WO2016054955A1 - 塑料制品和塑料基材表面选择性金属化方法 - Google Patents

塑料制品和塑料基材表面选择性金属化方法 Download PDF

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Publication number
WO2016054955A1
WO2016054955A1 PCT/CN2015/088395 CN2015088395W WO2016054955A1 WO 2016054955 A1 WO2016054955 A1 WO 2016054955A1 CN 2015088395 W CN2015088395 W CN 2015088395W WO 2016054955 A1 WO2016054955 A1 WO 2016054955A1
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Prior art keywords
tin oxide
doped tin
plastic
resin
substrate
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PCT/CN2015/088395
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English (en)
French (fr)
Inventor
周维
苗伟峰
毛碧峰
周芳享
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比亚迪股份有限公司
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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 KR1020177009342A priority Critical patent/KR101873222B1/ko
Priority to EP15849159.7A priority patent/EP3196338B1/en
Priority to JP2017518996A priority patent/JP6370999B2/ja
Publication of WO2016054955A1 publication Critical patent/WO2016054955A1/zh
Priority to US15/481,671 priority patent/US20170211186A1/en

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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
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
    • C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • C23C18/204—Radiation, e.g. UV, laser
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/285—Sensitising or activating with tin based compound or composition
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/09—Shape and layout
    • H05K2201/09009—Substrate related
    • H05K2201/09118—Moulded substrate
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H05K3/185—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method by making a catalytic pattern by photo-imaging

Definitions

  • the present invention relates to a method of selectively metallizing a plastic article and a surface of a plastic substrate.
  • a metal layer is selectively formed on the surface of an insulating substrate such as plastic, and is used as a path for electromagnetic signal transmission, and is widely used in the fields of automobiles, computers, and communications.
  • a metal layer can be formed on the surface of an insulating substrate such as plastic by various methods.
  • the metal oxide is usually preliminarily placed in an insulating substrate such as plastic, and electrolessly plated by laser irradiation to selectively metallize the surface of the insulating substrate.
  • the above metal oxide is usually doped with antimony-doped tin oxide, but the use of antimony-doped tin oxide has a problem that the light absorption performance is poor and the electroless plating activity is not high.
  • the object of the present invention is to overcome the problems of poor light absorption performance and low electroless plating activity of the above-mentioned antimony doped tin oxide, and to provide a plastic article with good light absorption performance and high electroless plating activity and surface selectivity of a plastic substrate.
  • Metallization method is to overcome the problems of poor light absorption performance and low electroless plating activity of the above-mentioned antimony doped tin oxide, and to provide a plastic article with good light absorption performance and high electroless plating activity and surface selectivity of a plastic substrate.
  • the inventors of the present invention have found through intensive research that doped tin oxide obtained by doping tin oxide with an oxide of one or more of oxonium, lanthanum, fluorine and lanthanum has a specific erbium doping.
  • the much higher light absorption of tin oxide allows the surface of the substrate containing such doped tin oxide to be peeled off even at a lower addition amount or by irradiation with a low-energy laser beam;
  • the heterochromic tin oxide has an extremely high electroless plating activity.
  • the present invention has been completed on this basis.
  • the present invention provides a plastic article.
  • the plastic article comprises: a plastic substrate, and a metal plating layer formed on the surface of the plastic substrate, wherein the surface of the plastic substrate in contact with the metal plating layer is formed of a plastic composition, the plastic combination
  • the material contains: a base resin; and doped tin oxide, and the doping element in the doped tin oxide is at least one selected from the group consisting of ruthenium, osmium, fluorine, and ruthenium.
  • the present invention also provides a method for selectively metallizing a surface of a plastic substrate, the method comprising: irradiating a surface of a plastic substrate with a beam of energy to be metallized with an energy beam, vaporizing the surface to be irradiated; and placing the surface on the plastic substrate
  • the surface after the energy beam irradiation is subjected to electroless plating to form a metal plating layer, wherein the surface of the plastic substrate in contact with the metal plating layer is formed of a plastic composition containing: a substrate resin; and doping oxidation
  • the tin, the doping element in the doped tin oxide is at least one selected from the group consisting of ruthenium, osmium, fluorine, and ruthenium.
  • the present invention provides a plastic article prepared by the above method.
  • the doped tin oxide can increase the energy absorption capacity of the obtained plastic article when added to the base resin, even if it is added to the substrate at a lower added amount,
  • the surface of the substrate irradiated with the energy beam is vaporized and peeled off, and the electroless plating activity of the doped tin oxide exposed is extremely high, and the metal layer is easily plated thereon.
  • a plastic article comprising a plastic substrate; and a metal plating layer formed on a surface of the plastic substrate, wherein a surface of the plastic substrate in contact with the metal plating layer is Formed by the plastic composition, the plastic composition comprises: a base resin; and doped tin oxide, the doping element in the doped tin oxide being at least one selected from the group consisting of ruthenium, osmium, fluorine and ruthenium.
  • the plastic article comprises a plastic substrate and a metal plating layer attached to at least a part of the surface of the plastic substrate, and the surface of the plastic substrate to which the metal plating layer is attached is formed of a plastic composition, the plastic combination
  • the substrate comprises a substrate resin and at least one doped tin oxide or a filler coated by the doped tin oxide, wherein the doping elements in the doped tin oxide are germanium, antimony, fluorine and antimony One or more.
  • the content of the tin element is 90-99.9 mol%, preferably 92-99 mol%, based on the total molar amount of the tin element and the doping element in the doped tin oxide
  • the doping element content is 0.1 to 10 mol%, preferably 1 to 8 mol%.
  • the total amount of doping elements in the doped tin oxide may be from 0.1 to 10 mol%, preferably 1 based on the total molar amount of the tin element and the doping element in the doped tin oxide.
  • the content of the tin element is from 90 to 99.9% by mole, preferably from 92 to 99% by mole.
  • the ratio of the plurality of elements in the present invention is not particularly limited as long as the total amount of the plurality of elements satisfies the foregoing requirements.
  • the doped tin oxide is preferably antimony doped tin oxide, antimony doped tin oxide, fluorine doped tin oxide or antimony doped tin oxide.
  • the particle size of the doped tin oxide can be appropriately selected depending on its specific application.
  • the doped tin oxide may have a volume average particle diameter of from 50 nm to 10 ⁇ m, preferably from 300 nm to 5 ⁇ m, more preferably from 1 to 3.5 ⁇ m. The volume average particle diameter is measured by a laser particle size analyzer.
  • the plastic composition comprises a filler having a surface coated with doped tin oxide.
  • the particle size of the filler coated with the doped tin oxide is not particularly limited, and those skilled in the art can flexibly select according to actual needs.
  • the surface is coated with doping
  • the filler of tin oxide may have a volume average particle diameter of 50 nm to 10 ⁇ m, preferably 300 nm to 5 ⁇ m, more preferably 1 to 3.5 ⁇ m. That is, the filler coated with the doped tin oxide may have a volume average particle diameter of 50 nm to 10 ⁇ m, preferably 300 nm to 5 ⁇ m, more preferably 1-3.5 ⁇ m.
  • the volume average particle diameter is measured by a laser particle size analyzer.
  • the filler i.e., the filler coated with the doped tin oxide
  • the filler may be various fillers conventionally used in the art, and preferably, the filler is at least one selected from the group consisting of mica and silica. Typically, the filler is preferably mica and/or silica.
  • the doped tin oxide has a light color.
  • the tin oxide refers to a compound formed of a tin element and an oxygen element, generally tin dioxide
  • the oxide of the lanthanum refers to a compound formed of a lanthanum element and an oxygen element, generally cerium oxide
  • the oxide of cerium refers to a compound formed of cerium element and oxygen element, generally cerium oxide
  • the oxide of cerium refers to a compound formed of cerium element and oxygen element, generally cerium pentoxide.
  • the doped tin oxide when the doped tin oxide is doped with fluorine, it is present in the form of a fluorine element instead of the oxygen element in the tin oxide.
  • the doped tin oxide according to an embodiment of the present invention can be prepared according to a method known in the art, for example, by a liquid phase sintering method and a solid phase sintering method.
  • the liquid phase sintering method may be, for example, the following method A, method B, and method C.
  • the method A includes the steps of: after dissolving a tin-containing compound, a compound containing the doping element, and citric acid and ethylene glycol in a solvent, esterifying the obtained mixture, and then sintering the obtained product.
  • method A is suitable for the preparation of doped tin oxide doped with one or more elements of lanthanum, cerium and lanthanum elements.
  • the method B includes the steps of: after dissolving the tin-containing compound with citric acid and ethylene glycol in a solvent, esterifying the obtained mixture, and then adding hydrogen fluoride to the obtained product for sintering.
  • method B is suitable for preparing a doped tin oxide doped with a fluorine element.
  • Process C includes the steps of: esterifying a tin-containing compound, a compound containing the doping element (excluding fluorine), and citric acid and ethylene glycol in a solvent, and then esterifying the obtained mixture, and then obtaining The product is sintered by adding hydrogen fluoride.
  • method C is suitable for preparing doped tin oxide doped with fluorine and other doping elements of the invention.
  • the tin-containing compound is preferably tin citrate and/or tin acetate.
  • the compound containing the doping element is preferably hexahydrate hexahydrate.
  • cerium nitrate, cerium nitrate hexahydrate, cerium pentachloride and hydrofluoric acid is preferably hexahydrate hexahydrate.
  • the tin-containing compound and the compound containing the doping element may be used in an amount according to a desired tin element in the doped tin oxide and the doping element.
  • the content is chosen. Specifically, the content of the tin element is from 90 to 99.9% by mole based on the total molar amount of the tin element and the doping element in the tin-containing compound and the compound containing the doping element, preferably 92 to 99 mol%; the total amount of the doping element is from 0.1 to 10 mol%, preferably from 1 to 8 mol%.
  • the amount of the citric acid and the ethylene glycol may be selected according to the tin-containing compound, and the amount of the citric acid and the ethylene glycol is based on 1 mole of the tin-containing compound. It is 4-6 moles and 10-12 moles, respectively.
  • the solvent may be one or more of nitric acid, hydrochloric acid, and phosphoric acid. It is preferably nitric acid.
  • the amount of the solvent to be used is not particularly limited as long as the raw material can be sufficiently dissolved.
  • the conditions of the esterification are not particularly limited, and for example, the esterification temperature may be 160 to 190 ° C, and the esterification time may be 30 to 240 minutes (preferably 60 to 180). minute).
