WO2016101703A1 - 经表面处理的金属基材和金属-树脂复合体及其制备方法和应用以及电子产品外壳及其制备方法 - Google Patents

经表面处理的金属基材和金属-树脂复合体及其制备方法和应用以及电子产品外壳及其制备方法 Download PDF

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WO2016101703A1
WO2016101703A1 PCT/CN2015/093243 CN2015093243W WO2016101703A1 WO 2016101703 A1 WO2016101703 A1 WO 2016101703A1 CN 2015093243 W CN2015093243 W CN 2015093243W WO 2016101703 A1 WO2016101703 A1 WO 2016101703A1
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WIPO (PCT)
Prior art keywords
etching
water
soluble
metal substrate
resin
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PCT/CN2015/093243
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English (en)
French (fr)
Inventor
孙剑
吴彦琴
张云侠
宋文广
陈梁
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比亚迪股份有限公司
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Publication of WO2016101703A1 publication Critical patent/WO2016101703A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • 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
    • C25D11/04—Anodisation of aluminium or alloys based thereon

Definitions

  • the invention relates to a surface treated metal substrate and a preparation method thereof, and to a metal-resin composite and a preparation method and application thereof, and to an electronic product casing and a preparation method thereof.
  • a commonly used method of combining aluminum or an aluminum alloy with a resin is a gluing technique.
  • the method combines aluminum or an aluminum alloy with a formed resin by a chemical adhesive to obtain a composite.
  • the bonding strength of the aluminum or aluminum alloy matrix to the resin is poor, and the adhesive bonding layer is not resistant to acid and alkali, which affects the use of the composite.
  • the adhesive bonding layer has a certain thickness, it affects the size of the final product.
  • One method is to surface-etch aluminum or aluminum alloy with an amine substance such as an aqueous solution of urethane, hydrazine monohydrate or ethylenediamine to form nano-scale micropores on the surface of aluminum or aluminum alloy, and The amine substance is retained in the formed micropores, and then the resin is injection molded on the treated surface, and the resin and the aluminum alloy are combined by a reaction between the amine substance and the resin, thereby obtaining a certain tensile shear. Intensity of aluminum-plastic integrated products.
  • an amine substance such as an aqueous solution of urethane, hydrazine monohydrate or ethylenediamine
  • the aluminum alloy is etched by the above-mentioned amines, and the pores formed on the surface of the aluminum alloy are too small, and it is difficult for the resin to be directly injected into the micropores of the nanometer order, so that it is difficult to significantly improve the bonding strength between the aluminum alloy and the resin.
  • Another method is to directly corrode the surface of the aluminum alloy with an acidic etching solution containing an inorganic halogen compound, and then inject the resin to obtain an aluminum-plastic integrated product.
  • an acidic etching solution containing an inorganic halogen compound containing an inorganic halogen compound
  • inject the resin to obtain an aluminum-plastic integrated product.
  • the aluminum-plastic integrated product obtained by this method the bonding strength between the aluminum alloy and the resin still needs to be further improved.
  • an anodizing may be performed on the surface of the aluminum alloy to form a porous aluminum oxide film layer on the surface of the aluminum alloy, and then the resin is injection molded on the surface having the aluminum oxide film layer to obtain an aluminum-plastic integrated product.
  • the bonding strength between the aluminum alloy and the resin is not high.
  • An object of the present invention is to overcome the technical problem that the bonding strength between a metal and a resin is not high in the conventional metal-resin composite.
  • the resin is filled in some of the holes of the substrate to function to anchor the resin layer in the substrate, thereby improving The bonding strength between the resin and the substrate; however, the substrate is etched using an alkaline etching solution containing an amine substance or an acidic etching solution containing an inorganic halogen compound, or a porous anodized film formed on the surface of the substrate, Then, the bonding strength of the metal-resin composite formed by the injection molding resin is still not high.
  • a metal substrate surface treatment method comprising providing a metal substrate comprising a metal substrate and attached thereto An anodized film layer of at least a portion of the surface of the metal substrate; the metal substrate is sequentially subjected to a first etching and a second etching;
  • a first etching hole is distributed on the surface of the anodized film layer, and after the second etching, a surface of the metal substrate contacting the anodized film layer is distributed with a second etching hole, at least part of The ratio of the depth of the first etching hole to the thickness of the anodized film layer is 1:1.
  • a surface treated metal substrate obtained by the treatment method of the invention.
  • a surface-treated metal substrate the metal being aluminum or an aluminum alloy
  • the metal substrate comprising a metal substrate and attached to at least a portion of a surface of the metal substrate
  • An anodic oxide film layer the metal substrate comprising a base layer and an etching layer, wherein the base layer and the etching layer are integrated, and the etching layer is in contact with the anodized film layer and is an integrated structure.
  • a surface of the anodized film layer is distributed with a first etching hole, and a surface of the etching layer is distributed with a second etching hole, and a ratio of a depth of at least a portion of the first etching hole to a thickness of the anodized film layer is 1:1. .
  • a metal-resin composite the metal being aluminum or an aluminum alloy
  • the composite comprising a metal substrate and attached to at least a portion of a surface of the metal substrate a resin layer which is a surface-treated metal substrate provided by the present invention, a portion of the resin in the resin layer extending downward and filling the first etching hole and the second etching of the metal substrate In the hole.
  • a process for producing a metal-resin composite which comprises injecting a resin-containing composition onto a surface of a surface-treated metal substrate provided by the present invention and partially The composition is filled in the first etching hole and the second etching hole, and is formed into a resin layer after molding.
  • a metal-resin composite prepared by the method according to the fifth aspect of the invention.
  • the invention provides the use of a metal-resin composite according to the invention in the preparation of an outer casing of an electronic product.
  • an electronic product casing comprising a metal casing body and at least one resin member attached to at least a portion of an inner surface and/or at least a portion of an outer surface of the metal casing body
  • the metal shell body is a surface treated metal substrate according to the present invention.
  • the present invention provides a method of preparing an electronic product casing, the method comprising At least a portion of the inner surface and/or at least a portion of the outer surface of the metal shell body forms at least one resin member, wherein the resin member is formed using the method of preparing the metal-resin composite according to the present invention.
  • the metal substrate and the resin layer exhibit higher bonding strength, and the resin layer is less likely to be from the surface of the metal substrate.
  • the metal-resin composite provided by the present invention has high structural stability and can meet the requirements for use in applications requiring high structural stability, and is suitable as an outer casing of an electronic product.
  • FIG. 1 is a cross-sectional view for schematically explaining a casing of a mobile phone according to the present invention, including a front view and a plan view;
  • Fig. 2 is a cross-sectional view for schematically explaining a smart watch case according to the present invention.
  • opening 4 smart watch metal shell body
  • the metal may be pure aluminum or aluminum alloy.
  • the aluminum alloy refers to an alloy formed by adding other elements to aluminum as a base element, and may be various common aluminum alloys.
  • the metal substrate is various molded bodies formed of aluminum or an aluminum alloy, and may have various shapes depending on specific use requirements.
  • a metal substrate surface treatment method comprising providing a metal substrate comprising a metal substrate and attached thereto An anodized film layer of at least a portion of the surface of the metal substrate; the metal substrate is sequentially subjected to a first etching and a second etching.
  • the thickness of the anodized film layer is generally from 0.1 to 50 ⁇ m.
  • the anodized film layer has a thickness of 1 to 20 ⁇ m, whereby the metal-resin composite formed has a higher bonding strength between the metal and the resin. More preferably, the anodized film layer has a thickness of 4 to 10 ⁇ m.
  • the anodized film layer formed by anodization is a porous film layer containing a large number of micropores, and the anode formed by anodization is further improved from the viewpoint of further improving the bonding strength between the resin of the finally formed metal-resin composite and the metal substrate.
  • the pore diameter of the micropores in the oxide film layer is in the range of 10 to 100 nm.
  • the pore size of the micropores in the formed anodized film layer can be adjusted by selecting the conditions of the anodization.
  • the metal substrate can be obtained by subjecting the metal substrate to an electrolytic solution for anodization.
  • the method for the anodization of the present invention is not particularly limited, and a conventional anodization method can be employed.
  • the metal substrate may be placed in an electrolyte under anodizing conditions, the metal substrate is used as an anode, and a conductive material that does not react with the electrolyte is used as a cathode, and the cathode and the anode are respectively connected to the positive and negative electrodes of the power source. After the electrical connection, after electrification, electrolysis is performed to form an aluminum oxide film on the surface of the metal substrate.
  • the electrolyte in the electrolytic solution is preferably one or more of H 2 SO 4 , chromic acid, and oxalic acid.
  • the electrolyte may be contained in an amount of 10 to 40% by weight, preferably 15 to 25% by weight.
  • the temperature of the electrolyte may be 10 to 30 ° C, preferably 20 to 30 ° C.
  • the voltage may be from 10 to 100 V, preferably from 10 to 50 V, more preferably from 15 to 25 V.
  • the electrolysis may be carried out for a period of from 1 to 40 minutes, preferably from 10 to 20 minutes.
  • the metal substrate is preferably pretreated by various methods commonly used in the art prior to anodization.
  • the pretreatment includes mechanical grinding or grinding to remove significant foreign matter on the surface of the metal substrate, and then the metal substrate is sequentially degreased and cleaned to remove grease from the surface of the metal substrate.
  • the metal substrate in the first etching, is immersed in an alkaline etching solution.
  • the alkaline etching solution is derived from cerium containing a water-soluble hydroxide, a water-soluble basic salt, ammonia, a water-soluble amine, hydrazine, and one or more hydrogen atoms substituted by a hydrocarbon group.
  • the water-soluble hydroxide may be an alkali metal hydroxide, preferably sodium hydroxide and/or potassium hydroxide, more preferably sodium hydroxide.
  • the water-soluble basic salt refers to a water-soluble basic salt whose aqueous solution has a pH of more than 7.
  • the water-soluble basic salt may be a water-soluble carbonate, a water-soluble hydrogencarbonate, a water-soluble phosphate, a water-soluble monohydrogen phosphate, a water-soluble dihydrogen phosphate, and a water-soluble borate.
  • the water-soluble basic salt may be an alkali metal salt, preferably a sodium salt or a potassium salt, more preferably a sodium salt.
  • the water-soluble basic salt is selected from the group consisting of Na 2 CO 3 , NaHCO 3 , NaH 2 PO 4 , Na 2 HPO 4 , Na 3 PO 4 and Na 2 B 4 O 7 .
  • the water-soluble amine may be a common variety of amines which are soluble in water.
  • the water soluble amine is selected from the group consisting of ethylene diamine, diethylamine, ethanolamine, trimethylamine, methylamine and dimethylamine.
  • the anthracene derivative refers to a compound in which one or more hydrogen atoms in the molecular structure of hydrazine (ie, H 2 N—NH 2 ) are substituted with a hydrocarbon group, and the hydrocarbon group is preferably a C 1 -C 4 alkyl group, specifically It may be monomethyl hydrazine and 1,1-dimethyl hydrazine.
  • the alkaline etching solution is preferably an aqueous solution containing a water-soluble hydroxide and/or a water-soluble basic salt. More preferably, the alkaline etching solution is an aqueous solution containing a water-soluble basic salt, and the water-soluble basic salt is preferably Na 2 CO 3 and/or NaHCO 3 , more preferably Na 2 CO 3 or NaHCO 3 .
  • the pH of the alkaline etching solution is preferably in the range of 10-13, so that a suitable etching rate can be obtained, and the etching process is gentle and easy to control.
  • the alkaline etching solution is an alkaline buffer solution, so that the finally formed corrosion holes are more uniformly distributed and the pore size is more concentrated.
  • the alkaline etching solution may be an aqueous solution containing a water-soluble hydroxide and a water-soluble basic salt.
  • the cation of the water-soluble hydroxide and the water-soluble basic salt may be the same or different, and preferably the same.
  • the water-soluble hydroxide may be an alkali metal hydroxide, preferably sodium hydroxide and/or potassium hydroxide, more preferably sodium hydroxide.
  • the water-soluble basic salt may be one of a water-soluble carbonate, a water-soluble hydrogencarbonate, a water-soluble phosphate, a water-soluble monohydrogen phosphate, a water-soluble dihydrogen phosphate, and a water-soluble borate or Two or more.
  • the water-soluble basic salt may be an alkali metal salt, preferably a sodium salt or a potassium salt, more preferably a sodium salt.
  • the water-soluble basic salt is one or more selected from the group consisting of Na 2 CO 3 , NaHCO 3 , NaH 2 PO 4 , Na 2 HPO 4 , Na 3 PO 4 and Na 2 B 4 O 7 .
  • the water-soluble basic salt is a water-soluble monohydrogen phosphate and/or a water-soluble dihydrogen phosphate. More preferably, the water-soluble basic salt is a water-soluble dihydrogen phosphate.
  • the alkaline etching solution may also be an aqueous solution containing a water-soluble normal salt and a water-soluble acid salt.
  • the normal salt refers to a salt in which a cation contains only a metal ion and/or an ammonium ion
  • the acid salt refers to a salt containing a hydrogen ion in addition to a metal ion and/or an ammonium ion.
  • the water-soluble normal salt and the cation and acid ion of the water-soluble acid salt may each be the same or different, and are preferably the same.
  • the alkaline etching solution is preferably an aqueous solution containing a water-soluble carbonate and a water-soluble hydrogencarbonate, or an aqueous solution containing a water-soluble phosphate and a water-soluble monohydrogen phosphate.
  • the alkaline etching solution may be an aqueous solution containing Na 2 CO 3 and NaHCO 3 or an aqueous solution containing Na 3 PO 4 and Na 2 HPO 4 .
  • the alkaline etching solution may also be an aqueous solution containing ammonia and a water-soluble ammonium salt.
  • the water-soluble ammonium salt is preferably one or more of NH 4 Cl, (NH 4 ) 2 SO 4 , NH 4 HCO 3 and NH 4 NO 3 .
  • the alkaline etching solution may be an aqueous solution containing NH 3 and NH 4 Cl, an aqueous solution containing NH 3 and (NH 4 ) 2 SO 4 , an aqueous solution containing NH 3 and NH 4 HCO 3 or containing NH 3 and An aqueous solution of NH 4 NO 3 .
