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WO2018068625A1 - 金属树脂复合体及其制备方法和用途 - Google Patents

金属树脂复合体及其制备方法和用途 Download PDF

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Publication number
WO2018068625A1
WO2018068625A1 PCT/CN2017/102910 CN2017102910W WO2018068625A1 WO 2018068625 A1 WO2018068625 A1 WO 2018068625A1 CN 2017102910 W CN2017102910 W CN 2017102910W WO 2018068625 A1 WO2018068625 A1 WO 2018068625A1
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WO
WIPO (PCT)
Prior art keywords
slit
injection molding
metal
metal substrate
resin
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2017/102910
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English (en)
French (fr)
Inventor
吴英远
张国强
赵桂网
孙剑
陈梁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BYD Co Ltd
Original Assignee
BYD Co Ltd
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 BYD Co Ltd filed Critical BYD Co Ltd
Priority to EP17860354.4A priority Critical patent/EP3527346A1/en
Priority to US16/341,826 priority patent/US20190232538A1/en
Priority to KR1020197010497A priority patent/KR20190049840A/ko
Publication of WO2018068625A1 publication Critical patent/WO2018068625A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B29C45/16—Making multilayered or multicoloured articles
    • B29C45/1671—Making multilayered or multicoloured articles with an insert
    • 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
    • B29C45/14336—Coating a portion of the article, e.g. the edge of the article
    • B29C45/14344—Moulding in or through a hole in the article, e.g. outsert moulding
    • 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
    • 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
    • B29C45/14336—Coating a portion of the article, e.g. the edge of the article
    • 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
    • B29C45/0003—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor of successively moulded portions rigidly joined to each other
    • 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
    • B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
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    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0053—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor combined with a final operation, e.g. shaping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • 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
    • B29C45/1418—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 inserts being deformed or preformed, e.g. by the injection pressure
    • 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
    • B29C45/14336—Coating a portion of the article, e.g. the edge of the article
    • B29C45/14409—Coating profiles or strips by injecting end or corner or intermediate parts
    • 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
    • B29C45/16—Making multilayered or multicoloured articles
    • B29C45/1642—Making multilayered or multicoloured articles having a "sandwich" structure
    • B29C45/1643—Making multilayered or multicoloured articles having a "sandwich" structure from at least three different materials or with at least four layers
    • 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
    • B29C45/16—Making multilayered or multicoloured articles
    • B29C45/1657—Making multilayered or multicoloured articles using means for adhering or bonding the layers or parts to each other
    • 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
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/76—Measuring, controlling or regulating
    • B29C45/78—Measuring, controlling or regulating of temperature
    • 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
    • B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
    • 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
    • B29C45/0053—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor combined with a final operation, e.g. shaping
    • B29C2045/0079—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor combined with a final operation, e.g. shaping applying a coating or covering
    • 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
    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76—Measuring, controlling or regulating
    • B29C2945/76494—Controlled parameter
    • B29C2945/76531—Temperature
    • 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
    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76—Measuring, controlling or regulating
    • B29C2945/76494—Controlled parameter
    • B29C2945/76551—Time
    • 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
    • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
    • B29K2101/12—Thermoplastic materials
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • 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
    • B29K2507/00—Use of elements other than metals as filler
    • B29K2507/04—Carbon
    • 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
    • B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
    • B29K2509/08—Glass
    • 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
    • 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
    • B29L2031/3406—Components, e.g. resistors
    • 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
    • B29L2031/3456—Antennas, e.g. radomes

Definitions

  • the present disclosure relates to the field of materials science, and in particular to a metal resin composite, a method of preparing the metal resin composite, a personal electronic device casing and a personal electronic device including the metal resin composite, and a metal resin composite. Machined parts.
  • the metal casing For various portable electronic communication devices such as mobile phones, notebook computers, and tablet computers, the metal casing has a more beautiful appearance and better texture than the plastic casing, and has better wear resistance and compression resistance. Therefore, metal is used.
  • As a casing for electronic communication equipment it is a trend in the future.
  • the existing antenna technology restricts the development of this trend. Because metals have electromagnetic shielding, many manufacturers still choose plastic casings as electronic communication equipment casings, and some manufacturers use plastic strips to block metal technology to avoid shielding electromagnetic signals.
  • the plastic strips are wider, generally have a width of 1 to 2 mm, and the appearance of metal and plastic is different. From the external light, the entire metal shell is divided into a plurality of wide plastic strips. Block, no appearance integration effect.
  • a fine slit (width less than 1 mm) obtained by precision machining in the metal back shell and a glue filling the slit to obtain an antenna structure capable of releasing an electromagnetic signal, which can obtain a good appearance integration effect, but sacrifices
  • the bonding strength of the structure at the antenna (bonding strength is less than 15 MPa).
  • the purpose of the present disclosure is to provide a preparation method which uses a precision processing method to process a slit, and the slit can improve the visual effect of the appearance of the metal back shell; using a PMH (ploymer metal hybrid) technique to perform a secondary injection molding process to obtain a high A slit of strength (not less than 30 MPa) and a bonding effect.
  • PMH ploymer metal hybrid
  • the present disclosure provides a metal resin composite, the metal resin composite
  • the metal substrate includes an upper surface having at least one upper surface slit, and a lower surface of the metal substrate has at least one lower surface groove at a position opposite to the upper surface slit, the upper surface
  • the surface slit is in communication with the lower surface groove;
  • the upper surface slit is injection-molded with a first injection molding resin
  • the lower surface groove is injection-molded with a second injection molding resin
  • the first injection molding resin and The second injection molding resin is selected from the same or different injection molding resins, and the second injection molding resin in the lower surface groove constitutes a lower surface support structure capable of supporting the first injection molding resin.
  • the present disclosure provides a method of preparing a metal resin composite, wherein the method comprises:
  • the first injection molding resin and the second injection molding resin are selected from the same or different injection molding resins.
  • the present disclosure provides a metal resin composite prepared by the method as described above.
  • the present disclosure also provides a personal electronic device housing containing the metal resin composite as described above.
  • the present disclosure also provides a personal electronic device comprising a personal electronic device core component and a personal electronic device housing as described above.
  • the present disclosure also provides a metal resin composite workpiece, the metal resin composite workpiece comprising a metal substrate, the upper surface of the metal substrate having at least one upper surface slit, the upper surface The bottom of the slit has at least one vent opening that is open on the lower surface of the metal substrate.
  • the present disclosure adopts the method of precision machining and overmolding, that is, firstly processing the area of the slit on the outer surface of the substrate, and then performing the first PMH injection molding, and then milling the metal substrate under the slit. Leave a space and perform a second PMH injection to fill the vacant space.
  • the vent hole is machined to the metal substrate, and the vent hole and the slit are completely penetrated.
  • Such an exhaust structure is advantageous for the metal casing to vent the slag during the injection molding process, and enhance the bonding force between the metal and the plastic.
  • the metal-resin composite can make the electronic product more aesthetically pleasing as well as obtaining high strength. Metal composites and improve the yield of processing.
  • FIG. 1 is a cross-sectional view of a slit of a casing obtained by the present disclosure.
  • Figure 2 is an optical microscopic analysis of the metal composite of the embodiment, with a magnification of 200 times.
  • orientation words such as "up, down, left, and right” as used generally refer to the direction of the drawing as shown in FIG. 1 without the contrary.
  • the inner surface of the metal resin composite is defined as a surface of the metal casing facing the inside of the communication device when the metal resin composite is used in a metal casing of a communication device.
  • the outer surface of the metal casing is defined as the surface of the metal casing facing the outside when it is used in a communication device.
  • the present disclosure provides a metal resin composite including a metal substrate having an upper surface having at least one upper surface slit, and a lower surface of the metal substrate at the upper surface
  • the opposite positions of the slit have at least one lower surface groove, the upper surface slit and the lower surface groove communicate with each other;
  • the upper surface slit is injection molded with a first injection molding resin, and the lower surface groove
  • Medium injection molding has a second injection molding resin, the first injection molding resin and the second injection molding resin are selected from the same or different injection molding resins, and the second injection molding resin in the lower surface groove
  • a lower surface support structure capable of supporting the first injection molding resin.
  • the opposite position of the upper surface slit refers to a position at which the upper surface slit is projected on the lower surface of the metal resin composite.
  • the upper surface slit is shown in the "slit region", and the "slit region” is referred to as the antenna on the casing and the electronic device. Corresponding area.
  • the size of the "slit area” those skilled in the art can appropriately select according to the setting range of the antenna of the electronic device.