  • the sintering temperature may be 450 to 1000 ° C, preferably 500 to 900 ° C, and the sintering time may be 6 to 24 hours, preferably 10 to 20 hours.
  • the solid phase sintering method comprises the steps of: calcining a powder mixture containing tin oxide and a compound containing the doping element, containing the doping element
  • the compound is an oxide containing the doping element.
  • the oxide of the doping element is an oxide containing cerium, such as cerium oxide; when the doping element contains cerium, the oxide of the doping element is cerium-containing oxide
  • antimony trioxide when the doping element contains antimony, the oxide of the doping element is an oxide containing antimony, such as antimony pentoxide.
  • the content of the tin element is from 90 to 99.9% by mole, preferably from 92 to 99% by mole based on the total molar amount of the tin element and the doping element in the powder mixture; the content of the doping element is 0.1 - 10 mol%, preferably 1-8 mol%.
  • the doping element is a plurality of cerium, lanthanum, fluorine, and cerium
  • the ratio of the plurality of elements in the present invention is not particularly limited as long as the total amount of the plurality of elements satisfies the foregoing requirements.
  • the method for preparing the powder mixture is not particularly limited and may be a conventional selection.
  • tin oxide and a compound containing a doping element may be ground to obtain the powder mixture.
  • the grinding may be dry grinding, wet grinding, or semi-dry grinding.
  • the wet-milled dispersant may be various dispersants commonly used in the grinding process.
  • the dispersing agent may be water and/or a C 1 -C 5 alcohol such as ethanol.
  • the amount of the dispersant used may be a conventional one, and is not particularly limited.
  • wet or semi-dry grinding it is also included to dry the milled mixture to obtain the powder mixture.
  • the drying can be a conventional choice.
  • the drying temperature may be 40 to 120 ° C, may be carried out in an oxygen-containing atmosphere, or may be carried out in an inert atmosphere.
  • the oxygen-containing atmosphere may be, for example, an air atmosphere or an atmosphere formed by mixing oxygen and an inert gas.
  • the inert atmosphere refers to a gas that does not chemically interact with each component or a metal compound formed in the powder mixture, and may be, for example, a gas of a group of elements or nitrogen, and the gas of the group of elements may be argon.
  • the particle diameter of the powder mixture is not particularly limited and may be a conventional selection.
  • the powder mixture may have a volume average particle diameter of 50 nm to 10 ⁇ m.
  • the calcination temperature may be from 800 to 1100 ° C, preferably from 850 to 1050 ° C.
  • the calcination conditions may be appropriately selected depending on the temperature of the calcination, and may generally be from 1 to 24 hours, preferably from 12 to 20 hours.
  • the calcination may be carried out in an oxygen-containing atmosphere or in an inert atmosphere.
  • the product obtained by calcination may be further ground to have a particle size which satisfies the requirements of a specific use case.
  • the conditions of the grinding are such that the calcined product after grinding has a volume average particle diameter of 50 nm to 10 ⁇ m, preferably 300 nm to 5 ⁇ m, more preferably 1-3.5 ⁇ m.
  • the grinding may be dry grinding, wet grinding, or semi-dry grinding.
  • the wet-milled dispersant may be various dispersants commonly used in the grinding process.
  • the dispersing agent may be water and/or a C 1 -C 5 alcohol such as ethanol.
  • the amount of the dispersant used may be a conventional one, and is not particularly limited.
  • a method of preparing the doped tin oxide-coated filler is not particularly limited, and a coating method commonly used in the art may be employed.
  • the filler may be added to the above method A in accordance with the conditions of the method A. That is, after dissolving the tin-containing compound, the compound containing the doping element, the filler, and citric acid and ethylene glycol in a solvent, the resulting mixture is esterified, and then the obtained product is sintered.
  • the amount of the filler used may be a conventional amount in the art.
  • the filler is used in an amount of from 0.01 to 0.1 mol, more preferably from 0.02 to 0.05 mol, still more preferably from 0.02 to 0.03 mol, per mol of the tin-containing compound.
  • the doped tin oxide in the plastic composition, is contained in an amount of 1 to 20 parts by weight relative to 100 parts by weight of the base resin; preferably, relative to 100 parts by weight
  • the base resin has a content of the doped tin oxide of 3 to 10 parts by weight.
  • the content of the filler surface-coated with the doped tin oxide is 1-20 parts by weight with respect to 100 parts by weight of the base resin.
  • the filler is coated with the doped tin oxide in an amount of 3 to 10 parts by weight with respect to 100 parts by weight of the base resin.
  • the content of the filler coated with the doped tin oxide is from 1 to 20 parts by weight relative to 100 parts by weight of the base resin; preferably, relative to 100 parts by weight
  • the base resin is contained in an amount of 3 to 10 parts by weight of the filler coated with the doped tin oxide.
  • the base resin may be a thermoplastic resin or a thermosetting resin.
  • the substrate resin may include, but are not limited to, polyolefins (such as polystyrene, polypropylene, polymethyl methacrylate, and poly(acrylonitrile-butadiene-styrene)), polycarbonate, Polyester (such as polybutylene terephthalate p-diethanol ester, poly(diallyl isophthalate), poly(terephthalate), polybutylene naphthalate, polyterephthalate Ethylene glycol ester and polybutylene terephthalate), polyamide (such as polyhexamethylene adipamide, polyphthalamide, polysuccinamide, polydodecanedioyl) Hexamethylenediamine, polydecamethylenediamine, polydecanoyldiamine, polyundecamide, polydodecamide, polyoctanoic acid, poly 9-a
  • the plastic composition may further contain at least one auxiliary agent such as a filler, an antioxidant, a light stabilizer, and a lubricant to improve the performance or impart of the plastic article obtained by the plastic composition.
  • auxiliary agent such as a filler, an antioxidant, a light stabilizer, and a lubricant to improve the performance or impart of the plastic article obtained by the plastic composition.
  • the content of the auxiliary agent can be appropriately selected depending on the kind and specific use requirements, and is not particularly limited.
  • the filler may be a filler that does not have any physical or chemical action on the laser, such as talc and calcium carbonate.
  • talc glass fiber
  • the inorganic filler may also be an inorganic filler that plays a role in laser light.
  • the filler may also be glass microbeads, calcium sulfate, barium sulfate, titanium dioxide, pearl powder, wollastonite, diatomaceous earth, kaolin, One or more of clay, mica, oil shale ash, aluminum silicate, alumina, silica, and zinc oxide.
  • the antioxidant can improve the oxidation resistance of the plastic article obtained by the plastic composition of the present invention, thereby increasing the service life of the article.
  • the antioxidant may be various antioxidants commonly used in the field of polymers, and may, for example, contain a primary antioxidant and a secondary antioxidant.
  • the relative amount of the primary antioxidant and the auxiliary antioxidant can be appropriately selected depending on the kind.
  • the weight ratio of the primary antioxidant to the secondary antioxidant may range from 1 to 4 .
  • the primary antioxidant may be a hindered phenol type antioxidant, and specific examples thereof may include, but are not limited to, an antioxidant 1098 and an antioxidant 1010, wherein the main component of the antioxidant 1098 is N, N'-double- (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, the main component of the antioxidant 1010 is tetrakis[3-(3,5-di-tert-butyl-4- Hydroxyphenyl) propionic acid] pentaerythritol.
  • an antioxidant 1098 is N, N'-double- (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine
  • the main component of the antioxidant 1010 is tetrakis[3-(3,5-di-tert-butyl-4- Hydroxyphenyl) propionic acid] pentaerythritol.
  • the auxiliary antioxidant may be a phosphite type antioxidant, and specific examples thereof may include, but are not limited to, an antioxidant 168 whose main component is tris(2,4-di-tert-butylphenyl)phosphite.
  • the light stabilizer may be various known light stabilizers, such as a hindered amine type light stabilizer, and specific examples thereof may include, but are not limited to, double (2, 2, 6, 6-tetra Base-4-piperidinyl) sebacate.
  • the lubricant may be various substances capable of improving the fluidity of the polymer melt, and may be, for example, a copolymer wax (EVA wax) selected from ethylene/vinyl acetate, and a polyethylene wax (PE wax). And one or more of stearates.
  • EVA wax copolymer wax
  • PE wax polyethylene wax
  • the content of the auxiliary agent can be appropriately selected depending on the function and kind of the auxiliary agent.
  • the filler may be included in an amount of 1 to 40 parts by weight, and the antioxidant may be contained in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of the base resin, of the light stabilizer. It may be 0.1 to 10 parts by weight, and the lubricant may be contained in an amount of 0.1 to 10 parts by weight.
  • a plastic article according to an embodiment of the present invention wherein the plastic substrate may be formed only by a surface in contact with the metal plating layer, or only a surface to which the metal plating layer is attached, or may be integrally formed of the plastic composition Formed, that is, the plastic substrate is formed from the plastic composition.
  • the plastic substrate is formed from the plastic composition.
  • the size of the plastic substrate is large, from the viewpoint of cost reduction, only the surface on which the metal substrate is adhered to the plastic substrate may be formed of the plastic composition; when the size of the plastic substrate is not large, the whole may be The plastic composition is formed.
  • the specific size of the plastic substrate can be selected according to the intended use, and is not particularly limited.
  • the plastic substrate may also have various shapes depending on specific needs.
  • the plastic substrate can be prepared by a conventional method such as an extrusion molding process or an injection molding process.
  • the thickness of the metal plating layer may be determined according to specific use requirements, and is not particularly limited, and may generally be 0.1 to 10 ⁇ m.
  • the metal plating layer may have various shapes depending on specific use requirements. For example, when the plastic article is used to make a wiring board, the metal layer may form a wiring pattern.
  • the present invention also provides a method for selectively metallizing a surface of a plastic substrate, the method comprising: irradiating a surface of a plastic substrate with a beam of energy to irradiate the surface of the irradiated surface with an energy beam; And electroless plating the surface of the plastic substrate irradiated with the energy beam to form a metal plating layer, wherein a surface of the plastic substrate in contact with the metal plating layer is formed of a plastic composition.
  • the plastic composition contains: a base resin; and doped tin oxide, and the doping element in the doped tin oxide is at least one selected from the group consisting of ruthenium, osmium, fluorine, and ruthenium.
  • the method includes: irradiating the surface of the plastic substrate with the energy beam with the energy beam to vaporize the surface to be irradiated; and electroless plating the irradiated plastic substrate, wherein the plastic substrate
  • the surface to be metallized is formed from a plastic composition comprising a substrate resin and at least one doped tin oxide or a filler coated with the doped tin oxide, the doping
  • the doping element in the tin oxide is one or more of cerium, lanthanum, fluorine and cerium.
