EP2561117B1 - Procede de revetement d'une surface d'un substrat en materiau non metallique par une couche metallique - Google Patents

Procede de revetement d'une surface d'un substrat en materiau non metallique par une couche metallique Download PDF

Info

Publication number
EP2561117B1
EP2561117B1 EP11723649.7A EP11723649A EP2561117B1 EP 2561117 B1 EP2561117 B1 EP 2561117B1 EP 11723649 A EP11723649 A EP 11723649A EP 2561117 B1 EP2561117 B1 EP 2561117B1
Authority
EP
European Patent Office
Prior art keywords
substrate
metal
treatment
ions
acid
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.)
Active
Application number
EP11723649.7A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2561117A1 (fr
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/fr
Application granted granted Critical
Publication of EP2561117B1 publication Critical patent/EP2561117B1/fr
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 render it capable of being treated, thanks to the strong adhesion of the coating, by conventional metallization processes such as electroplating .
  • Materials metallization processes involve 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 industry, automotive, cosmetics, household appliances, sanitary ware, connectors , microelectronics ...
  • the step of activating the surface consists in 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 the step of forming 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 conventional method of metallization of an ABS substrate is modified by replacement of the Sn / Pd colloid with an Ag / Sn colloid and after total elimination of Sn ions, the self-catalytic metal deposition step is a deposition step of nickel.
  • 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.
  • the activation step is a step of adsorption in which a colloidal preparation is used or formed by addition of stannous ions, which must then be completely removed to allow the smooth and uniform development of the metal layer during the electroless metal deposition step.
  • US Patents 4,981,715 and US 4,701,351 describe a method of 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 auto-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 the irradiation treatment which also allows the regioselective attachment of this layer of polymer capable of chelating and thus the possibility of metallizing the substrate selectively.
  • the present invention makes it possible to simplify the various steps of this method of coating non-metallic materials and to make it more environmentally friendly and less expensive, by developing a simpler coating process that does not use toxic and polluting reagents, without adding a step and an additional layer.
  • 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.
  • step d) of activation is performed by contact with a solution containing a single metal ion and its counterion.
  • steps b) and c) are performed in a single step b ') and the treatment is an oxidative 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 substrate of non-metallic material must first be prepared in order to obtain a good adhesion of the metal layer on 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 is meant a treatment to remove 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 carried out by oxidative treatment.
  • oxidizing treatment any treatment that makes it possible to prepare the surface by increasing the roughness and therefore the specific surface area for step b) and creating functions capable of chelating and / or complexing metal cations for step c) .
  • the oxidizing treatment is selected 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 oxidative treatments.
  • the substrate may be a nanoparticle, a microparticle, a cosmetic stopper, an electronic element, a door handle, an electrical appliance, spectacles, a decorative object, a bodywork element, an element of cabin, airplane wing, a flexible driver or connector.
  • Non-metallic materials are any material belonging to the family of organic materials, the family of mineral materials and the family of composite materials. Non-limiting examples include wood, paper, cardboard, ceramics, plastics, silicones, textiles and glass.
  • the organic material is selected 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 non-metallic material is a polymer selected from the group consisting of natural, artificial, synthetic, thermoplastic, thermosetting, thermostable, elastomeric, one-dimensional and three-dimensional.
  • the non-metallic material may further comprise at least one member selected from the group consisting of fillers, plasticizers and additives.
  • the fillers are mineral fillers selected from the group consisting of silica, talc, fibers or glass beads.
  • the fillers are organic fillers selected from the group consisting of cereal flour and cellulose pulp.
