CN105522782A

CN105522782A - Metal base subjected to surface treatment, metal-resin compound, preparation methods and uses of metal-resin compound and metal base subjected to surface treatment, electronic product housing and preparation method of electronic product housing

Info

Publication number: CN105522782A
Application number: CN201410826354.1A
Authority: CN
Inventors: 孙剑; 宋文广; 陈梁; 吴彦琴
Original assignee: BYD Co Ltd
Current assignee: BYD Co Ltd
Priority date: 2014-12-25
Filing date: 2014-12-25
Publication date: 2016-04-27
Also published as: WO2016101694A1

Abstract

The invention discloses a metal base subjected to surface treatment and a preparation method thereof. The metal is aluminum or an aluminum alloy. The metal base comprises a metal base and a hard anodic oxide film layer adhering to at least one part of the surface of the metal base. The surface of the hard anodic oxide film layer is provided with first etch pits. The invention also provides a metal-resin compound. The metal is aluminum or an aluminum alloy. The metal-resin compound comprises the metal base subjected to surface treatment and a resin layer coating at least one part of the surface of the metal base, wherein a part of resin in the resin layer extends downward and fills the etch pits of the metal base. In the metal-resin compound, bonding strength between the resin and the metal base is high and the resin layer does not easily fall from the metal base surface so that the metal-resin compound has high structural stability, satisfies high structural stability requirements of a use field and can be used as an electronic product housing.

Description

Surface treated metal base and metal-resin complex and preparation method and application and electronic product casing and preparation method

Technical field

The present invention relates to a kind of surface treated metal base and its preparation method and application, the invention still further relates to a kind of metal-resin complex and its preparation method and application, the invention further relates to a kind of electronic product casing and preparation method thereof.

Background technology

In the part manufacture field of automobile, household electrical appliance goods, industrial machine etc., need aluminum or aluminum alloy and resin integrated molding technology.

Method aluminum or aluminum alloy and resin-phase combined conventional is at present bonding technique.Aluminum or aluminum alloy is obtained complex by chemical adhesive by the method together with molded resin-bonded.But in the complex obtained by the method, the adhesion of aluminum or aluminum alloy 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 other for the method by aluminum or aluminum alloy and resin-bonded.

One method adopts amine substance, such as: the aqueous solution of carbamate, a hydrazine hydrate, ethylenediamine etc. carries out surface corrosion to aluminum or aluminum alloy, to form nano level micropore on aluminum or aluminum alloy surface, and amine substance is retained in the micropore of formation, then resin is injection-moulded in treated surface, by the reaction between amine substance and resin, resin and aluminum or aluminum alloy are combined, thus obtain the plastic-aluminum integration product with certain tensile shear strength.But adopt above-mentioned amine substance to etch aluminum or aluminum alloy, the hole formed on aluminum or aluminum alloy surface is too little, and resin is difficult to direct injection moulding and enters in nano level micropore, so that is difficult to the bond strength significantly improving aluminium alloy and resin.

Another kind method adopts the acidic etching liquid containing inorganic halogen compounds directly to corrode aluminum alloy surface, and then casting resin obtains plastic-aluminum integration product.But adopt the plastic-aluminum integration product obtained in this way, the bond strength between aluminium alloy and resin still awaits further raising.

In addition, anodic oxidation can also be carried out in aluminum alloy surface thus form track-etch membrane layer in aluminum alloy surface, then resin being injection-moulded in the surface with aluminium oxide rete and obtaining plastic-aluminum integration product.But in the plastic-aluminum integration product adopting the method to obtain, the bond strength of aluminium alloy and resin is not high yet.

Summary of the invention

The object of the invention is to overcome in existing metal-resin complex, the technical problem that the bond strength between metal base and resin bed is not high.

According to a first aspect of the invention, the invention provides a kind of surface treated metal base, described metal is aluminum or aluminum alloy, this metal base comprises metallic matrix and is formed at the horniness anode oxide film layer at least part of surface of described metallic matrix, and the surface distributed of described horniness anode oxide film layer has the first etch pit.

According to a second aspect of the invention, the invention provides a kind of surface treatment method of metal base, described metal is aluminum or aluminum alloy, the method comprises provides metal base, and described metal base comprises metallic matrix and is formed at the horniness anode oxide film layer at least part of surface of described metallic matrix; Described metal base is carried out the first etching, to form the first etch pit in described horniness anode oxide film layer.

According to a third aspect of the present invention, the invention provides a kind of surface treated metal base prepared by method according to a second aspect of the invention.

According to a fourth aspect of the present invention, the invention provides a kind of metal-resin complex, described metal is aluminum or aluminum alloy, this complex comprises metal base and resin bed, described metal base is surface treated metal base provided by the invention, described resin bed is attached at least part of surface of described metal base, and the part resin in described resin bed extends downwards and is filled in the first etch pit of metal base or the first etch pit and the second etch pit.

According to a fifth aspect of the present invention, the invention provides a kind of preparation method of metal-resin complex, described metal is aluminum or aluminum alloy, described metal-resin complex comprises metal base and is attached to the resin bed at least part of surface of described metal base, described metal base is surface treated metal base provided by the invention, the method at least part of surface imp lantation comprised to metal base contains the composition of resin and makes fraction compositions be filled in the first etch pit of metal base or the first etch pit and the second etch pit, shaping rear formation resin bed.

According to a sixth aspect of the invention, the invention provides a kind of metal-resin complex prepared by method according to a fifth aspect of the present invention.

According to a seventh aspect of the present invention, the invention provides metal-resin complex according to the present invention and prepare the application in electronic product casing.

According to an eighth aspect of the present invention, the invention provides a kind of electronic product casing, this shell comprises metal-back body and is attached at least part of inner surface of described metal-back body and/or at least one resin piece of at least part of outer surface, wherein, described metal-back body is according to metal base of the present invention.

According to a ninth aspect of the present invention, the invention provides a kind of preparation method of electronic product casing, the method be included in metal-back body at least part of inner surface and/or at least partly outer surface form at least one resin piece, wherein, adopt and form described resin piece according to the preparation method of metal-resin complex of the present invention.

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, requirement structural stability being required to higher use occasion can be met, such as can as the shell of various electronic product.

Accompanying drawing explanation

Fig. 1 is the sectional view for schematically illustrating according to phone housing of the present invention, comprises front view and top view;

Fig. 2 is the sectional view for schematically illustrating according to intelligent meter shell of the present invention.

Description of reference numerals

1: mobile phone metal-back body 2: resin bed

3: opening 4: intelligent meter metal-back body

5: resin-lined layer 6: signal element opening

Detailed description of the invention

Herein, metal can be fine aluminium, also can be aluminium alloy.Described aluminium alloy refers to that element adds the alloy of other element formation based on aluminium, can be common various aluminium alloys.Metal base is the various formed bodys formed with aluminum or aluminum alloy, can have various shape according to concrete instructions for use.

When surface treated metal base to be used for resin-bonded to prepare metal-resin complex, described first etch pit may be used for holding resin, thus resin is anchored on metallic substrate surface.Bond strength between resin and metal base can be improved by selecting the size of the first etch pit.

The aperture of described first etch pit is preferably in the scope of 10-200nm.When the aperture of described first etch pit is within above-mentioned scope, can not have a negative impact to the intensity of horniness anode oxide film layer itself on the one hand, on the other hand when for the preparation of metal-resin complex, resin bed firmly can also be anchored in metal base, make that there is between resin bed and metal base higher bond strength, thus make metal-resin complex have higher structural stability.From improving the metal-resin complex prepared by this surface treated metal base and resin integrated molding further, the angle of the bond strength between metal base and resin bed is set out, the aperture of described first etch pit is preferably in the scope of 50-200nm, more preferably in the scope of 80-200nm, preferred in the scope of 100-200nm further.Herein, for illustration of number range term " ... scope in " include two end values.