  • the alkaline etching solution is preferably an aqueous solution containing a water-soluble hydroxide and a water-soluble basic salt, or an aqueous solution containing a water-soluble normal salt and a water-soluble acid salt, more preferably An aqueous solution containing a water-soluble normal salt and a water-soluble acid salt.
  • the alkaline etching solution is preferably an alkaline buffer solution having a pH of 10 to 13, so that a suitable etching rate can be obtained, and the etching process is gentle and easy to control.
  • the first etched metal substrate is immersed in an acidic etching solution.
  • the acidic etching solution may be a common acidic etching solution capable of etching a metal.
  • the acidic etching solution is an aqueous solution containing an acid, preferably an aqueous solution containing a halogen acid (such as HCl) and/or phosphoric acid. More preferably, the acidic etching solution is hydrochloric acid or phosphoric acid.
  • the pH of the acidic etching solution is preferably 1-3, so that the surface-treated metal substrate thus formed has a more uniform distribution of corrosion holes and a more concentrated pore size distribution, and the metal-resin prepared from the metal substrate.
  • the bonding strength of the resin to the metal substrate in the composite is higher.
  • the acidic etching liquid further contains one or two or more water-soluble salts, which can further improve the stability of etching and the distribution of the formed corrosion pores. More uniform, the pore size distribution is more concentrated.
  • the acid salt of the water-soluble salt is preferably the same as the acid group of the acid contained in the acidic etching solution.
  • the acidic etching solution when the acidic etching solution is an aqueous solution containing a halogen acid, the acidic etching solution preferably further contains one or two or more water-soluble hydrohalic acid salts; and when the acidic etching liquid is an aqueous solution containing phosphoric acid
  • the acidic etching solution preferably further contains one or two or more water-soluble phosphates.
  • the content of the water-soluble salt in the acidic etching solution varies with the amount of acid in the acidic etching solution set.
  • the molar ratio of the water soluble salt to the acid may range from 0.1 to 1:1, preferably from 0.2 to 0.8:1, more preferably from 0.4 to 0.6:1.
  • the acidic etching solution is hydrochloric acid
  • the water-soluble salt is one or more selected from the group consisting of NaCl, KCl, and AlCl 3 .
  • the acidic etching solution is phosphoric acid
  • the water-soluble salt is one or more of a water-soluble phosphate, a water-soluble monohydrogen phosphate, and a water-soluble dihydrogen phosphate, such as One or more of NaH 2 PO 4 , Na 2 HPO 4 , Na 3 PO 4 , KH 2 PO 4 , K 2 HPO 4 and K 3 PO 4 .
  • a second etching hole is formed.
  • the first etching hole penetrates the second etching hole.
  • the etching exotherm is small during the etching process, and the etching process is gentle and easy to control, thereby being able to form a corrosion hole having a desired pore size and pore depth.
  • first etching holes the etching holes distributed on the surface of the anodized film layer
  • Second corrosion hole the etching holes distributed on the surface of the metal substrate layer contacting the anodized film layer
  • the conditions of the first etching and the second etching may be selected according to the expected pore size and pore depth of the etching hole.
  • the inventors of the present invention found during the research that the conditions of the first etching and the second etching are selected such that the aperture of the first etching hole is not larger than the second etching hole, and the surface-treated In the metal-resin composite formed of the metal substrate, a higher bonding strength is exhibited between the metal substrate and the resin layer.
  • the conditions of the first etching and the second etching are more preferable such that
  • the first etching hole has a pore diameter in the range of 10 to 200 nm, preferably in the range of 100 to 200 nm;
  • the second etching hole has a pore diameter in the range of 200 to 2000 nm, preferably in the range of 500 to 2000 nm, more preferably In the range of 1000-1500 nm.
  • the ratio of the depth of at least a portion of the first etching holes to the thickness of the anodized film layer is 1:1, preferably 50% or more, more preferably 60% or more, further preferably 70% or more.
  • the ratio of the depth to the thickness of the anodized film layer is 1:1.
  • the ratio of the depth of the first etching hole formed after the first etching to the thickness of the anodized film layer is in the range of 0.1 to 1:1, preferably in the range of 0.5 to 1:1;
  • the depth of the second etching hole formed after the second etching is in the range of 0.1 to 500 ⁇ m, preferably in the range of 10 to 400 ⁇ m, more preferably in the range of 50 to 200 ⁇ m, so that further improvement can be obtained.
  • the resin-metal bond strength does not adversely affect the strength of the metal substrate itself.
  • the pore size and depth of the first etching hole and the second etching hole can be determined by a microscope method.
  • the depth of the etching hole refers to the vertical distance from the hole top of the etching hole to the bottom of the hole of the etching hole; the etching hole (including the first etching hole and the second etching hole)
  • the aperture refers to the largest dimension in the radial direction of the upper port of the etched hole (ie, the port at the surface).
  • the temperature of the alkaline etching solution may be 10 to 60 ° C, preferably 20 to 40 ° C.
  • the first etching time may be from 1 to 60 minutes, preferably from 1 to 30 minutes, more preferably from 1 to 15 minutes.
  • the temperature of the acidic etching solution is preferably 20-30 °C.
  • the second etching time may be 1-60 minutes, excellent It is selected to be 10-40 minutes, more preferably 15-30 minutes.
  • Each of the first etching and the second etching may be performed only once or sequentially, and the duration of each etching is not particularly limited as long as the total etching time satisfies the above requirements.
  • the surface-treated substrate is cleaned after the second etching is completed to remove the etching liquid remaining on the surface of the substrate and the etching hole.
  • a surface treated metal substrate obtained by the surface treatment method provided by the present invention.
  • a surface-treated metal substrate the metal being aluminum or an aluminum alloy
  • the metal substrate comprising a metal substrate and attached to at least a portion of a surface of the metal substrate And an anodized film layer
  • the metal substrate comprising a base layer and an etching layer, wherein the base layer and the etching layer are integrated, and the etching layer is in contact with the anodized film layer and has an integral structure.
  • the base layer is a dense layer, that is, the base layer does not contain corrosion holes.
  • the corrosion layer refers to a portion in which a corrosion hole is distributed in the metal matrix.
  • a surface of the anodized film layer is distributed with a first etching hole, a surface of the etching layer is distributed with a second etching hole, and a diameter of the first etching hole is not larger than a diameter of the second etching hole.
  • the first etching hole has a pore diameter in the range of 10 to 200 nm, preferably in the range of 100 to 200 nm;
  • the pore diameter of the second etching hole is in the range of 200 to 2000 nm, preferably in the range of 500 to 2000 nm, more preferably in the range of 1000 to 1500 nm.
  • the anodized film layer further contains micropores formed by anodization.
  • the pore size of the micropores formed by anodization is generally in the range of 10 to 100 nm.
  • Micropores formed by anodization are in communication with the first and second etching holes.
  • part of the resin enters the second etching hole through the first etching hole, and at the same time, part of the resin is immersed in the micropores formed by the anodization, a resin network is formed in the metal substrate, and the resin layer is further formed. To be firmly anchored in the metal substrate, the bonding strength between the resin and the metal substrate in the formed metal-resin composite is improved.
  • the thickness of the anodized film layer may generally be from 0.1 to 50 ⁇ m, preferably from 1 to 20 ⁇ m, more preferably from 4 to 10 ⁇ m.
  • the ratio of the depth of at least a portion of the first etching holes to the thickness of the anodized film layer is 1:1.
  • the ratio of the depth of the first etching hole to the thickness of the anodized film layer of preferably 50% or more, more preferably 60% or more, and further preferably 70% or more is preferably 1:1.
  • the ratio of the depth of the first etching hole to the thickness of the anodized film layer is in the range of 0.1 to 1:1. More preferably, the ratio of the depth of the first etching hole to the thickness of the anodized film layer is in the range of 0.5 to 1:1.
  • the thickness of the etching layer may be determined by the depth of the second etching hole therein, and the depth of the second etching hole having the largest depth in the etching layer is generally taken as the thickness of the etching layer.
  • the thickness of the etching layer may be selected according to the thickness of the anodized film layer.
  • the depth of the second etching hole is in the range of 0.1 to 500 ⁇ m, preferably in the range of 10 to 400 ⁇ m, more preferably in the range of 50 to 200 ⁇ m.
  • a metal-resin composite the metal being aluminum or an aluminum alloy
  • the composite comprising a metal substrate and attached to at least a portion of a surface of the metal substrate Resin layer, the metal The substrate is the surface-treated metal substrate provided by the present invention, and a part of the resin in the resin layer extends downward and is filled in the first etching hole and the second etching hole of the metal substrate.
  • the host resin in the resin layer can be selected according to specific use requirements as long as the resin can be combined with aluminum or an aluminum alloy.
  • the host resin in the resin layer may be selected from a thermoplastic resin, and may be, for example, one or more of polyphenylene sulfide, polyester, polyamide, polycarbonate, and polyolefin.
  • the polyester may be a common polymer obtained by condensing a dicarboxylic acid and a diol, and specific examples thereof may include, but are not limited to, polybutylene terephthalate and/or polyethylene terephthalate. ester.
  • the polyamide may be a common polymer obtained by condensing a diamine and a dicarboxylic acid, and specific examples thereof may include, but are not limited to, polyhexamethylene adipamide, polysebacyldiamine, polysuccinic acid.
  • polystyrene polystyrene
  • polypropylene polymethyl methacrylate
  • poly(acrylonitrile-butadiene-styrene) polystyrene
  • the resin layer may contain at least one filler in addition to the host resin.
  • the type of the filler can be selected according to specific use requirements.
  • the filler may be a fibrous filler and/or a powder filler.
  • the fibrous filler may be one or more selected from the group consisting of glass fibers, carbon fibers, and aramid fibers.
  • the powder type filler may be one or more selected from the group consisting of calcium carbonate, magnesium carbonate, silica, heavy barium sulfate, talc, glass, and clay.
  • the content of the filler may be a conventional selection.
  • the filler may be included in an amount of 20 to 150 parts by weight, preferably 25 to 100 parts by weight, more preferably 30 to 50 parts by weight based on 100 parts by weight of the main body resin.
  • the thickness of the metal substrate and the resin layer may be selected according to the specific application of the metal-resin composite to meet the requirements for use.
  • the resin layer may have a thickness of 0.5 to 10 mm, preferably 0.5 to 5 mm.
  • the metal substrate may have a thickness of from 0.5 to 20 mm, preferably from 0.5 to 10 mm, more preferably from 1 to 5 mm.
  • a process for producing a metal-resin composite which comprises injecting a resin-containing composition onto a surface of a surface-treated metal substrate provided by the present invention and partially The composition is filled in the first etching hole and the second etching hole, and is formed into a resin layer after molding.
  • the resin in the resin-containing composition (hereinafter referred to as a host resin) is the same as the type of the host resin in the resin layer described above, and will not be described in detail herein.
  • the resin-containing composition may contain, in addition to the host resin, at least one filler and/or at least one fluidity improver.
  • the type of the filler is the same as that of the filler in the foregoing resin layer, and will not be described in detail herein.
  • the content of the filler may be a conventional selection.
  • the filler may be included in an amount of 20 to 150 parts by weight, preferably 25 to 100 parts by weight, more preferably 30 to 50 parts by weight based on 100 parts by weight of the main body resin.
  • the fluidity improver is used to improve the flowability of the host resin, further improve the bonding force between the metal substrate and the resin, and the processability of the resin.
  • the fluidity improver may be any of various substances capable of achieving the above effects, and is preferably a cyclic polyester.
  • the amount of the fluidity improver is based on the ability to increase the flowability of the host resin.
  • the fluidity improver is contained in an amount of from 1 to 5 parts by weight based on 100 parts by weight of the main body resin.
  • the resin-containing composition may also contain various conventional auxiliaries such as colorants and/or anti-drugs depending on the specific use requirements.
  • An oxygen agent to improve the properties of the resin layer in the finally formed metal-resin composite or to impart new properties to the resin layer.
  • the resin-containing composition can be obtained by uniformly mixing a host resin, an optional filler, an optional fluidity improver, and an optional auxiliary.
  • the host resin, the optional filler, the optional fluidity improver, and the optional auxiliary agent may be uniformly mixed and subjected to extrusion granulation.
  • the resin-containing composition can be injected into the surface of the surface-treated metal substrate by various conventional methods.
  • the surface-treated metal substrate is placed in a mold, and the resin-containing composition is injected into the surface of the metal substrate by injection molding.
  • the conditions of the injection molding may be selected depending on the kind of the host resin in the resin-containing composition.
  • the conditions of the injection molding include: a mold temperature of 50-300 ° C, a nozzle temperature of 200-450 ° C, a dwell time of 1-50 seconds, an injection pressure of 50-300 MPa, and an injection time of 1-30 seconds.
  • the delay time is 1-30 seconds.
  • the amount of the resin-containing composition to be injected can be selected in accordance with the intended thickness of the resin layer.
  • the resin-containing composition is injected in an amount such that the thickness of the formed resin layer is from 0.5 to 10 mm, preferably from 0.5 to 5 mm.
  • the metal substrate may have a thickness of from 0.5 to 20 mm, preferably from 0.5 to 10 mm, more preferably from 1 to 5 mm.
  • the surface on which the resin layer is not formed can be treated to remove surface holes and surface color change due to etching, and the treatment can be carried out in the injection.
  • the composition of the resin may be carried out before molding, or may be carried out after the resin-containing composition is injected and molded, and is not particularly limited.
  • a metal-resin composite prepared by the method according to the fifth aspect of the invention comprises a metal substrate and a resin layer attached to at least a part of a surface of the metal substrate, a part of the resin in the resin layer extending downward and filling the metal base The first corrosion hole and the second corrosion hole of the material.
  • the bonding strength between the resin layer and the metal substrate is high, and thus the structural stability of the composite is good.
  • the invention provides the use of a metal-resin composite according to the invention in the preparation of an outer casing of an electronic product.
  • an electronic product casing comprising a metal casing body and at least one resin member attached to at least a portion of an inner surface and/or at least a portion of an outer surface of the metal casing body
  • the metal shell body is a surface treated metal substrate according to the present invention.
  • the outer casing includes not only an outer casing which is a sheet-like structure but also various frame structures such as an outer frame.
  • At least one opening may be disposed on the metal casing body to cover the components of the metal casing body at a corresponding position of the opening.