  • the substrate and the substrate resin have been described in detail above and will not be described in detail herein.
  • a method of selectively metallizing a surface of a plastic substrate which may be a laser, an electron beam or an ion beam, preferably a laser.
  • the conditions of the energy beam irradiation are such that the surface of the irradiated polymer article can be vaporized to expose the doped tin oxide.
  • the energy beam when the energy beam is a laser, the laser may have a wavelength of 157-10600 nm and a power of 1-100 W; when the energy beam is an electron beam, the power density of the electron beam may be 10 -10 11 W/cm 2 ; when the energy beam is an ion beam, the energy of the ion beam may be 10-10 6 eV.
  • the energy beam is preferably a laser from the viewpoint of further improving the accuracy of the pattern formed by electroless plating. Since the surface of the polymer substrate that needs to be metallized contains the doped tin oxide, the doped tin oxide has a higher absorption capacity for the energy beam, and thus is irradiated even with a lower energy energy beam.
  • the surface of the polymer substrate can also be vaporized and stripped.
  • the energy beam is preferably a laser having a wavelength of 1064 to 10600 nm and a power of 3 to 50 W, more preferably a wavelength of 1064 nm and a power of 3 to 40 W (more preferably 5-20W) laser.
  • the method may include contacting the irradiated plastic article with a copper plating solution containing a copper salt and a reducing agent, having a pH of 12-13, the reducing agent capable of transferring copper
  • the copper ion in the salt is reduced to a simple substance of copper.
  • the reducing agent may be one or more of glyoxylic acid, hydrazine, and sodium hypophosphite.
  • the thickness of the metal plating layer formed by electroless plating may be determined according to specific use requirements, and is not particularly limited, and may generally be 0.1 to 10 ⁇ m.
  • the metal layer may have various shapes depending on the specific use requirements. For example, when used to make a wiring board, the metal layer may form a wiring pattern.
  • electroplating may be further performed or one or more electroless plating may be performed to further increase the thickness of the plating layer or form other metal plating layers on the electroless plating layer.
  • a layer of nickel may be electrolessly plated to prevent the surface of the copper plating layer from being oxidized.
  • the metal plating on the surface of the plastic substrate obtained by the surface selective metallization method of the plastic substrate according to the embodiment of the present invention is continuous and has high adhesion to the substrate.
  • ICP inductively coupled plasma optical emission spectroscopy
  • the volume average particle diameter was measured using a laser particle size tester commercially available from Chengdu Jingxin Powder Testing Equipment Co., Ltd.
  • the light absorption of doped tin oxide at a wavelength of 1064 nm was measured using a lambda 750 ultraviolet/visible/near infrared spectrophotometer.
  • the adhesion of the metal layer formed on the surface of the substrate was measured by a hundred-knife method.
  • the body test method is: using a hundred grid knife to draw 10 ⁇ 10 small grids of 1 mm ⁇ 1 mm on the surface of the sample to be tested, each line is deep and the bottom layer of the metal layer is used, and the debris of the test area is brushed with a brush.
  • Stick the small mesh to be tested with tape (3M600 adhesive tape) grasp the end of the tape with your hand, quickly pull off the adhesive tape in the vertical direction, perform the same test twice at the same position, and determine the adhesion level according to the following criteria. :
  • the edge of the scribe line is smooth, and no metal layer falls off at the edge of the scribe line and at the intersection;
  • the doped tin oxide obtained in the step (1) is added to the polycarbonate, and after mixing uniformly, the obtained mixture is sent to an extruder to carry out extrusion granulation.
  • the obtained pellets were fed into an injection molding machine and injection molded to obtain a plastic sheet containing doped tin oxide.
  • the doped tin oxide was used in an amount of 3 parts by weight based on 100 parts by weight of the polycarbonate.
  • the surface of the plastic sheet obtained in the step (2) was irradiated with a laser light generated by a YAG laser to form a pattern of an antenna as a receiver on the surface of the plastic sheet.
  • the conditions of laser irradiation include: the laser wavelength is 1064 nm, the power is 8 W, the frequency is 20 kHz, the wire speed is 2000 mm/s, and the filling pitch is 30 ⁇ m.
  • the plastic sheet obtained in the step (3) is placed in a plating solution, and electrolessly plated to form a metal plating layer of an antenna pattern to obtain a plastic product.
  • the composition of the plating solution is: CuSO 4 ⁇ 5H 2 O 0.12mol/L, Na 2 EDTA ⁇ 2H 2 O 0.14mol/L, potassium ferrocyanide 10mg/L, 2,2'-bipyridyl 10mg/L, B
  • the aldehyde acid was 0.10 mol/L, and the pH of the plating solution was adjusted to 12.5-13 with NaOH and H 2 SO 4 , and the temperature of the plating solution was 50 °C.
  • Example 1 The procedure of the step (1) in Example 1 was carried out, except that the amount of LaN 3 O 9 ⁇ 6H 2 O was 2.45 mmol, the amount of citric acid was 1 mol, and the amount of ethylene glycol was 2.5 mol.
  • the calcined product was ground to a volume average particle diameter of 1 ⁇ m to obtain doped tin oxide.
  • the composition of the doped tin oxide was determined to be 0.95SnO 2 ⁇ 0.05La 2 O 3 . Its light absorption at a wavelength of 1064 nm is shown in Table 1.
  • a plastic sheet was prepared in the same manner as in the step (2) of Example 1, except that the doped tin oxide was the doped tin oxide prepared in the step (1) of Example 2, and was relative to 100 weight.
  • the polycarbonate was doped in an amount of 5 parts by weight.
  • Example 1 The procedure of the step (1) in Example 1 was carried out, except that the amount of LaN 3 O 9 ⁇ 6H 2 O was 4.04 mmol, the amount of citric acid was 1.2 mol, and the amount of ethylene glycol was 2.8. Mol, the calcined product was ground to a volume average particle diameter of 3 ⁇ m to obtain doped tin oxide.
  • the composition of the doped tin oxide was determined to be 0.92 SnO 2 ⁇ 0.08 La 2 O 3 . Its light absorption at a wavelength of 1064 nm is shown in Table 1.
  • a plastic sheet was prepared in the same manner as in the step (2) of Example 1, except that the doped tin oxide was the doped tin oxide prepared in the step (1) of Example 3, and was relative to 100 weight.
  • the polycarbonate was doped in an amount of 10 parts by weight.
  • the doped tin oxide obtained in the step (1) is added to the polycarbonate, and after mixing uniformly, the obtained mixture is sent to an extruder to carry out extrusion granulation.
  • the obtained pellets were fed into an injection molding machine and injection molded to obtain a plastic sheet containing doped tin oxide.
  • the doped tin oxide was used in an amount of 3 parts by weight based on 100 parts by weight of the polycarbonate.
  • the surface of the plastic sheet obtained in the step (2) was irradiated with a laser light generated by a YAG laser to form a pattern of an antenna as a receiver on the surface of the plastic sheet.
  • the conditions of laser irradiation include: the laser wavelength is 1064 nm, the power is 8 W, the frequency is 20 kHz, the wire speed is 2000 mm/s, and the filling pitch is 30 ⁇ m.
  • the plastic sheet obtained in the step (3) is placed in a plating solution, and electrolessly plated to form a metal plating layer of an antenna pattern to obtain a plastic product.
  • the composition of the plating solution is: CuSO 4 ⁇ 5H 2 O 0.12mol/L, Na 2 EDTA ⁇ 2H 2 O 0.14mol/L, potassium ferrocyanide 10mg/L, 2,2'-bipyridyl 10mg/L, B
  • the aldehyde acid was 0.10 mol/L, and the pH of the plating solution was adjusted to 12.5-13 with NaOH and H 2 SO 4 , and the temperature of the plating solution was 50 °C.
  • Example 1 The procedure of the step (1) in Example 1 was carried out, except that the amount of CeN 3 O 9 ⁇ 6H 2 O was 2.45 mmol, the amount of citric acid was 1 mol, and the amount of ethylene glycol was 2.5 mol.
  • the calcined product was ground to a volume average particle diameter of 1 ⁇ m to obtain doped tin oxide.
  • the doped tin oxide composition was determined to be 0.95SnO 2 ⁇ 0.05CeO 2 . Its light absorption at a wavelength of 1064 nm is shown in Table 1.
  • a plastic sheet was prepared in the same manner as in the step (2) of Example 4 except that the doped tin oxide was the doped tin oxide prepared in the step (1) of Example 5, and was relative to 100 weight.
  • the polycarbonate was doped in an amount of 5 parts by weight.
  • Example 1 The procedure of the step (1) in Example 1 was carried out, except that the amount of CeN 3 O 9 ⁇ 6H 2 O was 4.04 mmol, the amount of citric acid was 1.2 mmol, and the amount of ethylene glycol was 2.8.
  • the calcined product was ground to a volume average particle diameter of 3 ⁇ m to obtain doped tin oxide.
  • the doped tin oxide composition was determined to be 0.92 SnO 2 ⁇ 0.08 CeO 2 . Its light absorption at a wavelength of 1064 nm is shown in Table 1.
  • a plastic sheet was prepared in the same manner as in the step (2) of Example 4 except that the doped tin oxide was the doped tin oxide prepared in the step (1) of Example 6, and was relative to 100 weight.
  • the polycarbonate was doped in an amount of 10 parts by weight.
  • the doped tin oxide obtained in the step (1) is added to the polycarbonate, and after mixing uniformly, the obtained mixture is sent to an extruder to carry out extrusion granulation.
  • the obtained pellets were fed into an injection molding machine and injection molded to obtain a plastic sheet containing doped tin oxide.
  • the doped tin oxide was used in an amount of 3 parts by weight based on 100 parts by weight of the polycarbonate.
  • the surface of the plastic sheet obtained in the step (2) was irradiated with a laser light generated by a YAG laser to form a pattern of an antenna as a receiver on the surface of the plastic sheet.
  • the conditions of laser irradiation include: the laser wavelength is 1064 nm, the power is 8 W, the frequency is 20 kHz, the wire speed is 2000 mm/s, and the filling pitch is 30 ⁇ m.
  • the plastic sheet obtained in the step (3) is placed in a plating solution, and electrolessly plated to form a metal plating layer of an antenna pattern to obtain a plastic product.
  • the composition of the plating solution is: CuSO 4 ⁇ 5H 2 O 0.12mol/L, Na 2 EDTA ⁇ 2H 2 O 0.14mol/L, potassium ferrocyanide 10mg/L, 2,2'-bipyridyl 10mg/L, B
  • the aldehyde acid was 0.10 mol/L, and the pH of the plating solution was adjusted to 12.5-13 with NaOH and H 2 SO 4 , and the temperature of the plating solution was 50 °C.
  • Example 1 The procedure of the step (1) in Example 1 was carried out, except that the amount of Ta 2 O 5 was 1.225 mmol.
  • the composition of the doped tin oxide was determined to be 0.95SnO 2 ⁇ 0.025Ta 2 O 5 . Its light absorption at a wavelength of 1064 nm is shown in Table 1.
  • a plastic sheet was prepared in the same manner as in the step (2) of Example 7, except that the doped tin oxide was the doped tin oxide prepared in the step (1) of Example 8, and was relative to 100 weight.
  • the polycarbonate was doped in an amount of 5 parts by weight.
  • Example 1 The procedure of the step (1) in Example 1 was carried out, except that the amount of Ta 2 O 5 was 2.02 mmol.
  • the composition of the doped tin oxide was determined to be 0.92 SnO 2 ⁇ 0.04 Ta 2 O 5 . Its light absorption at a wavelength of 1064 nm is shown in Table 1.
  • a plastic sheet was prepared in the same manner as in the step (2) of Example 7, except that the doped tin oxide was the doped tin oxide prepared in the step (1) of Example 9, and was relative to 100 weight.
  • the polycarbonate was doped in an amount of 10 parts by weight.
  • the doped tin oxide obtained in the step (1) is added to the polycarbonate, and after mixing uniformly, the obtained mixture is sent to an extruder to carry out extrusion granulation.
  • the obtained pellets were fed into an injection molding machine and injection molded to obtain a plastic sheet containing doped tin oxide.
  • the doped tin oxide was used in an amount of 3 parts by weight based on 100 parts by weight of the polycarbonate.
  • the surface of the plastic sheet obtained in the step (2) was irradiated with a laser light generated by a YAG laser to form a pattern of an antenna as a receiver on the surface of the plastic sheet.
  • the conditions of laser irradiation include: the laser wavelength is 1064 nm, the power is 8 W, the frequency is 20 kHz, the wire speed is 2000 mm/s, and the filling pitch is 30 ⁇ m.
  • the plastic sheet obtained in the step (3) is placed in a plating solution, and electrolessly plated to form a metal plating layer of an antenna pattern to obtain a plastic product.
  • the composition of the plating solution is: CuSO 4 ⁇ 5H 2 O 0.12mol/L, Na 2 EDTA ⁇ 2H 2 O 0.14mol/L, potassium ferrocyanide 10mg/L, 2,2'-bipyridyl 10mg/L, B
  • the aldehyde acid was 0.10 mol/L, and the pH of the plating solution was adjusted to 12.5-13 with NaOH and H 2 SO 4 , and the temperature of the plating solution was 50 °C.
  • Example 10 The procedure of the step (1) in Example 10 was carried out, except that the amount of hydrofluoric acid was 2.45 mmol, the amount of citric acid was 1 mmol, and the amount of ethylene glycol was 2.5 mmol, and the calcined product was ground. The volume average particle diameter was 1 ⁇ m to obtain doped tin oxide.
  • the composition of the doped tin oxide was determined to be SnO 1.947 F 0.053 . Its light absorption at a wavelength of 1064 nm is shown in Table 1.
  • a plastic sheet was prepared in the same manner as in the step (2) of Example 10 except that the doped tin oxide was the doped tin oxide prepared in the step (1) of Example 11, and was relative to 100 weight.
  • the polycarbonate was doped in an amount of 5 parts by weight.
  • Example 10 The procedure of the step (1) in Example 10 was carried out, except that hydrofluoric acid was 4.04 mmol, the amount of citric acid was 1.2 mmol, and the amount of ethylene glycol was 2.8 mmol, and the calcined product was ground into The volume average particle diameter was 3 ⁇ m to obtain doped tin oxide.
  • the composition of the doped tin oxide was determined to be SnO 1.913 F 0.087 . Its light absorption at a wavelength of 1064 nm is shown in Table 1.
  • a plastic sheet was prepared in the same manner as in the step (2) of Example 10 except that the doped tin oxide was the doped tin oxide prepared in the step (1) of Example 3, and was relative to 100 weight.
  • the polycarbonate was doped in an amount of 10 parts by weight.
  • a doped tin oxide was prepared in the same manner as in the step (1) of Example 1, except that tin citrate (46.5 mmol), LaN 3 O 9 ⁇ 6H 2 O (0.47 mmol), and citric acid were used. (248 mmol), ethylene glycol (511 mmol) and mica (1 mmol) were mixed to obtain a filler coated with doped tin oxide.
  • the composition of the doped tin oxide was determined to be 0.99SnO 2 ⁇ 0.01La 2 O 3 . Its light absorption at a wavelength of 1064 nm is shown in Table 1.
  • a plastic sheet was prepared in the same manner as in the step (2) of Example 1, except that the doped tin oxide was a doped tin oxide-coated filler prepared in the step (1) of Example 13, And the amount of the filler coated with the doped tin oxide is 5 parts by weight with respect to 100 parts by weight of the polycarbonate.
  • a doped tin oxide was prepared in the same manner as in the step (1) of Example 1, except that LaN 3 O 9 ⁇ 6H 2 O was replaced with the same molar amount of SbCl 3 .
  • the composition of the doped tin oxide was determined to be 0.99SnO 2 ⁇ 0.01SbO 2 . Its light absorption at a wavelength of 1064 nm is shown in Table 1.
  • a plastic sheet was prepared in the same manner as in the step (2) of Example 1, except that the doped tin oxide was the doped tin oxide prepared in the step (1) of Comparative Example 1.
  • Example 1 Plating speed ( ⁇ m/h) Adhesion Absorbance of doped tin oxide (%) Example 1 7 0 70 Example 2 8 1 75 Example 3 10 0 77 Example 4 7 0 66 Example 5 9 1 70 Example 6 11 0 78 Example 7 6 1 60 Example 8 7 0 66 Example 9 8 0 75 Example 10 8 0 71 Example 11 9 1 80 Example 12 11 1 85 Example 13 11 1 84 Comparative example 1 5 2 60

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Abstract

一种塑料制品以及塑料基材表面选择性金属化的方法，该塑料制品包括塑料基材，以及形成在塑料基材表面上的金属镀层，其中，塑料基材与金属镀层接触的表面是由塑料组合物形成的，该塑料组合物含有：基材树脂；以及掺杂的氧化锡，掺杂的氧化锡中的掺杂元素为选自铈、镧、氟和钽中的至少一种。

Description

塑料制品和塑料基材表面选择性金属化方法 技术领域
本发明涉及一种塑料制品以及塑料基材表面选择性金属化的方法。
背景技术
在如塑料的绝缘性基材表面选择性形成金属层，将其作为电磁信号传导的通路，广泛用于汽车、计算机和通讯等领域。可以采用多种方法在如塑料的绝缘性基材表面形成金属层。
目前，在塑料基材表面选择性形成金属层时，通常将金属氧化物预置在如塑料的绝缘性基材中，经激光照射后进行化学镀，从而将绝缘性基材表面选择性金属化。上述金属氧化物通常使用锑掺杂氧化锡，但是，使用锑掺杂氧化锡存在吸光性能不好和化学镀活性不高的问题。
发明内容
本发明的目的在于克服上述使用锑掺杂氧化锡所存在的吸光性能不好和化学镀活性不高的问题，提供一种吸光性能好和化学镀活性高的塑料制品以及塑料基材表面选择性金属化的方法。
本发明的发明人经过深入的研究发现，在氧化锡中掺杂氧铈、镧、氟和钽中的一种或多种元素的氧化物而得到的掺杂的氧化锡，具有比锑掺杂氧化锡高得多的吸光性，即使在较低的添加量下，或者使用低能量的激光束进行照射，也能使含有这种掺杂的氧化锡的基材表面剥离；并且，暴露出掺杂的氧化锡的化学镀活性极高。在此基础上完成了本发明。
为了实现上述目的，本发明提供了一种塑料制品。根据本发明的实施例，该塑料制品包括：塑料基材，以及形成在塑料基材表面上的金属镀层，其中，塑料基材与金属镀层接触的表面是由塑料组合物形成的，该塑料组合物含有：基材树脂；以及掺杂的氧化锡，所述掺杂的氧化锡中的掺杂元素为选自铈、镧、氟和钽中的至少一种。
本发明还提供了一种塑料基材表面选择性金属化方法，该方法包括：用能量束照射塑料基材的需要进行金属化的表面，使被照射的表面气化；以及将塑料基材上经能量束照射后的表面进行化学镀，以便形成金属镀层，其中，塑料基材与金属镀层接触的表面是由塑料组合物形成的，该塑料组合物含有：基材树脂；以及掺杂的氧化锡，该掺杂的氧化锡中的掺杂元素为选自铈、镧、氟和钽中的至少一种。
此外，本发明还提供一种由上述方法制备的塑料制品。
根据本发明，所述掺杂的氧化锡在添加到基材树脂中时，能够使得到的塑料制品对能量束的吸收能力强，即使以较低的添加量添加到基材中，也足以使被能量束照射的基材表面气化剥离，并且，暴露出所述掺杂的氧化锡的化学镀活性极高，易于在其上镀覆金属层。
本发明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。
具体实施方式
以下对本发明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发明，并不用于限制本发明。
根据本发明的第一方面，本发明提供了一种塑料制品，该塑料制品包括塑料基材；以及形成在塑料基材表面上的金属镀层，其中，塑料基材与金属镀层接触的表面是由塑料组合物形成的，该塑料组合物含有：基材树脂；以及掺杂的氧化锡，该掺杂的氧化锡中的掺杂元素为选自铈、镧、氟和钽中的至少一种。或者可以说，该塑料制品包括塑料基材以及附着在所述塑料基材的至少部分表面的金属镀层，附着有所述金属镀层的塑料基材表面由一种塑料组合物形成，所述塑料组合物含有基材树脂和至少一种掺杂的氧化锡或由该掺杂的氧化锡包覆的填料，其中，所述掺杂的氧化锡中的掺杂元素为铈、镧、氟和钽中的一种或多种。
根据本发明的实施例，基于掺杂的氧化锡中锡元素和掺杂元素的总摩尔量，锡元素的含量为90-99.9摩尔％，优选为92-99摩尔％，掺杂元素的含量为0.1-10摩尔％，优选为1-8摩尔％。换句话说，以该掺杂的氧化锡中锡元素和掺杂元素的总摩尔量为基准，所述掺杂的氧化锡中掺杂元素的总量可以为0.1-10摩尔％，优选为1-8摩尔％，锡元素的含量为90-99.9摩尔％，优选为92-99摩尔％。在所述掺杂元素为铈、镧、氟和钽中的多种时，本发明对于所述多种元素之间的比例没有特别限定，只要多种元素的总量满足前述要求即可。
根据本发明的实施例，所述掺杂的氧化锡优选为铈掺杂的氧化锡、镧掺杂的氧化锡、氟掺杂的氧化锡或钽掺杂的氧化锡。根据本发明的实施例，所述掺杂的氧化锡的粒径可以根据其具体应用场合进行适当的选择。一般地，所述掺杂的氧化锡的体积平均粒径可以为50nm至10μm，优选为300nm至5μm，更优选为1-3.5μm。所述体积平均粒径是采用激光粒度仪测定的。
根据本发明的实施例，塑料组合物包括：表面包覆有掺杂的氧化锡的填料。
根据本发明的实施例，所述表面包覆有掺杂的氧化锡的填料的粒径不受特别限制，本领域技术人员可以根据实际需要灵活选择。在本发明的一些实施例中，表面包覆有掺杂的 氧化锡的填料的体积平均粒径可以为50nm至10μm，优选为300nm至5μm，更优选为1-3.5μm。也就是说，由所述掺杂的氧化锡包覆的填料的体积平均粒径可以为50nm至10μm，优选为300nm至5μm，更优选为1-3.5μm。所述体积平均粒径是采用激光粒度仪测定的。
根据本发明的实施例，填料(即由所述掺杂的氧化锡包覆的填料)可以本领域常规使用的各种填料，优选情况下，填料为选自云母和二氧化硅中的至少一种，也就是说，填料优选为云母和/或二氧化硅。
根据本发明的实施例，所述掺杂的氧化锡的颜色为浅色。
根据本发明的实施例，所述掺杂的氧化锡掺杂有铈、镧和钽元素时，锡、铈、镧和钽元素是以各自的氧化物形态存在的。所述锡的氧化物是指由锡元素与氧元素形成的化合物，一般为二氧化锡；所述铈的氧化物是指由铈元素与氧元素形成的化合物，一般为二氧化铈；所述镧的氧化物是指由镧元素与氧元素形成的化合物，一般为三氧化二镧；所述钽的氧化物是指由钽元素与氧元素形成的化合物，一般为五氧化二钽。
根据本发明的实施例，所述掺杂的氧化锡掺杂有氟时，是以氟元素替代氧化锡中的氧元素的形态存在的。
根据本发明实施例的掺杂的氧化锡可以按照本领域公知的方法进行制备，例如可以采用液相烧结法和固相烧结法进行制备。
根据本发明的实施例，所述液相烧结法例如可以为下述方法A、方法B和方法C。
方法A包括以下步骤：将含锡化合物、含所述掺杂元素的化合物与柠檬酸和乙二醇溶解于溶剂中后，将所得到的混合物进行酯化，然后，将得到的产物进行烧结。
根据本发明的实施例，方法A适合于制备掺杂有铈、镧和钽元素的一种或多种元素的掺杂氧化锡。
方法B包括以下步骤：将含锡化合物与柠檬酸和乙二醇溶解于溶剂中后，将所得到的混合物进行酯化，然后，在得到的产物中加入氟化氢进行烧结。
根据本发明的实施例，方法B适用于制备掺杂有氟元素的掺杂氧化锡。
方法C包括以下步骤：将含锡化合物、含所述掺杂元素(不包括氟)的化合物与柠檬酸和乙二醇溶解于溶剂中后，将所得到的混合物进行酯化，然后，在得到的产物中加入氟化氢进行烧结。
根据本发明的实施例，方法C适合于制备掺杂有氟和本发明其它掺杂元素的掺杂氧化锡。
根据本发明实施例的液相烧结法中，所述含锡化合物优选为柠檬酸锡和/或乙酸锡。
根据本发明实施例的液相烧结法中，作为含所述掺杂元素的化合物优选为六水合硝酸 镧、六水合硝酸铈、五氯化钽和氢氟酸中的一种或多种。
根据本发明实施例的液相烧结法中，所述含锡化合物和含所述掺杂元素的化合物的用量，可以根据期望得到的掺杂的氧化锡中的锡元素与所述掺杂元素的含量来选择。具体地，以所述含锡化合物和含所述掺杂元素的化合物中的锡元素和所述掺杂元素的合计摩尔量为基准，所述锡元素的含量为90-99.9摩尔％，优选为92-99摩尔％；所述掺杂元素的总量为0.1-10摩尔％，优选为1-8摩尔％。
根据本发明实施例的液相烧结法中，所述柠檬酸和乙二醇的用量可以根据含锡化合物来选择，以1摩尔的含锡化合物为基准，所述柠檬酸和乙二醇的用量分别为4-6摩尔和10-12摩尔。
根据本发明实施例的液相烧结法中，所述溶剂可以为硝酸、盐酸和磷酸中的一种或多种。优选为硝酸。所述溶剂的用量没有特别的限定，只要能够将原料充分溶解即可。
根据本发明实施例的液相烧结法中，所述酯化的条件没有特别的限定，例如酯化的温度可以为160-190℃，酯化的时间为30-240分钟(优选为60-180分钟)。
根据本发明实施例的液相烧结法中，所述烧结的温度可以为450-1000℃，优选为500-900℃，烧结的时间可以为6-24小时，优选为10-20小时。
根据本发明的实施例，所述固相烧结法包括以下步骤：将一种粉体混合物进行焙烧，所述粉体混合物含有氧化锡和含所述掺杂元素的化合物，含所述掺杂元素的化合物为含所述掺杂元素的氧化物。
在掺杂元素含有铈时，所述掺杂元素的氧化物为含有铈的氧化物，如二氧化铈；在掺杂元素含有镧时，所述掺杂元素的氧化物为含有镧的氧化物，如三氧化二镧；在掺杂元素含有钽时，所述掺杂元素的氧化物为含有钽的氧化物，如五氧化二钽。
以所述粉体混合物中锡元素和掺杂元素的总摩尔量为基准，所述锡元素的含量为90-99.9摩尔％，优选为92-99摩尔％；所述掺杂元素的含量为0.1-10摩尔％，优选为1-8摩尔％。在所述掺杂元素为铈、镧、氟和钽中的多种时，本发明对于所述多种元素之间的比例没有特别限定，只要多种元素的总量满足前述要求即可。
在本发明的固相烧结法中，对于制备所述粉体混合物的方法没有特别限定，可以为常规选择。例如：可以将氧化锡和含掺杂元素的化合物进行研磨，从而得到所述粉体混合物。所述研磨可以为干法研磨，也可以为湿法研磨，还可以为半干法研磨。所述湿法研磨的分散剂可以为研磨工艺中常用的各种分散剂。具体地，所述分散剂可以为水和/或C1-C5的醇(如乙醇)。分散剂的用量可以为常规选择，没有特别限定。在采用湿法研磨或半干法研磨时，还包括将研磨得到的混合物进行干燥，以得到所述粉体混合物。所述干燥可以为常规 选择。具体地，所述干燥的温度可以为40-120℃，可以在含氧气氛中进行，也可以在非活性气氛中进行。本文中，所述含氧气氛例如可以为空气气氛，或者将氧气与非活性气体混合形成的气氛。所述非活性气氛是指不与粉体混合物中的各组分或者生成的金属化合物发生化学相互作用的气体，例如可以为零族元素气体或者氮气，所述零族元素气体可以为氩气。
在本发明的固相烧结法中，所述粉体混合物的粒径没有特别限定，可以为常规选择。一般地，所述粉体混合物的体积平均粒径可以为50nm至10μm。
在本发明的固相烧结法中，所述焙烧的温度可以为800-1100℃，优选为850-1050℃。所述焙烧的条件可以根据焙烧的温度进行适当的选择，一般可以为1-24小时，优选为12-20小时。所述焙烧可以在含氧气氛中进行，也可以在非活性气氛中进行。
在本发明的固相烧结法中，焙烧得到的产物可以进一步进行研磨，以使其粒径满足具体使用场合的要求。一般地，所述研磨的条件使得研磨后的焙烧产物的体积平均粒径为50nm至10μm，优选为300nm至5μm，更优选为1-3.5μm。所述研磨可以为干法研磨，也可以为湿法研磨，还可以为半干法研磨。所述湿法研磨的分散剂可以为研磨工艺中常用的各种分散剂。具体地，所述分散剂可以为水和/或C1-C5的醇(如乙醇)。分散剂的用量可以为常规选择，没有特别限定。
根据本发明的实施例，对于掺杂的氧化锡包覆的填料的制备方法没有特别的限定，可以采用本领域常用的包覆方法。例如可以在上述方法A中加入所述填料，按照方法A的条件进行。也即，将含锡化合物、含所述掺杂元素的化合物、所述填料与柠檬酸和乙二醇溶解于溶剂中后，将所得到的混合物进行酯化，然后，将得到的产物进行烧结。所述填料的用量，可以为本领域的常规用量。优选地，相对于1mol的所述含锡化合物，所述填料的用量为0.01-0.1摩尔，更优选为0.02-0.05摩尔，进一步优选为0.02-0.03摩尔。
根据本发明的一些实施例，在塑料组合物中，相对于100重量份的所述基材树脂，所述掺杂的氧化锡的含量为1-20重量份；优选地，相对于100重量份的所述基材树脂，所述掺杂的氧化锡的含量为3-10重量份。
根据本发明的另一些实施例，在塑料组合物中，相对于100重量份的所述基材树脂，表面包覆有所述掺杂的氧化锡的所述填料的含量为1-20重量份，优选地，相对于100重量份的所述基材树脂，表面包覆有所述掺杂的氧化锡的所述填料的含量为3-10重量份。或者说，在塑料组合物中，相对于100重量份的所述基材树脂，由所述掺杂的氧化锡包覆的填料的含量为1-20重量份；优选地，相对于100重量份的所述基材树脂，由所述掺杂的氧化锡包覆的填料的含量为3-10重量份。
根据本发明的实施例，所述基材树脂可以为热塑性树脂，也可以为热固性树脂。所述基材树脂的具体实例可以包括但不限于：聚烯烃(如聚苯乙烯、聚丙烯、聚甲基丙烯酸甲酯和聚(丙烯腈-丁二烯-苯乙烯))、聚碳酸酯、聚酯(如聚对苯二甲酸环己烷对二甲醇酯、聚间苯二甲酸二烯丙酯、聚对苯二甲酸二烯丙酯、聚萘二酸丁醇酯、聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯)、聚酰胺(如聚己二酰己二胺、聚壬二酰己二胺、聚丁二酰己二胺、聚十二烷二酰己二胺、聚癸二酰己二胺、聚癸二酰癸二胺、聚十一酰胺、聚十二酰胺、聚辛酰胺、聚9-氨基壬酸、聚己内酰胺、聚对苯二甲酰苯二胺、聚间苯二甲酰己二胺、聚对苯二甲酰己二胺和聚对苯二甲酰壬二胺)、聚芳醚、聚醚酰亚胺、聚碳酸酯/(丙烯腈-丁二烯-苯乙烯)合金、聚苯醚、聚苯硫醚、聚酰亚胺、聚砜、聚醚醚酮、聚苯并咪唑、酚醛树脂、脲醛树脂、三聚氰胺-甲醛树脂、环氧树脂、醇酸树脂和聚氨酯中的一种或两种以上。
根据本发明的实施例，所述塑料组合物根据需要还可以含有至少一种助剂，如填料、抗氧剂、光稳定剂和润滑剂，以改善塑料组合物得到的塑料制品的性能或者赋予塑料制品以新的性能。所述助剂的含量可以根据其种类和具体使用要求进行适当的选择，没有特别限定。
根据本发明的实施例，所述填料可以是对激光不起任何物理或者化学作用的填料，例如，滑石粉和碳酸钙。玻璃纤维虽然对激光不敏感，但是加入玻璃纤维可以大大加深激光活化后塑料基体凹陷的深度，有利于化学镀铜中铜的粘附。所述无机填料还可以是对激光起到一定作用的无机填料，例如，所述填料还可以为玻璃微珠、硫酸钙、硫酸钡、二氧化钛、珠光粉、硅灰石、硅藻土、高岭土、陶土、云母、油页岩灰、硅酸铝、氧化铝、二氧化硅和氧化锌中的一种或多种。
根据本发明的实施例，所述抗氧剂可以提高本发明的塑料组合物得到的塑料制品的抗氧化性能，从而提高制品的使用寿命。所述抗氧剂可以为聚合物领域中常用的各种抗氧剂，例如可以含有主抗氧剂和辅助抗氧剂。所述主抗氧剂与所述辅助抗氧剂之间的相对用量可以根据种类进行适当的选择。一般地，所述主抗氧剂与所述辅助抗氧剂的重量比可以为1：1-4。所述主抗氧剂可以为受阻酚型抗氧剂，其具体实例可以包括但不限于抗氧剂1098和抗氧剂1010，其中，抗氧剂1098的主要成分为N,N’-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺，抗氧剂1010的主要成分为四[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇。所述辅助抗氧剂可以为亚磷酸酯型抗氧剂，其具体实例可以包括但不限于抗氧剂168，其主要成分为三(2,4-二叔丁基苯基)亚磷酸酯。
根据本发明的实施例，所述光稳定剂可以为公知的各种光稳定剂，例如受阻胺型光稳定剂，其具体实例可以包括但不限于双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯。
根据本发明的实施例，所述润滑剂可以为各种能够改善聚合物熔体的流动性的物质，例如可以为选自乙烯/醋酸乙烯的共聚蜡(EVA蜡)、聚乙烯蜡(PE蜡)以及硬脂酸盐中的一种或两种以上。
根据本发明的实施例，所述助剂的含量可以根据助剂的功能以及种类进行适当的选择。一般地，相对于100重量份的所述基材树脂，所述填料的含量可以为1-40重量份，所述抗氧剂的含量可以为0.1-10重量份，所述光稳定剂的含量可以为0.1-10重量份，所述润滑剂的含量可以为0.1-10重量份。
根据本发明实施例的塑料制品，所述塑料基材可以仅与金属镀层接触的表面，或者说仅附着有金属镀层的表面由所述塑料组合物形成，也可以整体均由所述塑料组合物形成，即所述塑料基材由所述塑料组合物形成。在塑料基材的尺寸较大时，从降低成本的角度出发，可以仅塑料基材附着有金属镀层的表面由所述塑料组合物形成；在塑料基材的尺寸不大时，可以整体均由所述塑料组合物形成。
根据本发明的实施例，所述塑料基材的具体尺寸可以根据预期的使用场合进行选择，没有特别限定。所述塑料基材根据具体需要也可以具有各种形状。
根据本发明的实施例，所述塑料基材可以采用常规方法制备，例如挤出成型工艺、注塑成型工艺。
根据本发明实施例的塑料制品，所述金属镀层的厚度可以根据具体使用要求而定，没有特别限定，一般可以为0.1-10μm。
根据具体使用要求，所述金属镀层可以具有各种形状。例如：在所述塑料制品用于制作线路板时，所述金属层可以形成线路图案。
根据本发明的第二方面，本发明还提供了一种塑料基材表面选择性金属化方法，该方法包括：用能量束照射塑料基材的需要进行金属化的表面，使被照射的表面气化；以及将所述塑料基材上经所述能量束照射后的表面进行化学镀，以便形成金属镀层，其中，所述塑料基材与所述金属镀层接触的表面是由塑料组合物形成的，所述塑料组合物含有：基材树脂；以及掺杂的氧化锡，所述掺杂的氧化锡中的掺杂元素为选自铈、镧、氟和钽中的至少一种。换句话说，该方法包括：用能量束照射塑料基材的需要进行金属化的表面，使被照射的表面气化；以及将照射后的塑料基材进行化学镀，其中，所述塑料基材的需要进行金属化的表面由一种塑料组合物形成，所述塑料组合物含有基材树脂和至少一种掺杂的氧化锡或由该掺杂的氧化锡包覆的填料，所述掺杂的氧化锡中的掺杂元素为铈、镧、氟和钽中的一种或多种。
根据本发明实施例的塑料基材表面选择性金属化方法，所述掺杂的氧化锡、塑料组合 物以及基材树脂在前文已经进行了详细的描述，此处不再详述。
根据本发明实施例的塑料基材表面选择性金属化方法，所述能量束可以为激光、电子束或离子束，优选为激光。根据本发明的方法，所述能量束照射的条件以能够使得被照射的聚合物制品表面气化，裸露出掺杂的氧化锡为准。具体地，在所述能量束为激光时，所述激光的波长可以为157-10600nm，功率可以为1-100W；在所述能量束为电子束时，所述电子束的功率密度可以为10-1011W/cm2；在所述能量束为离子束时，所述离子束的能量可以为10-106eV。从进一步提高化学镀形成的图案的精度的角度出发，所述能量束优选为激光。由于所述聚合物基材的需要进行金属化的表面含有所述掺杂的氧化锡，该掺杂的氧化锡对能量束具有更高的吸收能力，因此即使使用能量更低的能量束进行照射，也能使聚合物基材表面气化剥离，例如所述能量束优选为波长为1064-10600nm且功率为3-50W的激光，更优选为波长为1064nm且功率为3-40W(更优选为5-20W)的激光。
对照射后的塑料制品进行化学镀的方法已经为本领域技术人员所公知。例如，进行化学镀铜时，该方法可以包括将照射后的塑料制品与铜镀液接触，所述铜镀液含有铜盐和还原剂，pH值为12-13，所述还原剂能够将铜盐中铜离子还原为铜单质，例如所述还原剂可以为乙醛酸、肼和次亚磷酸钠中的一种或多种。
根据本发明实施例的方法，化学镀形成的金属镀层的厚度可以根据具体使用要求而定，没有特别限定，一般可以为0.1-10μm。
根据具体使用要求，所述金属层可以具有各种形状。例如：在用于制作线路板时，所述金属层可以形成线路图案。
根据本发明的实施例，在进行化学镀之后，还可以接着进行电镀或者再进行一次或多次化学镀，以进一步增加镀层的厚度或者在化学镀层上形成其它金属镀层。例如，在化学镀铜结束后，可以再化学镀一层镍来防止铜镀层表面被氧化。