The ratio of the degree of depth of described first etch pit and the thickness of described horniness anode oxide film layer is preferably in the scope of 0.1-1:1, more preferably in the scope of 0.2-1:1, preferred in the scope of 0.5-1:1 further.Further preferably, the ratio of the degree of depth of at least part of first etch pit and the thickness of described horniness anode oxide film layer is 1:1, as preferably at least 50%, more preferably at least 60%, further preferably at least 70% the first etch pit the degree of depth and as described in the ratio of thickness of horniness anode oxide film layer be 1:1.

Herein, 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 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.

According to surface treated metal base of the present invention, can not there is etch pit in the surface of described metallic matrix.

In a preferred embodiment, described metallic matrix comprises base layer and corrosion layer, described base layer and described corrosion layer are structure as a whole, described corrosion layer connects with described horniness anode oxide film layer and is structure as a whole, the surface distributed of described corrosion layer has the second etch pit, and the ratio of the thickness of the degree of depth of at least part of first etch pit and described horniness anode oxide film layer is 1:1.When described metallic matrix comprises described base layer and described corrosion layer, can significantly improve in the metal-resin complex obtained by this metal base and resin integrated molding, the bond strength between metal base and resin bed.

Herein, for clearly object, the etch pit being distributed in horniness anode oxide film layer surface is called " the first etch pit ", the etch pit being distributed in the metal base surface connected with horniness anode oxide film layer is called " the second etch pit ".

This preferred embodiment in, described base layer is compacted zone.That is, etch pit is not had in described base layer.

This preferred embodiment in, the aperture of described second etch pit is preferably in the scope of 200-2000nm, more preferably in the scope of 400-2000nm, preferred in the scope of 800-1500nm further, as in the scope of 1000-1500nm.The degree of depth of described second etch pit in the scope of 0.1-500 μm, preferably in the scope of 10-400 μm, more preferably in the scope of 50-200 μm.

This preferred embodiment in, the ratio of the degree of depth of at least part of first etch pit and the thickness of described horniness anode oxide film layer is 1:1, preferably at least 50%, more preferably at least 60%, preferably the degree of depth of the first etch pit of at least 70% and the ratio of the thickness of described horniness anode oxide film layer are 1:1 further.This preferred embodiment in, the aperture of described first etch pit as mentioned before, is no longer described in detail herein.

According to surface treated metal base of the present invention, described horniness anode oxide film layer has higher hardness, its microhardness is generally 2000-2500HV, when this metal base is used for preparing metal-resin complex with resin-bonded, compared with being anode oxidation membrane with metallic substrate surface, more securely resin can be fixed in metal base, thus obtain higher bond strength.The present invention is not particularly limited for the thickness of described horniness anode oxide film layer.Usually, the thickness of described horniness anode oxide film layer can in the scope of 0.1-500 μm, preferably in the scope of 1-200 μm, more preferably in the scope of 5-100 μm, preferred in the scope of 10-50 μm further.Described horniness anode oxide film layer is without sealing pores.

According to a second aspect of the invention, the invention provides a kind of surface treatment method of metal base, described metal is aluminum or aluminum alloy, the method comprises provides metal base, and described metal base comprises metallic matrix and is formed at the horniness anode oxide film layer at least part of surface of described metallic matrix.Herein, " at least partly " expression partly or entirely.

Conventional various methods can be adopted to carry out hard anodizing to metal base thus obtain the metal base that surface has hardening oxidation rete.Particularly, can under hard anodizing condition, metal base is placed in electrolyte, with described metal base for anode, with the conductive material do not reacted with electrolyte for negative electrode, negative electrode and anode are connected, after energising respectively with the positive pole of power supply and negative electricity, carry out electrolysis, thus form horniness anode oxide film on described metallic matrix.Electrolyte in described electrolyte can one or more for being selected from sulfuric acid, oxalic acid, formic acid and citric acid.

The condition of described hard anodizing can be selected according to the thickness of the horniness anode oxide film layer of expection.Preferably, the condition of described hard anodizing makes the thickness of the horniness anode oxide film layer formed be 0.1-500 μm, is preferably 1-200 μm, is more preferably 10-100 μm, more preferably 15-50 μm.Particularly, voltage can be 10-100V, is preferably 40-80V; The temperature of electrolyte can be 0-60 DEG C, is preferably 0-10 DEG C.The time of electrolysis can be selected according to concrete electrolytic condition, and meeting the demands with the thickness of the horniness anode oxide film layer enabling formation is as the criterion, and usually, the time of described electrolysis can be 1-60 minute, is preferably 10-30 minute.

Described metal base preferably adopted the conventional various methods in this area to carry out pre-treatment before carrying out hard anodizing.Usually, described pre-treatment comprises mechanical grinding or grinding, to remove the obvious foreign matter of metallic substrate surface, then carries out degreasing and cleaning successively to metal base, to remove the grease of metallic substrate surface.

According to method of the present invention, also comprise and described metal base is carried out the first etching, to form the first etch pit in described horniness anode oxide film layer.

The condition of described first etching makes the aperture of described first etch pit preferably in the scope of 10-200nm, more preferably in the scope of 50-200nm, preferred in the scope of 80-200nm further, most preferably in the scope of 100-200nm; The ratio of the degree of depth of described first etch pit and the thickness of described horniness anode oxide film layer is preferably in the scope of 0.1-1:1, more preferably in the scope of 0.2-1:1, preferred in the scope of 0.5-1:1 further, and the ratio of the thickness of the degree of depth of at least part of first etch pit and described horniness anode oxide film layer is 1:1, as preferably more than 50%, more preferably more than 60%, further preferably more than at least 70% first etch pit the degree of depth and as described in the ratio of thickness of horniness anode oxide film layer be 1:1.

Can adopt conventional various methods that metal base is carried out the first etching, thus form the first etch pit in horniness anode oxide film layer.

In one embodiment, described first etching comprises: be soaked in alkaline etching liquid by described metal base, thus form the first etch pit in horniness anode oxide film layer.

Described alkaline etching liquid can for the common etching solution that can corrode horniness anode oxide film layer.Preferably, described etching solution is the combination of one of following two kinds of etching solutions or two kinds.Adopt the combination of one of following two kinds of etching solutions or two kinds to etch metal base, good etch effect can be obtained.Below these two kinds of etching solutions are described respectively.

1, described alkaline etching liquid is the aqueous solution containing one or more materials be selected from hydrazine derivate that water soluble hydroxide, water-soluble alkaline salt, ammonia, water-soluble amine, hydrazine and one or more hydrogen atom replaced by alkyl.

Described water soluble hydroxide can be alkali metal hydroxide, is preferably NaOH and/or potassium hydroxide, is more preferably NaOH.

Described water-soluble alkaline salt refer to the pH value of its aqueous solution be greater than 7 water-soluble alkaline salt.Particularly, described water-soluble alkaline salt can be one or more in water soluble carbonate, water soluble carbonate hydrogen salt, water-soluble phosphate, water-soluble phosphoric acid monohydric salt, water-soluble phosphoric acid dihydric salt and water-soluble borate.Described water-soluble alkaline salt can be alkali metal salt, is preferably sodium salt or sylvite, is more preferably sodium salt.Preferably, described water-soluble alkaline salt is Na ₂cO ₃, NaHCO ₃, NaH ₂pO ₄, Na ₂hPO ₄, Na ₃pO ₄and Na ₂b ₄o ₇in one or more.

