EP2510133B1 - Method for preparing a metallized polymer substrate - Google Patents

Method for preparing a metallized polymer substrate Download PDF

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Publication number
EP2510133B1
EP2510133B1 EP10787795.3A EP10787795A EP2510133B1 EP 2510133 B1 EP2510133 B1 EP 2510133B1 EP 10787795 A EP10787795 A EP 10787795A EP 2510133 B1 EP2510133 B1 EP 2510133B1
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EP
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Prior art keywords
treatment
substrate
group
precursor
poly
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EP10787795.3A
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German (de)
French (fr)
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EP2510133A1 (en
Inventor
Alexandre Garcia
Thomas Berthelot
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
    • 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

Definitions

  • the invention belongs to the technical field of surface coatings and, more particularly, to the technical field of metallization of surfaces.
  • the present invention relates to a simplified metallization process using polymer substrates.
  • the metallization consists in coating the surface of a part with a thin layer of metal.
  • the metallization of a plastic part is particularly used in areas such as automobiles and boats where some accessories (co) polymer are coated with chromium; the electronics industry, household appliances and lighting fixtures; cosmetics and fashion accessories; optics and watchmaking; etc. There is therefore a great interest in the development of a metallization process of a plastic surface and, more generally, polymers.
  • the metallization of polymers is a process developed for more than fifty years. She involves alternative techniques to those used for conductive substrates.
  • the metallization of the polymers is generally carried out in 3 steps.
  • the 1st step is a surface modification step which provides, firstly, a surface roughness in order to improve the adhesion of the metal layer by mechanical anchoring.
  • This modification also makes it possible to increase the wettability of the polymer surface, in particular by adding hydrophilic groups generally incorporating oxygen or nitrogen in order to facilitate activation of the surface. Indeed, it is necessary that the polymer has groups promoting the adsorption of the activating metal agent.
  • the metal agent is palladium, chemisorption thereof is only possible on nitrogen elements [1].
  • the pretreatment roughness and CO and / or CN bonding to the surface of the polymer to be metallized are mandatory.
  • the 2 nd step is a surface activation step of depositing metal particles on the surface of the modified polymer. These particles subsequently play the role of catalyst for the metallization. Thus, it is necessary to maintain on the surface of the polymer metal cations which will subsequently be reduced.
  • the last step uses a metallization bath in which the activated polymers are immersed. In this bath, metal growth is catalyzed by the metal particles deposited in the previous step.
  • the metallization bath is a stable solution containing at least one metal cation and its complexing agent, a reducing agent and a stabilizer, generally in an alkaline medium.
  • Processes used in particular at the industrial level consisting of oxidizing the surface to be metallized and then adsorbing palladium on the latter via the tin / palladium colloid, which corresponds to the activation step.
  • an acceleration step is implemented, to remove the tin and thus promote the activity of the precursor of the metal layer which is, in this case, palladium. Traces of tin can, in fact, induce metal growth in unwanted places.
  • the acceleration step is followed by a step in the presence of a metallization bath as defined above.
  • the present invention makes it possible to meet this expectation and to solve the technical problems of metallization processes of the state of the art.
  • the work of the inventors has made it possible to develop a metallization process in which several steps of the conventional metallization processes of the polymers are eliminated since the process of the invention consists in depositing and maintaining metal cations on the surface of the metal. a polymer at the same time as its surface oxidation.
  • metal-material coating means a substrate coated on the surface with a thin layer, typically from a few nanometers to several microns, of a metal and / or a metal oxide. This thin layer may cover all or part of the surface of the substrate.
  • the thus coated substrate may be called a "metallized substrate”.
  • the metallized substrates it is possible to distinguish the substrates metallized only by a metal or only by a metal oxide, substrates metallized by the two types of metal entities.
  • the substrate according to the present invention can have any size and shape. Indeed, the size of the substrate used in the context of the present invention may be nanometric, micrometric, millimetric or metric. Thus, the present invention applies, as non-limiting examples, to a substrate that can be chosen from the group consisting of a nanoparticle, a microparticle, a button, a cosmetic product cap, an electronic element, a handle door, an electrical appliance, glasses, a decorative object such as a luminaire, a bodywork element, etc.
  • surface of a substrate (co) polymer means not only a substrate (co) polymer but also a substrate of which only the surface is in (co) polymer, the rest of the substrate can be in any material .
  • (co) polymer is meant in the context of the present invention a substrate or a surface consisting essentially of a single (co) polymer or several (co) polymers.
  • essentially constituted is meant in the context of the present invention a substrate or a surface of which at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least less 95% and / or at least 98% of the constituents expressed by weight are one (or more) (co) polymer (s).
  • the substrate or the surface of the substrate consists solely of one (or more) (co) polymer (s).
  • the substrate or substrate surface comprises, in addition to one (or more) (co) polymer (s), at least one member selected from the group consisting of fillers, plasticizers and additives.
  • This (or these) element (s) additional (s) is (are) advantageously incorporated (s) and / or dispersed (s) in the polymeric material.
  • a plastic or plastic material is formed (e) of at least one (co) polymer advantageously having a degree of polymerization greater than 3000 and at least one additive. Therefore, the substrate or surface of the polymer substrate used in the context of the present invention comprises substrates or substrate surfaces of plastic or plastic.
  • Mineral fillers such as silica, talc, glass or organic fibers or beads such as cereal flour or cellulose pulp are generally used to reduce the cost and improve certain properties such as the mechanical properties of the polymeric material.
  • the additives are mainly used to improve a specific property of the polymer material, said property possibly being crosslinking, slipping, resistance to degradation, fire and / or bacterial and fungal attacks.
  • Any natural, artificial, synthetic, thermoplastic, thermosetting, thermostable, elastomeric, linear (i.e. one-dimensional, linear or branched) and / or three-dimensional polymer is usable within the scope of the present invention.
  • natural polymers mention may be made of sugars.
  • the (co) polymer used in the context of the present invention is a thermosetting (co) polymer selected from the group consisting of an aminoplast such as urea-formaldehyde, melanin-formaldehyde, melanin-formaldehyde / polyesters, one of their copolymers, blends and combinations thereof; polyurethane; unsaturated polyester; a polysiloxane; a resin formophenolic, epoxy, allylic or vinylester; an alkyd; polyurea; a polyisocyanurate; a poly (bismaleimide); a polybenzimidazole; polydicyclopentadiene; one of their copolymers, one of their mixtures and one of their combinations.
  • an aminoplast such as urea-formaldehyde, melanin-formaldehyde, melanin-formaldehyde / polyesters, one of their copolymers, blends and combinations thereof
  • polyurethane unsatur
  • ABS acrylonitrile butadiene styrene
  • ABS / PC acrylonitrile butadiene styrene / polycarbonate
  • PA polyamide
  • PET polyethylene terephthalate
  • the substrate to be metallized Prior to step (a) of the process according to the invention, the substrate to be metallized has no precursor of the metallic material adsorbed on the surface.
  • oxidizing treatment is meant in the context of the present invention a treatment for oxidizing the surface of the substrate used.
  • Such an oxidative treatment is also susceptible to increase the hydrophilicity of the surface of the substrate used.
  • This treatment relies on the use of various reagents to create on the surface of the (co) polymer constituting the surface of the substrate and / or the substrate, a surface oxidation allowing a better grip and / or a better maintenance on the surface of the substrate precursor of a metallic material present during the oxidizing treatment.
  • This attachment and / or this maintenance implements a chelation (or complexation) between the precursor of a metallic material and groups present on the oxidized surface. All or part of the precursor of the metallic material remains in particular on the surface of the (co) polymer and can be reduced thereafter.
  • step (a) of the process according to the present invention is carried out at a temperature below 60 ° C., in particular between 5 ° C. and 50 ° C. and, in particular, between 10 ° C. and 40 ° C. vs.
  • Step (a) according to the invention is carried out, in a particular embodiment, at room temperature.
  • ambient temperature is meant a temperature of 20 ° C ⁇ 5 ° C.
  • the oxidizing treatment used during step (a) is based on the chemical reaction of Fenton (1894). This oxidizing treatment can therefore be designated oxidative treatment by Fenton-type chemical reaction.
  • the chemical reaction of Fenton consists of an acidic oxidation of hydrogen peroxide by ferrous ions represented by the following reaction scheme: Fe 2+ + H 2 O 2 ⁇ Fe 3+ + ⁇ OH + OH -
  • the generalized Fenton chemical reaction applied to the oxidizing treatment of step (a) of the process of the present invention comprises contacting said surface of the substrate with a solution containing at least one precursor of the metallic material and a compound of formula ROOR wherein R represents a hydrogen, an alkyl group comprising from 1 to 15 carbon atoms, an acyl group -COR 'with R' representing an alkyl group comprising from 1 to 15 carbon atoms or an aroyl group -COAr with Ar representing a aromatic group comprising from 6 to 15 carbon atoms.
  • R represents a hydrogen, an alkyl group comprising from 1 to 15 carbon atoms, an acyl group -COR 'with R' representing an alkyl group comprising from 1 to 15 carbon atoms or an aroyl group -COAr with Ar representing a aromatic group comprising from 6 to 15 carbon atoms.
  • alkyl group comprising 1 to 15 carbon atoms is meant an optionally substituted linear, branched or cyclic alkyl group comprising from 1 to 15 carbon atoms, especially from 1 to 10 carbon atoms, and in particular , from 2 to 6 carbon atoms and optionally a heteroatom such as N, O, F, Cl, P, Si, Br or S.
  • aromatic group comprising from 6 to 15 carbon atoms
  • aromatic or heteroaromatic group consisting of one or more aromatic rings or heteroaromatic atoms each containing from 3 to 10 atoms, the heteroatom (s) possibly being N, O, P or S.
  • substituted is meant, in the context of the present invention, an alkyl or aromatic group, mono- or poly-substituted, with a linear or branched alkyl group comprising from 1 to 4 carbon atoms, by a group amine, with a carboxylic group and / or with a nitro group.
  • OR radicals with R as defined above are obtained by cleavage of the ROOR peroxide by the precursor of the metallic material.
  • the reaction in step (a) of the process of the present invention can be represented by the following reaction scheme: Z n + + ROOR ⁇ Z (n + 1) + + .
  • the integer n is advantageously chosen from the group consisting of 1, 2, 3, 4 and 5.
  • the precursor (s) of the metallic material used during step (a) of the process according to the invention plays (s) a role of catalyst (s) for the metal growth and therefore the metallization of the surface of the substrate.
  • the precursor (s) of the metallic material is (are) advantageously one (or more) metal cation (s), in particular chosen from the noble metals of group IB or group VIII. More particularly, the precursor (s) of the metallic material is (are) chosen from the group formed by the ions of copper, silver, gold, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum.
  • the precursors of the metallic material are present in the solution comprising at least one precursor of the metallic material and a compound of formula ROOR at a concentration of between 0.05 and 5 M, in particular between 0.1 and 3 M and, in particular, between 0.5 and 2.5 M.
