5 μm of Rz be maximal roughness height roughness face.The complex of the metal and resin can be with It is made of following methods：Base material is processed into defined shape using machining, chemical etching is then carried out with by surface Dissolving, and the thin layer of Cu oxide is formed on surface by oxidant under strong basicity, using injection molding by the first resin group Compound or the second resin combination and substrate surface directly in conjunction with.
CN102371697A discloses a kind of preparation method of the complex of metal and resin, and this method includes following step Suddenly：(1) metalwork is provided, wherein, the metalwork can be copper or copper alloy；(2) degreasing degreasing is carried out to the metalwork Cleaning；(3) local masking is carried out to the metalwork to handle；The metalwork is sprayed using hard particles, with what is exposed in metalwork Surface forms micropore；The metalwork is embedded into a molding tool, and heats metalwork to 100-350 DEG C；In the mould The crystal type thermoplastic resin of middle injection melting is simultaneously cooled down, and resin enters to be combined in the micropore on metalwork surface with metalwork.
But, in the complex of the metal-resin prepared using the above method, the combination between resin and metal base is strong Degree still awaits further raising.In addition, method disclosed in CN101528437B also has certain requirement to the species of resin, This limits the application scenario of metal-resin complex to a certain extent.
The content of the invention
It is an object of the invention to overcome in existing copper or copper alloy-resin composite body, resin bed and copper or copper alloy The not high technical problem of bond strength between base material there is provided a kind of copper or copper alloy-resin composite body and preparation method thereof, by In copper or copper alloy-resin prepared by the method for the present invention, there is higher combination between resin bed and copper or copper alloy substrate Intensity.
According to the first aspect of the invention, it is described the invention provides a kind of preparation method of metal-resin complex Metal is copper or copper alloy, and this method comprises the following steps：
(1) a kind of metal base is provided, the metal base includes metallic base layer and is attached to the metallic base layer At least part surface oxide membranous layer, the metallic base layer is structure as a whole with the oxide membranous layer；
(2) by the metal base carry out chemical etching, with the oxidation film layer surface formation etch pit, obtain through The metal base of surface treatment；
(3) resiniferous composition is injected to the surface of the surface treated metal base, and makes fraction compositions Extend downwardly and be filled in the etch pit, resin bed is formed after shaping.
According to the second aspect of the invention, the invention provides metal-resin prepared by a kind of method by the present invention Complex.
According to the third aspect of the present invention, the invention provides a kind of metal-resin complex, the metal be copper or Copper alloy, the complex includes metal base and is attached to the resin bed at least part surface of the metal base, described Metal base includes metallic base layer and is attached to the oxide membranous layer at least part surface of the metallic base layer, described Oxide membranous layer is structure as a whole with the metallic base layer, and the surface distributed of the oxide membranous layer has etch pit, the tree Part resin in lipid layer is extended downwardly and is filled in the etch pit.
According to the metal-resin complex of the present invention, the bond strength between resin and metal base is high, and resin bed is difficult Come off from metallic substrate surface, thus the metal-resin complex that the present invention is provided has higher structural stability, Neng Gouman Foot requires structural stability the requirement of higher use occasion.
The applicability of the preparation method for the metal-resin complex that the present invention is provided is good, can be used for by various kinds of resin with Metal base is combined, so as to meet the requirement of a variety of use occasions.
Embodiment
In the present invention, the metal is copper or copper alloy.The copper alloy refers to that element addition is other based on copper The alloy of element formation, can be common each Albatra metal, such as brass.Metal base be with copper or copper alloy formation it is various Formed body, can have variously-shaped according to specifically used requirement.
According to the first aspect of the invention, the invention provides a kind of preparation method of metal-resin complex, the party Method includes step (1)：A kind of metal base is provided, the metal base includes metallic base layer and is attached to the metallic matrix The oxide membranous layer at least part surface of layer, the metallic base layer is structure as a whole with the oxide membranous layer.The oxygen Compound film layer is for oxidation copper film layer or using cupric oxide as the oxide membranous layer of main component, for example：In the metal base During for copper alloy, the oxide membranous layer can also contain other alloying element formation in copper alloy in addition to containing cupric oxide Oxide.
The thickness of the oxide membranous layer is generally 0.1-50 μm, more preferably preferably 1-25 μm, 5-10 μm.From entering one The angle that step improves the structural stability of the metal-resin complex finally prepared is set out, the oxide membranous layer and the gold The ratio for belonging to the thickness of base layer is 0.001-1：1, preferably 0.005-0.5：1, more preferably 0.005-0.01：1.
The oxide membranous layer can be formed using various methods.The present invention it is a kind of preferred embodiment in, The oxide membranous layer is that is, described oxide membranous layer is anodic oxidation by the way that metallic matrix is carried out formed by anodic oxidation The oxide membranous layer of formation, the metal-resin complex being consequently formed has higher structural stability.
The present invention is not particularly limited for the method for anodic oxidation, can be conventional selection.Specifically, can be by inciting somebody to action The metallic matrix is placed in electrolyte, using the metallic matrix as anode, using conductive material not with electrolyte reaction as the moon Pole, makes negative electrode and anode be electrically connected respectively with the positive pole and negative pole of power supply, after energization, is electrolysed, so that in the Metal Substrate Oxide membranous layer is formed on the surface of body.The electrolyte can be various under anodic oxidation condition for what is commonly used, can be in copper Or the electrolyte of copper alloy surface formation oxide membranous layer.