Described water-soluble amine can for the common various amine that can be dissolved in water.Preferably, described water-soluble amine is one or more in ethylenediamine, diethylamide, monoethanolamine, Trimethylamine, methyl amine and dimethyl amine.

Described hydrazine derivate refers to hydrazine (that is, H ₂n-NH ₂) one or more hydrogen atoms in molecular structure replace the compound formed by alkyl, described alkyl is preferably C ₁-C ₄alkyl, be specifically as follows MMH and/or 1,1-dimethylhydrazine.

Described alkaline etching liquid is preferably the aqueous solution containing water soluble hydroxide and/or water-soluble alkaline salt.More preferably, described alkaline etching liquid is the aqueous solution containing water-soluble alkaline salt, and water-soluble alkaline salt is preferably Na ₂cO ₃and/or NaHCO ₃, be more preferably Na ₂cO ₃or NaHCO ₃.

The pH value of described alkaline etching liquid, preferably in the scope of 10-13, can not only obtain suitable etching speed like this, and the gentle easily control of etching process.

2, described alkaline etching liquid is alkaline buffer solution, and the distribution of the etch pit of so final formation is more even and pore size is more concentrated.

Described alkaline etching liquid can for the aqueous solution containing water soluble hydroxide and water-soluble alkaline salt.Described water soluble hydroxide can be identical with the cation of described water-soluble alkaline salt, also can be different, preferably identical.

Described water-soluble alkaline salt can be one or more in water soluble carbonate, water soluble carbonate hydrogen salt, water-soluble phosphate, water-soluble phosphoric acid monohydric salt, water-soluble phosphoric acid dihydric salt and water-soluble borate.Described water-soluble alkaline salt can be alkali metal salt, is preferably sodium salt or sylvite, is more preferably sodium salt.Preferably, described water-soluble alkaline salt is Na ₂cO ₃, NaHCO ₃, NaH ₂pO ₄, Na ₂hPO ₄, Na ₃pO ₄and Na ₂b ₄o ₇in one or more.Preferably, described water-soluble alkaline salt is water-soluble phosphoric acid monohydric salt and/or water-soluble phosphoric acid dihydric salt.More preferably, described water-soluble alkaline salt is water-soluble phosphoric acid dihydric salt, as one or more in sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate (ADP) and aluminium dihydrogen phosphate.

Described alkaline etching liquid also can for the aqueous solution containing water-soluble normal salt and water soluble acid salt.Described normal salt refers to that cation only contains the salt of metal ion and/or ammonium radical ion, and described acid salt refers to that cation is except containing except metal ion and/or ammonium radical ion, also containing hydrionic salt.The cation of described water-soluble normal salt and described water soluble acid salt can be identical with acid ion separately, also can be different, preferably identical.

Described alkaline etching liquid is preferably the aqueous solution containing water soluble carbonate and water soluble carbonate hydrogen salt, or contains the aqueous solution of water-soluble phosphate and water-soluble phosphoric acid monohydric salt.Particularly, described alkaline etching liquid can for containing Na ₂cO ₃and NaHCO ₃the aqueous solution, or containing Na ₃pO ₄and Na ₂hPO ₄the aqueous solution.

Described alkaline etching liquid can also for the aqueous solution containing ammonia and water soluble salt of ammonia.Described water soluble salt of ammonia is preferably NH ₄cl, (NH ₄) ₂sO ₄, NH ₄hCO ₃and NH ₄nO ₃in one or more.Particularly, described alkaline etching liquid can for containing NH ₃and NH ₄the aqueous solution of Cl, containing NH ₃(NH ₄) ₂sO ₄the aqueous solution, containing NH ₃and NH ₄hCO ₃the aqueous solution or containing NH ₃and NH ₄nO ₃the aqueous solution.

Described alkaline etching liquid is preferably the aqueous solution containing water soluble hydroxide and water-soluble alkaline salt, or is the aqueous solution containing water-soluble normal salt and water soluble acid salt, is more preferably the aqueous solution containing water-soluble normal salt and water soluble acid salt.

Described alkaline etching liquid is preferably the alkaline buffer solution that pH value is 10-13, can obtain suitable etching speed like this, and the gentle easily control of etching process.

In described first etching, the temperature of alkaline etching liquid can be 10-60 DEG C, is preferably 20-40 DEG C; The time of the first etching can be 1-60 minute, is preferably 5-20 minute.

Being etched in through first the metal base defining the first etch pit in horniness anode oxide film layer can directly as surface treated metal base, with resin integrated molding, to prepare metal-resin complex.

One more preferred embodiment in, by through first etching metal base carry out the second etching, to form the second etch pit at the metal base surface connected with described horniness anode oxide film layer.By through second etch the surface treated metal base obtained be used for preparing metal-resin complex with resin-bonded time, demonstrate higher bond strength between resin bed and metal base.

The condition of described second etching preferably makes the aperture of described second etch pit preferably in the scope of 200-2000nm, more preferably in the scope of 400-2000nm, preferred in the scope of 800-1500nm further, as in the scope of 1000-1500nm.From improving by the metal-resin complex formed after this surface treated metal base and resin integrated molding further, the angle of the bond strength between metal base and resin bed is set out, the condition of described second etching makes the degree of depth of described second etch pit in the scope of 0.1-500 μm, preferably in the scope of 10-400 μm, more preferably in the scope of 50-200 μm.

Various method can be adopted to form described second etch pit.In a preferred embodiment, described second etching comprises: be soaked in acidic etching liquid by the metal base through the first etching.

Described acidic etching liquid is for containing aqueous acid, and described acid is halogen acids and/or H ₃pO ₄, be preferably HCl or H ₃pO ₄.

Preferably, described acidic etching liquid also containing one or more water soluble salts, can improve the stability of etching so further.The acid group of described water soluble salt is preferably identical with the acid group of the acid contained in acidic etching liquid.Such as, when described acidic etching liquid is the aqueous solution containing halogen acids, described acidic etching liquid is preferably also containing one or more water-soluble halogen acid salts; At described acidic etching liquid for during containing phosphorus aqueous acid, described acidic etching liquid is preferably also containing one or more water-soluble phosphates.Particularly, when described acidic etching liquid is hydrochloric acid, described water soluble salt is preferably NaCl, KCl and AlCl ₃in one or more.When described acidic etching liquid is phosphoric acid, described water soluble salt is one or more in water-soluble phosphate, water-soluble phosphoric acid monohydric salt and water-soluble phosphoric acid dihydric salt, as NaH ₂pO ₄, Na ₂hPO ₄, Na ₃pO ₄, KH ₂pO ₄, K ₂hPO ₄and K ₃pO ₄in one or more.

The content of described water soluble salt in described acidic etching liquid with acidic etching liquid in the amount of acid and fixed.Usually, the mol ratio of described water soluble salt and described acid can be 0.1-1:1, is preferably 0.2-0.8:1, is more preferably 0.4-0.6:1.

The pH value of described acidic etching liquid is preferably 1-3, in the surface treated metal base of such formation, the distribution of etch pit is more even, pore-size distribution is also more concentrated, and in the metal-resin complex prepared by this metal base, the bond strength of resin and metal base is higher.

Particularly, the temperature of described acidic etching liquid can be 20-30 DEG C, and the soak time of metal base in described acidic etching liquid can be 1-60 minute, is preferably 10-30 minute.

According to method of the present invention, in a preferred example, in described first etching, described metal base is soaked in alkaline etching liquid; In described second etching, the metal base through the first etching is soaked in acidic etching liquid.Adopt and etch in this way, in etching process, etch heat release little, the gentle easily control of etching process, the first etch pit of formation and the distribution of the second etch pit more even, hole dimension (comprising aperture and the degree of depth) is more concentrated; Further, when being used for preparing metal-resin complex with resin-bonded by the surface treated metal base obtained by the method, higher bond strength between resin bed and metal base, is demonstrated.