  • an interface may be observed between the first injection molding resin in the upper surface slit and the second injection molding resin in the lower surface groove.
  • the interface between the first injection molding resin and the second injection molding resin can be observed on the cut surface by a naked eye or a microscope, for example, as shown in Fig. 2, the interface may be formed by a difference in the injection molding order or the specific molding parameters of the injection molding.
  • the upper surface of the metal substrate may have at least one upper surface slit group, the upper surface slit group may include at least two upper surface slits; and at least two upper surface narrowities in the upper surface slit group
  • the slits may be in communication with the lower surface support structure, respectively.
  • the size of the upper surface slit may be a size commonly used in the art, for example, the depth of the upper surface slit may be 0.1-3 mm, optionally 0.1-1.5 mm, and the thickness of the metal substrate may be It is 0.1-9mm.
  • the upper surface slit may have a width of 0.05 mm to 1 mm; the upper surface slit may have a length of 2 to 300 mm, optionally 60 to 150 mm; between two adjacent upper surfaces and parallel slits
  • the spacing can be from 0.1 to 30 mm, optionally from 0.5 to 15 mm.
  • the upper surface of the metal substrate may have at least two upper surface slit groups. Further, the number and shape of the slits are not particularly limited as long as communication can be realized.
  • the upper surface slits may be parallel or intersect with each other, and the shape of the upper surface slit may be linear, wavy or zigzag, and the cross-sectional shape of the upper surface slit may be rectangular or trapezoidal.
  • the material of the metal substrate may be any conventional metal material that can be used for the outer casing of the electronic device, for example, at least one selected from the group consisting of aluminum, magnesium, iron, titanium, titanium alloy, aluminum alloy, and stainless steel.
  • the injection molding resin has no special requirements, and may be selected, for example, from polyethylene, polypropylene, polyacetal, polystyrene, modified polyphenylene ether, polyethylene terephthalate, polyterephthalic acid.
  • magnesium polycarbonate, polyamide, and acrylonitrile-butadiene-styrene copolymers.
  • the metal resin composite may further include a decorative layer covering the upper surface of the metal substrate and the opening of the upper surface slit for aesthetic purposes.
  • the decorative layer may be selected from at least one of an anodized layer, a micro-arc oxidation layer, an electrophoretic layer and a spray coating.
  • the coating may have a thickness of 5 to 60 ⁇ m.
  • the injection molding resin may further contain a filler, and the filler is glass fiber and/or carbon fiber.
  • the strength of the injection molding resin can be further enhanced.
  • the filler may be contained in an amount of 10 to 50% by weight based on the total weight of the injection molding resin.
  • the present disclosure also provides a method of preparing a metal resin composite, wherein the method comprises:
  • the first injection molding resin and the second injection molding resin are selected from the same or different injection molding resins.
  • the above method adopts a method of precision machining and double injection molding, that is, first processing a vent hole in a metal substrate at a region where a slit is processed on the outer surface of the substrate, and the vent hole and the slit are completely penetrated, such an exhaust structure, Conducive to the metal shell in the injection process of the slit exhaust slag, enhance the bonding of metal and plastic, and then use a single injection, and then mill the metal substrate under the slit, leaving vacancies, and secondary injection Filling the milled vacancies, the metal-resin composite makes the overall electronic product more aesthetic, while obtaining a high-strength metal composite and improving the yield of the processing.
  • the method further includes: after step S5, performing the operation of step S6:
  • step S1 at least one upper surface slit group may be processed on the upper surface of the metal substrate, the upper surface slit group may include at least two upper surface slits; and, in step S4, the At least two upper surface slits in the upper surface slit group are respectively in communication with the lower surface support structure.
  • the thickness of the metal substrate may be 0.1-9 mm, and the processing conditions are such that the depth of the upper surface slit is 0.1-3 mm, and the width of the upper surface slit may be 0.05 mm-1 mm; It is also possible that the length of the upper surface slit may be 2-300 mm, optionally 60-150 mm; and the spacing between adjacent two parallel surfaces of the upper surface may be 0.1-30 mm. Choose 0.5-15mm.
  • the processing conditions may be such that the upper surface of the metal substrate has at least two upper surface slit groups;
  • the upper surface slits may be parallel or intersect with each other, and the shape of the upper surface slit may be linear, wavy or zigzag, and the cross-sectional shape of the upper surface slit may be rectangular or trapezoidal.
  • the size of the area of the slit can be appropriately selected by those skilled in the art according to the setting range of the antenna of the communication device.
  • the vent hole is processed on the metal substrate, and the number of the vent holes is one or more groups, and the vent hole may be a rectangle, a polygon, an ellipse. Shape or other shape, the distance between the vent holes may be the same or different, and the vent hole and the slit are completely penetrated.
  • Such an exhaust structure is beneficial to the slit venting of the metal casing during the injection molding process, and the metal base is reinforced. The combination of materials and plastics.
  • the air holes may have a rectangular shape, the air hole length may be 3-10 mm, the width may be 0.8-5 mm, and the vent hole spacing may be 3-20 mm, optionally, the air hole length is 4-6 mm, and the width is 0.8- 1.5mm, vent spacing 8-14mm.
  • the ratio of the total area of the bottom of the upper surface slit to the total opening area of the vent hole at the bottom of the surface slit may be 100: (0.5-10).
  • the material of the metal substrate is selected from at least one of aluminum, magnesium, iron, titanium, titanium alloy, aluminum alloy and stainless steel;
  • the injection molding resin may be selected from the group consisting of polyethylene, polypropylene, polyacetal, and poly Styrene, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polyimide, polyamide One or more of imide, polyetherimide, polysulfone, polyethersulfone, polyetherketone, polyetheretheroxide, polycarbonate, polyamide, and acrylonitrile-butadiene-styrene copolymerkind.
  • the conditions of the first injection molding and the conditions of the second injection molding may independently include: a mold temperature of 50-310 ° C, a nozzle temperature of 200-450 ° C, a dwell time of 1-50 s, and an injection.
  • the pressure is 50-300 MPa
  • the injection time is 1-30 s
  • the cooling time is 1-60 s.
  • the conditions of the first injection molding and the conditions of the second injection molding may be such that the thickness of the formed resin is 0.4-10 mm.
  • processing the upper surface slit, processing the vent hole, and processing the lower surface groove are independently performed by laser processing, electron beam processing, water cutting processing, CNC processing, and etching processing. At least one of the completions.
  • the specific operations and conditions are commonly used in the prior art.
  • the laser cutting conditions are: power of 50-200 W, cutting speed of 10-5000 mm/s, laser frequency of 10 -200kHz, output wavelength is 250-1064nm.
  • the slit width formed by the above laser cutting method is usually from 10 to 100 ⁇ m.
  • the electron beam cutting method is: cutting in a vacuum of 10 -3 -10 -4 Pa in a current of 5-10 mA and a power density of 10 6 -10 8 W/cm 2 . .
  • the slit width formed by the above electron beam cutting method is usually from 30 to 150 ⁇ m.
  • the conditions of the CNC machining are: feed rate: 200-600 mm/min; feed amount: 10-40 ⁇ m. Pass
  • the slit width formed by the above-described method of CNC machining is usually 0.2 mm to 1 mm.
  • the metal substrate can be pretreated.
  • the pretreatment is a pretreatment process performed on a metal surface commonly used by those skilled in the art, and generally includes mechanical grinding or grinding to remove foreign matter on the surface, and then degreasing and cleaning the processing oil adhered to the metal surface.
  • the pretreatment comprises abrading the metal substrate, for example; using a 100-600 mesh sandpaper or placing it in a polishing machine to sand the metal substrate such that the metal substrate produces micron-sized holes or pits. Then, the steps of degreasing, first water washing, alkali washing, second water washing, neutralization, third water washing, etc.
  • the metal is cleaned in ultrasonic waves by various reagents commonly used by those skilled in the art, and the cleaning time is 10 min-2 h, and the removal is performed.
  • the metal oil is preferentially washed with detergent, and then immersed in an aqueous solution of 30-70 g/L of sodium hydroxide at a temperature of 50-80 ° C for alkali etching. After 1-10 minutes, it is taken out and rinsed with deionized water. Treatment can increase the surface roughness of the metal substrate.
  • a plurality of micropits can be provided on at least the inner surface of the slit region of the metal substrate, so that the tightness of the obtained plastic layer and metal can be injected.
  • the first injection molding and the second injection molding may be performed by PMH technology.