  • the solution comprising at least one precursor of the metallic material and a compound of formula ROOR additionally comprises counterions such as tetrafluoroborate, sulphate, bromide, fluoride, iodide, nitrate, phosphate or chloride. .
  • the compound of formula ROOR is present in the solution comprising at least one precursor of the metallic material and. a compound of formula ROOR at a concentration of between 5 ⁇ 10 -4 M and 5 M, especially between 0.1 and 3 M and in particular between 0.5 and 2.5 M.
  • the solution comprising at least one precursor of the metallic material and a compound of formula ROOR is advantageously an acidic solution.
  • acid solution is meant a solution whose pH is less than 7, especially between 2 and 4 and, in particular, of the order of 3 (i.e. 3 ⁇ 0.5).
  • This solution also comprises sulfuric acid and in particular at a concentration of between 0.05 and 50 mM, in particular between 0.1 and 10 mM and, more particularly, of the order of 1 mM (ie 1 ⁇ 0.25 mM).
  • the duration of the Fenton-type chemical reaction treatment may be variable. As examples non-limiting, this duration is advantageously between 5 min and 5 h, in particular between 10 min and 3 h, in particular between 15 min and 2 h and, more particularly, of the order of 25 min (ie 25 ⁇ 5 min ).
  • the precursors of the metallic material are only provided by the solution used during the Fenton reaction i.e. the solution implemented during step (a) of the process of the invention.
  • the Fenton reaction is used to oxidize the surface of the substrate to be metallized but also to adsorb the metal cations acting thereafter as precursors of the metal layer deposited by Electroless.
  • Step (b) of the process according to the present invention is a step well known to those skilled in the field of metallization of materials since it consists in transforming the precursor of the metallic material into said metallic material.
  • step (b 1 ) of the process according to the present invention Any technique for reducing the precursor of the metallic material can be used in the context of step (b 1 ) of the process according to the present invention.
  • this reduction step is a chemical reduction in a single step.
  • This preferred variant consists in bringing into contact the surface of the substrate on which the precursor (s) of the metallic material is (are) with a reducing solution S R.
  • the reducing solution S R is basic.
  • the reducing solution S R comprises a reducing agent, in particular chosen from the group consisting of sodium borohydride (NaBH 4 ), dimethylamine borane (DMAB-H (CH 3 ) 2 NBH 3 ) and hydrazine (N 2 H 4 ) .
  • the pH of the reducing solution S R is neutral or basic, whereas for DMAB the pH of the solution S R is basic.
  • a solvent advantageously used is NaOH and in particular at a concentration between 10 -4 M and 5 M, especially between 0.05 and 1 M and, in particular, of the order of 0.1 M (ie 0.1 M ⁇ 0.01 M).
  • the reducing agent is present in the reducing solution S R at a concentration of between 10 -4 and 5 M, in particular between 0.01 and 1 M and, in particular, of the order of 0.3 M (ie 0, 3 M ⁇ 0.05 M).
  • the reduction step (b 1 ) can be carried out at a temperature between 20 ° C and 100 ° C, in particular between 30 ° C and 70 ° C and, in particular, of the order of 50 ° C (ie 50 ° C ⁇ 5 ° C).
  • the reduction step (b 1 ) can last between 30 sec and 1 h, in particular between 1 and 30 min and, in particular, between 2 and 20 min.
  • the precursors of the metallic material reduced following step (b 1 ) of the process according to the invention mainly have an oxidation degree of 0.
  • the metallization can then take place by immersion in a metallization bath and growth on the precursor particles at an oxidation degree of 0.
  • this reduction step may be optional. Indeed, in some cases, the precursor of the metallic material can be reduced during contacting with the solution containing at least one ion of the metallic material during step (b 2 ) without a prior reduction step be necessary. Indeed, if the precursor of the metallic material has a higher oxidation-reduction potential than the metal deposited by Electroless, the precursor of the metallic material can be, initially, reduced upon contact with the ion of the metallic material before the metal growth is initiated.
  • Step (b 2 ) therefore consists in bringing said reduced precursor into contact following step (b 1 ) in a solution containing at least one ion of the metallic material.
  • the solution containing an ion of the metal material hereinafter designated S M corresponds to a metallization bath well known to those skilled in the art, just like its components.
  • the solution containing at least one ion of the metallic material S M implemented in step (b 2 ) comprises ions of the metallic material, a complexing agent for the ions of the metallic material, a reducing agent and a pH regulator.
  • said solution S M is an aqueous solution.
  • several metallization solutions are commercially available.
  • the ion (s) of the metallic material used in the context of the present invention may be any ion of a metallic material.
  • the present invention relates more particularly to the ions of a transition metal.
  • the ion (s) of the metallic material according to the invention is (are) chosen from the group consisting of Ag + , Ag 2+ , Ag 3+ , Au + , Au 3+ , Co 2+ , Cu + , Cu 2+ , Fe 2+ , Ni 2+ , Pd + , and Pt + .
  • the ion (s) of the metallic material is (are) associated with a counter-ion anionic.
  • anionic counterions that may be used, mention may be made of a chloride, a bromide, a fluoride, an iodide, a sulphate, a nitrate, a phosphate, an acetate and any organic or inorganic acid salt.
  • the complexing agent ions of the metallic material is necessary to compensate for the loss of solubility of these ions under the basic conditions used and avoid their precipitation.
  • a complexing agent is in particular chosen from organic acids and their salts such as tartaric acid, EDTA or EDTP.
  • the reducing agent advantageously used may especially be formaldehyde, DMAB or H 2 PO 2 .
  • DMAB formaldehyde
  • H 2 PO 2 a group consisting of reducing agents used in the context of the present invention.
  • Those skilled in the art know different ion pairs of the metallic material / reducing agent used in the context of the present invention. Similarly, depending on the particular couple chosen, those skilled in the art the pH and temperature conditions of the solution S M to implement.
  • the reducing agent advantageously used under basic conditions is formaldehyde in an amount of between 0.1 and 5% (v / v) with respect to total volume of the solution S M.
  • basic conditions is meant a solution whose pH is between 10 and 14 and in particular between 12 and 13, such a pH is reached using NaOH as a pH regulator.
  • the metallization step (b 2 ) can be carried out at a temperature of between 20 ° C. and 80 ° C., in particular between 30 ° C. and 60 ° C. and, in particular, of the order of 40 ° C. (ie 40 ° C. ⁇ 5 ° C.). ° C).
  • the metallization step (b 2 ) can last between 1 min and 1 h, in particular between 5 and 45 min and, in particular, between 10 and 30 min.
  • the metallization of the surface of the substrate i.e. the presence of a thin layer of metallic material on the surface of the substrate is easily verifiable, typically, visually and in particular with the naked eye.
  • the surface of the substrate to be metallized may possibly undergo different pre-treatments.
  • These pretreatments may be conventional treatments in the field of metallization of surfaces such as degreasing or polishing.
  • the surface of the substrate may optionally be subjected, prior to step (a) of the process according to the invention, to a treatment capable of increasing its hydrophilicity and / or roughness, said treatment being chosen from the group consisting of a sandblasting, abrasion, chemical treatment with pickling bath, flame treatment, corona treatment and plasma treatment and combinations thereof.
  • step (a) does not bring any additional roughness to the surface of the substrate which can be verified by AFM measurement. Also, according to the initial roughness of the (Co) polymer constituting the surface of the substrate or the substrate, a pretreatment preceding step (a) to bring a surface roughness must be performed.
  • the hydrophilicity of the (co) polymer constituting the surface of the substrate or the substrate to be treated may be necessary to increase the hydrophilicity of the (co) polymer constituting the surface of the substrate or the substrate to be treated.
  • Some (co) polymers already have nitrogen or oxygen groups such as poly (acrylic acid), polyanilines and polyamides. If these oxygens or nitrogens are accessible on the surface of the substrate to be metallized, the step providing hydrophilicity is not mandatory.
  • the surface roughness with or without hydrophilic function can be provided by mechanical pretreatment, chemical or dry and will, in some cases, accompanied by surface oxidation.
  • Mechanical pretreatment of the surface to be treated consists of sandblasting or abrasion with grains of larger or smaller size. It does not modify in any way the chemical composition of the surface and therefore does not oxidize the surface of the (co) polymer constituting the surface of the substrate or the substrate to be treated. In addition, it is not always effective and remains possible only in the case of substrates of adequate size such as substrates in the form of large flat parts.
  • a chemical pretreatment (acid / base) (or chemical treatment with pickling bath) is based on contacting the surface to be treated with a bath acid or basic pickling and is specific to the (co) polymers to be metallized. It brings surface roughness and very generally surface oxidation. In each case, etching, also called “satin”, will degrade the surface (co) polymer constituting the surface of the substrate or the substrate to be treated by etching. This stripping follows the laws of the chemical reactivity of the polymer chains.
  • this degradation causes a rupture of chains of (co) polymers on the surface, thereby causing their solubilization in order to reveal a roughness on the surface of the (co) polymer.
  • an acid attack on polyamide-type polymers allows degradation of the organic material.
  • a basic attack allows the degradation and the dissolution of the polycarbonate contained in the surface in the ABS-PC increasing the surface roughness.
  • an acidic aqueous solution comprising at least one inorganic acid.
  • Said inorganic acid is especially selected from the group consisting of chromic acid, sulfuric acid, nitric acid, hypochlorous acid and mixtures thereof.
  • mixture is meant a mixture of at least two different inorganic acids such as a mixture of chromic acid and sulfuric acid or a mixture of at least three different inorganic acids such as an acid mixture nitric acid, hypochlorous acid and sulfuric acid.
  • the chemical pre-treatment is advantageously carried out for a period of between 1 and 60 min, in particular between 2 and 30 min and, in particular, between 5 and 20 min and at a temperature of between 20 and 120 ° C, in particular between 40 and 110 ° C and in particular between 60 and 100 ° C.
  • the surface to be treated may also be subjected to a dry pretreatment.
  • physicochemical treatments comprising a flame treatment, a corona treatment and a plasma treatment also have a double effect: i) the oxidation of chemical bonds on the surface and ii) the increase in roughness.
  • the flame treatment also known as "flaming” consists in exposing the surface of the substrate and / or the substrate to the action of a flame and in particular to the action of a stable and slightly oxidizing flame.
  • the high temperatures of this treatment generate active species that can correspond to radicals, ions or excited molecules.
  • the (co) polymer constituting the surface of the substrate and / or the substrate is oxidized to a thickness of about 4 to 9 mm.
  • a diffusion phenomenon is observed inside the polymer of chemical species resulting from its degradation. There is a real restructuring of the surface. These changes are result in an improvement of the wettability and roughness of the surface to be coated.
  • the flame is in particular disposed at a distance from the surface of the substrate and / or the substrate of between 0.1 and 20 cm, in particular between 0.3 and 10 cm and more particularly between 0.5 and 5 cm.
  • This flame is advantageously generated by a mixture of at least two gases, the first and second gases being respectively chosen from the group consisting of hydrogen, methane, ethane and propane and the group consisting of air , ozone and oxygen.
  • the temperature of the flame thus obtained is between 500 and 1600 ° C, especially between 800 and 1400 ° C and, in particular, of the order of 1200 ° C (i.e. 1200 ⁇ 100 ° C).
  • the duration of the flame treatment is between 0.01 and 10 sec, in particular between 0.015 and 1 sec, and in particular between 0.02 and 0.1 sec.
