CN105196652A - Metal-resin compound and preparation method thereof - Google Patents
Metal-resin compound and preparation method thereof Download PDFInfo
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- CN105196652A CN105196652A CN201410305849.XA CN201410305849A CN105196652A CN 105196652 A CN105196652 A CN 105196652A CN 201410305849 A CN201410305849 A CN 201410305849A CN 105196652 A CN105196652 A CN 105196652A
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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
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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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- 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
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- 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
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- 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
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- 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
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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
- 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
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/542—Shear strength
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
Abstract
The invention provides a metal-resin compound and a preparation method thereof and discloses a copper/copper alloy-resin compound and a preparation method thereof. The preparation method comprises the following steps: providing a metal base material comprising a metal matrix layer and an oxide film layer attached to the partial surface of the metal matrix layer; carrying out chemical etching on the metal base material to form corrosion holes in the surface of the metal matrix layer so as to obtain a metal base material subjected to surface treatment; injecting a composition containing resin to the surface of the metal base material subjected to surface treatment and enabling the corrosion holes to be filled with the partial composition so as to form a resin layer after forming. In the metal-resin compound, the bonding strength between the resin and the metal base material is high, and the resin layer is unlikely to fall off from the surface of the metal base material, so that relatively high structure stability is realized and requirements of use occasions for relatively high structure stability can be met. The preparation method provided by the invention is good in applicability, and can combine various resins with the metal base material so as to meet requirements of various use occasions.
Description
Technical field
The present invention relates to a kind of metal-resin complex and preparation method thereof, more specifically, the present invention relates to a kind of copper or copper alloy-resin composite body and preparation method thereof.
Background technology
In the part manufacture field of automobile, household electrical appliance goods, industrial machine etc., need metal and resin integrated molding technology.
Method metal and resin-phase combined conventional is at present bonding technique.Metal is obtained complex by chemical adhesive by the method together with molded resin-bonded.But in the complex obtained by the method, the bond strength of metal and resin is poor, and adhesive binder course not acid and alkali-resistance, affect the use occasion of complex.In addition, because adhesive binder course has certain thickness, the size of final products can thus be affected.
For adhesive method above shortcomings, researcher develops multiple for the method by metal and resin-bonded.
CN101528437B discloses the complex of a kind of metal and resin, formed by the base material of copper or copper alloy and the first resin combination or the second resin combination, the base material of described copper or copper alloy is formed in the following way: be processed into regulation shape utilizing machining after, in order to surface dissolution is carried out chemical etching, and described surface is covered by the Cu oxide thin layer formed by oxidant under strong basicity, described first resin combination or described second resin combination utilize injection mo(u)lding and directly engage with described surface, described first resin combination is using polyphenylene sulfide as principal component, described second resin combination is using polybutylene terephthalate (PBT) as principal component, described surface has following ultra tiny male and fomale(M&F) and has the face be made up of following roughness face simultaneously, wherein, described ultra tiny male and fomale(M&F) refers to that by gap periods be 10-500nm, diameter is 10-150nm and the degree of depth or be highly the recess of 10-500nm or the covered ultra tiny male and fomale(M&F) of protuberance, described roughness face refers to that the large concavo-convex cycle of described male and fomale(M&F) is 0.5-10 μm of RSm and mountain valley average period, and the concavo-convex difference of height of this matsurface is the roughness face of 0.2-5 μm of Rz and maximal roughness height.The complex of this metal and resin can adopt following methods to make: utilize machining base material to be processed into the shape of regulation, then chemical etching is carried out with by surface dissolution, and under strong basicity, formed the thin layer of Cu oxide on surface by oxidant, utilize injection mo(u)lding the first resin combination or the second resin combination to be directly combined with substrate surface.
CN102371697A discloses the preparation method of the complex of a kind of metal and resin, and the method comprises the following steps: (1) provides a metalwork, and wherein, described metalwork can be copper or copper alloy; (2) degreasing degreasing cleaning is carried out to this metalwork; (3) local is carried out to this metalwork and cover process; Use hard particles to spray this metalwork, form micropore with the surface exposed at metalwork; This metalwork is embedded in a molding tool, and heating of metal part is to 100-350 DEG C; In described mould, inject the crystal type thermoplastic resin of melting and cool, resin enters in the micropore on metalwork surface and is combined with metalwork.
But in the complex of the metal-resin adopting said method to prepare, the bond strength between resin and metal base still awaits further raising.In addition, method disclosed in CN101528437B also has certain requirement to the kind of resin, and this limits the application scenario of metal-resin complex to a certain extent.
Summary of the invention
The object of the invention is to overcome in existing copper or copper alloy-resin composite body, the technical problem that bond strength between resin bed and copper or copper alloy substrate is not high, a kind of copper or copper alloy-resin composite body and preparation method thereof are provided, in the copper prepared by method of the present invention or copper alloy-resin, between resin bed and copper or copper alloy substrate, there is higher bond strength.
According to a first aspect of the invention, the invention provides a kind of preparation method of metal-resin complex, described metal is copper or copper alloy, and the method comprises the following steps:
(1) provide a kind of metal base, this metal base comprises metallic base layer and is attached to the oxide membranous layer at least part of surface of described metallic base layer, and described metallic base layer and described oxide membranous layer are structure as a whole;
(2) described metal base is carried out chemical etching, to form etch pit on described oxide membranous layer surface, obtain surface treated metal base;
(3) to the resiniferous composition of surface imp lantation of described surface treated metal base, and make fraction compositions to downward-extension and be filled in described etch pit, shaping rear formation resin bed.
According to a second aspect of the invention, the invention provides a kind of metal-resin complex prepared by method of the present invention.
