EP4043110A1 - Verfahren zur funktionalisierung von oberflächen - Google Patents

Verfahren zur funktionalisierung von oberflächen Download PDF

Info

Publication number
EP4043110A1
EP4043110A1 EP22167257.9A EP22167257A EP4043110A1 EP 4043110 A1 EP4043110 A1 EP 4043110A1 EP 22167257 A EP22167257 A EP 22167257A EP 4043110 A1 EP4043110 A1 EP 4043110A1
Authority
EP
European Patent Office
Prior art keywords
paa
solution
typically
polymer
metallization
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.)
Pending
Application number
EP22167257.9A
Other languages
English (en)
French (fr)
Inventor
Pascal Viel
Thomas Berthelot
Xavier Lefevre
Jérôme POLESEL MARIS
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.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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 Commissariat a lEnergie Atomique CEA, Commissariat a lEnergie Atomique et aux Energies Alternatives CEA filed Critical Commissariat a lEnergie Atomique CEA
Publication of EP4043110A1 publication Critical patent/EP4043110A1/de
Pending legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/062—Pretreatment
    • B05D3/064—Pretreatment involving also the use of a gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/107—Post-treatment of applied coatings
    • B05D3/108—Curing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • 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
    • C23C18/1889—Multistep pretreatment with use of metal first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—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
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/208—Multistep pretreatment with use of metal first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/101—Pretreatment of polymeric substrate
    • 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
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
    • C23C18/2066—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
    • 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
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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