  • Corona treatment is also referred to as “corona treatment” or “corona discharge treatment” and involves exposing the surface of the substrate and / or the substrate to an ionization field created by passing an alternating current of high voltage between two electrodes distant a few mm and in particular 1 to 2 mm.
  • an electrical discharge driven by the ionization of the medium surrounding a conductor occurs when the electric potential exceeds a critical value but the conditions do not allow the formation of an arc.
  • the emitted electrons are precipitated in the electric field and transmit their energy to the molecules of the medium surrounding the surface of the substrate and / or the substrate which is advantageously air or an inert gas optionally enriched with oxygen.
  • the surface of the (co) polymer constituting the surface of the substrate and / or the substrate is oxidized.
  • Density be sitting corona discharge is advantageously between 10 to 500 W.min / m 2, in particular from 20 to 400 W.min / m 2 and, particularly, from 30 to 300 W.min / m 2.
  • the duration of treatment with the corona effect is between 0.1 and 600 sec, especially between 1 and 120 sec, and in particular between 10 to 50 sec.
  • Plasma treatment involves exposing the surface of the solid support and / or the solid support to a plasma.
  • plasma is a gas in the ionized state, classically considered as a fourth state of matter.
  • the energy required for the ionization of a gas is provided by means of an electromagnetic wave (radio frequency or microwave).
  • Plasma is composed of neutral molecules, ions, electrons, radical species (chemically very active) and excited species that will react with the surface of materials. If the plasma gas contains Oxygen or nitrogen, these atoms will react instantly with the surface of the (co) polymer and create active sites there.
  • the modification of the (co) polymers by the plasmas results in the formation of radicals and double bonds, by the crosslinking and the functionalization of the surface.
  • Plasma treatment is usually limited to the extreme surface and the surface roughness provided is limited.
  • the so-called “cold” plasmas and the so-called “hot” plasmas which are distinguished from each other with respect to the ionization rate of the species contained in the plasma.
  • the ionization rate of the reactive species is less than 10 -4 while for so-called “hot” plasmas it is greater than 10 -4 .
  • the terms “hot” and “cold” come from the fact that the so-called “hot” plasma is much more energetic than the so-called “cold” plasma.
  • a so-called “cold” plasma is more suitable.
  • the plasma is advantageously generated by one (or more) plasma gas (s).
  • the first and second gases are respectively selected from the group consisting of inert gases and the group consisting of air and oxygen.
  • the duration of the plasma treatment is between 1 sec and 5 min, especially between 10 to 60 sec and, in particular, between 20 and 40 sec.
  • step (a) it may be necessary between two treatment steps; prior to step (a); between steps (a) and (b) or between steps (b 1 ) and (b 2 ) subjecting the surface of the substrate and / or substrate to rinsing or rinsing using identical or different rinsing solutions .
  • this rinsing solution is selected from water, distilled water, deionized water, MilliQ water, an aqueous solution containing a detergent such as TDF4 or sodium hydroxide including sodium hydroxide in a concentration of between 0.01 and 1 M.
  • the rinsing solution when it is brought into contact with the surface of the substrate or the substrate, can be agitated, in particular by using a stirrer, a magnetic bar, an ultrasound bath or a homogenizer.
  • Each rinsing step can last from 1 to 30 min and in particular from 5 to 20 min.
  • the present invention finally relates to a substrate whose surface is coated with a metallic material that can be obtained by the method of the invention as previously defined.
  • ABS acrylonitrile butadiene styrene
  • PC acrylonitrile butadiene styrene / polycarbonate
  • PA polyamide
  • This metallization process is carried out in 3 steps (Fenton Treatment / Reduction / Metallization electroless) and before treating the polymer, it should be prepared, degreased and cleaned.
  • the plates are subjected to polishing to minimize edge effects and other defects introduced during the cutting of the plates.
  • the plates are rinsed with a soap solution industrial TDF4 mixed with water (1 mL of TDF4 for 4 mL of H 2 O MilliQ), under ultrasound for 10 min.
  • the plates are then rinsed with MilliQ water, under ultrasound for 10 min.
  • Iron (II) sulfate (6.961 g, 0.1 mol) was solubilized in 50 mL of 10 -3 M sulfuric acid in water. In this solution, the polymer plates were immersed. 10 mL (0.124 mol) of 35% hydrogen peroxide in water was then added dropwise. After 25 min, the samples were rinsed with MilliQ water before being dried.
  • the contact angle is clearly lowered.
  • the surface has become very hydrophilic because of its oxidation.
  • bands at 3600-3200 cm -1 and between 1150-1100 cm -1 is typical of the contribution of C-OH bonds.
  • the band at 1700-1640 cm -1 could mean the appearance of amide groups originating from the oxidation of the nitrile groups of polyacrylonitrile.
  • the bands 1150-1100 and 1700 are confused with the strips of the virgin polymer.
  • the XPS analysis of the ABS plate before / after treatment of Fenton shows a Fe 2+ / Fe 3+ ion supply and a strong oxidation of the surface by an oxygen supply.
  • the atomic ratios with respect to the carbon signal are shown in Table 3 below.
  • NaBH 4 sodium borohydride (0.316 g, 0.8 X 10 -2 mol) is dissolved in 25 ml of a 0.1 M sodium hydroxide solution (NaOH). This solution is heated to 80 ° C. at room temperature. using a water bath and the samples are immersed in it. After 12 min, the samples were rinsed with MilliQ water before being dried.
  • IR analysis reveals the preservation of the oxidation obtained after Fenton with the bands at 3600-3100 cm -1 , and the bands 1700-1640 cm -1 , whatever the polymer.
  • the XPS analysis of the ABS plate before / after reduction shows a slight decrease of all elements except the appearance of bohr. According to the XPS spectra, it is in oxidized form and thus confirms the reduction of Fe 2+ / Fe 3+ ions by borohydride BH 4 - .
  • the iron is, in turn, oxidized in air and water before the XPS analysis and is in oxidized form.
  • the atomic ratios with respect to the carbon signal are shown in Table 4 below.
  • the copper layer is also visible to the eye.
  • the presence of carbon, nitrogen and oxygen after metallization is due to the presence of organic impurities at the extreme surface of the metallized substrate.
  • Oxygen can also come from the air oxidation of the copper layer prior to analysis.
  • Electrochemical set up consisted of a saturated KCl calomel reference electrode and a graphite counter electrode.
  • the electrodes were soaked in a solution of CuSO 4 at 10 g / L, the initial potential was about 0.1 V.
  • the confirmation of the copper deposit is also visual. Indeed, the copper layer deposited by electrochemistry has a slightly more homogeneous appearance.
  • This metallization process is carried out in 4 stages (Pretreatment Oxidizer / Fenton Treatment / Reduction / Electroless Metallization) and before treating the polymer, it is necessary to prepare it, degrease and clean.
  • the plates are subjected to polishing to minimize edge effects and other defects introduced during the cutting of the plates.
  • the plates were rinsed using an industrial soap solution TDF4 mixed with water (1 mL TDF4 4 mL of MilliQ H 2 0) under ultrasound for 10 min. The plates are then rinsed with MilliQ water, under ultrasound for 10 min.
  • the plates are immersed for 10 min in a 60% nitric acid solution at a temperature of 60 ° C.
  • the plates are then rinsed in a NaOH solution (0.1M) in ultrashons for 10 min and then in MilliQ water under ultrasound for 10 min.
  • the contact angle is lowered.
  • the surface has become more hydrophilic due to its oxidation and the surface roughness has increased.
  • the bands at 1570-1530 cm -1 and at 1320-1280 cm -1 are characteristic of carbonyl groups, carboxylate type COO - . This confirms surface oxidation.
  • Iron (II) sulfate (6.961 g, 0.1 mol) was solubilized in 50 mL of 10 -3 M sulfuric acid in water. In this solution, the polymer plates were immersed. 10 mL (0.124 mol) of 35% hydrogen peroxide in water were then added, drip. After 25 min, the samples were rinsed with MilliQ water before being dried.
  • the contact angle is clearly lowered.
  • the surface has become very hydrophilic because of its oxidation.
  • the amplification of the 3600-3200 cm -1 band after Fenton treatment as well as the appearance of the band between 1150-1100 cm -1 are typical of the addition of C-OH bonds.
  • the appearance of the band at 1700-1600 cm -1 and the amplification of the band 1320-1280 cm -1 confirm the presence of carbonyl groups on the surface of the ABS plates.
  • NaBH 4 sodium borohydride (0.316 g, 0.8 ⁇ 10 -2 mol) is dissolved in 25 ml of a 0.1 M sodium hydroxide solution (NaOH). This solution is heated to 80 ° C. using a bain-marie and the samples are immersed in it. After 12 min, the samples were rinsed with MilliQ water before being dried.
  • IR analysis reveals the conservation of oxidation obtained after Fenton with bands at 3600-3200 cm -1 and bands 1700-1640 cm -1 .
  • the samples are immersed in a commercial Electroless plating bath (M Copper 85, MacDermid) with formaldehyde as reducing agent. At least the plates are immersed for 10 minutes at 48 ° C.
  • a commercial Electroless plating bath M Copper 85, MacDermid
  • the copper layer is visible to the eye.
  • the mechanical strength is considered bad. If the layer remains insensitive to the adhesive, the mechanical strength is considered good.
  • the adhesive tape that was used is a high performance invisible adhesive tape, branded PROGRESS.
  • the electrodes were soaked in a solution of CuSO 4 at 10 g / L, the initial potential was about 0 V.
  • the confirmation of the copper deposit is also visual. Indeed, the copper layer deposited by electrochemistry has a slightly more homogeneous appearance.
  • This metallization process is carried out in 4 steps (Pretreatment Oxidizer / Fenton Treatment / Reduction / Electroless Metallization) and before treating the polymer, it is necessary to prepare it, degrease and clean.
  • the plates are subjected to polishing to minimize edge effects and other defects introduced during the cutting of the plates.
  • the plates were rinsed using an industrial soap solution TDF4 mixed with water (1 mL TDF4 4 mL of MilliQ H 2 0) under ultrasound for 10 min. The plates are then rinsed with MilliQ water, under ultrasound for 10 min.
  • the plates are immersed for 10 min in a 30 wt% NaOH solution at a temperature of 90 ° C.
  • the plates are then rinsed in 0.5M HCl solution under ultrasound for 10 min and then with MilliQ water under ultrasound for 10 min.
  • the contact angle is lowered.
  • the surface has become more hydrophilic due to its oxidation and the surface roughness has increased.
  • bands at 3600-3200 cm -1 and 1660-1610 cm -1 may be due to the presence of traces of water.
  • the bands at 1740-1700 cm -1 and at 1320-1280 cm -1 are characteristic of carbonyl groups, carboxylic type COOH. This confirms surface oxidation.
  • the disappearance of the ester band at 1772 cm -1 characteristic of polycarbonate is noted.
  • Iron (II) sulfate (6.961 g, 0.1 mol) was solubilized in 50 mL of 10 -3 M sulfuric acid in water. In this solution, the polymer plates were immersed. 10 mL (0.124 mol) of 35% hydrogen peroxide in water were then added, drip. After 25 min, the samples were rinsed with MilliQ water before being dried.
  • the contact angle is clearly lowered.
  • the surface has become very hydrophilic because of its oxidation.
  • NaBH 4 sodium borohydride (0.316 g, 0.8 ⁇ 10 -2 mol) is dissolved in 25 ml of a 0.1 M sodium hydroxide solution (NaOH). This solution is heated to 80 ° C. using a bain-marie and the samples are immersed in it. After 12 min, the samples were rinsed with MilliQ water before being dried.
  • IR analysis reveals the conservation of oxidation obtained after Fenton with bands at 3600-3200 cm -1 and bands 1700-1640 cm -1 .
  • the samples are immersed in a commercial Electroless plating bath (M Copper 85, MacDermid) with formaldehyde as reducing agent.
  • the exact composition of the copper bath is not known. At least the plates are immersed for 10 minutes at 48 ° C.
  • the copper layer is visible to the eye.
  • the electrochemical system put in place consisted of a saturated KCl calomel reference electrode and a graphite counter electrode.
  • the electrodes were soaked in a solution of CuSO 4 at 10 g / L, the initial potential was about 0 V.
  • the confirmation of the copper deposit is also visual. Indeed, the copper layer deposited by electrochemistry has a slightly more homogeneous appearance.