Specifically, the electrolyte contains at least one alkali compounds.Herein, " at least one " represents one kind or two More than kind.The alkali compounds can be for example alkali and/or basic salt, be preferably selected from alkali metal hydroxide (such as hydroxide Sodium and/or potassium hydroxide), the alkali metal salt of the alkali metal salt of carbonic acid and phosphoric acid.The alkali metal salt can be sodium salt or sylvite. It is highly preferred that the alkali compounds is selected from sodium hydroxide, sodium carbonate and sodium phosphate.In the electrolyte, alkali compounds Concentration typically can be 1-50 weight %, more preferably preferably 10-30 weight %, 20-30 weight %.
The present invention it is a kind of preferred embodiment in, the electrolyte is also containing at least one molybdate, so not The speed of anodic oxidation can be only improved, production efficiency is improved；And the metal-resin complex finally prepared show it is higher Structural stability.The molybdate is the alkali metal salt of water-soluble molybdenum hydrochlorate, preferably molybdic acid, such as sodium molybdate and/or molybdic acid Potassium, more preferably sodium molybdate.Depending on amount of the concentration of the molybdate with the alkali compounds.Preferably, the electrolyte The concentration of middle molybdate is 1-10 weight %.It is highly preferred that the concentration of molybdate is 1-5 weight % in the electrolyte.
The condition of anodic oxidation can be conventional selection, and use requirement is disclosure satisfy that with the thickness of the oxide membranous layer of formation It is defined.Preferably, the condition of anodic oxidation includes：Voltage is 10-100V, preferably 10-50V, more preferably 15-30V；Time For 1-60 minutes, preferably 5-30 minutes, more preferably 5-20 minutes.Electrolyte temperature is -20 DEG C to 80 DEG C, preferably 20- 60 DEG C, more preferably 40-60 DEG C.
The method according to the invention also includes step (2)：The metal base is subjected to chemical etching, with the oxidation Thing film surface formation etch pit, obtains surface treated metal base.
The method according to the invention, by the way that the metal base is carried out into chemical etching, is formed in oxidation film layer surface Etch pit, so in metallic substrate surface formation resin bed, the part resin in resin bed is filled in the etch pit, from And can improve in the metal-resin complex of preparation, the bond strength between resin bed and metal base.
The method according to the invention, the condition of the chemical etching is preferably so that the etch pit formed in oxide membranous layer Aperture in the range of 200-2000nm, the ratio of the thickness of the depth of the etch pit and the oxide membranous layer typically exists 0.1-1：In the range of 1.It is highly preferred that the condition of the etching causes the aperture of the etch pit formed in oxide membranous layer to exist In the range of 800-1500nm, the ratio of the thickness of the depth of the etch pit and the oxide membranous layer is in 0.1-0.5：1 In the range of, in the metal-resin complex being consequently formed, there is higher structural stability between resin bed and metal base. It is further preferred that the condition of the chemical etching causes the aperture of the etch pit formed in oxide membranous layer in 1000- In the range of 1500nm, the ratio of the thickness of the depth of the etch pit and the oxide membranous layer is in 0.2-0.4：1 scope It is interior.In the present invention, the aperture of etch pit refers to the upper port of etch pit (that is, positioned at the port of oxidation film layer surface) radially Full-size, the depth of etch pit refers to the vertical range between the two ends of an etch pit.The aperture of etch pit and depth can To be determined using electron microscopy.
Chemical etching can be carried out to metal base using conventional various methods, so that in the oxidation film layer surface Form etch pit.The present invention it is a kind of preferred embodiment in, the method for the chemical etching includes：By the Metal Substrate Material is soaked in acidic etching liquid.The acidic etching liquid is preferably to contain at least one sour aqueous solution.The acid can be selected From halogen acids, H3PO4、H2SO4And HNO3, the halogen acids is preferably HCl.
Sour concentration is preferably 0.1-50 weight % in the acidic etching liquid.It is highly preferred that in the acidic etching liquid The concentration of acid is 1-30 weight %.It is further preferred that concentration sour in the acidic etching liquid is 20-30 weight %, so Etch pit can not only be formed in oxide membranous layer, and the corrosion that size is more homogeneous and more uniformly spreads can be formed Hole, so as to obtain the metal-resin complex with higher structural stability.
In a kind of embodiment being more highly preferred to, the acidic etching liquid also contains at least one water soluble salt, so The stability of etching can be further improved, is made in the metal-resin complex that finally prepares, between resin bed and metal base With higher structural stability.Depending on the amount of the water soluble salt is with the sour amount in acidic etching liquid.Preferably, the water Soluble is 0.1-1 with the sour mol ratio：1.
The water soluble salt is preferably selected from halogen acid salt, phosphate, sulfate and nitrate.The water soluble salt it is specific Example can include but is not limited to：NaCl、KCl、AlCl3、NaH2PO4、Na2HPO4、Na3PO4、KH2PO4、K2HPO4、K3PO4、 Na2SO4、K2SO4、NaNO3And KNO3.It is highly preferred that the water soluble salt is NaCl, NaH2PO4、Na2HPO4、NaNO3With Na2SO4In it is a kind of two or more.It is further preferred that sour in the acid group of the water soluble salt and the acidic etching liquid Acid group is identical.For example, when the acid in the acidic etching liquid is halogen acids, the water soluble salt is preferably halogen acid salt.