Definitions

  • the present invention relates to a method for functionalizing a surface of an organic or inorganic solid support with at least one polymer layer based on acrylic acid, the substrates that can be obtained by this method, and their use for the preparation of implantable medical devices, for the surface preparation of biosensors, for structural bonding, for the manufacture of composite materials, for printed electronics, for the complete or localized metallization of glass or plastic surfaces, for the production of hydrophilic glazing or hydrophobic, for the treatment of heavy metals in liquid effluents.
  • the grafting of thiols onto a gold surface is based on the privileged chemical interaction of sulfur atoms on a gold surface.
  • This process makes it possible to manufacture self-organized organic monolayers [ Chem. Rev., 2005, 105 (4), pp 1103-1170 ].
  • the process is generally reserved for fundamental studies and is not very stable because the thiol layer can be desorbed. They are not strictly covalent interfacial bonds.
  • grafting of a silane layer on glass or oxide is based on the privileged interaction of silicon atoms with oxygen atoms. This process is widely used in microelectronics [ Silanes and Other Coupling Agents, Volume 4, KL Mittal, CRC Press 2007 ]. Covalent siloxane bonds can be created under certain conditions but they will remain sensitive to hydrolysis.
  • cathodic electrografting makes it possible to create a real covalent bond between the organic layer and the substrate.
  • these methods require the implementation of an electrically conductive or semiconductive substrate.
  • the Graftfast ® process is a surface coating process for conductive, semiconductive and insulating substrates, with a thin layer of organic polymer, via the redox activation of aryldiazonium salts in the presence of vinyl monomers, in an acidic aqueous medium ( Mévellec et al. Chem. Mater. 2007, 19, 6323-6330 ; EP 2 121 814 B1 ).
  • the aryldiazonium salts are reduced with an iron powder to form surface-reactive aryl radicals, leading to (i) the formation of polyphenylene-like films on the surface of the substrate and (ii) initiating polymerization of the vinyl monomer in solution.
  • the radical-terminated macromolecular chains formed in solution are then able to react with the polyphenylene-based primer to form a very thin and homogeneous organic film on the surface.
  • these methods require a step of bringing the surface of the solid support into contact with at least one solvent and a cleavable aryl salt, in particular an aryl diazonium salt, followed by a step of reducing these salts under non-electrochemical conditions, allowing the formation of radical entities from the cleavable aryl salt.
  • This reduction generally carried out in the presence of iron filings, also requires an additional step of separation of the reducing agent.
  • this process which makes it possible to graft films onto supports of a varied nature, does not make it possible to obtain effective functionalization of glass surfaces or on stainless steels.
  • an adhesion primer in particular via cleavable aryl salts, in particular aryldiazonium salts.
  • the polymer layer immobilized on the surface of the solid support constitutes in itself an adhesion layer, capable of reacting with other molecules present in its environment, via the carboxylic acid and/or anhydride functions of the polymer based on acrylic acid.
  • the acrylic acid polymer is a biocompatible polymer, which makes it particularly suitable for the functionalization of supports intended for a biological or medical application.
  • this process makes it possible to very easily control the thickness of the adhesion layer based on acrylic acid polymer, either through the concentration by mass of the polymer based on acrylic acid in the solvent, or by taking advantage of the polyelectrolytic properties of the acrylic acid polymer which allow it to be strongly adsorbed on substrates which have surface electrostatic charges (such as, for example, oxides, metals or materials which have undergone surface oxidation). Under these conditions, it is then possible to obtain, in a reproducible and compliant manner (ie the layer perfectly follows the topography of the surface of the material), a residual thin layer (in particular ⁇ 20 nm in thickness) of acid polymer acrylic.
  • the process of the invention also advantageously makes it possible to modulate the swelling of the adhesion layer via in particular the crosslinking of the polymer based on acrylic acid during the heat or radiation treatment.
  • this method makes it possible to functionalize organic or inorganic solid supports of various kinds, in particular glass and stainless steel, or even polymers known to be very difficult to modify such as, for example, polytetrafluoroethylene (PTFE) whose metallization according to the method of the invention offers significant advantages in the field of high-frequency electronics.
  • PTFE polytetrafluoroethylene
  • Said solution not comprising an adhesion primer based on cleavable aryl salts, in particular aryldiazonium salts; ii) removing the solvent from the solution in contact with said surface; and iii) fixing the polymer on said surface by thermal or radiative treatment.
  • the solid support implemented in step i) can be an organic or inorganic support, in particular a conductor, semiconductor or insulator. It may in particular be chosen from metals such as copper, nickel, stainless steel, aluminum, iron, titanium, or their oxides, such as titanium dioxide (TiO 2 ), iron oxides, or aluminum oxides; mineral oxides, in particular those based on silicon oxide commonly called glasses; plastics; cellulosic papers, synthetic papers such as Teslin® , carbon fibres, in particular woven or non-woven and composite materials such as epoxy resins reinforced with glass fibres, carbon fibers or natural fibres.
  • metals such as copper, nickel, stainless steel, aluminum, iron, titanium, or their oxides, such as titanium dioxide (TiO 2 ), iron oxides, or aluminum oxides
  • mineral oxides in particular those based on silicon oxide commonly called glasses
  • plastics cellulosic papers, synthetic papers such as Teslin® , carbon fibres, in particular woven or non-woven and composite materials such as epoxy resins reinforced
  • the method comprises a step o), prior to step i), consisting in subjecting the solid support to a pretreatment of surface of oxidative type, in particular chemical and/or radiative, so as to increase the affinity of the solid support with the solution containing the polymer based on acrylic acid.
  • This treatment may include a step of exposure to an oxygen or argon plasma, to UV-Ozone activation or chemical oxidation with acids.
  • the method comprises a step o′), prior to step i), consisting in subjecting the solid support to a surface pretreatment of the oxidative type followed by deposition of a thin film (in particular ⁇ 5 nm thick) of a cationic polymer, typically polyethylene imine (PEI) or polyallylamine so as to increase the affinity of the solid support with the solution containing the polymer based on acrylic acid, by developing interactions electrostatic.
  • a cationic polymer typically polyethylene imine (PEI) or polyallylamine
  • polymer based on acrylic acid is understood to mean a polymer comprising the following repeating unit: -(CH2-CX(COOH)) n - where X is H, or an alkyl group in C 1 -C 6 , in particular CH3 or C 2 H 5 .
  • a copolymer mention may be made of the copolymer of acrylic acid and of maleic acid.
  • the molecular weight of the polymer based on polyacrylic acid can vary to a large extent, in particular from 2,000 g.mol ⁇ 1 to 1,000,000 g.mol ⁇ 1 .
  • the molecular weight of the polymer based on polyacrylic acid is between 50,000 g.mol -1 and 300,000 g.mol -1 .
  • the polymer is a homopolymer of acrylic acid, also designated PAA below, having in particular a molecular weight of 130,000 g.mol ⁇ 1 .
  • the solution implemented in step i) may also comprise a second or more homopolymers of acrylic acid of different molecular mass.
  • the solvent can be chosen from water, alcohols, or a mixture of these.
  • the alcohols can be chosen in particular from C1-C6 alcohols, in particular ethanol.
  • the solvent is a hydroalcoholic mixture, including a water-ethanol mixture.
  • the water-alcohol fraction can vary to a large extent, in particular depending on the surface energies of the materials to be functionalized.
  • the solution implemented in step i) may also comprise a second polymer based on acrylic acid of a different nature from the first.
  • This solution may also comprise adjuvants such as wetting agents, thinners, emulsifiers or pigments, complexing agents, fluorophores. It can also comprise cross-linking agents such as polyallylamine hydrochloride, hexamethylene diamine hydrochloride, polyethylene glycol or polyethylene glycol-diamine.
  • the solution implemented in step i) does not comprise an adhesion primer based on cleavable aryl salts, in particular aryldiazonium salts. According to one embodiment, the solution implemented in step i) does not comprise any adhesion primer other than the polymer based on acrylic acid.
  • adhesion primer means any organic molecule capable, under certain conditions, of adhering, in particular of chemisorbing to the surface of a solid support, in particular by radical reaction such as than radical chemical grafting. Such molecules contain at least one functional group capable of forming a radical.
  • adhesion primers include in particular cleavable aryl salts such as aryldiazonium salts.
  • cleavable aryl salts is meant, within the meaning of the present description, aryl salts (ArX n+ , Y n- ) capable of generating an aryl radical (Ar ⁇ ), in particular by homolytic cleavage of the bond Ar-X.
  • cleavable aryl salts include aryldiazonium salts, aryl ammonium salts, aryl phosphonium salts, aryl iodonium salts, and aryl sulfonium salts. These molecules are thus capable of forming a crosslinked and adherent film on the surface of the solid support via these radical reactions.
  • the solution can be applied to the surface of the solid support using various methods, in particular by soaking (immersion-emersion), centrifugation (spinner), spraying (spray), projection (inkjet, spraying), transfer (brush, marker, stamp).
  • the thickness of the polymer layer based on acrylic acid obtained in step iii) is easily adjustable via the concentration of the polymer based on of acrylic acid in the solution of step i) and/or via the successive deposition of layers of polymers based on acrylic acid on the surface of the support, that is to say via the repetition of steps i) to iii), step iii) being optional between two successive deposits.
  • a concentration of PAA in ethanol of 2% by weight makes it possible to obtain a layer of PAA 1000 nm thick.
  • Step ii) consists of removing the solvent from the solution of step i) deposited on the surface of the solid support, generally in the form of a homogeneous film.
  • the elimination of the solvent can be carried out by any suitable technique well known to those skilled in the art, such as simple air drying, in particular for solutions based on alcoholic solvents, for example with ethanol, evaporation under reduced pressure, in particular for solutions based on hydroalcoholic solvents.
  • Stage ii 1 makes it possible to eliminate the polyacrylic acid-based polymer not specifically and/or chemically adsorbed on the surface of the solid support at the end of stages i) and ii).
  • This step may include several successive rinsings with water, until a conformal layer is obtained, that is to say a layer of residual polymer, of constant thickness, on the surface of the solid support. .
  • steps ii 1 ) and ii 2 ) advantageously make it possible to control the thickness of the polymer layer based on acrylic acid fixed on the surface of the solid support, in particular to obtain a thin residual layer (thickness less than 20 nm), compliant and reproducible, by eliminating by rinsing with water, the parts not specifically adsorbed on the surface at the end of step ii).
  • the polymer based on acrylic acid behaves like a polyelectrolyte which can be adsorbed by electrostatic interactions on certain surfaces such as oxides, metals, or even materials having undergone surface oxidation (chemical and/or radiation) beforehand, thus creating electrostatic charges favorable to the expression of adsorption phenomena.