  • the PMH technology is a polymer metal combined forming technology, generally refers to a metal substrate, a large number of nano-etching holes and micro-corrosion holes are formed on the metal surface, and a melt of a polymer material is injected on the surface thereof, and the melt is along the space. Gradually fill, and enter the nanopore and micropores, gradually cooled, complete the filling with the appropriate parameters and combine with the matrix to form a metal composite structure.
  • the nano-etching holes of the metal surface can be obtained by chemical or electrochemical methods, the pore size of the nano-pore is 10-100 nm, and the depth of the etching hole is 1 ⁇ m-10 ⁇ m.
  • the aluminum alloy metal is preferentially placed as an anode in an anodizing bath containing 20% by weight of sulfuric acid, and the aluminum alloy is electrolytically etched at a voltage of 16 V at 18 ° C for 8 minutes, washed with water, and baked at a temperature of 80 ° C. 5 minutes.
  • the injection molding direction of the first injection molding may be to inject a first injection molding resin perpendicular to the surface of the metal substrate, so that the first injection molding resin enters the upper surface slit from top to bottom.
  • the injection molding direction of the second injection molding may be to inject a second injection molding resin parallel to the lower surface of the metal substrate, such that the second injection molding resin enters the lower surface concave along the direction of the lower surface of the metal substrate. groove.
  • the method of forming the decorative layer may include at least one of anodization, micro-arc oxidation, electrophoresis, and spray coating.
  • the anodizing condition may be a condition known in the art, for example, a sulfuric acid having a concentration of 150-210 g/L as a bath, a voltage of 10-25 V, a current density of 1-2 A/dm 2 , and a temperature of 10
  • the anodic oxidation time is -20 ° C
  • the sealing time is 20-60 min
  • the sealing liquid component such as NiSO 4 aqueous solution
  • the sealing temperature is 50-95 ° C
  • the sealing time is 10-50 min.
  • the thickness of the decorative layer formed by the above anodizing method is usually 5 to 50 ⁇ m.
  • the micro-arc oxidation conditions may be under conditions known in the art, for example, pH 6-12, voltage 0-800V, current density 1-10 A/dm 2 , temperature 15-60 ° C, time 10 -60min, the sealing liquid is pure water, the sealing temperature is 70-90 ° C, and the sealing time is 1-10 min.
  • the thickness of the decorative layer formed by the above micro-arc oxidation method is usually from 10 to 50 ⁇ m.
  • the electrophoresis conditions may be under conditions known in the art, for example, cathodic electrophoresis: voltage is 20-60 V, pH is 4-6, temperature is 15-30 ° C, time is 20-60 s; anodic electrophoresis: voltage is 40 -100V, pH 6-8, temperature 15-30 ° C, time 40-90 s; baking temperature 120-200 ° C, baking time 30-60 min.
  • the thickness of the decorative layer formed by the above electrophoresis method is usually from 5 to 35 ⁇ m.
  • the decorative layer is formed by spraying, and the spraying conditions may be conditions known in the art, for example, may be: electrostatic high pressure: 60-90 kV; electrostatic current: 10-20 ⁇ A; flow rate pressure: 0.3-0.55 Mpa; atomization pressure: 0.33-0.45 Mpa; conveying speed: 4.5-5.5 m/min; curing temperature: 150-220 ° C; curing time: 30-180 min.
  • the thickness of the decorative layer formed by the above spraying is usually from 10 to 60 ⁇ m.
  • the injection molding resin further contains a filler.
  • the filler may be glass fibers and/or carbon fibers.
  • the filler may be included in an amount of 10 to 50% by weight based on the total weight of the injection molding resin.
  • the filler may be incorporated into the injection molding resin by a method conventional in the art, for example, by screw extrusion into the injection molding resin, and then injection molding.
  • the present disclosure also provides a metal resin composite prepared by the method described.
  • the present disclosure also provides a personal electronic device housing containing the metal resin composite as described above.
  • the present disclosure also provides a personal electronic device comprising a personal electronic device core component and a personal electronic device housing as described above.
  • the present disclosure also provides a metal resin composite workpiece, the metal resin composite workpiece comprising a metal substrate, the upper surface of the metal substrate having at least one upper surface slit, the upper surface The bottom of the slit has at least one vent opening that is open on the lower surface of the metal substrate.
  • the metal resin composite workpiece can be used as a semi-finished product in the processing of the metal resin composite.
  • the precision CNC is used to machine the slit on the outer surface of the aluminum alloy.
  • the aluminum alloy material is 6013 and the thickness is 5.1 mm.
  • Two sets of slits were machined, the cutter head diameter was 0.35 mm, the machining speed was 300 r/min, and the machining speed was 0.2 mm/min.
  • the metal substrate under the slit is milled to obtain five sets of venting holes, the air holes are connected with the slit, the air hole length is 4.4 mm, the width is 1.1 mm, and the vent hole spacing is 10 mm.
  • the obtained outer casing was subjected to PMH injection molding, and PBT resin containing 40% glass fiber was injection-molded as a plastic support member to obtain a reinforced outer casing A12.
  • the mold temperature is 140 ° C
  • the nozzle temperature is 260 ° C
  • the dwell time is 15 s
  • the injection pressure is 120 MPa
  • the injection time is 1 s
  • the cooling time is 15 s
  • the thickness of the formed resin is 1.1 mm.
  • Milling the metal substrate under the slit leaves some vacancies with a vacancy length of 77 mm and a depth of 4 mm. Then, the above vacancies were subjected to secondary PMH injection molding, and PBT resin containing 40% glass fiber was injected.
  • the injection molding conditions were mold temperature 140 ° C, nozzle temperature: 260 ° C, dampening time: 12 s, injection pressure: 115 MPa, injection time: 0.8. s, the cooling time was 12 s, and the thickness of the formed resin was 2.1 mm.
  • the outer casing A13 of the overmolded reinforcement is obtained.
  • the outer casing A13 reinforced by the injection molding support is subjected to alkali etching, water washing, pickling, and water washing to remove surface grease and impurities, and then immersed in an electrolytic bath having a sulfuric acid concentration of 180 g/L H 2 SO 4 aqueous solution, using A13 as an anode, and stainless steel.
  • the plate was used as a cathode, and was anodized for 45 min under the conditions of a voltage of 14 V, a current density of 1 A/dm 2 and a temperature of 11 ° C. After anodizing, it was taken out and ultrasonically cleaned for 10 min to prevent the acid from being affected by the slit at the slit. An anodized shell A14 was obtained.
  • the outer casing A14 was immersed in the prepared dyeing solution for 10 min, the acid dyeing solution concentration was 5 g/L, the pH value was 5.5, and the dyeing liquid temperature was adjusted to 50 ° C. After completion, it was taken out and cleaned. A dyed outer casing A15 was obtained.
  • the outer shell A15 was immersed in a sealing agent (aqueous solution of NiSO 4 at a concentration of 10 g/L) for 20 min at a temperature of 95 ° C, and after sealing, it was cleaned with pure water at 90 ° C and baked at 60 ° C for 15 min. .
  • a surface decorative coating having a thickness of 20 um was obtained.
  • the slit is processed on the aluminum alloy by a laser cutting machine (Model LCY20 laser produced by Huagong Laser, wavelength 1064 nm), wherein the thickness of the aluminum alloy is 5.1 mm, and the model of the aluminum alloy is 6013.
  • the slit has a width of 50 ⁇ m, a length of 80 mm, a number of processed strips of 4, and a slit pitch of 0.8 mm.
  • the laser processing power is 60 W, the speed is 20 mm/s, and the frequency is 1.5 kHz. Sample B11 was obtained.
  • the metal substrate under the slit was milled to obtain five sets of vent holes, and the air holes communicated with the slits, the air holes were 4.4 mm long, 1.6 mm wide, and the vent holes were 10 mm apart.
  • the obtained outer casing is subjected to PMH injection molding, and PBT resin containing 30% glass fiber is injection-molded as a plastic support member to obtain a reinforced outer casing B12.
  • the mold temperature is 140 ° C
  • the nozzle temperature is 260 ° C
  • the dwell time is 18 s
  • the injection pressure is 110 MPa
  • the injection time is 1 s
  • the cooling time is 15 s
  • the thickness of the formed resin is 1.1 mm.
  • the injection molding conditions were mold temperature 140 ° C, nozzle temperature: 260 ° C, dwell time: 12 s, injection pressure: 115 MPa, injection time: 0.8. s, the cooling time was 12 s, and the thickness of the formed resin was 2.1 mm.