According to method of the present invention, described first etching and described second etching can only be carried out once separately, also can gradation, and the duration at every turn etched is not particularly limited, as long as total etching period meet above-mentioned requirements.Wash with water between twice etching, to remove the etching solution of a front etch residue.

Described surface treated metal base and preparation method thereof is described in detail above, no longer describes in detail herein.

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 can in the scope of 0.1-10mm, preferably in the scope of 0.5-5mm.Herein, the thickness of resin bed refer to the upper surface of horniness anode oxide film layer to resin bed upper surface between vertical range.

Matrix resin in described resin bed can be selected according to concrete instructions for use, as long as this resin can be combined with aluminum or aluminum 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, preferably, with 100 weight portion matrix resins for benchmark, the content of described filler can be 20-150 weight portion, is preferably 25-100 weight portion, is more preferably 30-50 weight portion.

Resin (hereinafter referred to as matrix resin) in described resiniferous composition is identical with the kind of the matrix resin in described resin bed above, no longer describes in detail herein.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 is identical with the kind of the filler in described resin bed above, no longer describes in detail herein.

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 25-100 weight portion, is more preferably 30-50 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.

Conventional various methods can be adopted to inject described resiniferous composition to the etched surfaces of metal base.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.

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 is 50-300 DEG C, and nozzle temperature is 200-450 DEG C, and the dwell time is 1-50 second, and injection pressure is 50-300MPa, and the injection time is 1-30 second, and time delay is 1-30 second.

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 to be 0.1-10mm, is preferably 0.5-5mm.

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 be carried out before injection-moulding step, also can carry out after injection-moulding step, be not particularly limited.

According to a sixth aspect of the invention, present invention also offers a kind of metal-resin complex prepared by method according to a fifth aspect of the present invention.

According to an eighth aspect of the present invention, the invention provides a kind of electronic product casing, this shell comprises metal-back body and is attached at least part of inner surface of described metal-back body and/or at least one resin piece of at least part of outer surface, wherein, described metal-back body is according to metal base of the present invention.In the present invention, described shell not only comprises the shell for laminated structure, also comprises various frame structure, as housing.

According to electronic product casing of the present invention, according to specific needs, described metal-back body can be provided with at least one opening, with this opening correspondence position install electronic product need the element avoiding metal-back body.In one embodiment, because metal pair electromagnetic signal has shielding action, therefore the position of opening can correspond to the installation site of signal radiated element and/or signal receiving element at least partly, now described aperture position preferably arranges resin piece, and making the part resin in described resin piece be filled in described opening, signal radiated element and/or signal receiving element can be arranged on described resin piece.

According to electronic product casing of the present invention, described metal-back body can be structure as a whole, and also can be splicing construction.Described splicing construction refers to that described metal-back body comprises at least two parts mutually disconnected, and two parts are mutually stitched together and form metal-back body.

When described metal-back body is splicing construction, adjacent two parts can stick with glue agent and be bonded together.In a preferred embodiment, adjacent two-part stitching position is provided with described resin piece, this resin piece overlaps with adjacent two parts respectively and covers described stitching position (i.e. these adjacent two parts of this resin piece bridge joint), can improve the bond strength of stitching position like this; Further, according to the internal structure of electronic product, metal-back body can be divided into multiple part, described resin piece, while playing and making metal-back body form as a whole effect, can also be used as the installation matrix of some electronic components.

According to electronic product casing of the present invention, at least part of outer surface of described metal-back body can be attached with resin piece, described resin piece can cover whole outer surface, also can the partial outer face of covering metal shell body to form pattern, such as decorative pattern.

According to electronic product casing of the present invention, when the inner surface of described metal-back body is attached with resin piece, described resin piece can be arranged on one or more positions of needs.In a preferred embodiment, described resin piece is attached to the whole inner surface of described metal-back body, and now described resin piece is preferably integrative-structure.According to this preferred embodiment, the occasion that metal-back body is splicing construction is specially adapted to.

According to electronic product casing of the present invention, can be various needs using metal as the electronic product casing of shell, such as: the shell of mobile terminal or housing, the shell of wearable electronic or housing.Described mobile terminal refers to and can be in mobile status and the equipment with wireless transmission function, such as: mobile phone, portable computer (comprising notebook computer and panel computer).Described wearable electronic refers to intelligentized wearable device, such as: intelligent meter, Intelligent bracelet.Described electronic product be specifically as follows but be not limited in mobile phone, portable computer (as notebook computer and panel computer), intelligent meter and Intelligent bracelet one or more.

Fig. 1 shows front view and the top view of a kind of embodiment when described electronic product casing is phone housing.As shown in Figure 1, mobile phone metal-back body 1 offers multiple opening 3, the position of opening 3 can corresponding to the position fixed up an aerial wire and the position of installing various button.Resin bed 2 is attached to the whole inner surface of mobile phone metal-back body 1, and resin bed 2 is structure as a whole and part resin in resin bed 2 is filled in opening 3.

Fig. 2 shows the front view that described electronic product casing is a kind of embodiment of the shell of intelligent meter.As indicated with 2, intelligent meter metal-back body 4 is provided with the signal element opening 6 corresponding to and install signal radiated element and/or signal receiving element, the inner surface of intelligent meter metal-back body 4 is attached with resin-lined layer 5, part resin in resin-lined layer 5 is filled in signal element opening 6, and signal element can be arranged on the relevant position on resin-lined layer 5.

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, with reference to the method that ASTMD1002-10 specifies, the average shear strength in INSTRON3369 type universal test aircraft measurements metal-resin complex between metallic matrix and resin bed.

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.

In following examples and comparative example, the model purchased from Shanghai optical instrument one factory is adopted to be the microhardness that HX-1000TM/LCD microhardness testers measure horniness anode oxide film layer.

Embodiment 1-12 is for illustration of the present invention.

Embodiment 1

(1) by commercially available thickness be the rectangular pieces that 5052 aluminium alloy plates of 1mm are 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 aluminum alloy sheet through pre-treatment.

(2) aluminum alloy sheet step (1) obtained puts into the hard anodizing groove of the aqueous solution containing the NaOH of 1 % by weight and the sodium metasilicate of 0.1 % by weight as electrolyte as anode, using graphite carbon plate as negative electrode, under the voltage of 60V, 10 DEG C of electrolysis 15 minutes, to carry out hard anodizing.Aluminum alloy sheet through hard anodizing taken out and dries up, obtaining the aluminum alloy sheet that surface has horniness anode oxide film layer.Observe with the cross section of microscope to this aluminum alloy sheet, determine that the thickness of horniness anode oxide film layer is 25 μm, the microhardness of horniness anode oxide film layer is 2200HV.

(3) aluminum alloy sheet surface that step (2) obtains with horniness anode oxide film layer be soaked in temperature be 20 DEG C as etching solution containing Na ₂hPO ₄the aqueous solution (pH=11) in.After 15 minutes, aluminum alloy sheet is taken out, soak 1 minute in water, then take out and dry up, obtain the aluminum alloy sheet through alkaline etching.

The cross section of the aluminum alloy sheet adopting microscopic examination step (3) to obtain, find: in horniness anode oxide film layer, be distributed with the etch pit of aperture within the scope of 50-200nm, the ratio of the degree of depth of this etch pit and the thickness of horniness anode oxide film layer is in the scope of 0.2-1:1, and the degree of depth of etch pit of more than 60% and the ratio of the thickness of horniness anode oxide film layer are 1:1.

(4) aluminum alloy sheet that step (3) obtains is placed in injecting molding die, the resin combination of glass fibre and polyphenylene sulfide (PPS) is contained (relative to 100 weight portion PPS in a surperficial injection moulding of aluminum alloy sheet, the content of glass fibre is 35 weight portions), the demoulding also cools.Wherein, injecting condition comprises: mold 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 5mm), its average shear strength is listed in Table 1.

Embodiment 2

The method identical with embodiment 1 is adopted to carry out surface treatment to aluminum alloy sheet and prepare metal-resin complex, unlike, in step (2), the electrolyte of use is the aqueous solution containing the NaOH of 1 % by weight and the sodium phosphate of 0.1 % by weight, and electrolysis time is 10 minutes.

The cross section of the aluminum alloy sheet adopting microscopic examination step (3) to obtain, find: in horniness anode oxide film layer, be distributed with the etch pit of aperture within the scope of 10-200nm, the ratio of the degree of depth of this etch pit and the thickness of horniness anode oxide film layer is in the scope of 0.1-1:1, and the degree of depth of etch pit of more than 50% and the ratio of the thickness of horniness anode oxide film layer are 1:1.The average shear strength of the metal-resin complex of preparation is listed in Table 1.

Embodiment 3

The method identical with embodiment 1 is adopted to carry out surface treatment to aluminum alloy sheet and prepare metal-resin complex, unlike, in step (3), etching solution is the aqueous solution (pH=11) of NaOH.

Comparative example 1

(1) the employing method identical with embodiment 1 step (1) prepares the aluminum alloy sheet through pre-treatment.

(2) method identical with embodiment 1 step (4) is adopted resin combination to be injection-moulded in the surface of the aluminum alloy sheet that comparative example 1 step (1) obtains, form resin bed, thus obtaining metal-resin complex, its average shear strength is listed in Table 1.

Comparative example 2

(2) adopt the method identical with embodiment 1 step (2) that the aluminum alloy sheet that comparative example 2 step (1) obtains is carried out hard anodizing.

(3) method identical with embodiment 1 step (4) is adopted resin combination to be injection-moulded in the surface of the aluminum alloy sheet that comparative example 2 step (2) obtains, form resin bed, thus obtaining metal-resin complex, its average shear strength is listed in Table 1.

Comparative example 3

(2) aluminum alloy sheet step (1) obtained adopts following methods to carry out anodic oxidation, obtains through anodised aluminum alloy sheet:

The aluminum alloy sheet that step (1) is obtained as anode put into concentration be 20 % by weight H ₂sO ₄the aqueous solution as in the anodizing tank of electrolyte, using graphite carbon plate as negative electrode, under the voltage of 18V, 20 DEG C of electrolysis 15 minutes.To take out through anodised aluminum alloy sheet and dry up, obtain the aluminum alloy sheet that surface has anode oxidation membrane.Observe with the cross section of microscope to this aluminum alloy sheet, determine that the thickness of anode oxidation membrane is 25 μm, microhardness is 200HV.

(3) aluminum alloy sheet surface that step (2) obtains with anode oxidation membrane be soaked in temperature be 20 DEG C containing Na ₂hPO ₄the aqueous solution (pH=11) in.After 15 minutes, aluminum alloy sheet is taken out, soak 1 minute in water, then take out and dry up, obtain the aluminum alloy sheet through alkaline etching.

The cross section of the aluminum alloy sheet adopting microscopic examination step (3) to obtain, find: in anode oxidation membrane, be distributed with the etch pit of aperture within the scope of 50-200nm, the ratio of the degree of depth of this etch pit and the thickness of anode oxidation membrane is in the scope of 0.2-1:1, and the degree of depth of etch pit of more than 60% and the ratio of the thickness of hardening oxidation rete are 1:1.

(4) adopt the method identical with embodiment 1 step (4) to prepare metal-resin complex, its average shear strength is listed in Table 1.

Embodiment 4

The method identical with embodiment 1 is adopted to carry out surface treatment to aluminum alloy sheet and prepare metal-resin complex, unlike, step (3) is divided into step (3-1) and step (3-2), in step (3-1), adopt the method identical with embodiment 1 step (3) to etch the aluminum alloy sheet through hard anodizing, in step (3-2), adopt acidic etching liquid to etch the aluminum alloy sheet through alkaline etching, step (3-2) is specific as follows:

The aluminum alloy sheet through alkaline etching that step (3-1) obtains being soaked in temperature is in the hydrochloric acid as etching solution (pH=2) of 20 DEG C.After 12 minutes, aluminum alloy sheet is taken out, soak 1 minute in water, then take out and dry up, obtain the aluminum alloy sheet through acid etching.

The cross section of the aluminum alloy sheet adopting microscopic examination step (3-2) to obtain, find: in horniness anode oxide film layer, be distributed with first etch pit of aperture within the scope of 50-200nm, the ratio of the degree of depth of the first etch pit and the thickness of horniness anode oxide film layer is in the scope of 0.2-1:1, and the degree of depth of the first etch pit of more than 60% and the ratio of the thickness of hardening oxidation oxidation film layer are 1:1; Alloy matrix aluminum is divided into fine and close base layer and has the corrosion layer of the second etch pit, and corrosion layer connects with horniness anode oxide film layer, and the aperture of the second etch pit is within the scope of 200-2000nm, and the degree of depth of the second etch pit is in the scope of 0.1-400 μm.The average shear strength of the metal-resin complex of preparation is listed in Table 1.

Comparative example 4

The method identical with embodiment 4 is adopted to carry out surface treatment to aluminum alloy sheet and prepare metal-resin complex, unlike, step (2) adopts the method identical with comparative example 3 step (2) to form anode oxidation membrane on aluminum alloy sheet surface;

In step (3-1), the aluminum alloy sheet surface that step (2) obtains with anode oxidation membrane be soaked in temperature be 20 DEG C containing Na ₂hPO ₄the aqueous solution (pH=11) in.After 15 minutes, aluminum alloy sheet is taken out, soak 1 minute in water, then take out and dry up, obtain the aluminum alloy sheet through alkaline etching;

In step (3-2), the aluminum alloy sheet through alkaline etching that step (3-1) obtains being soaked in temperature is in the hydrochloric acid (pH=2) of 20 DEG C.After 12 minutes, aluminum alloy sheet is taken out, soak 1 minute in water, then take out and dry up, obtain the aluminum alloy sheet through acid etching.

The cross section of the aluminum alloy sheet adopting microscopic examination step (3-2) to obtain, find: in anode oxidation membrane, be distributed with first etch pit of aperture within the scope of 50-200nm, the ratio of the degree of depth of the first etch pit and the thickness of anode oxidation membrane is in the scope of 0.2-1:1, and the degree of depth of the first etch pit of more than 60% and the ratio of the thickness of anode oxidation membrane are 1:1; Alloy matrix aluminum is divided into fine and close base layer and has the corrosion layer of the second etch pit, and corrosion layer connects with anode oxidation membrane, and the aperture of the second etch pit is within the scope of 200-2000nm, and the degree of depth of the second etch pit is in the scope of 0.1-400 μm.The average shear strength of the metal-resin complex of preparation is listed in Table 1.

Comparative example 5

The method identical with embodiment 1 is adopted to carry out surface treatment to aluminum alloy sheet and prepare metal-resin complex, unlike, step (3) is divided into step (3-1) and step (3-2), in step (3-1), adopt the method identical with the step (3-2) in embodiment 4 to etch the aluminum alloy sheet through hard anodizing, in step (3-2), adopt the method identical with embodiment 1 step (3) to etch the aluminum alloy sheet through acid etching.