  • Stage iii) is a stage allowing the attachment of the polymer based on acrylic acid to the surface of the solid support by thermal or radiative treatment of the surface obtained in stage ii).
  • fixation is meant in particular covalent or non-covalent grafting, in particular via polyelectrolytic interactions, of the polymer onto the surface of the solid support.
  • the deposit obtained in step ii) undergoes a thermal or radiative treatment, in particular via light or electronic irradiation, to make it adhere to this surface.
  • This treatment in fact creates chemical hardening mechanisms, in particular via the homo-crosslinking of the polymer based on acrylic acid, which make the layer of polymer insoluble, difficult to dissolve and mechanically difficult to tear off.
  • this process makes it possible to obtain adhesion of the polymer layer based on acrylic acid on any type of material.
  • This adherence would result from various physico-chemical phenomena which can vary according to the nature of the support and/or the nature of the treatment in step iii), that is to say thermal or radiative.
  • the thermal or radiative treatment would in particular make it possible to generate reactive radical species which will confer cohesive properties, due to the crosslinking between the polymer chains between them, and/or adhesive properties, of by the reaction of radical species with the solid support.
  • the adhesion of the polymer layer based on acrylic acid on solid supports could result from covalent grafting via the thermal decarboxylation of the polymer at acrylic acid base.
  • the adhesion could result from a polyelectrolytic adhesion, that is to say from the interaction between the calcium or aluminum ions of the glass and the carboxylate functions of the polymer based on acrylic acid via the formation of salt bridges ( U. Lohbauer, Materials 2010, 3, 76-96 ).
  • the adhesion and therefore the adhesion of the acrylic acid-based polymer results from several factors or from a combination of these, including in particular the viscoelastic dissipation capacities of the polymer, the polyelectrolyte character of the latter and/or the crosslinking induced by a thermal or radiative treatment via the decarboxylation of the anhydride functions.
  • step (iii) is carried out by heat treatment, in particular at a temperature of between 150°C and 300°C, more particularly at a temperature of approximately 200°C.
  • this treatment is carried out on materials that can withstand such temperatures, for a period that can range up to 60 minutes, typically from 2 to 30 minutes.
  • the heat treatment can in particular be applied to supports such as metals (stainless steel, aluminum, copper, titanium), glasses, silicon and certain heat-stable polymers such as polyimide or polytetrafluoroethylene.
  • This treatment leads to dehydration by condensation of the carboxylic acid functions of the polymer based on acrylic acid and thus to the formation of anhydride functions.
  • the polymer layer has a very high concentration of residual anhydride groups which can be engaged spontaneously in chemical reactions, for example and in a non-limiting manner with amine, alcohol, acid or thiol functions.
  • the annealed film retains its swelling character with respect to solvents, in particular aqueous solvents; essential property for certain applications such as metallization for example.
  • step iii) is carried out by radiative treatment.
  • This treatment consists in subjecting the polymer to ultraviolet radiation (Vacuum UV, or VUV), that is to say at a wavelength of between 100 and 200 nm. It is particularly suitable for flat or shaped surfaces allowing exposure to light, in particular solid supports chosen from layers of gold, polyvinyl chloride (PVC), polyethylene terephthalate (PET), polyvinylidene fluoride (PVDF ), and polytetrafluoroethylene (PTFE).
  • VUV ultraviolet radiation
  • PVC polyvinyl chloride
  • PET polyethylene terephthalate
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • the radiative route advantageously makes it possible to immobilize thin films of polymer based on acrylic acid on thermally fragile substrates.
  • the 172 nm radiation from the Excimer lamp of the OSRAM brand of the XERADEX ® type makes it possible to break the bonds of the polymer based on acrylic acid and to create excited species, in particular radicals and/or ions.
  • Diagram 4 shows that at 172 nm, many chemical bonds in polymers can absorb light and be excited.
  • the radicals are notably capable of recombining by interchain mechanisms making it possible to crosslink the film in its volume but also to recombine with the surface when they are formed nearby.
  • the substrate itself is organic (such as PVC, PET, PVDF, PTFE) and reached by the radiation, it can be, in the same way, excited and recombine with the polymer which covers it.
  • the radiative treatment therefore makes it possible to confer cohesive (cross-linking) and adhesive (surface grafting) properties. ( See diagram 5 below).
  • the adhesion of the polymer layer based on acrylic acid on the surface implies that the radiation reaches the film-substrate interface.
  • the thickness of the layer can thus be adjusted according to the rules of decreasing absorption of the radiation, of the duration and/or of the power of irradiation.
  • films from 1 to 150 nm can be immobilized with irradiation times of between 2 and 15 minutes for an irradiation power of the order of 140 W.
  • the polymer layer still has a very high concentration of carboxylic groups which can be engaged spontaneously in chemical reactions, for example and in a non-limiting manner with amine, alcohol, acid or thiol functions.
  • the irradiated film retains its swelling character vis-à-vis solvents, aqueous in particular; essential property for certain applications such as metallization for example.
  • the anhydride and/or carboxylic acid functions thus advantageously make it possible to graft molecules or materials of interest to the surface of the polymer layer, via their covalent coupling with other chemical functions, the polymer layer based on acrylic acid thus playing a role of "primary adhesion".
  • the method according to the invention comprises a step subsequent to step iii) of covalent grafting of molecules of interest onto the polymer layer obtained, in particular a biological molecule or a resin, that is to say a natural or synthetic polymer, in particular thermoplastic or thermosetting, more particularly two-component resins.
  • Two-component resins are resins obtained from two components: the resin on the one hand, which can be a first monomer or a prepolymer, and the hardener on the other hand, which can be a second monomer or prepolymer, also called an agent. cross-linking.
  • the resins listed in the table below are examples of the resins listed in the table below.
  • the biological molecule can be grafted by a bioconjugation reaction between the carboxylic acid groups of the surface (obtained after VUV treatment or after hydrolysis of the anhydride functions) and the amine functions of proteins, as is conventionally done with peptide couplings employing a combination of activating agents such as N-hydroxysuccinimide and N,N' dicyclohexylcarbodiimide (NHS/DCC) in organic medium or sulfo-N- hydroxysuccinimide and ethyl-3-(3-dimethylaminopropyl; carbodiimide) hydrochloride (sulfo-NHS/EDC) in an aqueous medium.
  • activating agents such as N-hydroxysuccinimide and N,N' dicyclohexylcarbodiimide (NHS/DCC) in organic medium or sulfo-N- hydroxysuccinimide and ethyl-3-(3-dimethylamin
  • the activated esters formed react with the neighboring acid groups to reform, chemically this time, anhydride functions, even at room temperature.
  • this embodiment makes it possible to obtain a coating having anhydride functions without resorting to heat treatment. This is particularly advantageous for substrates that are thermally fragile and therefore incapable of withstanding the treatment at a temperature of between 150° C. and 300° C., required to obtain the anhydride functions directly.
  • a spontaneous direct coupling can be made with resins, in particular two-component resins: as example with the amino groups of two-component resins of the epoxy type (polyepoxide resins (EP)), polyimides (thermosetting polyimide resins PIRP) and melamine-formaldehyde (aminoplast melanin-formaldehyde resins (MF)) or with the alcohol groups of bi-polyurethane resins -components (cross-linked polyurethane resins (PUR)).
  • resins in particular two-component resins: as example with the amino groups of two-component resins of the epoxy type (polyepoxide resins (EP)), polyimides (thermosetting polyimide resins PIRP) and melamine-formaldehyde (aminoplast melanin-formaldehyde resins (MF)) or with the alcohol groups of bi-polyurethane resins -components (cross-linked polyurethane
  • the polymer solution in step (i) comprises metal salts.
  • the method then comprises a step subsequent to step iii) of reducing the metal salts, whereby a metallization of the surface of the solid support is obtained.
  • the subject of the invention is the substrates capable of being obtained by the method as defined above.
  • the polymer layer based on acrylic acid immobilized on the surface of the solid support generally has a thickness of between 3 nm and 5000 nm, in particular between 10 nm and 1000 nm, more particularly between 20 nm and 500 nm, in particular between 10 and 100 nm, for example between 20 nm and 70 nm. More particularly for radiative treatments, the polymer layer based on acrylic acid immobilized on the surface of the solid support has a thickness of between 3 nm and 300 nm, in particular between 10 nm and 100 nm, for example between 20 nm and 70 nm. n.
  • the intensity of the infrared absorption signal of the characteristic bands of the immobilized PAA in particular of the characteristic absorption bands of the acid functions carboxylic acid at 1721 cm -1 etc. carboxylates at 1576 cm -1 , varies by less than 20%, advantageously by less than 10%, preferentially by less than 5%.
  • the degree of crosslinking obtained following the heat or radiation treatment the elimination of the non-crosslinked chains is possible (cavities can thus advantageously form). It is then important to observe the stabilization of the quantity of material with respect to the washings.
  • the intensity of the absorption peak of the COOH carboxylic function (1721 cm -1 ) of a 100 nm thick layer of PAA immobilized thermally on a substrate such as stainless steel then hydrolysed in an aqueous medium will lose 5% of material on the first wash and then remains stable after immersion for 72 hours in seawater.
  • the intensity of the absorption peak of the carboxylate function COO - (1576 cm -1 ) of a 200 nm thick layer of thermally immobilized PAA on a substrate golden will lose 5% of material in the first wash and then will decrease by barely 3% after immersion for 120 hours in an aqueous solution at pH 10, the thickness of the PAA layer remaining almost stable beyond that.
  • a 100 nm thick layer of PAA thermally immobilized on a glass-type substrate and having undergone 24 h immersion in water, then successive rinsings with alcohol, acetone and DMF under ultrasound for 15 min, still resists subsequent immersion for 48 h in seawater, with a decrease in the intensity of the absorption signal of less than 5%.
  • the subject of the invention is the use of the substrates which can be obtained according to the method of the invention, and/or the use of the method according to the invention for the treatment of liquid effluents by capturing heavy metals, the preparation of stents, prostheses, implantable medical devices, for the production of electrical circuits on glass, plastic, optical resin (such as resins based on cyclic olefin polymer (Cyclo Olefin Polymer or COP in English) , for example) or paper (Teslin ® type for example) such as RFID antenna circuits, or for producing reflective surfaces, for grafting biological molecules onto paper, glass, plastic or metal, for structural bonding applications , for the manufacture of composite materials reinforced with carbon fiber (or Carbon Fiber Reinforced Polymer, in English).
  • optical resin such as resins based on cyclic olefin polymer (Cyclo Olefin Polymer or COP in English)
  • paper Teslin ® type for example
  • RFID antenna circuits or for producing reflective