The temperature of the acidic etching liquid can be conventional selection.Usually, the temperature of the acidic etching liquid can be 10-60 DEG C, preferably 20-40 DEG C.
Depending on the time of the chemical etching is with species and concentration sour in acidic etching liquid.Usually, the chemistry The time of etching is 1-60 minutes.It is described from the angle for the dimensional homogeneity for further improving the etch pit ultimately formed The time of chemical etching is preferably 10-30 minutes.The chemical etching can be carried out once, can also carry out (that is, carrying out by several times Chemical etching more than twice), required as long as the total time of chemical etching meets.It is progress by several times in the chemical etching When, can by several times it be etched using identical etching solution, it would however also be possible to employ different etching solutions is etched by several times.By several times When carrying out chemical etching, after the completion of each chemical etching, the etched metal base of preferred pair is cleaned, to remove residual Etching solution.
The method according to the invention also includes step (3)：Contain to the surface injection of the surface treated metal base The composition of resin, and fraction compositions is filled in the etch pit, resin bed is formed after shaping.
Resin (hereinafter referred to as matrix resin) in the resiniferous composition can enter according to specific use requirement Row selection, as long as the resin can be combined with copper or copper alloy.Usually, the matrix resin can be selected from thermoplastic resin Fat, for example, can be more than one or both of polyphenylene sulfide, polyester, polyamide, makrolon and polyolefin.The polyester It can include but is not limited to poly- pair for the common various polymer being condensed by dicarboxylic acids and glycol, its instantiation Benzene dicarboxylic acid butanediol ester and/or polyethylene terephthalate.The polyamide can for it is common it is various by diamines with Dicarboxylic acids condensation polymer, its instantiation can include but is not limited to polyhexamethylene adipamide, poly- nonanedioyl oneself two Amine, polybutadiene acyl hexamethylene diamine, nylon 612, polyhexamethylene sebacamide, nylon 1010, poly- undecanoyl Amine, poly-lauramide, poly-caprylamide, poly- 9 aminononanoic acid, polycaprolactam, poly-paraphenylene terephthalamide's phenylenediamine, poly- isophthalic diformazan Acyl hexamethylene diamine, poly- hexamethylene terephthalamide and poly-paraphenylene terephthalamide's nonamethylene diamine.The instantiation of the polyolefin can include But it is not limited to polystyrene, polypropylene, polymethyl methacrylate and poly- (acrylonitrile-butadiene-styrene (ABS)).
The resiniferous composition can also contain at least one filler and/or at least one in addition to containing matrix resin Plant fluidity improver.
The species of the filler can be selected according to specific use requirement.The filler can be various fibrous types Filler and/or powder-type filler.The fibrous type filler can be in glass fibre, carbon fiber and aramid fibre One or more.The powder-type filler can be selected from calcium carbonate, magnesium carbonate, silica, heavy barium sulfate, cunning It is more than one or both of stone flour, glass and clay.The size of the filler can be conventional selection, as long as being able to ensure that shape Into fine and close resin bed.Typically, for fibrous type filler, its length can be 1-10mm；For powder-type filler, its Particle diameter can be 1-200 μm.
The content of the filler can be conventional selection.Usually, it is described to fill out on the basis of 100 parts by weight matrix resins The content of material can be 20-150 parts by weight, preferably 30-60 parts by weight.
The fluidity improver is used to improve the fluid ability of matrix resin, further improve metal base and resin it Between bond strength and resin processing characteristics.The fluidity improver can realize the thing of the effect above to be various Matter, preferably cyclic polyester.
The consumption of the fluidity improver is defined by the fluid ability that can improve matrix resin.Preferably, relative to 100 parts by weight matrix resins, the content of the fluidity improver is 1-5 parts by weight.
The resiniferous composition can also contain common various auxiliary agents, such as colouring agent according to specifically used requirement And/or antioxidant, with improve in the metal-resin complex that ultimately forms the performance of resin bed or assign the resin bed with New performance.
Resiniferous composition can by by matrix resin, optional filler, optional fluidity improver and appoint The auxiliary agent of choosing is well mixed and obtains.Usually, can by matrix resin, optional filler, optional fluidity improver with And optional auxiliary agent is well mixed, and carries out extruding pelletization and obtain.
Conventional various methods can be used to inject the resiniferous composition to the surface of metal base, and carried out into Type, such as flow casting molding or injection molding.The present invention it is a kind of preferred embodiment in, the metal base is placed in mould In tool, the resiniferous composition is injected by the method for injection and is molded.
The condition of the injection can be selected according to the species of matrix resin in resiniferous composition.Preferably, The condition of the injection includes：Mold temperature (that is, mould temperature) is 50-300 DEG C；Nozzle temperature is 200-450 DEG C；Dwell time is 1-50 seconds, preferably 3-10 seconds；Injection pressure is 50-300MPa, preferably 80-200MPa；The injection time is 1-30 seconds, preferably For 3-10 seconds；Time delay is 1-30 seconds, preferably 1-10 seconds.Preferably, mold temperature is 100-180 DEG C of (such as 120-160 DEG C), nozzle temperature is 280-350 DEG C (such as 290-320 DEG C), so on the one hand can make resiniferous composition well into corrosion Kong Zhong, makes in the metal-resin complex that ultimately forms, has higher bond strength between resin bed and metal base；Separately On the one hand it is easy to regulate and control mold temperature.
