EP2561117A1 - Process for coating a surface of a substrate made of nonmetallic material with a metal layer - Google Patents

Process for coating a surface of a substrate made of nonmetallic material with a metal layer

Info

Publication number
EP2561117A1
EP2561117A1 EP11723649A EP11723649A EP2561117A1 EP 2561117 A1 EP2561117 A1 EP 2561117A1 EP 11723649 A EP11723649 A EP 11723649A EP 11723649 A EP11723649 A EP 11723649A EP 2561117 A1 EP2561117 A1 EP 2561117A1
Authority
EP
European Patent Office
Prior art keywords
substrate
metal
treatment
layer
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP11723649A
Other languages
German (de)
French (fr)
Other versions
EP2561117B1 (en
Inventor
Sébastien ROUSSEL
Frida Gilbert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PEGASTECH
Original Assignee
PEGASTECH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by PEGASTECH filed Critical PEGASTECH
Publication of EP2561117A1 publication Critical patent/EP2561117A1/en
Application granted granted Critical
Publication of EP2561117B1 publication Critical patent/EP2561117B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • 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
    • C23C18/1646—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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
    • 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1855—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1896—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by electrochemical pretreatment
    • 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
    • C23C18/2046—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
    • 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
    • C23C18/18—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
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble 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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • 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
    • C23C18/44—Coating with noble metals 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—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 only coatings only including layers of metallic material
    • C23C28/023—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 only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the present invention relates to a method of coating a surface of a non-metallic material substrate with a metal layer to make it capable of being treated, thanks to the strong adhesion of the coating, by conventional metallization processes such as than electroplating.
  • Materials metallization processes consist in depositing a thin layer of metal on the surface of a substrate.
  • the interest of these processes is multiple: visual, decorative, conductive, reinforcement ... It is commonly used for parts used in the aerospace, automotive, cosmetics, appliances, sanitary, connectivity, microelectronics ...
  • the activation step of the surface consists of depositing and maintaining on the surface of the non-metallic material metal particles or metal cations which will subsequently be reduced to form metal particles.
  • This step requires the use of colloidal palladium / tin particles which react only on a certain type of polymer and which requires the use of large quantities of palladium.
  • the stripping step of ABS panels is carried out with a solution of potassium permanganate and phosphoric acid and Step of formation of the Sn / Pd colloid is carried out by successive applications of a solution of tin chloride and then of a solution of palladium chloride.
  • the self-catalytic metal deposition step is a conventional copper deposition step.
  • the activation step is a adsorption step in which a colloidal preparation is used or formed by addition of stannous ions, which must then be completely removed to allow smooth and uniform development of the metal layer during the autocatalytic metal deposition step.
  • US Pat. Nos. 4,981,715 and 4,701,351 describe a process for coating a substrate with a thin layer of a polymer, for example polyacrylic acid, capable of complexing a noble metal compound comprising a step of covering the substrate with a polymer capable of chelating metal ions, followed by a step of contacting the polymer with metal particles.
  • the substrate is then subjected to the self-catalytic metal deposition step.
  • the metal cations used are
  • the main drawback of this method is that it entails the need to manage the quality of an additional interface, namely that which is created between the substrate and the polymer layer capable of chelating a metal ion. Solutions are proposed for example for irradiation treatment which also allows the regioselective fixing of this layer of polymer capable of drying and thus the possibility of metallizing the substrate selectively.
  • the present invention simplifies the various steps of this method of coating non-metallic materials and make it more environmentally friendly and less expensive, by developing a simpler coating process n ' using no toxic and polluting reagents, without adding a step and an additional layer.
  • the present invention therefore relates to a method of coating a surface of a substrate of non-metallic material with a metal layer, consisting of the following steps:
  • step b) subjecting at least a portion of at least one surface of said substrate to a physical or chemical surface-specific increase treatment; c) subjecting the surface of said substrate treated in step b) to a treatment; oxidant,
  • step c) the surface of said substrate treated in step c) is brought into contact with a solution containing at least one ion of at least one metal and its counterion, said metal being chosen from the group consisting of the metals of groups IB and VIII of the table of its periodic classification of elements,
  • step f) contacting the surface comprising particles of at least one metal obtained in step f) with a solution containing ions of at least one metal.
  • step h) obtaining on the treated surface of said substrate a coating with a layer of at least one metal,
  • steps possibly being followed or preceded by one or more rinsing steps.
  • Step g) is a self-catalytic deposition step also called electroless.
  • step f) the atoms of at least one metal attached to the non-metallic material constituting the substrate are fixed by ligand-metal interactions.
  • the activation step d) is carried out by contact with a solution containing an ion of a single metal and its counter-ion.
  • steps b) and c) are carried out in a single step b ') and the treatment is an oxidizing treatment.
  • the metal of step f) and the metal of the ions of step g) are identical.
  • steps f) and g) are performed in a single step f).
  • the surface of said non-metallic material substrate must be, firstly, prepared in order to obtain good adhesion of the metal layer to the surface.
  • the surface of the substrate is cleaned of all its contaminants by simultaneously creating a hooking relief for the adhesion of the future coating during step b) of the process.
  • the surface of the substrate may be treated in whole or in part using masking techniques well known to those skilled in the art such as the use of protective varnishes resistant to oxidation steps.
  • step b) is implemented by physical processing.
  • physical treatment means a treatment for removing the weak cohesion layers and increase the surface roughness.
  • the physical treatment is selected from the group of impact treatments.
  • steps b) or b ') or c) are implemented by oxidative treatment.
  • oxidizing treatment any treatment to prepare the surface by increasing the roughness so the surface area of the surface for step b) and creating functions that can chelate and / or complex metal cations for the step c).
  • the oxidizing treatment is chosen from the group of chemical oxidizing treatments.
  • the oxidizing treatment is chosen from the group of electrochemical oxidizing treatments.
  • the oxidizing treatment of step c) is selected from the group of physical oxidizing treatments.
  • the substrate may be a nanoparticle, a microparticle, a stopper of cosmetic products, an electronic element, a door handle, an electrical appliance, glasses, a decorative object, a bodywork element, a cabin element, airplane wing, a flexible conductor or a connector.
  • Non-metallic materials are understood to mean any material belonging to the family of organic materials, to the family of mineral materials and to the family of composite materials.
  • Non-limiting examples include wood, paper, cardboard, ceramics, plastics, silicones, textiles and glass.
  • the organic material is chosen from plastics.
  • metal layer is meant a thin layer, from a few nanometers to several hundred microns, a metal and / or a metal oxide deposited on the surface of a substrate.
  • the nonmetallic material is a polymer chosen from the group comprising the polymers, natural, artificial, synthetic, thermoplastic, thermosetting, thermostable, elastomeric, one-dimensional and three-dimensional.
  • the non-metallic material may further comprise at least one element selected from the group consisting of fillers, plasticizers and additives.
  • the fillers are mineral fillers chosen from the group comprising silica, talc, fibers or glass beads.
  • the fillers are organic fillers chosen from the group comprising cereal flour and cellulose pulp.
  • the additives are used to improve a specific property of the non-metallic material such as its color, its crosslinking, its sliding, resistance to degradation, fire and / or bacterial and / or fungal attacks.
  • the polymer is a thermoplastic (co) polymer selected from the group comprising a polyolefin, a polyester, a polyether, a vinyl polymer, a vinylidene polymer, a styrenic polymer, a (meth) acrylic polymer.
  • a polyamide a fluoropolymer, a cellulosic polymer, a poly (arylenesulfone), a polysulfide, a poly (arylether) ketone, a polyamide-imide, a poly (ether) imide, a polybenzimidazole, a poly ( indene / coumarone), a poly (paraxylylene), isolated, in admixture, in copolymers or in combination.
  • the polyolefins may be chosen from the group comprising a polyethylene, a polypropylene, an ethylene / propylene copolymer, a polybutylene, a polyethylpentene, an ethylene / vinyl acetate copolymer, an ethylene / vinyl alcohol copolymer, an ethylene / acrylate copolymer. methyl, alone, in admixture, in copolymers or in combination.
  • the polyesters may be chosen from the group comprising a polyethylene terephthalate, modified or unmodified by glycoi, a polybutylene terephthalate, a polyactide, a polycarbonate, alone, as a mixture, copolymers or in combination.
  • the polyethers may be chosen from the group comprising a poly (oxymethylene), a poly (oxyethylene), a poly (oxypropylene), a poly (phenylene ether), alone, in a mixture, in copolymers or in combination.
  • the vinyl polymers may be chosen from the group comprising an optionally chlorinated polyvinyl chloride, a polyvinyl alcohol, a polyvinyl acetate, a polyvinyl acetal, a poly (formaldehyde) and a polyvinyl alcohol.
  • vinyl a poly (vinyl fluoride), a poly (vinyl chloride / vinyl acetate), whether alone, in admixture, in copolymers or in combination.
  • the vinylidene polymers may be chosen from the group comprising a polyvinylidene chloride, a polyvinylidene fluoride, alone, in a mixture, in copolymers or in combination.
  • the styrenic polymers may be selected from the group consisting of polystyrene, poly (styrene / butadiene), poly (acrylonitrile / butadiene / styrene), poly (acrylonitrile / styrene), poly (acrylonitrile / ethylene / propylene) styrene), a poly (acrylonitrile / styrene / acrylate), alone, in admixture, in copolymers or in combination.
  • the (meth) acrylic polymers may be chosen from the group comprising a polyacrylonitrile, a poly (methyl acrylate), a poly (methyl methacrylate), alone, in a mixture, in copolymers or in combination.
  • the polyamides may be chosen from the group comprising a poly (caprolactam), a poly (hexamethylene adipamide), a poly (! Auroamide), a polyether-block-amide, a poly (metaxylylene adipamide), a polyamide (metaphenylene isophthalamide), whether alone, in admixture, in copolymers or in combination.
  • the fluoropolymers may be chosen from the group comprising a polytetrafluoroethylene, a polychlorotrifluoroethylene, a perfluorinated poly (ethylene / propylene), a poly (vinylidene fluoride), alone, in a mixture, in copolymers or in combination.
  • the cellulosic polymers may be chosen from the group comprising a cellulose acetate, a cellulose nitrate, a methylcellulose, a carboxymethylcellulose, an ethylmethylcellulose, alone, in a mixture, in copolymers or in combination,
  • the poly (arylenesulfone) may be chosen from the group comprising a polysulfone, a polyethersulfone, a polyarylsulphone, alone, in a mixture, in copolymers or in combination.
  • the polysulfides may be poly (phenylene sulfide).
  • Potyl (aryl ether ketones) can be chosen from the group comprising a polyetherketone, a polyether etherketone, a polyetherketone ketone, alone, as a mixture, copolymers or in combination.
  • the polymer is a thermosetting (co) polymer chosen from the group comprising an aminoplast such as ureaformol, melanin-formaldehyde, melanin-formaldehyde / polyesters, alone, copolymers, in a mixture or in combination, a polyurethane, an unsaturated polyester, a polysiloxane, a formophenolic resin, epoxide, allyl or vinylester, an alkyd, a polyurea, a polyisocyanurate, a poly (bismaleimide), a polybenzimidazole, a polydicyclopentadiene, alone, in copolymers, in admixture or in combination.
  • an aminoplast such as ureaformol, melanin-formaldehyde, melanin-formaldehyde / polyesters, alone, copolymers, in a mixture or in combination
  • a polyurethane an unsaturated polyester
  • the (co) polymer is selected from the group consisting of acrylonitrile butadiene styrene (ABS), acrylonitrile butadiene styrene / polycarbonate (ABS / PC), methyl methacrylate acrylonitrile butadiene styrene (MABS ), a polyamide (PA) such as nylon, polyamine, polyacrylic acid, polyaniline and polyethylene terephthalate (PET).
  • ABS acrylonitrile butadiene styrene
  • ABS / PC acrylonitrile butadiene styrene / polycarbonate
  • MABS methyl methacrylate acrylonitrile butadiene styrene
  • PA polyamide
  • nylon polyamine
  • PET polyacrylic acid
  • PET polyaniline
  • PET polyethylene terephthalate
  • the metal of the metal ion used in step d) is selected from copper, silver, nickel, platinum, palladium or cobalt ions.
  • the metal of the metal ion used in step d) is selected from the group consisting of copper and nickel.
  • the metal of the metal ion used in step d) is copper.
  • the metal of the metal ions used in step g) or f) is selected from the elements of groups IB and VIII of the Periodic Table.
  • the metal of the metal ion used in step g) or f) is selected from copper, silver, gold, nickel, platinum, palladium, iron or cobalt ions.
  • the metal of the metal ion used in step g) or f) is selected from the group consisting of copper and nickel.
  • the metal of the metal ion used in step g) or f) is copper
  • the metal of the metal ion used in step g) or f) is nickel.
  • the group of impact treatments includes sandblasting, shot blasting, microbiiling and sanding by abrasive cloths.
  • the chemical oxidizing treatment is chosen from the group comprising Fenton's reagent, alcoholic potash, a strong acid, sodium hydroxide, a strong oxidant, ozone, alone or in combination.
  • the strong acid is chosen from the group comprising hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, acetic acid and oxic acid. , phosphorous acid, phosphoric acid, hypophosphorous acid alone or as a mixture.
  • the strong oxidant is selected from the group comprising KMn0 4 and KCI0 3 , alone or in admixture.
  • the strong oxidant is KMnO 4 -
  • the oxidizing treatments are chosen depending on the nature of the constituent materials of the substrates, in Table 1 below are illustrated by way of examples, different chemical oxidizing treatments applicable when the substrate is ABS or ABS / PC .
  • the solid acid mass ratios are between 5 and 100%.
  • they are between 50 and 95%.
  • the duration of the strong acid treatment is between 20 seconds and 5 hours.
  • it is between 30 seconds and 3 hours.
  • it is between 30 seconds and 20 minutes.
  • the duration of the Fenton chemical reaction treatment is between 5 minutes and 5 hours.
  • it is between 10 minutes and 3 hours.
  • it is between 15 minutes and 2 hours.
  • it is of the order of 25 minutes.
  • the potassium hydroxide is diluted in a solution containing as solvent an alcohol selected from the group comprising methanol, ethanol, and propanol.
  • said potassium hydroxide is diluted in a solution containing as solvent ethanol. In one embodiment, the concentration of potassium hydroxide in the alcoholic solution is between 0.1 and 10M.
  • it is between 0.5M and 5M.
  • it is of the order of 3.5M.
  • its duration of treatment with alcoholic potash is between 5 minutes and 5 hours.
  • it is between 1 minute and 3 hours.
  • it is between 5 minutes and 1 hour.
  • the mass ratios of sodium hydroxide are between 10 and 100%.
  • they are between 15 and 70%.
  • they are between 20 and 50%.
  • the strong oxidant solution is neutral, acidic or basic.
  • the strong oxidant solution is acidic.
  • the strong oxidant is selected from the group consisting of KMnO 4 and KClO 3 , alone or in admixture, in hydrochloric acid, in sulfuric acid, in nitric acid, in oxalic acid, in phosphoric acid, in hydrophosphorous acid or in phosphorous acid.
  • the concentration of K n0 4 or KG0 3 is between 10mM and 1M.
  • it is between 0.1M and 0.5.
  • it is of the order of 0.2M.
  • the acid concentration is between 0.1M and 10M.
  • it is between 0.5M and 5M.
  • the duration of the treatment for a strong oxidant is between 1 minute and 3 hours.
  • it is between 5 minutes and 1 hour.
  • it is between 6 minutes and 30 minutes.
  • chemical oxidizing treatment is an electrochemical treatment.
  • the counter-ion of the at least one metal of step d) is chosen from the group comprising tetrafluoroborate, sulfate, bromide, fluoride, iodide, nitrate, phosphate and chloride ions.
  • the solution of step d) containing at least one ion of at least one metal and its counterion is a basic solution.
  • the basic solution has a pH greater than 7.
  • it has a pH between 9 and 11.
  • it has a pH of about 10.
  • the duration of the treatment of step d) is between 30 seconds and 2 hours.
  • it is between 1 minute and 1 hour.
  • it is of the order of 15 minutes.
  • the reducing solution of the reducing treatment in step f) is basic.
  • the reducing solution comprises a reducing agent chosen from the group comprising solutions of sodium borohydride, dimethyfamineborane or hydrazine.
  • the reducing agent is a solution of sodium borohydride.
  • its sodium borohydride solution has a neutral or basic pH.
  • the dimethylamineborane solution has a basic pH.
  • the pH is basic
  • the sodium hydroxide solution is used as a solvent.
  • its concentration of sodium hydroxide is between 10 -4 and 5M.
  • it is between 0.05M and 1M.
  • it is of the order of 0.1M.
  • the concentration of reducing agent in the reducing solution of step f) is between 10 -4 M and 5M.
  • it is between 0.01M and 1M.
  • it is of the order of 0.3M.
  • the reduction step is carried out at a temperature of between 10 ° C. and 90 ° C. In one embodiment, it is carried out at a temperature between 30 ° C and 70 ° C.
  • it is carried out at a temperature of the order of 50 ° C.
  • the duration of the reduction step is between 30 seconds and 1 hour.
  • it is between 1 minute and 30 minutes.
  • it is between 2 minutes and 20 minutes.
  • the solution of step f) comprises metal ions, a metal ion complexing agent, a reducing agent and a pH regulator.
  • said solution of step f) is an aqueous solution.
  • the solution of step f) is an electroless bath solution containing a metal cation chosen from: Ag + , Ag 2+ , Ag 3+ , Au + , Au 3+ , Co 2 + , Cu + , Cu 2+ , Fe 2+ , Ni 2+ , Pd + and Pt + .
  • a metal cation chosen from: Ag + , Ag 2+ , Ag 3+ , Au + , Au 3+ , Co 2 + , Cu + , Cu 2+ , Fe 2+ , Ni 2+ , Pd + and Pt + .
  • the solution of step f) is an electroless bath solution containing a metal cation chosen from: Co 2+ , Cu + , Cu 2+ , Ni 2+ , and Pt + .
  • the solution of step g) containing ions of at least one meta! is an aqueous solution.
  • said solution of step g) is an electroless bath solution containing a metal cation chosen from: Ag + , Ag + , Ag 3+ , Au + , Au 3+ , Co 2+ , Cu + , Cu 2+ , Fe + , Ni 2+ , Pd + and Pt + .
  • a metal cation chosen from: Ag + , Ag + , Ag 3+ , Au + , Au 3+ , Co 2+ , Cu + , Cu 2+ , Fe + , Ni 2+ , Pd + and Pt + .
  • the solution of step g) is an electroless bath solution containing a metal cation chosen from: Co 2+ , Cu + , Cu 2+ , Ni 2+ , and Pt + .
  • the solution of step g) is an electroless bath solution containing a metal cation selected from: Cu + and Ni z + .
  • the duration of step g) is between 1 minute and 1 hour.
  • the surface of the substrate and / or the substrate is / are subjected to one or more rinses with at least one rinsing solution.
  • the rinsing solutions are identical or different.
  • the rinsing solution is selected from the group consisting of water, distilled water, deionized water or an aqueous solution containing a detergent.
  • the detergent contained in an aqueous solution is selected from the group comprising TDF4 and sodium hydroxide.
  • the concentration of sodium hydroxide is between 0.01 and 1M.
  • the rinsing solution is agitated upon contact with the surface of the substrate and / or the substrate.
  • the stirring is carried out using an agitator, a recirculation pump, a bubbling air or a gas, an ultrasonic bath or a homogenizer.
  • the duration of each rinsing step is between 1 second to 30 minutes
  • it is between 5 seconds to 20 minutes.
  • the contacting of the surface of the substrate and / or the substrate with the solutions of the various steps can be done by immersion in a bath or by spraying and / or showering.
  • the homogenization of said bath is carried out using an agitator, a recirculation pump, a bubbling air or a gas, a bath ultrasound or a homogenizer.
  • the invention also relates to the substrate obtained according to the process of the invention for which the surface of said substrate of non-metallic material is coated with a metal layer.
  • the invention relates to a substrate of non-metallic material, at least one surface of which is coated with a metal activation layer consisting of metal atoms bound by metal-ligand interaction directly to the constituent material of the substrate by groups.
  • carboxylic acid -COOH
  • hydroxyl -OH
  • alkoxyl -OR
  • carbonyl -00
  • percarboxylic acid -CO-O-OH
  • amide amide
  • the invention relates to a substrate made of ABS, the surface of which is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the constituent ABS of FIG. substrate, said activation layer being covered with a layer of copper deposited by autocataiytique deposition.
  • the invention relates to a substrate made of ABS, the surface of which is coated with an activation layer made of nickel, the atoms of which are bonded to the constituent ABS of the substrate. said activation layer being coated with a copper layer deposited by autocatalytic deposition.
  • the invention relates to a substrate made of ABS / PC, the surface of which is coated with an activation layer consisting of copper, the atoms of which are bonded to a meta-ligand interaction with ABS.
  • PC constituting the substrate, said activation layer being covered with a layer of copper deposited by autocataiytic deposition
  • the invention relates to a substrate made of ABS / PC, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are linked by meta-ligand interaction at ⁇ / PC. constituent of the substrate, said activation layer being covered with a layer of copper deposited by autocataiytic deposition
  • the invention relates to a substrate consisting of PA, the surface of which is coated with an activation layer consisting of copper, the atoms of which are bonded by meta-ligand interaction to the constituent PA of the substrate, activation layer being covered with a layer of copper deposited by autocatalytic deposit
  • the invention relates to a substrate consisting of PA, the surface of which is coated with an activation layer made of nickel, the atoms of which are bonded to the substrate PA; of activation being covered with a layer of copper deposited by autocatalytic deposit
  • the invention relates to a substrate consisting of PC, the surface of which is coated with an activation layer consisting of copper whose atoms are bonded by metal-Sigand interaction to the PC constituting the substrate, said activation layer being covered with a layer of copper deposited by autocatalytic deposit
  • the invention relates to a substrate made of PC, the surface of which is coated with an activation layer made of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PC of the substrate, said activation layer being covered with a layer of copper deposited by autocatalytic deposition
  • the invention relates to a substrate consisting of MABS, the surface of which is coated with an activation layer consisting of copper whose atoms are bonded by metal-ligand interaction to the MABS constitutive of the substrate, said activation layer being covered with a layer of copper deposited by autocatalytic deposition
  • the invention relates to a substrate consisting of MABS, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the MABS constituting the substrate, said activation layer being covered with a layer of copper deposited by autocatalytic deposition
  • the invention relates to a substrate made of PP, the surface of which is coated with an activation layer consisting of copper whose atoms are bonded by metal-ligand interaction to the constituent PP of the substrate, iadite activation layer being covered with a layer of copper deposited by autocatalytic deposition
  • the invention relates to a substrate consisting of PP, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PP of the substrate, activation layer being coated with a copper layer or deposited by autocatalytic deposition
  • the invention relates to a substrate consisting of PPS, the surface of which is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the constituent PPS of the substrate.
  • activation layer being coated with a copper layer or deposited by autocatalytic deposition
  • the invention relates to a substrate consisting of PPS, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PPS of the substrate, activation layer being covered with a layer of copper deposited by autocatalytic deposition
  • the invention relates to a substrate made of ABS, the surface of which is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the ABS constituting the substrate, said activation layer being coated with a nickel layer deposited by autocatalytic deposition.
  • the invention relates to a substrate made of ABS, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent ABS of the invention. substrate, said activation layer being coated with a nickel layer deposited by autocatalytic deposition.
  • the invention relates to a substrate made of ABS / PC, the surface of which is coated with an activation layer consisting of copper whose atoms are linked by metal-ligand interaction with ABS. / PC constituting the substrate, said activation layer being coated with a layer of nickel deposited by autocatalytic deposition
  • the invention relates to a substrate made of ABS / PC, the surface of which is coated with an activation layer made of nickel, the atoms of which are bound by metal-ligand interaction with ABS. / PC constituting the substrate, said activation layer being coated with a layer of nickel deposited by autocatalytic deposition
  • the invention relates to a substrate consisting of PA, the surface of which is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the constituent PA of the substrate.
  • activation layer being coated with a nickel layer deposited by autocatalytic deposition
  • the invention relates to a substrate consisting of PA, the surface of which is coated with an activation layer made of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PA of the substrate.
  • activation layer being coated with a nickel layer deposited by autocatalytic deposition
  • the invention relates to a substrate made up of PC whose surface is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the constituent PC of the substrate.
  • activation layer being coated with a nickel layer deposited by autocatalytic deposition
  • the invention relates to a substrate made up of PC whose surface is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PC of the substrate, said activation layer being coated with a nickel layer deposited by autocatalytic deposition
  • the invention relates to a substrate consisting of MABS, the surface of which is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the MABS constitutive of the substrate. activation layer being coated with a nickel layer deposited by autocatalytic deposition
  • the invention relates to a substrate consisting of MABS, the surface of which is coated with an activation layer consisting of nickel, whose atoms are bonded by meta- ⁇ gand interaction to the MABS constitutive of the substrate.
  • activation layer being coated with a nickel layer deposited by autocatalytic deposit
  • the invention relates to a substrate consisting of PP, the surface of which is coated with an activation layer consisting of copper, the atoms of which are bonded by metal-ligand interaction to the constituent PP of the substrate.
  • activation layer being coated with a nickel layer deposited by autocatalytic deposit
  • the invention relates to a substrate made of PP, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PP of the substrate, fadite activation layer being coated with a nickel layer deposited by autocatalytic deposition
  • the invention relates to a substrate consisting of PPS, the surface of which is coated with an activation layer consisting of copper whose atoms are linked by metal-ligand interaction to the constituent PPS of the substrate, said activation layer being coated with a nickel layer deposited by autocatalytic deposition
  • the invention relates to a substrate consisting of PPS, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PPS of the substrate, activation layer being coated with a nickel layer deposited by autocatalytic deposition
  • the invention also relates to a method according to the invention further comprising a metallization step.
  • the metallization treatment is an electroplating treatment.
  • the invention and its modes of implementation are illustrated in the following examples.
  • ABS acrylonitrile butadiene styrene
  • PC acrylonitrile butadiene styrene / polycarbonate
  • This method of coating with a copper layer of a substrate of non-metallic material is carried out in 4 steps (chemical oxidizing treatment with nitric acid / chelation and / or complexation / reduction / electro-bath).
  • ABS acrylonitrile butadiene styrene
  • ABS / PC acrylonitrile butadiene styrene / polycarbonate
  • Copper sulfate (23.7 g) is solubilized in a solution of water (1000 ml) and ammonia (30 ml). In this bath are immersed parts that have undergone the chemical oxidizing treatment of step 1.1 for 15 minutes. The ABS parts are then rinsed in 0.2 M sodium hydroxide solution.
  • NaBH 4 sodium borohydride (0.316 g, 0.8 ⁇ 10 -2 mol) is dissolved in 25 ml of a 0.1 M sodium hydroxide solution (NaOH). This solution is heated to 80.degree. using a water bath and His samples are immersed in it. After 12 minutes, the samples were rinsed with MilliQ water before being dried.
  • a solution is prepared containing 100 ml of the solution M Copper® 85 B. Then, 40 ml of the solution M Copper® 85 A, then 30 ml of the solution M Copper® 85 D, then 2 ml of the solution M Copper® 85 G and finally 5 ml of formaldehyde 37% are added. The level of the solution is completed to reach 1 liter of solution. The bath is heated to 60 ° C. with mechanical stirring. The ABS plates are then introduced. [000194] The parts will be covered with the chemical copper metal film after 3 minutes of immersion.
  • the Electroiess bath is a prepared solution containing: 40 ml of the PegCopper 100 solution, 100 ml of the PegCopper 200 solution, 30 ml of PegCopper 400 and 2 ml of PegCopper 500 (products sold by the PEGASTECH company). 3.5 ml of PegCopper 600 are then added. The level is completed to reach 1 liter with water and the mixture is brought to 50 ° C. under bulking. The parts to be treated are then introduced.
  • the parts will be covered with the chemical copper metal film after 3 minutes of immersion.
  • Example 2 The copper layer is visible to the naked eye.
  • Example 2 The copper layer is visible to the naked eye.
  • the coating process is carried out with a substrate consisting of Minlon® polyamide.
  • step 1.2 copper ions are chelated on the surface of the substrate.
  • step 1.4. or I.5. the polyamide substrate is covered with a chemical copper metal film.
  • the copper layer is visible to the naked eye.
  • the coating process is implemented with a Lexan® polycarbonate substrate.
  • the polycarbonate substrate is immersed in a solution containing a mixture of strong acids (34% nitric acid and 66% tallow) at 25 ° C. for 5 minutes and then in a concentrated suifuric acid bath at 25 ° C. for 3 minutes. The whole is neutralized in a 5N potassium hydroxide solution at 65 ° C. for 5 minutes. The polycarbonate substrate is then rinsed with water.
  • a mixture of strong acids (34% nitric acid and 66% tallow) at 25 ° C. for 5 minutes and then in a concentrated suifuric acid bath at 25 ° C. for 3 minutes.
  • the whole is neutralized in a 5N potassium hydroxide solution at 65 ° C. for 5 minutes.
  • the polycarbonate substrate is then rinsed with water.
  • step 1.2 copper ions are chelated on the surface of the substrate.
  • step 1.4. or I.5. the polycarbonate substrate is covered with a chemical copper metal film.
  • the copper layer is visible to the naked eye.
  • Adhesion tests according to the NF ISO 2409 / NF T30-038 standard and corrosion tests according to DIN ISO 9227 were carried out on the substrates obtained in Examples 1 to 3, and the performances are in accordance with the requirements of these tests and comparable to the performanes obtained with substrates obtained according to the methods of the prior art.

Abstract

The present invention relates to a process for coating a surface of a substrate made of nonmetallic material with a metal layer. According to this invention, the coating process consists of the following steps: a. a substrate made of nonmetallic material is provided, b. at least part of at least one surface of said substrate is subjected to a physical or chemical treatment for increasing the specific surface area thereof, c. that surface of said substrate which was treated in step b) is subjected to an oxidizing treatment, d. that surface of said substrate which was treated in step c) is brought into contact with a solution containing at least one ion of at least one metal and its counterion, said metal being chosen from the group formed by the metals of groups IB and VIII of the Periodic Table of the Elements, e. a substrate comprising ions of at least one metal that are chemically attached to the nonmetallic material constituting the substrate on at least part of at least one of its surfaces is obtained, f. said ions of at least one metal that are chemically attached to the nonmetallic material constituting the substrate on a surface of said substrate are subjected to a reducing treatment and a substrate comprising atoms of at least one metal that are chemically attached to the nonmetallic material constituting the substrate on at least part of at least one of its surfaces is obtained, g. the surface comprising particles of at least one metal which was obtained in step f) is brought into contact with a solution containing ions of at least one metal, h. a coating formed by a layer of at least one metal is obtained on the treated surface of said substrate, said steps optionally being followed or preceded by one or more rinsing steps. The invention also relates to a substrate made of nonmetallic material, at least one surface of which is coated with a metal activation layer formed by atoms of a metal that are bonded, through metal-ligand interaction, directly to the constituent material of the substrate by carboxyl (-COOH), hydroxyl (-OH), alkoxyl (-OR), carbonyl (-C=O), percarbonic (-CO-O-OH), nitro (N=O) or amide (-CONH) groups, said activation layer being covered with a layer of an identical or different metal deposited by electroless deposition.

Description

Procédé de revêtement d'une surface d'un substrat en matériau non  Method of coating a surface of a substrate of non-material
métallique par une couche métallique  metallic by a metal layer
[0001] La présente invention concerne un procédé de revêtement d'une surface d'un substrat en matériau non métallique par une couche métallique pour le rendre apte à être traité, grâce à la forte adhésion du revêtement, par les procédés classiques de métallisation tels que la galvanoplastie. The present invention relates to a method of coating a surface of a non-metallic material substrate with a metal layer to make it capable of being treated, thanks to the strong adhesion of the coating, by conventional metallization processes such as than electroplating.
[0002] Les procédés de métallisation de matériaux consistent à déposer une fine couche de métal sur la surface d'un substrat. L'intérêt de ces procédés est multiple : fonctions visuelle, décorative, conductrice, de renforcement... On l'utilise couramment pour les pièces utilisées dans l'industrie aéronautique, automobile, la cosmétique, l'électroménager, le sanitaire, !a connectique, la microélectronique...  Materials metallization processes consist in depositing a thin layer of metal on the surface of a substrate. The interest of these processes is multiple: visual, decorative, conductive, reinforcement ... It is commonly used for parts used in the aerospace, automotive, cosmetics, appliances, sanitary, connectivity, microelectronics ...
[0003] De nombreux procédés de métallisation de substrats non métalliques ont été décrits dans la littérature et les brevets. Many metallization processes for non-metallic substrates have been described in the literature and patents.
[0004] La plupart de ces procédés de métallisation utilisent les propriétés électroconductrices ou de potentiel électrochimique des particules métalliques qui ont été déposées sur les substrats non métalliques lors d'une étape dite d'activation. Cette étape d'activation est en outre couramment précédée par une étape d'augmentation de fa surface spécifique pour que le substrat soit suffisamment « rugueux » pour permettre une bonne accroche des particules métalliques.  [0004] Most of these metallization processes use the electroconductive or electrochemical potential properties of the metal particles that have been deposited on the non-metallic substrates during a so-called activation step. This activation step is also usually preceded by a step of increasing the surface area so that the substrate is sufficiently "rough" to allow good adhesion of the metal particles.
[0005] L'inconvénient majeur de ces procédés est notamment l'utilisation de chrome hexavalent iors de l'étape de décapage ou modification de la rugosité de surface du substrat, un puissant oxydant qui permet d'obtenir une rugosité importante nécessaire à l'accroche des particules métalliques mais qui est connu pour sa haute toxicité.  The major disadvantage of these processes is in particular the use of hexavalent chromium during the etching step or modification of the surface roughness of the substrate, a powerful oxidant which provides a high roughness necessary for the hangs metal particles but is known for its high toxicity.
[0006] L'étape d'activation de la surface consiste à déposer et à maintenir sur la surface du matériau non métallique des particules métalliques ou des cations métalliques qui seront par la suite réduits pour former des particules métalliques. Cette étape nécessite l'utilisation de particules colloïdales palladium/étain qui ne réagissent que sur un certain type de polymères et qui requiert l'utilisation de quantités importantes de palladium.  The activation step of the surface consists of depositing and maintaining on the surface of the non-metallic material metal particles or metal cations which will subsequently be reduced to form metal particles. This step requires the use of colloidal palladium / tin particles which react only on a certain type of polymer and which requires the use of large quantities of palladium.
[0007] L'article de Nagao T et al. (Galvanotechnik, 2006, 97, 7, 2124-2130) fait par exemple une synthèse des techniques utilisées pour la métallisation de substrats en ABS qui comprennent outre des étapes de nettoyage et de conditionnement des surfaces, une étape de décapage par des solutions de chrome hexavalent, une étape de dépôt de colloïde Sn-Pd puis une étape de dépôt autocataiytique de métal et plus particulièrement de cuivre. Cet article fait également le point sur une technique dite « Direct Acid Copper Plating » C P qui ne comporte pas l'étape de dépôt autocataiytique de métal, mais qui requiert l'addition de palladium dans le bain de décapage et/ou de grandes quantités de colloïde Pd/Sn dans le bain de catalyse. The article by Nagao T et al. (Galvanotechnik, 2006, 97, 7, 2124-2130) for example a synthesis of the techniques used for the metallization of ABS substrates which include steps of cleaning and conditioning of the surfaces, a stripping step by chromium solutions hexavalent, a step depositing colloid Sn-Pd then a step of autocataiytique deposition of metal and more particularly of copper. This article also reviews a technique called "Direct Acid Copper Plating" CP which does not include the autocatalytic metal deposition step, but which requires the addition of palladium in the pickling bath and / or large amounts of Pd / Sn colloid in the catalyst bath.
[0008] Pour limiter l'usage des solutions de décapage à base de chrome hexavalent, dans la demande US 3598630 l'étape de décapage de panneaux d'ABS est effectuée par une solution de permanganate de potassium et d'acide phosphorique et l'étape de formation du colloïde Sn/Pd est réalisée par applications successives d'une solution de chlorure d'étain puis d'une solution de chlorure de palladium. Dans le procédé décrit, l'étape de dépôt auto-catalytique de métal est une étape classique de dépôt de cuivre.  To limit the use of the hexavalent chromium-based pickling solutions, in the application US Pat. No. 3,598,630, the stripping step of ABS panels is carried out with a solution of potassium permanganate and phosphoric acid and Step of formation of the Sn / Pd colloid is carried out by successive applications of a solution of tin chloride and then of a solution of palladium chloride. In the process described, the self-catalytic metal deposition step is a conventional copper deposition step.
[0009] Pour limiter l'usage du Palladium, des solutions alternatives ont été proposées, par exemple dans la demande WO 02/36853, le procédé classique de métallisation d'un substrat en ABS est modifié par remplacement du colloïde Sn/Pd par un colioïde Ag/Sn puis après élimination totale des ions Sn l'étape de dépôt auto- catalytique de métal est une étape de dépôt de nickel. Après l'étape de décapage par les solutions chromiques classiques et rinçage un traitement de la surface décapée par une solution de produits susceptibles d'améliorer l'adsorption comme des polyélectrolytes sous forme de polymères cationiques peut être effectué.  To limit the use of Palladium, alternative solutions have been proposed, for example in the application WO 02/36853, the conventional method of metallization of an ABS substrate is modified by replacing the Sn / Pd colloid by a Ag / Sn colioid then after complete removal of Sn ions the self-catalytic metal deposition step is a nickel deposition step. After the pickling step by conventional chromic solutions and rinsing treatment of the etched surface with a solution of adsorption enhancing products such as polyelectrolytes in the form of cationic polymers can be carried out.
[00010] Outre l'utilisation importante de palladium dont le coût et la rareté sont un problème lorsque celui-ci n'est pas substitué par de l'argent, dans tous les procédés ci-dessus décrits l'étape d'activation est une étape d'adsorption dans laquelle une préparation colloïdale est utilisée ou formée par addition d'ions stanneux, qui doivent ensuite être complètement éliminés pour permettre le développement harmonieux et régulier de la couche métallique lors de l'étape de dépôt autocataiytique de métal. In addition to the important use of palladium whose cost and scarcity are a problem when it is not substituted by silver, in all the processes described above the activation step is a adsorption step in which a colloidal preparation is used or formed by addition of stannous ions, which must then be completely removed to allow smooth and uniform development of the metal layer during the autocatalytic metal deposition step.
[00011] Des procédés alternatifs ne mettant pas en œuvre, lors de l'étape d'activation de solutions colloïdales, et, remplaçant l'adsorption par une liaison chimique des ions métalliques sous forme de complexes ou chélates ont été proposés. Alternative methods not implementing, during the colloidal solution activation step, and replacing the adsorption by a chemical bond metal ions in the form of complexes or chelates have been proposed.
[00012] Par exemple, les brevets US 4,981,715 et US 4,701,351 décrivent un procédé de revêtement d'un substrat par une fine couche d'un polymère, par exemple l'acide polyacrylique, apte à complexer un composé de métal noble comprenant une étape de recouvrement du substrat par un polymère apte à chélater des ions métalliques, suivie d'une étape de mise en contact du polymère avec des particules métalliques. Le substrat est ensuite soumis à l'étape de dépôt auto-catalytique de métal, Dans les exemples de mise en œuvre les cations métalliques utilisés sont des cations palladium, mais le principal inconvénient de ce procédé est qu'il entraine la nécessité de gérer la qualité d'une interface supplémentaire, à savoir celle qui est créée entre !e substrat et la couche de polymère apte à chélater un ion métallique. Des solutions sont proposées par exemple pour Se traitement par irradiation qui permet également la fixation régioséîective de cette couche de polymère apte à chéîater et ainsi la possibilité de métalliser le substrat de façon sélective. For example, US Pat. Nos. 4,981,715 and 4,701,351 describe a process for coating a substrate with a thin layer of a polymer, for example polyacrylic acid, capable of complexing a noble metal compound comprising a step of covering the substrate with a polymer capable of chelating metal ions, followed by a step of contacting the polymer with metal particles. The substrate is then subjected to the self-catalytic metal deposition step. In the exemplary embodiments, the metal cations used are However, the main drawback of this method is that it entails the need to manage the quality of an additional interface, namely that which is created between the substrate and the polymer layer capable of chelating a metal ion. Solutions are proposed for example for irradiation treatment which also allows the regioselective fixing of this layer of polymer capable of drying and thus the possibility of metallizing the substrate selectively.
[00013] Cette solution si elle permet de s'affranchir de l'utilisation des colloïdes entraîne la formation d'une couche supplémentaire, dont la cohésion avec le substrat ou la solidité de la fixation sur le substrat sera à gérer au niveau industriel ainsi qu'une étape supplémentaire dans le procédé de fabrication . De plus, des problèmes de compatibilité entre le matériau constitutif du substrat et le polymère apte à chélater peuvent également survenir. This solution if it eliminates the use of colloids leads to the formation of an additional layer, the cohesion with the substrate or the strength of the fastening on the substrate will be managed at the industrial level as well as an additional step in the manufacturing process. In addition, compatibility problems between the constituent material of the substrate and the polymer capable of chelating can also occur.
[00014] La présente invention permet de simplifier les différentes étapes de ce procédé de revêtement de matériaux non métalliques et de le rendre plus respectueux de l'environnement et moins coûteux, par la mise au point d'un procédé de revêtement plus simple n'utilisant pas de réactifs toxiques et polluants, sans toutefois ajouter une étape et une couche supplémentaire. The present invention simplifies the various steps of this method of coating non-metallic materials and make it more environmentally friendly and less expensive, by developing a simpler coating process n ' using no toxic and polluting reagents, without adding a step and an additional layer.
[00015] La présente invention concerne donc un procédé de revêtement d'une surface d'un substrat en matériau non métallique par une couche métallique, consistant en les étapes suivantes : The present invention therefore relates to a method of coating a surface of a substrate of non-metallic material with a metal layer, consisting of the following steps:
a) on dispose d'u n substrat en matériau non métallique,  a) there is a substrate of non-metallic material,
b) on soumet au moins une partie d'au moins une surface dudit substrat à u n traitement physique ou chimique d'aug mentation de la surface spécifique, c) on soumet la surface dudit substrat traitée à l'étape b), à un traitement oxydant,  b) subjecting at least a portion of at least one surface of said substrate to a physical or chemical surface-specific increase treatment; c) subjecting the surface of said substrate treated in step b) to a treatment; oxidant,
d) on met en contact la surface dudit substrat traitée à l'étape c), avec une solution contenant au moins un ion d'au moins un métal et son contre-ion, ledit métal étant choisi dans le groupe constitué par les métaux des groupes IB et VIII du tableau de Sa classification périod ique des éléments,  d) the surface of said substrate treated in step c) is brought into contact with a solution containing at least one ion of at least one metal and its counterion, said metal being chosen from the group consisting of the metals of groups IB and VIII of the table of its periodic classification of elements,
e) on obtient un substrat comprenant des ions d'au moins un métal fixés chimiquement au matériau non métallique constituant le substrat sur au moins une partie d'au moins une de ses surfaces,  e) obtaining a substrate comprising ions of at least one metal chemically bonded to the nonmetallic material constituting the substrate on at least a part of at least one of its surfaces,
f) on soumet lesdits ions d'au moins un métal fixés au matériau non métallique constituant le substrat sur une surface dudit substrat, à un traitement réducteur et on obtient un substrat comprenant des atomes d'au moins un métal fixés au matériau non métallique constituant le substrat sur au moins une partie d'au moins une de ses surfaces, f) subjecting said ions of at least one metal attached to the non-metallic material constituting the substrate on a surface of said substrate to a reducing treatment and obtaining a substrate comprising atoms of at least one metal fixed to the non-metallic material constituting the substrate on at least a part of at least one of its surfaces,
g) on met en contact la surface comprenant des particules d'au moins un métal obtenue à l'étape f) avec une solution contenant des ions d'au moins un métal. h) on obtient sur la surface traitée dudit substrat un revêtement par une couche d'au moins un métal,  g) contacting the surface comprising particles of at least one metal obtained in step f) with a solution containing ions of at least one metal. h) obtaining on the treated surface of said substrate a coating with a layer of at least one metal,
lesdites étapes étant éventuellement suivies ou précédées de une ou plusieurs étapes de rinçage.  said steps possibly being followed or preceded by one or more rinsing steps.
[00016] L'étape g) est une étape de dépôt auto-catalytique également appelée electroless. Step g) is a self-catalytic deposition step also called electroless.
[00017] On entend par des ions et/ou des atomes liés chimiquement des atomes ou des ions liés par chélation et/ou complexation par des fonctions ou groupements par exemple carboxylique (-CÛOH), hydroxyle (-OH), aicoxyle (-OR), carbonyie (-C=0), percarbonique (-CO-0-OH), nitro (N=0) et amide (-CONH) à la surface dudit matériau.  By ions and / or chemically bonded atoms are meant atoms or ions bonded by chelation and / or complexation by functions or groups, for example carboxylic (-COH), hydroxyl (-OH), aicoxyl (-OR ), carbonyl (-C = O), percarboxylic (-CO-O-OH), nitro (N = O) and amide (-CONH) on the surface of said material.
[00018] A l'étape f) les atomes d'au moins un métal fixés au matériau non métallique constituant le substrat sont fixés par des interactions ligand-métal.  In step f) the atoms of at least one metal attached to the non-metallic material constituting the substrate are fixed by ligand-metal interactions.
[00019] Dans un mode de réalisation, l'étape d) d'activation est effectuée par contact avec une solution contenant un ion d'un unique métal et son contre-ion.  In one embodiment, the activation step d) is carried out by contact with a solution containing an ion of a single metal and its counter-ion.
[00020] Dans un mode de réalisation, les étapes b) et c) sont effectuées en une seule étape b') et le traitement est un traitement oxydant. In one embodiment, steps b) and c) are carried out in a single step b ') and the treatment is an oxidizing treatment.
[00021] Dans un mode de réalisation, le métal de l'étape f) et le métal des ions de l'étape g) sont identiques.  In one embodiment, the metal of step f) and the metal of the ions of step g) are identical.
[00022] Dans un mode de réalisation, les étapes f) et g) sont effectuées en une seufe étape f).  In one embodiment, steps f) and g) are performed in a single step f).
[00023] Lors du procédé de revêtement, la surface dudit substrat en matériau non métallique doit être, en premier lieu, préparée afin d'obtenir une bonne adhérence de la couche métallique sur la surface. La surface du substrat est nettoyée de tous ses contaminants en créant simultanément un relief d'accrochage pour l'adhérence du futur revêtement lors de l'étape b) du procédé. During the coating process, the surface of said non-metallic material substrate must be, firstly, prepared in order to obtain good adhesion of the metal layer to the surface. The surface of the substrate is cleaned of all its contaminants by simultaneously creating a hooking relief for the adhesion of the future coating during step b) of the process.
[00024] La surface du substrat peut être traitée en totalité ou en partie en utilisant les techniques de masquage bien connues de l'homme de l'art telles que l'utilisation de vernis protecteurs résistants aux étapes d'oxydation.  The surface of the substrate may be treated in whole or in part using masking techniques well known to those skilled in the art such as the use of protective varnishes resistant to oxidation steps.
[00025] Dans un mode de réalisation, l'étape b) est mise en œuvre par traitement physique. [00026] Par traitement physique, on entend un traitement permettant de supprimer les couches de faible cohésion et d'augmenter la rugosité de surface. In one embodiment, step b) is implemented by physical processing. By physical treatment means a treatment for removing the weak cohesion layers and increase the surface roughness.
[00027] Dans un mode de réaiisation, le traitement physique est choisi dans le groupe des traitements par impacts.  In one embodiment, the physical treatment is selected from the group of impact treatments.
[00028] Dans un mode de réalisation, les étapes b) ou b') ou c) sont mises en œuvre par traitement oxydant.  In one embodiment, steps b) or b ') or c) are implemented by oxidative treatment.
[00029] Par traitement oxydant, on entend tout traitement permettant de préparer la surface en augmentant ia rugosité donc la surface spécifique de la surface pour l'étape b) et créant des fonctions susceptibles de chélater et/ou complexer des cations métalliques pour l'étape c).  By oxidizing treatment is meant any treatment to prepare the surface by increasing the roughness so the surface area of the surface for step b) and creating functions that can chelate and / or complex metal cations for the step c).
[00030] Dans un mode de réalisation, le traitement oxydant est choisi dans le groupe des traitements oxydants chimiques.  In one embodiment, the oxidizing treatment is chosen from the group of chemical oxidizing treatments.
[00031] Dans un mode de réalisation, le traitement oxydant est choisi dans le groupe des traitements oxydants électrochimiques.  In one embodiment, the oxidizing treatment is chosen from the group of electrochemical oxidizing treatments.
[00032] Dans un mode de réalisation, le traitement oxydant de l'étape c) est choisi dans le groupe des traitements oxydants physiques.  In one embodiment, the oxidizing treatment of step c) is selected from the group of physical oxidizing treatments.
[00033] Selon la présente invention, le substrat peut être une nanoparticule, une microparticule, un bouchon de produits cosmétiques, un élément électronique, une poignée de porte, un appareil électrodomestique, des lunettes, un objet de décoration, un élément de carrosserie, un élément de carlingue, d'aile d'avion, un conducteur souple ou un connecteur. According to the present invention, the substrate may be a nanoparticle, a microparticle, a stopper of cosmetic products, an electronic element, a door handle, an electrical appliance, glasses, a decorative object, a bodywork element, a cabin element, airplane wing, a flexible conductor or a connector.
[00034] On entend par matériaux non métalliques, tout matériau appartenant à ia famille des matériaux organiques, à la famille des matériaux minéraux et à la famille des matériaux composites. On peut citer à titre d'exemples non limitatifs ie bois, le papier, le carton, les céramiques, les matières plastiques, les siiicones, le textile, le verre. [00034] Non-metallic materials are understood to mean any material belonging to the family of organic materials, to the family of mineral materials and to the family of composite materials. Non-limiting examples include wood, paper, cardboard, ceramics, plastics, silicones, textiles and glass.
[00035] Dans un mode de réalisation le matériau organique est choisi parmi les matières plastiques. In one embodiment, the organic material is chosen from plastics.
[00036] Par couche métallique on entend une couche mince, de quelques nanomètres à plusieurs centaines de micromètres, d'un métal et/ou d'un oxyde métallique déposée à fa surface d'un substrat. By metal layer is meant a thin layer, from a few nanometers to several hundred microns, a metal and / or a metal oxide deposited on the surface of a substrate.
[00037] Dans un mode de réalisation, le matériau non métallique est un polymère choisi dans le groupe comprenant les polymères naturel, artificiel, synthétique, thermoplastique, thermodurcissable, thermostable, élastomère, monodimensionnel et tridimensionnel. In one embodiment, the nonmetallic material is a polymer chosen from the group comprising the polymers, natural, artificial, synthetic, thermoplastic, thermosetting, thermostable, elastomeric, one-dimensional and three-dimensional.
[00038] Dans un mode de réalisation, le matériau non métallique peut comprendre en outre au moins un élément choisi dans le groupe comprenant les charges, ies plastifiants et les additifs.  In one embodiment, the non-metallic material may further comprise at least one element selected from the group consisting of fillers, plasticizers and additives.
[00039] Dans un mode de réalisation, les charges sont des charges minérales choisies dans le groupe comprenant la silice, le talc, les fibres ou billes de verre.  In one embodiment, the fillers are mineral fillers chosen from the group comprising silica, talc, fibers or glass beads.
[00040] Dans un mode de réalisation, les charges sont des charges organiques choisies dans le groupe comprenant la farine céréalière et la pâte de cellulose.  In one embodiment, the fillers are organic fillers chosen from the group comprising cereal flour and cellulose pulp.
[00041] Les additifs sont utilisés pour améliorer une propriété spécifique du matériau non métallique telle que sa couleur, sa réticulation, son glissement, sa résistance à la dégradation, au feu et/ou aux attaques bactériennes et/ou fongiques.  The additives are used to improve a specific property of the non-metallic material such as its color, its crosslinking, its sliding, resistance to degradation, fire and / or bacterial and / or fungal attacks.
[00042] Dans un mode de réalisation, le polymère est un (co)polymère thermoplastique choisi dans le groupe comprenant une polyoiéfine, un polyester, un polyéther, un polymère vinylique, un polymère vinylidénique, un polymère styrénique, un polymère (méth)acrylique, un polyamide, un polymère fluoré, un polymère cellulosique, un poly(arylènesulfone), un polysulfure, un po!y(aryléther)cétone, une polyamide-imide, une poly(éther)imide, une polybenzimidazole, un po!y(indène/coumarone), un poly(paraxylylène), seuis, en mélange, en copolymères ou en combinaison. In one embodiment, the polymer is a thermoplastic (co) polymer selected from the group comprising a polyolefin, a polyester, a polyether, a vinyl polymer, a vinylidene polymer, a styrenic polymer, a (meth) acrylic polymer. , a polyamide, a fluoropolymer, a cellulosic polymer, a poly (arylenesulfone), a polysulfide, a poly (arylether) ketone, a polyamide-imide, a poly (ether) imide, a polybenzimidazole, a poly ( indene / coumarone), a poly (paraxylylene), isolated, in admixture, in copolymers or in combination.
[00043] Les polyoléfines peuvent être choisies dans le groupe comprenant un polyéthylène, un polypropylène, un copolymère éthylène/propyiène, un polybutylène, un poiyméthylpentène, un copolymère éthylène/acétate vinylique, un copolymère éthylène/aicool vinylique, un copolymère éthylène/acryfate de méthyle, seuls, en mélange, en copolymères ou en combinaison. The polyolefins may be chosen from the group comprising a polyethylene, a polypropylene, an ethylene / propylene copolymer, a polybutylene, a polyethylpentene, an ethylene / vinyl acetate copolymer, an ethylene / vinyl alcohol copolymer, an ethylene / acrylate copolymer. methyl, alone, in admixture, in copolymers or in combination.
[00044] Les polyesters peuvent être choisis dans le groupe comprenant un polyéthylène téréphtalate, modifié ou non modifié par du glycoi, un polybutylène téréphtalate, un polyactide, un polycarbonate, seuls, en mélange, en copolymères ou en combinaison.  The polyesters may be chosen from the group comprising a polyethylene terephthalate, modified or unmodified by glycoi, a polybutylene terephthalate, a polyactide, a polycarbonate, alone, as a mixture, copolymers or in combination.
[00045] Les polyéthers peuvent être choisis dans le groupe comprenant un poly(oxyméthylène), un po!y(oxyéthylène), un poly(oxypropylène), un poiy(phénylène éther), seuls, en mélange, en copolymères ou en combinaison.  The polyethers may be chosen from the group comprising a poly (oxymethylene), a poly (oxyethylene), a poly (oxypropylene), a poly (phenylene ether), alone, in a mixture, in copolymers or in combination.
[00046] Les polymères vinyiiques peuvent être choisis dans le groupe comprenant un poîy(chlorure de vinyle) éventuellement chloré, un poly(alcool vinylique), un poly(acétate de vinyle), un poly(acétal de vinyle), un poly(formal de vinyle), un poly(fluorure de vinyle), un poiy(chlorure de vinyle/acétate de vinyle), seuls, en mélange, en copolymères ou en combinaison. The vinyl polymers may be chosen from the group comprising an optionally chlorinated polyvinyl chloride, a polyvinyl alcohol, a polyvinyl acetate, a polyvinyl acetal, a poly (formaldehyde) and a polyvinyl alcohol. vinyl), a poly (vinyl fluoride), a poly (vinyl chloride / vinyl acetate), whether alone, in admixture, in copolymers or in combination.
[00047] Les polymères vinylidéniques peuvent être choisis dans le groupe comprenant un poly(chiorure de vinylidène), un poly(fluorure de vinylidène), seuls, en mélange, en copolymères ou en combinaison. The vinylidene polymers may be chosen from the group comprising a polyvinylidene chloride, a polyvinylidene fluoride, alone, in a mixture, in copolymers or in combination.
[00048] Les polymères styréniques peuvent être choisis dans le groupe comprenant un polystyrène, un poly(styrène/butadiène), un poly(acrylonitriie/butadiène/styrène), un poiy(acrylonitrile/styrène), un poly(acrylonitrile/éthylène/propylène/styrène), un poly(acrylonitrile/styrène/acrylate), seuls, en mélange, en copolymères ou en combinaison.  The styrenic polymers may be selected from the group consisting of polystyrene, poly (styrene / butadiene), poly (acrylonitrile / butadiene / styrene), poly (acrylonitrile / styrene), poly (acrylonitrile / ethylene / propylene) styrene), a poly (acrylonitrile / styrene / acrylate), alone, in admixture, in copolymers or in combination.
[00049] Les polymères (méth)acryliques peuvent être choisis dans le groupe comprenant un polyacrylonitrile, un poly(acrylate de méthyle), un poly(méthacryiate de méthyle), seuls, en mélange, en copolymères ou en combinaison. The (meth) acrylic polymers may be chosen from the group comprising a polyacrylonitrile, a poly (methyl acrylate), a poly (methyl methacrylate), alone, in a mixture, in copolymers or in combination.
[00050] Les polyamides peuvent être choisis dans le groupe comprenant un poly(caprolactame), un poly(hexaméthylène adipamide), un poly(!auroamide), un polyéther-bloc-amide, un poly(métaxylylène adipamide), un po!y(métaphénylène isophtalamide), seuls, en mélange, en copolymères ou en combinaison. The polyamides may be chosen from the group comprising a poly (caprolactam), a poly (hexamethylene adipamide), a poly (! Auroamide), a polyether-block-amide, a poly (metaxylylene adipamide), a polyamide (metaphenylene isophthalamide), whether alone, in admixture, in copolymers or in combination.
[00051] Les polymères fluorés peuvent être choisis dans le groupe comprenant un polytétrafluoroéthylène, un polychlorotrifluoroéthylène, un poly(éthylène/propylène) perfluoré, un poly(fluorure de vinylidène), seuls, en mélange, en copolymères ou en combinaison. The fluoropolymers may be chosen from the group comprising a polytetrafluoroethylene, a polychlorotrifluoroethylene, a perfluorinated poly (ethylene / propylene), a poly (vinylidene fluoride), alone, in a mixture, in copolymers or in combination.
[00052] Les polymères cellulosiques peuvent être choisis dans le groupe comprenant un acétate de cellulose, un nitrate de cellulose, une méthylcellulose, un carboxyméthylcellulose, un éthylméthyicelîulose, seuls, en mélange, en copolymères ou en combinaison, The cellulosic polymers may be chosen from the group comprising a cellulose acetate, a cellulose nitrate, a methylcellulose, a carboxymethylcellulose, an ethylmethylcellulose, alone, in a mixture, in copolymers or in combination,
[00053] Les poly(arylènesulfone) peuvent être choisis dans le groupe comprenant un polysulfone, un polyéthersulfone, un polyarylsulfone, seuls, en mélange, en copolymères ou en combinaison. The poly (arylenesulfone) may be chosen from the group comprising a polysulfone, a polyethersulfone, a polyarylsulphone, alone, in a mixture, in copolymers or in combination.
[00054] Les polysulfures peuvent être du poly(su!fure de phénylène). [00055] Les poty(aryléther cétones) peuvent être choisis dans le groupe comprenant un poly(éther cétone}, un poly(éther éther cétone), un poly(éther cétone cétone), seuls, en mélange, en copoiymères ou en combinaison. [00054] The polysulfides may be poly (phenylene sulfide). Potyl (aryl ether ketones) can be chosen from the group comprising a polyetherketone, a polyether etherketone, a polyetherketone ketone, alone, as a mixture, copolymers or in combination.
[00056] Dans un mode de réalisation, le polymère est un {co)polymère thermodurcissable choisi dans ie groupe comprenant un aminoplaste tel que de i'urée- formol, de la mélanine-formol, de la mélanine-formol/polyesters, seuls, en copoiymères, en mélange ou en combinaison, un polyuréthane, un polyester insaturé, un polysiloxane, une résine formophénolique, époxyde, allylique ou vinylester, un a!kyde, une polyurée, un polyisocyanurate, un poly(bismaléimide), un polybenzimidazole, un polydicyclopentadiène, seuls, en copoiymères, en mélange ou en combinaison. In one embodiment, the polymer is a thermosetting (co) polymer chosen from the group comprising an aminoplast such as ureaformol, melanin-formaldehyde, melanin-formaldehyde / polyesters, alone, copolymers, in a mixture or in combination, a polyurethane, an unsaturated polyester, a polysiloxane, a formophenolic resin, epoxide, allyl or vinylester, an alkyd, a polyurea, a polyisocyanurate, a poly (bismaleimide), a polybenzimidazole, a polydicyclopentadiene, alone, in copolymers, in admixture or in combination.
[00057] Dans un mode de réalisation, le (co)polymère est choisi dans ie groupe comprenant l'acrySonitrile butadiène styrène (ABS), l'acrylonitrile butadiène styrène/polycarbonate (ABS/PC), le méthyl méthacrylate acrylonitrîle butadiène styrène (MABS), un polyamide (PA) tel que du nylon, une poiyamine, un poly(acide acrylique), une polyaniline et du poiyéthylène téréphtalate (PET).  In one embodiment, the (co) polymer is selected from the group consisting of acrylonitrile butadiene styrene (ABS), acrylonitrile butadiene styrene / polycarbonate (ABS / PC), methyl methacrylate acrylonitrile butadiene styrene (MABS ), a polyamide (PA) such as nylon, polyamine, polyacrylic acid, polyaniline and polyethylene terephthalate (PET).
[00058] Dans un mode de réalisation ie métal de l'ion métallique utilisé à l'étape d) est choisi parmi les ions cuivre, argent, nickel, platine, palladium ou cobalt. In one embodiment, the metal of the metal ion used in step d) is selected from copper, silver, nickel, platinum, palladium or cobalt ions.
[00059] Dans un mode de réalisation le métal de l'ion métallique utilisé à Î'étape d) est choisi dans le groupe constitué par ie cuivre et le nickel. [00059] In one embodiment, the metal of the metal ion used in step d) is selected from the group consisting of copper and nickel.
[00060] Dans un mode de réalisation le métal de l'ion métallique utilisé à l'étape d) est le cuivre.  In one embodiment, the metal of the metal ion used in step d) is copper.
[00061] Dans un mode de réalisation, le métal des ions métalliques utilisés à l'étape g) ou f) est choisi parmi les éléments des groupes IB et VIII de la classification périodique. In one embodiment, the metal of the metal ions used in step g) or f) is selected from the elements of groups IB and VIII of the Periodic Table.
[00062] Dans un mode de réalisation le métal de l'ion métallique utilisé à l'étape g) ou f) est choisi parmi les ions cuivre, argent, or, nickel, platine, palladium, fer ou cobalt.  In one embodiment, the metal of the metal ion used in step g) or f) is selected from copper, silver, gold, nickel, platinum, palladium, iron or cobalt ions.
[00063] Dans un mode de réalisation le métal de l'ion métallique utilisé à l'étape g) ou f) est choisi dans le groupe constitué par le cuivre et le nickel.  In one embodiment, the metal of the metal ion used in step g) or f) is selected from the group consisting of copper and nickel.
[00064] Dans un mode de réalisation le métal de l'ion métallique utilisé à l'étape g) ou f) est le cuivre, In one embodiment, the metal of the metal ion used in step g) or f) is copper,
[00065] Dans un mode de réalisation le métal de l'ion métallique utilisé à l'étape g) ou f) est le nickel. [00066] Selon l'invention, le groupe des traitements par impacts comprend le sablage, le grenaillage, le microbi!lage et le ponçage par toiles abrasives. In one embodiment, the metal of the metal ion used in step g) or f) is nickel. According to the invention, the group of impact treatments includes sandblasting, shot blasting, microbiiling and sanding by abrasive cloths.
[00067] On entend par traitement oxydant chimique un traitement permettant d'oxyder la surface du substrat en y fixant et/ou en y introduisant des groupements riches en oxygène tels que des groupements carboxylique (-COOH), hydroxyle (-OH), alcoxyle (-OR), carbonyle (-C=0), percarbonique (-CO-0-OH), nitro (N=0) et amide (- CONH) susceptibles de lier chimiquement les cations métalliques, puis les métaux réduits par chélation et/ou complexation. By chemical oxidizing treatment is meant a treatment for oxidizing the surface of the substrate by fixing and / or introducing oxygen-rich groups such as carboxylic groups (-COOH), hydroxyl (-OH), alkoxyl (-OR), carbonyl (-C = O), percarbonic (-CO-O-OH), nitro (N = O) and amide (- CONH) which can chemically bind the metal cations, then the metals reduced by chelation and / or complexation.
[00068] Selon l'invention, le traitement oxydant chimique est choisi dans le groupe comprenant le réactif de Fenton, la potasse alcoolique, un acide fort, la soude, un oxydant fort, l'ozone, seuls ou en combinaisons.  According to the invention, the chemical oxidizing treatment is chosen from the group comprising Fenton's reagent, alcoholic potash, a strong acid, sodium hydroxide, a strong oxidant, ozone, alone or in combination.
[00069] Dans un mode de réalisation, l'acide fort est choisi dans le groupe comprenant l'acide chlorhydrique, l'acide sulfurique, l'acide nitrique, l'acide perchlorique, l'acide acétique, l'acide oxa!ique, l'acide phosphoreux, l'acide phosphorique, l'acide hypophosphoreux seuls ou en mélange.  In one embodiment, the strong acid is chosen from the group comprising hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, acetic acid and oxic acid. , phosphorous acid, phosphoric acid, hypophosphorous acid alone or as a mixture.
[00070] Dans un mode de réalisation, l'oxydant fort est choisi dans le groupe comprenant KMn04 et KCI03, seuls ou en mélange. In one embodiment, the strong oxidant is selected from the group comprising KMn0 4 and KCI0 3 , alone or in admixture.
[00071] Dans un mode de réalisation, l'oxydant fort est KMn04-In one embodiment, the strong oxidant is KMnO 4 -
[00072] Les traitement oxydants sont choisis en fonction de la nature des matériaux constitutifs des substrats, dans le tableau 1 ci-après sont illustrés à titre d'exemples, différents traitements oxydants chimiques applicables lorsque le substrat est en ABS ou en ABS/PC. The oxidizing treatments are chosen depending on the nature of the constituent materials of the substrates, in Table 1 below are illustrated by way of examples, different chemical oxidizing treatments applicable when the substrate is ABS or ABS / PC .
Tableau 1  Table 1
[00073] Dans le tableau 2 ci-après sont illustrés différents traitements oxydants en fonction de la nature du substrat. In Table 2 below are illustrated various oxidizing treatments depending on the nature of the substrate.
Tableau 2 Table 2
[00074] Dans un mode de réalisation, les rapports massiques en acide fort sont compris entre 5 et 100%. In one embodiment, the solid acid mass ratios are between 5 and 100%.
[00075] Dans un mode de réalisation, ils sont compris entre 50 et 95%.  In one embodiment, they are between 50 and 95%.
[00076] Dans un mode de réalisation, ils sont compris entre 70 et 90%.  In one embodiment, they are between 70 and 90%.
[00077] Dans un mode de réalisation, la durée du traitement à l'acide fort est comprise entre 20 secondes et 5 heures.  In one embodiment, the duration of the strong acid treatment is between 20 seconds and 5 hours.
[00078] Dans un mode de réalisation, elle est comprise entre 30 secondes et 3 heures.  In one embodiment, it is between 30 seconds and 3 hours.
[00079] Dans un mode de réalisation, elle est comprise entre 30 secondes et 20 minutes.  In one embodiment, it is between 30 seconds and 20 minutes.
[00080] Dans un mode de réalisation, la durée du traitement par réaction chimique de Fenton est comprise entre 5 minutes et 5 heures. In one embodiment, the duration of the Fenton chemical reaction treatment is between 5 minutes and 5 hours.
[00081] Dans un mode de réalisation, elle est comprise entre 10 minutes et 3 heures.  In one embodiment, it is between 10 minutes and 3 hours.
[00082] Dans un mode de réalisation, elle est comprise entre 15 minutes et 2 heures.  In one embodiment, it is between 15 minutes and 2 hours.
[00083] Dans un mode de réalisation, elle est de l'ordre de 25 minutes.  In one embodiment, it is of the order of 25 minutes.
[00084] Dans un mode de réalisation, pour le traitement à la potasse alcoolique, l'hydroxyde de potassium est dilué dans une solution contenant comme solvant un alcool choisi dans le groupe comprenant le méthanol, l'éthanol, et le propanol. In one embodiment, for the treatment with alcoholic potassium hydroxide, the potassium hydroxide is diluted in a solution containing as solvent an alcohol selected from the group comprising methanol, ethanol, and propanol.
[00085] Dans un mode de réalisation, ledit hydroxyde de potassium est dilué dans une solution contenant comme solvant l'éthanol. [00086] Dans un mode de réalisation, la concentration en hydroxyde de potassium dans !a solution alcoolique est comprise entre 0,1 et 10M. In one embodiment, said potassium hydroxide is diluted in a solution containing as solvent ethanol. In one embodiment, the concentration of potassium hydroxide in the alcoholic solution is between 0.1 and 10M.
[00087] Dans un mode de réalisation, elle est comprise entre 0,5M et 5M.  In one embodiment, it is between 0.5M and 5M.
[00088] Dans un mode de réalisation, elle est de l'ordre de 3,5M.  In one embodiment, it is of the order of 3.5M.
[00089] Dans un mode de réalisation, Sa durée du traitement à la potasse alcoolique est comprise entre 5 minutes et 5 heures.  In one embodiment, its duration of treatment with alcoholic potash is between 5 minutes and 5 hours.
[00090] Dans un mode de réalisation, eile est comprise entre 1 minute et 3 heures.  In one embodiment, it is between 1 minute and 3 hours.
[00091] Dans un mode de réalisation, elle est comprise entre 5 minutes et 1 heure.  In one embodiment, it is between 5 minutes and 1 hour.
[00092] Dans un mode de réalisation, pour le traitement à la soude, les rapports massiques en soude sont compris entre 10 et 100%. In one embodiment, for treatment with sodium hydroxide, the mass ratios of sodium hydroxide are between 10 and 100%.
[00093] Dans un mode de réalisation, ils sont compris entre 15 et 70%.  In one embodiment, they are between 15 and 70%.
[00094] Dans un mode de réalisation, ils sont compris entre 20 et 50%.  In one embodiment, they are between 20 and 50%.
[00095] Dans un mode de réalisation, pour ie traitement par un oxydant fort, la solution en oxydant fort est neutre, acide ou basique. In one embodiment, for the treatment with a strong oxidant, the strong oxidant solution is neutral, acidic or basic.
[00096] Dans un mode de réalisation, la solution en oxydant fort est acide.  In one embodiment, the strong oxidant solution is acidic.
[00097] Dans un mode de réalisation, l'oxydant fort est choisi dans le groupe comprenant KMn04 et KCI03, seui ou en mélange, dans i'acide chlorhydrique, dans l'acide sulfurique, dans l'acide nitrique, dans l'acide oxalique, dans l'acide phosphorique, dans l'acide hydrophosphoreux ou dans l'acide phosphoreux. In one embodiment, the strong oxidant is selected from the group consisting of KMnO 4 and KClO 3 , alone or in admixture, in hydrochloric acid, in sulfuric acid, in nitric acid, in oxalic acid, in phosphoric acid, in hydrophosphorous acid or in phosphorous acid.
[00098] Dans un mode de réalisation, la concentration en K n04 ou KG03 est comprise entre lOmM et 1M. In one embodiment, the concentration of K n0 4 or KG0 3 is between 10mM and 1M.
[00099] Dans un mode de réalisation, elle est comprise entre 0,1M et 0,5 .  In one embodiment, it is between 0.1M and 0.5.
[000100] Dans un mode de réalisation, elle est de l'ordre de 0,2M. In one embodiment, it is of the order of 0.2M.
[000101] Dans un mode de réalisation, la concentration en acide est comprise entre 0,1M et 10M. [000101] In one embodiment, the acid concentration is between 0.1M and 10M.
[000102] Dans un mode de réalisation, elle est comprise entre 0,5M et 5M.  In one embodiment, it is between 0.5M and 5M.
[000103] Dans un mode de réalisation, eile est de l'ordre de 3,5M. [000103] In one embodiment, it is of the order of 3.5M.
[000104] Dans un mode de réalisation, la durée du traitement pour un oxydant fort est comprise entre 1 minute et 3 heures. In one embodiment, the duration of the treatment for a strong oxidant is between 1 minute and 3 hours.
[000105] Dans un mode de réalisation, elle est comprise entre 5 minutes et 1 heure.  In one embodiment, it is between 5 minutes and 1 hour.
[000106] Dans un mode de réalisation, elle est comprise entre 6 minutes et 30 minutes. In one embodiment, it is between 6 minutes and 30 minutes.
[000107] Dans un mode de réalisation, eile est de l'ordre de 15 minutes.  [000107] In one embodiment, it is of the order of 15 minutes.
[000108] Dans un mode de réalisation, traitement oxydant chimique est un traitement électrochimique. [000109] Selon l'invention, le contre-ion du au moins un métal de l'étape d) est choisi dans le groupe comprenant les ions tétrafluoroborate, sulfate, bromure, fluorure, iodure, nitrate, phosphate et chlorure. In one embodiment, chemical oxidizing treatment is an electrochemical treatment. According to the invention, the counter-ion of the at least one metal of step d) is chosen from the group comprising tetrafluoroborate, sulfate, bromide, fluoride, iodide, nitrate, phosphate and chloride ions.
[000110] Dans un mode de réalisation, la solution de l'étape d) contenant au moins un ion d'au moins un métal et son contre-ion est une solution basique.  In one embodiment, the solution of step d) containing at least one ion of at least one metal and its counterion is a basic solution.
[000111] Dans un mode de réalisation, la solution basique a un pH supérieur à 7.  In one embodiment, the basic solution has a pH greater than 7.
[000112] Dans un mode de réalisation, elle a un pH entre 9 et 11.  In one embodiment, it has a pH between 9 and 11.
[000113] Dans un mode de réalisation, elle a un pH de l'ordre de 10.  In one embodiment, it has a pH of about 10.
[000114] Dans un mode de réalisation, la durée du traitement de l'étape d) est comprise entre 30 secondes et 2 heures.  In one embodiment, the duration of the treatment of step d) is between 30 seconds and 2 hours.
[000115] Dans un mode de réalisation, elle est comprise entre 1 minute et 1 heure.  In one embodiment, it is between 1 minute and 1 hour.
[000116] Dans un mode de réalisation, elle est de l'ordre de 15 minutes.  In one embodiment, it is of the order of 15 minutes.
[000117] Selon l'invention, la solution réductrice du traitement réducteur à l'étape f) est basique. According to the invention, the reducing solution of the reducing treatment in step f) is basic.
[000118] Dans un mode de réalisation, la solution réductrice comprend un agent réducteur choisi dans le groupe comprenant les solutions de borohydrure de sodium, de diméthyfamineborane ou d'hydrazine.  In one embodiment, the reducing solution comprises a reducing agent chosen from the group comprising solutions of sodium borohydride, dimethyfamineborane or hydrazine.
[000119] Dans un mode de réalisation l'agent réducteur est une solution de borohydrure de sodium.  In one embodiment, the reducing agent is a solution of sodium borohydride.
[000120] Dans un mode de réalisation, Sa solution de borohydrure de sodium a un pH neutre ou basique.  [000120] In one embodiment, its sodium borohydride solution has a neutral or basic pH.
[000121] Dans un mode de réalisation, ia solution de diméthylamineborane a un pH basique.  [000121] In one embodiment, the dimethylamineborane solution has a basic pH.
[000122] Dans un mode de réalisation, ie pH est basique, l'hydroxyde de sodium en solution est utilisé comme solvant.  In one embodiment, the pH is basic, the sodium hydroxide solution is used as a solvent.
[000123] Dans un mode de réalisation, Sa concentration en hydroxyde de sodium est comprise entre 10'4 et 5M. In one embodiment, its concentration of sodium hydroxide is between 10 -4 and 5M.
[000124] Dans un mode de réalisation, elle est comprise entre 0,05M et 1M.  In one embodiment, it is between 0.05M and 1M.
[000125J Dans un mode de réalisation, elle est de l'ordre de 0, 1M. In one embodiment, it is of the order of 0.1M.
[000126] Dans un mode de réalisation, la concentration en agent réducteur dans la solution réductrice de l'étape f) est comprise entre 10"4M et 5M. In one embodiment, the concentration of reducing agent in the reducing solution of step f) is between 10 -4 M and 5M.
[000127] Dans un mode de réalisation, elle est comprise entre 0,01M et 1M.  In one embodiment, it is between 0.01M and 1M.
[000128] Dans un mode de réalisation, elle est de l'ordre de 0,3M.  In one embodiment, it is of the order of 0.3M.
[000129] Dans un mode de réalisation, l'étape de réduction est réalisée à une température comprise entre 10°C et 90°C. [000130] Dans un mode de réalisation, elle est réalisée à une température comprise entre 30°C et 70°C. In one embodiment, the reduction step is carried out at a temperature of between 10 ° C. and 90 ° C. In one embodiment, it is carried out at a temperature between 30 ° C and 70 ° C.
[000131] Dans un mode de réalisation, elle est réalisée à une température de l'ordre de 50°C.  In one embodiment, it is carried out at a temperature of the order of 50 ° C.
[000132] Dans un mode de réalisation, la durée de l'étape de réduction est comprise entre 30 secondes et 1 heure.  In one embodiment, the duration of the reduction step is between 30 seconds and 1 hour.
[000133] Dans un mode de réalisation, elle est comprise entre 1 minute et 30 minutes.  In one embodiment, it is between 1 minute and 30 minutes.
[000134] Dans un mode de réalisation, elle est comprise entre 2 minutes et 20 minutes.  In one embodiment, it is between 2 minutes and 20 minutes.
[000135] Dans un mode de réalisation, la solution de l'étape f) comprend des ions du métal, un agent complexant les ions du métal, un agent réducteur et un régulateur de pH . In one embodiment, the solution of step f) comprises metal ions, a metal ion complexing agent, a reducing agent and a pH regulator.
[000136] Dans un mode de réalisation, ladite solution de l'étape f) est une solution aqueuse.  In one embodiment, said solution of step f) is an aqueous solution.
[000137] Dans un mode de réalisation, la solution de l'étape f) est une solution de bain électroless contenant un cation métallique choisi parmi : Ag+, Ag2+, Ag3+, Au+, Au3+, Co2+, Cu+, Cu2+, Fe2+, Ni2+, Pd+ et Pt+. In one embodiment, the solution of step f) is an electroless bath solution containing a metal cation chosen from: Ag + , Ag 2+ , Ag 3+ , Au + , Au 3+ , Co 2 + , Cu + , Cu 2+ , Fe 2+ , Ni 2+ , Pd + and Pt + .
[000138] Dans un mode de réalisation, la solution de l'étape f) est une solution de bain électroless contenant un cation métallique choisi parmi : Co2+, Cu+, Cu2+, Ni2+, et Pt+. In one embodiment, the solution of step f) is an electroless bath solution containing a metal cation chosen from: Co 2+ , Cu + , Cu 2+ , Ni 2+ , and Pt + .
[000139] Dans un mode de réalisation, fa solution de l'étape g) contenant des ions d'au moins un méta! est une solution aqueuse. In one embodiment, the solution of step g) containing ions of at least one meta! is an aqueous solution.
[000140] Dans un mode de réalisation, ladite solution de l'étape g) est une solution de bain électroless contenant un cation métallique choisi parmi : Ag+, Ag +, Ag3+, Au+, Au3+, Co2+, Cu+, Cu2+, Fe +, Ni2+, Pd+ et Pt+. [000140] In one embodiment, said solution of step g) is an electroless bath solution containing a metal cation chosen from: Ag + , Ag + , Ag 3+ , Au + , Au 3+ , Co 2+ , Cu + , Cu 2+ , Fe + , Ni 2+ , Pd + and Pt + .
[000141] Dans un mode de réalisation, la solution de l'étape g) est une solution de bain électroless contenant un cation métallique choisi parmi : Co2+, Cu+, Cu2+, Ni2+, et Pt+. In one embodiment, the solution of step g) is an electroless bath solution containing a metal cation chosen from: Co 2+ , Cu + , Cu 2+ , Ni 2+ , and Pt + .
[000142] Dans un mode de réalisation, la solution de l'étape g) est une solution de bain électroless contenant un cation métallique choisi parmi : Cu + et Niz+. In one embodiment, the solution of step g) is an electroless bath solution containing a metal cation selected from: Cu + and Ni z + .
[000143] Dans un mode de réalisation, la durée de l'étape g) est comprise entre 1 minute et 1 heure. [000144] Selon l'invention, préalablement et entre chaque étape du procédé la surface du substrat et/ou le substrat est/sont soumis/e à un ou plusieurs rinçages avec au moins une solution de rinçage. In one embodiment, the duration of step g) is between 1 minute and 1 hour. According to the invention, before and between each step of the method, the surface of the substrate and / or the substrate is / are subjected to one or more rinses with at least one rinsing solution.
[000145] Dans un mode de réalisation, les solutions de rinçage sont identiques ou différentes.  In one embodiment, the rinsing solutions are identical or different.
[000146] Dans un mode de réalisation, la solution de rinçage est choisie dans le groupe comprenant l'eau, l'eau distillée, l'eau désionisée ou une solution aqueuse contenant un détergent.  In one embodiment, the rinsing solution is selected from the group consisting of water, distilled water, deionized water or an aqueous solution containing a detergent.
[000147] Dans un mode de réalisation, le détergent contenu dans une solution aqueuse est choisi dans le groupe comprenant le TDF4 et la soude.  In one embodiment, the detergent contained in an aqueous solution is selected from the group comprising TDF4 and sodium hydroxide.
[000148] Dans un mode de réalisation, la concentration en soude est comprise entre 0,01 et 1M.  In one embodiment, the concentration of sodium hydroxide is between 0.01 and 1M.
[000149] Dans un mode de réalisation, la solution de rinçage est agitée lors de la mise en contact avec la surface du substrat et/ou le substrat.  In one embodiment, the rinsing solution is agitated upon contact with the surface of the substrate and / or the substrate.
[000150] Dans un mode de réalisation, l'agitation est réalisée à l'aide d'un agitateur, une pompe de recirculation, un bullage d'air ou d'un gaz, un bain à ultrasons ou un homogénéisateur.  [000150] In one embodiment, the stirring is carried out using an agitator, a recirculation pump, a bubbling air or a gas, an ultrasonic bath or a homogenizer.
[000151] Dans un mode de réalisation, la durée de chaque étape de rinçage est comprise entre 1 seconde à 30 minutes,  In one embodiment, the duration of each rinsing step is between 1 second to 30 minutes,
[000152] Dans un mode de réalisation, elle est comprise entre 5 secondes à 20 minutes.  In one embodiment, it is between 5 seconds to 20 minutes.
[000153] La mise en contact de la surface du substrat et/ou le substrat avec les solutions des différentes étapes peut se faire par immersion dans un bain ou par pulvérisation et/ou douchage.  [000153] The contacting of the surface of the substrate and / or the substrate with the solutions of the various steps can be done by immersion in a bath or by spraying and / or showering.
[000154] Lorsque cette mise en contact se fait par immersion dans un bain, l'homogénéisation dudit bain est réalisée à l'aide d'un agitateur, une pompe de recirculation, un bullage d'air ou d'un gaz, un bain à ultrasons ou un homogénéisateur.  When this contacting is by immersion in a bath, the homogenization of said bath is carried out using an agitator, a recirculation pump, a bubbling air or a gas, a bath ultrasound or a homogenizer.
[000155] L'invention concerne également le substrat obtenu selon le procédé de l'invention pour lequel la surface dudit substrat en matériau non métallique est revêtue par une couche métallique. The invention also relates to the substrate obtained according to the process of the invention for which the surface of said substrate of non-metallic material is coated with a metal layer.
[000156] L'invention concerne un substrat en matériau non métallique dont au moins une surface est revêtue par une couche métallique d'activation constituée par des atomes d'un métal liés par interaction métal-ligand directement au matériau constitutif du substrat par des groupements carboxylique (-COOH), hydroxyle (-OH), aicoxyle (-OR), carbonyle (-00), percarbonique (-CO-0-OH), nitro (N=0) ou amide (-CONH), ladite couche d'activation étant recouverte d'une couche d'un métal identique ou différent déposé par dépôt auto-catalytique. The invention relates to a substrate of non-metallic material, at least one surface of which is coated with a metal activation layer consisting of metal atoms bound by metal-ligand interaction directly to the constituent material of the substrate by groups. carboxylic acid (-COOH), hydroxyl (-OH), alkoxyl (-OR), carbonyl (-00), percarboxylic acid (-CO-O-OH), nitro (N = 0) or amide (-CONH), said activation layer being coated with a layer of the same or different metal deposited by self-catalytic deposition.
[000157] Dans un mode de réalisation l'invention concerne un substrat constitué d'ABS, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-iigand à l'ABS constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocataiytique.  In one embodiment, the invention relates to a substrate made of ABS, the surface of which is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the constituent ABS of FIG. substrate, said activation layer being covered with a layer of copper deposited by autocataiytique deposition.
[000158] Dans un mode de réalisation l'invention concerne un substrat constitué d'ABS, dont la surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont liés interaction métaS-iigand à l'ABS constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocataiytique.  In one embodiment, the invention relates to a substrate made of ABS, the surface of which is coated with an activation layer made of nickel, the atoms of which are bonded to the constituent ABS of the substrate. said activation layer being coated with a copper layer deposited by autocatalytic deposition.
[000159] Dans un mode de réalisation l'invention concerne un substrat constitué d'ABS/PC, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés interaction métai-ligand à l'ABS/PC constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocataiytique  In one embodiment, the invention relates to a substrate made of ABS / PC, the surface of which is coated with an activation layer consisting of copper, the atoms of which are bonded to a meta-ligand interaction with ABS. PC constituting the substrate, said activation layer being covered with a layer of copper deposited by autocataiytic deposition
[000160] Dans un mode de réalisation l'invention concerne un substrat constitué d'ABS/PC, dont ia surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont liés par interaction métai-ligand à ΑΒΞ/PC constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocataiytique  [000160] In one embodiment, the invention relates to a substrate made of ABS / PC, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are linked by meta-ligand interaction at ΑΒΞ / PC. constituent of the substrate, said activation layer being covered with a layer of copper deposited by autocataiytic deposition
[000161] Dans un mode de réalisation l'invention concerne un substrat constitué de PA, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métai-ligand au PA constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocataiytique  In one embodiment, the invention relates to a substrate consisting of PA, the surface of which is coated with an activation layer consisting of copper, the atoms of which are bonded by meta-ligand interaction to the constituent PA of the substrate, activation layer being covered with a layer of copper deposited by autocatalytic deposit
[000162] Dans un mode de réalisation l'invention concerne un substrat constitué de PA, dont la surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont liés interaction métal-iigand au PA constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocataiytique  In one embodiment, the invention relates to a substrate consisting of PA, the surface of which is coated with an activation layer made of nickel, the atoms of which are bonded to the substrate PA; of activation being covered with a layer of copper deposited by autocatalytic deposit
[000163] Dans un mode de réalisation l'invention concerne un substrat constitué de PC, dont ia surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-Sigand au PC constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocataiytique [000164] Dans un mode de réalisation l'invention concerne un substrat constitué de PC, dont la surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont liés par interaction métal-ligand au PC constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocatalytique [000163] In one embodiment, the invention relates to a substrate consisting of PC, the surface of which is coated with an activation layer consisting of copper whose atoms are bonded by metal-Sigand interaction to the PC constituting the substrate, said activation layer being covered with a layer of copper deposited by autocatalytic deposit In one embodiment, the invention relates to a substrate made of PC, the surface of which is coated with an activation layer made of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PC of the substrate, said activation layer being covered with a layer of copper deposited by autocatalytic deposition
[000165] Dans un mode de réalisation l'invention concerne un substrat constitué de MABS, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-ligand au MABS constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate consisting of MABS, the surface of which is coated with an activation layer consisting of copper whose atoms are bonded by metal-ligand interaction to the MABS constitutive of the substrate, said activation layer being covered with a layer of copper deposited by autocatalytic deposition
[000166] Dans un mode de réalisation l'invention concerne un substrat constitué de MABS, dont la surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont liés par interaction métal-ligand au MABS constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate consisting of MABS, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the MABS constituting the substrate, said activation layer being covered with a layer of copper deposited by autocatalytic deposition
[000167] Dans un mode de réalisation l'invention concerne un substrat constitué de PP, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-ligand au PP constitutif du substrat,iadite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate made of PP, the surface of which is coated with an activation layer consisting of copper whose atoms are bonded by metal-ligand interaction to the constituent PP of the substrate, iadite activation layer being covered with a layer of copper deposited by autocatalytic deposition
[000168] Dans un mode de réalisation l'invention concerne un substrat constitué de PP, dont la surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont liés par interaction métal-ligand au PP constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre ou déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate consisting of PP, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PP of the substrate, activation layer being coated with a copper layer or deposited by autocatalytic deposition
[000169] Dans un mode de réalisation l'invention concerne un substrat constitué de PPS, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-ligand au PPS constitutif du substrat,ladite couche d'activation étant recouverte d'une couche de cuivre ou déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate consisting of PPS, the surface of which is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the constituent PPS of the substrate. activation layer being coated with a copper layer or deposited by autocatalytic deposition
[000170] Dans un mode de réalisation l'invention concerne un substrat constitué de PPS, dont la surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont liés par interaction métal-ligand au PPS constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate consisting of PPS, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PPS of the substrate, activation layer being covered with a layer of copper deposited by autocatalytic deposition
[000171] Dans un mode de réalisation l'invention concerne un substrat constitué d'ABS, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-ligand à l'ABS constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocatalytique. In one embodiment, the invention relates to a substrate made of ABS, the surface of which is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the ABS constituting the substrate, said activation layer being coated with a nickel layer deposited by autocatalytic deposition.
[000172] Dans un mode de réalisation l'invention concerne un substrat constitué d'ABS, dont la surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont liés par interaction métal-ligand à l'ABS constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocatalytique.  In one embodiment, the invention relates to a substrate made of ABS, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent ABS of the invention. substrate, said activation layer being coated with a nickel layer deposited by autocatalytic deposition.
[000173] Dans un mode de réalisation l'invention concerne un substrat constitué d'ABS/PC, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-ligand à l'ABS/PC constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate made of ABS / PC, the surface of which is coated with an activation layer consisting of copper whose atoms are linked by metal-ligand interaction with ABS. / PC constituting the substrate, said activation layer being coated with a layer of nickel deposited by autocatalytic deposition
[000174] Dans un mode de réalisation l'invention concerne un substrat constitué d'ABS/PC, dont la surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont liés par interaction métal-ligand à l'ABS/PC constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate made of ABS / PC, the surface of which is coated with an activation layer made of nickel, the atoms of which are bound by metal-ligand interaction with ABS. / PC constituting the substrate, said activation layer being coated with a layer of nickel deposited by autocatalytic deposition
[000175] Dans un mode de réalisation l'invention concerne un substrat constitué de PA, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-ligand au PA constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate consisting of PA, the surface of which is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the constituent PA of the substrate. activation layer being coated with a nickel layer deposited by autocatalytic deposition
[000176] Dans un mode de réalisation l'invention concerne un substrat constitué de PA, dont la surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont liés par interaction métal-ligand au PA constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate consisting of PA, the surface of which is coated with an activation layer made of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PA of the substrate. activation layer being coated with a nickel layer deposited by autocatalytic deposition
[000177] Dans un mode de réalisation l'invention concerne un substrat constitué de PC, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-ligand au PC constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate made up of PC whose surface is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the constituent PC of the substrate. activation layer being coated with a nickel layer deposited by autocatalytic deposition
[000178] Dans un mode de réalisation l'invention concerne un substrat constitué de PC, dont la surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont liés par interaction métal-ligand au PC constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocatalytique [000179] Dans un mode de réalisation l'invention concerne un substrat constitué de MABS, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-ligand au MABS constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocatalytique In one embodiment, the invention relates to a substrate made up of PC whose surface is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PC of the substrate, said activation layer being coated with a nickel layer deposited by autocatalytic deposition In one embodiment, the invention relates to a substrate consisting of MABS, the surface of which is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the MABS constitutive of the substrate. activation layer being coated with a nickel layer deposited by autocatalytic deposition
[000180] Dans un mode de réalisation l'invention concerne un substrat constitué de MABS, dont la surface est revêtue d'une couche d'activation constituée de nickel dont fes atomes sont liés par interaction métai-ûgand au MABS constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocataiytique  [000180] In one embodiment, the invention relates to a substrate consisting of MABS, the surface of which is coated with an activation layer consisting of nickel, whose atoms are bonded by meta-γgand interaction to the MABS constitutive of the substrate. activation layer being coated with a nickel layer deposited by autocatalytic deposit
[000181] Dans un mode de réalisation i'invention concerne un substrat constitué de PP, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-ligand au PP constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocataiytique  In one embodiment, the invention relates to a substrate consisting of PP, the surface of which is coated with an activation layer consisting of copper, the atoms of which are bonded by metal-ligand interaction to the constituent PP of the substrate. activation layer being coated with a nickel layer deposited by autocatalytic deposit
[000182] Dans un mode de réalisation l'invention concerne un substrat constitué de PP, dont la surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont fiés par interaction métal-iigand au PP constitutif du substrat, fadite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate made of PP, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PP of the substrate, fadite activation layer being coated with a nickel layer deposited by autocatalytic deposition
[000183] Dans un mode de réalisation l'invention concerne un substrat constitué de PPS, dont ia surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-ligand au PPS constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocatalytique  [000183] In one embodiment, the invention relates to a substrate consisting of PPS, the surface of which is coated with an activation layer consisting of copper whose atoms are linked by metal-ligand interaction to the constituent PPS of the substrate, said activation layer being coated with a nickel layer deposited by autocatalytic deposition
[000184] Dans un mode de réalisation l'invention concerne un substrat constitué de PPS, dont la surface est revêtue d'une couche d'activation constituée de nickel dont les atomes sont liés par interaction métal-ligand au PPS constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de nickel déposée par dépôt autocatalytique  In one embodiment, the invention relates to a substrate consisting of PPS, the surface of which is coated with an activation layer consisting of nickel, the atoms of which are bonded by metal-ligand interaction to the constituent PPS of the substrate, activation layer being coated with a nickel layer deposited by autocatalytic deposition
[000185] [000185]
[000186] L'invention concerne également un procédé selon l'invention comprenant en outre une étape de métallisation. [000186] The invention also relates to a method according to the invention further comprising a metallization step.
[000187] Dans un mode de réalisation, le traitement de métallisation est un traitement par galvanoplastie. [000188] L'invention et ses modes de mises en oeuvre sont illustrés dans les exemples suivants. [000187] In one embodiment, the metallization treatment is an electroplating treatment. The invention and its modes of implementation are illustrated in the following examples.
Exemple 1 Example 1
I. Revêtement par une couche de cuivre de plaques d'acrylonitrile butadiène styrène (ABS) et d'acrylonitrile butadiène styrène/polycarbonate (ABS/PC).  I. Coating with a copper layer of acrylonitrile butadiene styrene (ABS) and acrylonitrile butadiene styrene / polycarbonate (ABS / PC) plates.
[000189] Ce procédé de revêtement par une couche de cuivre d'un substrat en matériau non métallique s'effectue en 4 étapes (Traitement oxydant chimique à l'acide nitrique/ chélation et/ou complexation/ Réduction/ bain Electro!ess). This method of coating with a copper layer of a substrate of non-metallic material is carried out in 4 steps (chemical oxidizing treatment with nitric acid / chelation and / or complexation / reduction / electro-bath).
1.1. Traitement oxydant chimique à l'acide nitrique 1.1. Chemical oxidizing treatment with nitric acid
[000190] De l'acide nitrique pur est porté à 50°C. Dans cette solution, ont été immergées pendant 8 minutes les plaques d'acrylonitrile butadiène styrène (ABS) et d'acrylonitrile butadiène styrène/polycarbonate (ABS/PC). Les plaques sont ensuite rincées par deux fois dans un bain d'eau (1 litre).  [000190] Pure nitric acid is brought to 50 ° C. In this solution, the acrylonitrile butadiene styrene (ABS) and acrylonitrile butadiene styrene / polycarbonate (ABS / PC) plates were immersed for 8 minutes. The plates are then rinsed twice in a water bath (1 liter).
1.2. chélation et/ou complexation des ions cuivre 1.2. chelation and / or complexation of copper ions
[000191] Du sulfate de cuivre (23,7g) est solubilisé dans une solution d'eau (1000 mi) et d'ammoniaque (30 ml). Dans ce bain sont immergées les pièces qui ont subit le traitement oxydant chimique de l'étape 1.1 pendant 15 minutes. Les pièces d'ABS sont ensuite rincées dans une solution de soude 0.2 M.  [000191] Copper sulfate (23.7 g) is solubilized in a solution of water (1000 ml) and ammonia (30 ml). In this bath are immersed parts that have undergone the chemical oxidizing treatment of step 1.1 for 15 minutes. The ABS parts are then rinsed in 0.2 M sodium hydroxide solution.
1.3 Traitement réducteur des ions cuivre 1.3 Reducing treatment of copper ions
[000192] Du borohydrure de sodium NaBH4 (0,316 g, 0,8 X 10-2 mol) est dissout dans 25 mL d'une solution de soude (NaOH) 0,1 M. Cette solution est chauffée à 80°C à l'aide d'un bain-marie et Ses échantillons y sont immergés. Après 12 minutes, les échantillons ont été rincés à l'eau MilliQ avant d'être séchés. NaBH 4 sodium borohydride (0.316 g, 0.8 × 10 -2 mol) is dissolved in 25 ml of a 0.1 M sodium hydroxide solution (NaOH). This solution is heated to 80.degree. using a water bath and His samples are immersed in it. After 12 minutes, the samples were rinsed with MilliQ water before being dried.
1.4. Bain Electroless de cuivre (Bain Mac-Dermid M Copper®} 1.4. Copper Electroless Bath (Mac-Dermid M Copper® Bath)
[000193] Une solution est préparée contenant 100 ml de la solution M Copper® 85 B. Ensuite, 40 ml de la solution M Copper® 85 A, puis 30 ml de la solution M Copper® 85 D, puis 2 ml de la solution M Copper® 85 G et enfin 5 ml de formaldéhyde 37% sont ajoutés. Le niveau de la solution est complété pour atteindre 1 litre de solution. Le bain est porté à 60°C sous agitation mécanique. Les plaques d'ABS sont alors introduites. [000194] Les pièces seront recouvertes du film métallique de cuivre chimique après 3 minutes d'immersion. A solution is prepared containing 100 ml of the solution M Copper® 85 B. Then, 40 ml of the solution M Copper® 85 A, then 30 ml of the solution M Copper® 85 D, then 2 ml of the solution M Copper® 85 G and finally 5 ml of formaldehyde 37% are added. The level of the solution is completed to reach 1 liter of solution. The bath is heated to 60 ° C. with mechanical stirring. The ABS plates are then introduced. [000194] The parts will be covered with the chemical copper metal film after 3 minutes of immersion.
[000195] La couche de cuivre est visible à l'œil nu.  [000195] The copper layer is visible to the naked eye.
I.5. Bain Electroiess de cuivre I.5. Copper Electroiess Bath
[000196] Dans un mode de réalisation alternatif, le bain Electroiess est une solution préparée contenant : 40 ml de la solution PegCopper 100, 100 ml de la solution PegCopper 200, 30 ml de PegCopper 400 et 2 mi de PegCopper 500 (produits commercialisés par la société PEGASTECH). Sont ensuite ajoutés 3,5 mL de PegCopper 600. Le niveau est complété pour atteindre 1 litre avec de l'eau et le mélange est porté à 50°C sous buliage. Les pièces à traiter sont alors introduites.  [000196] In an alternative embodiment, the Electroiess bath is a prepared solution containing: 40 ml of the PegCopper 100 solution, 100 ml of the PegCopper 200 solution, 30 ml of PegCopper 400 and 2 ml of PegCopper 500 (products sold by the PEGASTECH company). 3.5 ml of PegCopper 600 are then added. The level is completed to reach 1 liter with water and the mixture is brought to 50 ° C. under bulking. The parts to be treated are then introduced.
[000197] Les pièces seront recouvertes du film métallique de cuivre chimique après 3 minutes d'immersion.  The parts will be covered with the chemical copper metal film after 3 minutes of immersion.
[000198] La couche de cuivre est visible à l'œil nu. Exemple 2  [000198] The copper layer is visible to the naked eye. Example 2
II. Revêtement par une couche de cuivre d'un substrat en polyamide.  II. Coating with a copper layer of a polyamide substrate.
[000199] Le procédé de revêtement est mis en œuvre avec un substrat constitué de polyamide Minlon®.  [000199] The coating process is carried out with a substrate consisting of Minlon® polyamide.
11.1. Traitement oxydant chimique à l'acide chlorhydrique et l'isopropanol 11.1. Chemical oxidizing treatment with hydrochloric acid and isopropanol
[000200] Dans une solution aqueuse contenant de l'eau 130 mL, de l'acide chlorhydrique (37M), 28 mL et de l'isopropanol 55 mL, a été immergé le substrat en polyamide à 28°C pendant 17 minutes. Le substrat est ensuite rincé à l'eau.  In an aqueous solution containing water 130 mL, hydrochloric acid (37M), 28 mL and isopropanol 55 mL, was immersed polyamide substrate at 28 ° C for 17 minutes. The substrate is then rinsed with water.
11.2. Chélation et/ou complexation des ions cuivre 11.2. Chelation and / or complexation of copper ions
[000201] Selon un procédé similaire à celui décrit à l'exemple 1, étape 1.2 des ions cuivre sont chélatés à la surface du substrat.  [000201] According to a process similar to that described in Example 1, step 1.2, copper ions are chelated on the surface of the substrate.
11.3 Traitement réducteur des ions cuivre 11.3 Reducing treatment of copper ions
[000202] Selon le mode opératoire décrit en 1.3 les ions cuivre chélatés sont réduits à la surface du substrat  [000202] According to the procedure described in 1.3, the chelated copper ions are reduced on the surface of the substrate
11.4 Bain Electroiess de cuivre 11.4 Copper Electroiess Bath
[000203] Selon un procédé similaire à celui décrit à l'exemple 1, étape 1.4. ou I.5., le substrat en polyamide est recouvert d'un film métallique de cuivre chimique. [000204] La couche de cuivre est visible à l'oeil nu. [000203] According to a method similar to that described in Example 1, step 1.4. or I.5., the polyamide substrate is covered with a chemical copper metal film. [000204] The copper layer is visible to the naked eye.
Exemple 3 Example 3
III. Revêtement par une couche de cuivre d'un substrat en polycarbonate.  III. Coating with a copper layer of a polycarbonate substrate.
[000205] Le procédé de revêtement est mis en œuvre avec un substrat en polycarbonate Lexan®.  [000205] The coating process is implemented with a Lexan® polycarbonate substrate.
III.1. Traitement oxydant chimique aux acides forts III.1. Chemical oxidizing treatment with strong acids
[000206] Le substrat en polycarbonate est immergé dans une solution contenant un mélange d'acides forts (acide nitrique 34% et suifurique 66%) à 25°c pendant 5 minutes, puis dans un bain d'acide suifurique concentré à 25°C pendant 3 minutes. L'ensemble est neutralisé dans une solution de potasse 5N à 65°C pendant 5 minutes. Le substrat en polycarbonate est ensuite rincé à l'eau.  The polycarbonate substrate is immersed in a solution containing a mixture of strong acids (34% nitric acid and 66% tallow) at 25 ° C. for 5 minutes and then in a concentrated suifuric acid bath at 25 ° C. for 3 minutes. The whole is neutralized in a 5N potassium hydroxide solution at 65 ° C. for 5 minutes. The polycarbonate substrate is then rinsed with water.
III.2. Chélation et/ou complexation des ions cuivre III.2. Chelation and / or complexation of copper ions
[000207] Selon un procédé similaire à celui décrit à l'exemple 1, étape 1.2 des ions cuivre sont chélatés à la surface du substrat.  [000207] According to a process similar to that described in Example 1, step 1.2, copper ions are chelated on the surface of the substrate.
111.3 Traitement réducteur des ions cuivre 111.3 Reducing treatment of copper ions
[000208] Selon le mode opératoire décrit en 1.3 les ions cuivre sont chélatés réduits à la surface du substrat  [000208] According to the procedure described in 1.3, the copper ions are chelated reduced to the surface of the substrate
111.4 Bain Electroless de cuivre 111.4 Copper Electroless Bath
[000209] Selon un procédé similaire à celui décrit à l'exemple 1, étape 1.4. ou I.5., le substrat en polycarbonate est recouvert d'un film métallique de cuivre chimique.  [000209] According to a method similar to that described in Example 1, step 1.4. or I.5., the polycarbonate substrate is covered with a chemical copper metal film.
[000210] La couche de cuivre est visible à l'œil nu. [000210] The copper layer is visible to the naked eye.
Exempte 4 Exempt 4
[000211] Des tests d'adhérence selon la norme NF ÏSO 2409/ NF T30-038 et des tests de corrosion selon la norme DIN ISO 9227 ont été effectués sur les substrats obtenus aux exemples 1 à 3, et les performances sont conformes aux exigences de ces tests et comparables aux performanes obtenues avec des substrats obtenus selon les procédés de l'art antérieur.  [000211] Adhesion tests according to the NF ISO 2409 / NF T30-038 standard and corrosion tests according to DIN ISO 9227 were carried out on the substrates obtained in Examples 1 to 3, and the performances are in accordance with the requirements of these tests and comparable to the performanes obtained with substrates obtained according to the methods of the prior art.

Claims

Revendications claims
1. Procédé de revêtement d'u ne surface d'un substrat en matériau non métallique par une couche métallique caractérisé en ce qu'il consiste en les étapes suivantes : 1. A method of coating a surface of a substrate of non-metallic material with a metal layer, characterized in that it consists of the following steps:
a . on dispose d'un substrat en matériau non métallique,  at . there is a substrate of non-metallic material,
b. on sou met au moins une partie d'au moins une surface dudit substrat à un traitement physique ou chimique d'augmentation de la su rface spécifique,  b. at least a portion of at least one surface of said substrate is subjected to a physical or chemical treatment for increasing the specific surface,
c. on soumet Sa su rface dudit substrat traitée à l'étape b), à un traitement oxydant,  vs. subjecting said substrate treated in step b) to an oxidizing treatment,
d . on met en contact la surface dud it substrat traitée à l'étape c), avec u ne solution contenant au moins u n ion d'au moins un métal et son contre- ion, ledit métal étant choisi dans le groupe constitué par les métaux des groupes IB et VIII de la classification périodique des éléments, e. on obtient un substrat comprenant des ions d'au moins un métal fixés chimiquement au matériau non métallique constituant le substrat sur au moins u ne partie d'au moins une de ses surfaces,  d. the surface of the substrate treated in step c) is brought into contact with a solution containing at least one ion of at least one metal and its counterion, said metal being chosen from the group consisting of the metals of Groups IB and VIII of the Periodic Table of Elements, e. a substrate is obtained comprising ions of at least one metal chemically bonded to the nonmetallic material constituting the substrate on at least part of at least one of its surfaces,
f. on soumet lesdits ions d'au moins un métal fixés chimiquement au matériau non métallique constituant le substrat sur une surface dud it substrat, à un traitement réducteur et on obtient un substrat comprenant des atomes d'au moins un métal fixés chimiquement au matériau non métallique constituant le substrat sur au moi ns u ne partie d'au moins une de ses su rfaces,  f. said ions of at least one metal chemically bonded to the non-metallic material constituting the substrate on a surface of said substrate are subjected to a reducing treatment and a substrate is obtained comprising atoms of at least one metal chemically fixed to the non-metallic material constituting the substrate on the e ns u not part of at least one of its su rfaces,
g . on met en contact la surface comprenant des particules d'au moins un métal obtenue à l'étape f) avec une solution contenant des ions d'au moins un métal.  boy Wut . the surface comprising particles of at least one metal obtained in step f) is brought into contact with a solution containing ions of at least one metal.
h . on obtient sur la su rface traitée dudit substrat un revêtement par une couche d'au moins un métal,  h. the treated surface of said substrate is coated with a layer of at least one metal,
lesdites étapes étant éventuellement suivies ou précédées de une ou plusieurs étapes de rinçage.  said steps possibly being followed or preceded by one or more rinsing steps.
2. Procédé selon la revendication 1, caractérisé en ce que les étapes b) et c) sont effectuées en une seule étape b') et le traitement est un traitement oxydant. 2. Method according to claim 1, characterized in that steps b) and c) are carried out in a single step b ') and the treatment is an oxidizing treatment.
3. Procédé selon la revendication 1, caractérisé en ce que le métal de l'étape f) et le métal des tons de l'étape g) sont identiques. 3. Method according to claim 1, characterized in that the metal of step f) and the tonal metal of step g) are identical.
4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les étapes f) et g) sont effectuées en une seule étape f). 4. Method according to any one of the preceding claims, characterized in that steps f) and g) are performed in a single step f).
5. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'étape b) est mise en œuvre par traitement physique. 5. Method according to one of the preceding claims, characterized in that step b) is implemented by physical treatment.
6. Procédé selon la revendication 5, caractérisé en ce que le traitement physique est choisi dans le groupe des traitements par impacts. 6. Process according to claim 5, characterized in that the physical treatment is chosen from the group of impact treatments.
7. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que les étapes b) ou b') ou c) sont mises en œuvre par traitement oxydant. 7. Method according to one of claims 1 to 4, characterized in that steps b) or b ') or c) are implemented by oxidative treatment.
8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que le traitement oxydant est choisi dans le groupe des traitements oxydants chimiques. 8. Method according to one of claims 1 to 7, characterized in that the oxidizing treatment is chosen from the group of chemical oxidizing treatments.
9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le métal de l'ion métallique utilisé à l'étape d) est choisi parmi les ions cuivre, argent, nickel, platine, palladium ou cobalt. 9. Process according to any one of the preceding claims, characterized in that the metal of the metal ion used in step d) is selected from copper, silver, nickel, platinum, palladium or cobalt ions.
10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le métal de l'ion métallique utilisé à l'étape d) est choisi dans le groupe constitué par le cuivre et le nickel. 10. Method according to any one of the preceding claims, characterized in that the metal of the metal ion used in step d) is selected from the group consisting of copper and nickel.
11. Procédé l'une quelconque des revendications précédentes, caractérisé en ce que le traitement oxydant chimique est choisi dans le groupe constitué par le réactif de Fenton, la potasse alcoolique, un acide fort, la soude, un oxydant fort, l'ozone, seuls ou en combinaisons. 11. Process according to any one of the preceding claims, characterized in that the chemical oxidizing treatment is chosen from the group consisting of Fenton's reagent, alcoholic potassium hydroxide, a strong acid, sodium hydroxide, a strong oxidizing agent and ozone, alone or in combinations.
12. Procédé selon la revendication 11, caractérisé en ce que l'acide fort est choisi dans ie groupe constitué par l'acide chiorhydrique, l'acide sulfurique, l'acide nitrique, l'acide perchlorique, l'acide phosphoreux, l'acide phosphorique, l'acide hypophosphoreux, l'acide oxalique, l'acide acétique seuls ou en mélange. 12. Process according to claim 11, characterized in that the strong acid is chosen from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphorous acid, phosphoric acid, hypophosphorous acid, oxalic acid, acetic acid alone or as a mixture.
13. Procédé selon la revendication 11, caractérisée en ce que l'oxydant fort est choisi dans le groupe constitué par KMn04 et KCI03, seuls ou en mélange 13. The method of claim 11, characterized in that the strong oxidant is selected from the group consisting of KMn0 4 and KCI0 3 , alone or in mixture
14. Procédé selon la revendication 11, caractérisé en ce que le traitement oxydant chimique est un traitement électrochimique. 14. The method of claim 11, characterized in that the chemical oxidizing treatment is an electrochemical treatment.
15. Procédé selon la revendication 1, caractérisé en ce que Sa solution réductrice comprend un agent réducteur choisi dans le groupe constitué par les solutions de borohydrure de sodium, de diméthylamineborane ou d'hydrazine. 15. The method of claim 1, characterized in that its reducing solution comprises a reducing agent selected from the group consisting of sodium borohydride solutions, dimethylamineborane or hydrazine.
16. Procédé selon la revendication 1, caractérisé en ce que la solution de l'étape f) comprend des ions du métal, un agent compîexant les ions du métal, un agent réducteur et un régulateur de pH. 16. The method of claim 1, characterized in that the solution of step f) comprises ions of the metal, a metal ion compaction agent, a reducing agent and a pH regulator.
17. Procédé selon la revendication 1, caractérisé en ce que préalablement et entre chaque étape du procédé la surface du substrat et/ou le substrat est soumis à un ou plusieurs rinçages avec au moins une solution de rinçage. 17. The method of claim 1, characterized in that before and between each step of the method the surface of the substrate and / or the substrate is subjected to one or more rinses with at least one rinsing solution.
18. Procédé selon la revendication précédente, caractérisé en ce que fa solution de rinçage est agitée lors de la mise en contact avec la surface du substrat et/ou le substrat. 18. Method according to the preceding claim, characterized in that the rinsing solution is agitated during contacting with the surface of the substrate and / or the substrate.
19. Procédé selon l'une quelconque des revendications 1 à 18, caractérisé en ce qu'il comprend en outre une étape de métailisation. 19. Method according to any one of claims 1 to 18, characterized in that it further comprises a metailization step.
20. Procédé se!on la revendication 19, caractérisé en ce que l'étape de métailisation est une étape de traitement par galvanoplastie. 20. Process according to claim 19, characterized in that the meta-conversion step is an electroplating treatment step.
21. Substrat en matériau non métallique dont au moins une surface est revêtue par une couche métallique d'activation constituée par des atomes d'un métal liés par interaction métal-ligand directement au matériau constitutif du substrat par des groupements carboxyiique (-COOH), hydroxyle (-OH), alcoxyle (-OR), carbonyle (- C=0), percarbonique (-CO-0-OH), nitro (N=0) ou amide (-CONH), ladite couche d'activation étant recouverte d'une couche d'un métal identique ou différent déposé par dépôt auto-catalytique. 21. Substrate of non-metallic material, at least one surface of which is coated with a metal activation layer consisting of metal atoms bound by metal-ligand interaction directly to the constituent material of the substrate by carboxylic groups (-COOH), hydroxyl (-OH), alkoxyl (-OR), carbonyl (- C = O), percarbonic (-CO-O-OH), nitro (N = O) or amide (-CONH), said activation layer being covered a layer of the same or different metal deposited by self-catalytic deposition.
22. Substrat constitué d'ABS, dont la surface est revêtue d'une couche d'activation constituée de cuivre dont les atomes sont liés par interaction métal-ligand à l'ABS constitutif du substrat, ladite couche d'activation étant recouverte d'une couche de cuivre déposée par dépôt autocatalytique.  22. Substrate made of ABS, the surface of which is coated with an activation layer made of copper, the atoms of which are bonded by metal-ligand interaction to the ABS constituting the substrate, said activation layer being covered with a copper layer deposited by autocatalytic deposition.
EP11723649.7A 2010-04-19 2011-04-19 Process for coating a surface of a substrate made of nonmetallic material with a metal layer Active EP2561117B1 (en)

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US20110256413A1 (en) 2011-10-20
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US8962086B2 (en) 2015-02-24
PL2561117T3 (en) 2016-09-30
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