  • the invention relates to the use of the process according to the invention for depositing a metallization primer on a substrate by electroless means, in particular on glass, polymers, in particular composites such as polymers with fiber reinforcement carbon or fiberglass.
  • electroless metallization means a process of metallization by chemical means, that is to say without electricity or an electroless bath, via a process of controlled autocatalytic reduction of metal ions leading to the formation of a uniform metallic layer.
  • Silanes are compounds capable at the same time of grafting onto glass and of capturing catalytic metals from electroless processes.
  • Their drawbacks are, on the one hand, the hydrolysable nature of the deposited layers. In fact, the Si-O-Si siloxane bond is very polar, and therefore very hydrolysable.
  • the leaching of a glazing on the facade is 1 ⁇ m per year, i.e. several nanometers per day. Consequently, with the silane layers a risk of detachment is observed.
  • the silane solutions used to produce the coatings are not chemically stable over time. The solution is prepared and condensation mechanisms occur. It is therefore necessary to constantly redo the solutions before application.
  • the method according to the invention advantageously makes it possible to overcome these drawbacks.
  • the fuselage or wing elements of aircraft are generally made of electrically conductive materials.
  • the aeronautical industry tends more and more to substitute these conductive materials by carbon composites, which have an insulating nature and which it is therefore necessary to metallize.
  • This metallization is currently done by adding copper fabrics or adding copper wires in carbon composites.
  • this metallization is very costly and cumbersome to implement.
  • Another method consists in projecting metallic particles onto the composite material so as to physically embed these particles in the material.
  • the continuity of the layer and the resulting conduction properties are however not satisfactory.
  • the metallization process according to the invention makes it possible to metallize at lower cost, superficially, in continuous and thin layers, such composites, in particular carbon fiber-epoxy resin composites, to make them conductive.
  • this process is easy to implement, and allows elements to be metallized directly on site.
  • the method is thus particularly useful for metallizing the constituents of the cell of an airplane, in particular the fuselage or the wing, made of polymer composite materials, in particular with carbon fiber reinforcement.
  • the process according to the invention is also particularly useful for metallizing heat-resistant polymers, which are difficult to treat on the surface.
  • the process makes it possible to metallize Kevlar, in particular in the form of fabric for intelligent textile applications, or even polyimide for printed flexible electronics applications.
  • the method according to the invention is also particularly useful for metallizing semiconductor materials. Indeed, a recurring problem in microelectronics is the production of barrier layers to the diffusion of copper atoms (making the conductive parts) towards silicon (semiconducting part) to prevent copper from poisoning the semiconducting properties of silicon. .
  • the metallization of titanium nitride is currently carried out via physical vacuum metallization processes, which are particularly heavy and complex to implement.
  • the process according to the invention allows the formation of barrier layers, for example of nickel, having electrical continuity between the copper on the one hand, and the titanium nitride on the other hand.
  • the method according to the invention is also useful for the preparation of depollution coatings, for example for the manufacture of a material for filtering liquid effluents contaminated by dissolved metal salts.
  • the film is chemically grafted onto the substrate and crosslinked. It is in a totally anhydride chemical form for the functions which have not undergone decarboxylation.
  • the PAA film is then treated in a basic aqueous solution in order to rehydrate the anhydrides and restore the polyacrylic acid form.
  • This chemical form of polyacrylic acid can advantageously effectively capture metal salts and is therefore particularly useful for depollution or metallization applications.
  • the process is also useful for the preparation of self-adhesive adhesion reinforcement via the anhydride functions.
  • the method according to the invention thus makes it possible to deposit, on a wide range of substrates, thin coatings in an anhydride form capable of reacting spontaneously and very easily at room temperature with resins or two-component paints such as epoxy resins or paints. or polyurethane.
  • the anhydride forms, for example, react very effectively with the amino groups of the resin before it is crosslinked.
  • This grafted coating is particularly advantageous when the substrates to be bonded or to be coated have very smooth, that is to say highly polished, surfaces. Indeed, in these cases, it is not possible in adhesion phenomena to use mechanical anchoring which is very often involved in overall adhesion.
  • the process according to the invention advantageously makes it possible to obtain excellent chemical adhesion on these very smooth surfaces, in particular weakly chemically reactive surfaces where the mechanical anchoring is not present.
  • the method is particularly useful for improving the adhesion of gemstones to mirror-polished precious metal surfaces.
  • the invention relates to the use of the method according to the invention for metallizing plastics, or metal or mineral oxides such as silica (SiO 2 ) or even indium titanium oxide (ITO).
  • metal or mineral oxides such as silica (SiO 2 ) or even indium titanium oxide (ITO).
  • the invention relates to the use of the method according to the invention for functionalizing a surface of a solid support with biological molecules.
  • the invention relates to the use of the method according to the invention for functionalizing a surface of a solid support with an adhesion primer comprising or consisting of a polymer layer based on acrylic acid.
  • Example 1 Metallization of surfaces.
  • Example 1-a/ Full surface metallization of a glass surface. (Heat treatment)
  • a solution of PAA (Mn 130,000) at a concentration of 50 mg in 10 ml of ethanol is prepared by dissolution.
  • a glass slide of the microscopy object slide type (7.5x2.5 cm) is degreased (washing with a surfactant then typically an alcohol rinse) then dried (by a blower of dry nitrogen gas then by passage through oven at 100°C for 15 min).
  • the application of the PAA solution is made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a covering and homogeneous PAA film with a thickness of 50 to 70nm.
  • the deposition of PAA then occurs on both sides of the glass slide.
  • the glass slides coated with PAA are then typically heated to 200° C. for 30 min in a simple oven at atmospheric pressure and without any particular precautions.
  • the solution can be prepared in advance.
  • the activated glass slide is immersed in an electroless bath (that is to say an electroless bath) regulated at a temperature of 34°C.
  • an electroless bath that is to say an electroless bath
  • the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
  • the reducing agent is sodium hypophosphite (NaH 2 PO 2 ,H 2 O).
  • the activated glass slides are left for 10 minutes in order to have a complete and homogeneous metallization.
  • the thickness of the nickel film is typically 500 nm.
  • the adhesion/adhesion of the metal layer is determined by applying the standard ASTM D3359 tape test.
  • a glass slide which had not been covered with a layer of PAA was metallized by immersion in the palladium acetate activation solution described above. Due to the hydrophilic nature of the glass substrate, palladium ions adsorb on this surface. This is then transferred to the electroless bath and the metallization process develops. Rinsing with water then drying with a dry gas blower is sufficient. The thickness of the nickel film is typically 200 nm.
  • Figure 1 shows:
  • Example 1-b/ Full-surface metallization of a glass surface with a PAA film of consistent residual thickness. (Heat treatment)
  • Example 1-b/ Full-surface metallization of a glass surface with a PAA film of consistent residual thickness. (Heat treatment)
  • a solution of PAA (Mn 130,000) at a concentration of 5 mg in 10 ml of ethanol is prepared by dissolution.
  • a microscopy slide-type glass slide (7.5x2.5 cm) is degreased (washing with a surfactant then typically an alcohol rinse) then dried with a heat gun at a temperature exceeding 200°C without exceeding 300° C for 1 minute.
  • the application of the PAA solution is made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a covering and homogeneous PAA film with a thickness of 10 nm. .
  • the deposition of PAA then occurs on both sides of the glass slide.
  • the glass slides coated with PAA are then typically rinsed with deionized water in order to eliminate the non-adsorbed PAA chains.
  • Polyelectrolytic interactions govern the persistence of a residual thin film of a few nanometers (less than 5 nm). This residual film is then heat treated by a heat gun for 90 seconds at a temperature exceeding 200°C and not exceeding 300°C.
  • the solution can be prepared in advance.
  • the activated glass slide is immersed in an electroless bath (that is to say an electroless bath) regulated at a temperature of 34°C.
  • an electroless bath that is to say an electroless bath
  • the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
  • the reducing agent is sodium hypophosphite (NaH 2 PO 2 ,H 2 O).
  • the activated glass slides are left for 10 minutes in order to have a complete and homogeneous metallization.
  • the thickness of the nickel film is typically 500 nm.
  • the Figure 1-e shows that a PAA film of residual thickness (less than 5 nm), thanks to its perfectly conforming character, makes it possible to obtain a metallic layer of high optical quality of the “mirror polish” type. Furthermore, an adhesive tape test was carried out and no detachment was observed.
  • a solution of PAA (Mn 130,000) at a concentration of 50 mg in 10 ml of ethanol is prepared by dissolution.
  • a glass slide of the microscopy object slide type (7.5 x 2.5 cm) is degreased (washing with a surfactant then an alcohol rinse) then dried (by a blower of dry nitrogen gas then by passage through oven at 100°C for 15 min).
  • the PAA solution is applied with a stencil (masking) and a sprayer.
  • the pattern of the adhesive stencil here is water drops. ( Figure 2 ).
  • the adhesive stencil is removed after the PAA layer has dried.
  • the glass slides coated with PAA are then typically heated to 200° C. for 30 min in a simple oven at atmospheric pressure and without any particular precautions.
  • the solution can be prepared in advance.
  • the activated glass slide is immersed in the electroless bath regulated at a temperature of 34°C.
  • the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
  • the reducing agent is sodium hypophosphite (NaH 2 PO 2 ,H 2 O).
  • the activated glass slides are left for 10 minutes in order to have a complete and homogeneous metallization.
  • the thickness of the nickel film is typically 500 nm.
  • the Figure 2 shows that only the areas initially coated with PAA have been metallized.
  • a solution of PAA (typically Mn 130,000) with a concentration of typically 50 mg in 10 ml of ethanol is prepared by dissolution.
  • the flexible PVC plate (format and manufacture for credit card) is degreased (typically washing with a surfactant then typically an alcohol rinse) then dried (typically by a blower of dry nitrogen gas).
  • the application of the PAA solution is typically made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a covering and homogeneous PAA film with a thickness of typically 50 at 70nm.
  • the deposition of PAA will then occur on both sides of the PVC plate ( Figure 3 ).
  • the PVC plates are typically exposed by VUV (Vacuum Ultraviolet) radiation for 2 minutes at a distance of 15 cm in an atmosphere purged of air by sweeping with dry nitrogen.
  • VUV Vauum Ultraviolet
  • the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm.
  • the solution can be prepared in advance.
  • the PVC plates are placed at room temperature for 10 min in the activation solution. A DI water rinse is done.
  • the activated PVC plate is immersed in the electroless bath regulated at a temperature of 34°C.