  • the position of the at least part of the opening may correspond to the mounting position of the signal transmitting element and/or the signal receiving element, and the opening position is preferably provided with a resin member, and A part of the resin in the resin member is filled in the opening, and a signal emitting element and/or a signal receiving element may be mounted on the resin member.
  • the metal shell body may be an integral structure or a splicing structure.
  • the splicing structure means that the metal shell body includes at least two portions that are disconnected from each other, and the two portions are spliced together Formed into a metal shell body.
  • the adjacent two portions may be bonded together with an adhesive.
  • the splicing positions of two adjacent portions are provided with the resin member, and the resin members respectively overlap the adjacent two portions and cover the splicing position (ie, the resin member bridges the adjacent two Partly), the bonding strength of the splicing position can be improved; and the metal shell body can be divided into a plurality of portions according to the internal structure of the electronic product, and the resin member functions to form the metal shell body as a whole. It can also be used as a mounting base for some electronic components.
  • At least a part of the outer surface of the metal shell body may be attached with a resin member, which may cover the entire outer surface, or may cover a part of the outer surface of the metal shell body to form a pattern, such as decoration. Sexual pattern.
  • the resin member when the inner surface of the metal shell body is attached with a resin member, the resin member can be disposed at one or more positions required.
  • the resin member is attached to the entire inner surface of the metal shell body, and the resin member is preferably a unitary structure. According to the preferred embodiment, it is particularly suitable for the case where the metal shell body is a spliced structure.
  • the electronic product casing according to the present invention may be any electronic product casing that requires a metal as a casing, such as a casing or a frame of a mobile terminal, a casing or a frame of the wearable electronic device.
  • the mobile terminal refers to a device that can be in a mobile state and has a wireless transmission function, such as a mobile phone, a portable computer (including a laptop and a tablet).
  • the wearable electronic device refers to an intelligent wearable device, such as a smart watch or a smart bracelet.
  • the electronic product may specifically be, but not limited to, one or more of a mobile phone, a portable computer (such as a notebook computer and a tablet), a smart watch, and a smart wristband.
  • Fig. 1 shows a front view and a top view of an embodiment of the electronic product casing when it is a casing of a mobile phone.
  • a plurality of openings 3 are formed in the metal shell body 1 of the mobile phone.
  • the position of the opening 3 may correspond to the position where the antenna is mounted and the position at which various buttons are mounted.
  • the resin layer 2 is attached to the entire inner surface of the metal shell body 1 of the mobile phone, the resin layer 2 is an integral structure, and a part of the resin in the resin layer 2 is filled in the opening 3.
  • Fig. 2 shows a front view of an embodiment of the outer casing of the electronic product being a smart watch.
  • the smart watch metal shell body 4 is provided with a signal element opening 6 corresponding to the mounting signal emitting element and/or the signal receiving element, and the inner surface of the smart watch metal shell body 4 is adhered with a resin inner liner 5, resin A part of the resin in the inner liner 5 is filled in the signal element opening 6, and the signal element can be mounted at a corresponding position on the resin inner liner 5.
  • the present invention provides a method of fabricating an outer casing of an electronic product, the method comprising forming at least one resin member on at least a portion of an inner surface and/or at least a portion of an outer surface of the metal shell body, wherein The resin member is formed according to the method for producing a metal-resin composite of the present invention.
  • the average shear strength between the metal substrate and the resin layer in the metal-resin composite was measured on an INSTRON 3369 universal testing machine in accordance with the method specified in ASTM D1002-10.
  • the thickness of the anodized film layer and the depth of the etching hole were measured using a metallographic microscope of the model Axio Imager Alm available from ZEISS (five different positions of the same sample were observed, and the field of view was measured. The depth of all the corrosion holes that appear), using the scanning power of the model JSM-7600F purchased from JEOL Ltd.
  • the sub-microscope measures the pore size of the corrosion hole (observation of five different positions of the same sample to determine the pore size of all the corrosion holes appearing in the field of view).
  • a commercially available 5052 aluminum alloy plate having a thickness of 1 mm was cut into a rectangular piece of 15 mm ⁇ 80 mm.
  • the rectangular piece is placed in a polishing machine for polishing. Then, it was washed with absolute ethanol, and then immersed in a 2% by weight aqueous sodium hydroxide solution. After 2 minutes, it was taken out and rinsed with deionized water to obtain a pretreated aluminum alloy sheet.
  • the aluminum alloy sheet obtained in the step (1) is placed as an anode in an anodizing bath having a concentration of 20% by weight of an aqueous solution of H 2 SO 4 as an electrolytic solution, and a graphite carbon plate is used as a cathode at a voltage of 15 V. , electrolyze at 20 ° C for 10 minutes.
  • the anodized aluminum alloy sheet was taken out, immersed in water for 1 minute, and then blown dry to obtain an aluminum alloy sheet having an anodized film on its surface.
  • the aluminum alloy sheet was observed in the thickness direction with a microscope to determine that the average thickness of the anodized film layer was 6.4 ⁇ m, and the pore diameter of the micropores in the anodized film layer was in the range of 10 to 100 nm.
  • the cross section of the aluminum alloy obtained in the step (4) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 100-200 nm was distributed in the anodized film layer, and the depth of the first etching hole and the anodized film layer were
  • the ratio of the thickness is in the range of 0.5-1:1, the ratio of the depth of the first etching hole to the thickness of the anodized film layer is more than 1:1;
  • the aluminum alloy substrate is divided into a dense base layer and has a second Corroding the corrosion layer of the hole, the etching layer is in contact with the anodized film layer, the second etching hole has a pore diameter in the range of 1000-1500 nm, and the second etching hole has a depth in the range of 10-300 ⁇ m.
  • the injection molding conditions include: the mold temperature is 140 ° C, the nozzle temperature is 305 ° C, the dwell time is 5 seconds, the injection pressure is 120 MPa, the injection time is 5 seconds, and the delay time is 3 seconds.
  • the cooled product was placed in a constant temperature drying oven at 120 ° C for 1.5 h, and then naturally cooled to room temperature with the furnace to obtain a metal-resin composite (resin layer thickness of 5 mm), and the average shear strength thereof is shown in Table 1. Listed.
  • the cross section of the aluminum alloy obtained in the step (3) was observed by a microscope, and it was found that the anodized film layer was distributed with etching holes having a pore diameter in the range of 100 to 200 nm, and the ratio of the depth of the etching hole to the thickness of the anodized film layer. In the range of 0.5-1:1, there is substantially no corrosion hole in the aluminum alloy matrix.
  • the cross section of the aluminum alloy obtained by the step (3) was observed by a microscope, and it was found that the anodized film layer had substantially no corrosion holes; the aluminum alloy substrate was divided into a dense base layer and an etching layer having corrosion holes, an etching layer and an anodized film layer.
  • the pore diameter of the etching hole is in the range of 100 to 3000 nm, and the depth of the etching hole is in the range of 0.01 to 500 ⁇ m.
  • the cross section of the aluminum alloy obtained in the step (3) was observed by a microscope, and it was found that the pores of the etching holes distributed on the surface of the aluminum alloy substrate were in the range of 1000 to 5000 nm, and the depth of the etching holes was in the range of 0.1 to 500 ⁇ m.
  • the cross section of the aluminum alloy obtained in the step (4) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 100-200 nm was distributed in the anodized film layer, and the depth of the first etching hole and the anodized film layer were The ratio of the thickness is in the range of 0.5-1:1; the aluminum alloy substrate is divided into a dense base layer and an etching layer having a second etching hole, the etching layer is in contact with the anodized film layer, and the pore diameter of the second etching hole is In the range of 100-3500 nm, the depth of the second etching hole is in the range of 0.01 to 500 ⁇ m.
  • a commercially available 5052 aluminum alloy plate having a thickness of 1 mm was cut into a rectangular piece of 15 mm ⁇ 80 mm.
  • the rectangular piece is placed in a polishing machine for polishing. Then, it was washed with absolute ethanol, and then immersed in a 2% by weight aqueous solution of sodium hydroxide. After 2 minutes, it was taken out and rinsed with deionized water to obtain a pretreated aluminum alloy sheet;
  • the aluminum alloy sheet obtained in the step (1) is placed as an anode in an anodizing bath having a concentration of 20% by weight of sulfuric acid as an electrolytic solution, and a graphite carbon plate is used as a cathode at a voltage of 20 V at 20 ° C Electrolyze for 12 minutes.
  • the anodized aluminum alloy sheet was taken out, immersed in water for 1 minute, and then blown dry to obtain an aluminum alloy sheet having an anodized film on its surface.
  • the cross section of the aluminum alloy sheet was observed with a microscope to determine that the average thickness of the anodized film layer was 8 ⁇ m, and the pore diameter of the micropores in the anodized film layer was in the range of 20 to 100 nm.
  • the cross section of the aluminum alloy obtained in the step (4) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 120-200 nm was distributed in the anodized film layer, and the depth of the first etching hole and the anodized film layer were
  • the ratio of the thickness is in the range of 0.6 to 1:1, preferably 60% or more, and the ratio of the depth of the first etching hole to the thickness of the anodized film layer is 1:1;
  • the aluminum alloy substrate is divided into a dense base layer and has A corrosion layer of the second etching hole, the etching layer is in contact with the anodized film layer, the second etching hole has a pore diameter in the range of 1100-1500 nm, and the second etching hole has a depth in the range of 10-300 ⁇ m.
  • the second etching of the aluminum alloy obtained in the step (3) of the third embodiment is carried out in the same manner as in the step (4) of the second embodiment, except that the etching solution further contains NaCl, and the molar ratio of NaCl to HCl is 0.5. :1.
  • the cross section of the aluminum alloy obtained in the step (4) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 120-200 nm was distributed in the anodized film layer, and the depth of the first etching hole and the anodized film layer were
  • the ratio of the thickness is in the range of 0.6 to 1:1, preferably 60% or more, and the ratio of the depth of the first etching hole to the thickness of the anodized film layer is 1:1;
  • the aluminum alloy substrate is divided into a dense base layer and has The etching layer of the second etching hole, the etching layer is in contact with the anodized film layer, the second etching hole has a pore diameter in the range of 1000-1500 nm, and the second etching hole has a depth in the range of 100-200 ⁇ m.
  • Example 3 The aluminum alloy obtained in the step (4) of Example 3 was placed in an injection mold by injection molding in the same manner as in the step (5) of Example 2 to obtain an aluminum alloy-resin composite having an average shear strength of Table 1 is listed.
  • the cross section of the aluminum alloy obtained in the step (4) was observed by a microscope, and it was found that an aperture was distributed in the anodized film layer.
  • the ratio of the depth of the first etching hole to the thickness of the anodized film layer is in the range of 0.2 to 1:1, and the depth of the first etching hole is 50% or more
  • the ratio of the thickness of the anodized film layer is 1:1;
  • the aluminum alloy substrate is divided into a dense base layer and a corrosion layer having a second etching hole, the etching layer is in contact with the anodized film layer, and the second etching hole has a pore diameter of 220.
  • the depth of the second etching hole is in the range of 0.1 to 400 ⁇ m.
  • Example 4 The aluminum alloy obtained in the step (4) of Example 4 was placed in an injection mold by injection molding in the same manner as in the step (5) of Example 2 to obtain an aluminum alloy-resin composite having an average shear strength of Table 1 is listed.
  • the cross section of the aluminum alloy obtained in the step (4) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 10 to 200 nm was distributed in the anodized film layer, and the depth of the first etching hole and the anodized film layer were The ratio of the thickness is in the range of 0.1 to 1:1, and the ratio of the depth of the first etching hole to the thickness of the anodized film layer of 50% or more is 1:1; the aluminum alloy substrate is divided into a dense base layer and has the first The etching layer of the second etching hole, the etching layer is in contact with the anodized film layer, the second etching hole has a pore diameter in the range of 200-2000 nm, and the second etching hole has a depth in the range of 0.1-400 ⁇ m.
  • Example 5 The aluminum alloy obtained in the step (4) of Example 5 was placed in an injection mold for injection and molding in the same manner as in the step (5) of Example 2 to obtain an aluminum alloy-resin composite having an average shear strength. Listed in Table 1.
  • the cross section of the aluminum alloy obtained in the step (4) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 20-200 nm was distributed in the anodized film layer, and the depth of the first etching hole and the anodized film layer were The ratio of the thickness is in the range of 0.1 to 1:1, and the ratio of the depth of the first etching hole to the thickness of the anodized film layer of 50% or more is 1:1; the aluminum alloy substrate is divided into a dense base layer and has the first The etching layer of the second etching hole, the etching layer is in contact with the anodized film layer, the second etching hole has a pore diameter in the range of 200-2000 nm, and the second etching hole has a depth in the range of 0.1-400 ⁇ m.
  • Example 6 The aluminum alloy obtained in the step (4) of Example 6 was placed in an injection mold by injection molding in the same manner as in the step (5) of Example 2 to obtain an aluminum alloy-resin composite having an average shear strength of Table 1 is listed.
  • a commercially available 5052 aluminum alloy plate having a thickness of 1 mm was cut into a rectangular piece of 15 mm ⁇ 80 mm.
  • the rectangular piece is placed in a polishing machine for polishing. Then, it was washed with absolute ethanol, and then immersed in a 2% by weight aqueous sodium hydroxide solution. After 2 minutes, it was taken out and rinsed with deionized water to obtain a pretreated aluminum alloy sheet.
  • the aluminum alloy sheet obtained in the step (1) is placed as an anode in an anodizing bath having a concentration of 15% by weight of oxalic acid as an electrolytic solution, and a graphite carbon plate is used as a cathode at a voltage of 20 V at 30 ° C. Electrolyze for 20 minutes.
  • the anodized aluminum alloy sheet was taken out, immersed in deionized water for 1 minute, and then blown dry to obtain an aluminum alloy sheet having an anodized film on its surface.
  • the cross section of the aluminum alloy sheet was observed with a microscope to determine that the average thickness of the anodized film layer was 5 ⁇ m, and the pore diameter of the micropores in the anodized film layer was in the range of 30 to 80 nm.
  • the cross section of the aluminum alloy obtained in the step (4) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 10 to 200 nm was distributed in the anodized film layer, and the depth of the first etching hole and the anodized film layer were The ratio of the thickness is in the range of 0.3-1:1, and the ratio of the depth of the first etching hole to the thickness of the anodized film layer of more than 60% is 1:1; the aluminum alloy substrate is divided into a dense base layer and has a The etching layer of the second etching hole, the etching layer is in contact with the anodized film layer, the second etching hole has a pore diameter in the range of 200-2000 nm, and the second etching hole has a depth in the range of 0.1-400 ⁇ m.