  • the outer casing B13 is obtained by overmolding.
  • the outer casing B13 is anodized and dyed to obtain a metal outer casing B2.
  • the slit is machined on an aluminum alloy using a precision CNC, the aluminum alloy material is 6013 and the thickness is 0.8 mm.
  • Two sets of slits were machined, the cutter head diameter was 0.35 mm, the machining speed was 300 r/min, and the machining speed was 0.2 mm/min.
  • the obtained outer casing is subjected to PMH injection molding, and PBT resin containing 40% glass fiber is injection molded as a plastic support member to obtain a reinforced outer casing DS12.
  • the injection molding conditions were mold temperature 140 ° C, nozzle temperature: 260 ° C, dampening time: 18 s, injection pressure: 125 MPa, injection time: 0.8 s, cooling time 12 s, and the thickness of the formed resin was 2 mm.
  • a metal casing DS1 is obtained.
  • the slit is machined on the aluminum alloy using a precision CNC, the aluminum alloy material is 6013 and the thickness is 1.1 mm. Two sets of slits were machined, the cutter head diameter was 0.5 mm, the machining speed was 400 r/min, and the machining speed was 0.25 mm/min. 4 slits in the slit group The slits are 80 mm in length, 0.5 mm in width, 1.1 mm in thickness, 1 mm apart, and have a slit shape in a straight shape to obtain a shell DS21.
  • the above products were pretreated, and the obtained outer casing was subjected to PMH injection molding, and PBT resin containing 40% glass fiber was injection molded as a plastic support member to obtain a reinforced outer casing DS22.
  • the mold temperature is 140 ° C
  • the nozzle temperature is 260 ° C
  • the dwell time is 15 s
  • the injection pressure is 110 MPa
  • the injection time is 1 s
  • the cooling time is 15 s
  • the thickness of the formed resin is 2 mm.
  • a metal casing DS2 is obtained.
  • the slit is machined on the aluminum alloy using a precision CNC, the aluminum alloy material is 6013 and the thickness is 1.1 mm. Two sets of slits were machined, the cutter head diameter was 0.3 mm, the machining speed was 250 r/min, and the machining speed was 0.2 mm/min. There are a total of 3 slits in the slit group, each having a length of 80 mm, a width of 0.3 mm, a thickness of 1.1 mm, a pitch of 0.6 mm, and a slit shape in a straight shape to obtain a shell DS31.
  • the above-mentioned slit is filled with liquid glue by a dispenser, the speed of the dispenser is 10 mm/s, the dispensing pressure is 0.6 kPa, and the diameter of the dispensing nozzle is 0.6 mm. After the dispensing of the product is completed, the product is allowed to stand for 10 minutes. After baking in an oven at 120 ° C for 1 hour, the glue solidified.
  • the slit widths of the examples 1 and 2 and the comparative examples 1-3 and the metal composite molding method are shown in Table 1.
  • the slit of A1 precision CNC machining has no corners and no clogging. It can be successfully processed only once.
  • the first injection slit is not deformed. After the second injection, the slit has no plastic lack of glue, deformation, and the appearance and bonding effect are good.
  • Figure 1 is a cross-sectional view of the housing slit of A1.
  • the upper surface of the metal casing 1 has a single injection molding to form a narrow
  • the slit 2 is formed by injection molding on the lower surface corresponding to the slit to form a plastic support member 3 on the lower surface, and the upper surface of the metal casing 1 and the opening of the slit 2 have a decorative layer.
  • Figure 2 is an optical microscopic analysis of the A1 product with a multiple of 200 times.
  • the metal casing 21 is shown in Fig. 2, and the slit 22 is formed by one injection molding and the plastic support member 23 is formed by overmolding.
  • the glass fiber of the first injection of the slit in Fig. 2 is perpendicular to the surface of the picture, and the glass fiber is overmolded. It is roughly parallel to the face where the picture is located; there is a clear interface between the primary injection slit region of the slit in FIG. 2 and the secondary injection support region of FIG.
  • the slit of B2 precision laser processing is transparent and has no clogging phenomenon. It can be successfully processed only once. By means of laser processing, slits of smaller width can be obtained.
  • the product slit is deformed and deformed many times, and the yield is low.