  • the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
  • the reducing agent is sodium hypophosphite (NaH 2 PO 2 ,H 2 O).
  • the activated PVC is left for 10 minutes in order to have a complete and homogeneous metallization.
  • the thickness of the nickel film is typically 500 nm.
  • a 10-minute argon plasma treatment allows the surface of the PTFE support to be homogeneously wetted by the PAA solution and thus to deposit a PAA film of uniform thickness. On the side not exposed to the plasma, the wettability was not sufficient to coat the PTFE with the PAA film.
  • the application of the PAA solution is typically made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a covering and homogeneous PAA film with a thickness of typically 50 at 70nm.
  • the PAA-coated PTFE supports are then typically heated to 200° C. for 30 min in a simple oven at atmospheric pressure and without any particular precautions.
  • the PAA is in the form of anhydride functions. Immersion for 10 minutes in water makes it possible to hydrolyse the anhydride functions and to restore the chemical form of the PAA.
  • the solution can be prepared in advance.
  • the PTFE supports are placed at ambient temperature for 10 min in the activation solution. A DI water rinse is done.
  • the activated PTFE support is immersed in the electroless bath regulated at a temperature of 34°C.
  • the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
  • the reducing agent is sodium hypophosphite (NaH 2 PO 2 ,H 2 O).
  • the activated PTFE is left for 10 minutes in order to have a complete and homogeneous metallization.
  • the thickness of the nickel film is typically 500 nm.
  • PTFE supports that have not been ( Figure 3-c ) or poorly covered with a layer of PAA ( Figure 3-d ) are immersed in the palladium acetate-based activator solution described above.
  • the Pd 2+ ions and/or the PAA coating cannot be adsorbed on the substrate and allow the development of the metallization process.
  • the Figure 3-e shows the metallized zone (activation and metallization) corresponding to the presence of the PAA coating.
  • the flexible PVC plate (format and manufacture for credit card) is degreased (washing with a surfactant then typically an alcohol rinse) then dried (typically by a blower of dry nitrogen gas).
  • the localization of the deposit of the PAA solution is carried out in this example using a writing nib previously dipped in the PAA solution ( Figure 4 ).
  • the PVC plates are typically exposed by VUV radiation for 2 minutes at a distance of 15 cm in an atmosphere purged of air by sweeping with dry nitrogen.
  • the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm.
  • the solution can be prepared in advance.
  • the PVC plates are placed at room temperature for 10 min in the activation solution. A DI water rinse is done.
  • the activated PVC plate is immersed in the electroless bath regulated at a temperature of 34°C.
  • the bath is typically a NipositTM PM 988 commercial bath. Its pH is 9.4.
  • the reducing agent is sodium hypophosphite (NaH 2 PO 2 ,H 2 O).
  • the activated PVC is left for 10 minutes in order to have a complete and homogeneous metallization.
  • the thickness of the nickel film is typically 500 nm.
  • the Figure 4 shows that a localized metallization of the PVC has been obtained: the metallized parts have been obtained by using the PAA solution as an ink. The pattern was made with a writing quill.
  • Example 2-a/ Thermal immobilization of PAA on polyimide.
  • a solution of PAA (Mn 130,000) with a concentration of 100 mg in 10 ml of ethanol is prepared by dissolution.
  • a flexible sheet of 50 ⁇ m of polyimide (PI) is degreased (washing with a surfactant then an alcohol rinse) then dried (by a blower of dry nitrogen gas then by passage in an oven at 100°C for 15 min ).
  • the application of the PAA solution is typically made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a covering and homogeneous PAA film with a thickness typically of 150 to 250 nm. PAA deposition will then occur on both sides of the polyimide sheet.
  • the flexible sheets of polyimide coated with PAA are then typically heated to 200° C. for 30 min in a simple oven at atmospheric pressure and without any particular precautions.
  • the PAA is in the form of anhydride functions which can be used to couple with other complementary functions of materials of interest.
  • the Figure 5 shows that the peaks linked to the presence of a 200 nm PAA film on the PI persist after washing for 120 h in water.
  • Example 2-b/ Immobilization by VUV exposure of a film of PAA on a flexible sheet of polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • a solution of PAA (typically Mn 130,000) with a concentration of typically 50 mg in 10 ml of ethanol is prepared by dissolution.
  • a flexible sheet of 50 ⁇ m of polyethylene terephthalate (PET) is degreased (typically washing with a surfactant then typically an alcohol rinse) then dried (typically using a blower of dry nitrogen gas).
  • PET polyethylene terephthalate
  • the application of the PAA solution is typically made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a covering and homogeneous PAA film with a thickness typically of 50 to 70 nm. PAA deposition will then occur on both sides of the PET sheet ( Figure 6 ).
  • the flexible sheets of PET coated with the PAA are then typically irradiated by VUV (Vacuum Ultraviolet) radiation for 2 minutes at a distance of 15 cm in an atmosphere purged of air by sweeping with dry nitrogen.
  • VUV Vauum Ultraviolet
  • the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm.
  • Example 2-c/ Immobilization by VUV exposure of a film of PAA on a flexible sheet of polyethylene (PE).
  • a solution of PAA (Mn 130,000) at a concentration of 50 mg in 10 ml of ethanol is prepared by dissolution.
  • a 50 ⁇ m flexible sheet of polyethylene (PE) is degreased (washing with a surfactant then an alcohol rinse) then dried (using a blower of dry nitrogen gas).
  • the application of the PAA solution is made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a covering and homogeneous PAA film with a thickness of typically 50 at 70nm. PAA deposition will then occur on both sides of the PE sheet. ( Picture 7 ).
  • An oxidative pre-treatment of the surface by UV-ozone, or oxygen plasma can be done before its coating to improve the wetting of the PAA solution.
  • VUV Vauum Ultraviolet
  • the flexible sheets of PE coated with the PAA are then irradiated by VUV (Vacuum Ultraviolet) radiation for 2 minutes at a distance of 15 cm in an atmosphere purged of air by flushing with dry nitrogen.
  • the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm.
  • Example 3 Immobilization and structuring by VUV insolation of a thin film of PAA on Gold.
  • This example demonstrates the possibility of immobilizing and structuring a PAA thin film on any surface at sub-millimeter scales by photolithographic methods.
  • a solution of PAA (Mn 130,000) with a concentration of 100 mg in 10 ml of ethanol is prepared by dissolution.
  • a gold surface (golden glass slide) is cleaned by UV-ozone treatment for 5 minutes to remove superficial organic contaminants.
  • the application of the PAA solution is made by soaking-removal (immersion-emersion) in order to obtain after evaporation of the ethanol a homogeneous and covering PAA film with a thickness of typically 150 to 250 nm.
  • a mask is deposited by direct contact on the gold surface coated with the PAA, then the assembly is irradiated by VUV (Vacuum Ultraviolet) radiation for 15 minutes at a distance of 7 cm in an atmosphere purged of air by scanning at dry nitrogen.
  • VUV Vauum Ultraviolet
  • the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm.
  • the mask After irradiation, the mask is removed and the sample is washed thoroughly with water.
  • the PAA film which has not undergone irradiation is eliminated by washing with water, whereas the irradiated film resists this washing.
  • the experience is illustrated by the figure (8 ).
  • the photographic image (top) of the gold surface is seen after VUV irradiation and effective removal by water washing of unirradiated PAA.
  • the white lines of the optical image correspond to the drying beads. Inside the white lines, the PAA film is grafted by insolation and resists abundant rinsing with water. Outside the white lines, the PAA film was removed by the copious rinsing with water.
  • the black line represents the line measured by profilometry (bottom left) and shows that the difference in thickness between the irradiated zone and the non-irradiated zone is of the order of 200 nm, i.e. of the same order of magnitude as the initial thickness of the PAA film on the gold substrate.
  • Example 4 Structural bonding via anhydride groups. (Heat treatment)
  • Example 4-a Bonding of an epoxy resin on a stainless steel surface.
  • a solution of PAA (Mn 130,000) at a concentration of 50 mg in 10 ml of ethanol is prepared by dissolution.
  • a stainless steel blade mechanically polished to a roughness of 1 ⁇ m is degreased (typically washing with a surfactant then typically rinsing with alcohol) then dried (typically with a blower of dry nitrogen gas then by passage through oven at 100°C for 15 min).
  • the application of the PAA solution is typically made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a covering and homogeneous PAA film with a thickness typically of 70 to 100 nm.
  • the stainless steel surfaces coated with PAA are then typically heated to 200° C. for 30 min in a simple oven at atmospheric pressure and without any particular precautions.
  • the heating will allow the PAA to adhere to the stainless steel, to form reactive anhydride groups and to crosslink the film by decarboxylation.
  • the mixture is made and applied in a thin layer of 300 ⁇ m on the stainless steel (use of a silk-screen type stencil).
  • the bubbles are eliminated naturally in 5 minutes and a final drying at 100°C for 1 hour is done.
  • the epoxy film is applied to a virgin stainless steel surface (comparative substrate) and under the same conditions to a stainless steel surface with a PAA-anhydride coating.
  • a standardized adhesion test with ASTM D3359 tape is carried out (so-called “squares” test with a 6-blade grid comb).
  • a solution of PAA (typically Mn 130,000) with a concentration of typically 50 mg in 10 ml of ethanol is prepared by dissolution.
  • the flexible PVC plate (format and manufacture for credit card) is degreased (typically washing with a surfactant then typically an alcohol rinse) then dried (typically by a blower of dry nitrogen gas). At this stage, the PVC surface is very hydrophobic.
  • the application of the PAA solution is typically made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a covering and homogeneous PAA film with a thickness typically of 50 to 70 nm.
  • the PVC sheets are typically exposed by VUV (Vacuum Ultraviolet) radiation for 2 minutes at a distance of 15 cm in an atmosphere purged of air by sweeping with dry nitrogen.
  • VUV Vauum Ultraviolet
  • the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm.
  • the surface energy of the substrate is determined by measuring the contact angle.
  • the contact angle measurements were carried out with an Apollo Instrument brand device, controlled via the Sca 20 software.
  • Raw PVC is very hydrophobic when clean and has a contact angle close to 100°. Its surface energy is low. Once modified by a PAA-grafted film, the surface energy is increased and the measured contact angle is close to 30°.
  • Example 5-b/ A hydrophobic modified hydrophilic substrate (glass substrate covered with a layer of gold)
  • a solution of PAA (typically Mn 130,000) with a concentration of typically 50 mg in 10 ml of ethanol is prepared by dissolution.
  • a microscopy slide-type glass slide (7.5x2.5 cm) covered with a layer of gold (golden substrate) is directly treated with UV-Ozone for 5 min to eliminate traces of organic contamination. of atmospheric origin.
  • the application of the PAA solution is typically made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a covering and homogeneous PAA film with a thickness typically of 50 to 70 nm.
  • the glass slides coated with PAA are then typically heated to 200° C. for 30 min in a simple oven at atmospheric pressure and without any particular precautions.
  • the heating will allow the PAA to adhere to the golden substrate, to form reactive anhydride groups and to crosslink the film by decarboxylation.