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Description

DOMAINE TECHNIQUETECHNICAL AREA

L'invention appartient au domaine technique des revêtements de surface et, plus particulièrement, au domaine technique de la métallisation des surfaces.The invention belongs to the technical field of surface coatings and, more particularly, to the technical field of metallization of surfaces.

Ainsi, la présente invention concerne un procédé de métallisation simplifié mettant en oeuvre des substrats en polymères.Thus, the present invention relates to a simplified metallization process using polymer substrates.

ÉTAT DE LA TECHNIQUE ANTÉRIEURESTATE OF THE PRIOR ART

De façon générale, la métallisation consiste à revêtir la surface d'une pièce d'une mince couche de métal.In general, the metallization consists in coating the surface of a part with a thin layer of metal.

La métallisation d'une pièce en matières plastiques est notamment utilisée dans les domaines tels que l'automobile et les bâteaux où certains accessoires en (co)polymère sont revêtus de chrome ; l'industrie électronique, les appareils électrodomestiques et les luminaires ; la cosmétique et les accessoires de mode ; l'optique et l'horlogerie ; etc.... Il y a donc un grand intérêt dans la mise au point d'un procédé de métallisation d'une surface en matières plastiques et, de façon plus générale, en polymères.The metallization of a plastic part is particularly used in areas such as automobiles and boats where some accessories (co) polymer are coated with chromium; the electronics industry, household appliances and lighting fixtures; cosmetics and fashion accessories; optics and watchmaking; etc. There is therefore a great interest in the development of a metallization process of a plastic surface and, more generally, polymers.

La métallisation des polymères est un procédé développé depuis plus d'une cinquantaine d'années. Elle fait intervenir des techniques alternatives à celles utilisées pour les substrats conducteurs.The metallization of polymers is a process developed for more than fifty years. She involves alternative techniques to those used for conductive substrates.

Actuellement, la métallisation des polymères s'effectue généralement en 3 étapes.Currently, the metallization of the polymers is generally carried out in 3 steps.

La 1ère étape est une étape de modification de la surface qui apporte, tout d'abord, une rugosité de surface afin d'améliorer l'adhérence de la couche métallique par ancrage mécanique.The 1st step is a surface modification step which provides, firstly, a surface roughness in order to improve the adhesion of the metal layer by mechanical anchoring.

Cette modification permet également d'augmenter la mouillabilité de la surface du polymère, notamment par apport de groupements hydrophiles incorporant généralement des oxygènes ou des azotes et ce, afin de faciliter l'activation de la surface. En effet, il faut que le polymère possède des groupements favorisant l'adsorption de l'agent métallique activant.This modification also makes it possible to increase the wettability of the polymer surface, in particular by adding hydrophilic groups generally incorporating oxygen or nitrogen in order to facilitate activation of the surface. Indeed, it is necessary that the polymer has groups promoting the adsorption of the activating metal agent.