The injection rate of the resiniferous composition can be selected according to expected resin layer thickness.Usually, institute The injection rate of resiniferous composition is stated so that the thickness of the resin bed formed is 0.5-10mm.Herein, the thickness of resin bed Refer to the upper surface of oxide membranous layer that connects with resin bed to the vertical range between the upper surface of resin bed.
The method according to the invention, can be to not necessarily forming tree only in the part surface formation resin bed of metal base The surface of lipid layer is handled, and to remove surface hole defect and surface color changes caused by etching, the processing can be with Carried out before injecting resiniferous composition and being molded, resiniferous composition can also injected and shaping is carried out After carry out, be not particularly limited.
Have in the metal-resin complex prepared by the method for the present invention, between resin bed and metal base higher Bond strength, disclosure satisfy that the requirement of the use occasion higher to structural stability.
Thus, according to the second aspect of the invention, present invention also offers gold prepared by a kind of method by the present invention Category-resin composite body.
According to the third aspect of the present invention, the invention provides a kind of metal-resin complex, the metal be copper or Copper alloy, the complex includes metal base and is attached to the resin bed at least part surface of the metal base, described Metal base includes metallic base layer and is attached to the oxide membranous layer on metallic base layer at least part surface, the oxygen Compound film layer is structure as a whole with the metallic base layer, and the surface distributed of the oxide membranous layer has etch pit, the resin Part resin in layer is extended downwardly and is filled in the etch pit.
The thickness of the oxide membranous layer is generally 0.1-50 μm, more preferably preferably 1-25 μm, 5-10 μm.The oxygen The ratio of compound film layer and the thickness of the metallic base layer is 0.001-1：1, preferably 0.005-0.5：1, more preferably 0.005-0.01：1.
According to the complex of the present invention, the aperture of the etch pit more preferably exists preferably in the range of 200-2000nm In the range of 800-1500nm, further preferably in the range of 1000-1500nm；The depth of the etch pit and the oxidation The ratio of the thickness of thing film layer is preferably in 0.1-1：In the range of 1, more preferably in 0.1-0.5：In the range of 1, further preferably In 0.2-0.4：In the range of 1.
Matrix resin in the resin bed can be selected according to specific use requirement, as long as the resin energy and copper Or copper alloy is combined.Usually, the matrix resin in the resin bed can be selected from thermoplastic resin, for example, can be poly- It is more than one or both of diphenyl sulfide, polyester, polyamide, makrolon and polyolefin.The polyester can for it is common by The polymer that dicarboxylic acids is condensed with glycol, its instantiation can include but is not limited to polybutylene terephthalate (PBT) And/or polyethylene terephthalate.The polyamide can be common by diamines and polymerizeing that dicarboxylic acids is condensed Thing, its instantiation can include but is not limited to polyhexamethylene adipamide, poly-hexamethylene azelamide, polybutadiene acyl hexamethylene diamine, poly- Hexamethylene dodecanoamide, polyhexamethylene sebacamide, nylon 1010, nylon 11, poly-lauramide, poly- decoyl Amine, poly- 9 aminononanoic acid, polycaprolactam, poly-paraphenylene terephthalamide's phenylenediamine, poly-6I hexamethylene isoterephalamide, poly- paraphenylene terephthalamide Hexamethylene diamine and poly-paraphenylene terephthalamide's nonamethylene diamine.The instantiation of the polyolefin can include but is not limited to polystyrene, poly- third Alkene, polymethyl methacrylate and poly- (acrylonitrile-butadiene-styrene (ABS)).
The resin bed can also contain at least one filler in addition to containing matrix resin.The species of the filler can be with Selected according to specific use requirement.The filler can be fibrous type filler and/or powder-type filler.The fibrous type Filler can be more than one or both of glass fibre, carbon fiber and aramid fibre.The powder-type is filled out Material can be selected from one or both of calcium carbonate, magnesium carbonate, silica, heavy barium sulfate, talcum powder, glass and clay More than.The content of the filler can be conventional selection.Usually, on the basis of 100 parts by weight matrix resins, the filler Content can be 20-150 parts by weight, preferably 30-60 parts by weight.The size of the filler can be conventional selection, as long as energy Enough ensure the resin bed to form densification.Typically, for fibrous type filler, its length can be 1-10mm；For powder Type filler, its particle diameter can be 1-200 μm.
According to the complex of the present invention, the thickness of the resin bed can be selected according to specific use occasion.One As, the thickness of the resin bed is in the range of 0.5-10mm.
Describe the present invention in detail with reference to embodiments, but therefore do not limit the scope of the present invention.
In following examples and comparative example, the method according to as defined in ASTM D1002-10 is omnipotent in INSTRON3369 types Test the average shear force in aircraft measurements metal-resin complex between metal base and resin bed and observe fracture mode.
In following examples and comparative example, using the metallographic microscope of the model Axio Imager Alm purchased from ZEISS The depth of the thickness and etch pit that determine anode oxidation membrane (is observed five diverse locations of same sample, determined The depth of the whole etch pits occurred within sweep of the eye), using the model JSM-7600F's purchased from Jeol Ltd. (five diverse locations of same sample are observed, field range is determined in the aperture that SEM determines etch pit The aperture of whole etch pits of interior appearance).