  • a molecule comprising a hydrophobic part (C11 alkyl group) and a primary amine function is applied to the activated surface, in a pure form (undiluted) by placing a drop then spreading it by applying a strip of glass on it, or in a form diluted in a solvent, for example of the hexane or cyclohexane type, which does not interfere with the coupling reaction between the anhydrides and the amines ( Picture 11 ). ( See diagram below).
  • the contact angle of clean gold after UV-O3 treatment is between 20 and 30°.
  • This substrate coated with PAA has a contact angle typically between 30 and 50°. Then, when the C11 amine is grafted onto the PAA-coated substrate, this contact angle reaches 100°.
  • IR spectroscopy makes it possible to highlight the chemical reaction between the acid surface of the golden substrate covered with PAA and the amine by the presence of the amide bands ( Picture 11 ).
  • the methods of coating by spraying or by transfer are limited in quality of deposition by the step of application then evaporation of the solvent which are never perfectly homogeneous.
  • PAA is a polyelectrolyte which can be adsorbed by electrostatic interactions on certain surfaces. These interactions develop over a distance which is dependent on the nature of the polymer and the substrate and can therefore be variable. The balance of these different forces leads to the deposition of a thin layer of perfectly defined thickness after several successive rinsings. The thickness asymptotically obtained after the rinses is then governed by the surface.
  • a method of preparing these thin layers of conformal PAA consists in applying a coating of PAA with a thickness greater than the desired thickness without any particular precaution, then in eliminating by rinsing the polymer chains of PAA which do not physically interact with the surface.
  • a film of PAA is deposited by dipping-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a homogeneous and covering PAA film with a thickness of typically 50 to 70 nm.
  • the residual films obtained on gold converge asymptotically towards a constant thickness of 15 nm as shown by the IR intensities of the Picture 12 .
  • This residual thickness is controlled by polyelectrolytic interactions in relation to surface properties.
  • a final annealing at 200° C. for 30 minutes makes it possible to stabilize the film definitively and again to exploit either the anhydride or acid functions for chemical couplings.
  • Example 7 coupling of biological molecules on a PAA surface
  • Stable coupling of biological molecules to a surface is an important goal of many analytical and medical diagnostic methods.
  • the following example illustrates the possibility of chemically and covalently grafting proteins onto an activated adhesion primer itself covalently grafted onto a substrate.
  • activated surfaces are created and then these activated surfaces are used to carry out the actual coupling with the proteins.
  • the coupling of proteins is carried out in a conventional way for biologists by passing through the activated form of the acid called activated ester.
  • This activated ester reacts preferentially in a buffered medium with the amine groups of proteins to create stable amide bonds that are resistant to hydrolysis.
  • the figure 13 illustrates the formation of activated esters on the surface of the PAA film ( figure 13-a ) then the result of the coupling with the protein: appearance of a component bound to the protein ( figure 13-b ). Since the PAA film is not swollen by acetonitrile, the NHS and DCC reagents have not penetrated the PAA layer and only the surface carboxylic acid (COOH) groups are modified.
  • the PAA surface prepared according to the conditions described above is immersed in 2 ml of the protein solution. The whole is placed in an incubator at 37° C. with gentle stirring for 1 hour.
  • the Picture 14 illustrates the formation of anhydrides chemically in an aqueous medium, in the presence of NHS and EDC ( figure 14-a ), and the result of the coupling with the protein ( figure 14-b ). It was verified beforehand that the anhydride functions persisted after immersion of the activated support for 15 minutes in DI water at a pH equal to 6 ( figure 14-c ). Thus the disappearance of the anhydride functions after coupling with the protein is indeed the result of the reaction which has taken place between these functions and the protein.
  • Example 8 Thermal Immobilization of PAA on Carbon Felt for the Production of Industrial Heavy Metal Filter Elements (Cu, Zn, Ni, etc.) for the Treatment of Liquid Effluents.
  • a solution of PAA, Mn 130,000, typically at a concentration of 50 mg in 10 ml of ethanol is prepared by dissolution.
  • PEI Polyethylene imine
  • a first impregnation is made with an aqueous solution of polyethylene imine (PEI) at 5 mg/10 ml.
  • PEI polyethylene imine
  • the felt is filled using a Pasteur pipette until visual detection of complete impregnation.
  • the felt is left to dry.
  • the PEI coating (polymer with positive charges) reinforces the polyelectrolytic properties of the PAA (negatively charged) and leads to a better subsequent coating of the fibers by the PAA.
  • a second impregnation is carried out with a 50 mg/10 ml solution of PAA in ethanol until visual detection of complete impregnation.
  • the felt is left to dry.
  • Baking is carried out at 200° C. for 30 min.
  • the process allows for an encapsulation covering individual fibers of the carbon felt.
  • interference tints are detected on all of the fibers, whether on the surface of the felt or inside the felt.
  • the PAA is in the anhydride chemical form.
  • the dry residue after drying is 16 mg and represents an average thickness of PAA film coating the fibers of 70 nm.
  • 13 felts thus prepared (which represents 211 mg of PAA immobilized on the 13 felts) are placed in a column (100 ml plastic syringe), 2.4 l of a solution of 45 mg/l of Cu++ in water from the tap are filtered slowly on the column.
  • the copper concentration of the filtrate recovered is 100 ⁇ g/L, which demonstrates the effectiveness of the capture.
  • Example 9 Electroless metallization of woven Kevlar fibers with nickel and copper.
  • PAA polyacrylic acid
  • a solution of PAA (Mn 130,000) at a concentration of 50 mg in 10 ml of ethanol is prepared by dissolution.
  • the application of the PAA solution is made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous thickness from 50 to 70 nm. The deposition of PAA then occurs on all the fibres.
  • the fabric of Kevlar fibers coated with PAA is then typically heated to 200° C. for 30 min in a simple oven at atmospheric pressure and without any particular precautions.
  • a DI water rinse is performed.
  • the solution can be prepared in advance.
  • the fabric of activated fibers is immersed in an electroless bath (that is to say an electroless bath) regulated at a temperature of 34°C.
  • the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
  • the reducing agent is sodium hypophosphite (NaH2PO2, H2O).
  • the fabric of activated fibers is left for 10 minutes in order to have a complete and homogeneous metallization.
  • the thickness of the nickel film is typically 500 nm.
  • the reduction bath is set at 50°C and the reduction is carried out typically for 5 to 10 min. the fabric is rinsed with DI water.
  • a Kevlar fabric metallized with copper is obtained.
  • PAA polyacrylic acid
  • a solution of PAA (Mn 130,000) at a concentration of 50 mg in 10 ml of ethanol is prepared by dissolution.
  • the application of the PAA solution is made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous thickness of 50 to 70 nm. The deposition of PAA then occurs on the submerged plate fraction.
  • the carbon-epoxy composite plate coated with PAA is then typically heated to 200° C. for 30 min in a simple oven at atmospheric pressure and without any particular precautions.
  • a DI water rinse is performed.
  • the solution can be prepared in advance.
  • the carbon-epoxy composite plate is immersed in an electroless bath (that is to say an electroless bath) regulated at a temperature of 34°C.
  • the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
  • the reducing agent is sodium hypophosphite (NaH2PO2, H2O).
  • the carbon-epoxy composite plate is left for 10 minutes in order to have a complete and homogeneous metallization.
  • the thickness of the nickel film is typically 500 nm.
  • the lower part has been coated with grafted PAA, then metallized. The metallization was only done on the PAA treated part.
  • An electrical measurement with a conventional meter typically observes 30 ohms of resistance between the two electrodes 5 cm apart.
  • the metal coating is therefore conductive.
  • Example 11 Metallization of polymer substrates of the ABS type.
  • PAA polyacrylic acid
  • a solution of PAA (typically Mn 130,000) with a concentration of typically 50 mg in 10 ml of ethanol is prepared by dissolution.
  • ABS surfaces are mirror quality convex surfaces. These are blank ABS parts used in particular in sanitary facilities such as, for example, bathtub stoppers. The parts are prepared with simple degreasing with a surfactant and rinsing with water, then dried (typically by a blower of dry nitrogen gas).
  • the application of the PAA solution is typically made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a covering and homogeneous PAA film of thickness typically 50 to 70 nm.
  • the samples are typically exposed by VUV radiation for 2 minutes at a distance of 15 cm in an atmosphere purged of air by sweeping with dry nitrogen for 10 minutes.
  • the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm. These characteristics remain the same for the following examples.
  • Immobilization of PAA thin films is tested by washing with ethanol and water which are very good solvents for PAA. Film strength is observed on all substrates. Rinsing tests with alcohol or water before irradiation obviously show complete elimination of the PAA.
  • the solution can be prepared in advance.
  • the ABS substrate is immersed in an electroless bath (ie an electroless bath) regulated at a temperature of 34°C.
  • an electroless bath ie an electroless bath
  • the bath is typically a NipositTM PM 988 commercial bath. Its pH is 9.4.
  • the reducing agent is sodium hypophosphite (NaH2PO2, H2O).
  • ABS substrate is left for 10 minutes in order to have a complete and homogeneous metallization.
  • the thickness of the nickel film is typically 500 nm.
  • PAA polyacrylic acid
  • a solution of PAA (typically Mn 130,000) with a concentration of typically 50 mg in 10 ml of ethanol is prepared by dissolution.
  • COP cyclic Olefin Polymer surfaces by the company Zeon (Zeonex ® ) are prepared with simple degreasing with a surfactant and rinsing with water, then dried (typically using a blower of dry nitrogen gas).
  • the application of the PAA solution is typically made by dipping-removal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a covering and homogeneous PAA film of thickness typically from 50 to 70 nm.
  • the samples are typically exposed by VUV radiation for 2 minutes at a distance of 4 cm in an atmosphere purged of air by sweeping with dry nitrogen for 10 minutes.
  • Immobilization of PAA thin films is tested by washing with ethanol and water which are very good solvents for PAA. Film strength is observed on all substrates. Rinsing tests with alcohol or water before irradiation obviously show complete elimination of the PAA.
  • the solution can be prepared in advance.
  • the COP substrate is immersed in an electroless bath (ie an electroless bath) regulated at a temperature of 34°C.
  • the bath is typically a NipositTM PM 988 commercial bath. Its pH is 9.4.
  • the reducing agent is sodium hypophosphite (NaH2PO2, H2O).
  • the COP substrate is left for 10 minutes in order to have a complete and homogeneous metallization.
  • the thickness of the nickel film is typically 500 nm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Laminated Bodies (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP22167257.9A 2014-04-03 2015-04-03 Verfahren zur funktionalisierung von oberflächen Pending EP4043110A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1452978A FR3019477B1 (fr) 2014-04-03 2014-04-03 Procede de fonctionnalisation de surface
EP15721851.2A EP3126064B1 (de) 2014-04-03 2015-04-03 Oberflächenfunktionalisierungsverfahren
PCT/IB2015/052462 WO2015151070A2 (fr) 2014-04-03 2015-04-03 Procede de fonctionnalisation de surface