Par exemple, si l'agent métallique est le palladium, la chimisorption de celui-ci n'est possible que sur des éléments azotés [1]. Quel que soit le prétraitement, rugosité et apport de liaisons C-O et/ou C-N à la surface du polymère à métalliser sont obligatoires.For example, if the metal agent is palladium, chemisorption thereof is only possible on nitrogen elements [1]. Whatever the pretreatment, roughness and CO and / or CN bonding to the surface of the polymer to be metallized are mandatory.

La 2nde étape est une étape d'activation de la surface qui consiste à déposer des particules métalliques en surface du polymère modifié. Ces particules jouent, par la suite, le rôle de catalyseur pour la métallisation. Ainsi, il faut maintenir à la surface du polymère des cations métalliques qui seront par la suite réduits.The 2 nd step is a surface activation step of depositing metal particles on the surface of the modified polymer. These particles subsequently play the role of catalyst for the metallization. Thus, it is necessary to maintain on the surface of the polymer metal cations which will subsequently be reduced.

La dernière étape met en oeuvre un bain de métallisation dans lequel les polymères activés sont immergés. Dans ce bain, la croissance métallique est catalysée par les particules métalliques déposées à l'étape précédente. Le bain de métallisation est une solution stable contenant au moins un cation métallique et son complexant, un réducteur et un stabilisateur, généralement en milieu alcalin.The last step uses a metallization bath in which the activated polymers are immersed. In this bath, metal growth is catalyzed by the metal particles deposited in the previous step. The metallization bath is a stable solution containing at least one metal cation and its complexing agent, a reducing agent and a stabilizer, generally in an alkaline medium.

Des procédés notamment utilisés au niveau industriel consistant à oxyder la surface à métalliser puis à adsorber, sur cette dernière, du palladium via le colloïde étain/palladium, ce qui correspond à l'étape d'activation. Suite à cette dernière, une étape d'accélération est mise en oeuvre, permettant d'éliminer l'étain et ainsi de favoriser l'activité du précurseur de la couche métallique qui est, dans ce cas, le palladium. Des traces d'étain peuvent, en effet, induire une croissance métallique dans des endroits non désirés. L'étape d'accélération est suivie, d'une étape en présence d'un bain de métallisation tel que précédemment défini.Processes used in particular at the industrial level consisting of oxidizing the surface to be metallized and then adsorbing palladium on the latter via the tin / palladium colloid, which corresponds to the activation step. Following the latter, an acceleration step is implemented, to remove the tin and thus promote the activity of the precursor of the metal layer which is, in this case, palladium. Traces of tin can, in fact, induce metal growth in unwanted places. The acceleration step is followed by a step in the presence of a metallization bath as defined above.

Ce procédé est notamment décrit dans la demande de brevet CA 1 203 720 [2]. Toutefois, le procédé objet de cette demande ne présente pas une oxydation de type Fenton en présence des précurseurs du matériau métallique. En effet, ce dernier n'est pas présent lors de l'étape mettant en oeuvre le peroxyde d'hydrogène.This process is described in particular in the patent application CA 1 203 720 [2] . However, the process that is the subject of this application does not exhibit a Fenton type oxidation in the presence of the precursors of the metallic material. Indeed, the latter is not present during the step using hydrogen peroxide.

Compte-tenu de la diversité des domaines dans lesquels la métallisation des polymères et notamment des plastiques est utilisée et des enjeux économiques, il existe un réel besoin d'un procédé de métallisation simplifié et donc à moindre coût vis-à-vis des procédés actuellement utilisés.Given the diversity of the fields in which the metallization of polymers and in particular plastics is used and economic stakes, there is a real need for a simplified metallization process and therefore at a lower cost compared to processes currently used. used.

EXPOSÉ DE L'INVENTIONSTATEMENT OF THE INVENTION

La présente invention permet de répondre à cette attente et de résoudre les problèmes techniques des procédés de métallisation de l'état de la technique.The present invention makes it possible to meet this expectation and to solve the technical problems of metallization processes of the state of the art.

En effet, les travaux des inventeurs ont permis de mettre au point un procédé de métallisation dans lequel plusieurs étapes des procédés classiques de métallisation des polymères sont éliminées puisque le procédé de l'invention consiste à déposer et à maintenir des cations métalliques à la surface d'un polymère en même temps que son oxydation de surface.In fact, the work of the inventors has made it possible to develop a metallization process in which several steps of the conventional metallization processes of the polymers are eliminated since the process of the invention consists in depositing and maintaining metal cations on the surface of the metal. a polymer at the same time as its surface oxidation.

Plus particulièrement, la présente invention concerne un procédé de revêtement d'une surface d'un substrat en (co)polymère par un matériau métallique comprenant les étapes successives consistant à :

  1. a) soumettre ladite surface à un traitement oxydant par réaction chimique de type Fenton en présence d'au moins un précurseur dudit matériau métallique ;
  2. b) transformer ledit précurseur en ledit matériau métallique
ledit traitement oxydant de ladite étape (a) consistant à mettre en contact ladite surface du substrat avec une solution contenant au moins un précurseur du matériau métallique et un composé de formule ROOR dans laquelle R représente un hydrogène, un groupe alkyle comprenant de 1 à 15 atomes de carbone, un groupe acyle -COR' avec R' représentant un groupe alkyle comprenant de 1 à 15 atomes de carbone ou un groupe aroyle -COAr avec Ar représentant un groupe aromatique comprenant de 6 à 15 atomes de carbone.More particularly, the present invention relates to a method of coating a surface of a (co) polymer substrate with a metallic material comprising the successive steps of:
  1. a) subjecting said surface to an oxidizing treatment by Fenton-type chemical reaction in the presence of at least one precursor of said metallic material;
  2. b) converting said precursor into said metallic material
said oxidative treatment of said step (a) of contacting said surface of the substrate with a solution containing at least one precursor of the metallic material and a compound of formula ROOR wherein R represents a hydrogen, an alkyl group comprising from 1 to 15 carbon atoms, an acyl group -COR 'with R' representing an alkyl group comprising from 1 to 15 carbon atoms or an aroyl group -COAr with Ar representing an aromatic group comprising from 6 to 15 carbon atoms.

Par « revêtement par un matériau métallique », on entend dans le cadre de la présente invention un substrat revêtu en surface par une couche mince, typiquement de quelques nanomètres à plusieurs micromètres, d'un métal et/ou d'un oxyde métallique. Cette couche mince peut recouvrir tout ou partie de la surface du substrat. Le substrat ainsi revêtu peut être appelé « substrat métallisé ».For the purposes of the present invention, the term "metal-material coating" means a substrate coated on the surface with a thin layer, typically from a few nanometers to several microns, of a metal and / or a metal oxide. This thin layer may cover all or part of the surface of the substrate. The thus coated substrate may be called a "metallized substrate".

Parmi les substrats métallisés, on peut notamment distinguer les substrats métallisés uniquement par un métal ou uniquement par un oxyde métallique, des substrats métallisés par les deux types d'entités métalliques.Among the metallized substrates, it is possible to distinguish the substrates metallized only by a metal or only by a metal oxide, substrates metallized by the two types of metal entities.

Le substrat selon la présente invention peut avoir n'importe quelles taille et forme. En effet, la taille du substrat mis en oeuvre dans le cadre de la présente invention peut être nanométrique, micrométrique, millimétrique ou métrique. Ainsi, la présente invention s'applique, à titre d'exemples non limitatifs, à un substrat qui peut être choisi dans le groupe constitué par une nanoparticule, une microparticule, un bouton, un bouchon de produits cosmétiques, un élément électronique, une poignée de porte, un appareil électrodomestique, des lunettes, un objet de décoration tel qu'un luminaire, un élément de carrosserie, etc.The substrate according to the present invention can have any size and shape. Indeed, the size of the substrate used in the context of the present invention may be nanometric, micrometric, millimetric or metric. Thus, the present invention applies, as non-limiting examples, to a substrate that can be chosen from the group consisting of a nanoparticle, a microparticle, a button, a cosmetic product cap, an electronic element, a handle door, an electrical appliance, glasses, a decorative object such as a luminaire, a bodywork element, etc.

Par « surface d'un substrat en (co)polymère », on entend non seulement un substrat en (co)polymère mais aussi un substrat dont seule la surface est en (co)polymère, le reste du substrat pouvant être en un quelconque matériau.By "surface of a substrate (co) polymer" means not only a substrate (co) polymer but also a substrate of which only the surface is in (co) polymer, the rest of the substrate can be in any material .

Par « en (co)polymère », on entend dans le cadre de la présente invention un substrat ou une surface essentiellement constitué(e) par un seul (co)polymère ou plusieurs (co)polymères différents.By "(co) polymer" is meant in the context of the present invention a substrate or a surface consisting essentially of a single (co) polymer or several (co) polymers.

Par « essentiellement constitué(e) », on entend dans le cadre de la présente invention un substrat ou une surface dont au moins 50%, au moins 60%, au moins 70%, au moins 80%, au moins 90%, au moins 95% et/ou au moins 98% des constituants exprimés en poids sont un (ou plusieurs) (co)polymère(s).By "essentially constituted" is meant in the context of the present invention a substrate or a surface of which at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least less 95% and / or at least 98% of the constituents expressed by weight are one (or more) (co) polymer (s).

Avantageusement, le substrat ou la surface du substrat est uniquement constitué(e) par un (ou plusieurs) (co)polymère(s).Advantageously, the substrate or the surface of the substrate consists solely of one (or more) (co) polymer (s).

En variante, le substrat ou la surface du substrat comprend, en plus d'un (ou plusieurs) (co)polymère(s), au moins un élément choisi dans le groupe constitué par les charges, les plastifiants et les additifs. Ce (ou ces) élément(s) additionnel(s) est(sont) avantageusement incorporé(s) et/ou dispersé(s) dans le matériau polymère.Alternatively, the substrate or substrate surface comprises, in addition to one (or more) (co) polymer (s), at least one member selected from the group consisting of fillers, plasticizers and additives. This (or these) element (s) additional (s) is (are) advantageously incorporated (s) and / or dispersed (s) in the polymeric material.

Pour rappel, un plastique ou matière plastique est formé (e) d'au moins un (co)polymère avantageusement présentant un degré de polymérisation supérieur à 3000 et d'au moins un additif. Par conséquent, le substrat ou la surface du substrat en polymère mis(e) en oeuvre dans le cadre de la présente invention comprend les substrats ou les surfaces de substrat en plastique ou en matière plastique.As a reminder, a plastic or plastic material is formed (e) of at least one (co) polymer advantageously having a degree of polymerization greater than 3000 and at least one additive. Therefore, the substrate or surface of the polymer substrate used in the context of the present invention comprises substrates or substrate surfaces of plastic or plastic.

Les charges minérales telles que silice, talc, fibres ou billes de verre ou organiques telles que farine céréalière ou pâte de cellulose sont généralement utilisées pour réduire le coût et améliorer certaines propriétés telles que les propriétés mécaniques du matériau polymère. Les additifs sont principalement utilisés pour améliorer une propriété spécifique du matériau, polymère, ladite propriété pouvant être la réticulation, le glissement, la résistance à la dégradation, au feu et/ou aux attaques bactériennes et fongiques.Mineral fillers such as silica, talc, glass or organic fibers or beads such as cereal flour or cellulose pulp are generally used to reduce the cost and improve certain properties such as the mechanical properties of the polymeric material. The additives are mainly used to improve a specific property of the polymer material, said property possibly being crosslinking, slipping, resistance to degradation, fire and / or bacterial and fungal attacks.

Tout polymère naturel, artificiel, synthétique, thermoplastique, thermodurcissable, thermostable, élastomère, linéaire (i.e. monodimensionnel, linéaire ou ramifié) et/ou tridimensionnel est utilisable dans le cadre de la présente invention. A titre d'exemples non limitatifs de polymères naturels, on peut citer les sucres.Any natural, artificial, synthetic, thermoplastic, thermosetting, thermostable, elastomeric, linear (i.e. one-dimensional, linear or branched) and / or three-dimensional polymer is usable within the scope of the present invention. As non-limiting examples of natural polymers, mention may be made of sugars.

Avantageusement, le polymère mis en oeuvre dans le cadre de la présente invention est un (co)polymère thermoplastique choisi dans le groupe constitué par

  • une polyoléfine telle qu'un polyéthylène, un polypropylène, un copolymère éthylène/propylène, un polybutylène, un polyméthylpentène, un copolymère éthylène/acétate vinylique, un copolymère éthylène/alcool vinylique, un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ;
  • un polyester tel qu'un poyéthylène téréphthalate éventuellement modifié par du glycol, un polybutylène téréphthalate, un polylactide, un polycarbonate, un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ;
  • un polyéther tel qu'un poly(oxyméthylène), un poly(oxyéthylène), un poly(oxypropylène), un poly(phénylène éther), un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ;
  • un polymère vinylique tel qu'un poly(chlorure de vinyle) éventuellement chloré, un poly(alcool vinylique), un poly(acétate de vinyle), un poly(acétal de vinyle), un poly(formal de vinyle), un poly(fluorure de vinyle), un poly(chlorure de vinyle/acétate de vinyle), un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ;
  • un polymère vinylidénique tel qu'un poly(chlorure de vinylidène), un poly(fluorure de vinylidène), un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ;
  • un polymère styrénique tel qu'un polystyrène, un poly(styrène/butadiène), un poly(acrylonitrile/ butadiène/styrène), un poly(acrylonitrile/styrène), un poly(acrylonitrile/éthylène/propylène/styrène), un poly(acrylonitrile/styrène/acrylate), un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ;
  • un polymère (méth)acrylique tel qu'un polyacrylonitrile, un poly(acrylate de méthyle), un poly(méthacrylate de méthyle), un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ;
  • une polyamide tel qu'un poly(caprolactame), un poly(hexaméthylène adipamide), un poly(lauroamide), un polyéther-bloc-amide, un poly(métaxylylène adipamide), un poly(métaphénylène isophtalamide), un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ;
  • un polymère fluoré (ou polyfluoréthène) tel qu'un polytétrafluoroéthylène, un polychlorotrifluoroéthylène, un poly(éthylène/propylène) perfluoré, un poly(fluorure de vinylidène), un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ;
  • un polymère cellulosique tel qu'un acétate de cellulose, un nitrate de cellulose, une méthylcellulose, un carboxyméthylcellulose, un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ;
  • un poly(arylènesulfone) tel qu'un polysulfone, un polyéthersulfone, un polyarylsulfone, un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ;
  • un polysulfure tel que du poly(sulfure de phénylène) ;
  • un poly(aryléther)cétone tel qu'un poly(éther cétone), un poly(éther éther cétone), un poly(éther cétone cétone), un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ;
  • une polyamide-imide ;
  • une poly(éther)imide ;
  • une polybenzimidazole ;
  • un poly(indène/coumarone) ;
  • un poly(paraxylylène) ;
  • un de leurs copolymères, un de leurs mélanges et une de leurs combinaisons.
Advantageously, the polymer used in the context of the present invention is a thermoplastic (co) polymer selected from the group consisting of
  • a polyolefin such as polyethylene, polypropylene, an ethylene / propylene copolymer, a polybutylene, a polymethylpentene, an ethylene / vinyl acetate copolymer, an ethylene / vinyl alcohol copolymer, a copolymer thereof, a mixture thereof and a their combinations;
  • a polyester such as polyethylene terephthalate optionally modified with glycol, a polybutylene terephthalate, a polylactide, a polycarbonate, a copolymer thereof, mixtures thereof and combinations thereof;
  • a polyether such as poly (oxymethylene), poly (oxyethylene), poly (oxypropylene), poly (phenylene ether), a copolymer thereof, mixtures thereof and combinations thereof;
  • a vinyl polymer such as optionally chlorinated polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyvinyl acetal, polyvinyl formal, poly vinyl fluoride), a poly (chloride of vinyl / vinyl acetate), one of their copolymers, blends and combinations;
  • a vinylidene polymer such as a polyvinylidene chloride, a polyvinylidene fluoride, a copolymer thereof, mixtures thereof and combinations thereof;
  • a styrenic polymer such as polystyrene, poly (styrene / butadiene), poly (acrylonitrile / butadiene / styrene), poly (acrylonitrile / styrene), poly (acrylonitrile / ethylene / propylene / styrene), poly ( acrylonitrile / styrene / acrylate), one of their copolymers, blends and combinations thereof;
  • a (meth) acrylic polymer such as polyacrylonitrile, poly (methyl acrylate), poly (methyl methacrylate), a copolymer thereof, mixtures thereof and combinations thereof;
  • a polyamide such as a poly (caprolactam), a poly (hexamethylene adipamide), a poly (lauroamide), a polyether-block-amide, a poly (metaxylylene adipamide), a poly (metaphenylene isophthalamide), a their copolymers, blends and combinations;
  • a fluorinated polymer (or polyfluoroethene) such as polytetrafluoroethylene, polychlorotrifluoroethylene, perfluoro poly (ethylene / propylene), polyvinylidene fluoride, a copolymer thereof, mixtures thereof and combinations thereof;
  • a cellulosic polymer such as cellulose acetate, cellulose nitrate, methylcellulose, carboxymethylcellulose, a copolymer thereof, mixtures thereof and combinations thereof;
  • poly (arylenesulfone) such as polysulfone, polyethersulfone, polyarylsulfone, a copolymer thereof, mixtures thereof and combinations thereof;
  • a polysulfide such as polyphenylene sulfide;
  • a poly (aryl ether) ketone such as a poly (ether ketone), a poly (ether ether ketone), a poly (ether ketone ketone), a copolymer thereof, mixtures thereof and combinations thereof;
  • a polyamide-imide;
  • a poly (ether) imide;
  • a polybenzimidazole;
  • a poly (indene / coumarone);
  • poly (paraxylylene);
  • one of their copolymers, one of their mixtures and one of their combinations.

En variante, le (co)polymère mis en oeuvre dans le cadre de la présente invention est un (co)polymère thermodurcissable choisi dans le groupe constitué par un aminoplaste tel que de l'urée-formol, de la mélanine-formol, de la mélanine-formol/polyesters, un(e) de leurs copolymères, de leurs mélanges et de leurs combinaisons ; un polyuréthane ; un polyester insaturé ; un polysiloxane ; une résine formophénolique, époxyde, allylique ou vinylester ; un alkyde ; une polyurée ; un polyisocyanurate ; un poly(bismaléimide) ; un polybenzimidazole ; un polydicyclopentadiène ; un de leurs copolymères, un de leurs mélanges et une de leurs combinaisons.Alternatively, the (co) polymer used in the context of the present invention is a thermosetting (co) polymer selected from the group consisting of an aminoplast such as urea-formaldehyde, melanin-formaldehyde, melanin-formaldehyde / polyesters, one of their copolymers, blends and combinations thereof; polyurethane; unsaturated polyester; a polysiloxane; a resin formophenolic, epoxy, allylic or vinylester; an alkyd; polyurea; a polyisocyanurate; a poly (bismaleimide); a polybenzimidazole; polydicyclopentadiene; one of their copolymers, one of their mixtures and one of their combinations.

Des informations complémentaires sur les polymères utilisables dans le cadre de la présente invention sont accessibles dans l'article de Naudin, 1995 [3]. Additional information on the polymers that can be used in the context of the present invention can be found in the article by Naudin, 1995 [3].

A titre d'exemples non limitatifs de (co)polymère utilisable dans le cadre de la présente invention, on peut citer l'acrylonitrile butadiène styrène (ABS), l'acrylonitrile butadiène styrène/polycarbonate (ABS/PC), un polyamide (PA) tel que du nylon, une polyamine, un poly(acide acrylique), une polyaniline et du polyéthylène téréphtalate (PET).By way of nonlimiting examples of (co) polymer that may be used in the context of the present invention, mention may be made of acrylonitrile butadiene styrene (ABS), acrylonitrile butadiene styrene / polycarbonate (ABS / PC), polyamide (PA ) such as nylon, polyamine, polyacrylic acid, polyaniline and polyethylene terephthalate (PET).

Préalablement à l'étape (a) du procédé selon l'invention, le substrat à métalliser ne présente aucun précurseur du matériau métallique adsorbé à la surface.Prior to step (a) of the process according to the invention, the substrate to be metallized has no precursor of the metallic material adsorbed on the surface.

Par « traitement oxydant », on entend dans le cadre de la présente invention un traitement visant à oxyder la surface du substrat mis en oeuvre. Cette oxydation modifie la surface du substrat notamment en y fixant et/ou en y introduisant des groupements riches en oxygène et notamment des groupements polaires et/ou hydrophiles tels que des groupements de type carboxylique (-COOH), hydroxyle (-OH), alcoxyle (-OR) avec R tel que défini ci-après), carbonyle (-C=O), percarbonique (-C-O-OH) et parfois amide (-CONH). Un tel traitement oxydant est également susceptible d'augmenter l'hydrophilie de la surface du substrat mis en oeuvre.By "oxidizing treatment" is meant in the context of the present invention a treatment for oxidizing the surface of the substrate used. This oxidation modifies the surface of the substrate, in particular by fixing and / or introducing therein groups that are rich in oxygen and in particular polar and / or hydrophilic groups such as carboxylic (-COOH), hydroxyl (-OH) and alkoxyl groups. (-OR) with R as defined below), carbonyl (-C = O), percarboxylic (-CO-OH) and sometimes amide (-CONH). Such an oxidative treatment is also susceptible to increase the hydrophilicity of the surface of the substrate used.

Ce traitement repose sur l'utilisation de divers réactifs afin de créer en surface du (co)polymère constituant la surface du substrat et/ou le substrat, une oxydation de surface permettant une meilleure accroche et/ou un meilleur maintien à la surface du substrat du précurseur d'un matériau métallique présent lors du traitement oxydant. Cette accroche et/ou ce maintien mettent en oeuvre une chélation (ou complexation) entre le précurseur d'un matériau métallique et des groupes présents sur la surface oxydée. Tout ou partie du précurseur du matériau métallique reste notamment en surface du (co)polymère et peut être, par la suite, réduit.This treatment relies on the use of various reagents to create on the surface of the (co) polymer constituting the surface of the substrate and / or the substrate, a surface oxidation allowing a better grip and / or a better maintenance on the surface of the substrate precursor of a metallic material present during the oxidizing treatment. This attachment and / or this maintenance implements a chelation (or complexation) between the precursor of a metallic material and groups present on the oxidized surface. All or part of the precursor of the metallic material remains in particular on the surface of the (co) polymer and can be reduced thereafter.

Avantageusement, l'étape (a) du procédé selon la présente invention est mise en oeuvre à une température inférieure à 60°C, notamment comprise entre 5°C et 50°C et, en particulier, comprise entre 10°C et 40°C. L'étape (a) selon l'invention est réalisée, dans une forme de mise en oeuvre plus particulière, à température ambiante. Par « température ambiante », on entend une température de 20°C ± 5°C.Advantageously, step (a) of the process according to the present invention is carried out at a temperature below 60 ° C., in particular between 5 ° C. and 50 ° C. and, in particular, between 10 ° C. and 40 ° C. vs. Step (a) according to the invention is carried out, in a particular embodiment, at room temperature. By "ambient temperature" is meant a temperature of 20 ° C ± 5 ° C.

Le traitement oxydant mis en oeuvre lors de l'étape (a) est basé sur la réaction chimique de Fenton (1894). Ce traitement oxydant peut donc être désigné traitement oxydant par réaction chimique de type Fenton. Pour rappel, la réaction chimique de Fenton consiste en une oxydation en milieu acide de peroxyde d'hydrogène par des ions ferreux représentée par le schéma réactionnel suivant :

        Fe2+ + H2O2 → Fe3+ + ·OH + OH-

The oxidizing treatment used during step (a) is based on the chemical reaction of Fenton (1894). This oxidizing treatment can therefore be designated oxidative treatment by Fenton-type chemical reaction. As a reminder, the chemical reaction of Fenton consists of an acidic oxidation of hydrogen peroxide by ferrous ions represented by the following reaction scheme:

Fe 2+ + H 2 O 2 → Fe 3+ + · OH + OH -

Cette réaction génère des radicaux hydroxyles (·OH) qui sont très réactifs notamment envers les surfaces plastiques, les ions ferreux jouant le rôle de précurseur du matériau métallique.This reaction generates hydroxyl radicals ( · OH) which are very reactive especially towards the plastic surfaces, the ferrous ions acting as a precursor of the metallic material.

La réaction chimique de Fenton généralisée et appliquée au traitement oxydant de l'étape (a) du procédé de la présente invention consiste à mettre en contact ladite surface du substrat avec une solution contenant au moins un précurseur du matériau métallique et un composé de formule ROOR dans laquelle R représente un hydrogène, un groupe alkyle comprenant de 1 à 15 atomes de carbone, un groupe acyle -COR' avec R' représentant un groupe alkyle comprenant de 1 à 15 atomes de carbone ou un groupe aroyle -COAr avec Ar représentant un groupe aromatique comprenant de 6 à 15 atomes de carbone.The generalized Fenton chemical reaction applied to the oxidizing treatment of step (a) of the process of the present invention comprises contacting said surface of the substrate with a solution containing at least one precursor of the metallic material and a compound of formula ROOR wherein R represents a hydrogen, an alkyl group comprising from 1 to 15 carbon atoms, an acyl group -COR 'with R' representing an alkyl group comprising from 1 to 15 carbon atoms or an aroyl group -COAr with Ar representing a aromatic group comprising from 6 to 15 carbon atoms.

Par « groupe alkyle comprenant de 1 à 15 atomes de carbone », on entend un groupe alkyle, linéaire, ramifié ou cyclique, éventuellement substitué, comprenant de 1 à 15 atomes de carbone, notamment de 1 à 10 atomes de carbone et, en particulier, de 2 à 6 atomes de carbone et éventuellement un hétéroatome tel que N, O, F, Cl, P, Si, Br ou S.By "alkyl group comprising 1 to 15 carbon atoms" is meant an optionally substituted linear, branched or cyclic alkyl group comprising from 1 to 15 carbon atoms, especially from 1 to 10 carbon atoms, and in particular , from 2 to 6 carbon atoms and optionally a heteroatom such as N, O, F, Cl, P, Si, Br or S.

Par « groupe aromatique comprenant de 6 à 15 atomes de carbone », on entend, dans le cadre de la présente invention, un groupe aromatique ou hétéroaromatique, éventuellement substitué, constitué d'un ou plusieurs cycles aromatiques ou hétèroaromatiques comportant chacun de 3 à 10 atomes, le ou les hétéroatomes pouvant être N, O, P ou S.By "aromatic group comprising from 6 to 15 carbon atoms" is meant, in the context of the present invention, an optionally substituted aromatic or heteroaromatic group consisting of one or more aromatic rings or heteroaromatic atoms each containing from 3 to 10 atoms, the heteroatom (s) possibly being N, O, P or S.

Par « substitué », on entend, dans le cadre de la présente invention, un groupe alkyle ou aromatique, mono- ou poly-substitué, par un groupe alkyle, linéaire ou ramifié, comprenant de 1 à 4 atomes de carbone, par un groupe amine, par un groupe carboxylique et/ou par un groupe nitro.By "substituted" is meant, in the context of the present invention, an alkyl or aromatic group, mono- or poly-substituted, with a linear or branched alkyl group comprising from 1 to 4 carbon atoms, by a group amine, with a carboxylic group and / or with a nitro group.

Des radicaux OR avec R tel que précédemment défini sont obtenus par coupure du peroxyde ROOR par le précurseur du matériau métallique. La réaction lors de l'étape (a) du procédé de la présente invention peut être représentée par le schéma réactionnel suivant :

        Zn+ + ROOR → Z(n+1)+ + .OR + OR-

avec Z représentant le précurseur du matériau métallique et n représentant un nombre entier compris entre 1 et 7 et notamment entre 1 et 5. Le nombre entier n est avantageusement choisi dans le groupe constitué par 1, 2, 3, 4 et 5.OR radicals with R as defined above are obtained by cleavage of the ROOR peroxide by the precursor of the metallic material. The reaction in step (a) of the process of the present invention can be represented by the following reaction scheme:

Z n + + ROOR → Z (n + 1) + + . OR + OR -

with Z representing the precursor of the metallic material and n representing an integer between 1 and 7 and in particular between 1 and 5. The integer n is advantageously chosen from the group consisting of 1, 2, 3, 4 and 5.