  • the cross section of the aluminum alloy obtained in the step (4) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 130-200 nm was distributed in the anodized film layer, and the depth of the first etching hole and the anodized film layer were The ratio of the thickness is in the range of 0.6 to 1:1, and the ratio of the depth of the first etching hole to the thickness of the anodized film layer of more than 70% is 1:1; the aluminum alloy substrate is divided into a dense base layer and has the first A corrosion layer of the etching hole, the etching layer is in contact with the anodized film layer, the second etching hole has a pore diameter in the range of 1000-1500 nm, and the second etching hole has a depth in the range of 10-300 ⁇ m.
  • Example 8 The aluminum alloy obtained in the step (4) of Example 8 was placed in an injection mold for injection and molding in the same manner as in the step (5) of Example 7, to obtain an aluminum alloy-resin composite having an average shear strength. Listed in Table 1.
  • Example 9 The aluminum alloy sheet obtained in the step (3) of Example 9 was subjected to the second etching in the same manner as in the step (4) of Example 7, except that the etching liquid (the pH value was the same as in Example 7) further contained. Na 2 HPO 4 .
  • the cross section of the aluminum alloy obtained in the step (4) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 10 to 200 nm was distributed in the anodized film layer, and the depth of the first etching hole and the anodized film layer were The ratio of the thickness is in the range of 0.3-1:1, and the ratio of the depth of the first etching hole to the thickness of the anodized film layer is more than 1:1; the aluminum alloy substrate is divided into a dense base layer and has a The etching layer of the second etching hole, the etching layer is in contact with the anodized film layer, the second etching hole has a pore diameter in the range of 500-2000 nm, and the second etching hole has a depth in the range of 50-200 ⁇ m.
  • Example 9 The aluminum alloy obtained in the step (4) of Example 9 was placed in an injection mold by injection molding in the same manner as in the step (5) of Example 7, to obtain an aluminum alloy-resin composite having an average shear strength of Table 1 is listed.
  • a commercially available 5052 aluminum alloy plate having a thickness of 1 mm was cut into a rectangular piece of 15 mm ⁇ 80 mm.
  • the rectangular piece is placed in a polishing machine for polishing. Then, it was washed with absolute ethanol, and then immersed in a 2% by weight aqueous sodium hydroxide solution. After 2 minutes, it was taken out and rinsed with deionized water to obtain a pretreated aluminum alloy sheet.
  • the aluminum alloy sheet obtained in the step (1) is placed as an anode in an anodizing bath having a concentration of 25% by weight of chromic acid as an electrolytic solution, and a graphite carbon plate is used as a cathode at a voltage of 15 V at 25 Electrolyze at °C for 15 minutes.
  • the anodized aluminum alloy sheet was taken out and blown dry to obtain an aluminum alloy sheet having an anodized film on its surface.
  • the cross section of the aluminum alloy sheet was observed with a microscope to determine that the thickness of the anodized film layer was 4.5 ⁇ m, and the pore diameter of the micropores in the anodized film layer was in the range of 10 to 90 nm.
  • the cross section of the aluminum alloy obtained in the step (4) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 10 to 200 nm was distributed in the anodized film layer, and the depth of the first etching hole and the anodized film layer were The ratio of the thickness is in the range of 0.1 to 1:1, and the ratio of the depth of the first etching hole to the thickness of the anodized film layer of 50% or more is 1:1; the aluminum alloy substrate is divided into a dense base layer and has the first The etching layer of the second etching hole, the etching layer is in contact with the anodized film layer, the second etching hole has a pore diameter in the range of 200-2000 nm, and the second etching hole has a depth in the range of 0.1-400 ⁇ m.
  • the aluminum alloy sheet obtained in the step (4) is placed in an injection molding mold, and a resin composition containing glass fiber and polyphenylene sulfide (PPS) is injection molded on one surface of the aluminum alloy sheet (relative to 100 parts by weight of PPS, The content of the glass fiber is 40 parts by weight), demolding and cooling; the cooled product is placed in a constant temperature drying oven at 120 ° C for 1.5 h, and then naturally cooled to room temperature with the furnace to obtain an aluminum alloy-resin composite ( The thickness of the resin layer was 5 mm), and the average shear strength thereof is listed in Table 1.
  • PPS polyphenylene sulfide
  • the cross section of the aluminum alloy obtained in the step (4) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 100-200 nm was distributed in the anodized film layer, and the depth of the first etching hole and the anodized film layer were The ratio of the thickness is in the range of 0.5-1:1, and the ratio of the depth of the first etching hole to the thickness of the anodized film layer is more than 1:1; the aluminum alloy substrate is divided into a dense base layer and has the first A corrosion layer of the etching hole, the etching layer is in contact with the anodized film layer, the second etching hole has a pore diameter in the range of 1000-1400 nm, and the second etching hole has a depth in the range of 10-300 ⁇ m.
  • Example 11 The aluminum alloy sheet obtained in the step (4) of Example 11 was placed in an injection molding die by the same method as in the step (5) of Example 10 in the same manner as in the step (5) of Example 10 to obtain an aluminum.
  • the average shear strength of the alloy-resin composite is shown in Table 1.
  • Example 1 Comparing Example 1 with Comparative Examples 1-6, it can be seen that the metal substrate is surface-treated by the method of the present invention, and then the resin is injection molded on the treated surface to obtain a metal-resin composite, the resin layer. It has a higher average shear strength (i.e., has a higher bonding strength) with the metal substrate, and thus the composite has higher structural stability.

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Abstract

一种经表面处理的金属基材及其制备方法，所述方法包括将金属基材进行阳极氧化，以在金属基材的表面形成阳极氧化膜层，将经阳极氧化的金属基材依次用碱性蚀刻液和酸性蚀刻液进行蚀刻，以形成腐蚀孔。一种金属－树脂复合体及其制备方法，该复合体包括经表面处理的金属基材以及附着在金属基材的至少部分表面上的树脂层（2），树脂层中的部分树脂向下延伸并填充于金属基材的腐蚀孔中。该金属－树脂复合体能够满足对结构稳定性要求较高的使用场合的要求。

Description

经表面处理的金属基材和金属-树脂复合体及其制备方法和应用以及电子产品外壳及其制备方法
相关申请的交叉引用
本申请基于申请号为201410827226.9、申请日为2014/12/25的中国专利申请提出，并要求该中国专利申请的优先权，该中国专利申请的全部内容在此引入本申请作为参考。
技术领域
本发明涉及一种经表面处理的金属基材及其制备方法，本发明还涉及一种金属-树脂复合体及其制备方法和应用，本发明进一步涉及一种电子产品外壳及其制备方法。
背景技术
在汽车、家用电器制品、工业机器等的零件制造领域中，需要铝或铝合金与树脂一体化成型技术。
目前常用的将铝或铝合金和树脂相结合的方法是胶合技术。该方法通过化学胶粘剂将铝或铝合金与已成型树脂结合在一起得到复合体。但是，由该方法得到的复合体中，铝或铝合金基体与树脂的结合力较差，且胶粘剂结合层不耐酸碱，影响复合体的使用场合。另外，由于胶粘剂结合层具有一定的厚度，因而会影响最终产品的尺寸。
针对胶粘剂法存在的上述不足，研究人员开发了其它用于将铝或铝合金与树脂结合的方法。
一种方法是采用胺类物质，例如：氨基甲酸酯、一水合肼、乙二胺等的水溶液对铝或铝合金进行表面腐蚀，以在铝或铝合金表面形成纳米级的微孔，并把胺类物质保留在形成的微孔中，然后将树脂注塑在经处理的表面，通过胺类物质与树脂之间的反应，将树脂与铝合金结合到一起，从而得到具有一定拉伸剪切强度的铝塑一体化产品。但是，采用上述胺类物质对铝合金进行蚀刻，在铝合金表面形成的孔洞太小，树脂难以直接注塑进入纳米级的微孔中，以致难以明显提高铝合金和树脂的结合强度。
另一种方法是采用含无机卤素化合物的酸性蚀刻液直接对铝合金表面进行腐蚀，然后注塑树脂得到铝塑一体化产品。但是，采用这种方法得到的铝塑一体化产品，铝合金与树脂之间的结合强度仍有待于进一步提高。
此外，还可以在铝合金表面进行阳极氧化从而在铝合金表面形成多孔性氧化铝膜层，然后将树脂注塑在具有氧化铝膜层的表面得到铝塑一体化产品。但是，采用该方法得到的铝塑一体化产品中，铝合金和树脂的结合强度也不高。
发明内容
本发明的目的在于克服现有的金属-树脂复合体中，金属与树脂之间的结合强度不高的技术问题。
尽管现在已经发现通过在例如铝或铝合金的金属基材表面形成孔洞，然后注塑树脂，树脂会填充在基材的一些孔洞中，起到将树脂层锚定在基材中的作用，从而提高树脂与基材之间的结合强度；但是，采用含胺类物质的碱性蚀刻液或含无机卤素化合物的酸性蚀刻液对基材进行蚀刻，或者在基材表面形成的多孔性阳极氧化膜，然后注塑树脂形成的金属-树脂复合体的结合强度仍然不高。
根据本发明的第一个方面，本发明提供了一种金属基材表面处理方法，所述金属为铝或铝合金，该方法包括提供金属基材，所述金属基材包括金属基体以及附着在所述金属基体的至少部分表面的阳极氧化膜层；将所述金属基材依次进行第一蚀刻和第二蚀刻；
在所述第一蚀刻中，将所述金属基材浸泡于碱性蚀刻液中；
在所述第二蚀刻中，将经第一蚀刻的金属基材浸泡于酸性蚀刻液中；
进行所述第一蚀刻后在阳极氧化膜层的表面分布有第一腐蚀孔，进行所述第二蚀刻后与所述阳极氧化膜层相接的金属基体表面分布有第二腐蚀孔，至少部分第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值为1:1。
根据本发明的第二个方面，本发明提供了一种由本发明的处理方法得到的经表面处理的金属基材。
根据本发明的第三个方面，本发明提供了一种经表面处理的金属基材，所述金属为铝或铝合金，该金属基材包括金属基体以及附着在所述金属基体的至少部分表面上的阳极氧化膜层，所述金属基体包括基体层和腐蚀层，所述基体层与所述腐蚀层为一体结构，所述腐蚀层与所述阳极氧化膜层相接并为一体结构，所述阳极氧化膜层的表面分布有第一腐蚀孔，所述腐蚀层的表面分布有第二腐蚀孔，至少部分第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值为1:1。
根据本发明的第四个方面，本发明提供了一种金属-树脂复合体，所述金属为铝或铝合金，该复合体包括金属基材以及附着在所述金属基材的至少部分表面上的树脂层，所述金属基材为本发明提供的经表面处理的金属基材，所述树脂层中的部分树脂向下延伸并填充于所述金属基材的第一腐蚀孔和第二腐蚀孔中。
根据本发明的第五个方面，本发明提供了一种金属-树脂复合体的制备方法，该方法包括向本发明提供的经表面处理的金属基材的表面注入含树脂的组合物并使部分组合物填充于第一腐蚀孔和第二腐蚀孔中，成型后形成树脂层。
根据本发明的第六个方面，本发明提供了一种由根据本发明的第五个方面的方法制备的金属-树脂复合体。
根据本发明的第七个方面，本发明提供了根据本发明的金属-树脂复合体在制备电子产品外壳中的应用。
根据本发明的第八个方面，本发明提供了一种电子产品外壳，该外壳包括金属壳本体以及附着于所述金属壳本体的至少部分内表面和/或至少部分外表面的至少一个树脂件，其中，所述金属壳本体为根据本发明的经表面处理的金属基材。
根据本发明的第九个方面，本发明提供了一种电子产品外壳的制备方法，该方法包括在 金属壳本体的至少部分内表面和/或至少部分外表面形成至少一个树脂件，其中，采用根据本发明的金属-树脂复合体的制备方法来形成所述树脂件。
与仅用酸性蚀刻液进行蚀刻，或者仅用碱性蚀刻液进行蚀刻，或者依次用酸性蚀刻液和碱性蚀刻液进行蚀刻，或者仅将基材进行阳极氧化而不进行化学蚀刻相比，由根据本发明的经表面处理的金属基材与树脂一体化成型而得到的金属-树脂复合体中，金属基材与树脂层之间显示出更高的结合强度，树脂层不易从金属基材表面脱落，因而本发明提供的金属-树脂复合体具有较高的结构稳定性，能够满足对结构稳定性要求较高的使用场合的要求，适于作为电子产品外壳。
附图说明
图1为用于示意性地说明根据本发明的手机外壳的剖视图，包括主视图和俯视图；
图2为用于示意性地说明根据本发明的智能表外壳的剖视图。
<附图标记说明>
1：手机金属壳本体 2：树脂层
3：开口           4：智能表金属壳本体
5：树脂内衬层     6：信号元件开口
具体实施方式
本文中，金属可以为纯铝，也可以为铝合金。所述铝合金是指以铝作为基础元素加入其它元素形成的合金，可以为常见的各种铝合金。金属基材是用铝或铝合金形成的各种成型体，根据具体使用要求可以具有各种形状。
根据本发明的第一个方面，本发明提供了一种金属基材表面处理方法，所述金属为铝或铝合金，该方法包括提供金属基材，所述金属基材包括金属基体以及附着在所述金属基体的至少部分表面的阳极氧化膜层；将所述金属基材依次进行第一蚀刻和第二蚀刻。
所述阳极氧化膜层的厚度一般为0.1-50μm。优选地，所述阳极氧化膜层的厚度为1-20μm，由此形成的金属-树脂复合体中金属与树脂之间具有更高的结合强度。更优选地，所述阳极氧化膜层的厚度为4-10μm。阳极氧化形成的阳极氧化膜层为含有大量微孔的多孔性膜层，从进一步提高最终形成的金属-树脂复合体的树脂与金属基材之间的结合强度的角度出发，阳极氧化形成的阳极氧化膜层中的微孔的孔径在10-100nm的范围内。可以通过选择阳极氧化的条件来对形成的阳极氧化膜层中的微孔的孔径进行调节。
可以通过将所述金属基体置于电解液中进行阳极氧化而得到所述金属基材。本发明对于所述阳极氧化的方法没有特别限定，可以采用常规的阳极氧化方法。具体地，可以在阳极氧化条件下，将金属基体置于电解液中，以所述金属基体为阳极，以不与电解液反应的导电材料为阴极，使阴极和阳极分别与电源的正极和负极电连接，通电后，进行电解，从而在所述金属基体表面上形成氧化铝膜。
所述阳极氧化的条件以形成的阳极氧化膜层的厚度以及阳极氧化膜层中的微孔尺寸能 够满足要求为准。本发明中，所述电解液中的电解质优选为H2SO4、铬酸和草酸中的一种或两种以上。所述电解液中，电解质的含量可以为10-40重量％，优选为15-25重量％。电解液的温度可以为10-30℃，优选为20-30℃。电压可以为10-100V，优选为10-50V，更优选为15-25V。一般地，所述电解的时间可以为1-40分钟，优选为10-20分钟。
所述金属基体在进行阳极氧化之前优选采用本领域常用的各种方法进行前处理。一般地，所述前处理包括机械打磨或研磨，以去除金属基体表面明显的异物，然后对金属基体依次进行脱脂和清洗，以清除金属基体表面的油脂。
根据本发明的金属基材表面处理方法，在所述第一蚀刻中，将所述金属基材浸泡于碱性蚀刻液中。
以下对碱性蚀刻液的种类以及第一蚀刻的条件进行说明。
在第一种实施方式中，所述碱性蚀刻液为含有选自水溶性氢氧化物、水溶性碱性盐、氨、水溶性胺、肼以及一个或多个氢原子被烃基取代的肼衍生物中的一种或两种以上物质的水溶液。
所述水溶性氢氧化物可以为碱金属氢氧化物，优选为氢氧化钠和/或氢氧化钾，更优选为氢氧化钠。
所述水溶性碱性盐是指其水溶液的pH值为大于7的水溶性碱性盐。具体地，所述水溶性碱性盐可以为水溶性碳酸盐、水溶性碳酸氢盐、水溶性磷酸盐、水溶性磷酸一氢盐、水溶性磷酸二氢盐和水溶性硼酸盐中的一种或两种以上。所述水溶性碱性盐可以为碱金属盐，优选为钠盐或钾盐，更优选为钠盐。优选地，所述水溶性碱性盐选自Na2CO3、NaHCO3、NaH2PO4、Na2HPO4、Na3PO4和Na2B4O7。
所述水溶性胺可以为常见的各种能够溶解于水的胺。优选地，所述水溶性胺选自乙二胺、二乙基胺、乙醇胺、三甲基胺、甲基胺和二甲基胺。
所述肼衍生物是指肼(即，H2N-NH2)分子结构中的一个或多个氢原子被烃基取代形成的化合物，所述烃基优选为C1-C4的烷基，具体可以为一甲基肼和1,1-二甲基肼。
在第一种实施方式中，所述碱性蚀刻液优选为含有水溶性氢氧化物和/或水溶性碱性盐的水溶液。更优选地，所述碱性蚀刻液为含有水溶性碱性盐的水溶液，水溶性碱性盐优选为Na2CO3和/或NaHCO3，更优选为Na2CO3或NaHCO3。
在第一种实施方式中，所述碱性蚀刻液的pH值优选在10-13的范围内，这样既能获得适宜的蚀刻速度，而且蚀刻过程温和易控。
在第二种实施方式中，所述碱性蚀刻液为碱性缓冲溶液，这样最终形成的腐蚀孔的分布更为均匀且孔径大小更为集中。
在第二种实施方式中，所述碱性蚀刻液可以为含有水溶性氢氧化物以及水溶性碱性盐的水溶液。所述水溶性氢氧化物和所述水溶性碱性盐的阳离子可以为相同，也可以为不同，优选为相同。
所述水溶性氢氧化物可以为碱金属氢氧化物，优选为氢氧化钠和/或氢氧化钾，更优选为氢氧化钠。
所述水溶性碱性盐可以为水溶性碳酸盐、水溶性碳酸氢盐、水溶性磷酸盐、水溶性磷酸一氢盐、水溶性磷酸二氢盐和水溶性硼酸盐中的一种或两种以上。所述水溶性碱性盐可以为碱金属盐，优选为钠盐或钾盐，更优选为钠盐。优选地，所述水溶性碱性盐为Na2CO3、NaHCO3、NaH2PO4、Na2HPO4、Na3PO4和Na2B4O7中的一种或两种以上。优选地，所述水溶性碱性盐为水溶性磷酸一氢盐和/或水溶性磷酸二氢盐。更优选地，所述水溶性碱性盐为水溶性磷酸二氢盐。
在第二种实施方式中，所述碱性蚀刻液也可以为含有水溶性正盐以及水溶性酸式盐的水溶液。所述正盐是指阳离子只含有金属离子和/或铵根离子的盐，所述酸式盐是指阳离子除含有金属离子和/或铵根离子外，还含有氢离子的盐。所述水溶性正盐与所述水溶性酸式盐的阳离子和酸根离子各自可以为相同，也可以为不同，优选为相同。
在第二种实施方式中，所述碱性蚀刻液优选为含有水溶性碳酸盐和水溶性碳酸氢盐的水溶液，或者含有水溶性磷酸盐和水溶性磷酸一氢盐的水溶液。具体地，所述碱性蚀刻液可以为含有Na2CO3和NaHCO3的水溶液，或者含有Na3PO4和Na2HPO4的水溶液。
在第二种实施方式中，所述碱性蚀刻液还可以为含有氨以及水溶性铵盐的水溶液。所述水溶性铵盐优选为NH4Cl、(NH4)2SO4、NH4HCO3和NH4NO3中的一种或两种以上。具体地，所述碱性蚀刻液可以为含有NH3和NH4Cl的水溶液、含有NH3和(NH4)2SO4的水溶液、含有NH3和NH4HCO3的水溶液或者含有NH3和NH4NO3的水溶液。
在第二种实施方式中，所述碱性蚀刻液优选为含有水溶性氢氧化物以及水溶性碱性盐的水溶液，或者为含有水溶性正盐以及水溶性酸式盐的水溶液，更优选为含有水溶性正盐以及水溶性酸式盐的水溶液。
在第二种实施方式中，所述碱性蚀刻液优选为pH值为10-13的碱性缓冲溶液，这样能够获得适宜的蚀刻速度，而且蚀刻过程温和易控。
根据本发明的金属基材表面处理方法，在所述第二蚀刻中，将经第一蚀刻的金属基材浸泡于酸性蚀刻液中。
所述酸性蚀刻液可以为常见的各种能够蚀刻金属的酸性蚀刻液，优选地，所述酸性蚀刻液为含有酸的水溶液，优选为含有氢卤酸(如HCl)和/或磷酸的水溶液。更优选地，所述酸性蚀刻液为盐酸或磷酸。
所述酸性蚀刻液的pH值优选为1-3，这样形成的经表面处理的金属基材中腐蚀孔的分布更为均匀，孔径分布也更为集中，由该金属基材制备的金属-树脂复合体中树脂与金属基材的结合强度更高。
更优选地，在所述酸性蚀刻液中的酸性物质为酸时，所述酸性蚀刻液还含有一种或两种以上水溶性盐，这样能够进一步提高蚀刻的稳定性，形成的腐蚀孔的分布更为均匀，孔径分布更为集中。所述水溶性盐的酸根优选为与酸性蚀刻液中含有的酸的酸根相同。例如，在所述酸性蚀刻液为含有氢卤酸的水溶液时，所述酸性蚀刻液优选还含有一种或两种以上水溶性氢卤酸盐；在所述酸性蚀刻液为含有磷酸的水溶液时，所述酸性蚀刻液优选还含有一种或两种以上水溶性磷酸盐。所述水溶性盐在所述酸性蚀刻液中的含量随酸性蚀刻液中酸的量而 定。一般地，所述水溶性盐与所述酸的摩尔比可以为0.1-1:1，优选为0.2-0.8:1，更优选为0.4-0.6:1。
在一个优选的实例中，所述酸性蚀刻液为盐酸，所述水溶性盐为NaCl、KCl和AlCl3中的一种或两种以上。
在另一个优选的实例中，所述酸性蚀刻液为磷酸，所述水溶性盐为水溶性磷酸盐、水溶性磷酸一氢盐和水溶性磷酸二氢盐中的一种或两种以上，如NaH2PO4、Na2HPO4、Na3PO4、KH2PO4、K2HPO4和K3PO4中的一种或两种以上。
通过第一蚀刻和第二蚀刻可以在所述阳极氧化膜层表面形成至少部分为贯穿阳极氧化膜层的第一腐蚀孔，还能在与所述阳极氧化膜层相接的金属基材的表面形成第二腐蚀孔。第一腐蚀孔与第二腐蚀孔贯通。并且，在蚀刻过程中蚀刻放热小，蚀刻过程温和易控，从而能够形成具有预期孔径大小和孔深的腐蚀孔。将该金属基材与树脂一体化成型制备的金属-树脂复合体时，金属基材与树脂层之间具有更高的结合强度。本文中，出于清楚的目的，将分布在阳极氧化膜层表面的腐蚀孔称为“第一腐蚀孔”，将分布在与阳极氧化膜层相接的金属基体层表面的腐蚀孔称为“第二腐蚀孔”。
所述第一蚀刻和所述第二蚀刻的条件可以根据预期的腐蚀孔的孔径大小和孔深进行选择。本发明的发明人在研究过程中发现，选择所述第一蚀刻和所述第二蚀刻的条件，使得所述第一腐蚀孔的孔径不大于所述第二腐蚀孔，由该经表面处理的金属基材形成的金属-树脂复合体中，金属基体与树脂层之间显示出更高的结合强度。从进一步提高由该经表面处理的金属基材形成的金属-树脂复合体中金属基体与树脂层之间的结合强度的角度出发，所述第一蚀刻和所述第二蚀刻的条件更优选使得第一腐蚀孔的孔径在10-200nm的范围内，优选在100-200nm的范围内；所述第二腐蚀孔的孔径在200-2000nm的范围内，优选在500-2000nm的范围内，更优选在1000-1500nm的范围内。
根据本发明的方法，至少部分第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值为1:1，优选50％以上、更优选60％以上、进一步优选70％以上第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值为1:1。优选地，进行第一蚀刻后形成的所述第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.1-1:1的范围内，优选在0.5-1:1的范围内；进行所述第二蚀刻后形成的所述第二腐蚀孔的深度在0.1-500μm的范围内，优选在10-400μm的范围内，更优选在50-200μm的范围内，这样既能够获得进一步提高的树脂-金属结合强度，同时也不会对金属基材本身的强度产生不利影响。
所述第一腐蚀孔和所述第二腐蚀孔的孔径和深度可以采用显微镜法测定。本文中，腐蚀孔(包括第一腐蚀孔和第二腐蚀孔)的深度是指腐蚀孔的孔顶至该腐蚀孔的孔底的垂直距离；腐蚀孔(包括第一腐蚀孔和第二腐蚀孔)的孔径是指腐蚀孔的上端口(即，位于表面的端口)在径向的最大尺寸。
具体地，在所述第一蚀刻中，所述碱性蚀刻液的温度可以为10-60℃，优选为20-40℃。所述第一蚀刻的时间可以为1-60分钟，优选为1-30分钟，更优选为1-15分钟。在所述第二蚀刻中，所述酸性蚀刻液的温度优选为20-30℃。所述第二蚀刻的时间可以为1-60分钟，优 选为10-40分钟，更优选为15-30分钟。
所述第一蚀刻和所述第二蚀刻各自可以只进行一次，也可以分次进行，每次蚀刻的持续时间没有特别限定，只要总的蚀刻时间满足上述要求即可。在所述第一蚀刻和所述第二蚀刻为分次进行时，在两次蚀刻之间优选用水进行洗涤，以除去前一次蚀刻残留的蚀刻液。根据本发明的表面处理方法，在第二蚀刻完成后对经表面处理的基材进行清洗，以除去残留在基材表面以及腐蚀孔中的蚀刻液。
根据本发明的第二个方面，本发明提供了一种由本发明提供的表面处理方法得到的经表面处理的金属基材。
根据本发明的第三个方面，本发明提供了一种经表面处理的金属基材，所述金属为铝或铝合金，该金属基材包括金属基体以及附着在所述金属基体的至少部分表面上的阳极氧化膜层，所述金属基体包括基体层和腐蚀层，所述基体层与所述腐蚀层为一体结构，所述腐蚀层与所述阳极氧化膜层相接并为一体结构。
所述基体层为致密层，即所述基体层不含腐蚀孔。所述腐蚀层是指金属基体中分布有腐蚀孔的部分。
所述阳极氧化膜层的表面分布有第一腐蚀孔，所述腐蚀层的表面分布有第二腐蚀孔，并且所述第一腐蚀孔的孔径不大于所述第二腐蚀孔的孔径。从进一步提高最终形成的金属-树脂复合体中金属与树脂之间的结合强度的角度出发，所述第一腐蚀孔的孔径在10-200nm范围内，优选在100-200nm的范围内；所述第二腐蚀孔的孔径在200-2000nm范围内，优选在500-2000nm的范围内，更优选在1000-1500nm的范围内。
除所述第一腐蚀孔外，所述阳极氧化膜层中还含有阳极氧化形成的微孔。由阳极氧化形成的微孔的孔径大小一般在10-100nm的范围内。由阳极氧化形成的微孔与所述第一腐蚀孔和第二腐蚀孔连通。在制备金属-树脂复合体时，部分树脂通过第一腐蚀孔进入第二腐蚀孔中，同时还有部分树脂浸入阳极氧化形成的微孔中，在金属基材中形成树脂网络，将树脂层更为牢固地锚定在金属基材中，从而提高形成的金属-树脂复合体中树脂与金属基材之间的结合强度。
所述阳极氧化膜层的厚度一般可以为0.1-50μm，优选为1-20μm，更优选为4-10μm。
至少部分第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值为1:1。优选50％以上、更优选60％以上、进一步优选70％以上第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1。优选地，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.1-1:1的范围内。更优选地，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.5-1:1的范围内。
所述腐蚀层的厚度可以由其中的第二腐蚀孔的深度确定，一般将腐蚀层中深度最大的第二腐蚀孔的深度作为腐蚀层的厚度。所述腐蚀层的厚度可以根据所述阳极氧化膜层的厚度进行选择。一般地，所述第二腐蚀孔的深度在0.1-500μm的范围内，优选在10-400μm的范围内，更优选在50-200μm的范围内。
根据本发明的第四个方面，本发明提供了一种金属-树脂复合体，所述金属为铝或铝合金，该复合体包括金属基材以及附着在所述金属基材的至少部分表面上的树脂层，所述金属 基材为本发明提供的经表面处理的金属基材，所述树脂层中的部分树脂向下延伸并填充于所述金属基材的第一腐蚀孔和第二腐蚀孔中。
所述树脂层中的主体树脂可以根据具体的使用要求进行选择，只要该树脂能与铝或铝合金结合即可。一般地，所述树脂层中的主体树脂可以选自热塑性树脂，例如可以为聚苯硫醚、聚酯、聚酰胺、聚碳酸酯和聚烯烃中的一种或两种以上。所述聚酯可以为常见的由二羧酸与二醇缩合而成的聚合物，其具体实例可以包括但不限于聚对苯二甲酸丁二醇酯和/或聚对苯二甲酸乙二醇酯。所述聚酰胺可以为常见的由二胺与二羧酸缩合而成的聚合物，其具体实例可以包括但不限于聚己二酰己二胺、聚壬二酰己二胺、聚丁二酰己二胺、聚十二烷二酰己二胺、聚癸二酰己二胺、聚癸二酰癸二胺、聚十一酰胺、聚十二酰胺、聚辛酰胺、聚9-氨基壬酸、聚己内酰胺、聚对苯二甲酰苯二胺、聚间苯二甲酰己二胺、聚对苯二甲酰己二胺和聚对苯二甲酰壬二胺。所述聚烯烃的具体实例可以包括但不限于聚苯乙烯、聚丙烯、聚甲基丙烯酸甲酯和聚(丙烯腈-丁二烯-苯乙烯)。
所述树脂层除含有主体树脂外，还可以含有至少一种填料。所述填料的种类可以根据具体的使用要求进行选择。所述填料可以为纤维型填料和/或粉末型填料。所述纤维型填料可以为选自玻璃纤维、碳纤维和芳族聚酰胺纤维中的一种或两种以上。所述粉末型填料可以为选自碳酸钙、碳酸镁、二氧化硅、重质硫酸钡、滑石粉、玻璃和粘土中的一种或两种以上。所述填料的含量可以为常规选择。一般地，以100重量份主体树脂为基准，所述填料的含量可以为20-150重量份，优选为25-100重量份，更优选为30-50重量份。
所述金属基材和所述树脂层的厚度可以根据该金属-树脂复合体的具体应用场合进行选择，以能满足使用要求为准。一般地，所述树脂层的厚度可以为0.5-10mm，优选为0.5-5mm。所述金属基材的厚度可以为0.5-20mm，优选为0.5-10mm，更优选为1-5mm。
根据本发明的第五个方面，本发明提供了一种金属-树脂复合体的制备方法，该方法包括向本发明提供的经表面处理的金属基材的表面注入含树脂的组合物并使部分组合物填充于第一腐蚀孔和第二腐蚀孔中，成型后形成树脂层。
所述含树脂的组合物中的树脂(以下称为主体树脂)与前文所述树脂层中的主体树脂的种类相同，此处不再详述。所述含树脂的组合物除含有主体树脂外，还可以含有至少一种填料和/或至少一种流动性改进剂。所述填料的种类与前文树脂层中的填料种类相同，此处不再详述。
所述填料的含量可以为常规选择。一般地，以100重量份主体树脂为基准，所述填料的含量可以为20-150重量份，优选为25-100重量份，更优选为30-50重量份。
所述流动性改进剂用于提高主体树脂的流动能力，进一步提高金属基材与树脂之间的结合力以及树脂的加工性能。所述流动性改进剂可以为各种能够实现上述效果的物质，优选为环状聚酯。
所述流动性改进剂的用量以能够提高主体树脂的流动能力为准。优选地，相对于100重量份主体树脂，所述流动性改进剂的含量为1-5重量份。
所述含树脂的组合物根据具体使用要求还可以含有常见的各种助剂，如着色剂和/或抗 氧剂，以改善最终形成的金属-树脂复合体中树脂层的性能或者赋予所述树脂层以新的性能。
含树脂的组合物可以通过将主体树脂、任选的填料、任选的流动性改进剂以及任选的助剂混合均匀而获得。一般地，可以将主体树脂、任选的填料、任选的流动性改进剂以及任选的助剂混合均匀，并进行挤出造粒而得到。
可以采用常用的各种方法向经表面处理的金属基材的表面注入所述含树脂的组合物。在本发明的一种优选的实施方式中，将所述经表面处理的金属基材置于模具中，通过注塑的方法向金属基材的表面注入所述含树脂的组合物。
所述注塑的条件可以根据含树脂的组合物中主体树脂的种类进行选择。优选地，所述注塑的条件包括：模具温度为50-300℃，喷嘴温度为200-450℃，保压时间为1-50秒，射出压力为50-300MPa，射出时间为1-30秒，延迟时间为1-30秒。
所述含树脂的组合物的注入量可以根据预期的树脂层厚度进行选择。一般地，所述含树脂的组合物的注入量使得形成的树脂层的厚度为0.5-10mm，优选为0.5-5mm。所述金属基材的厚度可以为0.5-20mm，优选为0.5-10mm，更优选为1-5mm。
根据本发明的方法，仅在金属基材的部分表面形成树脂层时，可以对无需形成树脂层的表面进行处理，以除去表面孔洞以及由于蚀刻而引起的表面颜色变化，该处理可以在注入含树脂的组合物并成型之前进行，也可以在注入含树脂的组合物并成型之后进行，没有特别限定。
根据本发明的第六个方面，本发明提供了一种由根据本发明的第五个方面的方法制备的金属-树脂复合体。由本发明的方法制备的金属-树脂复合体包括金属基材以及附着在所述金属基材的至少部分表面上的树脂层，所述树脂层中的部分树脂向下延伸并填充于所述金属基材的第一腐蚀孔和第二腐蚀孔中。
由本发明的方法制备的金属-树脂复合体中，树脂层与金属基材之间的结合力高，因而复合体的结构稳定性好。
根据本发明的第七个方面，本发明提供了根据本发明的金属-树脂复合体在制备电子产品外壳中的应用。
根据本发明的第八个方面，本发明提供了一种电子产品外壳，该外壳包括金属壳本体以及附着于所述金属壳本体的至少部分内表面和/或至少部分外表面的至少一个树脂件，其中，所述金属壳本体为根据本发明的经表面处理的金属基材。本发明中，所述外壳不仅包括为片状结构的外壳，也包括各种框架结构，如外框。
根据本发明的电子产品外壳，根据具体需要，所述金属壳本体上可以设置有至少一个开口，以在该开口的对应位置安装电子产品的需要避开金属壳本体的元件。在一种实施方式中，由于金属对电磁信号具有屏蔽作用，因此至少部分开口的位置可以对应于信号发射元件和/或信号接受元件的安装位置，此时所述开口位置优选设置树脂件，并使所述树脂件中的部分树脂填充于所述开口中，信号发射元件和/或信号接受元件可以安装在所述树脂件上。
根据本发明的电子产品外壳，所述金属壳本体可以为一体结构，也可以为拼接结构。所述拼接结构是指所述金属壳本体包括相互断开的至少两个部分，两个部分相互拼接在一起形 成金属壳本体。
在所述金属壳本体为拼接结构时，相邻两个部分可以用胶粘剂粘结在一起。在一种优选的实施方式中，相邻两部分的拼接位置设置有所述树脂件，该树脂件分别与相邻两部分搭接并覆盖所述拼接位置(即该树脂件桥接该相邻两部分)，这样能够提高拼接位置的结合强度；并且，可以根据电子产品的内部结构，将金属壳本体分成多个部分，所述树脂件在起到使金属壳本体形成为一个整体的作用的同时，还能用作一些电子元件的安装基体。
根据本发明的电子产品外壳，所述金属壳本体的至少部分外表面可以附着有树脂件，所述树脂件可以覆盖整个外表面，也可以覆盖金属壳本体的部分外表面以形成图案，例如装饰性图案。
根据本发明的电子产品外壳，所述金属壳本体的内表面附着有树脂件时，所述树脂件可以设置在需要的一个或多个位置。在一种优选的实施方式中，所述树脂件附着于所述金属壳本体的整个内表面，此时所述树脂件优选为一体结构。根据该优选的实施方式，特别适用于金属壳本体为拼接结构的场合。
根据本发明的电子产品外壳，可以为各种需要以金属作为外壳的电子产品外壳，例如：移动终端的外壳或者外框，可穿戴电子设备的外壳或者外框。所述移动终端是指可以处于移动状态且具有无线传输功能的设备，例如：移动电话、便携式电脑(包括笔记本电脑和平板电脑)。所述可穿戴电子设备是指智能化的穿戴设备，例如：智能表、智能手环。所述电子产品具体可以为但不限于移动电话、便携式电脑(如笔记本电脑和平板电脑)、智能表和智能手环中的一种或两种以上。
图1示出了所述电子产品外壳为手机外壳时的一种实施方式的主视图和俯视图。如图1所示，在手机金属壳本体1上开设有多个开口3，开口3的位置可以对应于安装天线的位置以及安装各种按键的位置。树脂层2附着在手机金属壳本体1的整个内表面，树脂层2为一体结构并且树脂层2中的部分树脂填充于开口3中。
图2示出了所述电子产品外壳为智能表的外壳的一种实施方式的主视图。如2所示，智能表金属壳本体4上设置有对应于安装信号发射元件和/或信号接收元件的信号元件开口6，智能表金属壳本体4的内表面附着有树脂内衬层5，树脂内衬层5中的部分树脂填充在信号元件开口6中，信号元件可以安装在树脂内衬层5上的相应位置。
根据本发明的第九个方面，本发明提供了一种电子产品外壳的制备方法，该方法包括在金属壳本体的至少部分内表面和/或至少部分外表面形成至少一个树脂件，其中，采用根据本发明的金属-树脂复合体的制备方法来形成所述树脂件。
以下结合实施例详细说明本发明，但不因此限定本发明的范围。
以下实施例和对比例中，参照ASTM D1002-10规定的方法，在INSTRON 3369型万能试验机上测定金属-树脂复合体中金属基体与树脂层之间的平均剪切强度。
以下实施例和对比例中，采用购自ZEISS的型号为Axio Imager Alm的金相显微镜测定阳极氧化膜层的厚度以及腐蚀孔的深度(对同一样品的五个不同位置进行观察，测定视野范围内出现的全部腐蚀孔的深度)，采用购自日本电子株式会社的型号为JSM-7600F的扫描电 子显微镜测定腐蚀孔的孔径(对同一样品的五个不同位置进行观察，测定视野范围内出现的全部腐蚀孔的孔径)。
实施例1-11用于说明本发明。
实施例1
(1)将市售厚度为1mm的5052铝合金板切成15mm×80mm的长方形片。将长方形片放入抛光机内进行抛光。接着用无水乙醇洗净，然后浸泡于浓度为2重量％的氢氧化钠水溶液中，2分钟后取出用去离子水冲洗干净，得到经过前处理的铝合金片。
(2)将步骤(1)得到的铝合金片作为阳极放入以浓度为20重量％的H2SO4水溶液作为电解液的阳极氧化槽中，以石墨碳板作为阴极，在15V的电压下，在20℃电解10分钟。将经阳极氧化的铝合金片取出，在水中浸泡1分钟后吹干，得到表面具有阳极氧化膜的铝合金片。用显微镜对该铝合金片沿厚度方向进行观察，确定阳极氧化膜层的平均厚度为6.4μm，阳极氧化膜层中的微孔的孔径在10-100nm的范围内。
(3)将步骤(2)得到的表面具有阳极氧化膜层的铝合金片浸泡于温度为25℃的作为蚀刻液的含有Na2CO3和NaHCO3的水溶液(pH＝10)中。1分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经第一蚀刻的铝合金。
(4)将步骤(3)得到的经第一蚀刻的铝合金浸泡于温度为25℃的作为蚀刻液的盐酸(pH＝1)中。15分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经第二蚀刻的铝合金。
采用显微镜观察步骤(4)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径在100-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.5-1:1的范围内，50％以上第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在1000-1500nm范围内，第二腐蚀孔的深度在10-300μm的范围内。
(5)将步骤(4)得到的铝合金片置于注射成型模具中，在铝合金片的一个表面注塑含有玻璃纤维和聚苯硫醚(PPS)的树脂组合物(相对于100重量份PPS，玻璃纤维的含量为30重量份)，脱模并冷却。其中，注塑条件包括：模具温度为140℃，喷嘴温度为305℃，保压时间为5秒，射出压力为120MPa，射出时间为5秒，延迟时间为3秒。
将冷却后的产品放入120℃的恒温干燥箱中保温1.5h，然后随炉自然冷却至室温，制得金属-树脂复合体(树脂层厚度为5mm)，其平均剪切强度在表1中列出。
对比例1
(1)采用与实施例1步骤(1)相同的方法对铝合金进行切割和前处理。
(2)采用与实施例1步骤(5)相同的方法将对比例1步骤(1)得到的铝合金片置于注射成型模具中进行注射成型，得到金属-树脂复合体，其平均剪切强度在表1中列出。
对比例2
(1)采用与实施例1步骤(1)相同的方法对铝合金进行切割和前处理。
(2)采用与实施例1步骤(2)相同的方法对对比例2步骤(1)得到的铝合金片进行阳极氧化，得到表面具有阳极氧化膜层的铝合金片。
(3)采用与实施例1步骤(5)相同的方法将对比例2步骤(2)得到的铝合金片置于注射模具中进行注射成型，得到铝合金-树脂复合体，其平均剪切强度在表1中列出。
对比例3
(1)采用与实施例1步骤(1)相同的方法对铝合金进行切割和前处理。
(2)采用与实施例1步骤(2)相同的方法对对比例3步骤(1)得到的铝合金片进行阳极氧化，得到表面具有阳极氧化膜层的铝合金片。
(3)采用与实施例1步骤(3)相同的方法对对比例3步骤(2)得到的铝合金进行蚀刻。
采用显微镜观察步骤(3)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径在100-200nm范围内的腐蚀孔，腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.5-1:1的范围内，铝合金基体中基本没有腐蚀孔。
(4)采用与实施例1步骤(5)相同的方法将对比例3步骤(3)得到的铝合金片置于注射模具中进行注射成型，得到铝合金-树脂复合体，其平均剪切强度在表1中列出。