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP15721851.2A Division EP3126064B1 (de) 2014-04-03 2015-04-03 Oberflächenfunktionalisierungsverfahren

Publications (1)

Publication Number Publication Date
EP4043110A1 true EP4043110A1 (de) 2022-08-17

Family

ID=50780805

Family Applications (2)

Application Number Title Priority Date Filing Date
EP15721851.2A Active EP3126064B1 (de) 2014-04-03 2015-04-03 Oberflächenfunktionalisierungsverfahren
EP22167257.9A Pending EP4043110A1 (de) 2014-04-03 2015-04-03 Verfahren zur funktionalisierung von oberflächen

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP15721851.2A Active EP3126064B1 (de) 2014-04-03 2015-04-03 Oberflächenfunktionalisierungsverfahren

Country Status (4)

Country Link
US (1) US11014121B2 (de)
EP (2) EP3126064B1 (de)
FR (1) FR3019477B1 (de)
WO (1) WO2015151070A2 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6882689B2 (ja) * 2016-09-01 2021-06-02 Jsr株式会社 基材表面の選択的修飾方法及び組成物
FR3060025B1 (fr) 2016-12-09 2022-06-24 Commissariat Atomique Et Aux Energies Alternatives Procede de metallisation d'une surface d'un support solide
KR102165361B1 (ko) * 2019-01-08 2020-10-14 주식회사 아이엠기술 강건성이 요구되는 플라스틱 외형의 금속코팅방법
WO2022187954A1 (en) * 2021-03-10 2022-09-15 Nicoya Lifesciences, Inc. Surface plasmon resonance signal amplification

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998602A (en) * 1975-02-07 1976-12-21 Carl Horowitz Metal plating of polymeric substrates
US4160756A (en) * 1973-03-02 1979-07-10 Amchem Products, Inc. Use of metal compound in an autodeposition coating composition
GB2169925A (en) * 1985-01-16 1986-07-23 Canning W Materials Ltd Process for providing a metal coating on a polymer surface
WO1997004880A1 (en) * 1995-07-25 1997-02-13 Henkel Corporation Composition and process for autodeposition with modifying rinse of wet autodeposited coating film
WO1998044172A1 (fr) 1997-03-27 1998-10-08 Centre National De La Recherche Scientifique (C.N.R.S) Procede de realisation par voie electrochimique d'un materiau carbone dont la surface est modifiee par des groupes organiques, utilisation du materiau modifie
US6033492A (en) * 1995-07-25 2000-03-07 Henkel Corporation Composition and process for autodeposition with modifying rinse of wet autodeposited coating film
US6211283B1 (en) * 1996-02-21 2001-04-03 Henkel Corporation Electrically insulated metallic surfaces with interior corners and methods and compositions therefor
WO2006075796A1 (en) * 2005-01-13 2006-07-20 Fujifilm Corporation Metal film and formation method of metal film
WO2007048894A1 (fr) 2005-10-26 2007-05-03 Alchimer Procede de modification de surfaces isolantes ou semi- conductrices, et produits tels qu'obtenus
WO2009121944A2 (fr) 2008-04-03 2009-10-08 Commissariat A L'energie Atomique Procede pour assembler deux surfaces ou une surface avec une molecule d'interet
US20090269696A1 (en) * 2008-04-24 2009-10-29 Youichi Ohsawa Sulfonium salt-containing polymer, resist composition, and patterning process
EP2121814A2 (de) 2006-12-19 2009-11-25 Commissariat A L'energie Atomique Verfahren zur herstellung eines organischen films an der oberfläche eines festen substrats unter nicht-elektrochemischen bedingungen, auf diese weise hergestelltes festsubstrat und herstellungsset
WO2010125189A2 (fr) 2009-04-30 2010-11-04 Commissariat à l'énergie atomique et aux énergies alternatives Procédé de préparation d'un substrat métallisé, ledit substrat et ses utilisations
WO2012126943A1 (fr) 2011-03-22 2012-09-27 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede de preparation d'un film organique a la surface d'un support solide par transfert ou par projection
DE102011076148A1 (de) * 2011-05-19 2012-11-22 Bayer Materialscience Aktiengesellschaft Verfahren zum Beschichten von Kunststoffsubstraten mit Polyelektrolyten
WO2012172066A1 (fr) 2011-06-17 2012-12-20 Commissariat à l'énergie atomique et aux énergies alternatives Procédé pour fonctionnaliser une surface avec un objet ou une molécule d'intérêt