The cross section of the aluminum alloy sheet adopting microscopic examination step (3-2) to obtain, find: in horniness anode oxide film layer, be distributed with first etch pit of aperture within the scope of 50-200nm, the ratio of the degree of depth of the first etch pit and the thickness of horniness anode oxide film layer is in the scope of 0.2-1:1, and the degree of depth of the first etch pit of more than 60% and the ratio of the thickness of horniness anode oxide film layer are 1:1; Alloy matrix aluminum is divided into fine and close base layer and has the corrosion layer of the second etch pit, and corrosion layer connects with horniness anode oxide film layer, and the aperture of the second etch pit is within the scope of 500-4500nm, and the degree of depth of the second etch pit is in the scope of 0.1-400 μm.The average shear strength of the metal-resin complex of preparation is listed in Table 1.

Comparative example 6

The method identical with embodiment 1 is adopted to carry out surface treatment to aluminum alloy sheet and prepare metal-resin complex, unlike, adopt the method identical with embodiment 4 step (3-2) to etch the aluminum alloy sheet through hard anodizing in step (3).

The cross section of the aluminum alloy sheet adopting microscopic examination step (3) to obtain, finds: substantially do not have etch pit in horniness anode oxide film layer; Alloy matrix aluminum is divided into fine and close base layer and has the corrosion layer of etch pit, and corrosion layer connects with horniness anode oxide film layer, and the aperture of etch pit is within the scope of 800-5000nm, and the degree of depth of etch pit is in the scope of 0.01-500 μm.The average shear strength of the metal-resin complex of preparation is listed in Table 1.

Embodiment 5

The method identical with embodiment 4 is adopted to carry out surface treatment to aluminum alloy sheet and prepare metal-resin complex, unlike, in step (3-2), etching solution is the hydrochloric acid (pH=2) containing NaCl, and the mol ratio of NaCl and HCl is 0.5:1.

The cross section of the aluminum alloy sheet adopting microscopic examination step (3-2) to obtain, find: in horniness anode oxide film layer, be distributed with first etch pit of aperture within the scope of 50-200nm, the ratio of the degree of depth of the first etch pit and the thickness of horniness anode oxide film layer is in the scope of 0.2-1:1, and the degree of depth of the first etch pit of more than 60% and the ratio of the thickness of horniness anode oxide film layer are 1:1; Alloy matrix aluminum is divided into fine and close base layer and has the corrosion layer of the second etch pit, and corrosion layer connects with horniness anode oxide film layer, and the aperture of the second etch pit is within the scope of 500-2000nm, and the degree of depth of the second etch pit is in the scope of 50-200 μm.The average shear strength of the metal-resin complex of preparation is listed in Table 1.

Embodiment 6

The method identical with embodiment 4 is adopted to carry out surface treatment to aluminum alloy sheet and prepare metal-resin complex, unlike, in step (3-1), etching solution is for containing Na ₃pO ₄and Na ₂hPO ₄the aqueous solution (pH=11).

The cross section of the aluminum alloy sheet adopting microscopic examination step (3-2) to obtain, find: in horniness anode oxide film layer, be distributed with first etch pit of aperture within the scope of 100-200nm, the ratio of the degree of depth of the first etch pit and the thickness of horniness anode oxide film layer is in the scope of 0.5-1:1, and the degree of depth of the first etch pit of more than 70% and the ratio of the thickness of horniness anode oxide film layer are 1:1; Alloy matrix aluminum is divided into fine and close base layer and has the corrosion layer of the second etch pit, and corrosion layer connects with horniness anode oxide film layer, and the aperture of the second etch pit is within the scope of 1000-1500nm, and the degree of depth of the second etch pit is in the scope of 10-300 μm.The average shear strength of the metal-resin complex of preparation is listed in Table 1.

Embodiment 7

(2) it is that the oxalic acid of 20 % by weight is as the hard anodizing groove of electrolyte that aluminum alloy sheet step (1) obtained is put into as anode using concentration, using graphite carbon plate as negative electrode, under the voltage of 60V, 5 DEG C of electrolysis 15 minutes, carry out hard anodizing.Aluminum alloy sheet through hard anodizing taken out and dries up, obtaining the aluminum alloy sheet that surface has horniness anode oxide film layer.Observe with the cross section of microscope to this aluminum alloy sheet and determine that the thickness of horniness anode oxide film layer is 10 μm, the microhardness of horniness anode oxide film layer is 2500HV.

(3-1) aluminum alloy sheet surface that step (2) obtains with horniness anode oxide film layer is soaked in the Na as etching solution that temperature is 25 DEG C ₂cO ₃and NaHCO ₃the aqueous solution (pH=12) in.After 20 minutes, aluminum alloy sheet is taken out, soak 1 minute in water, then take out and dry up, obtain the aluminum alloy sheet through alkaline etching.

(3-2) aluminum alloy sheet through alkaline etching that step (3-1) obtains being soaked in temperature is in the hydrochloric acid as etching solution (pH=1) of 25 DEG C.After 5 minutes, aluminum alloy sheet is taken out, soak 1 minute in water, then take out and dry up, obtain the aluminum alloy sheet through acid etching.

The cross section of the aluminum alloy sheet adopting microscopic examination step (3-2) to obtain, find: in horniness anode oxide film layer, be distributed with first etch pit of aperture within the scope of 100-200nm, the ratio of the degree of depth of the first etch pit and the thickness of horniness anode oxide film layer is in the scope of 0.7-1:1, and the degree of depth of the first etch pit of more than 70% and the ratio of the thickness of horniness anode oxide film layer are 1:1; Alloy matrix aluminum is divided into fine and close base layer and has the corrosion layer of the second etch pit, and corrosion layer connects with horniness anode oxide film layer, and the aperture of the second etch pit is within the scope of 1000-1500nm, and the degree of depth of the second etch pit is in the scope of 10-300 μm.

(4) aluminum alloy sheet that step (3-2) obtains is placed in injecting molding die, the resin combination of glass fibre and PETG (PET) is contained (relative to 100 weight portion PET in a surperficial injection moulding of aluminum alloy sheet, the content of glass fibre is 40 weight portions), the demoulding also cools.Wherein, injecting condition comprises: mold temperature is 110 DEG C, and nozzle temperature is 300 DEG C, and the dwell time is 8 seconds, and injection pressure is 110MPa, and the injection time is 4 seconds, and time delay is 2 seconds.

Embodiment 8

The method identical with embodiment 7 is adopted to carry out surface treatment to aluminium alloy and prepare aluminium alloy-resin composite body, unlike, in step (3-1), etching solution is the aqueous solution (pH=12) of ethylenediamine.

The cross section of the aluminum alloy sheet adopting microscopic examination step (3-2) to obtain, find: in horniness anode oxide film layer, be distributed with first etch pit of aperture within the scope of 10-200nm, the ratio of the degree of depth of the first etch pit and the thickness of horniness anode oxide film layer is in the scope of 0.1-1:1, and the degree of depth of the first etch pit of more than 50% and the ratio of the thickness of horniness anode oxide film layer are 1:1; Alloy matrix aluminum is divided into fine and close base layer and has the corrosion layer of the second etch pit, and corrosion layer connects with horniness anode oxide film layer, and the aperture of the second etch pit is within the scope of 200-2000nm, and the degree of depth of the second etch pit is in the scope of 0.1-400 μm.The average shear strength of the metal-resin complex of preparation is listed in Table 1.

Embodiment 9

The method identical with embodiment 7 is adopted to carry out surface treatment to aluminium alloy and prepare aluminium alloy-resin composite body, unlike, in step (3-1), etching solution is in the aqueous solution (pH=12) of hydrazine.

Embodiment 10

(2) it is that the citric acid of 20 % by weight is as the hard anodizing groove of electrolyte that aluminum alloy sheet step (1) obtained is put into as anode using concentration, using graphite carbon plate as negative electrode, under the voltage of 60V, 20 DEG C of electrolysis 15 minutes, to carry out hard anodizing.Aluminum alloy sheet through hard anodizing taken out and dries up, obtaining the aluminum alloy sheet that surface has horniness anode oxide film.Observe with the cross section of microscope to this aluminum alloy sheet and determine that the thickness of horniness anode oxide film layer is 21 μm, the microhardness of horniness anode oxide film layer is 2000HV.

(3-1) aluminium flake surface that step (2) obtains with horniness anode oxide film layer be soaked in temperature be 25 DEG C as in the NaOH aqueous solution (pH=13) of etching solution.After 5 minutes, aluminum alloy sheet is taken out, soak 1 minute in water, then take out and dry up, obtain the aluminum alloy sheet through alkaline etching.

(3-2) aluminum alloy sheet through alkaline etching that step (3-1) obtains being soaked in temperature is in the phosphoric acid as etching solution (pH=3) of 30 DEG C.After 20 minutes, aluminum alloy sheet is taken out, soak 1 minute in water, then take out and dry up, obtain the aluminum alloy sheet through acid etching.

The cross section of the aluminum alloy sheet adopting microscopic examination step (3-2) to obtain, find: in horniness anode oxide film layer, be distributed with first etch pit of aperture within the scope of 10-200nm, the ratio of the degree of depth of the first etch pit and the thickness of horniness anode oxide film layer is in the scope of 0.1-1:1, and the degree of depth of the first etch pit of more than 60% and the ratio of the thickness of horniness anode oxide film layer are 1:1; Alloy matrix aluminum is divided into fine and close base layer and has the corrosion layer of the second etch pit, and corrosion layer connects with horniness anode oxide film layer, and the aperture of the second etch pit is within the scope of 200-2000nm, and the degree of depth of the second etch pit is in the scope of 0.1-400 μm.

(4) aluminum alloy sheet that step (3-2) obtains is placed in injecting molding die, the resin combination of glass fibre and nylon-66 (PA-66) is contained (relative to 100 weight portion PA-66 in a surperficial injection moulding of aluminum alloy sheet, the content of glass fibre is 50 weight portions), the demoulding also cools.Wherein, injecting condition comprises: mold temperature is 100 DEG C, and nozzle temperature is 300 DEG C, and the dwell time is 6 seconds, and injection pressure is 100MPa, and the injection time is 5 seconds, and time delay is 5 seconds.

Embodiment 11

The method identical with embodiment 10 is adopted to carry out surface treatment to aluminum alloy sheet and prepare metal-resin complex, unlike, in step (3-1), etching solution (pH value is identical with embodiment 10) is also containing Na ₂cO ₃.

The cross section of the aluminum alloy sheet adopting microscopic examination step (3-2) to obtain, find: in horniness anode oxide film layer, be distributed with first etch pit of aperture within the scope of 80-200nm, the ratio of the degree of depth of the first etch pit and the thickness of horniness anode oxide film layer is in the scope of 0.5-1:1, and the degree of depth of the first etch pit of more than 60% and the ratio of the thickness of hard anode rete are 1:1; Alloy matrix aluminum is divided into fine and close base layer and has the corrosion layer of the second etch pit, and corrosion layer connects with horniness anode oxide film layer, and the aperture of the second etch pit is within the scope of 1000-1500nm, and the degree of depth of the second etch pit is in the scope of 10-300 μm.The average shear strength of the metal-resin complex of preparation is listed in Table 1.

Embodiment 12

The method identical with embodiment 10 is adopted to carry out surface treatment to aluminum alloy sheet and prepare metal-resin complex, unlike, in step (3-2), etching solution (pH value is identical with embodiment 10) is also containing Na ₂hPO ₄, Na ₂hPO ₄with H ₃pO ₄mol ratio be 0.3:1.

The cross section of the aluminium flake adopting microscopic examination step (3-2) to obtain, find: in horniness anode oxide film layer, be distributed with first etch pit of aperture within the scope of 10-200nm, the ratio of the degree of depth of the first etch pit and the thickness of horniness anode oxide film layer is at 0.1-1:1, and the degree of depth of the first etch pit of more than 60% and the ratio of the thickness of horniness anode oxide film layer are 1:1; Aluminum substrate is divided into fine and close base layer and has the corrosion layer of the second etch pit, and corrosion layer connects with horniness anode oxide film layer, and the aperture of the second etch pit is within the scope of 400-2000nm, and the degree of depth of the second etch pit is in the scope of 50-200 μm.The average shear strength of the metal-resin complex of preparation is listed in Table 1.

Embodiment 1 is compared can find out with comparative example 1-3, in metal-resin complex prepared by surface treated metal base according to the present invention and resin integrated molding, there is higher average shear strength (namely between resin bed and metal base, there is higher bond strength), thus complex has higher structural stability.

Table 1

Numbering	Average shear strength (MPa)
		Embodiment 1	18.1
Embodiment 2	17.6
		Embodiment 3	19.4
Comparative example 1	0.2
		Comparative example 2	4
Comparative example 3	10.4
		Embodiment 4	23.5
Comparative example 4	14.9
		Comparative example 5	7.2
Comparative example 6	5.5
		Embodiment 5	24.7
Embodiment 6	25.3
		Embodiment 7	22.1
Embodiment 8	20.5
		Embodiment 9	20.3
Embodiment 10	18.8
		Embodiment 11	21.6
Embodiment 12	20.2

Claims

1. a surface treated metal base, described metal is aluminum or aluminum alloy, this metal base comprises metallic matrix and is formed at the horniness anode oxide film layer at least part of surface of described metallic matrix, and the surface distributed of described horniness anode oxide film layer has the first etch pit.

2. surface treated metal base according to claim 1, wherein, the aperture of described first etch pit in the scope of 10-200nm, preferably in the scope of 50-200nm, more preferably in the scope of 80-200nm, preferred in the scope of 100-200nm further; The ratio of the degree of depth of described first etch pit and the thickness of described horniness anode oxide film layer in the scope of 0.1-1:1, preferably in the scope of 0.2-1:1, more preferably in the scope of 0.5-1:1.

3. surface treated metal base according to claim 1 and 2, wherein, the ratio of the degree of depth of at least part of first etch pit and the thickness of described horniness anode oxide film layer is 1:1, and preferably the degree of depth of the first etch pit of more than 50% and the ratio of the thickness of described horniness anode oxide film layer are 1:1.

4. according to the surface treated metal base in claim 1-3 described in any one, wherein, described metallic matrix comprises base layer and corrosion layer, described base layer and described corrosion layer are structure as a whole, described corrosion layer connects with described horniness anode oxide film layer and is structure as a whole, and the surface distributed of described corrosion layer has the second etch pit.

5. surface treated metal base according to claim 4, wherein, the aperture of described second etch pit in the scope of 200-2000nm, preferably in the scope of 400-2000nm, more preferably in the scope of 800-1500nm.

6. the surface treated metal base according to claim 4 or 5, wherein, the degree of depth of described second etch pit in the scope of 0.1-500 μm, preferably in the scope of 10-400 μm, more preferably in the scope of 50-200 μm.

7. according to the surface treated metal base in claim 4-6 described in any one, wherein, described base layer is compacted zone.

8. according to the surface treated metal base in claim 1-7 described in any one, wherein, the thickness of described horniness anode oxide film layer is in the scope of 0.1-500 μm.

9. a surface treatment method for metal base, described metal is aluminum or aluminum alloy, and the method comprises provides metal base, and described metal base comprises metallic matrix and is formed at the horniness anode oxide film layer at least part of surface of described metallic matrix; Described metal base is carried out the first etching, to form the first etch pit in described horniness anode oxide film layer.