  • the pull force test was performed on A1 of Example 1, specifically, aluminum metal and plastic (PBT, 40GF) PMH were spliced to obtain test strips (bonding area was 75 mm 2 ), and the pull force test was performed, and the test results were as follows. Table 2 shows:
  • Test piece 1 Test piece 2 Test piece 3 Yield Strength 3146.42N/41.95MPa 3144.74N/41.93MPa 3103.21N/41.38MPa
  • the drawing force test of the DS3 of Comparative Example 3 was carried out. Specifically, the aluminum metal strip was bonded to the glue, the bonding area was 90 mm 2 , and the drawing force test was performed. The test results are shown in Table 3:
  • Test piece 1 Test piece 2 Test piece 3 Yield Strength 983.89N/10.93MPa 1069.25N/11.88MPa 956.94N/10.63MPa
  • the DS3 product can be filled with a complete structure of the slit cavity by means of glue-filled curing and CNC thinning, but the bonding strength of the metal to the glue is lower than that of the metal-resin composite of the present disclosure.

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  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

一种金属树脂复合体、其制备方法、包含该金属树脂复合体的个人电子设备外壳和个人电子设备以及一种金属树脂复合体加工件，该金属树脂复合体包括金属基材，金属基材的上表面具有至少一条上表面狭缝（2），金属基材的下表面在上表面狭缝（2）相对的位置具有至少一条下表面凹槽，上表面狭缝（2）与下表面凹槽互相连通；上表面狭缝（2）中注塑成型有第一注塑树脂，下表面凹槽中注塑成型有第二注塑树脂。

Description

金属树脂复合体及其制备方法和用途
相关申请的交叉引用
本公开主张在2016年10月14日在中国提交的中国专利申请号No.201610899065.3的优先权，其全部内容通过引用包含于此。
技术领域
本公开涉及材料科学领域，具体地，涉及一种金属树脂复合体、该金属树脂复合体的制备方法以及包含该金属树脂复合体的个人电子设备外壳和个人电子设备，还有一种金属树脂复合体加工件。
背景技术
对于手机、笔记本电脑、平板电脑等各种便携式电子通讯设备，采用金属外壳比用塑胶外壳具有更美的外观和更好的质感，同时具有更好的耐磨性能和抗压性能，因此，采用金属作为电子通讯设备的外壳成为今后的一种趋势。但是现有的天线技术制约着这一趋势的发展，因为金属具有电磁屏蔽作用，所以很多厂商依然选择塑胶外壳作为电子通讯设备外壳，也有一部分厂商采用塑胶条隔断金属的技术避免屏蔽电磁信号。
采用塑胶条隔断金属的技术虽然可以避免屏蔽电磁信号，但是塑胶条较宽，一般宽度为1～2mm，金属和塑料外观效果不一样，从外光上看整个金属外壳是被宽塑胶条分成几块的，没有外观一体化效果。
在金属后壳通过精密加工获的细小的狭缝(宽度小于1mm)和对狭缝填充胶水，得到可以释放电磁信号的天线结构，这种方法可以获得较好的外观一体化的效果，但是牺牲了天线处结构的结合强度(结合强度小于15MPa)。
发明内容
本公开的目的是提供一种制备方法，该方法采用精密加工方式加工狭缝，狭缝可改善金属后壳的外观视觉效果；采用PMH(ploymer metal hybrid)技术进行先后二次注塑工艺，获得高强度(不小于30MPa)和结合效果的狭缝。
为了实现上述目的，一方面，本公开提供了一种金属树脂复合体，该金属树脂复合体 包括金属基材，所述金属基材的上表面具有至少一条上表面狭缝，所述金属基材的下表面在所述上表面狭缝相对的位置具有至少一条下表面凹槽，所述上表面狭缝与所述下表面凹槽互相连通；所述上表面狭缝中注塑成型有第一注塑树脂，所述下表面凹槽中注塑成型有第二注塑树脂，所述第一注塑树脂与所述第二注塑树脂选自相同或不同的注塑树脂，且所述下表面凹槽中的所述第二注塑树脂构成能够支撑所述第一注塑树脂的下表面支撑结构。
另一方面，本公开提供了一种制备金属树脂复合体的方法，其中，该方法包括：
S1、在金属基材的上表面上加工出至少一条上表面狭缝；
S2、在所述上表面狭缝的底部加工出至少一个开口于所述金属基材的下表面上的排气孔；
S3、在所述上表面狭缝中进行第一PMH注塑成型，得到填充有第一注塑树脂的上表面狭缝；
S4、在所述金属基材的下表面在所述上表面狭缝相对的位置处去除金属基材部分直至到达所述上表面狭缝的底部并暴露所述第一注塑树脂，以加工出至少一条下表面凹槽，所述上表面狭缝与所述下表面凹槽互相连通；
S5、在所述下表面凹槽进行第二PMH注塑成型，得到填充有第二注塑树脂的下表面凹槽；所述下表面凹槽中的所述第二注塑树脂形成能够支撑所述第一注塑树脂的下表面支撑结构；
所述第一注塑树脂与所述第二注塑树脂选自相同或不同的注塑树脂。
再一方面，本公开提供了如上所述的方法制备得到的金属树脂复合体。
再一方面，本公开还提供了一种个人电子设备外壳，所述外壳中含有如上所述的金属树脂复合体。
再一方面，本公开还提供了一种个人电子设备，该个人电子设备包括个人电子设备内核元件和如上所述的个人电子设备外壳。
再一方面，本公开还提供了一种金属树脂复合体加工件，该金属树脂复合体加工件包括金属基材，所述金属基材的上表面具有至少一条上表面狭缝，所述上表面狭缝的底部具有至少一个开口于所述金属基材的下表面上的排气孔。
通过上述技术方案，本公开通过精密加工和二次注塑的方式，也就是首先在基材的外表加工狭缝的区域，然后进行第一次PMH注塑，接着对狭缝下面的金属基材铣去，留出空位，并进行第二次PMH注塑填补铣出来的空位，对金属基材加工排气孔，排气孔与狭缝完全贯通。这样的排气结构，有利于金属壳体在注塑过程中狭缝排气排渣，增强金属与塑胶的结合力。此外，这种金属树脂复合体能够使得电子产品整体更具有美感，同时获得强度高的 金属复合体，并且提高加工的成品率。
本公开的其他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是采用本公开得到的外壳狭缝处的剖视图。
图2是实施案例金属复合体的光学显微分析图，放大倍数是200倍。
附图标记说明
1 金属外壳
2 一次注塑形成狭缝
3 二次注塑形成塑胶支撑件
4 装饰层
21 金属外壳
22 一次注塑形成狭缝
23 二次注塑形成塑胶支撑件
具体实施方式
以下结合附图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。
在本公开中，在未作相反说明的情况下，使用的方位词如“上、下、左、右”通常是指按照图1所示的图面方向。所述金属树脂复合体的内表面定义为将金属树脂复合体用于通讯设备的金属外壳中时，金属外壳朝向通讯设备内部的表面。可以理解的是，金属外壳的外表面定义为将其用于通讯设备中时，金属外壳朝向外界的表面。
本公开提供了一种金属树脂复合体，该金属树脂复合体包括金属基材，所述金属基材的上表面具有至少一条上表面狭缝，所述金属基材的下表面在所述上表面狭缝相对的位置具有至少一条下表面凹槽，所述上表面狭缝与所述下表面凹槽互相连通；所述上表面狭缝中注塑成型有第一注塑树脂，所述下表面凹槽中注塑成型有第二注塑树脂，所述第一注塑树脂与所述第二注塑树脂选自相同或不同的注塑树脂，且所述下表面凹槽中的所述第二注塑树脂构 成能够支撑所述第一注塑树脂的下表面支撑结构。
其中，所述上表面狭缝相对的位置指的是所述上表面狭缝投影在该金属树脂复合体的下表面上的位置。该金属树脂复合体在用于电子设备中作为壳体时，所示上表面狭缝处于“狭缝的区域”内，所示“狭缝的区域”是指壳体上与电子设备的天线相对应的区域。另外，对于所述“狭缝的区域”的大小，本领域技术人员可以根据电子设备的天线的设置范围进行适当地选择。
其中，所述上表面狭缝中的所述第一次注塑树脂和所述下表面凹槽中的所述第二次注塑树脂间可以观察到具有界面。第一次注塑树脂和第二次注塑树脂之间的界面可以在切面上通过肉眼或显微镜观察到，例如图2所示，该界面形成的原因可能是注塑次序不同或注塑具体成型参数的不同。
其中，所述金属基材的上表面可以具有至少一个上表面狭缝组，所述上表面狭缝组可以包括至少二条上表面狭缝；所述上表面狭缝组中的至少二条上表面狭缝可以分别与所述下表面支撑结构连通。
其中，所述上表面狭缝的尺寸可以是本领域中常用的尺寸，例如所述上表面狭缝的深度可以为0.1-3mm，可选为0.1-1.5mm，所述金属基材的厚度可以为0.1-9mm。所述上表面狭缝的宽度可以为0.05mm-1mm；所述上表面狭缝的长度可以为2-300mm，可选为60-150mm；相邻两条所述上表面平行狭缝的之间的间距可以为0.1-30mm，可选为0.5-15mm。
其中，所述金属基材的上表面可以具有至少二个上表面狭缝组。另外，狭缝的条数和形状没有特别的限定，只要能够实现通讯即可。所述上表面狭缝之间可以互相平行或者相交，所述上表面狭缝的形状可以为直线状、波浪状或锯齿状，所述上表面狭缝的截面形状可以为矩形或梯形。
其中，所述金属基材的材料可以为常规的各种能够用于电子设备外壳的金属材料，例如可以选自铝、镁、铁、钛、钛合金、铝合金和不锈钢中的至少一种。
其中，所述注塑树脂没有特别的要求，例如可以选自聚乙烯、聚丙烯、聚缩醛、聚苯乙烯、改性聚苯醚、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚苯硫醚、聚酰亚胺、聚酰胺酰亚胺、聚醚酰亚胺、聚砜、聚醚砜、聚醚酮、聚醚醚镁、聚碳酸酯、聚酰胺和丙烯腈-丁二烯-苯乙烯共聚物中的一种或多种。
其中，根据本公开的实施方式，为了美观的目的，该金属树脂复合体还可以包括覆盖在所述金属基材的上表面和所述上表面狭缝的开口上的装饰层。
其中，所述装饰层可以选自阳极氧化层、微弧氧化层、电泳层和喷涂涂层中的至少一种。所述涂层的厚度可以为5-60μm。
其中，根据本公开的实施方式，所述注塑树脂中还可以含有填料，所述填料为玻璃纤维和/或碳纤维。在该实施方式中，可以进一步增强增加所述注塑树脂的强度。
其中，以所述注塑树脂的总重量计算，所述填料的含量可以为10-50重量％。
另一方面，本公开还提供了一种制备金属树脂复合体的方法，其中，该方法包括：
S1、在金属基材的上表面上加工出至少一条上表面狭缝；
S2、在所述上表面狭缝的底部加工出至少一个开口于所述金属基材的下表面上的排气孔；
S3、在所述上表面狭缝中进行第一PMH注塑成型，得到填充有第一注塑树脂的上表面狭缝；
S4、在所述金属基材的下表面在所述上表面狭缝相对的位置处去除金属基材部分直至到达所述上表面狭缝的底部并暴露所述第一注塑树脂，以加工出至少一条下表面凹槽，所述上表面狭缝与所述下表面凹槽互相连通；
S5、在所述下表面凹槽进行第二PMH注塑成型，得到填充有第二注塑树脂的下表面凹槽；所述下表面凹槽中的所述第二注塑树脂形成能够支撑所述第一注塑树脂的下表面支撑结构；
所述第一注塑树脂与所述第二注塑树脂选自相同或不同的注塑树脂。
上述方法通过精密加工和二次注塑的方式，也就是首先在基材的外表加工狭缝的区域，对金属基材加工排气孔，排气孔与狭缝完全贯通，这样的排气结构，有利于金属壳体在注塑过程中狭缝排气排渣，增强金属与塑胶的结合力，然后采用一次注塑，接着对狭缝下面的金属基材铣去，留出空位，并进行二次注塑填补铣出来的空位，金属树脂复合体使得电子产品整体更具有美感，同时获得强度高的金属复合体，并且提高加工的成品率。
其中，根据本公开的实施方式，该方法还包括：在步骤S5之后，进行步骤S6的操作：
S6、在所述金属基材的上表面和所述上表面狭缝的开口上形成装饰层。
其中，步骤S1中，在金属基材的上表面上可以加工出至少一个上表面狭缝组，所述上表面狭缝组可以包括至少二条上表面狭缝；并且，在步骤S4中使得所述上表面狭缝组中的至少二条上表面狭缝分别与所述下表面支撑结构连通。
其中，所述金属基材的厚度可以为0.1-9mm，加工的条件使得所述上表面狭缝的深度为0.1-3mm，还可以使得所述上表面狭缝的宽度可以为0.05mm-1mm；还可以使得所述上表面狭缝的长度可以为2-300mm，可选为60-150mm；还可以使得相邻两条所述上表面平行狭缝的之间的间距可以为0.1-30mm，可选为0.5-15mm。
其中，加工的条件可以使得所述金属基材的上表面具有至少二个上表面狭缝组；所述 上表面狭缝之间可以互相平行或者相交，所述上表面狭缝的形状可以为直线状、波浪状或锯齿状，所述上表面狭缝的截面形状可以为矩形或梯形。
其中，对于所述狭缝的区域的大小，本领域技术人员可以根据通讯设备的天线的设置范围进行适当地选择。
根据本公开，在加工出所述上表面狭缝后第一注塑成型前，对金属基材加工排气孔，排气孔数量是一组或者多组，排气孔可以是矩形，多边形、椭圆形或者其他形状，排气孔间的距离可以相同或者不同，排气孔与狭缝完全贯通，这样的排气结构，有利于金属壳体在注塑过程中狭缝排气排渣，增强金属基材与塑胶的结合力。本公开中，所述气孔可以为矩形形状，气孔长可以为3-10mm，宽可以为0.8-5mm，排气孔间距可以为3-20mm，可选地，气孔长4-6mm，宽0.8-1.5mm，排气孔间距8-14mm。其中，所述上表面狭缝的底部的总面积与所述排气孔在所述表面狭缝的底部的开口总面积的比例可以为100：(0.5-10)。
其中，所述金属基材的材料选自铝、镁、铁、钛、钛合金、铝合金和不锈钢中的至少一种；所述注塑树脂可以选自聚乙烯、聚丙烯、聚缩醛、聚苯乙烯、改性聚苯醚、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚苯硫醚、聚酰亚胺、聚酰胺酰亚胺、聚醚酰亚胺、聚砜、聚醚砜、聚醚酮、聚醚醚镁、聚碳酸酯、聚酰胺和丙烯腈-丁二烯-苯乙烯共聚物中的一种或多种。
其中，所述第一注塑成型的条件和所述第二注塑成型的条件可以各自独立地包括：模具温度为50-310℃，喷嘴温度为200-450℃，保压时间为1-50s，射出压力为50-300MPa，射出时间为1-30s，冷却时间为1-60s。
其中，所述第一注塑成型的条件和所述第二注塑成型的条件可以使得形成树脂的厚度为0.4-10mm。
其中，加工出所述上表面狭缝、加工出所述排气孔和加工出所述下表面凹槽的操作各自独立地通过激光加工、电子束加工、水切割加工、CNC加工和蚀刻加工中的至少一种完成。
采用上述各种方法进行加工时，其具体操作和条件是现有技术中常用的，例如，所述激光切割条件为：功率为50-200W，切割速度为10-5000mm/s，激光频率为10-200kHz，输出波长为250-1064nm。通过上述激光切割的方法形成的狭缝宽度通常在10-100μm。
例如，所述电子束切割方法为：在真空度为10-3-10-4Pa的环境中，在电流为5-10mA，功率密度为106-108W/cm2的条件下进行切割。通过上述电子束切割的方法形成的狭缝宽度通常在30-150μm。
例如，所述CNC加工的条件为：进给速度：200-600mm/min；进给量：10-40μm。通 过上述CNC加工的方法形成的狭缝宽度通常在0.2mm-1mm。
本公开中，可以对金属基材进行前处理。前处理是为本领域技术人员常用的对金属表面进行的前处理工序，一般包括进行机械打磨或研磨除去表面明显的异物，然后对金属表面粘附的加工油进行脱脂、清洗。可选地，前处理包括对金属基材进行打磨处理，例如；采用100-600目的砂纸或者将其放入抛光机内对金属基材进行打磨，使得金属基材产生微米级孔或坑。然后依次进行除油、第一水洗、碱洗、第二水洗、中和、第三水洗等步骤，用本领域技术人员常用的各种试剂在超声波中清洗金属，清洗时间为10min-2h，去除金属基材表面的油污；然后将金属基材放置于酸/碱性水溶液中超声清洗金属表面，例如：可以为氢氧化钠、硫酸等。本公开中，优先用洗洁精清洗金属油污后再浸入30-70g/L、温度50-80℃的氢氧化钠水溶液中进行碱蚀，1-10min后取出用去离子水冲洗干净，经由前处理可以增加金属基材的表面粗糙度。通过上述前处理，可至少在所述金属基材的狭缝区域的内表面具有多个微坑，从而能够注塑得到的塑料层和金属的紧密性。
在本公开中，可以通过PMH技术进行所述第一注塑成型和所述第二注塑成型。所述PMH技术即为聚合物金属组合成形技术，一般是指以金属做基板，金属表面形成大量的纳米腐蚀孔和微米腐蚀孔，在其表面注入高分子材料的熔体，熔体沿着空间逐渐填充，并进入纳米孔和微米孔，逐渐冷却，在参数选择合适的情况下完成填充并与基体组合成金属复合体结构。金属表面的纳米腐蚀孔，可以通过化学或者电化学的方法得到，纳米孔的孔径范围为10-100nm，腐蚀孔的深度为1μm-10μm。本公开中，优先将铝合金金属作为阳极放入含有20wt％浓度的硫酸阳极氧化槽中，于16V电压、18℃下电解腐蚀铝合金8分钟，水洗烘干，烘烤温度是80℃，持续5分钟。
其中，所述第一注塑成型的注塑方向可以为垂直于所述金属基材表面注入第一注塑树脂，使得第一注塑树脂由上向下进入所述上表面狭缝。
其中，所述第二注塑成型的注塑方向可以为平行于所述金属基材下表面注入第二注塑树脂，使得第二注塑树脂沿着所述金属基材下表面的方向进入所述下表面凹槽。
其中，步骤S6中，形成所述装饰层的方法可以包括阳极氧化、微弧氧化、电泳和喷涂中的至少一种。
所述阳极氧化条件可以本领域所公知的条件，例如可以为：以浓度为150-210g/L的硫酸作为槽液，电压为10-25V，电流密度为1-2A/dm2，温度为10-22℃，阳极氧化时间为20-60min，封孔槽液(成分例如为NiSO4水溶液)浓度为1-10g/L，封孔温度为50-95℃，封孔时间为10-50min。通过上述阳极氧化方法形成的装饰层厚度通常为5-50μm。
所述微弧氧化条件可以本领域所公知的条件，例如可以为：pH为6-12，电压为0-800V， 电流密度为1-10A/dm2，温度为15-60℃，时间为10-60min，封孔槽液为纯水，封孔温度为70-90℃，封孔时间为1-10min。通过上述微弧氧化方法形成的装饰层厚度通常为10-50μm。
所述电泳条件可以本领域所公知的条件，例如可以为：阴极电泳：电压为20-60V，pH为4-6，温度为15-30℃，时间为20-60s；阳极电泳：电压为40-100V，pH为6-8，温度为15-30℃，时间为40-90s；烘烤温度为120-200℃，烘烤时间为30-60min。通过上述电泳方法形成的装饰层厚度通常为5-35μm。
通过喷涂形成所述装饰层，所述喷涂条件可以本领域所公知的条件，例如可以为：静电高压：60-90kV；静电电流：10-20μA；流速压力：0.3-0.55Mpa；雾化压力：0.33-0.45Mpa；输送速度：4.5-5.5m/min；固化温度：150-220℃；固化时间：30-180min。通过上述喷涂形成的装饰层厚度通常为10-60μm。
其中，根据本公开的一种实施方式，所述注塑树脂中还含有填料。所述填料可以为玻璃纤维和/或碳纤维。以所述注塑树脂的总重量计算，所述填料的含量可以为10-50重量％。所述填料可以通过本领域常规的方式掺入到所述注塑树脂中，例如通过螺杆挤压的方式掺入到所述注塑树脂中，然后进行注塑。
另一方面，本公开还提供了所述的方法制备得到的金属树脂复合体。
另一方面，本公开还提供了一种个人电子设备外壳，所述外壳中含有如上所述的金属树脂复合体。
另一方面，本公开还提供了一种个人电子设备，该个人电子设备包括个人电子设备内核元件和如上所述的个人电子设备外壳。
另一方面，本公开还提供了一种金属树脂复合体加工件，该金属树脂复合体加工件包括金属基材，所述金属基材的上表面具有至少一条上表面狭缝，所述上表面狭缝的底部具有至少一个开口于所述金属基材的下表面上的排气孔。其中，所述金属树脂复合体加工件可以作为所述金属树脂复合体加工过程中的半成品。
以下通过实施例进一步详细说明本公开。
实施例1
1.狭缝精密加工
采用精密CNC在铝合金外表面加工狭缝，铝合金材料是6013，厚度是5.1毫米。加工两组狭缝，刀头直径0.35毫米，加工转速300r/min，加工走速0.2mm/min。狭缝组内共4条狭缝，长度均为80毫米，宽度为0.35毫米，厚度为1.1毫米，间距为1毫米，狭缝形状为直线形，得到外壳A11。
2.CNC加工排气槽
然后对狭缝下面的金属基材铣去，得到五组排气孔，气孔与狭缝相通，气孔长4.4毫米，宽1.1毫米，排气孔间距10毫米.
3.一次PMH注塑固定狭缝
产品经前处理后，将所得外壳进行一次PMH注塑，注塑含有40％玻璃纤维的PBT树脂，作为塑胶支撑件，得到加固后的外壳A12。其中，模具温度140℃，喷嘴温度：260℃，保压时间：15s，射出压力：120MPa，射出时间：1s，冷却时间15s，形成树脂的厚度为1.1mm。
4.CNC加工和二次PMH注塑
对狭缝下面的金属基材铣去，留出一些空位，空位长度77毫米，深度4毫米。再对上述空位进行二次PMH注塑，注塑含有40％玻璃纤维的PBT树脂，注塑的条件为模具温度140℃，喷嘴温度:260℃，保压时间：12s，射出压力：115MPa，射出时间：0.8s，冷却时间12s，形成树脂的厚度为2.1毫米。得到二次注塑加固的外壳A13。
5.表面装饰处理
将上述经过注塑支撑件加固后的外壳A13进行碱蚀、水洗、酸洗、水洗处理以去除表面油脂和杂质，之后浸入硫酸浓度为180g/L H2SO4水溶液的电解槽中，以A13作为阳极，不锈钢板作为阴极，在电压为14V、电流密度为1A/dm2、温度为11℃的条件下阳极氧化45min，完成阳极氧化后取出并超声清洗10min，避免狭缝处藏酸影响后续着色。得到阳极氧化后的外壳A14。
将上述外壳A14浸入已配制好的染液中染色10min，该酸性染液浓度为5g/L，PH值为5.5，染液温度调节至50℃，完成后取出并清洗干净。得到染色后的外壳A15。
将上述外壳A15在封孔剂(NiSO4水溶液，浓度为10g/L)中浸渍20min，温度为95℃，完成封孔后用90℃的纯水清洗干净，并在60℃条件下烘烤15min。得到厚度为20um的表面装饰涂层。
最终得到全金属外壳产品A1。
实施例2
1.狭缝精密加工
采用激光切割机(华工激光生产的型号为LCY20激光器，波长1064nm)在铝合金上加工狭缝，其中铝合金厚度为5.1毫米，铝合金型号为6013。所述狭缝宽度为50微米，长度为80毫米，加工条数为4条，狭缝间距为0.8毫米。激光加工的功率为60W，速度为20mm/s，频率为1.5kHz。得到样品B11。
2.CNC加工排气槽
然后对狭缝下面的金属基材铣去，得到五组排气孔，气孔与狭缝相通，气孔长4.4毫米，宽1.6毫米，排气孔间距10毫米。
3.一次PMH注塑固定狭缝
产品经前处理后，将上述所得外壳进行一次PMH注塑，注塑含有30％玻璃纤维的PBT树脂，作为塑胶支撑件，得到加固后的外壳B12。其中，模具温度140℃，喷嘴温度:260℃，保压时间：18s，射出压力：110MPa，射出时间：1s，冷却时间15s，形成树脂的厚度为1.1mm。
4.CNC加工和二次PMH注塑
对狭缝下面的金属基材铣去，留出一些空位，空位长度77毫米，深度4mm。再对上述空位进行二次PMH注塑，注塑含有30％玻璃纤维的PBT树脂，注塑的条件为模具温度140℃，喷嘴温度:260℃，保压时间：12s，射出压力：115MPa，射出时间：0.8s，冷却时间12s，形成树脂的厚度为2.1mm。得到二次注塑加固的外壳B13。
5.表面装饰处理
外壳B13经阳极氧化和染色处理，得到金属外壳B2。
对比例1
1.狭缝精密加工
采用精密CNC在铝合金上加工狭缝，铝合金材料是6013，厚度是0.8毫米。加工两组狭缝，刀头直径0.35毫米，加工转速300r/min，加工走速0.2mm/min。狭缝组内共4条狭缝，长度均为80毫米，宽度为0.35毫米，厚度为0.8毫米，间距为1毫米，狭缝形状为直线形，得到外壳DS11。
2.一次PMH注塑
产品经前处理后，将所得外壳进行一次PMH注塑，注塑含有40％玻璃纤维的PBT树脂，作为塑胶支撑件，得到加固后的外壳DS12。其中，注塑的条件为模具温度140℃，喷嘴温度:260℃，保压时间：18s，射出压力：125MPa，射出时间：0.8s，冷却时间12s，形成树脂的厚度为2毫米。得到金属外壳DS1。
对比例2
1.狭缝精密加工
采用精密CNC在铝合金上加工狭缝，铝合金材料是6013，厚度是1.1毫米。加工两组狭缝，刀头直径0.5毫米，加工转速400r/min，加工走速0.25mm/min。狭缝组内共4条狭 缝，长度均为80毫米，宽度为0.5毫米，厚度为1.1毫米，间距为1毫米，狭缝形状为直线形，得到外壳DS21。
2.一次PMH注塑
上述产品经前处理，将所得外壳进行一次PMH注塑，注塑含有40％玻璃纤维的PBT树脂，作为塑胶支撑件，得到加固后的外壳DS22。其中，模具温度140℃，喷嘴温度:260℃，保压时间：15s，射出压力：110MPa，射出时间：1s，冷却时间15s，形成树脂的厚度为2毫米。得到金属外壳DS2。
对比例3
1.狭缝精密加工
采用精密CNC在铝合金上加工狭缝，铝合金材料是6013，厚度是1.1毫米。加工两组狭缝，刀头直径0.3毫米，加工转速250r/min，加工走速0.2mm/min。狭缝组内共3条狭缝，长度均为80毫米，宽度为0.3毫米，厚度为1.1毫米，间距为0.6毫米，狭缝形状为直线形，得到外壳DS31。
2.胶水填充固化
将上述所得狭缝用点胶机填充液态胶水，点胶机速度是10mm/s，点胶压力是0.6kPa，点胶嘴直径是0.6mm，产品点胶完成后，静置10分钟，将产品放入烤箱中120℃烘烤1小时后，胶水固化。
3.产品表面CNC加工减薄处理
上述固化产品的外观面经CNC工艺减去0.2mm，得到金属外壳DS3。
实施例1和2以及对比例1-3的狭缝宽度和金属复合体成型方式如表1所示。
表1
序号 狭缝宽度 金属复合体成型方式
A1 0.35mm 二次注塑
B2 0.05mm 二次注塑
DS1 0.35mm 一次注塑
DS2 0.5mm 一次注塑
DS3 0.35mm 胶水填充固化
实施例1和2以及对比例1-3的结果显示：
A1精密CNC加工的狭缝无缺角，无堵塞现象，仅加工一次即可成功。第一次注塑狭缝不变形，二次注塑后，狭缝无塑胶缺胶，变形情况，外观和结合效果良好。
图1是A1的外壳狭缝处的剖视图。其中，金属外壳1的上表面上具有一次注塑形成狭 缝2，一次注塑形成狭缝对应的下表面上具有二次注塑形成塑胶支撑件3，金属外壳1的上表面上和狭缝2开口上具有装饰层。
图2是A1产品的光学显微分析图，倍数是200倍。图2中显示了金属外壳21，一次注塑形成狭缝22和二次注塑形成塑胶支撑件23，图2中狭缝的一次注塑的玻纤垂直于图片所在的面，而二次注塑的玻纤大致平行于图片所在的面；图2中狭缝的一次注塑狭缝区域和图2中二次注塑支撑区域存在较为清晰的界面。
B2精密激光加工的狭缝通透，无堵塞现象，仅加工一次即可成功。通过激光加工的方式，可以得到更小宽度的狭缝。
DS1产品在一次注塑成型时，多次出现产品狭缝被挤压变形的不良现象，良率较低。
DS2产品在一次成型时，多次出现产品内腔塑胶填充缺料缺角的现象，内腔结构不饱满，良率较低。
测试实施例1
对实施例1的A1进行拉拔力测试，具体地，铝金属与塑胶(PBT,40GF)PMH拼接成型得到测试样条(粘结面积是75mm2)，并进行拉拔力测试，测试结果如表2所示：
表2
产品编号 测试片1 测试片2 测试片3
屈服强度 3146.42N/41.95MPa 3144.74N/41.93MPa 3103.21N/41.38MPa