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900672A (en) * 1973-04-04 1975-08-19 Hoya Lens Co Ltd Process for coating an optical material and the resulting product
US4186226A (en) * 1978-06-21 1980-01-29 Union Carbide Corporation Autodeposited coatings with increased surface slip
US6224947B1 (en) * 1983-07-25 2001-05-01 Henkel Corporation Process for forming a resinous coating from an autodepositing composition which includes internally stabilized vinylidene chloride copolymer
US4800106A (en) * 1987-06-19 1989-01-24 Amchem Products, Inc. Gloss enhancement of autodeposited coatings
WO1992019092A1 (de) * 1991-04-22 1992-10-29 Atotech Deutschland Gmbh Verfahren zur selektiven beschichtung von nichtleitern mit kohlenstoff-partikeln und die verwendung von kupferhaltigen lösungen im verfahren
DE10047719A1 (de) * 2000-09-27 2002-04-11 Basf Ag Hydrophile, offenzellige, elastische Schaumstoffe auf Basis von Melamin/Formaldehyd-Harzen, ihre Herstellung und ihre Verwendung in Hygieneartikeln
WO2005014894A1 (en) * 2003-08-06 2005-02-17 Decoma International Inc. Protective coating for automotive trim pieces and method of making the same
US7399793B2 (en) * 2003-10-31 2008-07-15 Basf Corporation Coating composition curable with ultraviolet radiation
US20050221141A1 (en) * 2004-03-15 2005-10-06 Hampden-Smith Mark J Modified carbon products, their use in proton exchange membranes and similar devices and methods relating to the same
JP4544913B2 (ja) * 2004-03-24 2010-09-15 富士フイルム株式会社 表面グラフト形成方法、導電性膜の形成方法、金属パターン形成方法、多層配線板の形成方法、表面グラフト材料、及び導電性材料
JP2007131875A (ja) 2005-11-08 2007-05-31 Fujifilm Corp 金属膜形成方法及び金属パターン形成方法
BR112012018293A2 (pt) * 2010-01-22 2018-06-05 Asahi Glass Company, Limited processo para produção de substrato de resina tendo camada de revestimento duto, e substrato de resina tendo camada de revestimento duro
JP2011152747A (ja) * 2010-01-28 2011-08-11 Seiko Epson Corp 水性インク組成物、およびインクジェット記録方法ならびに記録物
US8574356B2 (en) * 2010-05-14 2013-11-05 Seiko Epson Corporation Ink composition and recording method
FR2983773B1 (fr) * 2011-12-09 2014-10-24 Arkema France Procede de preparation de surfaces

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4160756A (en) * 1973-03-02 1979-07-10 Amchem Products, Inc. Use of metal compound in an autodeposition coating composition
US3998602A (en) * 1975-02-07 1976-12-21 Carl Horowitz Metal plating of polymeric substrates
GB2169925A (en) * 1985-01-16 1986-07-23 Canning W Materials Ltd Process for providing a metal coating on a polymer surface
WO1997004880A1 (en) * 1995-07-25 1997-02-13 Henkel Corporation Composition and process for autodeposition with modifying rinse of wet autodeposited coating film
US6033492A (en) * 1995-07-25 2000-03-07 Henkel Corporation Composition and process for autodeposition with modifying rinse of wet autodeposited coating film
US6211283B1 (en) * 1996-02-21 2001-04-03 Henkel Corporation Electrically insulated metallic surfaces with interior corners and methods and compositions therefor
WO1998044172A1 (fr) 1997-03-27 1998-10-08 Centre National De La Recherche Scientifique (C.N.R.S) Procede de realisation par voie electrochimique d'un materiau carbone dont la surface est modifiee par des groupes organiques, utilisation du materiau modifie
WO2006075796A1 (en) * 2005-01-13 2006-07-20 Fujifilm Corporation Metal film and formation method of metal film
WO2007048894A1 (fr) 2005-10-26 2007-05-03 Alchimer Procede de modification de surfaces isolantes ou semi- conductrices, et produits tels qu'obtenus
EP2121814A2 (de) 2006-12-19 2009-11-25 Commissariat A L'energie Atomique Verfahren zur herstellung eines organischen films an der oberfläche eines festen substrats unter nicht-elektrochemischen bedingungen, auf diese weise hergestelltes festsubstrat und herstellungsset
WO2009121944A2 (fr) 2008-04-03 2009-10-08 Commissariat A L'energie Atomique Procede pour assembler deux surfaces ou une surface avec une molecule d'interet
US20090269696A1 (en) * 2008-04-24 2009-10-29 Youichi Ohsawa Sulfonium salt-containing polymer, resist composition, and patterning process
WO2010125189A2 (fr) 2009-04-30 2010-11-04 Commissariat à l'énergie atomique et aux énergies alternatives Procédé de préparation d'un substrat métallisé, ledit substrat et ses utilisations
WO2012126943A1 (fr) 2011-03-22 2012-09-27 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede de preparation d'un film organique a la surface d'un support solide par transfert ou par projection
DE102011076148A1 (de) * 2011-05-19 2012-11-22 Bayer Materialscience Aktiengesellschaft Verfahren zum Beschichten von Kunststoffsubstraten mit Polyelektrolyten
WO2012172066A1 (fr) 2011-06-17 2012-12-20 Commissariat à l'énergie atomique et aux énergies alternatives Procédé pour fonctionnaliser une surface avec un objet ou une molécule d'intérêt

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHEM. REV., vol. 105, no. 4, 2005, pages 1103 - 1170
CHEMPHYSCHEM, vol. 5, 2004, pages 1469 - 1481
GREG T HERMANSON: "Bioconjugate Techniques", 2008, ELSEVIER
MÉVELLEC ET AL., CHEM. MATER., vol. 19, 2007, pages 6323 - 6330
U. LOHBAUER, MATERIALS, vol. 3, 2010, pages 76 - 96

Also Published As

Publication number Publication date
EP3126064B1 (de) 2022-05-04
WO2015151070A3 (fr) 2015-11-26
FR3019477B1 (fr) 2023-03-17
WO2015151070A2 (fr) 2015-10-08
EP3126064A2 (de) 2017-02-08
US11014121B2 (en) 2021-05-25
US20170113249A1 (en) 2017-04-27
FR3019477A1 (fr) 2015-10-09

Similar Documents

Publication Publication Date Title
EP3126064B1 (de) Oberflächenfunktionalisierungsverfahren
Huang et al. Environmentally durable superhydrophobic surfaces with robust photocatalytic self-cleaning and self-healing properties prepared via versatile film deposition methods
EP2285923B1 (de) Verfahren zum verbinden von zwei oberflächen oder einer oberfläche mit einem teilgenommenen molekül
KR101411769B1 (ko) 초친수성 코팅 조성물 및 그의 제조방법
EP2121814B1 (de) Verfahren zur herstellung eines organischen films an der oberfläche eines festen substrats unter nicht-elektrochemischen bedingungen, auf diese weise hergestelltes festsubstrat und herstellungsset
EP2326747B1 (de) Nichtelektrolytisches inline-verfahren zur metallisierung eines substrats mit vorbehandlung der oberfläche und vorrichtung zur durchführung des verfahrens
EP2425039A2 (de) Verfahren zur herstellung eines metallisierten substrats, resultierendes substrat und verwendungen davon
EP2688963B1 (de) Verfahren zur herstellung eines organischen films auf der oberfläche eines festen trägers durch transfer oder durch sprühen
Chen et al. Formation of reflective and conductive silver film on ABS surface via covalent grafting and solution spray
EP2561117B1 (de) Verfahren zur beschichtung einer oberfläche eines substrats aus einem metallfreien material mit einer metallschicht
EP0708847B1 (de) Verfahren zur metallisierung von nichtleitenden substraten
KR101220652B1 (ko) 전처리를 포함하는 자기 조립 분자막 형성에 의한 금속표면처리방법
FR2910007A1 (fr) Procede de preparation d'un film organique a la surface d'un support solide dans des conditions non-electrochimiques, support solide ainsi obtenu et kit de preparation
WO2017060656A9 (fr) Procede de greffage de film mince polymerique sur substrat et procede de metallisation de ce film mince
EP2236524B1 (de) Haftpromoter mit Polymer das eine fotoreaktive funktionelle Gruppe beinhaltet
Tuong et al. Chemical fixation of polyelectrolyte multilayers on polymer substrates
Jeong et al. Gold Nanoparticle‐Hybridized “Nano‐Sponge” Polymer Coatings to Enhance the Reliability and Sensitivity of Biosensors
Phasuksom et al. Electroless copper deposition on PET sheets
WO2018104685A1 (fr) Procede de metallisation d'une surface d'un support solide
WO2018031043A1 (en) Surface-modified polymers
WO2018031046A1 (en) Surface-modified polymers
FR2910009A1 (fr) Procede de preparation d'un film organique a la surface d'un support solide dans des conditions non-electrochimiques, su pport solide ainsi obtenu et kit de preparation
FR2910008A1 (fr) Procede de preparation d'un film organique a la surface d'un support solide dans des conditions non-electrochimiques, support solide ainsi obtenu et kit de preparation

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

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

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AC Divisional application: reference to earlier application

Ref document number: 3126064

Country of ref document: EP

Kind code of ref document: P

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20230216

RBV Designated contracting states (corrected)

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

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS