CN102071411A - 一种塑料制品的制备方法及一种塑料制品 - Google Patents

一种塑料制品的制备方法及一种塑料制品 Download PDF

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Publication number
CN102071411A
CN102071411A CN2010102602360A CN201010260236A CN102071411A CN 102071411 A CN102071411 A CN 102071411A CN 2010102602360 A CN2010102602360 A CN 2010102602360A CN 201010260236 A CN201010260236 A CN 201010260236A CN 102071411 A CN102071411 A CN 102071411A
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China
Prior art keywords
preparation
layer
chemical
plastics
formula
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CN2010102602360A
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CN102071411B (zh
Inventor
宫清
周良
苗伟峰
张�雄
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BYD Co Ltd
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BYD Co Ltd
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Priority to CN2010102602360A priority Critical patent/CN102071411B/zh
Publication of CN102071411A publication Critical patent/CN102071411A/zh
Priority to EP11173897A priority patent/EP2420593B1/en
Priority to ES11173897T priority patent/ES2414412T3/es
Priority to DK11173897.7T priority patent/DK2420593T3/da
Priority to US13/186,280 priority patent/US8846151B2/en
Priority to PCT/CN2011/078487 priority patent/WO2012022255A1/en
Priority to JP2013524342A priority patent/JP5859003B2/ja
Priority to KR1020137006829A priority patent/KR101578585B1/ko
Priority to US13/354,512 priority patent/US8841000B2/en
Application granted granted Critical
Publication of CN102071411B publication Critical patent/CN102071411B/zh
Priority to US14/462,293 priority patent/US9770887B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • 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
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • 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
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C23C18/2013—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by mechanical pretreatment, e.g. grinding, sanding
    • 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
    • C23C18/22—Roughening, e.g. by etching
    • 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
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • 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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • 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
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
    • 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
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
    • H05K2203/107—Using laser light
    • 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
    • H05K3/105—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 by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Toxicology (AREA)
  • Chemically Coating (AREA)
  • Laminated Bodies (AREA)
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Abstract

本发明提供了一种塑料制品的制备方法及塑料制品，该方法包括：1)成型塑料基体；塑料基体中含有化学镀催化剂；化学镀催化剂为式I、II或III所示的化合物；2)去掉塑料基体表面选定区域的塑料，相应区域裸露出化学镀催化剂；3)化学镀铜或化学镀镍，继续进行至少一次化学镀和/或电镀，在塑料基体表面形成金属层。本发明提供的制备方法，工艺简单，对能量要求低，成本低廉；另外，化学镀催化剂分布于塑料基体中，所以化学镀后形成的镀层与塑料基体的结合力非常高。

Description

一种塑料制品的制备方法及一种塑料制品
技术领域
本发明属于非金属材料表面金属化领域，尤其涉及一种塑料制品的制备方法及一种塑料制品。
背景技术
在塑料表面形成金属层，作为电磁信号传导的通路，广泛用于汽车、工业、计算机、通讯等领域。塑料表面选择性地形成金属层是该类塑料制品制造的一个核心环节。塑料表面金属化生产线路有很多方法，现有技术中均采用先在塑料基材表面形成金属核作为化学镀催化活性中心，然后进行化学镀。
例如，US2003031803A1公开了采用金属氧化物颗粒如ZnO、TiO2、ZrO2、Al2O3、CeO2等涂布在塑料基体表面，然后用紫外激光还原成金属单质，作为化学镀铜的催化剂，接着再进行镀铜工艺。其中紫外激光移动的最大速度是100mm/s，而且对图案的生成没有选择性，且金属氧化物颗粒涂布于塑料基体表面，因与塑料基体附着力较差，使得最后形成的镀层与塑料基体附着力较差。
US7060421公开了一种塑料表面金属化的方法，通过在塑料基体中加入尖晶石结构的金属氧化物，其中金属元素可选自铜、镍、钴、铬、铁等，然后用紫外激光(波长为248nm、308nm、355nm、532nm)和红外激光(波长为1064nm和10600nm)进行活化，使金属氧化物分解释放出金属单质，这些金属单质作为后续化学镀的催化剂，从而可进行化学镀。该方法中采用尖晶石结构的金属氧化物，激光作用下还原出金属单质后诱导化学沉积金属层，工艺复杂、能量要求高且对设备和工艺的要求都比较高。
发明内容
本发明为解决现有技术中存在的塑料表面金属化工艺复杂、能量要求高的技术问题。
本发明提供了一种塑料制品的制备方法，包括以下步骤：
1)成型塑料基体；所述塑料基体为含有化学镀催化剂的热塑性或热固性塑料，化学镀催化剂均匀分布于热塑性或热固性塑料中；所述化学镀催化剂为式I、II或III所示的化合物；
CuFe2O4-δ....................................式I
Ca0.25Cu0.75TiO3-β...........................式II
TiO2-σ.......................................式III
其中，δ为式I所示的化合物中的氧缺位程度，0.05≤δ≤0.8；β为式II所示的化合物中的氧缺位程度，0.05≤β≤0.5；σ为式III所示的化合物中的氧缺位程度，0.05≤σ≤1.0；
2)去掉塑料基体表面选定区域的塑料，相应区域裸露出化学镀催化剂；
3)在步骤2)裸露出的化学镀催化剂表面化学镀铜或化学镀镍，继续进行至少一次化学镀和/或电镀，在塑料基体表面形成金属层。
本发明的发明人通过大量实验发现，本发明采用的化合物无需还原生成金属单质，也无需活化，即可直接作为化学镀催化剂，在该化学镀催化剂表面直接进行选择性化学镀，且该化学镀催化剂不会引起塑料降解。
本发明提供的塑料制品的制备方法中，所述化学镀催化剂均匀分布于塑料基体中，选择性去除塑料基体表面的塑料，无需过高的能量将化学镀催化剂还原成金属单质，仅需去除塑料裸露出化学镀催化剂，即可直接进行化学镀铜或化学镀镍，实现塑料表面选择性金属化，工艺简单，对能量要求低，成本低廉；另外，化学镀催化剂分布于塑料基体中，所以化学镀后形成的镀层与塑料基体中的结合力非常高。
具体实施方式
本发明提供了一种塑料制品的制备方法，包括以下步骤：
1)成型塑料基体；所述塑料基体为含有化学镀催化剂的热塑性或热固性塑料，化学镀催化剂均匀分布于热塑性或热固性塑料中；所述化学镀催化剂为式I、II或III所示的化合物；
CuFe2O4-δ....................................式I
Ca0.25Cu0.75TiO3-β...........................式II
TiO2-σ.......................................式III
其中，δ为式I所示的化合物中的氧缺位程度，0.05≤δ≤0.8；β为式II所示的化合物中的氧缺位程度，0.05≤β≤0.5；σ为式III所示的化合物中的氧缺位程度，0.05≤σ≤1.0；
2)去掉塑料基体表面选定区域的塑料，相应区域裸露出化学镀催化剂；
3)在步骤2)裸露出的化学镀催化剂表面化学镀铜或化学镀镍，继续进行至少一次化学镀和/或电镀，在塑料基体表面形成金属层。
本发明中，先成型塑料基体。所述塑料基体为含有化学镀催化剂的热塑性或热固性塑料，其中化学镀催化剂均匀分布于热塑性或热固性塑料中。
所采用的化学镀催化剂为具有活性氧缺位的金属氧化物多金属复合氧化物；金属氧化物或多金属复合氧化物中具有氧缺位，具有原金属氧化物或多金属复合氧化物所不具备的结构不稳定性和强还原性。
以具有活性氧缺位的铁酸铜(CuFe2Ox，x＜4)为例，说明本发明的化学镀催化剂的结构不稳定性和强还原性：(1)铁酸铜(CuFe2Ox，x＜4)晶格中存在氧缺位，能有效结合氧到CuFe2Ox晶格中；(2)在铁酸铜(CuFe2Ox，x＜4)晶体中，不仅Cu+/Cu2+、Fe2+/Fe3+之间存在电子迁移，Cu+/Fe3+之间也存在电子迁移；电子易发生迁移，极易失去电子表现出强的还原性；(3)CuFe2O4失氧生成具有活性氧缺位铁酸铜(CuFe2Ox，x＜4)的过程中，大量阳离子向晶格内聚集，使晶格间隙扩大、晶格扭曲产生变异，增加其化学势能，导致具有活性氧缺位的铁酸铜的结构不稳定，需要捕获O2-来填补氧缺位，从而表现出较强的还原性。
本发明的发明人通过大量实验发现，金属氧化物或多金属复合氧化物中氧缺位的程度在一定范围内，即本发明中式I、II或III所示的化合物，该类化合物可作为化学镀催化剂，在该类化合物表面能直接进行化学镀，并形成金属镀层。
本发明中所采用的化学镀催化剂的平均粒径为20nm-100μm，优选为50nm-10μm，更优选为200nm-4μm。以塑料基体的质量为基准，化学镀催化剂的含量为1-40％，优选为1-30％，更优选为2-15％。
本发明采用的化学镀催化剂中，优选情况下，式I所示的化合物为CuFe2O3.65或CuFe2O3.2，式II所示的化合物为Ca0.25Cu0.75TiO2.84或Ca0.25Cu0.75TiO2.5，式III所示的化合物为TiO或TiO1.9。更优选情况下，式I所示的化合物为CuFe2O3.65，式II所示的化合物为Ca0.25Cu0.75TiO2.84，式III所示的化合物为TiO。
本发明所采用的化学镀催化剂，可直接采用商购的产品，也可自己制备，其制备方法为本领域技术人员所公知。例如，首先通过共沉淀法、溶胶凝胶法、水热法、固相烧结法等本领域技术人员公知的技术制备普通分子结构的金属氧化物/多金属复合氧化物，或者直接采用金属氧化物/多金属复合氧化物的商购样品；然后在氮气或惰性气体气氛中进行高温烧结，使氧化物中的活性氧部分缺失，从而产生氧缺位，即可得到所述化学镀催化剂。
例如，式I所示的具有活性氧缺位的铁酸铜可采用如下方法制备：(1)在氢氧化钾的水溶液中，搅拌状态下，用蠕动泵以1ml/min的速度滴入配制好的Cu(NO3)2和Fe(NO3)3混合液，快速升温至80℃，继续搅拌24h；搅拌过程中在线测量pH值，保持pH为10-11；蒸馏水、丙酮洗涤沉淀，过滤后120℃下干燥24h研磨至300目；(2)高纯N2保护下1000℃高温煅烧步骤(1)的产物，煅烧时间4-6h，煅烧过程中CuFe2O4晶格氧损失，得到式I所示的化合物CuFe2O4-δ(0.05≤δ≤0.8)。
类似地，式II所示的化合物也可以采用式I同样的制备方法得到。式III所示的化合物可直接采用商购的纳米级二氧化钛在氮气气氛中高温烧结脱氧制备或者用还原性物质如NH3、H2、Mg单质进行还原而获得。
本发明中，所述化学镀催化剂也可直接通过商购获得，例如式III所示的化合物可直接采用日本Akoh Kasei公司生产型号为Tilack的钛黑和/或韩国BoKwang化学公司生产型号为Tilox的钛黑。
所述热塑性/热固性塑料为本领域技术人员公知，例如热塑性塑料可以为选自聚烯烃、聚酯、聚酰胺、聚芳醚、聚酯酰亚胺、聚碳酸酯(PC)、聚碳酸酯/(丙烯腈-丁二烯-苯乙烯)合金(PC/ABS)、聚苯醚(PPO)、聚苯硫醚(PPS)、聚酰亚胺(PI)、聚砜(PSU)、聚醚醚酮(PEEK)、聚苯并咪唑(PBI)或液晶聚合物(LCP)中的一种或多种。其中，聚烯烃可以为聚苯乙烯(PS)、聚丙烯(PP)、聚甲基丙烯酸甲酯或聚(丙烯腈-丁二烯-苯乙烯)。聚酯可以为聚对苯二甲酸环己烷对二甲醇酯(PCT)、聚间苯二甲酸二烯丙酯(PDAIP)、聚对苯二甲酸二烯丙酯(PDAP)、聚萘二酸丁醇酯(PBN)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)。聚酰胺可以为聚己二酰己二胺(PA-66)、聚壬二酰己二胺(PA-69)、聚丁二酰己二胺(PA-64)、聚十二烷二酰己二胺(PA-612)、聚癸二酰己二胺(PA-610)、聚癸二酰癸二胺(PA-1010)、聚十一酰胺(PA-11)、聚十二酰胺(PA-12)、聚辛酰胺(PA-8)、聚9-氨基壬酸(PA-9)、聚己内酰胺(PA-6)、聚对苯二甲酰苯二胺(PPTA)、聚间苯二甲酰己二胺(MXD6)、聚对苯二甲酰己二胺(PA6T)或聚对苯二甲酰壬二胺(PA9T)。液晶聚合物(LCP)是本领域技术人员公知的一种由刚性分子链构成的、在一定物理条件下既有液体流动性又有晶体物理性能各向异性状态(即液晶态)的高分子物质。所述热固性塑料可以选自酚醛树脂、脲醛树脂、三聚氰胺-甲醛树脂、环氧树脂、醇酸树脂、聚氨酯的一种或多种。
成型的方法可采用现有技术中的各种成型方法，先将化学镀催化剂、热塑性/热固性塑料聚合物树脂混合均匀，采用密炼机、单螺杆或双螺杆挤出机、混料机等常用塑料混配机械制备塑料组合物，然后经过注塑、吹塑、挤出或热压挤出设备，制造各种所需形状的塑料基体。
为提高本发明所采用的塑料基体的各种性能，所述塑料基体中还可以含有抗氧化剂、光稳定剂、润滑剂、无机填料。所述抗氧化剂、光稳定剂、润滑剂、无机填料均为本领域技术人员共公知，可直接采用商购产品。本发明中，将所述抗氧化剂、光稳定剂、润滑剂、无机填料与化学镀催化剂、热塑性/热固性塑料聚合物树脂混合均匀后，一并成型得到塑料基体。
以塑料基体的质量为基准，抗氧剂的含量可以为0.01-2％，所述光稳定剂的含量可以为0.01-2％，润滑剂的含量可以为0.01-2％，无机填料的含量为1-70％。
抗氧剂可以提高塑料基体的抗氧化性能。所述抗氧剂为本领域技术人员所公知，例如可以选自Ciba公司的抗氧剂1098、1076、1010、168。光稳定剂可以提高塑料基体的光稳定性。所述光稳定剂可以为各种公知的光稳定剂，优选为受阻胺类光稳定剂，例如可以选自Ciba公司的光稳定剂944。
所述润滑剂能提高塑料的流动性，从而使塑料基体混合得更均匀。所述润滑剂可以选自甲基聚硅氧烷、乙烯/醋酸乙烯的共聚蜡(EVA蜡)、聚乙烯蜡以及硬脂酸盐中的一种或多种。
无机填料可以为滑石粉、碳酸钙、玻璃纤维、硅酸钙纤维、氧化锡或炭黑。其中，玻璃纤维可以加深选定区域的塑料基体凹陷的深度，有利于化学镀铜中铜的粘附；氧化锡尤其是纳米氧化锡或炭黑可以加快选定区域塑料去除的速度，缩短工艺时间。所述无机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、煤粉、陶土、云母、油页岩灰、硅酸铝、氧化铝、碳纤维、二氧化硅或氧化锌。所述无机填料中优选不含有Cr等对环境和人体有害的元素。
本发明中，化学镀催化剂均匀分布于塑料基体中，所以化学镀催化剂与塑料基体的附着力非常高，而后续化学镀直接在所述化学镀催化剂表面进行，因此，使得最后形成的金属镀层与塑料基体的附着力也非常高。
根据本发明提供的制备方法，去掉塑料基体表面选定区域的塑料，在塑料基体表面形成图形。本发明中，去掉塑料基体表面选定区域的塑料的方式可以采用本领域技术人员常用的各种方式。优选情况下，所述选定区域可以为塑料基体的整个表面时，去掉塑料基体表面选定区域的塑料的方式为激光、电晕、化学腐蚀或磨削。所述选定区域为塑料基体的部分区域时，去掉塑料基体表面选定区域的塑料的方式为激光或电晕。
去掉塑料基体表面选定区域的塑料的方式采用激光或电晕时，可采用激光或电晕对塑料基体表面的选定区域进行照射，该照射区域内塑料基体中的聚合物树脂气化，在塑料基体表面形成图案，并将图案区域的化学镀催化剂暴露出来。激光照射采用的激光仪可为通用的红外激光器或紫外激光器，例如CO2激光体打标机。激光的条件包括：所述激光波长为157nm-10.6μm，扫描速度为500-8000mm/s，步长为3-9μm，延时为30-100μs，频率为30-40KHz，功率为3-4W，填充间距为10-50μm。电晕照射可采用南通三信电子的CW1003型电晕设备。电晕的条件包括：功率为大于0至3KW，速度为1-20m/min。本发明中，对激光或电晕的能量要求较低，仅需气化塑料基体表面露出化学镀催化剂即可，而无需还原化学镀催化剂为金属单质。
根据本发明提供的制备方法，去掉塑料基体整个表面的塑料时，可采用激光、电晕、化学腐蚀或磨削。其中，激光和电晕的条件如前所示。采用化学腐蚀的方式去除塑料时，化学腐蚀的条件包括：所采用的化学腐蚀液为N，N-二甲基甲酰胺(DMF)或四氢呋喃，腐蚀时间为5-60min。采用磨削的方式去除塑料时，采用金相砂纸研磨塑料基体表面，研磨掉的塑料基体的厚度为10-50μm。
一般成型后的塑料基体的厚度为500μm以上，选定区域表面去掉的塑料厚度为几百纳米至几十微米，从而使得塑料基体中的化学镀催化剂暴露出来，塑料基体表面的选定区域形成为微观上为具有高低不平的空隙的粗糙表面结构。在后续的化学镀铜时，铜内嵌到粗糙表面的孔隙中，从而与塑料样品之间形成很强的结合力。
根据本发明提供的制备方法，去掉塑料基体表面选定区域的塑料基体，裸露出化学镀催化剂，然后在该化学镀催化剂表面进行化学镀铜或化学镀镍。所述进行化学镀铜或化学镀镍的方法为本领域技术人员常用的化学镀方法，例如可以将去掉选定区域塑料后的塑料基体与化学镀铜液或化学镀镍液接触。
塑料基体中裸露出的化学镀催化剂，与化学镀铜液或化学镀镍液接触之后，化学镀催化剂能促进化学镀液中的铜离子或镍离子发生还原反应，生成金属铜或镍颗粒，包裹于化学镀催化剂表面，并互相连接形成一层致密的铜镀层或镍镀层，从而在塑料基体的选定区域快速形成第一层镀层。
为了提高镀层的表面装饰性、实用性以及耐腐蚀性，还可以在铜镀层或镍镀层表面继续进行至少一次化学镀和/或电镀，最后得到所述金属层。
例如，在化学镀促进剂表面进行化学镀镍，在塑料基体的选定区域形成镍镀层后，还可以通过现有技术中公开的方法继续在镍镀层上形成其他金属镀层。所述现有技术常规的方法包括化学镀、电镀。优选情况下，可以在镍镀层表面继续进行一次化学镀铜，在镍镀层表面形成铜镀层；再进行一次化学镀镍，得到复合金属层，该复合金属层从里至外具有Ni-Cu-Ni结构。更优选情况下，在复合金属层表面通过闪镀金层，使塑料基体表面的金属层从里至外具有Ni-Cu-Ni-Au结构。
在化学镀催化剂表面进行化学镀铜，在塑料基体的选定区域形成铜镀层后，也可以采用现有技术中公开的方法继续在铜镀层上形成其他金属镀层。优选情况下，为了防止塑料基体表面的铜镀层被氧化，可继续进行一次化学镀镍，在铜镀层表面形成一层镍镀层，得到的塑料基体表面的金属层从里至外具有Cu-Ni结构。更优选情况下，在Cu-Ni金属层表面通过闪镀金层，使塑料基体表面的金属层从里向外具有Cu-Ni-Au结构。
本发明中，具有Ni-Cu-Ni、Ni-Cu-Ni-Au、Cu-Ni或Cu-Ni-Au结构的金属层中，各种Ni层的厚度为0.1-50μm，优选为1-10μm，更优选为2-3μm；铜层厚度为0.1-100μm，优选为1-50μm，更优选为5-30μm；Au层的厚度为0.01-10μm，优选为0.01-2μm，更优选为0.1-1μm。
其中，所采用的化学镀铜液、化学镀镍液、电镀液铜液或电镀镍液、闪镀金层采用的镀金液均采用本领域技术人员常用的各种镀液。例如，所述化学镀铜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，还原剂可以为乙醛酸、肼和次亚磷酸钠中的一种或几种。所述化学镀铜也还可直接采用现有技术中公开的镀铜液，例如《表面技术》2002年12月，第31卷第6期中公开的一种镀液：CuSO4·5H2O 0.12mol/L，Na2EDTA·2H2O0.14mol/L，亚铁氰化钾10mg/L，2，2’-联吡啶10mg/L，乙醛酸(HCOCOOH)0.10mol/L，并用NaOH和H2SO4调节镀液的pH值为12.5-13。另外，化学镀铜后如果觉得铜镀层厚度不足，还可进行电镀铜。化学镀镍也可采用现有技术中的镀镍液，例如其组成为：硫酸镍：23g/l，次亚磷酸钠：18g/l，乳酸：20g/l，苹果酸：15g/l，用NaOH调节pH为5.2，温度：85-90℃。
本发明中，在化学镀催化剂表面进行化学镀铜的时间没有限制。优选情况下，在化学镀催化剂表面化学镀铜的时间为10-240分钟；在化学镀催化剂表面化学镀镍的时间为8-15分钟。
在镍镀层上闪镀金层的方法也为本领域技术人员所公知，本发明中不再赘述。其中闪镀金层时采用的镀金液可直接采用深圳精研创化工公司的BG-24中性镀金液。
塑料基体表面未去掉塑料的区域，即未处理区域，无化学镀催化剂存在，且其表面远不如所述选定区域表面粗糙，所以其金属化学沉积的速度非常慢且附着力很低，化学镀时基本没有金属沉积，若有少部分沉积但可轻易擦拭掉，从而实现本发明的直接在塑料表面选择性金属化的目的，并得到本发明提供的塑料制品。
所述塑料制品包括塑料基体和位于塑料基体表面形成图案的金属层。所述金属层从里到外为Cu-Ni层或Cu-Ni-Au层。
以下将结合实施例对本发明进行更详细地说明。
实施例1
(1)持续搅拌下，配制Cu(NO3)2和Fe(NO3)3浓度均为0.5mol/L的混合液，用蠕动泵以1ml/min的速度滴入氢氧化钾溶液中，快速升温至80℃，持续搅拌24h，搅拌过程中保证pH在10-11内。产物经过蒸馏水、丙酮洗涤、过滤后，120℃下干燥24h，研磨至300目。
(2)化学镀催化剂的制备：
在高纯N2保护下1000℃高温煅烧步骤(1)的产物，煅烧时间为4h，研磨10h至粉末平均粒径为700nm，得到本实施例的化学镀催化剂CuFe2O4-δ，化学分析法测量氧缺位程度δ＝0.35。
(3)塑料基体成型：
将PC/ABS树脂、步骤(2)的CuFe2O4-δ(δ＝0.35)、硅酸钙纤维和抗氧化剂1010，按照质量比为100∶10∶30∶0.2采用高混机混合后，用双螺杆挤出机(南京橡塑机械厂)挤出造粒、注塑成型为LED灯电路板载体。
(4)采用红外激光器(泰德，DPF-M12)照射LED灯电路板载体的选定区域，在该选定区域打印出金属线路图形，激光参数为：波长1064nm，扫描速度4000mm/s，步长9μm，延时30μs，频率40KHz，功率3W，填充间距50μm；激光照射完成后，超声清洗该塑料载体表面。
(5)浸入化学镀镍液中10分钟，形成厚度为4μm的镍层；浸入化学镀铜液中4小时，形成厚度为15μm的铜层；再浸入化学镀镍液10分钟，形成厚度为5μm的镍层；最后闪镀0.03微米厚的金层。其中，化学镀铜液：CuSO4·5H2O0.12mol/L，Na2EDTA·2H2O 0.14mol/L，亚铁氰化钾10mg/L，2，2’-联吡啶10mg/L，乙醛酸(HCOCOOH)0.10mol/L，并用NaOH和H2SO4调节镀液的pH值为12.5-13；化学镀镍液：硫酸镍：23g/l，次亚磷酸钠：18g/l，乳酸：20g/l，苹果酸：15g/l，用NaOH调节pH为5.2；闪镀金液采用深圳精研创化工公司公司的BG-24中性镀金液。
通过上述步骤，得到本实施例的用作LED灯电路板载体的塑料制品。
实施例2
(1)固相烧结法制备Ca0.25Cu0.75TiO3：
将CaCO3、CuO、TiO2粉末按化学计量比配料并混合均匀，转入球磨机中球磨，以无水酒精为研磨介质，研磨8h，经红外干燥后在800℃下预烧10h，得到Ca0.25Cu0.75TiO3。
(2)化学镀催化剂的制备：
在高纯氩气保护下900℃高温煅烧步骤(1)的Ca0.25Cu0.75TiO3，煅烧时间为4h，研磨至粉末平均粒径为500nm，得到本实施例的化学镀催化剂Ca0.25Cu0.75TiO3-β，化学分析法测量氧缺位程度β＝0.16。
3)塑料基体成型：
将PP树脂、步骤(2)的Ca0.25Cu0.75TiO3-β(β＝0.16)、抗氧化剂1076和聚乙烯蜡按质量比为100∶10∶0.2∶0.1混合后，挤出造粒，通过注塑成型，制作汽车发动机的电子连接器外壳。
(4)采用电晕设备(南通三信电子的CW1003)功率为2KW，处理速度为1m/min在汽车发动机的电子连接器外壳上刻蚀出金属线路图形。
(5)化学镀顺序：先化学镀镍8分钟形成2μm厚的镍层，再化学镀铜4小时形成15μm厚的铜金属层，然后化学镀镍10分钟形成3μm厚的镍层，最后闪镀0.03μm厚的金层。
通过上述步骤，得到本实施例的用作汽车发动机电子连接器外壳的塑料制品。
实施例3
(1)塑料基体成型：
将Tilack钛黑(日本Akoh Kasei公司，TiO2-σ，σ＝1，平均粒径50nm)；然后将PP树脂、Tilack钛黑、硅酸钙纤维和抗氧化剂1010，按照质量比为100∶10∶30∶0.2采用高混机混合后，用双螺杆挤出机(南京橡塑机械厂)挤出造粒、注塑成型为LED灯电路板载体。
(2)用N，N-二甲基甲酰胺(DMF)腐蚀LED灯电路板载体整个表面，腐蚀时间30min。
(3)采用与实施例1相同的顺序进行化学镀。
通过上述步骤，得到本实施例的用作LED灯电路板载体的塑料制品。
实施例4
采用与实施例2相同的步骤制备本实施例的用作汽车发动机电子连接器外壳的塑料制品，不同之处在于：
步骤(4)中，采用金相砂纸打磨卫浴器零部件的整个表面，打磨去掉的厚度为20μm。
通过上述步骤，得到本实施例的用作卫浴器零部件的塑料制品。

Claims (17)

1.一种塑料制品的制备方法，包括以下步骤：
1)成型塑料基体；所述塑料基体为含有化学镀催化剂的热塑性或热固性塑料，化学镀催化剂均匀分布于热塑性或热固性塑料中；所述化学镀催化剂为式I、II或III所示的化合物；
CuFe2O4-δ....................................式I
Ca0.25Cu0.75TiO3-β...........................式II
TiO2-σ.......................................式III
其中，δ为式I所示的化合物中的氧缺位程度，0.05≤δ≤0.8；β为式II所示的化合物中的氧缺位程度，0.05≤β≤0.5；σ为式III所示的化合物中的氧缺位程度，0.05≤σ≤1.0；
2)去掉塑料基体表面选定区域的塑料，相应区域裸露出化学镀催化剂；
3)在步骤2)裸露出的化学镀催化剂表面化学镀铜或化学镀镍，继续进行至少一次化学镀和/或电镀，在塑料基体表面形成金属层。
2.根据权利要求1所述的制备方法，其特征在于，步骤1)中，成型的方式为注塑、吹塑、挤出或热压。
3.根据权利要求1所述的制备方法，其特征在于，步骤2)中所述选定区域为塑料基体的整个表面或部分区域。
4.根据权利要求3所述的制备方法，其特征在于，所述选定区域为塑料基体的整个表面，去掉塑料基体表面选定区域的塑料的方式为激光、电晕、化学腐蚀或磨削。
5.根据权利要求3所述的制备方法，其特征在于，所述选定区域为塑料基体的部分区域，去掉塑料基体表面选定区域的塑料的方式为激光或电晕。
6.根据权利要求4或5所述的制备方法，其特征在于，激光的条件包括：激光的波长为157nm-10.6μm，扫描速度为500-8000mm/s，步长为3-9μm，延时为30-100μs，频率为30-40KHz，功率为3-4W，填充间距为10-50μm。
7.根据权利要求4或5所述的制备方法，其特征在于，电晕的条件包括：功率大于0至3KW，速度为1-20m/min。
8.根据权利要求4所述的制备方法，其特征在于，化学腐蚀的条件包括：采用的腐蚀液为N，N-二甲基甲酰胺或四氢呋喃，腐蚀时间为5-60min。
9.根据权利要求4所述的制备方法，其特征在于，磨削的条件包括：采用金相砂纸研磨塑料基体表面，研磨掉的塑料基体的厚度为10-50μm。
10.根据权利要求1所述的制备方法，其特征在于，步骤3)中在化学镀催化剂表面化学镀镍后，继续化学镀或/和电镀，在塑料基体表面形成Ni-Cu-Ni层、Ni-Cu-Ni-Au层；或在化学镀催化剂表面化学镀铜后，继续化学镀或/和电镀，在塑料基体表面形成Cu-Ni层或Cu-Ni-Au层。
11.根据权利要求10所述的制备方法，其特征在于，所述Ni-Cu-Ni层、Ni-Cu-Ni-Au层、Cu-Ni层或Cu-Ni-Au层中各种Ni层的厚度均为0.1-50μm，Cu层的厚度均为0.1-100μm，Au层的厚度均为0.01-10μm。
12.根据权利要求1所述的制备方法，其特征在于，所述化学镀催化剂的平均粒径为20nm-100μm；以塑料基体的质量为基准，其中化学镀催化剂的含量为1-40％。
13.根据权利要求1或12所述的制备方法，其特征在于，式I所示的化合物为CuFe2O3.65，式II所示的化合物为Ca0.25Cu0.75TiO2.84，式III所示的化合物为TiO。
14.根据权利要求1所述的制备方法，其特征在于，所述热塑性塑料选自聚烯烃、聚酯、聚酰胺、聚芳醚、聚酯酰亚胺、聚碳酸酯/(丙烯腈-丁二烯-苯乙烯)合金、聚苯硫醚、聚酰亚胺、聚砜、聚醚醚酮、聚苯并咪唑、液晶聚合物的一种或多种；所述热固性塑料选自酚醛树脂、脲醛树脂、三聚氰胺-甲醛树脂、环氧树脂、醇酸树脂、聚氨酯的一种或多种。
15.根据权利要求1所述的制备方法，其特征在于，所述塑料基体中还含有抗氧化剂、光稳定剂、润滑剂、无机填料。
16.一种塑料制品，所述塑料制品包括塑料基体和位于塑料基体表面的金属层；所述塑料制品由权利要求1所述的方法制备得到。
17.根据权利要求16所述的塑料制品，其特征在于，所述金属层从里到外为Ni-Cu-Ni层、Ni-Cu-Ni-Au层、Cu-Ni层或Cu-Ni-Au层。
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CN112996282A (zh) * 2021-02-10 2021-06-18 福建世卓电子科技有限公司 选择性化学镀与电镀交叉生产柔性线路板的工艺
CN112996282B (zh) * 2021-02-10 2023-12-22 福建世卓电子科技有限公司 选择性化学镀与电镀交叉生产柔性线路板的工艺

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US20120045658A1 (en) 2012-02-23
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EP2420593A1 (en) 2012-02-22
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