Embodiment 1-10 is used to illustrate metal-resin complex of the present invention and preparation method thereof.
Embodiment 1
(1) commercially available thickness is cut into 15mm × 80mm rectangular pieces for 1mm brass sheet.Rectangular pieces are put into polishing It is polished in machine.Then cleaned, be then soaked in the sodium hydrate aqueous solution that concentration is 2 weight % with absolute ethyl alcohol, Taking-up is rinsed well with deionized water after 2min, obtains the brass sheet material by pre-treatment.
(2) the brass sheet material for obtaining step (1) is put into the NaOH containing 20 weight % and 1 weight % as anode Sodium molybdate the aqueous solution as in the anodizing tank of electrolyte, using graphite carbon plate as negative electrode, under 15V voltage, 60 DEG C are electrolysed 5 minutes, to carry out anodic oxidation.Brass sheet material through anodic oxidation is taken out and dried up, obtaining surface has sun The brass substrate of pole oxidation film layer.After measured, the thickness of anode oxidation membrane is 8 μm.
(3) there is the brass substrate of anode oxidation membrane to be that 20 DEG C of concentration are 30 in temperature on the surface for obtaining step (2) After being soaked 10 minutes in weight % hydrochloric acid, take out and soaked 1 minute in water, then take out drying, obtain surface treated Brass substrate.
After measured：Aperture is distributed with the anode oxidation membrane of surface treated brass substrate in 800-1500nm scopes The ratio of interior etch pit, the depth of the etch pit and the thickness of anode oxidation membrane is in 0.1-0.5：In the range of 1.
(4) the surface treated brass substrate for obtaining step (3) is placed in injecting molding die, and injection contains polyphenyl (fibre length is 5mm, relative to 100 parts by weight PPS, and the content of glass fibre is 30 weight for thioether (PPS) and glass fibre Part) resin combination, be stripped and cool down.Wherein, injecting condition includes：Mould temperature is 120 DEG C, and nozzle temperature is 305 DEG C, pressurize Time is 5 seconds, and injection pressure is 120MPa, and the time of projecting is 5 seconds, and time delay is 3 seconds.
Product after cooling is put into 120 DEG C of thermostatic drying chamber and is incubated 1.5h, then room temperature is naturally cooled to stove, Metal-resin complex (thickness of resin bed is 2mm) is made, its average shear strength and fracture mode are listed in table 1.
Comparative example 1
(1) use and prepare brass sheet material with the step of embodiment 1 (1) identical method.
(2) using the brass that resin combination is molded into step (1) preparation with the step of embodiment 1 (4) identical method Sheet surface, so as to obtain metal-resin complex (thickness of resin bed is 2mm), its average shear strength and fracture mode Listed in table 1.
Comparative example 2
(1) use and prepare brass sheet material with the step of embodiment 1 (1) identical method.
(2) anodic oxidation is carried out using with the brass sheet material that the step of embodiment 1 (2) identical method prepares step (1), Obtaining surface has the brass substrate of anode oxidation membrane.
(3) resin combination is moulded in the surface that step (2) is obtained using with the step of embodiment 1 (4) identical method Brass substrate surface with anode oxidation membrane, so that metal-resin complex (thickness of resin bed is 2mm) is obtained, its Average shear strength and fracture mode are listed in table 1.
Comparative example 3
(1) use and prepare brass sheet material with the step of embodiment 1 (1) identical method.
(2) (etching solution is to contain 3 weights to the brass sheet material for preparing step (1) in the etching solution that temperature is 30 DEG C Measure the aqueous solution of % sulfuric acid and 3 weight % hydrogen peroxide) soak 15 minutes, take out and simultaneously soaked 1 minute in water, then take out and blow It is dry.Then, by brass sheet material in temperature is 70 DEG C of aqueous solution containing 10 weight % sodium hydroxides and 5 weight % sodium sulfites Immersion 1 minute, by brass sheet material surface oxidation.Soaked 1 minute in water after taking-up, obtain surface treated brass base Material.
(3) using with the step of embodiment 1 (4) identical method by resin combination be moulded in that step (2) obtains through table The brass substrate surface of face processing, so as to obtain metal-resin complex (thickness of resin bed is 2mm), its average shear is strong Degree and fracture mode are listed in table 1.
Embodiment 2
(1) use and prepare brass sheet material with the step of embodiment 1 (1) identical method.
(2) anode oxidation membrane is formed in brass sheet surface using with the step of embodiment 1 (2) identical method, it is different , electrolyte do not contain sodium molybdate, and electrolysis time is 8 minutes.After measured, the thickness of anode oxidation membrane is 8 μm.
(3) there is the brass substrate of anode oxidation membrane to be that 20 DEG C of concentration are 30 in temperature on the surface for obtaining step (2) After being soaked 10 minutes in weight % hydrochloric acid, take out and soaked 1 minute in water, then take out drying, obtain surface treated Brass substrate.
After measured：Aperture is distributed with the anode oxidation membrane of surface treated brass substrate in 800-1500nm scopes The ratio of interior etch pit, the depth of the etch pit and the thickness of anode oxidation membrane is in 0.1-0.5：In the range of 1.
(4) using with the step of embodiment 1 (4) identical method by resin combination be moulded in that step (3) obtains through table The surface of the brass substrate of face processing, so as to obtain metal-resin complex (thickness of resin bed is 2mm), its average shear Intensity and fracture mode are listed in table 1.
