WO2018001130A1 - 壳体及其制备方法和应用 - Google Patents

壳体及其制备方法和应用 Download PDF

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Publication number
WO2018001130A1
WO2018001130A1 PCT/CN2017/088946 CN2017088946W WO2018001130A1 WO 2018001130 A1 WO2018001130 A1 WO 2018001130A1 CN 2017088946 W CN2017088946 W CN 2017088946W WO 2018001130 A1 WO2018001130 A1 WO 2018001130A1
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WO
WIPO (PCT)
Prior art keywords
aqueous solution
anodic oxide
resin film
film layer
metal hard
Prior art date
Application number
PCT/CN2017/088946
Other languages
English (en)
French (fr)
Inventor
孙剑
陈梁
赵桂网
吴英远
江向荣
邹云飞
Original Assignee
比亚迪股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 比亚迪股份有限公司 filed Critical 比亚迪股份有限公司
Priority to US16/314,362 priority Critical patent/US20190159352A1/en
Priority to JP2018568231A priority patent/JP2019522727A/ja
Priority to KR1020197002648A priority patent/KR20190022794A/ko
Priority to EP17819127.6A priority patent/EP3481164A4/en
Publication of WO2018001130A1 publication Critical patent/WO2018001130A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance 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
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04M—TELEPHONIC COMMUNICATION
    • H04M1/00—Substation equipment, e.g. for use by subscribers
    • H04M1/02—Constructional features of telephone sets
    • H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
    • H04M1/0279—Improving the user comfort or ergonomics
    • H04M1/0283—Improving the user comfort or ergonomics for providing a decorative aspect, e.g. customization of casings, exchangeable faceplate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K5/00—Casings, cabinets or drawers for electric apparatus
    • H05K5/02—Details
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14811—Multilayered 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/20—Acidic compositions for etching aluminium or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • 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
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • 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
    • C25D11/16—Pretreatment, e.g. desmutting
    • 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
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • 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
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K5/00—Casings, cabinets or drawers for electric apparatus
    • H05K5/0086—Casings, cabinets or drawers for electric apparatus portable, e.g. battery operated apparatus
    • 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
    • B29C2045/1486—Details, accessories and auxiliary operations
    • B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning
    • 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
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2081/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material
    • B29K2081/04—Polysulfides, e.g. PPS, i.e. polyphenylene sulfide or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B29K2705/02—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3481—Housings or casings incorporating or embedding electric or electronic elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids

Definitions

  • the present disclosure relates to the field of electronic communications, and in particular, to a housing, a method of manufacturing the housing, and a housing and housing prepared by the method as an outer casing of an electronic product.
  • the purpose of the present disclosure is to overcome the defects of inconsistent and discontinuous visual effects of the overall electronic product casing in the prior art, and to provide a casing and a preparation method and application thereof.
  • the present disclosure provides a case, wherein the case includes a metal hard anodic oxide layer and a resin film layer attached to a first surface of the metal hard anodic oxide layer, The metal hard anodic oxide layer is integrated with the resin film layer.
  • the present disclosure also provides a method of preparing a housing, the method comprising:
  • the metal substrate is subjected to a hard anodizing treatment to obtain a substrate having a metal hard anodic oxide on the surface;
  • the second composite is subjected to acid etching to remove the metal substrate in the matrix.
  • the present disclosure also provides a housing prepared by the method of the present disclosure.
  • the present disclosure also provides the use of the housing of the present disclosure as an outer casing for an electronic product.
  • the appearance of the housing provided by the present disclosure is neat, smooth, and uniform; and the metal hard anodic oxide layer can exhibit a metallic visual effect, thereby satisfying the consumer's demand for appearance effects.
  • both the metal hard anodic oxide layer and the resin film layer are non-metallic materials, and are all capable of being penetrated by radio frequency, and thus the housing of the present disclosure is used as an outer casing of an electronic product, particularly a communication device (such as a mobile phone). The case does not interfere with the communication function when the case is).
  • the housing of the present disclosure can mold the metal hard anodic oxide layer together with the resin film layer by injection molding, which makes it easier to realize the structural design of the electronic product outer casing and solve the problem of inconsistent appearance effect.
  • Figure 1 is a schematic cross-sectional view of a pretreated metal substrate
  • Figure 2 is a schematic cross-sectional view of a substrate subjected to hard anodization
  • Figure 3 is a schematic cross-sectional view of the first composite body completed by injection molding
  • FIG. 4 is a schematic cross-sectional view showing a second composite body of a metal hard anodic oxide on a surface of a substrate on which a resin film layer is not formed;
  • Figure 5 is a schematic cross-sectional view of a housing for removing a metal substrate
  • Figure 6 is a schematic cross-sectional view of the dyed casing.
  • the present disclosure provides a housing as shown in FIG. 5, wherein the housing includes a metal hard anodic oxide layer 5 and a resin film layer attached to the first surface of the metal hard anodic oxide layer 5. 3.
  • the metal hard anodic oxide layer 5 and the resin film layer 3 have an integral structure.
  • the term "integral structure” means that the metal hard anodic oxide layer 5 and the resin film layer 3 are bonded tightly and without gaps, and do not exhibit inconsistencies in appearance.
  • the metal hard anodic oxide layer 5 is formed by hard anodization of aluminum or an 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 hard anodic oxide layer 5 has a double-layered pore structure including an inner layer having a macroporous structure and an outer layer having a small pore structure, wherein The resin film layer 3 is bonded to the inner layer having a macroporous structure.
  • the macropores and the small holes may be used to accommodate a resin composition to anchor the resin film layer 3 to the surface of the metal hard anodic oxide layer 5 so that the two can be bonded tightly and without gaps. together.
  • "macroporous" and "small pore” are relative concepts, mainly for explaining that pore structures of different sizes are distributed in different portions of the metal hard anodic oxide layer 5.
  • the size of the large pores and small pores in the metal hard anodic oxide layer 5 is not particularly limited and may be a conventional choice in the art.
  • the macropores have a pore diameter of from 200 to 2000 nm, particularly from 500 to 1800 nm, for example from 1000 to 1500 nm; and the pores have a pore diameter of from 10 to 100 nm, particularly from 20 to 70 nm, for example from 30 to 60 nm.
  • the thickness of the metal hard anodic oxide layer 5 is not particularly limited and may be a conventional choice in the art. However, in order to optimize the space of the pore structure, the resin film layer 3 and the metal hard anodic oxide layer 5 have a higher bonding force, and optionally, the metal hard anodic oxide layer 5
  • the thickness is from 5 to 90 ⁇ m, in particular from 10 to 70 ⁇ m, for example from 12 to 45 ⁇ m.
  • the hardness of the metal hard anodic oxide layer 5 is not particularly limited and may be a conventional choice in the art. However, in order to enhance the performance of the housing, optionally, the hardness of the metal hard anodic oxide layer 5 It is 350-800HV, especially 450-600HV.
  • the composition of the resin film layer 3 is not particularly limited as long as the resin film layer 3 can be made resistant to acid and alkali, and the resin film layer 3 and the metal hard anodic oxide layer are provided. 5 has a high bonding force.
  • the resin film layer 3 is formed of a resin composition containing a thermoplastic resin and, optionally, a filler.
  • the content of the thermoplastic resin and the content of the filler in the resin composition are not particularly limited and may be a conventional choice in the art.
  • the resin composition contains 50 to 99% by weight of a thermoplastic resin and 1 to 50% by weight of a filler, in particular, the resin composition contains 60 to 75% by weight of a thermoplastic resin and 25 to 40% by weight. Filler.
  • the selection of the thermoplastic resin is not particularly limited and may be a conventional choice in the art.
  • the thermoplastic resin is at least one of polyphenylene sulfide, polyphenylene ether and polyamide, in particular polyphenylene sulfide.
  • the selection of the filler is not particularly limited and may be a conventional choice in the art.
  • the filler is a fibrous filler and/or a powder filler.
  • the selection of the fibrous filler is not particularly limited and may be a conventional choice in the art.
  • the fibrous filler is at least one of glass fibers, carbon fibers and polyamide fibers, in particular glass fibers.
  • the selection of the powder filler is not particularly limited and may be a conventional choice in the art.
  • the powder filler is at least one of silica, talc, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, glass and kaolin, especially silica, talc, and hydroxide. At least one of aluminum and magnesium hydroxide.
  • the thickness of the resin film layer 3 is not particularly limited and may be selected according to specific use requirements.
  • the thickness of the resin film layer 3 is 0.1-10 mm, particularly 0.2-8 mm.
  • it is 0.4-5mm.
  • the thickness of the resin film layer 3 means a vertical distance between the upper surface of the metal hard anodic oxide layer 5 to the upper surface of the resin film layer 3.
  • the casing may further include a dyeing layer 4 formed on the second surface of the metal hard anodic oxide layer 5.
  • the upper side faces the resin film layer 3.
  • the color of the dye layer 4 is not particularly limited, and may be selected according to needs and appearance effects, and may be, for example, silver, white, or gold.
  • the present disclosure also provides a method of preparing a housing, the method comprising:
  • the second composite is subjected to acid etching to remove the metal substrate 1 in the substrate.
  • the embodiment of the hard anodizing treatment is not particularly limited, and the metal substrate 1 may be subjected to hard anodizing treatment in a manner conventional in the art to obtain a surface having a metal hard anodic oxide. 2 matrix.
  • the metal substrate 1 may be placed in an electrolyte under the conditions of a hard anodizing treatment, the metal substrate 1 is used as an anode, and a conductive material that does not react with the electrolyte is used as a cathode to make the cathode and
  • the anodes are electrically connected to the positive and negative electrodes of the power source, respectively, and after being energized, a hard anodization treatment is performed to form a metal hard anodic oxide 2 on the surface of the metal substrate 1, as shown in FIG.
  • the conditions of the hard anodizing treatment are not particularly limited, and may be selected in accordance with the thickness of the intended metal hard anodic oxide 2.
  • the hard anodized condition comprises: a current density of 0.1-10A / dm 2, in particular 1.5-5A / dm 2; a temperature of 0-20 deg.] C, particularly 2-10 °C; time 1-300 min, especially 30-120 min; the concentration of the electrolyte is 10-260 g/L, especially 30-180 g/L.
  • the selection of the electrolyte in the electrolytic solution is not particularly limited and may be a conventional choice in the art, and may be, for example, at least one of sulfuric acid, oxalic acid, formic acid, and citric acid, particularly sulfuric acid and/or Oxalic acid, such as sulfuric acid and oxalic acid.
  • the concentration of sulfuric acid and oxalic acid in the electrolytic solution of the present disclosure is not particularly limited.
  • the concentration of sulfuric acid in the electrolyte is 25-225 g/L, especially 100-200 g/L, for example 150-180 g/L; concentration of oxalic acid It is 5-35 g/L, especially 10-25 g/L, for example 15-20 g/L.
  • the surface of the hard anodized substrate is reamed.
  • the condition of the reaming is such that the surface of the metal hard anodic oxide 2 forms a large pore having a pore diameter of 200 to 2000 nm, particularly 500 to 1800 nm, for example, 1000 to 1500 nm.
  • the process of reaming is performed in a pore-expanding agent
  • concentration of the pore-expanding agent is not particularly limited in the present disclosure, and may be a conventional choice in the art, and optionally, the pore-expanding agent
  • the concentration is from 0.1 to 40 g/L, especially from 10 to 20 g/L.
  • the selection of the pore-expanding agent in the present disclosure is not particularly limited as long as the purpose of the present invention is achieved.
  • the pore-expanding agent is an aqueous solution of sodium carbonate, an aqueous solution of sodium hydrogencarbonate, an aqueous solution of sodium hydroxide, an aqueous solution of potassium carbonate, and carbon.
  • Potassium hydrogen phosphate aqueous solution potassium hydroxide aqueous solution, sodium hydrogen phosphate aqueous solution, potassium hydrogen phosphate aqueous solution, sodium dihydrogen phosphate aqueous solution, potassium dihydrogen phosphate aqueous solution, sodium hydroxide-sodium hydrogen phosphate aqueous solution, potassium hydroxide-potassium hydrogen phosphate aqueous solution, At least one of an aqueous ammonia solution, an aqueous solution of hydrazine, an aqueous solution of an anthraquinone derivative, an aqueous solution of a water-soluble amine compound, an aqueous solution of ammonium-ammonium chloride, an aqueous solution of sodium phosphate-sodium hydrogen phosphate, and an aqueous solution of potassium phosphate-potassium hydrogen phosphate; At least one of an aqueous solution of sodium hydrogenhydride, an aqueous solution of potassium dihydrogen phosphate
  • the method for providing the metal substrate 1 may be: grinding the metal into a polishing machine, then washing with anhydrous ethanol, and then immersing the metal in a 40-60 g/L aqueous sodium hydroxide solution. After 1-5 min, the metal was taken out and rinsed with deionized water to obtain a metal substrate 1 having a clean and flat surface as shown in FIG.
  • the metal may be aluminum or an aluminum alloy.
  • the manner of forming the resin film layer 3 includes injection molding using a resin composition.
  • the resin composition is filled into the large pores and small pores of the metal hard anodic oxide 2, and a layer is formed on the surface of the metal hard anodic oxide 2 to be firmly bonded to the metal hard anodic oxide 2
  • the resin film layer 3 is as shown in FIG.
  • the composition of the resin composition is not particularly limited as long as the resin film layer 3 can be made resistant to acid and alkali, and between the resin film layer 3 and the metal hard anodic oxide 2 It has a high binding force.
  • the resin composition contains 50 to 99% by weight of a thermoplastic resin and 1 to 50% by weight of a filler, in particular, the resin composition contains 60 to 75% by weight of a thermoplastic resin and 25 to 40% by weight filler.
  • thermoplastic resin is not particularly limited and may be a conventional choice in the art, and may be, for example, at least one of polyphenylene sulfide, polyphenylene ether, and polyamide.
  • the selection of the filler is not particularly limited and may be a conventional choice in the art, and may be, for example, a fibrous filler and/or a powder filler.
  • the selection of the fibrous filler is not particularly limited and may be a conventional choice in the art, and may be, for example, at least one of glass fiber, carbon fiber, and polyamide fiber.
  • the selection of the powder filler is not particularly limited and may be a conventional choice in the art, and may be, for example, silica, talc, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, glass, and At least one of kaolin.
  • the alkaline etching is performed to remove the metal hard anodic oxide 2 on the surface of the substrate where the resin film layer 3 is not formed.
  • the first composite is placed in the etching solution A for alkaline etching, and after the alkaline etching is completed, it is taken out to obtain a second composite including the metal substrate 1, the metal hard anodic oxide layer 5, and the resin film layer 3.
  • the body was rinsed with deionized water to obtain a second composite as shown in FIG.
  • the concentration of the etching solution A used for the alkaline etching is not particularly limited as long as the metal hard anodic oxide 2 on which the resin film layer 3 is not formed on the surface of the substrate can be removed, optionally,
  • the concentration of the etching solution A used for the alkaline etching is 5 to 60 g/L, particularly 30 to 50 g/L.
  • the selection of the etching liquid A used for the alkaline etching is not particularly limited and may be a conventional choice in the art.
  • the etching solution A contains at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, particularly sodium hydroxide and/or potassium hydroxide, such as sodium hydroxide.
  • the conditions of the alkaline etching are not particularly limited as long as the metal hard anodic oxide 2 on which the resin film layer 3 is not formed on the surface of the substrate can be effectively removed.
  • the conditions of the alkaline etching include: a temperature of 20-80 ° C, especially 40-60 ° C; a time of 0.1-10 min, especially 0.5-3 min.
  • the acidic etching is performed to remove the metal substrate 1 in the substrate.
  • the second composite is placed in the etching solution B for acid etching, and after the acid etching is completed, it is taken out and rinsed with deionized water, and the obtained casing is as shown in FIG. 5.
  • the concentration of the etching liquid B used for the acidic etching is not particularly limited as long as the metal substrate 1 in the substrate can be removed.
  • the etching solution B used for the acidic etching has a concentration of 1-900 g/L, particularly 300-800 g/L.
  • the selection of the etching liquid B used for the acidic etching is not particularly limited, and optionally, the etching liquid B contains at least one of ferric chloride, hydrochloric acid, and copper chloride, particularly Ferric chloride and hydrochloric acid.
  • the etching liquid B is a mixture of ferric chloride and hydrochloric acid, the weight ratio of ferric chloride to hydrochloric acid is from 1:10 to 10:1.
  • the conditions of the acidic etching are not particularly limited and may be a conventional choice in the art.
  • the conditions of the acidic etching include: a temperature of 5 to 40 ° C, particularly 20 to 30 ° C; a time of 1 to 60 min, particularly 15 to 30 min.
  • the method may further include: low on the metal hard anodic oxide layer 5 in which the resin film layer 3 is not formed
  • the surface is dyed and sealed.
  • the dyeing process may be performed in a dye tank.
  • the color of the dye is not particularly limited in the present disclosure, and may be selected according to needs and appearance effects, for example, may be silver, white or gold, and the dyeing is completed.
  • the deionized water is rinsed, and the dyed casing is as shown in Fig. 6; the sealing process can be carried out in the sealing groove.
  • the present disclosure also provides a housing prepared by the method of the present disclosure.
  • the casing includes a metal hard anodic oxide layer 5 and a resin film layer 3, and the metal hard anodic oxide layer 5 and the resin film layer 3 have an integral structure.
  • the metal hard anodic oxide layer 5 has a double-layered pore structure including an inner layer having a macroporous structure and an outer layer having a small pore structure, wherein the resin film layer 3 has the same
  • the inner layers of the macroporous structure are joined together.
  • the casing is neat and tidy, Smooth and consistent.
  • the present disclosure also provides the use of the housing of the present disclosure as an outer casing for an electronic product.
  • the electronic product casing may be any electronic product (such as a communication device) housing that requires a metal as a casing, and may be, for example, a casing or a frame of the 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, at least one of a mobile phone, a portable computer (such as a notebook computer and a tablet), a smart watch, and a smart bracelet.
  • the electronic product housing is a mobile phone housing.
  • the phone case has an all-metal appearance, and the case is neat, smooth, consistent, continuous, and capable of being penetrated by radio frequency.
  • the thickness of the metal hard anodic oxide was measured using a metallographic microscope of the model Axio Imager Alm available from ZEISS;
  • the hardness of the metal hard anodic oxide was measured by a model HX-1000TM/LCD microhardness tester purchased from Shanghai Optical Instrument Factory No. 1;
  • the pore diameter of the pore was measured by a scanning electron microscope of JSM-7600F available from Nippon Denshi Co., Ltd. (five different positions of the same sample were observed, and the pore diameters of all the pores appearing in the visual field range were measured);
  • the aluminum alloy sheets in the following examples and comparative examples were purchased from South-South Aluminum Corporation.
  • This embodiment is for explaining a method of preparing a casing.
  • the aluminum alloy sheet was placed as an anode in a hard anodizing bath containing 150 g/L of sulfuric acid and 15 g/L of oxalic acid, and hardened at 6 ° C and a current density of 1.5 A/dm 2 .
  • the thickness of the metal hard anodic oxide was measured by a metallographic microscope, and the hardness of the metal hard anodic oxide was measured by a microhardness tester. The results are shown in Table 1;
  • the first aluminum alloy resin composite injected into the mold is placed in a 40 g/L sodium hydroxide aqueous solution, immersed at 40 ° C for 1 min, and then taken out and rinsed with deionized water, and the metal in the uninjected area is removed by alkaline etching.
  • a hard anodic oxide resulting in a second aluminum alloy resin composite comprising an aluminum alloy layer, a metal hard anodic oxide layer and a resin film layer, as shown in FIG. 4;
  • the alkaline etching of the second aluminum alloy resin composite is carried out by immersing in a mixture of 300 g/L of ferric chloride and hydrochloric acid (weight ratio of ferric chloride to hydrochloric acid is 1:1) for immersion in acidity Etching, the temperature is 30 ° C, the time is 18 minutes to etch away the aluminum alloy layer, after the acid etching is completed, rinse with deionized water to obtain a casing as shown in FIG. 5;
  • the acid-etched casing is placed in a dye tank of a suitable color for dyeing for 10 minutes, and after the dyeing is completed, it is washed with deionized water to obtain a casing as shown in FIG. 6;
  • This embodiment is for explaining a method of preparing a casing.
  • the first aluminum alloy resin composite injected into the sample is placed in a 30 g/L sodium hydroxide aqueous solution, immersed at 50 ° C for 0.5 min, then taken out and rinsed with deionized water, and subjected to alkaline etching to remove the uninjected area.
  • a metal hard anodic oxide resulting in a second aluminum alloy resin composite comprising an aluminum alloy layer, a metal hard anodic oxide layer and a resin film layer, as shown in FIG. 4;
  • the acid-etched casing is placed in a dye tank of a suitable color for dyeing for 10 minutes, and after the dyeing is completed, it is washed with deionized water to obtain a casing as shown in FIG. 6;
  • This embodiment is for explaining a method of preparing a casing.
  • the first aluminum alloy resin composite injected into the mold is placed in a 50 g/L sodium hydroxide aqueous solution, immersed at 60 ° C for 3 min, and then taken out and rinsed with deionized water to obtain an unetched area after alkaline etching.
  • a metal hard anodic oxide resulting in a second aluminum alloy resin composite comprising an aluminum alloy layer, a metal hard anodic oxide layer and a resin film layer, as shown in FIG. 4;
  • the acid-etched casing is placed in a dye tank of a suitable color for dyeing for 10 minutes, and after the dyeing is completed, it is washed with deionized water to obtain a casing as shown in FIG. 6;
  • This example is intended to illustrate a housing prepared when the pore-expanding agent is an aqueous ammonium-ammonium chloride solution.
  • the shell was prepared in the same manner as in Example 1, except that the pore-expanding agent in the step (3) was an ammonium-ammonium chloride aqueous solution.
  • the measurement results are shown in Table 1.
  • This example is intended to illustrate a housing that is prepared when the concentration of the pore expander is not within the optimum range but is within the broader scope of the present disclosure.
  • the shell was prepared in the same manner as in Example 1 except that the concentration of the pore-expanding agent in the step (3) was 5 g/L.
  • the measurement results are shown in Table 1.
  • This embodiment is for explaining a housing prepared without the step of reaming.
  • the shell was prepared in the same manner as in Example 1, except that the hole expanding process of the step (3) was not performed, that is, the substrate having the metal hard anodic oxide obtained on the surface obtained in the step (2) was directly subjected to the injection molding process of the step (4). .
  • the measurement results are shown in Table 1.
  • the hardness of the casing prepared by the method of the present disclosure reaches the requirement (hardness greater than 180 HV) which can be used as an outer casing of an electronic product.
  • the casing has a clean, smooth, uniform and continuous all-metal appearance effect, and the casing prepared by the method of the present disclosure passes the metal hard anode through the large hole and the small hole filling resin.
  • the oxide layer is tightly bonded to the resin film layer to improve the performance of the casing.

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Abstract

本公开涉及电子通信领域，公开了一种壳体及其制备方法和应用。该壳体包括金属硬质阳极氧化物层(5)和附着于该金属硬质阳极氧化物层(5)的第一表面上的树脂膜层(3)，所述金属硬质阳极氧化物层(5)与所述树脂膜层(3)为一体结构；制备方法包括：将金属基材(1)进行硬质阳极氧化处理，然后依次进行注塑和蚀刻。

Description

壳体及其制备方法和应用
相关申请的交叉引用
本申请主张在2016年6月30日在中国提交的中国专利申请号No.201610502640.1的优先权，其全部内容通过引用包含于此。
技术领域
本公开涉及电子通信领域，具体地，涉及壳体，壳体的制备方法，由该方法制备的壳体和壳体作为电子产品外壳的应用。
背景技术
为了满足通信功能需求，目前市场上大多数手机的外壳设计都是采用能够被无线射频穿透的非金属材料，例如，塑料、玻璃和陶瓷等。然而，金属从古到今都是人们喜爱的外观材料，因其漂亮的外观效果越来越多地被设计用于手机的外壳上，但是金属是一种不能被无线射频穿透的材料。为了同时满足消费者的外观需求和通信需求，现有技术通常把金属和塑料连接在一起同时用于外壳设计。但是，因为金属和塑料的外观效果不一样，导致手机外壳整体视觉效果不一致、不连续。
发明内容
本公开的目的是克服现有技术中电子产品外壳整体视觉效果不一致、不连续的缺陷，提供壳体及其制备方法和应用。
为了实现上述目的，本公开提供了一种壳体，其中，该壳体包括金属硬质阳极氧化物层和附着于该金属硬质阳极氧化物层的第一表面上的树脂膜层，所述金属硬质阳极氧化物层与所述树脂膜层为一体结构。
本公开还提供了一种壳体的制备方法，该方法包括：
提供金属基材，将所述金属基材进行硬质阳极氧化处理，得到表面具有金属硬质阳极氧化物的基体；
在所述基体的第一表面上形成树脂膜层，得到第一复合体；
将所述第一复合体进行碱性蚀刻，以去除所述基体表面上未形成树脂膜层的金属硬质 阳极氧化物，得到第二复合体，所述第二复合体包括金属基材、金属硬质阳极氧化物层和树脂膜层；
将所述第二复合体进行酸性蚀刻，以去除基体中的金属基材。
本公开还提供了由本公开所述的方法制备的壳体。
本公开还提供了本公开所述的壳体作为电子产品外壳的应用。
本公开提供的所述壳体的外观整洁、光滑、平整一致；并且，金属硬质阳极氧化物层能够表现出金属感的视觉效果，从而满足消费者对于外观效果的需求。而且，金属硬质阳极氧化物层和树脂膜层均为非金属材质，均能够被无线射频穿透，因而将本公开所述的壳体用作电子产品外壳特别是通讯设备的外壳(如手机外壳)时，该壳体不会妨碍通信功能。
另外，本公开所述的壳体可以通过注塑的方式将金属硬质阳极氧化物层与树脂膜层一起成型，这样更便于实现电子产品外壳的结构设计，并解决外观效果不一致的问题。
本公开的其它特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本公开的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本公开，但并不构成对本公开的限制。在附图中：
图1是经过前处理的金属基材的截面示意图；
图2是经过硬质阳极氧化处理的基体的截面示意图；
图3是完成注塑成型的第一复合体的截面示意图；
图4是去除未形成树脂膜层的基体表面上的金属硬质阳极氧化物的第二复合体的截面示意图；
图5是去除金属基材的壳体的截面示意图；
图6是染色后的壳体的截面示意图。
附图标记说明
1    金属基材；                2    金属硬质阳极氧化物；
3    树脂膜层；                4    染料层；
5    金属硬质阳极氧化物层。
具体实施方式
以下对本公开的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本公开，并不用于限制本公开。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本公开提供了一种壳体，如图5所示，其中，该壳体包括金属硬质阳极氧化物层5和附着于该金属硬质阳极氧化物层5的第一表面上的树脂膜层3，所述金属硬质阳极氧化物层5与所述树脂膜层3为一体结构。
在本公开中，术语“一体结构”是指金属硬质阳极氧化物层5和树脂膜层3是紧密地、无间隙地结合在一起，从外观上没有表现出不一致。
特别地，所述金属硬质阳极氧化物层5由铝或铝合金经过硬质阳极氧化形成。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。
根据本公开的一种实施方式，所述金属硬质阳极氧化物层5具有双层孔洞结构，该双层孔洞结构包括具有大孔结构的内层和具有小孔结构的外层，其中，所述树脂膜层3与所述具有大孔结构的内层结合在一起。所述大孔与所述小孔可以用于容纳树脂组合物，从而将所述树脂膜层3锚定在金属硬质阳极氧化物层5表面，使得二者能够实现紧密、无间隙地结合在一起。在本公开中，“大孔”和“小孔”是相对于的概念，主要为了说明所述金属硬质阳极氧化物层5中的不同部位分布有尺寸不一致的孔结构。
本公开中，对所述金属硬质阳极氧化物层5中的大孔和小孔的尺寸没有特别的限定，可以为本领域中常规的选择。但是，为了进一步提高所述树脂膜层3与所述金属硬质阳极氧化物层5之间的结合强度，并且不对所述金属硬质阳极氧化物层5本身的强度产生不利影响，可选地，所述大孔的孔径为200-2000nm，特别为500-1800nm，例如为1000-1500nm；所述小孔的孔径为10-100nm，特别为20-70nm，例如为30-60nm。
本公开中，对所述金属硬质阳极氧化物层5的厚度没有特别的限定，可以为本领域常规的选择。但是，为了优化孔洞结构的空间，使所述树脂膜层3与所述金属硬质阳极氧化物层5之间具有更高的结合力，可选地，所述金属硬质阳极氧化物层5的厚度为5-90μm，特别为10-70μm，例如12-45μm。
本公开中，对所述金属硬质阳极氧化物层5的硬度没有特别的限定，可以为本领域常规的选择。但是，为了增强所述壳体的性能，可选地，所述金属硬质阳极氧化物层5的硬度 为350-800HV，特别为450-600HV。
本公开中，对所述树脂膜层3的组分没有特别的限定，只要能使所述树脂膜层3耐酸碱，并使所述树脂膜层3与所述金属硬质阳极氧化物层5之间具有较高的结合力即可。可选地，所述树脂膜层3由含有热塑性树脂以及任选的填料的树脂组合物形成。
本公开中，对所述树脂组合物中热塑性树脂的含量和填料的含量没有特别的限定，可以为本领域常规的选择。可选地，所述树脂组合物含有50-99重量％的热塑性树脂和1-50重量％的填料，特别地，所述树脂组合物含有60-75重量％的热塑性树脂和25-40重量％的填料。
本公开中，对所述热塑性树脂的选择没有特别的限定，可以为本领域常规的选择。可选地，所述热塑性树脂为聚苯硫醚、聚苯醚和聚酰胺中的至少一种，特别为聚苯硫醚。
本公开中，对所述填料的选择没有特别的限定，可以为本领域常规的选择。可选地，所述填料为纤维填料和/或粉末填料。
本公开中，对所述纤维填料的选择没有特别的限定，可以为本领域常规的选择。可选地，所述纤维填料为玻璃纤维、碳纤维和聚酰胺纤维中的至少一种，特别为玻璃纤维。
本公开中，对所述粉末填料的选择没有特别的限定，可以为本领域常规的选择。可选地，所述粉末填料为二氧化硅、滑石粉、氢氧化铝、氢氧化镁、碳酸钙、碳酸镁、玻璃和高岭土中的至少一种，特别为二氧化硅、滑石粉、氢氧化铝和氢氧化镁中的至少一种。
本公开中，对所述树脂膜层3的厚度没有特别的限定，可以根据具体的使用要求进行选择，可选地，所述树脂膜层3的厚度为0.1-10mm，特别为0.2-8mm，例如为0.4-5mm。本公开中，所述树脂膜层3的厚度是指金属硬质阳极氧化物层5的上表面至所述树脂膜层3的上表面之间的垂直距离。
为了使所述壳体的外观效果更佳，如图6所示，所述壳体还可以包括染色层4，所述染色层4形成于所述金属硬质阳极氧化物层5的第二表面上，与所述树脂膜层3相对。本公开中，对所述染色层4的颜色没有特别的限定，可以根据需要及外观效果进行选择，例如可以为银色、白色或金色。
本公开还提供了一种壳体的制备方法，该方法包括：
提供金属基材1，将所述金属基材1进行硬质阳极氧化处理，得到表面具有金属硬质阳极氧化物2的基体；
在所述基体的第一表面上形成树脂膜层3，得到第一复合体；
将所述第一复合体进行碱性蚀刻，以去除所述基体表面上未形成树脂膜层3的金属硬质阳极氧化物2，得到第二复合体，所述第二复合体包括金属基材1、金属硬质阳极氧化物 层5和树脂膜层3；
将所述第二复合体进行酸性蚀刻，以去除基体中的金属基材1。
本公开中，对所述硬质阳极氧化处理的实施方式没有特别的限定，可以采用本领域常规的方式对所述金属基材1进行硬质阳极氧化处理从而得到表面具有金属硬质阳极氧化物2的基体。具体地，可以在硬质阳极氧化处理的条件下，将金属基材1置于电解液中，以所述金属基材1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，进行硬质阳极氧化处理，从而在所述金属基材1的表面上形成金属硬质阳极氧化物2，如图2所示。
本公开中，对所述硬质阳极氧化处理的条件没有特别的限定，可以根据预期的金属硬质阳极氧化物2的厚度进行选择。可选地，所述硬质阳极氧化处理的条件包括：电流密度为0.1-10A/dm2，特别为1.5-5A/dm2；温度为0-20℃，特别为2-10℃；时间为1-300min，特别为30-120min；电解液的浓度为10-260g/L，特别为30-180g/L。
本公开中，对所述电解液中的电解质的选择没有特别的限定，可以为本领域常规的选择，例如可以为硫酸、草酸、甲酸和柠檬酸中的至少一种，特别为硫酸和/或草酸，例如硫酸和草酸。
当电解液中的电解质为硫酸和草酸时，本公开对所述电解液中的硫酸和草酸的浓度没有特别的限定。可选地，当电解液中的电解质为硫酸和草酸时，所述电解液中的硫酸的浓度为25-225g/L，特别为100-200g/L，例如150-180g/L；草酸的浓度为5-35g/L，特别为10-25g/L，例如15-20g/L。
经过硬质阳极氧化处理后的金属基材1表面上形成金属硬质阳极氧化物2，所述金属硬质阳极氧化物2具有孔径为10-100nm的小孔，特别为20-70nm，例如30-60nm。根据本公开的一种实施方式，为了使后续形成的树脂膜层3与所述金属硬质阳极氧化物层5牢固结合，在所述硬质阳极氧化处理之后并且在形成树脂膜层3之前对经过硬质阳极氧化处理的基体的表面进行扩孔。
本公开中，所述扩孔的条件使得所述金属硬质阳极氧化物2的表面形成孔径为200-2000nm的大孔，特别为500-1800nm，例如1000-1500nm。
本公开中，所述扩孔的过程在扩孔剂中进行，本公开对所述扩孔剂的浓度没有特别的限定，可以为本领域常规的选择，可选地，所述扩孔剂的浓度为0.1-40g/L，特别为10-20g/L。
本公开对所述扩孔剂的选择没有特别的限定，只要能达到本公开的扩孔目的即可。可选地，所述扩孔剂为碳酸钠水溶液、碳酸氢钠水溶液、氢氧化钠水溶液、碳酸钾水溶液、碳 酸氢钾水溶液、氢氧化钾水溶液、磷酸氢钠水溶液、磷酸氢钾水溶液、磷酸二氢钠水溶液、磷酸二氢钾水溶液、氢氧化钠-磷酸氢钠水溶液、氢氧化钾-磷酸氢钾水溶液、氨水溶液、肼水溶液、肼衍生物水溶液、水溶性胺系化合物水溶液、铵-氯化铵水溶液、磷酸钠-磷酸氢钠水溶液和磷酸钾-磷酸氢钾水溶液中的至少一种；特别为磷酸二氢钠水溶液、磷酸二氢钾水溶液、氢氧化钠-磷酸氢钠水溶液和氢氧化钾-磷酸氢钾水溶液中的至少一种；例如磷酸二氢钠水溶液。
本公开中，所述的提供金属基材1的方法可以为：将金属放入抛光机内研磨，后用无水乙醇清洗，然后将金属浸渍在40-60g/L的氢氧化钠水溶液中，1-5min后取出金属，用去离子水冲洗，得到具有干净和平整的表面的金属基材1，如图1所示。所述金属可以为铝或铝合金。
本公开中，形成所述树脂膜层3的方式包括：采用树脂组合物进行注塑。树脂组合物填充到所述金属硬质阳极氧化物2的大孔和小孔中，并在所述金属硬质阳极氧化物2的表面形成一层与所述金属硬质阳极氧化物2牢固结合的树脂膜层3，如图3所示。
本公开中，对所述树脂组合物的组成没有特别的限定，只要能使所述树脂膜层3耐酸碱，并使所述树脂膜层3与所述金属硬质阳极氧化物2之间具有较高的结合力即可。可选地，所述树脂组合物含有50-99重量％的热塑性树脂和1-50重量％的填料，特别，所述树脂组合物含有60-75重量％的热塑性树脂和25-40重量％的填料。
本公开中，对所述热塑性树脂的选择没有特别的限定，可以为本领域常规的选择，例如可以为聚苯硫醚、聚苯醚和聚酰胺中的至少一种。
本公开中，对所述填料的选择没有特别的限定，可以为本领域常规的选择，例如可以为纤维填料和/或粉末填料。
本公开中，对所述纤维填料的选择没有特别的限定，可以为本领域常规的选择，例如可以为玻璃纤维、碳纤维和聚酰胺纤维中的至少一种。
本公开中，对所述粉末填料的选择没有特别的限定，可以为本领域常规的选择，例如可以为二氧化硅、滑石粉、氢氧化铝、氢氧化镁、碳酸钙、碳酸镁、玻璃和高岭土中的至少一种。
本公开中，所述的碱性蚀刻是为了去除基体表面上未形成树脂膜层3的金属硬质阳极氧化物2。具体地，将第一复合体放入蚀刻液A中进行碱性蚀刻，碱性蚀刻完成后取出，获得包括金属基材1、金属硬质阳极氧化物层5和树脂膜层3的第二复合体，并用去离子水冲洗，得到的第二复合体如图4所示。
本公开中，对所述碱性蚀刻所用的蚀刻液A的浓度没有特别的限定，只要能去除基体表面上未形成树脂膜层3的金属硬质阳极氧化物2即可，可选地，所述碱性蚀刻所用的蚀刻液A的浓度为5-60g/L，特别为30-50g/L。
本公开中，对所述碱性蚀刻所用的蚀刻液A的选择没有特别的限定，可以为本领域常规的选择。可选地，所述蚀刻液A含有氢氧化钠、氢氧化钾、碳酸钠中的至少一种，特别为氢氧化钠和/或氢氧化钾，例如氢氧化钠。
本公开中，对所述碱性蚀刻的条件没有特别的限定，只要能有效去除基体表面上未形成树脂膜层3的金属硬质阳极氧化物2即可。可选地，所述碱性蚀刻的条件包括：温度为20-80℃，特别为40-60℃；时间为0.1-10min，特别为0.5-3min。
本公开中，所述的酸性蚀刻是为了去除基体中的金属基材1。具体地，将第二复合体放入蚀刻液B中进行酸性蚀刻，酸性蚀刻完成后取出并用去离子水冲洗，得到的壳体如图5所示。
本公开中，对所述酸性蚀刻所用的蚀刻液B的浓度没有特别的限定，只要能去除基体中的金属基材1即可。可选地，所述酸性蚀刻所用的蚀刻液B的浓度为1-900g/L，特别为300-800g/L。
本公开中，对所述酸性蚀刻所用的蚀刻液B的选择没有特别的限定，可选地，所述蚀刻液B含有三氯化铁、盐酸、和氯化铜中的至少一种，特别为三氯化铁和盐酸。当所述蚀刻液B为三氯化铁和盐酸的混合物时，三氯化铁和盐酸的重量比为1:10至10:1。
本公开中，对所述酸性蚀刻的条件没有特别的限定，可以为本领域常规的选择。但是，为了有效去除基体中的金属基材1，所述酸性蚀刻的条件包括：温度为5-40℃，特别为20-30℃；时间为1-60min，特别为15-30min。
按照本公开的一种实施方式，为了除去表面孔洞以及改善由于蚀刻而引起的表面颜色变化，所述方法还可以包括：对未形成树脂膜层3的金属硬质阳极氧化物层5的低的表面进行染色和封孔。具体地，所述染色的过程可以在染料槽中进行，本公开对染料的颜色没有特别的限定，可以根据需要及外观效果进行选择，例如可以为银色、白色或金色，所述染色完成后用去离子水冲洗，染色后的壳体如图6所示；所述封孔的过程可以在封孔槽中进行。
本公开还提供了由本公开所述的方法制备的壳体。该壳体包括金属硬质阳极氧化物层5和树脂膜层3，所述金属硬质阳极氧化物层5与所述树脂膜层3为一体结构。所述金属硬质阳极氧化物层5具有双层孔洞结构，该双层孔洞结构包括具有大孔结构的内层和具有小孔结构的外层，其中，所述树脂膜层3与所述具有大孔结构的内层结合在一起。该壳体表观整洁、 光滑一致、连续。
本公开还提供了本公开所述的壳体作为电子产品外壳的应用。所述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(如通讯设备)外壳，例如可以为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，例如可以为智能表或智能手环。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至少一种。
特别地，所述电子产品外壳为手机壳体。该手机壳体具有全金属外观效果，壳体表观整洁、光滑一致、连续，并且能够被无线射频穿透。
以下将通过实施例对本公开进行详细描述。
以下实施例和对比例中，金属硬质阳极氧化物的厚度采用购自ZEISS的型号为Axio Imager Alm的金相显微镜测定；
金属硬质阳极氧化物的硬度采用购自上海光学仪器一厂的型号为HX-1000TM/LCD显微硬度计测定；
孔的孔径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(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孔的孔径)；
以下实施例和对比例中的铝合金板购自南南铝业公司。
实施例1
该实施例用于说明壳体的制备方法。
(1)将市售的1mm厚5052铝合金板，切成15mm*80mm的长方形片，将其放入抛光机内研磨，后用无水乙醇洗净，然后将铝合金基材浸渍在50g/L的氢氧化钠水溶液中，2min后取出用去离子水冲洗干净，得到如图1所示的经过前处理的铝合金片；
(2)将上述铝合金片作为阳极放入含有150g/L的硫酸和15g/L的草酸的硬质阳极氧化槽中，于6℃、电流密度为1.5A/dm2的条件下进行硬质阳极氧化30min，洗净吹干，得到如图2所示的表面具有金属硬质阳极氧化物的基体。用金相显微镜测定金属硬质阳极氧化物的厚度，用显微硬度计测定金属硬质阳极氧化物的硬度，结果如表1所示；
(3)在烧杯中配制10g/L磷酸二氢钠的100ml的水溶液，20℃的条件下，将步骤(2)所得基体浸泡其中进行扩孔，60min后将其取出，放入装有水的烧杯中浸泡1min，后将基体 吹干。用扫描电子显微镜测定金属硬质阳极氧化物中孔的孔径，结果如表1所示；
(4)将烘干后的基体插入注射成型模具中，注塑含有25wt％玻璃纤维和75wt％聚苯硫醚(PPS)的树脂组合物，脱模并冷却后得到牢固结合在一起的铝合金与树脂组合物的第一铝合金树脂复合体，如图3所示；
(5)将注塑好的第一铝合金树脂复合体放入40g/L的氢氧化钠水溶液中，40℃下浸渍1min后取出用去离子水冲洗干净，经过碱性蚀刻去除未注塑区域的金属硬质阳极氧化物，得到包括铝合金层、金属硬质阳极氧化物层和树脂膜层的第二铝合金树脂复合体，如图4所示；
(6)将经过碱性蚀刻的第二铝合金树脂复合体放入300g/L的三氯化铁和盐酸的混合液(三氯化铁和盐酸的重量比为1：1)中浸渍进行酸性蚀刻，温度为30℃，时间为18分钟蚀刻去除铝合金层，酸性蚀刻完成后用去离子水冲洗干净，得到如图5所示的壳体；
(7)将经过酸性蚀刻的壳体放入配好的颜色的染料槽中进行染色10min，染色完成后用去离子水洗干净，得到如图6所示的壳体；
(8)将经过染色的壳体放入封孔槽中进行封孔10min。
实施例2
该实施例用于说明壳体的制备方法。
(1)将市售的1mm厚5052铝合金板，切成15mm*80mm的长方形片，将其放入抛光机内研磨，后用无水乙醇洗净，然后将铝合金基材浸渍在40g/L的氢氧化钠水溶液中，1min后取出用去离子水冲洗干净，得到如图1所示的经过前处理的铝合金片；
(2)将上述铝合金片作为阳极放入含有160g/L的硫酸和18g/L的草酸的硬质阳极氧化槽中，于5℃、电流密度为3A/dm2的条件下进行硬质阳极氧化60min，洗净吹干，得到如图2所示的表面具有金属硬质阳极氧化物的基体。用金相显微镜测定金属硬质阳极氧化物的厚度，用显微硬度计测定金属硬质阳极氧化物的硬度，结果如表1所示；
(3)在烧杯中配制15g/L氢氧化钠-磷酸氢钠的100ml的水溶液，20℃的条件下，将步骤(2)所得基体浸泡其中进行扩孔，60min后将其取出，放入装有水的烧杯中浸泡1min，后将基体吹干。用扫描电子显微镜测定金属硬质阳极氧化物中孔的孔径，结果如表1所示；
(4)将烘干后的基体插入注射成型模具中，注塑含有35wt％玻璃纤维和65wt％聚苯醚的树脂组合物，脱模并冷却后得到牢固结合在一起的铝合金与树脂组合物的第一铝合金树脂复合体，如图3所示；
(5)将注塑好的第一铝合金树脂复合体放入30g/L的氢氧化钠水溶液中，50℃下浸渍0.5min后取出用去离子水冲洗干净，经过碱性蚀刻去除未注塑区域的金属硬质阳极氧化物，得到包括铝合金层、金属硬质阳极氧化物层和树脂膜层的第二铝合金树脂复合体，如图4所示；
(6)将经过碱性蚀刻的第二铝合金树脂复合体放入浓度为600g/l的三氯化铁和盐酸的混合液(三氯化铁和盐酸的重量比为2：1)中浸渍进行酸性蚀刻，温度为20℃，时间为15分钟蚀刻去除铝合金层，酸性蚀刻完成后用去离子水冲洗干净，得到如图5所示的壳体；
(7)将经过酸性蚀刻的壳体放入配好的颜色的染料槽中进行染色10min，染色完成后用去离子水洗干净，得到如图6所示的壳体；
(8)将经过染色的壳体放入封孔槽中进行封孔10min。
实施例3
该实施例用于说明壳体的制备方法。
(1)将市售的1mm厚5052铝合金板，切成15mm*80mm的长方形片，将其放入抛光机内研磨，后用无水乙醇洗净，然后将铝合金基材浸渍在60g/L的氢氧化钠水溶液中，5min后取出用去离子水冲洗干净，得到如图1所示的经过前处理的铝合金片；
(2)将上述铝合金片作为阳极放入含有180g/L的硫酸和20g/L的草酸的硬质阳极氧化槽中，于10℃、电流密度为5A/dm2的条件下进行硬质阳极氧化120min，洗净吹干，得到如图2所示的表面具有金属硬质阳极氧化物的基体。用金相显微镜测定金属硬质阳极氧化物的厚度，用显微硬度计测定金属硬质阳极氧化物的硬度，结果如表1所示；
(3)在烧杯中配制20g/L磷酸二氢钾的100ml的水溶液，20℃的条件下，将步骤(2)所得基体浸泡其中进行扩孔，60min后将其取出，放入装有水的烧杯中浸泡1min，后将基体吹干。用扫描电子显微镜测定金属硬质阳极氧化物中孔的孔径，结果如表1所示；
(4)将烘干后的基体插入注射成型模具中，注塑含有40wt％二氧化硅和60wt％聚苯硫醚(PPS)的树脂组合物，脱模并冷却后得到牢固结合在一起的铝合金与树脂组合物的第一铝合金树脂复合体，如图3所示；
(5)将注塑好的第一铝合金树脂复合体放入50g/L的氢氧化钠水溶液中，60℃下浸渍3min后取出用去离子水冲洗干净，得到经过碱性蚀刻去除未注塑区域的金属硬质阳极氧化物，得到包括铝合金层、金属硬质阳极氧化物层和树脂膜层的第二铝合金树脂复合体，如图4所示；
(6)将经过碱性蚀刻的第二铝合金树脂复合体放入浓度为800g/l的三氯化铁和盐酸的混合液(三氯化铁和盐酸的重量比为4：1)中浸渍进行酸性蚀刻，温度为25℃，时间为30分钟蚀刻去除铝合金层，酸性蚀刻完成后用去离子水冲洗干净，得到如图5所示的壳体；
(7)将经过酸性蚀刻的壳体放入配好的颜色的染料槽中进行染色10min，染色完成后用去离子水洗干净，得到如图6所示的壳体；
(8)将经过染色的壳体放入封孔槽中进行封孔10min。
实施例4
该实施例用于说明扩孔剂为铵-氯化铵水溶液时制备的壳体。
按照实施例1的方法制备壳体，不同的是，步骤(3)中扩孔剂为铵-氯化铵水溶液。测定结果如表1所示。
实施例5
该实施例用于说明扩孔剂的浓度不在最优范围内但在本公开较大范围内时制备的壳体。
按照实施例1的方法制备壳体，不同的是，步骤(3)中扩孔剂的浓度为5g/L。测定结果如表1所示。
实施例6
该实施例用于说明不经过扩孔的步骤制备的壳体。
按照实施例1的方法制备壳体，不同的是，没有步骤(3)的扩孔过程，即将步骤(2)得到的表面具有金属硬质阳极氧化物的基体直接进行步骤(4)的注塑过程。测定结果如表1所示。
表1
Figure PCTCN2017088946-appb-000001
Figure PCTCN2017088946-appb-000002
由以上实施例的结果可知，采用本公开所述方法制备的壳体的硬度达到了可以作为电子产品的外壳的要求(硬度大于180HV)。所述壳体作为电子产品的外壳时具有表面整洁光滑、平整一致且连续的全金属外观效果，并且，采用本公开所述方法制备的壳体通过大孔与小孔填充树脂将金属硬质阳极氧化物层与树脂膜层紧紧结合，提高壳体的性能。
以上详细描述了本公开的具体实施方式，但是，本公开并不限于上述实施方式中的具体细节，在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，这些简单变型均属于本公开的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本公开对各种可能的组合方式不再另行说明。
此外，本公开的各种不同的实施方式之间也可以进行任意组合，只要其不违背本公开的思想，其同样应当视为本公开所公开的内容。

Claims (19)

  1. 一种壳体，包括金属硬质阳极氧化物层(5)和附着于该金属硬质阳极氧化物层(5)的第一表面上的树脂膜层(3)，所述金属硬质阳极氧化物层(5)与所述树脂膜层(3)为一体结构。
  2. 根据权利要求1所述的壳体，其中，所述金属硬质阳极氧化物层(5)的厚度为5-90μm，优选为10-70μm，进一步优选为12-45μm；
    优选地，所述金属硬质阳极氧化物层(5)的硬度为350-800HV，进一步优选为450-600HV。
  3. 根据权利要求1或2所述的壳体，其中，所述金属硬质阳极氧化物层(5)具有双层孔洞结构，该双层孔洞结构包括具有大孔结构的内层和具有小孔结构的外层，其中，所述树脂膜层(3)与所述具有大孔结构的内层结合在一起。
  4. 根据权利要求3所述的壳体，其中，大孔的孔径为200-2000nm，小孔的孔径为10-100nm。
  5. 根据权利要求1或2所述的壳体，其中，所述金属硬质阳极氧化物层(5)由铝或铝合金经过硬质阳极氧化形成。
  6. 根据权利要求1所述的壳体，其中，所述树脂膜层(3)的厚度为0.1-10mm，优选为0.2-8mm，进一步优选为0.4-5mm。
  7. 根据权利要求1或6所述的壳体，其中，所述树脂膜层(3)由含有热塑性树脂以及任选的填料的树脂组合物形成；
    优选地，所述树脂组合物含有50-99重量％的热塑性树脂和1-50重量％的填料；
    优选地，所述热塑性树脂为聚苯硫醚、聚苯醚和聚酰胺中的至少一种；
    优选地，所述填料为纤维填料和/或粉末填料，进一步优选地，所述纤维填料为玻璃纤维、碳纤维和聚酰胺纤维中的至少一种，所述粉末填料为二氧化硅、滑石粉、氢氧化铝、氢 氧化镁、碳酸钙、碳酸镁、玻璃和高岭土中的至少一种。
  8. 根据权利要求1、2或6所述的壳体，其中，所述壳体还包括染色层(4)，所述染色层(4)形成于所述金属硬质阳极氧化物层(5)的第二表面上，与所述树脂膜层(3)相对。
  9. 一种壳体的制备方法，包括：
    提供金属基材(1)，将所述金属基材(1)进行硬质阳极氧化处理，得到具有金属硬质阳极氧化物的基体；
    在所述基体的第一表面上形成树脂膜层(3)，得到第一复合体；
    将所述第一复合体进行碱性蚀刻，以去除未形成树脂膜层(3)的基体表面上的金属硬质阳极氧化物(2)，得到第二复合体，所述第二复合体包括金属基材(1)、金属硬质阳极氧化物层(5)和树脂膜层(3)；
    将所述第二复合体进行酸性蚀刻，以去除所述基体中的金属基材(1)。
  10. 根据权利要求9所述的方法，其中，在所述硬质阳极氧化处理之后并且在所述基体的第一表面上形成树脂膜层(3)之前对所述基体的表面进行扩孔。
  11. 根据权利要求10所述的方法，其中，所述扩孔的过程在扩孔剂中进行，所述扩孔剂的浓度为0.1-40g/L；
    优选地，所述扩孔剂为碳酸钠水溶液、碳酸氢钠水溶液、氢氧化钠水溶液、碳酸钾水溶液、碳酸氢钾水溶液、氢氧化钾水溶液、磷酸氢钠水溶液、磷酸氢钾水溶液、磷酸二氢钠水溶液、磷酸二氢钾水溶液、氢氧化钠-磷酸氢钠水溶液、氢氧化钾-磷酸氢钾水溶液、氨水溶液、肼水溶液、肼衍生物水溶液、水溶性胺系化合物水溶液、铵-氯化铵水溶液、磷酸钠-磷酸氢钠水溶液和磷酸钾-磷酸氢钾水溶液中的至少一种；进一步优选为磷酸二氢钠水溶液、磷酸二氢钾水溶液、氢氧化钠-磷酸氢钠水溶液和氢氧化钾-磷酸氢钾水溶液中的至少一种；更优选为磷酸二氢钠水溶液。
  12. 根据权利要求9或10所述的方法，其中，所述硬质阳极氧化处理的条件包括：电流密度为0.1-10A/dm2，优选为1.5-5A/dm2；温度为0-20℃，优选为2-10℃；时间为1-300min， 优选为30-120min；电解液的浓度为10-260g/L，优选为30-180g/L；
    优选地，所述电解液中的电解质为硫酸、草酸、甲酸和柠檬酸中的至少一种，进一步优选为硫酸和/或草酸，更优选为硫酸和草酸；
    进一步优选地，当电解液中的电解质为硫酸和草酸时，所述电解液中的硫酸的浓度为18-200g/L，草酸的浓度为5-35g/L。
  13. 根据权利要求9或10所述的方法，其中，形成所述树脂膜层(3)的方式包括：采用树脂组合物进行注塑；
    优选地，所述树脂组合物含有50-99重量％的热塑性树脂和1-50重量％的填料；
    优选地，所述热塑性树脂为聚苯硫醚、聚苯醚和聚酰胺中的至少一种；
    优选地，所述填料为纤维填料和/或粉末填料，进一步优选地，所述纤维填料为玻璃纤维、碳纤维和聚酰胺纤维中的至少一种，所述粉末填料为二氧化硅、滑石粉、氢氧化铝、氢氧化镁、碳酸钙、碳酸镁、玻璃和高岭土中的至少一种。
  14. 根据权利要求9或10所述的方法，其中，所述碱性蚀刻所用的蚀刻液A的浓度为5-60g/L；
    优选地，所述蚀刻液A含有氢氧化钠、氢氧化钾和碳酸钠中的至少一种，进一步优选为氢氧化钠；
    优选地，所述碱性蚀刻的条件包括：温度为20-80℃，优选为40-60℃；时间为0.1-10min，优选为0.5-3min。
  15. 根据权利要求9或10所述的方法，其中，所述酸性蚀刻所用的蚀刻液B的浓度为1-200g/L；
    优选地，所述蚀刻液B含有三氯化铁、盐酸和氯化铜中的至少一种，进一步优选含有三氯化铁和盐酸；
    优选地，所述酸性蚀刻的条件包括：温度为5-40℃，优选为20-30℃；时间为1-60min，优选为15-30min。
  16. 根据权利要求9-15中任意一项所述的方法，还包括：对未形成所述树脂膜层(3)的所述金属硬质阳极氧化层(5)的第二表面进行染色和封孔。
  17. 由权利要求9-16中任意一项所述的方法制备的壳体。
  18. 权利要求1-8和17中任意一项所述的壳体作为电子产品外壳的应用。
  19. 根据权利要求18所述的应用，所述电子产品外壳为手机壳体。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10830264B2 (en) 2016-11-17 2020-11-10 Sb Ingenierie Sas Arrangement for fastening a panel in a slot using two opposite wedges

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110129854B (zh) * 2018-02-08 2021-07-09 华为技术有限公司 一种氧化膜的制备方法和终端设备
CN108866553A (zh) * 2018-05-30 2018-11-23 株洲航发橡塑制品有限公司 铝合金工件阳极化表面的超声波清洗工艺
CN110545343B (zh) * 2019-09-06 2021-12-31 广州三星通信技术研究有限公司 包括金属壳体的电子设备及其制造方法
EP4082746A4 (en) * 2019-12-27 2023-12-06 DIC Corporation COMPOSITE STRUCTURE AND ITS MANUFACTURING METHOD
US20230366118A1 (en) 2020-09-25 2023-11-16 Beijing Huayu Chuangxin Technologies Co., Ltd. Method for Manufacturing Colored Product and Mobile Phone shell
CN114889040B (zh) * 2022-01-18 2024-04-30 深圳市栢迪科技有限公司 复合齿轮的制造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0902105B1 (fr) * 1997-09-10 2003-12-03 Seb S.A. Revêtement multicouche antiadhérent à dureté améliorée pour support en aluminium, articles et ustensiles culinaires comportant ce revêtement
CN102111969A (zh) * 2009-12-25 2011-06-29 深圳富泰宏精密工业有限公司 电子装置壳体
CN105306628A (zh) * 2015-09-24 2016-02-03 广东欧珀移动通信有限公司 一种手机陶瓷壳制作工艺及手机陶瓷壳
CN105522783A (zh) * 2014-12-25 2016-04-27 比亚迪股份有限公司 经表面处理的金属基材和金属-树脂复合体及制备方法和应用和电子产品外壳及制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102098887B (zh) * 2009-12-14 2013-08-07 深圳富泰宏精密工业有限公司 电子装置壳体
CN102268183A (zh) * 2010-06-04 2011-12-07 鸿富锦精密工业（深圳）有限公司 铝或铝合金与塑料的复合体及其制作方法
TW201240560A (en) * 2011-03-24 2012-10-01 Hon Hai Prec Ind Co Ltd Electronic device housing and method of manufacturing the same
CN104790009B (zh) * 2014-01-16 2017-09-29 深圳富泰宏精密工业有限公司 金属与树脂的复合体的制备方法及由该方法制得的复合体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0902105B1 (fr) * 1997-09-10 2003-12-03 Seb S.A. Revêtement multicouche antiadhérent à dureté améliorée pour support en aluminium, articles et ustensiles culinaires comportant ce revêtement
CN102111969A (zh) * 2009-12-25 2011-06-29 深圳富泰宏精密工业有限公司 电子装置壳体
CN105522783A (zh) * 2014-12-25 2016-04-27 比亚迪股份有限公司 经表面处理的金属基材和金属-树脂复合体及制备方法和应用和电子产品外壳及制备方法
CN105306628A (zh) * 2015-09-24 2016-02-03 广东欧珀移动通信有限公司 一种手机陶瓷壳制作工艺及手机陶瓷壳

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3481164A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10830264B2 (en) 2016-11-17 2020-11-10 Sb Ingenierie Sas Arrangement for fastening a panel in a slot using two opposite wedges

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