10. method according to claim 9, wherein, the condition of described first etching makes the aperture of described first etch pit in the scope of 10-200nm, preferably in the scope of 50-200nm, more preferably in the scope of 80-200nm, preferred in the scope of 100-200nm further; The ratio of the degree of depth of described first etch pit and the thickness of described horniness anode oxide film layer in the scope of 0.1-1:1, preferably in the scope of 0.2-1:1, more preferably in the scope of 0.5-1:1.

11. methods according to claim 9 or 10, wherein, the condition of described first etching makes the ratio of the thickness of the degree of depth of at least part of first etch pit and described horniness anode oxide film layer be 1:1, and preferably the degree of depth of the first etch pit of more than 50% and the ratio of the thickness of described horniness anode oxide film layer are 1:1.

12. according to the method in claim 9-11 described in any one, and wherein, described first etching comprises: be soaked in alkaline etching liquid by described metal base.

13. methods according to claim 12, wherein, described alkaline etching liquid is the aqueous solution containing one or more materials be selected from hydrazine derivate that water soluble hydroxide, water-soluble alkaline salt, ammonia, water-soluble amine, hydrazine and one or more hydrogen atom replaced by alkyl.

14. methods according to claim 13, wherein, described water soluble hydroxide is selected from alkali metal hydroxide, is preferably NaOH and/or potassium hydroxide; And/or

Described water-soluble alkaline salt is selected from water soluble carbonate, water soluble carbonate hydrogen salt, water-soluble phosphate, water-soluble phosphoric acid monohydric salt, water-soluble phosphoric acid dihydric salt and water-soluble borate, is preferably selected from Na ₂cO ₃, NaHCO ₃, NaH ₂pO ₄, Na ₂hPO ₄, Na ₃pO ₄and Na ₂b ₄o ₇; And/or

Described water-soluble amine is selected from ethylenediamine, diethylamide, monoethanolamine, Trimethylamine, methyl amine and dimethyl amine; And/or

Described hydrazine derivate is selected from MMH and 1,1-dimethylhydrazine.

15. methods according to claim 12, wherein, described alkaline etching liquid is alkaline buffer solution.

16. methods according to claim 15, wherein, described alkaline etching liquid is the aqueous solution containing water soluble hydroxide and water-soluble alkaline salt, or described alkaline etching liquid is the aqueous solution containing water-soluble normal salt and water soluble acid salt, or described alkaline etching liquid is the aqueous solution containing ammonia and water soluble salt of ammonia.

17. methods according to claim 16, wherein, described water soluble hydroxide is NaOH and/or potassium hydroxide; Described water-soluble alkaline salt is one or more in water soluble carbonate, water soluble carbonate hydrogen salt, water-soluble phosphate, water-soluble phosphoric acid monohydric salt, water-soluble phosphoric acid dihydric salt and water-soluble borate, be preferably water-soluble phosphoric acid dihydric salt, be more preferably one or more in sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate (ADP) and aluminium dihydrogen phosphate.

18. methods according to claim 16, wherein, described alkaline etching liquid is the aqueous solution containing water soluble carbonate and water soluble carbonate hydrogen salt, or is the aqueous solution containing water-soluble phosphate and water-soluble phosphoric acid monohydric salt.

19. methods according to claim 16, wherein, described water soluble salt of ammonia is selected from NH ₄cl, (NH ₄) ₂sO ₄, NH ₄hCO ₃and NH ₄nO ₃.

20. according to the method in claim 12-19 described in any one, and wherein, the pH value of described alkaline etching liquid is 10-13.

21. according to the method in claim 10-20 described in any one, and wherein, the temperature of described alkaline etching liquid is 10-60 DEG C, is preferably 20-40 DEG C; The time of described first etching is 1-60 minute, is preferably 5-20 minute.

22. according to the method in claim 9-21 described in any one, and wherein, the method also comprises carries out the second etching, to form the second etch pit at the metal base surface connected with described horniness anode oxide film layer by the metal base through the first etching.

23. methods according to claim 22, wherein, the condition of described second etching makes the aperture of described second etch pit in the scope of 200-2000nm, preferably in the scope of 400-2000nm, more preferably in the scope of 800-1500nm.

24. methods according to claim 22 or 23, wherein, the condition of described second etching makes the degree of depth of described second etch pit in the scope of 0.1-500 μm, preferably in the scope of 10-400 μm, more preferably in the scope of 50-200 μm.

25. according to the method in claim 22-24 described in any one, and wherein, described second etching comprises: be soaked in acidic etching liquid by the metal base through the first etching.

26. methods according to claim 25, wherein, described acidic etching liquid is for containing aqueous acid, and described acid is halogen acids and/or H ₃pO ₄, be preferably HCl or H ₃pO ₄.

27. methods according to claim 25 or 26, wherein, described acidic etching liquid is also containing one or more water soluble salts, and described water soluble salt is water-soluble halogen acid salt and/or water-soluble phosphate.

28. methods according to claim 27, wherein, the mol ratio of described water soluble salt and described acid is 0.1-1:1, is preferably 0.2-0.8:1, is more preferably 0.4-0.6:1.

29. according to the method in claim 25-28 described in any one, and wherein, the pH value of described acidic etching liquid is 1-3.

30. according to the method in claim 25-29 described in any one, and wherein, the temperature of described acidic etching liquid is 20-30 DEG C, and the time of described second etching is 1-60 minute, is preferably 10-30 minute.

31. according to the method in claim 9-30 described in any one, wherein, the method of metal base is provided to comprise: metal base to be placed in electrolyte and to carry out hard anodizing, electrolyte in described electrolyte is one or more in oxalic acid, phosphate, silicate and aluminate, the condition of described hard anodizing comprises: voltage is 10-100V, is preferably 40-80V; Time is 1-60 minute, is preferably 10-30 minute; The temperature of electrolyte is 0-60 DEG C, is preferably 0-10 DEG C.

32. according to the method in claim 9-31 described in any one, and wherein, the thickness of described horniness anode oxide film layer is in the scope of 0.1-500 μm.

Surface treated metal base prepared by the method in 33. claim 9-32 described in any one.

34. 1 kinds of metal-resin complexs, described metal is aluminum or aluminum alloy, this complex comprises metal base and resin bed, described metal base is the surface treated metal base in claim 1-8 and 33 described in any one, described resin bed is attached at least part of surface of described metal base, and the part resin in described resin bed extends downwards and is filled in the first etch pit of metal base or the first etch pit and the second etch pit.

The preparation method of 35. 1 kinds of metal-resin complexs, described metal is aluminum or aluminum alloy, described metal-resin complex comprises metal base and is attached to the resin bed at least part of surface of described metal base, described metal base is the surface treated metal base in claim 1-8 and 33 described in any one, the method at least part of surface imp lantation comprised to metal base contains the composition of resin and makes fraction compositions be filled in the first etch pit of metal base or the first etch pit and the second etch pit, shaping rear formation resin bed.

Metal-resin complex prepared by 36. methods according to claim 35.

37. claims 34 or metal-resin complex according to claim 36 are preparing the application in electronic product casing.

38. 1 kinds of electronic product casings, this shell comprises metal-back body and is attached at least part of inner surface of described metal-back body and/or at least one resin piece of at least part of outer surface, it is characterized in that, described metal-back body is the metal base in claim 1-8 described in any one.

The preparation method of 39. 1 kinds of electronic product casings, the method be included in metal-back body at least part of inner surface and/or at least partly outer surface form at least one resin piece, it is characterized in that, adopt method according to claim 35 to form described resin piece.