According to a third aspect of the present invention, the invention provides a kind of metal-resin complex, described metal is copper or copper alloy, this complex comprises metal base and is attached to the resin bed at least part of surface of described metal base, described metal base comprises metallic base layer and is attached to the oxide membranous layer at least part of surface of described metallic base layer, described oxide membranous layer and described metallic base layer are structure as a whole, the surface distributed of described oxide membranous layer has etch pit, part resin in described resin bed extends downwards and is filled in described etch pit.
According to metal-resin complex of the present invention, bond strength between resin and metal base is high, resin bed not easily comes off from metallic substrate surface, thus metal-resin complex provided by the invention has higher structural stability, can meet requirement structural stability being required to higher use occasion.
The applicability of the preparation method of metal-resin complex provided by the invention is good, may be used for various kinds of resin to be combined with metal base, thus meets the requirement of multiple use occasion.
Detailed description of the invention
In the present invention, described metal is copper or copper alloy.Described copper alloy refers to that element adds the alloy of other element formation based on copper, can be common each Albatra metal-, as brass.Metal base is the various formed bodys formed with copper or copper alloy, can have various shape according to concrete instructions for use.
According to a first aspect of the invention, the invention provides a kind of preparation method of metal-resin complex, the method comprising the steps of (1): provide a kind of metal base, this metal base comprises metallic base layer and is attached to the oxide membranous layer at least part of surface of described metallic base layer, and described metallic base layer and described oxide membranous layer are structure as a whole.Described oxide membranous layer is cupric oxide rete or using cupric oxide as the oxide membranous layer of main component, such as: when described metal base is copper alloy, described oxide membranous layer, except containing except cupric oxide, can also contain the oxide that in copper alloy, other alloying element is formed.
The thickness of described oxide membranous layer is generally 0.1-50 μm, is preferably 1-25 μm, is more preferably 5-10 μm.From the angle of the structural stability of the metal-resin complex of the final preparation of raising further, the ratio of the thickness of described oxide membranous layer and described metallic base layer is 0.001-1:1, is preferably 0.005-0.5:1, is more preferably 0.005-0.01:1.
Various method can be adopted to form described oxide membranous layer.One of the present invention preferred embodiment in, described oxide membranous layer is formed by metallic matrix is carried out anodic oxidation, namely described oxide membranous layer is the oxide membranous layer that anodic oxidation is formed, and the metal-resin complex formed thus has higher structural stability.
The present invention is not particularly limited for anodised method, can be conventional selection.Particularly, can by described metallic matrix be placed in electrolyte, with described metallic matrix for anode, with the conductive material do not reacted with electrolyte for negative electrode, negative electrode and anode are connected with the positive pole of power supply and negative electricity respectively, after energising, carry out electrolysis, thus form oxide membranous layer on the surface of described metallic matrix.Described electrolyte can be various under anodic oxidation condition for what commonly use, can form the electrolyte of oxide membranous layer at copper or copper alloy surface.
Particularly, described electrolyte contains at least one alkali compounds.Herein, " at least one " represents one or more.Described alkali compounds can be such as alkali and/or basic salt, is preferably selected from alkali metal hydroxide (as NaOH and/or potassium hydroxide), the alkali metal salt of carbonic acid and the alkali metal salt of phosphoric acid.Described alkali metal salt can be sodium salt or sylvite.More preferably, described alkali compounds is selected from NaOH, sodium carbonate and sodium phosphate.In described electrolyte, the concentration of alkali compounds can be generally 1-50 % by weight, is preferably 10-30 % by weight, is more preferably 20-30 % by weight.
One of the present invention preferred embodiment in, described electrolyte, also containing at least one molybdate, can not only improve anodised speed like this, enhance productivity; And the metal-resin complex of final preparation demonstrates higher structural stability.Described molybdate is water-soluble molybdenum hydrochlorate, is preferably the alkali metal salt of molybdic acid, as sodium molybdate and/or potassium molybdate, is more preferably sodium molybdate.The concentration of described molybdate is fixed with the amount of described alkali compounds.Preferably, in described electrolyte, the concentration of molybdate is 1-10 % by weight.More preferably, in described electrolyte, the concentration of molybdate is 1-5 % by weight.
Anodised condition can be conventional selection, can meet instructions for use be as the criterion with the thickness of the oxide membranous layer formed.Preferably, anodised condition comprises: voltage is 10-100V, is preferably 10-50V, is more preferably 15-30V; Time is 1-60 minute, is preferably 5-30 minute, is more preferably 5-20 minute.Electrolyte temperature is-20 DEG C to 80 DEG C, is preferably 20-60 DEG C, is more preferably 40-60 DEG C.
Also comprise step (2) according to method of the present invention: described metal base is carried out chemical etching, to form etch pit on described oxide membranous layer surface, obtain surface treated metal base.
According to method of the present invention, by described metal base is carried out chemical etching, etch pit is formed on oxide membranous layer surface, like this when metallic substrate surface forms resin bed, part resin in resin bed is filled in described etch pit, thus can improve in the metal-resin complex of preparation, the bond strength between resin bed and metal base.
According to method of the present invention, the condition of described chemical etching preferably makes the aperture of the etch pit formed in oxide membranous layer in the scope of 200-2000nm, and the ratio of the degree of depth of described etch pit and the thickness of described oxide membranous layer is generally in the scope of 0.1-1:1.More preferably, the condition of described etching makes the aperture of the etch pit formed in oxide membranous layer in the scope of 800-1500nm, the ratio of the degree of depth of described etch pit and the thickness of described oxide membranous layer is in the scope of 0.1-0.5:1, in the metal-resin complex formed thus, there is between resin bed and metal base higher structural stability.Further preferably, the condition of described chemical etching makes the aperture of the etch pit formed in oxide membranous layer in the scope of 1000-1500nm, and the ratio of the degree of depth of described etch pit and the thickness of described oxide membranous layer is in the scope of 0.2-0.4:1.In the present invention, the aperture of etch pit refers to the full-size of the upper port of etch pit (that is, being positioned at the port on oxide membranous layer surface) in radial direction, and the degree of depth of etch pit refers to the vertical range between the two ends of an etch pit.The aperture of etch pit and the degree of depth can adopt electron microscopy to measure.