Embodiment 3
(1) use and prepare brass sheet material with the step of embodiment 1 (1) identical method.
(2) using the brass sheet surface formation anode prepared with the step of embodiment 1 (2) identical method in step (1) Oxidation film layer, so that obtaining surface has the brass substrate of anode oxidation membrane.
(3) carried out using the brass substrate to surface with the step of embodiment 1 (3) identical method with anode oxidation membrane Chemical etching, unlike, the mol ratio that etching solution also contains NaCl, NaCl and HCl is 1：1, so as to obtain surface treated Brass substrate.
After measured：Aperture is distributed with the anode oxidation membrane of surface treated brass substrate in 1000-1500nm models The ratio of etch pit in enclosing, the depth of the etch pit and the thickness of anode oxidation membrane is in 0.2-0.4：In the range of 1.
(4) resin combination is molded into surface treated brass base using with the step of embodiment 1 (4) identical method Material surface, so as to obtain metal-resin complex (thickness of resin bed is 2mm), its average shear strength and fracture mode exist Listed in table 1.
Embodiment 4
(1) use and prepare brass sheet material with the step of embodiment 1 (1) identical method.
(2) using the brass sheet surface formation anode prepared with the step of embodiment 1 (2) identical method in step (1) Oxidation film layer, so that obtaining surface has the brass substrate of anode oxidation membrane.
(3) use and be etched with the step of embodiment 1 (3) identical method, unlike, brass substrate is in hydrochloric acid Soak time is 40 minutes.
After measured：Aperture is distributed with the anode oxidation membrane of surface treated brass substrate in 200-2000nm scopes The ratio of interior etch pit, the depth of the etch pit and the thickness of anode oxidation membrane is in 0.1-1：In the range of 1.
(4) resin combination is molded into surface treated brass base using with the step of embodiment 1 (4) identical method Material surface, so as to obtain metal-resin complex (thickness of resin bed is 2mm), its average shear strength and fracture mode exist Listed in table 1.
Embodiment 5
(1) commercially available thickness is cut into 15mm × 80mm rectangular pieces for 1mm brass sheet.Rectangular pieces are put into polishing It is polished in machine.Then cleaned, be then soaked in the sodium hydrate aqueous solution that concentration is 2 weight % with absolute ethyl alcohol, Taking-up is rinsed well with deionized water after 2min, obtains the brass sheet material by pre-treatment.
(2) the brass sheet material for obtaining step (1) is put into the Na containing 30 weight % as anode3PO4And 5 weights The % aqueous solution of sodium molybdate is measured as in the anodizing tank of electrolyte, using graphite carbon plate as negative electrode, in 25V voltage Under, it is electrolysed 15 minutes at 50 DEG C, to carry out anodic oxidation.Brass sheet material through anodic oxidation is taken out and dried up, surface is obtained Brass substrate with anode oxidation membrane.After measured, the thickness of anode oxidation membrane is 8.5 μm.
(3) there is the brass substrate of anode oxidation membrane to be that 35 DEG C of concentration are 25 in temperature on the surface for obtaining step (2) After being soaked 10 minutes in weight % sulfuric acid, take out and soaked 1 minute in water, then take out drying, obtain surface treated Brass substrate.
After measured：Aperture is distributed with the anode oxidation membrane of surface treated brass substrate in 800-1500nm scopes The ratio of interior etch pit, the depth of the etch pit and the thickness of anode oxidation membrane is in 0.1-0.5：1.
(4) the surface treated brass substrate for obtaining step (3) is placed in injecting molding die, and injection contains poly- pair (volume average particle size is 4 μm, relative to 100 parts by weight PBT, and talcum powder contains for benzene dicarboxylic acid butanediol ester (PBT) and talcum powder Measure as 40 parts by weight) resin combination, be stripped and cool down.Wherein, injecting condition includes：Mould temperature is 120 DEG C, and nozzle temperature is 305 DEG C, the dwell time is 5 seconds, and injection pressure is 120MPa, and the time of projecting is 5 seconds, and time delay is 3 seconds.
Product after cooling is put into 120 DEG C of thermostatic drying chamber and is incubated 1.5h, then room temperature is naturally cooled to stove, Metal-resin complex (thickness of resin bed is 4mm) is made, its average shear strength and fracture mode are listed in table 1.
Embodiment 6
(1) brass sheet material is provided using with the step of embodiment 5 (1) identical method.
(2) brass sheet material is subjected to anodic oxidation using with the step of embodiment 5 (2) identical method, so as to obtain surface Brass substrate with anode oxidation membrane.
(3) brass substrate is subjected to chemical etching using with the step of embodiment 5 (3) identical method, unlike, etching Also contain Na in liquid2SO4, wherein, Na2SO4With H2SO4Mol ratio be 0.5：1, so as to obtain surface treated brass base Material.
After measured：Aperture is distributed with the anode oxidation membrane of surface treated brass substrate in 1000-1500nm models The ratio of etch pit in enclosing, the depth of the etch pit and the thickness of anode oxidation membrane is in 0.2-0.4：In the range of 1.
(4) resin combination is molded into surface treated brass base using with the step of embodiment 5 (4) identical method The surface of material, so as to obtain metal-resin complex (resin layer thickness is 4mm), its average shear strength and fracture mode exist Listed in table 1.
Embodiment 7
(1) commercially available thickness is cut into 15mm × 80mm rectangular pieces for 1mm brass sheet.Rectangular pieces are put into polishing It is polished in machine.Then cleaned, be then soaked in the sodium hydrate aqueous solution that concentration is 2 weight % with absolute ethyl alcohol, Taking-up is rinsed well with deionized water after 2min, obtains the brass sheet material by pre-treatment.
(2) the brass sheet material for obtaining step (1) is put into the Na containing 25 weight % as anode2CO3And 5 weight % Sodium molybdate the aqueous solution as in the anodizing tank of electrolyte, using graphite carbon plate as negative electrode, under 20V voltage, 40 DEG C are electrolysed 20 minutes, to carry out anodic oxidation.Brass sheet material through anodic oxidation is taken out and dried up, obtaining surface has sun The brass substrate of pole oxidation film layer.After measured, the thickness of anode oxidation membrane is 10 μm.
(3) there is the brass substrate of anode oxidation membrane to be that 30 DEG C of concentration are 20 in temperature on the surface for obtaining step (2) After being soaked 30 minutes in weight % phosphoric acid, take out and soaked 1 minute in water, then take out drying, obtain surface treated Brass substrate.
After measured：Aperture is distributed with the anode oxidation membrane of surface treated brass substrate in 800-1500nm scopes The ratio of interior etch pit, the depth of the etch pit and the thickness of anode oxidation membrane is in 0.1-0.5：In the range of 1.
(4) the surface treated brass substrate for obtaining step (3) is placed in injecting molding die, and injection contains nylon (fibre length is 5mm, relative to 100 parts by weight PA-66, and the content of glass fibre is 50 weight for 66 (PA-66) and glass fibre Part) resin combination, be stripped and cool down.Wherein, injecting condition includes：Mould temperature is 150 DEG C, and nozzle temperature is 305 DEG C, pressurize Time is 5 seconds, and injection pressure is 120MPa, and the time of projecting is 5 seconds, and time delay is 3 seconds.
Product after cooling is put into 120 DEG C of thermostatic drying chamber and is incubated 1.5h, then room temperature is naturally cooled to stove, Metal-resin complex (resin layer thickness is 5mm) is made, its average shear strength and fracture mode are listed in table 1.
Embodiment 8
(1) brass sheet material is provided using with the step of embodiment 7 (1) identical method.
(2) brass sheet material is subjected to anodic oxidation using with the step of embodiment 7 (2) identical method, so as to obtain surface Brass substrate with anode oxidation membrane.
(3) brass substrate is subjected to chemical etching using with the step of embodiment 7 (3) identical method, unlike, etching Also contain Na in liquid2HPO4, wherein, Na2HPO4With H3PO4Mol ratio be 0.2：1, so as to obtain surface treated brass base Material.
After measured：Aperture is distributed with the anode oxidation membrane of surface treated brass substrate in 1000-1500nm models The ratio of etch pit in enclosing, the depth of the etch pit and the thickness of anode oxidation membrane is in 0.2-0.4：In the range of 1.
(4) resin combination is molded into surface treated brass base using with the step of embodiment 7 (4) identical method The surface of material, so as to obtain metal-resin complex (resin layer thickness is 5mm), its average shear strength and fracture mode exist Listed in table 1.
Embodiment 9
(1) use and prepare brass sheet material with the step of embodiment 1 (1) identical method.
(2) anodic oxidation is carried out using with the brass sheet material that the step of embodiment 1 (2) identical method prepares step (1), Obtaining surface has the brass substrate of anode oxidation membrane.
(3) brass substrate that surface has anode oxidation membrane is carried out using with the step of embodiment 1 (3) identical method Etching, unlike, etching solution is the HNO of same concentrations3, so as to obtain surface treated brass substrate.
After measured：Aperture is distributed with the anode oxidation membrane of surface treated brass substrate in 800-1500nm scopes The ratio of interior etch pit, the depth of the etch pit and the thickness of anode oxidation membrane is in 0.1-0.5：In the range of 1.
(4) resin combination is moulded in the surface that step (2) is obtained using with the step of embodiment 1 (4) identical method Brass substrate surface with anode oxidation membrane, so that metal-resin complex (thickness of resin bed is 2mm) is obtained, its Average shear strength and fracture mode are listed in table 1.
Embodiment 10
(1) use and prepare brass sheet material with the step of embodiment 1 (1) identical method.
(2) anodic oxidation is carried out using with the brass sheet material that the step of embodiment 1 (2) identical method prepares step (1), Obtaining surface has the brass substrate of anode oxidation membrane.
(3) brass substrate that surface has anode oxidation membrane is carried out using with the step of embodiment 9 (3) identical method Etching, unlike, etching solution also contains NaNO3, NaNO3With HNO3Mol ratio be 1：1, so as to obtain surface treated Brass substrate.
After measured：Aperture is distributed with the anode oxidation membrane of surface treated brass substrate in 1000-1500nm models The ratio of etch pit in enclosing, the depth of the etch pit and the thickness of anode oxidation membrane is in 0.2-0.4：In the range of 1.
(4) resin combination is moulded in the surface that step (2) is obtained using with the step of embodiment 1 (4) identical method Brass substrate surface with anode oxidation membrane, so that metal-resin complex (thickness of resin bed is 2mm) is obtained, its Average shear strength and fracture mode are listed in table 1.
Table 1
Numbering Average shear strength (MPa) Fracture mode
Embodiment 1 23 A types *
Comparative example 1 0.2 Type B * *
Comparative example 2 5 Type B
Comparative example 3 11 Type B
Embodiment 2 20.2 A types
Embodiment 3 26.8 A types
Embodiment 4 18.1 A types
Embodiment 5 20 A types
Embodiment 6 23.4 A types
Embodiment 7 27 A types
Embodiment 8 30.6 A types
Embodiment 9 21 A types
Embodiment 10 24.5 A types
*：Resin bed is broken * * in itself：Resin bed is broken with metallic bond
Table 1 as a result, it was confirmed that using the present invention method prepare metal-resin complex show that higher being averaged is cut Shearing stress, and fracture mode is that resin bed is broken in itself, in the metal-resin complex that this explanation present invention is provided, tree There is higher bond strength between lipid layer and metal base.Also, the adaptability to raw materials of the method for the present invention is good, can be used for Polytype resin bed is formed in metallic substrate surface.

Claims (25)

1. a kind of preparation method of metal-resin complex, the metal is copper or copper alloy, this method comprises the following steps：
(1) a kind of metal base is provided, the metal base includes metallic base layer and is attached to the metallic base layer extremely The oxide membranous layer on small part surface, the metallic base layer is structure as a whole with the oxide membranous layer, the oxidation film Layer is that the electrolyte that the anodic oxidation is used contains at least one alkali by the way that metallic matrix is carried out formed by anodic oxidation Property compound, the alkali compounds be selected from sodium hydroxide, sodium carbonate and sodium phosphate, the electrolyte also contain 1-10 weight % At least one molybdate；
(2) metal base is subjected to chemical etching, in oxidation film layer surface formation etch pit, to obtain through surface The metal base of processing, the method for the chemical etching includes：The metal base is soaked in acidic etching liquid, the acid Property etching solution be containing at least one sour aqueous solution, it is described acid be selected from halogen acids, H3PO4、H2SO4And HNO3；
(3) resiniferous composition is injected to the surface of the surface treated metal base, and makes fraction compositions downward Extend and be filled in the etch pit, resin bed is formed after shaping.
2. according to the method described in claim 1, wherein, at least one molybdate of the electrolyte also containing 1-5 weight %.
3. method according to claim 1 or 2, wherein, the molybdate is selected from the alkali metal salt of molybdic acid.
4. method according to claim 3, wherein, the molybdate is sodium molybdate.
5. method according to claim 1 or 2, wherein, the concentration of the electrolyte neutral and alkali compound is 1-50 weights Measure %.
6. method according to claim 5, wherein, the concentration of the electrolyte neutral and alkali compound is 10-30 weight %
7. method according to claim 1 or 2, wherein, the condition of the anodic oxidation includes：Voltage is 10-100V, when Between be 1-60 minute, the temperature of electrolyte is -20 DEG C to 80 DEG C.
8. method according to claim 3, wherein, the condition of the anodic oxidation includes：Voltage is 10-100V, time For 1-60 minutes, the temperature of electrolyte was -20 DEG C to 80 DEG C.
9. method according to claim 1 or 2, wherein, the thickness of the oxide membranous layer is 0.1-50 μm.
10. according to the method described in claim 1, wherein, the acidic etching liquid is described also containing at least one water soluble salt Water soluble salt is selected from halogen acid salt, phosphate, sulfate and nitrate.
11. method according to claim 10, wherein, the water soluble salt is 0.1-1 with the sour mol ratio：1.
12. according to the method described in claim 1, wherein, in the acidic etching liquid sour concentration be 0.1-50 weight %.
13. method according to claim 12, wherein, sour concentration is 20-30 weight % in the acidic etching liquid.
14. method according to claim 10, wherein, sour concentration is 0.1-50 weight % in the acidic etching liquid.
15. method according to claim 14, wherein, sour concentration is 20-30 weight % in the acidic etching liquid.
16. according to the method described in claim 1, wherein, time of the chemical etching is 1-60 minutes.
17. method according to claim 16, wherein, the time of the chemical etching is 10-30 minutes.
18. according to the method described in claim 1, wherein, the condition of the chemical etching causes the aperture of the etch pit to exist In the range of 200-2000nm；The ratio of the thickness of the depth of the etch pit and the oxide membranous layer is in 0.1-1：1 model In enclosing.
19. method according to claim 18, wherein, the condition of the chemical etching causes the aperture of the etch pit to exist In the range of 800-1500nm.
20. method according to claim 19, wherein, the condition of the chemical etching causes the aperture of the etch pit to exist In the range of 1000-1500nm.
21. method according to claim 18, wherein, the depth of the etch pit and the thickness of the oxide membranous layer Ratio is in 0.1-0.5：In the range of 1.
22. method according to claim 21, wherein, the depth of the etch pit and the thickness of the oxide membranous layer Ratio is in 0.2-0.4：In the range of 1.
23. according to the method described in claim 1, wherein, by flow casting molding or injection molding by the resiniferous combination Thing injects the surface of the surface treated metal base.
24. the method according to claim 1 or 23, wherein, the injection rate of the resiniferous composition causes what is formed The thickness of resin bed is 0.5-10mm.
25. metal-resin complex prepared by a kind of method in 1-24 as claim described in any one.
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