对比例4
(1)采用与实施例1步骤(1)相同的方法对铝合金进行切割和前处理。
(2)采用与实施例1步骤(2)相同的方法对对比例4步骤(1)得到的铝合金片进行阳极氧化，得到表面具有阳极氧化膜层的铝合金片。
(3)采用与实施例1步骤(4)相同的方法对对比例4步骤(2)得到的铝合金进行蚀刻。
采用显微镜观察步骤(3)得到的铝合金的横截面，发现：阳极氧化膜层基本没有腐蚀孔；铝合金基体分为致密的基体层和具有腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，腐蚀孔的孔径在100-3000nm范围内，腐蚀孔的深度在0.01-500μm的范围内。
(4)采用与实施例1步骤(5)相同的方法将对比例4步骤(3)得到的铝合金片置于注射模具中进行注射成型，得到铝合金-树脂复合体，其平均剪切强度在表1中列出。
对比例5
(1)采用与实施例1步骤(1)相同的方法对铝合金进行切割和前处理。
(2)采用与实施例1步骤(3)相同的方法对对比例5步骤(1)得到的铝合金片进行第一蚀刻。
(3)采用与实施例1步骤(4)相同的方法对对比例5步骤(2)得到的铝合金进行第 二蚀刻。
采用显微镜观察步骤(3)得到的铝合金的横截面，发现：在铝合金基体表面分布的腐蚀孔的孔径在1000-5000nm范围内，腐蚀孔的深度在0.1-500μm的范围内。
(4)采用与实施例1步骤(5)相同的方法将对比例5步骤(3)得到的铝合金置于注射模具中进行注射成型，得到铝合金-树脂复合体，其平均剪切强度在表1中列出。
对比例6
(1)采用与实施例1步骤(1)相同的方法对铝合金进行切割和前处理。
(2)采用与实施例1步骤(2)相同的方法对对比例6步骤(1)得到的铝合金片进行阳极氧化，得到表面具有阳极氧化膜层的铝合金片。
(3)采用与实施例1步骤(4)相同的方法对对比例6步骤(1)得到的铝合金片进行第一蚀刻。
(4)采用与实施例1步骤(3)相同的方法对对比例6步骤(2)得到的铝合金进行第二蚀刻。
采用显微镜观察步骤(4)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径在100-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.5-1:1的范围内；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在100-3500nm范围内，第二腐蚀孔的深度在0.01-500μm的范围内。
(5)采用与实施例1步骤(5)相同的方法将对比例6步骤(4)得到的铝合金置于注射模具中进行注射成型，得到铝合金-树脂复合体，其平均剪切强度在表1中列出。
实施例2
(1)将市售厚度为1mm的5052铝合金板切成15mm×80mm的长方形片。将长方形片放入抛光机内进行抛光。接着用无水乙醇洗净，然后浸泡于浓度为2重量％的氢氧化钠水溶液中，2min后取出用去离子水冲洗干净，得到经过前处理的铝合金片；
(2)将步骤(1)得到的铝合金片作为阳极放入以浓度为20重量％的硫酸作为电解液的阳极氧化槽中，以石墨碳板作为阴极，在20V的电压下，在20℃电解12分钟。将经阳极氧化的铝合金片取出，在水中浸泡1分钟后吹干，得到表面具有阳极氧化膜的铝合金片。用显微镜对该铝合金片的横截面进行观察确定阳极氧化膜层的平均厚度为8μm，阳极氧化膜层中的微孔的孔径在20-100nm的范围内。
(3)将步骤(2)得到的表面具有阳极氧化膜层的铝合金片浸泡于温度为25℃的Na3PO3和NaH2PO3的水溶液(pH＝11)中。15分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经第一蚀刻的铝合金。
(4)将步骤(3)得到的经第一蚀刻的铝合金浸泡于温度为25℃的盐酸(pH＝1)中。25分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经第二蚀刻的铝合金。
采用显微镜观察步骤(4)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径在120-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.6-1:1的范围内，优选60％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在1100-1500nm范围内，第二腐蚀孔的深度在10-300μm的范围内。
(5)将步骤(4)得到的铝合金片置于注射成型模具中，在铝合金片的一个表面注塑含有玻璃纤维和聚对苯二甲酸丁二醇酯(PBT)的树脂组合物(相对于100重量份PBT，玻璃纤维的含量为45重量份)，脱模并冷却；将冷却后的产品放入120℃的恒温干燥箱中保温1.5h，然后随炉自然冷却至室温，制得铝合金-树脂复合体(树脂层的厚度为5mm)，其平均剪切强度在表1中列出。
实施例3
(1)采用与实施例2相同的方法对铝合金进行切割和前处理。
(2)采用与实施例2步骤(2)相同的方法将实施例3步骤(1)得到的铝合金片进行阳极氧化。
(3)采用与实施例2步骤(3)相同的方法对实施例3步骤(2)得到的铝合金片进行第一蚀刻。
(4)采用与实施例2步骤(4)相同的方法对实施例3步骤(3)得到的铝合金进行第二蚀刻，不同的是，蚀刻液还含有NaCl，NaCl与HCl的摩尔比为0.5:1。
采用显微镜观察步骤(4)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径在120-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.6-1:1的范围内，优选60％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在1000-1500nm范围内，第二腐蚀孔的深度在100-200μm的范围内。
(5)采用与实施例2步骤(5)相同的方法将实施例3步骤(4)得到的铝合金置于注射模具中进行注射成型，得到铝合金-树脂复合体，其平均剪切强度在表1中列出。
实施例4
(1)采用与实施例2相同的方法对铝合金进行切割和前处理。
(2)采用与实施例2步骤(2)相同的方法将实施例4步骤(1)得到的铝合金片进行阳极氧化。
(3)采用与实施例2步骤(3)相同的方法对实施例4步骤(2)得到的铝合金片进行第一蚀刻，不同的是，蚀刻液为Na3PO4的水溶液(pH＝11)。
(4)采用与实施例2步骤(4)相同的方法对实施例4步骤(3)得到的铝合金进行第二蚀刻。
采用显微镜观察步骤(4)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径 在50-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.2-1:1的范围内，50％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在220-2000nm范围内，第二腐蚀孔的深度在0.1-400μm的范围内。
(5)采用与实施例2步骤(5)相同的方法将实施例4步骤(4)得到的铝合金置于注射模具中进行注射成型，得到铝合金-树脂复合体，其平均剪切强度在表1中列出。
实施例5
(1)采用与实施例2相同的方法对铝合金进行切割和前处理。
(2)采用与实施例2步骤(2)相同的方法将实施例5步骤(1)得到的铝合金片进行阳极氧化。
(3)采用与实施例2步骤(3)相同的方法对实施例5步骤(2)得到的铝合金片进行第一蚀刻，不同的是，蚀刻液为乙二胺的水溶液(pH＝12)。
(4)采用与实施例2步骤(4)相同的方法对实施例5步骤(3)得到的铝合金进行第二蚀刻。
采用显微镜观察步骤(4)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径在10-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.1-1:1的范围内，50％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在200-2000nm范围内，第二腐蚀孔的深度在0.1-400μm的范围内。
(5)采用与实施例2步骤(5)相同的方法将实施例5步骤(4)得到的铝合金置于注射模具中进行注射和成型，得到铝合金-树脂复合体，其平均剪切强度在表1中列出。
实施例6
(1)采用与实施例2相同的方法对铝合金进行切割和前处理。
(2)采用与实施例2步骤(2)相同的方法将实施例6步骤(1)得到的铝合金片进行阳极氧化。
(3)采用与实施例2步骤(3)相同的方法对实施例6步骤(2)得到的铝合金片进行第一蚀刻，不同的是，蚀刻液为肼的水溶液(pH＝10)。
(4)采用与实施例2步骤(4)相同的方法对实施例6步骤(3)得到的铝合金进行第二蚀刻。
采用显微镜观察步骤(4)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径在20-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.1-1:1的范围内，50％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在200-2000nm范围内，第二腐蚀孔的深度在0.1-400μm的范围内。
(5)采用与实施例2步骤(5)相同的方法将实施例6步骤(4)得到的铝合金置于注射模具中进行注射成型，得到铝合金-树脂复合体，其平均剪切强度在表1中列出。
实施例7
(1)将市售厚度为1mm的5052铝合金板切成15mm×80mm的长方形片。将长方形片放入抛光机内进行抛光。接着用无水乙醇洗净，然后浸泡于浓度为2重量％的氢氧化钠水溶液中，2min后取出用去离子水冲洗干净，得到经过前处理的铝合金片。
(2)将步骤(1)得到的铝合金片作为阳极放入以浓度为15重量％的草酸作为电解液的阳极氧化槽中，以石墨碳板作为阴极，在20V的电压下，在30℃电解20分钟。将经阳极氧化的铝合金片取出，在去离子水中浸泡1分钟后吹干，得到表面具有阳极氧化膜的铝合金片。用显微镜对该铝合金片的横截面进行观察确定阳极氧化膜层的平均厚度为5μm，阳极氧化膜层中的微孔的孔径在30-80nm的范围内。
(3)将步骤(2)得到的表面具有阳极氧化膜层的铝合金片浸泡于温度为25℃的NaOH水溶液(pH＝13)中。15分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经第一蚀刻的铝合金。
(4)将步骤(3)得到的经第一蚀刻的铝合金浸泡于温度为25℃的磷酸(pH＝3)中。30分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经第二蚀刻的铝合金。
采用显微镜观察步骤(4)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径在10-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.3-1:1的范围内，60％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在200-2000nm范围内，第二腐蚀孔的深度在0.1-400μm的范围内。
(5)将步骤(4)得到的铝合金片置于注射成型模具中，在铝合金片的一个表面注塑含有30重量％玻璃纤维和尼龙66(PA-66)的树脂组合物(相对于100重量份PA-66，玻璃纤维的含量为50重量份)，脱模并冷却；将冷却后的产品放入120℃的恒温干燥箱中保温1.5h，然后随炉自然冷却至室温，制得铝合金-树脂复合体(树脂层的厚度为5mm)，其平均剪切强度在表1中列出。
实施例8
(1)采用与实施例7相同的方法对铝合金进行切割和前处理。
(2)采用与实施例7步骤(2)相同的方法将实施例8步骤(1)得到的铝合金片进行阳极氧化。
(3)采用与实施例7步骤(3)相同的方法对实施例8步骤(2)得到的铝合金片进行第一蚀刻，不同的是，蚀刻液(pH值与实施例7相同)还含有Na2CO3。
(4)采用与实施例7步骤(4)相同的方法对实施例8步骤(3)得到的铝合金片进行第二蚀刻。
采用显微镜观察步骤(4)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径在130-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.6-1:1的范围内，70％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在1000-1500nm范围内，第二腐蚀孔的深度在10-300μm的范围内。
(5)采用与实施例7步骤(5)相同的方法将实施例8步骤(4)得到的铝合金置于注射模具中进行注射和成型，得到铝合金-树脂复合体，其平均剪切强度在表1中列出。
实施例9
(1)采用与实施例7相同的方法对铝合金进行切割和前处理。
(2)采用与实施例7步骤(2)相同的方法将实施例9步骤(1)得到的铝合金片进行阳极氧化。
(3)采用与实施例7步骤(3)相同的方法对实施例9步骤(2)得到的铝合金片进行第一蚀刻。
(4)采用与实施例7步骤(4)相同的方法对实施例9步骤(3)得到的铝合金片进行第二蚀刻，不同的是，蚀刻液(pH值与实施例7相同)还含有Na2HPO4。
采用显微镜观察步骤(4)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径在10-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.3-1:1的范围内，50％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在500-2000nm范围内，第二腐蚀孔的深度在50-200μm的范围内。
(5)采用与实施例7步骤(5)相同的方法将实施例9步骤(4)得到的铝合金置于注射模具中进行注射成型，得到铝合金-树脂复合体，其平均剪切强度在表1中列出。
实施例10
(1)将市售厚度为1mm的5052铝合金板切成15mm×80mm的长方形片。将长方形片放入抛光机内进行抛光。接着用无水乙醇洗净，然后浸泡于浓度为2重量％的氢氧化钠水溶液中，2min后取出用去离子水冲洗干净，得到经过前处理的铝合金片。
(2)将步骤(1)得到的铝合金片作为阳极放入以浓度为25重量％的铬酸作为电解液的阳极氧化槽中，以石墨碳板作为阴极，在15V的电压下，在25℃电解15分钟。将经阳极氧化的铝合金片取出并吹干，得到表面具有阳极氧化膜的铝合金片。用显微镜对该铝合金片的横截面进行观察确定阳极氧化膜层的厚度为4.5μm，阳极氧化膜层中的微孔的孔径在10-90nm的范围内。
(3)将步骤(2)得到的表面具有阳极氧化膜层的铝合金片浸泡于温度为35℃的作为蚀刻液的氨水(pH＝11)中。10分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经第一蚀刻的铝合金。
(4)将步骤(3)得到的经第一蚀刻的铝合金浸泡于温度为30℃的作为蚀刻液的盐酸(pH＝2)中。20分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经第二蚀刻的铝合金。
采用显微镜观察步骤(4)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径在10-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.1-1:1的范围内，50％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在200-2000nm范围内，第二腐蚀孔的深度在0.1-400μm的范围内。
(5)步骤(4)得到的铝合金片置于注射成型模具中，在铝合金片的一个表面注塑含有玻璃纤维和聚苯硫醚(PPS)的树脂组合物(相对于100重量份PPS，玻璃纤维的含量为40重量份)，脱模并冷却；将冷却后的产品放入120℃的恒温干燥箱中保温1.5h，然后随炉自然冷却至室温，制得铝合金-树脂复合体(树脂层的厚度为5mm)，其平均剪切强度在表1中列出。
实施例11
(1)采用与实施例10步骤(1)相同的方法对铝合金进行切割和前处理。
(2)采用与实施例10步骤(2)相同的方法对实施例11步骤(1)得到的铝合金进行阳极氧化。
(3)采用与实施例10步骤(3)相同的方法对实施例11步骤(2)得到的铝合金片进行第一蚀刻，不同的是，蚀刻液(pH值与实施例10相同)还含有NH4Cl。
(4)采用与实施例10步骤(4)相同的方法对实施例11步骤(3)得到的铝合金片进行第二蚀刻。
采用显微镜观察步骤(4)得到的铝合金的横截面，发现：阳极氧化膜层中分布有孔径在100-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.5-1:1的范围内，70％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在1000-1400nm范围内，第二腐蚀孔的深度在10-300μm的范围内。
(5)采用与实施例10步骤(5)相同的方法将实施例11步骤(4)相同的方法对实施例11步骤(4)得到的铝合金片置于注射成型模具进行注射成型，得到铝合金-树脂复合体，其平均剪切强度在表1。
表1
编号 平均剪切强度(MPa)
实施例1 15.3
对比例1 0.2
对比例2 3
对比例3 10.6
对比例4 7.1
对比例5 5.6
对比例6 7.2
实施例2 17.5
实施例3 19.5
实施例4 15.1
实施例5 15.2
实施例6 14.5
实施例7 16.2
实施例8 19.4
实施例9 17.1
实施例10 17.5
实施例11 20.2
将实施例1与对比例1-6进行比较可以看出，采用本发明的方法对金属基材进行表面处理，然后将树脂注塑在经处理的表面而得到的金属-树脂复合体中，树脂层与金属基材之间具有更高的平均剪切强度(即，具有更高的结合强度)，因而复合体具有更高的结构稳定性。

Claims (30)

  1. 一种金属基材表面处理方法，所述金属为铝或铝合金，该方法包括提供金属基材，所述金属基材包括金属基体以及附着在所述金属基体的至少部分表面的阳极氧化膜层；将所述金属基材依次进行第一蚀刻和第二蚀刻；
    在所述第一蚀刻中，将所述金属基材浸泡于碱性蚀刻液中；
    在所述第二蚀刻中，将经第一蚀刻的金属基材浸泡于酸性蚀刻液中；
    进行所述第一蚀刻后在阳极氧化膜层的表面分布有第一腐蚀孔，进行所述第二蚀刻的后与所述阳极氧化膜层相接的金属基体表面分布有第二腐蚀孔，至少部分第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值为1:1。
  2. 根据权利要求1所述的方法，其中，所述阳极氧化膜层的厚度为0.1-50μm。
  3. 根据权利要求1或2所述的方法，其中，提供所述金属基材的方法包括：将金属基材置于电解液中进行阳极氧化，所述电解液中的电解质为H2SO4、铬酸和草酸中的一种或两种以上，所述阳极氧化的条件包括：电解液的温度10-30℃，电压为10-100V，阳极氧化的时间为1-40分钟。
  4. 根据权利要求1所述的方法，其中，所述碱性蚀刻液为含有选自水溶性氢氧化物、水溶性碱性盐、氨、水溶性胺、肼以及一个或多个氢原子被烃基取代的肼衍生物中的一种或两种以上物质的水溶液。
  5. 根据权利要求4所述的方法，其中，所述水溶性氢氧化物选自碱金属氢氧化物，优选为氢氧化钠和/或氢氧化钾；和/或
    所述水溶性碱性盐选自水溶性碳酸盐、水溶性碳酸氢盐、水溶性磷酸盐、水溶性磷酸一氢盐、水溶性磷酸二氢盐和水溶性硼酸盐，优选选自Na2CO3、NaHCO3、NaH2PO4、Na2HPO4、Na3PO4和Na2B4O7；和/或
    所述水溶性胺选自乙二胺、二乙基胺、乙醇胺、三甲基胺、甲基胺和二甲基胺；和/或
    所述肼衍生物选自一甲基肼和1,1-二甲基肼。
  6. 根据权利要求1所述的方法，其中，所述碱性蚀刻液为碱性缓冲溶液。
  7. 根据权利要求1所述的方法，其中，所述碱性蚀刻液为含有水溶性氢氧化物以及水溶性碱性盐的水溶液，或者所述碱性蚀刻液为含有水溶性正盐以及水溶性酸式盐的水溶液，或者所述碱性蚀刻液为含有氨以及水溶性铵盐的水溶液。
  8. 根据权利要求7所述的方法，其中，所述水溶性氢氧化物为氢氧化钠和/或氢氧化钾；所述水溶性碱性盐为水溶性碳酸盐、水溶性碳酸氢盐、水溶性磷酸盐、水溶性磷酸一氢盐、水溶性磷酸二氢盐和水溶性硼酸盐中的一种或两种以上，优选为水溶性磷酸二氢盐，更优选为磷酸二氢钠、磷酸二氢钾、磷酸二氢铵和磷酸二氢铝中的一种或两种以上。
  9. 根据权利要求7所述的方法，其中，所述碱性蚀刻液为含有水溶性碳酸盐和水溶性碳酸氢盐的水溶液，或者为含有水溶性磷酸盐和水溶性磷酸一氢盐的水溶液。
  10. 根据权利要求7所述的方法，其中，所述水溶性铵盐为NH4Cl、(NH4)2SO4、NH4HCO3和NH4NO3中的一种或两种以上。
  11. 根据权利要求1和4-10中任意一项所述的方法，其中，所述碱性蚀刻液的pH值为10-13。
  12. 根据权利要求1所述的方法，其中，所述酸性蚀刻液为含有酸的水溶液，所述酸为氢卤酸和/或H3PO4，优选为HCl或H3PO4。
  13. 根据权利要求12所述的方法，其中，所述酸性蚀刻液还含有一种或两种以上水溶性盐，所述水溶性盐为水溶性氢卤酸盐和/或水溶性磷酸盐。
  14. 根据权利要求13所述的方法，其中，所述水溶性盐与所述酸的摩尔比为0.1-1:1。
  15. 根据权利要求1和12-14中任意一项所述的方法，其中，所述酸性蚀刻液的pH值为1-3。
  16. 根据权利要求1所述的方法，其中，所述碱性蚀刻液的温度为10-60℃，所述第一蚀刻的时间为1-60分钟；
    所述酸性蚀刻液的温度为20-30℃，所述第二蚀刻的时间为1-60分钟。
  17. 根据权利要求1-16中任意一项所述的方法，其中，进行所述第一蚀刻后形成的所述第一腐蚀孔的孔径不大于所述第二腐蚀孔的孔径，优选使得所述第一腐蚀孔的孔径在10-200nm的范围内，进行所述第二蚀刻后形成的所述第二腐蚀孔的孔径在200-2000nm的范围内。
  18. 根据权利要求1-17中任意一项所述的方法，其中，进行所述第一蚀刻后形成的所述第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.1-1:1的范围内，优选在0.5-1:1的范围内，更优选50％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；进行所述第二蚀刻后形成的所述第二腐蚀孔的深度在0.1-500μm的范围内，优选在10-400μm的范围内，更优选在50-200μm的范围内。
  19. 权利要求1-18中任意一项所述的方法制备的经表面处理的金属基材。
  20. 一种经表面处理的金属基材，所述金属为铝或铝合金，该金属基材包括金属基体以及附着在所述金属基体的至少部分表面上的阳极氧化膜层，所述金属基体包括基体层和腐蚀层，所述基体层与所述腐蚀层为一体结构，所述腐蚀层与所述阳极氧化膜层相接并为一体结构，所述阳极氧化膜层的表面分布有第一腐蚀孔，所述腐蚀层的表面分布有第二腐蚀孔，至少部分第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值为1:1。
  21. 根据权利要求20所述的经表面处理的金属基材，其中，所述第一腐蚀孔的深度与所述阳极氧化膜层的厚度的比值在0.1-1:1的范围内，优选在0.5-1:1的范围内，更优选50％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1:1；所述第二腐蚀孔的深度在0.1-500μm的范围内，优选在10-400μm的范围内，更优选在50-200μm的范围内。
  22. 根据权利要求20或21所述的经表面处理的金属基材，其中，所述第一腐蚀孔的孔径不大于所述第二腐蚀孔，所述第一腐蚀孔的孔径在10-200nm的范围内，所述第二腐蚀孔的孔径在200-2000nm的范围内。
  23. 根据权利要求20-22中任意一项所述的经表面处理的金属基材，其中，所述阳极氧化膜层的厚度为0.1-50μm。
  24. 根据权利要求20所述的经表面处理的金属基材，其中，所述基体层为致密层。
  25. 一种金属-树脂复合体，所述金属为铝或铝合金，该复合体包括金属基材以及附着在所述金属基材的至少部分表面上的树脂层，所述金属基材为权利要求19所述的经表面处理的金属基材或者权利要求20-24中任意一项所述的经表面处理的金属基材，所述树脂层中的部分树脂向下延伸并填充于所述金属基材的第一腐蚀孔和第二腐蚀孔中。
  26. 一种金属-树脂复合体的制备方法，该方法包括向权利要求19所述的经表面处理的金属基材或者权利要求20-24中任意一项所述的经表面处理的金属基材的表面注入含树脂的组合物并使部分组合物填充于第一腐蚀孔和第二腐蚀孔中，成型后形成树脂层。
  27. 一种由权利要求26所述的方法制备的金属-树脂复合体。
  28. 权利要求25或者权利要求27所述的金属-树脂复合体在制备电子产品壳体中的应用。
  29. 一种电子产品外壳，该外壳包括金属壳本体以及附着于所述金属壳本体的至少部分内表面和/或至少部分外表面的至少一个树脂件，其特征在于，所述金属壳本体为权利要求20-24中任意一项所述的经表面处理的金属基材。
  30. 一种电子产品外壳的制备方法，该方法包括在金属壳本体的至少部分内表面和/或至少部分外表面形成至少一个树脂件，其特征在于，采用权利要求26所述的方法形成所述树脂件。
PCT/CN2015/093243 2014-12-25 2015-10-29 经表面处理的金属基材和金属-树脂复合体及其制备方法和应用以及电子产品外壳及其制备方法 WO2016101703A1 (zh)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111893488A (zh) * 2020-08-04 2020-11-06 深圳市乾行达科技有限公司 蚀刻液及其制备方法
CN113667926A (zh) * 2021-07-19 2021-11-19 中国科学院宁波材料技术与工程研究所 一种铝合金表面碳基涂层制备方法及铝合金表面碳基涂层
US20220055346A1 (en) * 2018-04-20 2022-02-24 Taisei Plas Co., Ltd. Method for manufacturing a composite of aluminum alloy
CN114606560A (zh) * 2022-03-11 2022-06-10 东莞市慧泽凌化工科技有限公司 钛铝复合件的处理方法、钛铝复合件和树脂的结合体的制备方法及制品
CN114901458A (zh) * 2019-12-27 2022-08-12 Dic株式会社 复合结构体及其制造方法

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107385492A (zh) * 2016-05-17 2017-11-24 东莞市永宝金属表面处理材料有限公司 铝塑结合p处理工艺
CN107567221B (zh) * 2016-06-30 2019-11-22 比亚迪股份有限公司 一种壳体及其制备方法和应用
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CN107567217B (zh) * 2016-06-30 2019-11-22 比亚迪股份有限公司 一种壳体及其制备方法和应用
US11312048B2 (en) 2017-01-10 2022-04-26 Guangdong Everwin Precision Technology Co., Ltd. Surface treatment method of material, material product and composite material
CN108790012A (zh) * 2017-04-27 2018-11-13 优尔工业材料（廊坊）有限公司 铝基树脂复合材料及其制备方法
CN107177855B (zh) * 2017-05-18 2019-10-15 东莞市信成医疗器械科技有限公司 一种不锈钢表面处理方法及不锈钢塑胶复合体的制备方法
CN110438546B (zh) * 2019-08-21 2021-02-19 大连理工大学 一种在钛合金表面微弧氧化制备分级结构多孔涂层的电解液
CN111041478A (zh) * 2019-12-20 2020-04-21 深圳市裕展精密科技有限公司 金属制品、复合体及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103290450A (zh) * 2012-02-24 2013-09-11 比亚迪股份有限公司 一种铝合金树脂复合体的制备方法及铝合金树脂复合体
CN103286909A (zh) * 2012-02-24 2013-09-11 比亚迪股份有限公司 一种金属树脂一体化成型方法和一种金属树脂复合体
CN103448201A (zh) * 2012-05-28 2013-12-18 比亚迪股份有限公司 一种金属树脂复合体的制备方法及其制备的金属树脂复合体
CN103448202A (zh) * 2012-05-28 2013-12-18 比亚迪股份有限公司 一种金属树脂复合体的制备方法及其制备的金属树脂复合体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103290450A (zh) * 2012-02-24 2013-09-11 比亚迪股份有限公司 一种铝合金树脂复合体的制备方法及铝合金树脂复合体
CN103286909A (zh) * 2012-02-24 2013-09-11 比亚迪股份有限公司 一种金属树脂一体化成型方法和一种金属树脂复合体
CN103448201A (zh) * 2012-05-28 2013-12-18 比亚迪股份有限公司 一种金属树脂复合体的制备方法及其制备的金属树脂复合体
CN103448202A (zh) * 2012-05-28 2013-12-18 比亚迪股份有限公司 一种金属树脂复合体的制备方法及其制备的金属树脂复合体

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220055346A1 (en) * 2018-04-20 2022-02-24 Taisei Plas Co., Ltd. Method for manufacturing a composite of aluminum alloy
US11931988B2 (en) * 2018-04-20 2024-03-19 Taisei Plas Co., Ltd. Method for manufacturing a composite of aluminum alloy
CN114901458A (zh) * 2019-12-27 2022-08-12 Dic株式会社 复合结构体及其制造方法
CN111893488A (zh) * 2020-08-04 2020-11-06 深圳市乾行达科技有限公司 蚀刻液及其制备方法
CN113667926A (zh) * 2021-07-19 2021-11-19 中国科学院宁波材料技术与工程研究所 一种铝合金表面碳基涂层制备方法及铝合金表面碳基涂层
CN114606560A (zh) * 2022-03-11 2022-06-10 东莞市慧泽凌化工科技有限公司 钛铝复合件的处理方法、钛铝复合件和树脂的结合体的制备方法及制品

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