Conventional various methods can be adopted to carry out chemical etching to metal base, thus form etch pit on described oxide membranous layer surface.One of the present invention preferred embodiment in, the method for described chemical etching comprises: be soaked in acidic etching liquid by described metal base.Described acidic etching liquid is preferably containing at least one aqueous acid.Described acid can be selected from halogen acids, H
3pO
4, H
2sO
4and HNO
3, described halogen acids is preferably HCl.
In described acidic etching liquid, the concentration of acid is preferably 0.1-50 % by weight.More preferably, in described acidic etching liquid, the concentration of acid is 1-30 % by weight.Further preferably, in described acidic etching liquid, the concentration of acid is 20-30 % by weight, etch pit can not only be formed like this in oxide membranous layer, and the more homogeneous and more uniform etch pit of distribution of size can be formed, thus the metal-resin complex with higher structural stability can be obtained.
One more preferred embodiment in, described acidic etching liquid is also containing at least one water soluble salt, the stability of etching can be improved so further, make, in the metal-resin complex of final preparation, to there is between resin bed and metal base higher structural stability.The amount of described water soluble salt is fixed with the amount of the acid in acidic etching liquid.Preferably, the mol ratio of described water soluble salt and described acid is 0.1-1:1.
Described water soluble salt is preferably selected from halogen acid salt, phosphate, sulfate and nitrate.The instantiation of described water soluble salt can include but not limited to: NaCl, KCl, AlCl
3, NaH
2pO
4, Na
2hPO
4, Na
3pO
4, KH
2pO
4, K
2hPO
4, K
3pO
4, Na
2sO
4, K
2sO
4, NaNO
3and KNO
3.More preferably, described water soluble salt is NaCl, NaH
2pO
4, Na
2hPO
4, NaNO
3and Na
2sO
4in one two or more.Further preferably, the acid group of described water soluble salt is identical with the acid group of the acid in described acidic etching liquid.Such as, when the acid in described acidic etching liquid is halogen acids, described water soluble salt is preferably halogen acid salt.
The temperature of described acidic etching liquid can be conventional selection.Usually, the temperature of described acidic etching liquid can be 10-60 DEG C, is preferably 20-40 DEG C.
The time of described chemical etching is fixed with kind sour in acidic etching liquid and concentration.Usually, the time of described chemical etching is 1-60 minute.From the angle of the dimensional homogeneity of the etch pit of the final formation of raising further, the time of described chemical etching is preferably 10-30 minute.Described chemical etching can be carried out once, also can gradation carry out (that is, carrying out the chemical etching of more than twice), as long as meet the demands the total time of chemical etching.Described chemical etching be gradation carry out time, identical etching solution gradation can be adopted to etch, different etching solution gradation also can be adopted to etch.When chemical etching is carried out in gradation, after each chemical etching completes, preferably the metal base through etching is cleaned, to remove residual etching solution.
Also comprise step (3) according to method of the present invention: to the resiniferous composition of surface imp lantation of described surface treated metal base, and make fraction compositions be filled in described etch pit, shaping rear formation resin bed.
Resin (hereinafter referred to as matrix resin) in described resiniferous composition can be selected according to concrete instructions for use, as long as this resin can be combined with copper or copper alloy.Usually, described matrix resin can be selected from thermoplastic resin, such as, can be one or more in polyphenylene sulfide, polyester, polyamide, Merlon and polyolefin.Described polyester can be the common various polymer by dicarboxylic acids and glycol condensation, and its instantiation can include but not limited to polybutylene terephthalate (PBT) and/or PETG.Described polyamide can for common various by the polymer of diamines with dicarboxylic acids condensation, and its instantiation can include but not limited to polyhexamethylene adipamide, poly-hexamethylene azelamide, poly-succinyl hexamethylene diamine, nylon 612, polyhexamethylene sebacamide, nylon 1010, nylon 11, poly-lauramide, poly-caprylamide, poly-9 aminononanoic acid, polycaprolactam, poly-paraphenylene terephthalamide's phenylenediamine, poly-6I hexamethylene isoterephalamide, gather hexamethylene terephthalamide and poly-paraphenylene terephthalamide's nonamethylene diamine.Described polyolefinic instantiation can include but not limited to polystyrene, polypropylene, polymethyl methacrylate and gather (acrylonitrile-butadiene-styrene (ABS)).
Described resiniferous composition, except containing except matrix resin, can also contain at least one filler and/or at least one fluidity improver.
The kind of described filler can be selected according to concrete instructions for use.Described filler can be various fibrous type filler and/or powder-type filler.Described fibrous type filler can one or more for being selected from glass fibre, carbon fiber and aramid fibre.Described powder-type filler can one or more for being selected from calcium carbonate, magnesium carbonate, silica, heavy barium sulfate, talcum powder, glass and clay.The size of described filler can be conventional selection, as long as can guarantee to form fine and close resin bed.Usually, 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 described filler can be conventional selection.Usually, with 100 weight portion matrix resins for benchmark, the content of described filler can be 20-150 weight portion, is preferably 30-60 weight portion.
Described fluidity improver, for improving the fluid ability of matrix resin, improves further the processing characteristics of bond strength between metal base and resin and resin.Described fluidity improver can be the various material that can realize above-mentioned effect, is preferably cyclic polyester.
The consumption of described fluidity improver is as the criterion with the fluid ability that can improve matrix resin.Preferably, relative to 100 weight portion matrix resins, the content of described fluidity improver is 1-5 weight portion.
Described resiniferous composition can also contain common various auxiliary agents according to concrete instructions for use, as colouring agent and/or antioxidant, to improve the performance of resin bed in the final metal-resin complex formed or to give described resin bed with new performance.
Resiniferous composition can by mixing matrix resin, optional filler, optional fluidity improver and optional auxiliary agent and obtain.Usually, matrix resin, optional filler, optional fluidity improver and optional auxiliary agent can be mixed, and carry out extruding pelletization and obtain.
Can adopt surface imp lantation from conventional various methods to metal base described in resiniferous composition, and carry out shaping, such as flow casting molding or injection mo(u)lding.One of the present invention preferred embodiment in, described metal base is placed in mould, injects described resiniferous composition by the method for injection moulding and carry out shaping.
The condition of described injection moulding can be selected according to the kind of matrix resin in resiniferous composition.Preferably, the condition of described injection moulding comprises: mold temperature (that is, mould temperature) is 50-300 DEG C; Nozzle temperature is 200-450 DEG C; Dwell time is 1-50 second, is preferably 3-10 second; Injection pressure is 50-300MPa, is preferably 80-200MPa; The injection time is 1-30 second, is preferably 3-10 second; Time delay is 1-30 second, is preferably 1-10 second.Preferably, mold temperature is 100-180 DEG C (as 120-160 DEG C), nozzle temperature is 280-350 DEG C (as 290-320 DEG C), such one side can make resiniferous composition fully enter in etch pit, make, in the final metal-resin complex formed, to there is between resin bed and metal base higher bond strength; Be easy to mold temperature on the other hand.
The injection rate of described resiniferous composition can be selected according to the resin layer thickness of expection.Usually, the injection rate of described resiniferous composition makes the thickness of the resin bed formed be 0.5-10mm.Herein, the thickness of resin bed refer to the upper surface of the oxide membranous layer connected with resin bed to resin bed upper surface between vertical range.
According to method of the present invention, only when the part surface of metal base forms resin bed, surface without the need to forming resin bed can be processed, with the surface color change removing surface hole defect and cause due to etching, this process can injection resiniferous composition and carry out shaping before carry out, also can injection resiniferous composition and carry out shaping after carry out, be not particularly limited.
In the metal-resin complex prepared by method of the present invention, there is between resin bed and metal base higher bond strength, the requirement to the higher use occasion of structural stability can be met.
Thus, according to a second aspect of the invention, present invention also offers a kind of metal-resin complex prepared by method of the present invention.
According to a third aspect of the present invention, the invention provides a kind of metal-resin complex, described metal is copper or copper alloy, this complex comprises metal base and is attached to the resin bed at least part of surface of described metal base, described metal base comprises metallic base layer and is attached to described metallic base layer oxide membranous layer surperficial at least partly, described oxide membranous layer and described metallic base layer are structure as a whole, the surface distributed of described oxide membranous layer has etch pit, and the part resin in described resin bed extends downwards and is filled in described etch pit.
The thickness of described oxide membranous layer is generally 0.1-50 μm, is preferably 1-25 μm, is more preferably 5-10 μm.The ratio of the thickness of described oxide membranous layer and described metallic base layer is 0.001-1:1, is preferably 0.005-0.5:1, is more preferably 0.005-0.01:1.
According to complex of the present invention, the aperture of described etch pit is preferably in the scope of 200-2000nm, more preferably in the scope of 800-1500nm, preferred in the scope of 1000-1500nm further; The ratio of the degree of depth of described etch pit and the thickness of described oxide membranous layer is preferably in the scope of 0.1-1:1, more preferably in the scope of 0.1-0.5:1, preferred in the scope of 0.2-0.4:1 further.
Matrix resin in described resin bed can be selected according to concrete instructions for use, as long as this resin can be combined with copper or copper alloy.Usually, the matrix resin in described resin bed can be selected from thermoplastic resin, such as, can be one or more in polyphenylene sulfide, polyester, polyamide, Merlon and polyolefin.Described polyester can for common by the polymer of dicarboxylic acids and glycol condensation, and its instantiation can include but not limited to polybutylene terephthalate (PBT) and/or PETG.Described polyamide can for common by the polymer of diamines with dicarboxylic acids condensation, and its instantiation can include but not limited to polyhexamethylene adipamide, poly-hexamethylene azelamide, poly-succinyl hexamethylene diamine, nylon 612, polyhexamethylene sebacamide, nylon 1010, nylon 11, poly-lauramide, poly-caprylamide, poly-9 aminononanoic acid, polycaprolactam, poly-paraphenylene terephthalamide's phenylenediamine, poly-6I hexamethylene isoterephalamide, gather hexamethylene terephthalamide and poly-paraphenylene terephthalamide's nonamethylene diamine.Described polyolefinic instantiation can include but not limited to polystyrene, polypropylene, polymethyl methacrylate and gather (acrylonitrile-butadiene-styrene (ABS)).
Described resin bed, except containing except matrix resin, can also contain at least one filler.The kind of described filler can be selected according to concrete instructions for use.Described filler can be fibrous type filler and/or powder-type filler.Described fibrous type filler can one or more for being selected from glass fibre, carbon fiber and aramid fibre.Described powder-type filler can one or more for being selected from calcium carbonate, magnesium carbonate, silica, heavy barium sulfate, talcum powder, glass and clay.The content of described filler can be conventional selection.Usually, with 100 weight portion matrix resins for benchmark, the content of described filler can be 20-150 weight portion, is preferably 30-60 weight portion.The size of described filler can be conventional selection, as long as can guarantee to form fine and close resin bed.Usually, for fibrous type filler, its length can be 1-10mm; For powder-type filler, its particle diameter can be 1-200 μm.