  • the additives are used to improve a specific property of the non-metallic material such as its color, crosslinking, slipping, resistance to degradation, fire and / or bacterial and / or fungal attacks.
  • the polymer is a thermoplastic (co) polymer selected from the group consisting of 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), alone, in a mixture, in copolymers or in combination.
  • a thermoplastic (co) polymer selected from the group consisting of a polyolefin, a polyester, a polyether, a vinyl polymer, a vinylidene polymer, a styrenic poly
  • the polyolefins may be chosen from the group comprising a polyethylene, a polypropylene, an ethylene / propylene copolymer, a polybutylene, a polymethylpentene, an ethylene / vinyl acetate copolymer, an ethylene / vinyl alcohol copolymer or an ethylene / methyl acrylate copolymer, alone. , in a mixture, in copolymers or in combination.
  • the polyesters may be selected from the group consisting of polyethylene terephthalate, modified or unmodified by glycol, polybutylene terephthalate, polyactide, polycarbonate, alone, in admixture, 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 selected from the group consisting of optionally chlorinated polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyvinyl acetal, polyvinyl formaldehyde , a polyvinyl fluoride, polyvinyl chloride / vinyl acetate, whether alone, in admixture, in copolymers or in combination.
  • the vinylidene polymers may be selected from the group consisting of polyvinylidene chloride, polyvinylidene fluoride, alone, as a mixture, copolymer or 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, as a mixture, 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 (lauroamide), a polyether-block-amide, a poly (metaxylylene adipamide) and a poly (metaphenylene isophthalamide), alone. , in a mixture, in copolymers or in combination.
  • the fluorinated polymers may be chosen from the group comprising a polytetrafluoroethylene, a polychlorotrifluoroethylene, a perfluorinated poly (ethylene / propylene), a polyvinylidene fluoride, alone, in a mixture, in copolymers or in combination.
  • the cellulosic polymers may be selected from the group consisting of cellulose acetate, cellulose nitrate, methylcellulose, carboxymethylcellulose, ethylmethylcellulose, alone, in admixture, copolymers or in combination.
  • the poly (arylenesulfone) may be selected from the group consisting of a polysulfone, a polyethersulfone, a polyarylsulfone, alone, as a mixture, copolymers or in combination.
  • the polysulfides may be poly (phenylene sulfide).
  • the poly (aryl ether ketones) may be chosen from the group comprising a poly (ether ketone), a poly (ether ether ketone), a poly (ether ketone ketone), alone, as a mixture, by copolymers or in combination.
  • the polymer is a thermosetting (co) polymer selected from the group comprising an aminoplast such as urea-formaldehyde, melanin-formaldehyde, melanin-formaldehyde / polyesters, alone, as copolymers, mixed 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 combination.
  • an aminoplast such as urea-formaldehyde, melanin-formaldehyde, melanin-formaldehyde / polyesters, alone, as copolymers, mixed 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
  • 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 sanding, shot blasting, microbilling and abrasive sanding.
  • oxygen-rich groups such as carboxylic (-COOH), hydroxyl (-OH) and alkoxyl (-OR) groups.
  • carbonyl (-C O)
  • percarboxylic acid (-CO-O-OH) percarboxylic acid (-CO-O-OH)
  • nitro (N O)
  • amide (-CONH) capable of chemically binding the metal cations
  • 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 selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, acetic acid, oxalic acid, phosphorous acid , phosphoric acid, hypophosphorous acid alone or as a mixture.
  • the strong oxidant is selected from the group consisting of KMnO 4 and KClO 3 , alone or as a mixture.
  • the strong oxidant is KMnO 4 .
  • oxidizing treatments are chosen according to the nature of the constituent materials of the substrates, in Table 1 below are illustrated by way of examples, various chemical oxidizing treatments applicable when the substrate is ABS or ABS / PC.
  • Table 1 ⁇ / b> oxidizer Acid alone or in combination KMnO 4 H 3 PO 4 H 3 PO 2 H 3 PO 3 H 2 SO 4 C 2 H 2 O 4 H 2 PO 4 + C 2 H 2 O 4 H 3 PO 2 + C 2 H 2 O 4 H 3 PO 4 + H 2 SO 4 H 3 PO 2 + H 2 SO 4 HNO 3 + HCl HNO 3 HCl CH 3 COOH CH 3 COOH
  • 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 ethanol as the solvent.
  • the concentration of potassium hydroxide in the alcoholic solution is between 0.1M and 10M.
  • it is between 0.5M and 5M.
  • it is of the order of 3.5M.
  • the duration of the alcoholic potash treatment 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 as a mixture, in hydrochloric acid, in sulfuric acid, in nitric acid and in oxalic acid. , in phosphoric acid, in hydrophosphorous acid or in phosphorous acid.
  • the concentration of KMnO 4 or KClO 3 is between 10mM and 1M.
  • it is between 0.1M and 0.5M.
  • it is of the order of 0.2M.
  • the acid concentration is between 0.1M and 10M.
  • it is between 0.5M and 5M.
  • it is of the order of 3.5M.
  • 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.
  • it is of the order of 15 minutes.
  • chemical oxidative treatment is an electrochemical treatment.
  • the counter-ion of the at least one metal of step d) is selected from the group consisting of 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 the order of 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 selected from the group consisting of sodium borohydride, dimethylamineborane or hydrazine solutions.
  • the reducing agent is a solution of sodium borohydride.
  • the sodium borohydride solution has a neutral or basic pH.
  • the dimethylamineborane solution has a basic pH.
  • the pH is basic
  • the sodium hydroxide in solution is used as the solvent.
  • the concentration of sodium hydroxide is between 10 -4 M 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 between 10 ° C and 90 ° C.
  • it is carried out at a temperature of 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 metal is an aqueous solution.
  • said solution of step g) 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 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 2+ and Ni 2+ .
  • 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 the same or different.
  • the rinse 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 chosen from the group comprising TDF4 and sodium hydroxide.
  • the concentration of sodium hydroxide is between 0.01M and 1M.
  • the rinse 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 different 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, an ultrasonic bath or a homogenizer.
  • the invention also relates to the substrate obtained according to the method 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 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 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 nickel, the atoms of which are bonded to a metal-ligand interaction with the constituent ABS of the substrate, said layer activation 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 made of copper, the atoms of which are bonded metal-ligand interaction with the ABS / PC 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 ABS / 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 ABS / PC. of the substrate, said activation layer being covered with a layer of copper deposited by autocatalytic deposition
  • the invention relates to a PA substrate, 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 PA constituting the substrate, said layer of activation being covered with a layer of copper deposited by autocatalytic deposition
  • the invention relates to a PA substrate whose surface is coated with an activation layer made of nickel, the atoms of which are bonded to a metal-ligand interaction with the PA 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 PC, 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 PC of the substrate, said layer of activation being covered with a layer of copper deposited by autocatalytic deposition
  • 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 layer of activation being covered with a layer of copper deposited by autocatalytic deposition
  • the invention relates to a substrate made of MABS, the surface of which is coated with an activation layer made of copper whose atoms are bonded by metal-ligand interaction to the MABS constituting the substrate, said layer of activation 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 layer of activation 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 made of copper whose atoms are bonded by metal-ligand interaction to the constituent PP of the substrate, said layer of activation 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, said layer of activation being covered with a layer of copper or deposited by autocatalytic deposit
  • 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 with the PPS constituting the substrate, said layer of activation being covered with a layer of copper or deposited by autocatalytic deposit
  • 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, said layer of activation 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 made of nickel, 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 / PC, 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 / PC. of the substrate, said activation layer being covered 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 bonded by metal-ligand interaction to the constituent ABS / PC. of the substrate, said activation layer being covered with a layer of nickel deposited by autocatalytic deposition
  • the invention relates to a PA substrate, 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 PA constituting the substrate, said layer of activation being coated with a nickel layer deposited by autocatalytic deposit
  • the invention relates to a PA substrate whose surface 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, said layer of activation being coated with a nickel layer 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 copper, the atoms of which are bonded by metal-ligand interaction to the constituent PC of the substrate, said layer of activation being coated with a nickel layer 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 layer of activation being coated with a nickel layer deposited by autocatalytic deposit
  • the invention relates to a substrate made of MABS, the surface of which is coated with an activation layer made of copper whose atoms are bonded by metal-ligand interaction to the MABS constituting the substrate, said layer of activation being coated with a nickel layer deposited by autocatalytic deposit
  • 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 layer of activation 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 made of copper whose atoms are bonded by metal-ligand interaction to the constituent PP of the substrate, said layer of activation 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, said layer of activation being coated with a nickel layer deposited by autocatalytic deposit
  • 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 with the PPS constituting the substrate, said layer of activation being coated with a nickel layer deposited by autocatalytic deposit
  • 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, said layer of activation being coated with a nickel layer deposited by autocatalytic deposit
  • the invention also relates to a method according to the invention further comprising a metallization step.
  • the metallization treatment is an electroplating treatment.
  • ABS acrylonitrile butadiene styrene
  • PC acrylonitrile butadiene styrene / polycarbonate
  • This method of coating with a copper layer a substrate of non-metallic material is carried out in 4 steps (chemical oxidizing treatment with nitric acid / chelation and / or complexation / reduction / bath Electroless).
  • ABS acrylonitrile butadiene styrene
  • ABS / PC acrylonitrile butadiene styrene / polycarbonate
  • Copper sulphate (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 X 10 -2 mol) is dissolved in 25 ml of a 0.1 M sodium hydroxide solution (NaOH). This solution is heated to 80 ° C. using a bain-marie and the 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.
  • the pieces will be covered with the chemical copper metal film after 3 minutes of immersion.
  • the copper layer is visible to the naked eye.
  • the Electroless bath is a prepared solution containing: 40 ml of PegCopper 100 solution, 100 ml of PegCopper 200 solution, 30 ml of PegCopper 400 and 2 ml of PegCopper 500 (products marketed by PEGASTECH) ). 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 bubbling. The parts to be treated are then introduced.
  • the pieces will be covered with the chemical copper metal film after 3 minutes of immersion.
  • the copper layer is visible to the naked eye.
  • the coating process is carried out with a substrate made of Minlon ® polyamide.
  • step I.2 copper ions are chelated on the surface of the substrate.
  • the chelated copper ions are reduced on the surface of the substrate
  • the polyamide substrate is covered with a chemical copper metal film.
  • the copper layer is visible to the naked eye.
  • the coating process is carried out with a Lexan® polycarbonate substrate.
  • the polycarbonate substrate is immersed in a solution containing a mixture of strong acids (34% nitric acid and 66% sulfuric acid) at 25 ° C. for 5 minutes and then in a concentrated sulfuric 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% sulfuric acid) at 25 ° C. for 5 minutes and then in a concentrated sulfuric 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.
  • the copper ions are chelated reduced on the surface of the substrate
  • step I.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 performanes obtained with substrates obtained according to the methods of the prior art.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)
EP11723649.7A 2010-04-19 2011-04-19 Procede de revetement d'une surface d'un substrat en materiau non metallique par une couche metallique Active EP2561117B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US28290610P 2010-04-19 2010-04-19
FR1001663A FR2958944B1 (fr) 2010-04-19 2010-04-19 Procede de revetement d'une surface d'un substrat en materiau non metallique par une couche metallique
PCT/IB2011/051691 WO2011132144A1 (fr) 2010-04-19 2011-04-19 Procede de revetement d'une surface d'un substrat en materiau non metallique par une couche metallique

Publications (2)

Publication Number Publication Date
EP2561117A1 EP2561117A1 (fr) 2013-02-27
EP2561117B1 true EP2561117B1 (fr) 2016-03-30

Family

ID=43034368

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11723649.7A Active EP2561117B1 (fr) 2010-04-19 2011-04-19 Procede de revetement d'une surface d'un substrat en materiau non metallique par une couche metallique

Country Status (10)

Country Link
US (2) US8962086B2 (zh)
EP (1) EP2561117B1 (zh)
JP (1) JP5947284B2 (zh)
KR (1) KR101812641B1 (zh)
CN (1) CN102933745B (zh)
ES (1) ES2576278T3 (zh)
FR (1) FR2958944B1 (zh)
PL (1) PL2561117T3 (zh)
PT (1) PT2561117E (zh)
WO (1) WO2011132144A1 (zh)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2958944B1 (fr) * 2010-04-19 2014-11-28 Pegastech Procede de revetement d'une surface d'un substrat en materiau non metallique par une couche metallique
CN103436164B (zh) * 2013-09-03 2015-12-02 丽水学院 用于abs工程塑料表面处理的混合溶液及处理方法
KR101662759B1 (ko) * 2015-01-09 2016-10-10 건국대학교 글로컬산학협력단 무전해 도금법 및 전해 도금법을 연속 적용한 금속 도금 섬유의 제조방법, 상기 방법에 의해 제조된 금속 도금 섬유 및 상기 섬유를 적용한 필터
EP3216756A1 (en) * 2016-03-08 2017-09-13 ATOTECH Deutschland GmbH Method for recovering phosphoric acid from a spent phosphoric acid / alkali metal permanganate salt etching solution
FR3050215B1 (fr) * 2016-04-15 2018-04-13 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede de modification d'une surface en oxyde conducteur de l'electricite, utilisation pour l'electrodeposition de cuivre sur cette derniere
CN108624907A (zh) * 2018-04-26 2018-10-09 复旦大学 非金属基体高效催化电极及其制备方法
BR112021016763A2 (pt) * 2019-04-04 2021-10-13 Atotech Deutschland Gmbh Método de ativação de uma superfície de um substrato contendo fibras não condutoras ou de carbono para metalização
US20220338480A1 (en) * 2019-08-09 2022-10-27 Jnt Technologies, Llc Antimicrobial common touch surfaces
CN113564569B (zh) * 2021-03-18 2023-10-31 麦德美科技（苏州）有限公司 Lcp塑料的化学粗化及金属化工艺方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3553085A (en) * 1967-11-28 1971-01-05 Schering Ag Method of preparing surfaces of plastic for electro-deposition
US3598630A (en) 1967-12-22 1971-08-10 Gen Motors Corp Method of conditioning the surface of acrylonitrile-butadiene-styrene
US4701351A (en) * 1986-06-16 1987-10-20 International Business Machines Corporation Seeding process for electroless metal deposition
FI95816C (fi) * 1989-05-04 1996-03-25 Ad Tech Holdings Ltd Antimikrobinen esine ja menetelmä sen valmistamiseksi
US4981715A (en) 1989-08-10 1991-01-01 Microelectronics And Computer Technology Corporation Method of patterning electroless plated metal on a polymer substrate
US5160600A (en) * 1990-03-05 1992-11-03 Patel Gordhanbai N Chromic acid free etching of polymers for electroless plating
JPH0715114A (ja) * 1993-06-25 1995-01-17 Hitachi Ltd プリント回路板のパターン形成用表面処理槽
JP3535418B2 (ja) * 1999-07-14 2004-06-07 富士通株式会社 導体パターン形成方法
DE10054544A1 (de) * 2000-11-01 2002-05-08 Atotech Deutschland Gmbh Verfahren zum chemischen Metallisieren von Oberflächen
JP4670064B2 (ja) * 2001-02-07 2011-04-13 奥野製薬工業株式会社 無電解めっき用触媒付与方法
JP2003041375A (ja) * 2001-07-31 2003-02-13 Okuno Chem Ind Co Ltd 無電解めっき用触媒付与方法
CA2483342C (en) * 2002-04-25 2010-03-30 Ppg Industries Ohio, Inc. Coated articles having a protective coating and cathode targets for making the coated articles
JP2004203014A (ja) * 2002-10-31 2004-07-22 Toyoda Gosei Co Ltd めっき製品
CN1329554C (zh) 2004-01-13 2007-08-01 长沙力元新材料股份有限公司 非金属基材表面化学镀覆金属的方法及其采用的前处理体系
JP5177426B2 (ja) 2006-04-18 2013-04-03 奥野製薬工業株式会社 樹脂成形体に対するエッチング処理用組成物
CN100545305C (zh) 2007-05-29 2009-09-30 南京工业大学 非金属基体化学镀的一种活化工艺
PL2025708T3 (pl) 2007-08-10 2010-03-31 Enthone Roztwór trawiący do powierzchni tworzyw sztucznych nie zawierający chromu
CN101381865B (zh) 2008-10-23 2011-06-01 中国人民解放军第二炮兵工程学院 一种羧甲基纤维素钠螯合吸附镍的塑料基体表面无钯活化方法
FR2958944B1 (fr) * 2010-04-19 2014-11-28 Pegastech Procede de revetement d'une surface d'un substrat en materiau non metallique par une couche metallique

Also Published As

Publication number Publication date
JP2013525606A (ja) 2013-06-20
JP5947284B2 (ja) 2016-07-06
CN102933745B (zh) 2016-07-06
FR2958944B1 (fr) 2014-11-28
PT2561117E (pt) 2016-06-17
EP2561117A1 (fr) 2013-02-27
US20150111050A1 (en) 2015-04-23
US9249512B2 (en) 2016-02-02
CN102933745A (zh) 2013-02-13
PL2561117T3 (pl) 2016-09-30
WO2011132144A1 (fr) 2011-10-27
FR2958944A1 (fr) 2011-10-21
KR20130101978A (ko) 2013-09-16
KR101812641B1 (ko) 2017-12-27
US20110256413A1 (en) 2011-10-20
US8962086B2 (en) 2015-02-24
ES2576278T3 (es) 2016-07-06

Similar Documents

Publication Publication Date Title
EP2561117B1 (fr) Procede de revetement d'une surface d'un substrat en materiau non metallique par une couche metallique
EP2510133B1 (fr) Procédé de préparation d'un substrat en polymère métallisé
CN102248159B (zh) 一种银包铝粉的制备方法
US20060042954A1 (en) Method for plating resin material
CN101195911B (zh) 在具有塑料表面的基底上形成涂布金属层的预处理溶液和方法
KR102366687B1 (ko) 무전해 도금의 전처리용 조성물, 무전해 도금의 전처리 방법, 무전해 도금 방법
JP5269306B2 (ja) 誘電体の金属化
EP2937447A1 (en) Conductive coating film forming bath
EP3070185B1 (en) Conductive film-forming bath
EP1546435B1 (en) Method for pretreating a surface of a non-conducting material to be plated
JP2011062674A (ja) ポリマー層の形成方法
CH710579A1 (fr) Procédé de placage autocatalytique d'un métal précieux.
RU2063461C1 (ru) Способ получения никелевого покрытия на материалах из углеродных волокон
JP2005068497A (ja) めっき素材及びめっき被覆部材とそれらの製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20121029

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602011024629

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C23C0018220000

Ipc: C25D0005560000

17Q First examination report despatched

Effective date: 20150527

RIC1 Information provided on ipc code assigned before grant

Ipc: C25D 5/56 20060101AFI20150611BHEP

Ipc: C23C 18/20 20060101ALI20150611BHEP

Ipc: C23C 18/16 20060101ALI20150611BHEP

Ipc: C23C 18/38 20060101ALI20150611BHEP

Ipc: C23C 18/22 20060101ALI20150611BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150929

RIN1 Information on inventor provided before grant (corrected)

Inventor name: GILBERT, FRIDA

Inventor name: ROUSSEL, SEBASTIEN

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 785499

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160415

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011024629

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20160609

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2576278

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20160706

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160701

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160630

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20160330

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 785499

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160430

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011024629

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160430

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20170103

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160419

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20110419

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160419

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20190801 AND 20190807

REG Reference to a national code

Ref country code: SK

Ref legal event code: PC4A

Ref document number: E 22083

Country of ref document: SK

Owner name: ATOTECH DEUTSCHLAND GMBH, BERLIN, DE

Free format text: FORMER OWNER: PEGASTECH, GIF-SUR-YVETTE, FR

Effective date: 20200217

Ref country code: SK

Ref legal event code: TE4A

Ref document number: E 22083

Country of ref document: SK

Owner name: PEGASTECH, GIF-SUR-YVETTE, FR

Effective date: 20200217

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602011024629

Country of ref document: DE

Owner name: ATOTECH DEUTSCHLAND GMBH, DE

Free format text: FORMER OWNER: PEGASTECH, ORSAY, FR

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: ATOTECH DEUTSCHLAND GMBH

Effective date: 20201127

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: RO

Payment date: 20230411

Year of fee payment: 13

Ref country code: PT

Payment date: 20230406

Year of fee payment: 13

Ref country code: IT

Payment date: 20230426

Year of fee payment: 13

Ref country code: FR

Payment date: 20230420

Year of fee payment: 13

Ref country code: ES

Payment date: 20230627

Year of fee payment: 13

Ref country code: DE

Payment date: 20230420

Year of fee payment: 13

Ref country code: CZ

Payment date: 20230412

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20230417

Year of fee payment: 13

Ref country code: SK

Payment date: 20230413

Year of fee payment: 13

Ref country code: PL

Payment date: 20230412

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230419

Year of fee payment: 13