采用根据本发明实施例的塑料基材表面选择性金属化方法得到的塑料基材表面的金属镀层连续完整，并且对基材具有较高的附着力。
以下将通过实施例对本发明进行详细描述。
以下实施例中，采用电感耦合等离子体发射光谱法(ICP)来测定金属化合物的组成。
以下实施例和对比例中，体积平均粒径是采用商购自成都精新粉体测试设备有限公司的激光粒度测试仪测定的。
以下实施例和对比例中，采用lambda 750紫外/可见/近红外分光光谱仪测定掺杂的氧化锡在1064nm波长下的光吸收率。
以下实施例和对比例中，采用百格刀法来测定在基材表面形成的金属层的附着力。具 体测试方法为：用百格刀在待测样品表面划10×10个1mm×1mm的小网格，每一条划线深及金属层的最底层，用毛刷将测试区域的碎片刷干净后，用胶带(3M600号胶纸)粘住被测试的小网格，用手抓住胶带一端，在垂直方向迅速扯下胶纸，在同一位置进行2次相同测试，按照以下标准确定附着力等级：
0：划线边缘光滑，在划线的边缘及交叉点处均无金属层脱落；
1：在划线的交叉点处有小片的金属层脱落，且脱落总面积小于5％；
2：在划线的边缘及交叉点处有小片的金属层脱落，且脱落总面积在5-15％之间；
3：在划线的边缘及交叉点处有成片的金属层脱落，且脱落总面积在15-35％之间；
4：在划线的边缘及交叉点处有成片的金属层脱落，且脱落总面积在35-65％之间；
5：在划线的边缘及交叉点处有成片的金属层脱落，且脱落总面积大于65％。
实施例1
(1)将柠檬酸锡(46.5mmol)、LaN3O9·6H2O(0.47mmol)、柠檬酸(248mmol)和乙二醇(511mmol)混合，加入10重量％硝酸使原料完全溶解；将得到的混合物加热到180℃酯化60分钟；然后在900℃烧结15小时得到焙烧产物，将焙烧产物研磨成体积平均粒径为1.5μm，从而得到掺杂的氧化锡。经测定，掺杂的氧化锡组成为0.99SnO2·0.01La2O3。其在1064nm波长下的光吸收率如表1所示。
(2)将步骤(1)得到的掺杂的氧化锡添加到聚碳酸酯中，混合均匀后，将得到的混合物送入挤出机中，进行挤出造粒。将得到的粒料送入注塑机中，注塑成型，得到含有掺杂的氧化锡的塑料片材。其中，相对于100重量份的聚碳酸酯，掺杂的氧化锡的用量为3重量份。
(3)用YAG激光器产生的激光对步骤(2)得到的塑料片材的表面进行照射，以在塑料片材表面形成作为接收机的天线的图案。其中，激光照射的条件包括：激光波长为1064nm，功率为8W，频率为20kHz，走线速度为2000mm/s，填充间距为30μm。
(4)将步骤(3)得到的塑料片材置于镀液中，进行化学镀，形成为天线图案的金属镀层，得到塑料制品。镀液的组成为：CuSO4·5H2O 0.12mol/L，Na2EDTA·2H2O 0.14mol/L，亚铁氰化钾10mg/L，2,2’-联吡啶10mg/L，乙醛酸0.10mol/L，并用NaOH和H2SO4调节镀液的pH值为12.5-13，镀液的温度50℃。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
实施例2
(1)按照实施例1中的步骤(1)的方法进行，不同的是，LaN3O9·6H2O的用量为 2.45mmol，柠檬酸的用量为1mol和乙二醇的用量为2.5mol，将焙烧产物研磨成体积平均粒径为1μm，得到掺杂的氧化锡。经测定，掺杂的氧化锡组成为0.95SnO2·0.05La2O3。其在1064nm波长下的光吸收率如表1所示。
(2)采用与实施例1步骤(2)相同的方法制备塑料片材，不同的是，掺杂的氧化锡为实施例2步骤(1)制备的掺杂的氧化锡，且相对于100重量份的聚碳酸酯，掺杂的氧化锡的用量为5重量份。
(3)采用与实施例1步骤(3)相同的方法用激光对步骤(2)制备的塑料片材的表面进行照射。
(4)采用与实施例1步骤(4)相同的方法对步骤(3)得到的经激光照射的塑料片材进行化学镀。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
实施例3
(1)按照实施例1中的步骤(1)的方法进行，不同的是，LaN3O9·6H2O的用量为4.04mmol，柠檬酸的用量为1.2mol和乙二醇的用量为2.8mol，将焙烧产物研磨成体积平均粒径为3μm，得到掺杂的氧化锡。经测定，掺杂的氧化锡组成为0.92SnO2·0.08La2O3。其在1064nm波长下的光吸收率如表1所示。
(2)采用与实施例1步骤(2)相同的方法制备塑料片材，不同的是，掺杂的氧化锡为实施例3步骤(1)制备的掺杂的氧化锡，且相对于100重量份的聚碳酸酯，掺杂的氧化锡的用量为10重量份。
(3)采用与实施例1步骤(3)相同的方法用激光对步骤(2)制备的塑料片材的表面进行照射。
(4)采用与实施例1步骤(4)相同的方法对步骤(3)得到的经激光照射的塑料片材进行化学镀。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
实施例4
(1)将柠檬酸锡(46.5mmol)、CeN3O9·6H2O(0.47mmol)、柠檬酸(248mmol)和乙二醇(511mmol)混合，加入10重量％硝酸使原料完全溶解；将得到的混合物加热到180℃酯化60分钟；然后在900℃烧结15小时得到焙烧产物，将焙烧产物研磨成体积平均粒径为1.5μm，从而得到掺杂的氧化锡。经测定，掺杂的氧化锡的组成为0.99SnO2·0.01CeO2。 其在1064nm波长下的光吸收率如表1所示。
(2)将步骤(1)得到的掺杂的氧化锡添加到聚碳酸酯中，混合均匀后，将得到的混合物送入挤出机中，进行挤出造粒。将得到的粒料送入注塑机中，注塑成型，得到含有掺杂的氧化锡的塑料片材。其中，相对于100重量份的聚碳酸酯，掺杂的氧化锡的用量为3重量份。
(3)用YAG激光器产生的激光对步骤(2)得到的塑料片材的表面进行照射，以在塑料片材表面形成作为接收机的天线的图案。其中，激光照射的条件包括：激光波长为1064nm，功率为8W，频率为20kHz，走线速度为2000mm/s，填充间距为30μm。
(4)将步骤(3)得到的塑料片材置于镀液中，进行化学镀，形成为天线图案的金属镀层，得到塑料制品。镀液的组成为：CuSO4·5H2O 0.12mol/L，Na2EDTA·2H2O 0.14mol/L，亚铁氰化钾10mg/L，2,2’-联吡啶10mg/L，乙醛酸0.10mol/L，并用NaOH和H2SO4调节镀液的pH值为12.5-13，镀液的温度50℃。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
实施例5
(1)按照实施例1中的步骤(1)的方法进行，不同的是，CeN3O9·6H2O的用量为2.45mmol，柠檬酸的用量为1mol和乙二醇的用量为2.5mol，将焙烧产物研磨成体积平均粒径为1μm，得到掺杂的氧化锡。经测定，掺杂的氧化锡组成为0.95SnO2·0.05CeO2。其在1064nm波长下的光吸收率如表1所示。
(2)采用与实施例4步骤(2)相同的方法制备塑料片材，不同的是，掺杂的氧化锡为实施例5步骤(1)制备的掺杂的氧化锡，且相对于100重量份的聚碳酸酯，掺杂的氧化锡的用量为5重量份。
(3)采用与实施例4步骤(3)相同的方法用激光对步骤(2)制备的塑料片材的表面进行照射。
(4)采用与实施例4步骤(4)相同的方法对步骤(3)得到的经激光照射的塑料片材进行化学镀。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
实施例6
(1)按照实施例1中的步骤(1)的方法进行，不同的是，CeN3O9·6H2O的用量为4.04mmol，柠檬酸的用量为1.2mmol和乙二醇的用量为2.8mmol，将焙烧产物研磨成体积 平均粒径为3μm，得到掺杂的氧化锡。经测定，掺杂的氧化锡组成为0.92SnO2·0.08CeO2。其在1064nm波长下的光吸收率如表1所示。
(2)采用与实施例4步骤(2)相同的方法制备塑料片材，不同的是，掺杂的氧化锡为实施例6步骤(1)制备的掺杂的氧化锡，且相对于100重量份的聚碳酸酯，掺杂的氧化锡的用量为10重量份。
(3)采用与实施例4步骤(3)相同的方法用激光对步骤(2)制备的塑料片材的表面进行照射。
(4)采用与实施例4步骤(4)相同的方法对步骤(3)得到的经激光照射的塑料片材进行化学镀。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
实施例7
(1)将SnO2(465mmol)置于球磨机的球磨罐中，然后加入Ta2O5(2.35mmol)和乙醇，进行2小时的研磨。其中，相对于100重量份固体物质，乙醇的用量为300重量份。将球磨得到的混合物在80℃于空气气氛中干燥3小时，得到体积平均粒径为2.6μm的粉体混合物。将所述粉体混合物在1000℃于空气气氛中焙烧12小时，将焙烧产物研磨成体积平均粒径为1.6μm，从而得到掺杂的氧化锡。经测定，掺杂的氧化锡的组成为0.99SnO2·0.005Ta2O5。其在1064nm波长下的光吸收率如表1所示。
(2)将步骤(1)得到的掺杂的氧化锡添加到聚碳酸酯中，混合均匀后，将得到的混合物送入挤出机中，进行挤出造粒。将得到的粒料送入注塑机中，注塑成型，得到含有掺杂的氧化锡的塑料片材。其中，相对于100重量份的聚碳酸酯，掺杂的氧化锡的用量为3重量份。
(3)用YAG激光器产生的激光对步骤(2)得到的塑料片材的表面进行照射，以在塑料片材表面形成作为接收机的天线的图案。其中，激光照射的条件包括：激光波长为1064nm，功率为8W，频率为20kHz，走线速度为2000mm/s，填充间距为30μm。
(4)将步骤(3)得到的塑料片材置于镀液中，进行化学镀，形成为天线图案的金属镀层，得到塑料制品。镀液的组成为：CuSO4·5H2O 0.12mol/L，Na2EDTA·2H2O 0.14mol/L，亚铁氰化钾10mg/L，2,2’-联吡啶10mg/L，乙醛酸0.10mol/L，并用NaOH和H2SO4调节镀液的pH值为12.5-13，镀液的温度50℃。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
实施例8
(1)按照实施例1中的步骤(1)的方法进行，不同的是，Ta2O5的用量为1.225mmol。经测定，掺杂的氧化锡的组成为0.95SnO2·0.025Ta2O5。其在1064nm波长下的光吸收率如表1所示。
(2)采用与实施例7步骤(2)相同的方法制备塑料片材，不同的是，掺杂的氧化锡为实施例8步骤(1)制备的掺杂的氧化锡，且相对于100重量份的聚碳酸酯，掺杂的氧化锡的用量为5重量份。
(3)采用与实施例7步骤(3)相同的方法用激光对步骤(2)制备的塑料片材的表面进行照射。
(4)采用与实施例7步骤(4)相同的方法对步骤(3)得到的经激光照射的塑料片材进行化学镀。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
实施例9
(1)按照实施例1中的步骤(1)的方法进行，不同的是，Ta2O5的用量为2.02mmol。经测定，掺杂的氧化锡的组成为0.92SnO2·0.04Ta2O5。其在1064nm波长下的光吸收率如表1所示。
(2)采用与实施例7步骤(2)相同的方法制备塑料片材，不同的是，掺杂的氧化锡为实施例9步骤(1)制备的掺杂的氧化锡，且相对于100重量份的聚碳酸酯，掺杂的氧化锡的用量为10重量份。
(3)采用与实施例7步骤(3)相同的方法用激光对步骤(2)制备的塑料片材的表面进行照射。
(4)采用与实施例7步骤(4)相同的方法对步骤(3)得到的经激光照射的塑料片材进行化学镀。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
实施例10
(1)将柠檬酸锡(46.5mmol)、柠檬酸(248mmol)和乙二醇(511mmol)混合，加入10重量％硝酸使原料完全溶解；将得到的混合物加热到180℃酯化60分钟；然后在酯化产物中加入0.47mmol的氢氟酸后，在900℃烧结15小时得到焙烧产物，将焙烧产物研磨成体积平均粒径为1.5μm，从而得到掺杂的氧化锡。经测定，掺杂的氧化锡组成为 SnO1.99F0.01。其在1064nm波长下的光吸收率如表1所示。
(2)将步骤(1)得到的掺杂的氧化锡添加到聚碳酸酯中，混合均匀后，将得到的混合物送入挤出机中，进行挤出造粒。将得到的粒料送入注塑机中，注塑成型，得到含有掺杂的氧化锡的塑料片材。其中，相对于100重量份的聚碳酸酯，掺杂的氧化锡的用量为3重量份。
(3)用YAG激光器产生的激光对步骤(2)得到的塑料片材的表面进行照射，以在塑料片材表面形成作为接收机的天线的图案。其中，激光照射的条件包括：激光波长为1064nm，功率为8W，频率为20kHz，走线速度为2000mm/s，填充间距为30μm。
(4)将步骤(3)得到的塑料片材置于镀液中，进行化学镀，形成为天线图案的金属镀层，得到塑料制品。镀液的组成为：CuSO4·5H2O 0.12mol/L，Na2EDTA·2H2O 0.14mol/L，亚铁氰化钾10mg/L，2,2’-联吡啶10mg/L，乙醛酸0.10mol/L，并用NaOH和H2SO4调节镀液的pH值为12.5-13，镀液的温度50℃。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
实施例11
(1)按照实施例10中的步骤(1)的方法进行，不同的是，氢氟酸的用量为2.45mmol，柠檬酸的用量为1mmol和乙二醇的用量为2.5mmol，将焙烧产物研磨成体积平均粒径为1μm，得到掺杂的氧化锡。经测定，掺杂的氧化锡组成为SnO1.947F0.053。其在1064nm波长下的光吸收率如表1所示。
(2)采用与实施例10步骤(2)相同的方法制备塑料片材，不同的是，掺杂的氧化锡为实施例11步骤(1)制备的掺杂的氧化锡，且相对于100重量份的聚碳酸酯，掺杂的氧化锡的用量为5重量份。
(3)采用与实施例10步骤(3)相同的方法用激光对步骤(2)制备的塑料片材的表面进行照射。
(4)采用与实施例10步骤(4)相同的方法对步骤(3)得到的经激光照射的塑料片材进行化学镀。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
实施例12
(1)按照实施例10中的步骤(1)的方法进行，不同的是，氢氟酸为4.04mmol，柠檬酸的用量为1.2mmol和乙二醇的用量为2.8mmol，将焙烧产物研磨成体积平均粒径为 3μm，得到掺杂的氧化锡。经测定，掺杂的氧化锡组成为SnO1.913F0.087。其在1064nm波长下的光吸收率如表1所示。
(2)采用与实施例10步骤(2)相同的方法制备塑料片材，不同的是，掺杂的氧化锡为实施例3步骤(1)制备的掺杂的氧化锡，且相对于100重量份的聚碳酸酯，掺杂的氧化锡的用量为10重量份。
(3)采用与实施例10步骤(3)相同的方法用激光对步骤(2)制备的塑料片材的表面进行照射。
(4)采用与实施例10步骤(4)相同的方法对步骤(3)得到的经激光照射的塑料片材进行化学镀。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
实施例13
(1)采用与实施例1步骤(1)相同的方法制备掺杂的氧化锡，不同的是，将柠檬酸锡(46.5mmol)、LaN3O9·6H2O(0.47mmol)、柠檬酸(248mmol)、乙二醇(511mmol)和云母(1mmol)进行混合，从而得到由掺杂的氧化锡包覆的填料。经测定，掺杂的氧化锡组成为0.99SnO2·0.01La2O3。其在1064nm波长下的光吸收率如表1所示。
(2)采用与实施例1步骤(2)相同的方法制备塑料片材，不同的是，掺杂的氧化锡为实施例13步骤(1)制备的由掺杂的氧化锡包覆的填料，且相对于100重量份的聚碳酸酯，由掺杂的氧化锡包覆的填料的用量为5重量份。
(3)采用与实施例1步骤(3)相同的方法用激光对步骤(2)制备的塑料片材的表面进行照射。
(4)采用与实施例1步骤(4)相同的方法对步骤(3)得到的经激光照射的塑料片材进行化学镀。
经目测观察，发现形成的线路完整。镀覆速度以及金属层的附着力在表1中列出。
对比例1
(1)采用与实施例1步骤(1)相同的方法制备掺杂的氧化锡，不同的是，将LaN3O9·6H2O替换为相同摩尔量的SbCl3。经测定，掺杂的氧化锡组成为0.99SnO2·0.01SbO2。其在1064nm波长下的光吸收率如表1所示。
(2)采用与实施例1步骤(2)相同的方法制备塑料片材，不同的是，掺杂的氧化锡为对比例1步骤(1)制备的掺杂的氧化锡。
(3)采用与实施例1步骤(3)相同的方法用激光对步骤(2)制备的塑料片材的表面进行照射。
(4)采用与实施例1步骤(4)相同的方法对步骤(3)得到的经激光照射的塑料片材进行化学镀。
经目测观察，发现能形成金属层，但是存在溢镀和挂铜粉现象。镀覆速度以及金属层的附着力在表1中列出。
表1
  镀覆速度(μm/h) 附着力 掺杂的氧化锡的吸光率(％)
实施例1 7 0 70
实施例2 8 1 75
实施例3 10 0 77
实施例4 7 0 66
实施例5 9 1 70
实施例6 11 0 78
实施例7 6 1 60
实施例8 7 0 66
实施例9 8 0 75
实施例10 8 0 71
实施例11 9 1 80
实施例12 11 1 85
实施例13 11 1 84
对比例1 5 2 60
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
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，本发明对各种可能的组合方式不再另行说明。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明 的思想，其同样应当视为本发明所公开的内容。

Claims (25)

  1. 一种塑料制品，其特征在于，包括：
    塑料基材；
    金属镀层，所述金属镀层形成在所述塑料基材的表面上；
    其中，所述塑料基材与所述金属镀层接触的表面是由塑料组合物形成的，所述塑料组合物含有：
    基材树脂；以及
    掺杂的氧化锡，所述掺杂的氧化锡中的掺杂元素为选自铈、镧、氟和钽中的至少一种。
  2. 根据权利要求1所述的塑料制品，其中，所述金属镀层的厚度为0.1-10μm。
  3. 根据权利要求1所述的塑料制品，其中，基于所述掺杂的氧化锡中锡元素和掺杂元素的总摩尔量，所述锡元素的含量为90-99.9摩尔％，所述掺杂元素的含量为0.1-10摩尔％。
  4. 根据权利要求1-3中任一项所述的塑料制品，其中，所述掺杂的氧化锡为铈掺杂的氧化锡、镧掺杂的氧化锡、氟掺杂的氧化锡或钽掺杂的氧化锡。
  5. 根据权利要求1-4中任一项所述的塑料制品，其中，所述掺杂的氧化锡的体积平均粒径为50nm至10μm。
  6. 根据权利要求1-5中任一项所述的塑料制品，其中，所述塑料组合物包括：
    填料，所述填料的表面包覆有所述掺杂的氧化锡。
  7. 根据权利要求6所述的塑料制品，其中，所述填料的体积平均粒径为50nm至10μm。
  8. 根据权利要求6或7所述的塑料制品，其中，所述填料为选自云母和二氧化硅中的至少一种。
  9. 根据权利要求1-5中任一项所述的塑料制品，其中，在所述塑料组合物中，相对于 100重量份的所述基材树脂，所述掺杂的氧化锡的含量为1-20重量份。
  10. 根据权利要求6-8中任一项所述的塑料制品，其中，表面包覆有所述掺杂的氧化锡的所述填料的含量为1-20重量份。
  11. 根据权利要求1-10中任一项所述的塑料制品，其中，所述基材树脂为选自聚烯烃、聚碳酸酯、聚酯、聚酰胺、聚芳醚、聚醚酰亚胺、聚苯醚、聚苯硫醚、聚酰亚胺、聚砜、聚醚醚酮、聚苯并咪唑、酚醛树脂、脲醛树脂、三聚氰胺-甲醛树脂、环氧树脂、醇酸树脂和聚氨酯中的至少一种。
  12. 一种塑料基材表面选择性金属化的方法，其特征在于，包括：
    用能量束照射塑料基材的需要进行金属化的表面，使被照射的表面气化；以及
    将所述塑料基材上经所述能量束照射后的表面进行化学镀，以便形成金属镀层，
    其中，所述塑料基材与所述金属镀层接触的表面是由塑料组合物形成的，所述塑料组合物含有：
    基材树脂；以及
    掺杂的氧化锡，所述掺杂的氧化锡中的掺杂元素为选自铈、镧、氟和钽中的至少一种。
  13. 根据权利要求12所述的方法，其中，所述金属镀层的厚度为0.1-10μm。
  14. 根据权利要求12或13所述的方法，其中，基于所述掺杂的氧化锡中锡元素和掺杂元素的总摩尔量，所述锡元素的含量为90-99.9摩尔％，所述掺杂元素的含量为0.1-10摩尔％。
  15. 根据权利要求12-14中任一项所述的方法，其中，所述掺杂的氧化锡为铈掺杂的氧化锡、镧掺杂的氧化锡、氟掺杂的氧化锡或钽掺杂的氧化锡。
  16. 根据权利要求12-15中任一项所述的方法，其中，所述掺杂的氧化锡的体积平均粒径为50nm至10μm。
  17. 根据权利要求12-16中任一项所述的方法，其中，所述塑料组合物包括：
    填料，所述填料的表面包覆有所述掺杂的氧化锡。
  18. 根据权利要求17所述的方法，其中，所述填料的体积平均粒径为50nm至10μm。
  19. 根据权利要求17或18所述的方法，其中，所述填料为选自云母和二氧化硅中的至少一种。
  20. 根据权利要求12-16中任一项所述的方法，其中，在所述塑料组合物中，相对于100重量份的所述基材树脂，所述掺杂的氧化锡的含量为1-20重量份。
  21. 根据权利要求17-19中任一项所述的方法，其中，表面包覆有所述掺杂的氧化锡的所述填料的含量为1-20重量份。
  22. 根据权利要求12-21中任一项所述的方法，其中，所述基材树脂为选自聚烯烃、聚碳酸酯、聚酯、聚酰胺、聚芳醚、聚醚酰亚胺、聚苯醚、聚苯硫醚、聚酰亚胺、聚砜、聚醚醚酮、聚苯并咪唑、酚醛树脂、脲醛树脂、三聚氰胺-甲醛树脂、环氧树脂、醇酸树脂和聚氨酯中的至少一种。
  23. 根据权利要求12-22中任一项所述的方法，其中，所述能量束为激光。
  24. 根据权利要求23所述的方法，其中，所述能量束为波长为1064nm且功率为3-40W的激光。
  25. 一种塑料制品，其特征在于，是由权利要求12-24中任意一项所述的方法制备的。
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