对对比例3的DS3进行拉拔力测试，具体地，铝金属样条粘结合胶水，粘结面积是90mm2，并进行拉拔力测试，测试结果如表3所示：
表3
产品编号 测试片1 测试片2 测试片3
屈服强度 983.89N/10.93MPa 1069.25N/11.88MPa 956.94N/10.63MPa
DS3产品通过胶水填充固化和CNC减薄的方式，可得到狭缝内腔填充完整的结构，但是金属与胶水的结合强度较本公开的金属树脂复合体的强度低。
以上结合附图详细描述了本公开的示例性实施方式，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 (25)

  1. 一种金属树脂复合体，包括金属基材，其中所述金属基材的上表面具有至少一条上表面狭缝，所述金属基材的下表面在所述上表面狭缝相对的位置具有至少一条下表面凹槽，所述上表面狭缝与所述下表面凹槽互相连通；所述上表面狭缝中注塑成型有第一注塑树脂，所述下表面凹槽中注塑成型有第二注塑树脂，所述第一注塑树脂与所述第二注塑树脂选自相同或不同的注塑树脂，且所述下表面凹槽中的所述第二注塑树脂构成能够支撑所述第一注塑树脂的下表面支撑结构。
  2. 根据权利要求1所述的金属树脂复合体，其中，所述金属基材的上表面具有至少一个上表面狭缝组，所述上表面狭缝组包括至少二条上表面狭缝；所述上表面狭缝组中的至少二条上表面狭缝分别与所述下表面支撑结构连通。
  3. 根据权利要求1或2所述的金属树脂复合体，其中，所述上表面狭缝的宽度为0.05mm-1mm。
  4. 根据权利要求3所述的金属树脂复合体，其中，所述上表面狭缝的深度为0.1-3mm，所述金属基材的厚度为0.1-9mm。
  5. 根据权利要求2所述的金属树脂复合体，其中，所述金属基材的上表面具有至少二个上表面狭缝组；所述上表面狭缝之间互相平行或者相交，所述上表面狭缝的形状为直线状、波浪状或锯齿状，所述上表面狭缝的截面形状为矩形或梯形。
  6. 根据权利要求1或2所述的金属树脂复合体，其中，所述金属基材的材料选自铝、镁、铁、钛、钛合金、铝合金和不锈钢中的至少一种；所述注塑树脂选自聚乙烯、聚丙烯、聚缩醛、聚苯乙烯、改性聚苯醚、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚苯硫醚、聚酰亚胺、聚酰胺酰亚胺、聚醚酰亚胺、聚砜、聚醚砜、聚醚酮、聚醚醚镁、聚碳酸酯、聚酰胺和丙烯腈-丁二烯-苯乙烯共聚物中的一种或多种。
  7. 根据权利要求1或2所述的金属树脂复合体，其中，该金属树脂复合体还包括覆盖在所述金属基材的上表面和所述上表面狭缝的开口上的装饰层。
  8. 根据权利要求7所述的金属树脂复合体，其中，所述装饰层选自阳极氧化层、微弧氧化层、电泳层和喷涂涂层中的至少一种。
  9. 根据权利要求1或2所述的金属树脂复合体，其中，所述注塑树脂中还含有填料，所述填料为玻璃纤维和/或碳纤维。
  10. 根据9所述的金属树脂复合体，其中，以所述注塑树脂的总重量计算，所述填料的含量为10-50重量％。
  11. 一种制备金属树脂复合体的方法，包括：
    S1、在金属基材的上表面上加工出至少一条上表面狭缝；
    S2、在所述上表面狭缝的底部加工出至少一个开口于所述金属基材的下表面上的排气孔；
    S3、在所述上表面狭缝中进行第一PMH注塑成型，得到填充有第一注塑树脂的上表面狭缝；
    S4、在所述金属基材的下表面在所述上表面狭缝相对的位置处去除金属基材部分直至到达所述上表面狭缝的底部并暴露所述第一注塑树脂，以加工出至少一条下表面凹槽，所述上表面狭缝与所述下表面凹槽互相连通；
    S5、在所述下表面凹槽进行第二PMH注塑成型，得到填充有第二注塑树脂的下表面凹槽；所述下表面凹槽中的所述第二注塑树脂形成能够支撑所述第一注塑树脂的下表面支撑结构；
    所述第一注塑树脂与所述第二注塑树脂选自相同或不同的注塑树脂。
  12. 根据权利要求11所述的方法，还包括：在步骤S5之后，进行步骤S6的操作：
    S6、在所述金属基材的上表面和所述上表面狭缝的开口上形成装饰层。
  13. 根据权利要求11所述的方法，其中，步骤S1中，在金属基材的上表面上加工出至少一个上表面狭缝组，所述上表面狭缝组包括至少二条上表面狭缝；并且，在步骤S4中使得所述上表面狭缝组中的至少二条上表面狭缝分别与所述下表面支撑结构连通。
  14. 根据权利要求11-13中任意一项所述的方法，其中，所述金属基材的厚度为0.1-9mm，使得所述上表面狭缝的深度为0.1-3mm，宽度为0.05mm-1mm。
  15. 根据权利要求14所述的方法，其中，所述金属基材的上表面具有至少二个上表面狭缝组；所述上表面狭缝之间互相平行或者相交，所述上表面狭缝的形状为直线状、波浪状或锯齿状，所述上表面狭缝的截面形状为矩形或梯形。
  16. 根据权利要求11-13中任意一项所述的方法，其中，所述上表面狭缝的底部的总面积与所述排气孔在所述表面狭缝的底部的开口总面积的比例为100：(0.5-10)。
  17. 根据权利要求11-13中任意一项所述的方法，其中，所述金属基材的材料选自铝、镁、铁、钛、钛合金、铝合金和不锈钢中的至少一种；所述注塑树脂选自聚乙烯、聚丙烯、聚缩醛、聚苯乙烯、改性聚苯醚、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚苯硫醚、聚酰亚胺、聚酰胺酰亚胺、聚醚酰亚胺、聚砜、聚醚砜、聚醚酮、聚醚醚镁、聚碳酸酯、聚酰胺和丙烯腈-丁二烯-苯乙烯共聚物中的一种或多种。
  18. 根据权利要求11-13中任意一项所述的方法，其中，所述第一注塑成型的条件和所述第二注塑成型的条件各自独立地包括：模具温度为50-310℃，喷嘴温度为200-450℃，保压时间为1-50s，射出压力为50-300MPa，射出时间为1-30s，冷却时间为1-60s。
  19. 根据权利要求11-13中任意一项所述的方法，其中，加工出所述上表面狭缝、加工出所述排气孔和加工出所述下表面凹槽的操作各自独立地通过激光加工、电子束加工、水切割加工、CNC加工和蚀刻加工中的至少一种完成。
  20. 根据权利要求12所述的方法，其中，步骤S6中，形成所述装饰层的方法包括阳极氧化、微弧氧化、电泳和喷涂中的至少一种。
  21. 根据权利要求11-13中任意一项所述的方法，其中，所述注塑树脂中还含有填料，所述填料为玻璃纤维和/或碳纤维；以所述注塑树脂的总重量计算，所述填料的含量为10-50重量％。
  22. 权利要求11-21中任意一项所述的方法制备得到的金属树脂复合体。
  23. 一种个人电子设备外壳，含有权利要求1-10和22中任意一项所述的金属树脂复合体。
  24. 一种个人电子设备，包括个人电子设备内核元件和权利要求23所述的个人电子设备外壳。
  25. 一种金属树脂复合体加工件，包括金属基材，其中所述金属基材的上表面具有至少一条上表面狭缝，所述上表面狭缝的底部具有至少一个开口于所述金属基材的下表面上的排气孔。
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