According to complex of the present invention, the thickness of described resin bed can be selected according to concrete use occasion.Usually, the thickness of described resin bed is in the scope of 0.5-10mm.
Describe the present invention in detail below in conjunction with embodiment, but therefore do not limit scope of the present invention.
In following examples and comparative example, according to the method that ASTMD1002-10 specifies, the average shear force in INSTRON3369 type universal test aircraft measurements metal-resin complex between metal base and resin bed also observes fracture mode.
In following examples and comparative example, the metallographic microscope that to adopt purchased from the model of ZEISS be AxioImagerAlm measures the thickness of anode oxidation membrane and the degree of depth of etch pit (is observed five diverse locations of same sample, measure the degree of depth of the whole etch pits occurred within sweep of the eye), the SEM that to adopt purchased from the model of Jeol Ltd. be JSM-7600F measures the aperture (observe five diverse locations of same sample, measure the aperture of the whole etch pits occurred within sweep of the eye) of etch pit.
Embodiment 1-10 is for illustration of metal-resin complex of the present invention and preparation method thereof.
Embodiment 1
(1) by commercially available thickness be the rectangular pieces that the brass sheet of 1mm is cut into 15mm × 80mm.Rectangular pieces is put into polishing machine and carries out polishing.Then clean with absolute ethyl alcohol, being then soaked in concentration is in the sodium hydrate aqueous solution of 2 % by weight, and after 2min, taking-up is clean with deionized water rinsing, obtains the brass sheet material through pre-treatment.
(2) brass sheet material step (1) obtained puts into the anodizing tank using the aqueous solution containing the NaOH of 20 % by weight and the sodium molybdate of 1 % by weight as electrolyte as anode, using graphite carbon plate as negative electrode, under the voltage of 15V, 60 DEG C of electrolysis 5 minutes, to carry out anodic oxidation.To take out through anodised brass sheet material and dry up, obtain the brass substrate that surface has anode oxidation membrane.After measured, the thickness of anode oxidation membrane is 8 μm.
(3) after the brass substrate surface that step (2) obtains with anode oxidation membrane be 20 DEG C of concentration is soak 10 minutes in the hydrochloric acid of 30 % by weight in temperature, take out and soak 1 minute in water, then take out and dry up, obtain surface treated brass substrate.
After measured: in the anode oxidation membrane of surface treated brass substrate, be distributed with the etch pit of aperture within the scope of 800-1500nm, the ratio of the degree of depth of this etch pit and the thickness of anode oxidation membrane is in the scope of 0.1-0.5:1.
(4) the surface treated brass substrate that step (3) obtains is placed in injecting molding die, injection moulding contains polyphenylene sulfide (PPS) and glass fibre, and (fibre length is 5mm, relative to 100 weight portion PPS, the content of glass fibre is 30 weight portions) resin combination, the demoulding also cools.Wherein, injecting condition comprises: mould temperature is 120 DEG C, and nozzle temperature is 305 DEG C, and the dwell time is 5 seconds, and injection pressure is 120MPa, and the injection time is 5 seconds, and time delay is 3 seconds.
The thermostatic drying chamber that cooled product puts into 120 DEG C is incubated 1.5h, then naturally cools to room temperature with stove, obtained metal-resin complex (thickness of resin bed is 2mm), its average shear strength and fracture mode are listed in Table 1.
Comparative example 1
(1) method identical with embodiment 1 step (1) is adopted to prepare brass sheet material.
(2) resin combination is injected into brass sheet surface prepared by step (1) by the employing method identical with embodiment 1 step (4), thus obtaining metal-resin complex (thickness of resin bed is 2mm), its average shear strength and fracture mode are listed in Table 1.
Comparative example 2
(1) method identical with embodiment 1 step (1) is adopted to prepare brass sheet material.
(2) adopt the method identical with embodiment 1 step (2) that brass sheet material prepared by step (1) is carried out anodic oxidation, obtain the brass substrate that surface has anode oxidation membrane.
(3) to have the brass substrate of anode oxidation membrane surperficial adopt the method identical with embodiment 1 step (4) to be injection-moulded in by resin combination surface that step (2) obtains, thus obtaining metal-resin complex (thickness of resin bed is 2mm), its average shear strength and fracture mode are listed in Table 1.
Comparative example 3
(1) method identical with embodiment 1 step (1) is adopted to prepare brass sheet material.
(2) brass sheet material step (1) prepared is that in the etching solution of 30 DEG C, (described etching solution is the aqueous solution containing 3 % by weight sulfuric acid and 3 % by weight hydrogen peroxide) soaks 15 minutes in temperature, take out and soak 1 minute in water, then taking out and dry up.Then, by brass sheet material in temperature be 70 DEG C containing the aqueous solution of 10 % by weight NaOH and 5 % by weight sodium sulfites in soak 1 minute, with by brass sheet material surface oxidation.Soak 1 minute in water after taking-up, obtain surface treated brass substrate.
(3) resin combination is injection-moulded in the surface treated brass substrate surface that step (2) obtains by the employing method identical with embodiment 1 step (4), thus obtaining metal-resin complex (thickness of resin bed is 2mm), its average shear strength and fracture mode are listed in Table 1.
Embodiment 2
(1) method identical with embodiment 1 step (1) is adopted to prepare brass sheet material.
(2) method identical with embodiment 1 step (2) is adopted to form anode oxidation membrane in brass sheet surface, unlike, electrolyte is not containing sodium molybdate, and electrolysis time is 8 minutes.After measured, the thickness of anode oxidation membrane is 8 μm.
(3) after the brass substrate surface that step (2) obtains with anode oxidation membrane be 20 DEG C of concentration is soak 10 minutes in the hydrochloric acid of 30 % by weight in temperature, take out and soak 1 minute in water, then take out and dry up, obtain surface treated brass substrate.
After measured: in the anode oxidation membrane of surface treated brass substrate, be distributed with the etch pit of aperture within the scope of 800-1500nm, the ratio of the degree of depth of this etch pit and the thickness of anode oxidation membrane is in the scope of 0.1-0.5:1.
(4) method identical with embodiment 1 step (4) is adopted resin combination to be injection-moulded in the surface of the surface treated brass substrate that step (3) obtains, thus obtaining metal-resin complex (thickness of resin bed is 2mm), its average shear strength and fracture mode are listed in Table 1.
Embodiment 3
(1) method identical with embodiment 1 step (1) is adopted to prepare brass sheet material.
(2) the brass sheet surface adopting the method identical with embodiment 1 step (2) to prepare in step (1) forms anode oxidation membrane, thus obtains the brass substrate that surface has anode oxidation membrane.
(3) brass substrate adopting the method effects on surface identical with embodiment 1 step (3) to have anode oxidation membrane carries out chemical etching, unlike, the mol ratio of etching solution also containing NaCl, NaCl and HCl is 1:1, thus obtains surface treated brass substrate.
After measured: in the anode oxidation membrane of surface treated brass substrate, be distributed with the etch pit of aperture within the scope of 1000-1500nm, the ratio of the degree of depth of this etch pit and the thickness of anode oxidation membrane is in the scope of 0.2-0.4:1.
(4) method identical with embodiment 1 step (4) is adopted resin combination to be injected into surface treated brass substrate surface, thus obtaining metal-resin complex (thickness of resin bed is 2mm), its average shear strength and fracture mode are listed in Table 1.
Embodiment 4
(1) method identical with embodiment 1 step (1) is adopted to prepare brass sheet material.
(2) the brass sheet surface adopting the method identical with embodiment 1 step (2) to prepare in step (1) forms anode oxidation membrane, thus obtains the brass substrate that surface has anode oxidation membrane.
(3) method identical with embodiment 1 step (3) is adopted to etch, unlike, the soak time of brass substrate in hydrochloric acid is 40 minutes.
After measured: in the anode oxidation membrane of surface treated brass substrate, be distributed with the etch pit of aperture within the scope of 200-2000nm, the ratio of the degree of depth of this etch pit and the thickness of anode oxidation membrane is in the scope of 0.1-1:1.
(4) method identical with embodiment 1 step (4) is adopted resin combination to be injected into surface treated brass substrate surface, thus obtaining metal-resin complex (thickness of resin bed is 2mm), its average shear strength and fracture mode are listed in Table 1.
Embodiment 5
(1) by commercially available thickness be the rectangular pieces that the brass sheet of 1mm is cut into 15mm × 80mm.Rectangular pieces is put into polishing machine and carries out polishing.Then clean with absolute ethyl alcohol, being then soaked in concentration is in the sodium hydrate aqueous solution of 2 % by weight, and after 2min, taking-up is clean with deionized water rinsing, obtains the brass sheet material through pre-treatment.
(2) brass sheet material step (1) obtained is put into as anode with the Na containing 30 % by weight
3pO
4and the aqueous solution of the sodium molybdate of 5 % by weight is as in the anodizing tank of electrolyte, using graphite carbon plate as negative electrode, under the voltage of 25V, 50 DEG C of electrolysis 15 minutes, to carry out anodic oxidation.To take out through anodised brass sheet material and dry up, obtain the brass substrate that surface has anode oxidation membrane.After measured, the thickness of anode oxidation membrane is 8.5 μm.
(3) after the brass substrate surface that step (2) obtains with anode oxidation membrane be 35 DEG C of concentration is soak 10 minutes in the sulfuric acid of 25 % by weight in temperature, take out and soak 1 minute in water, then take out and dry up, obtain surface treated brass substrate.
After measured: be distributed with the etch pit of aperture within the scope of 800-1500nm in the anode oxidation membrane of surface treated brass substrate, the ratio of the degree of depth of this etch pit and the thickness of anode oxidation membrane is at 0.1-0.5:1.
(4) the surface treated brass substrate that step (3) obtains is placed in injecting molding die, injection moulding contains polybutylene terephthalate (PBT) (PBT) and talcum powder, and (volume average particle size is 4 μm, relative to 100 weight portion PBT, talcous content is 40 weight portions) resin combination, the demoulding also cools.Wherein, injecting condition comprises: mould temperature is 120 DEG C, and nozzle temperature is 305 DEG C, and the dwell time is 5 seconds, and injection pressure is 120MPa, and the injection time is 5 seconds, and time delay is 3 seconds.
The thermostatic drying chamber that cooled product puts into 120 DEG C is incubated 1.5h, then naturally cools to room temperature with stove, obtained metal-resin complex (thickness of resin bed is 4mm), its average shear strength and fracture mode are listed in Table 1.
Embodiment 6
(1) method identical with embodiment 5 step (1) is adopted to provide brass sheet material.
(2) adopt the method identical with embodiment 5 step (2) that brass sheet material is carried out anodic oxidation, thus obtain the brass substrate that surface has anode oxidation membrane.
(3) adopt the method identical with embodiment 5 step (3) that brass substrate is carried out chemical etching, unlike, also containing Na in etching solution
2sO
4, wherein, Na
2sO
4with H
2sO
4mol ratio be 0.5:1, thus obtain surface treated brass substrate.
After measured: in the anode oxidation membrane of surface treated brass substrate, be distributed with the etch pit of aperture within the scope of 1000-1500nm, the ratio of the degree of depth of this etch pit and the thickness of anode oxidation membrane is in the scope of 0.2-0.4:1.
(4) method identical with embodiment 5 step (4) is adopted resin combination to be injected into the surface of surface treated brass substrate, thus obtaining metal-resin complex (resin layer thickness is 4mm), its average shear strength and fracture mode are listed in Table 1.
Embodiment 7
(1) by commercially available thickness be the rectangular pieces that the brass sheet of 1mm is cut into 15mm × 80mm.Rectangular pieces is put into polishing machine and carries out polishing.Then clean with absolute ethyl alcohol, being then soaked in concentration is in the sodium hydrate aqueous solution of 2 % by weight, and after 2min, taking-up is clean with deionized water rinsing, obtains the brass sheet material through pre-treatment.
(2) brass sheet material step (1) obtained puts into the Na containing 25 % by weight as anode
2cO
3and the aqueous solution of the sodium molybdate of 5 % by weight is as in the anodizing tank of electrolyte, using graphite carbon plate as negative electrode, under the voltage of 20V, 40 DEG C of electrolysis 20 minutes, to carry out anodic oxidation.To take out through anodised brass sheet material and dry up, obtain the brass substrate that surface has anode oxidation membrane.After measured, the thickness of anode oxidation membrane is 10 μm.
(3) after the brass substrate surface that step (2) obtains with anode oxidation membrane be 30 DEG C of concentration is soak 30 minutes in the phosphoric acid of 20 % by weight in temperature, take out and soak 1 minute in water, then take out and dry up, obtain surface treated brass substrate.
After measured: in the anode oxidation membrane of surface treated brass substrate, be distributed with the etch pit of aperture within the scope of 800-1500nm, the ratio of the degree of depth of this etch pit and the thickness of anode oxidation membrane is in the scope of 0.1-0.5:1.
(4) the surface treated brass substrate that step (3) obtains is placed in injecting molding die, injection moulding contains nylon66 fiber (PA-66) and glass fibre, and (fibre length is 5mm, relative to 100 weight portion PA-66, the content of glass fibre is 50 weight portions) resin combination, the demoulding also cools.Wherein, injecting condition comprises: mould temperature is 150 DEG C, and nozzle temperature is 305 DEG C, and the dwell time is 5 seconds, and injection pressure is 120MPa, and the injection time is 5 seconds, and time delay is 3 seconds.
The thermostatic drying chamber that cooled product puts into 120 DEG C is incubated 1.5h, then naturally cools to room temperature with stove, obtained metal-resin complex (resin layer thickness is 5mm), its average shear strength and fracture mode are listed in Table 1.
Embodiment 8
(1) method identical with embodiment 7 step (1) is adopted to provide brass sheet material.
(2) adopt the method identical with embodiment 7 step (2) that brass sheet material is carried out anodic oxidation, thus obtain the brass substrate that surface has anode oxidation membrane.
(3) adopt the method identical with embodiment 7 step (3) that brass substrate is carried out chemical etching, unlike, also containing Na in etching solution
2hPO
4, wherein, Na
2hPO
4with H
3pO
4mol ratio be 0.2:1, thus obtain surface treated brass substrate.
After measured: in the anode oxidation membrane of surface treated brass substrate, be distributed with the etch pit of aperture within the scope of 1000-1500nm, the ratio of the degree of depth of this etch pit and the thickness of anode oxidation membrane is in the scope of 0.2-0.4:1.
(4) method identical with embodiment 7 step (4) is adopted resin combination to be injected into the surface of surface treated brass substrate, thus obtaining metal-resin complex (resin layer thickness is 5mm), its average shear strength and fracture mode are listed in Table 1.
Embodiment 9
(1) method identical with embodiment 1 step (1) is adopted to prepare brass sheet material.
(2) adopt the method identical with embodiment 1 step (2) that brass sheet material prepared by step (1) is carried out anodic oxidation, obtain the brass substrate that surface has anode oxidation membrane.
(3) brass substrate adopting the method identical with embodiment 1 step (3) surface to be had anode oxidation membrane etches, unlike, etching solution is the HNO of same concentrations
3, thus obtain surface treated brass substrate.
After measured: in the anode oxidation membrane of surface treated brass substrate, be distributed with the etch pit of aperture within the scope of 800-1500nm, the ratio of the degree of depth of this etch pit and the thickness of anode oxidation membrane is in the scope of 0.1-0.5:1.
(4) to have the brass substrate of anode oxidation membrane surperficial adopt the method identical with embodiment 1 step (4) to be injection-moulded in by resin combination surface that step (2) obtains, thus obtaining metal-resin complex (thickness of resin bed is 2mm), its average shear strength and fracture mode are listed in Table 1.
Embodiment 10
(1) method identical with embodiment 1 step (1) is adopted to prepare brass sheet material.
(2) adopt the method identical with embodiment 1 step (2) that brass sheet material prepared by step (1) is carried out anodic oxidation, obtain the brass substrate that surface has anode oxidation membrane.
(3) brass substrate adopting the method identical with embodiment 9 step (3) surface to be had anode oxidation membrane etches, unlike, etching solution is also containing NaNO
3, NaNO
3with HNO
3mol ratio be 1:1, thus obtain surface treated brass substrate.
After measured: in the anode oxidation membrane of surface treated brass substrate, be distributed with the etch pit of aperture within the scope of 1000-1500nm, the ratio of the degree of depth of this etch pit and the thickness of anode oxidation membrane is in the scope of 0.2-0.4:1.
(4) to have the brass substrate of anode oxidation membrane surperficial adopt the method identical with embodiment 1 step (4) to be injection-moulded in by resin combination surface that step (2) obtains, thus obtaining metal-resin complex (thickness of resin bed is 2mm), 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 type * |
| Comparative example 1 | 0.2 | Type B * * |
| Comparative example 2 | 5 | Type B |
| Comparative example 3 | 11 | Type B |
| Embodiment 2 | 20.2 | A type |
| Embodiment 3 | 26.8 | A type |
| Embodiment 4 | 18.1 | A type |
| Embodiment 5 | 20 | A type |
| Embodiment 6 | 23.4 | A type |
| Embodiment 7 | 27 | A type |
| Embodiment 8 | 30.6 | A type |
| Embodiment 9 | 21 | A type |
| Embodiment 10 | 24.5 | A type |
*: resin bed itself fracture * *: resin bed and metallic bond rupture
The result of table 1 confirms, the metal-resin complex adopting method of the present invention to prepare demonstrates higher average shear strength, and fracture mode is resin bed fracture itself, this illustrates in metal-resin complex provided by the invention, has higher bond strength between resin bed and metal base.Further, the adaptability to raw materials of method of the present invention is good, may be used for forming polytype resin bed in metallic substrate surface.
Claims (22)
1. a preparation method for metal-resin complex, described metal is copper or copper alloy, and the method comprises the following steps:
(1) provide a kind of metal base, this metal base comprises metallic base layer and is attached to the oxide membranous layer at least part of surface of described metallic base layer, and described metallic base layer and described oxide membranous layer are structure as a whole;
(2) described metal base is carried out chemical etching, to form etch pit on described oxide membranous layer surface, obtain surface treated metal base;
(3) to the resiniferous composition of surface imp lantation of described surface treated metal base, and make fraction compositions to downward-extension and be filled in described etch pit, shaping rear formation resin bed.
2. method according to claim 1, wherein, described oxide membranous layer is formed by metallic matrix is carried out anodic oxidation.
3. method according to claim 2, wherein, the electrolyte that described anodic oxidation uses contains at least one alkali compounds, and described alkali compounds is preferably selected from NaOH, sodium carbonate and sodium phosphate.
4. method according to claim 3, wherein, at least one molybdate of described electrolyte also containing 1-10 % by weight, preferably 1-5 % by weight.
5. method according to claim 4, wherein, described molybdate is selected from the alkali metal salt of molybdic acid, is preferably sodium molybdate.
6. according to the method in claim 3-5 described in any one, wherein, the concentration of described electrolyte neutral and alkali compound is 1-50 % by weight, is preferably 10-30 % by weight.
7. according to the method in claim 3-6 described in any one, wherein, described anodised condition comprises: voltage is 10-100V, and the time is 1-60 minute, and the temperature of electrolyte is-20 DEG C to 80 DEG C.
8. according to the method in claim 1-7 described in any one, wherein, the thickness of described oxide membranous layer is 0.1-50 μm.
9. method according to claim 1, wherein, the method for described chemical etching comprises: be soaked in acidic etching liquid by described metal base.
10. method according to claim 9, wherein, described acidic etching liquid is for containing at least one aqueous acid, and described acid is preferably selected from halogen acids, H
3pO
4, H
2sO
4and HNO
3.
11. methods according to claim 10, wherein, described acidic etching liquid is also containing at least one water soluble salt, and described water soluble salt is selected from halogen acid salt, phosphate, sulfate and nitrate.
12. methods according to claim 11, wherein, the mol ratio of described water soluble salt and described acid is 0.1-1:1.
13. according to the method in claim 10-12 described in any one, and wherein, in described acidic etching liquid, the concentration of acid is 0.1-50 % by weight, is preferably 20-30 % by weight.
14. according to the method in claim 1 and 9-13 described in any one, and wherein, the time of described chemical etching is 1-60 minute, is preferably 10-30 minute.
15. according to the method in claim 1 and 9-14 described in any one, wherein, the condition of described chemical etching makes the aperture of described etch pit in the scope of 200-2000nm, preferably in the scope of 800-1500nm, more preferably in the scope of 1000-1500nm; The ratio of the degree of depth of described etch pit and the thickness of described oxide membranous layer in the scope of 0.1-1:1, preferably in the scope of 0.1-0.5:1, more preferably in the scope of 0.2-0.4:1.
16. methods according to claim 1, wherein, inject the surface of described surface treated metal base by flow casting molding or injection mo(u)lding by described resiniferous composition.
17. methods according to claim 1 or 16, wherein, the injection rate of described resiniferous composition makes the thickness of the resin bed formed be 0.5-10mm.
18. 1 kinds of metal-resin complexs prepared by the method in claim 1-17 described in any one.
19. 1 kinds of metal-resin complexs, described metal is copper or copper alloy, this complex comprises metal base and is attached to the resin bed at least part of surface of described metal base, described metal base comprises metallic base layer and is attached to the oxide membranous layer at least part of surface of described metallic base layer, described oxide membranous layer and described metallic base layer are structure as a whole, the surface distributed of described oxide membranous layer has etch pit, and the part resin in described resin bed extends downwards and is filled in described etch pit.
20. complexs according to claim 19, wherein, the aperture of described etch pit in the scope of 200-2000nm, preferably in the scope of 800-1500nm, more preferably in the scope of 1000-1500nm; The ratio of the degree of depth of described etch pit and the thickness of described oxide membranous layer in the scope of 0.1-1:1, preferably in the scope of 0.1-0.5:1, more preferably in the scope of 0.2-0.4:1.
21. complexs according to claim 19 or 20, wherein, the thickness of described oxide membranous layer is 0.1-50 μm.
22. complexs according to claim 19, wherein, the thickness of described resin bed is 0.5-10mm.
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