Le (ou les) précurseur(s) du matériau métallique mis en oeuvre lors de l'étape (a) du procédé selon l'invention joue(nt) un rôle de catalyseur(s) de la croissance métallique et donc de la métallisation de la surface du substrat. Le (ou les) précurseur (s) du matériau métallique est(sont) avantageusement un (ou des) cation(s) métallique(s) notamment choisis parmi les métaux nobles du group IB ou du groupe VIII. Plus particulièrement, le (ou les) précurseur(s) du matériau métallique est(sont) choisi(s) dans le groupe constitué par les ions du cuivre, de l'argent, de l'or, du fer, du ruthénium, de l'osmium, du cobalt, du rhodium, de l'iridium, du nickel, du palladium et du platine.The precursor (s) of the metallic material used during step (a) of the process according to the invention plays (s) a role of catalyst (s) for the metal growth and therefore the metallization of the surface of the substrate. The precursor (s) of the metallic material is (are) advantageously one (or more) metal cation (s), in particular chosen from the noble metals of group IB or group VIII. More particularly, the precursor (s) of the metallic material is (are) chosen from the group formed by the ions of copper, silver, gold, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum.

Les précurseurs du matériau métallique sont présents dans la solution comprenant au moins un précurseur du matériau métallique et un composé de formule ROOR à une concentration comprise entre 0,05 et 5 M, notamment, entre 0,1 et 3 M et, en particulier, entre 0,5 et 2,5 M. La solution comprenant au moins un précurseur du matériau métallique et un composé de formule ROOR comprend en outre des contre-ions tels que tétrafluoroborate, sulfate, bromure, fluorure, iodure, nitrate, phosphate ou chlorure.The precursors of the metallic material are present in the solution comprising at least one precursor of the metallic material and a compound of formula ROOR at a concentration of between 0.05 and 5 M, in particular between 0.1 and 3 M and, in particular, between 0.5 and 2.5 M. The solution comprising at least one precursor of the metallic material and a compound of formula ROOR additionally comprises counterions such as tetrafluoroborate, sulphate, bromide, fluoride, iodide, nitrate, phosphate or chloride. .

Le composé de formule ROOR est présent dans la solution comprenant au moins un précurseur du matériau métallique et. un composé de formule ROOR à une concentration comprise entre 5 x 10-4 M et 5 M, notamment, entre 0,1 et 3 M et, en particulier, entre 0,5 et 2,5 M.The compound of formula ROOR is present in the solution comprising at least one precursor of the metallic material and. a compound of formula ROOR at a concentration of between 5 × 10 -4 M and 5 M, especially between 0.1 and 3 M and in particular between 0.5 and 2.5 M.

La solution comprenant au moins un précurseur du matériau métallique et un composé de formule ROOR est avantageusement une solution acide. Par "solution acide", on entend une solution dont le pH est inférieur à 7, notamment compris entre 2 et 4 et, en particulier, de l'ordre de 3 (i.e. 3 ± 0,5). Cette solution comprend en outre de l'acide sulfurique et notamment à une concentration comprise entre 0,05 et 50 mM, en particulier, entre 0,1 et 10 mM et, plus particulièrement, de l'ordre de 1 mM (i.e. 1 ± 0,25 mM).The solution comprising at least one precursor of the metallic material and a compound of formula ROOR is advantageously an acidic solution. By "acid solution" is meant a solution whose pH is less than 7, especially between 2 and 4 and, in particular, of the order of 3 (i.e. 3 ± 0.5). This solution also comprises sulfuric acid and in particular at a concentration of between 0.05 and 50 mM, in particular between 0.1 and 10 mM and, more particularly, of the order of 1 mM (ie 1 ± 0.25 mM).

La durée du traitement par réaction chimique de type Fenton peut être variable. A titre d'exemples non limitatifs, cette durée est avantageusement comprise entre 5 min et 5 h, notamment entre 10 min et 3 h, en particulier, entre 15 min et 2 h et, plus particulièrement, de l'ordre de 25 min (i.e. 25 ± 5 min).The duration of the Fenton-type chemical reaction treatment may be variable. As examples non-limiting, this duration is advantageously between 5 min and 5 h, in particular between 10 min and 3 h, in particular between 15 min and 2 h and, more particularly, of the order of 25 min (ie 25 ± 5 min ).

Il peut être nécessaire, après le traitement oxydant par réaction chimique de type Fenton, d'apporter d'autres précurseurs du matériau métallique et ce en mettant la surface du substrat et/ou le substrat en contact avec un bain de chélation dans des conditions bien connues de l'homme du métier.It may be necessary, after the oxidizing treatment by Fenton-type chemical reaction, to add other precursors of the metallic material and this by putting the surface of the substrate and / or the substrate in contact with a chelation bath under well-controlled conditions. known to those skilled in the art.

En variante, les précurseurs du matériau métallique ne sont apportés que par la solution utilisée lors de la réaction de Fenton i.e. la solution mise en oeuvre lors de l'étape (a) du procédé de l'invention.As a variant, the precursors of the metallic material are only provided by the solution used during the Fenton reaction i.e. the solution implemented during step (a) of the process of the invention.

Dans le cadre de la présente invention, la réaction de Fenton est utilisée pour oxyder la surface du substrat à métalliser mais aussi pour adsorber les cations métalliques agissant, par la suite, comme précurseurs de la couche métallique déposée par Electroless.In the context of the present invention, the Fenton reaction is used to oxidize the surface of the substrate to be metallized but also to adsorb the metal cations acting thereafter as precursors of the metal layer deposited by Electroless.

L'étape (b) du procédé selon la présente invention est une étape bien connue de l'homme du métier spécialisé dans la métallisation des matériaux puisqu'elle consiste à transformer le précurseur du matériau métallique en ledit matériau métallique.Step (b) of the process according to the present invention is a step well known to those skilled in the field of metallization of materials since it consists in transforming the precursor of the metallic material into said metallic material.

Toute technique permettant une telle transformation est utilisable dans le cadre de la présente invention.Any technique allowing such a transformation can be used in the context of the present invention.

Avantageusement, cette étape de transformation présente les sous-étapes successives consistant à

  • b1) éventuellement réduire ledit précurseur dudit matériau métallique présent à la surface dudit substrat ;
  • b2) mettre en contact ledit précurseur éventuellement réduit suite à l'étape (b1) dans une solution contenant au moins un ion du matériau métallique.
Advantageously, this transformation step has the successive sub-steps of
  • b 1 ) optionally reducing said precursor of said metal material present on the surface of said substrate;
  • b 2 ) contacting said precursor optionally reduced following step (b 1 ) in a solution containing at least one ion of the metallic material.

Toute technique permettant la réduction du précurseur du matériau métallique est utilisable dans le cadre de l'étape (b1) du procédé selon la présente invention.Any technique for reducing the precursor of the metallic material can be used in the context of step (b 1 ) of the process according to the present invention.

Avantageusement, cette étape de réduction est une réduction chimique en une seule étape. Cette variante préférée consiste à mettre en contact la surface du substrat sur laquelle se trouve(nt) le (ou les) précurseur(s) du matériau métallique avec une solution réductrice SR.Advantageously, this reduction step is a chemical reduction in a single step. This preferred variant consists in bringing into contact the surface of the substrate on which the precursor (s) of the metallic material is (are) with a reducing solution S R.

De façon avantageuse, la solution réductrice SR est basique. La solution réductrice SR comprend un agent réducteur, notamment choisi dans le groupe constitué par le borohydrure de sodium (NaBH4), le diméthylamineborane (DMAB - H(CH3)2NBH3) et l'hydrazine (N2H4).Advantageously, the reducing solution S R is basic. The reducing solution S R comprises a reducing agent, in particular chosen from the group consisting of sodium borohydride (NaBH 4 ), dimethylamine borane (DMAB-H (CH 3 ) 2 NBH 3 ) and hydrazine (N 2 H 4 ) .

Lorsque l'agent réducteur est NaBH4, le pH de la solution réductrice SR est neutre ou basique, alors que, pour du DMAB, le pH de la solution SR est basique. Lorsque la solution SR est basique, un solvant avantageusement utilisé est du NaOH et notamment à une concentration comprise entre 10-4 M et 5 M, notamment entre 0,05 et 1 M et, en particulier, de l'ordre de 0,1 M (i.e. 0,1 M ± 0,01 M).When the reducing agent is NaBH 4 , the pH of the reducing solution S R is neutral or basic, whereas for DMAB the pH of the solution S R is basic. When the solution S R is basic, a solvent advantageously used is NaOH and in particular at a concentration between 10 -4 M and 5 M, especially between 0.05 and 1 M and, in particular, of the order of 0.1 M (ie 0.1 M ± 0.01 M).

L'agent réducteur est présent dans la solution réductrice SR à une concentration comprise entre 10-4 et 5 M, notamment entre 0,01 et 1 M et, en particulier, de l'ordre de 0,3 M (i.e. 0,3 M ± 0,05 M).The reducing agent is present in the reducing solution S R at a concentration of between 10 -4 and 5 M, in particular between 0.01 and 1 M and, in particular, of the order of 0.3 M (ie 0, 3 M ± 0.05 M).

L'étape de réduction (b1) peut être effectuée à une température comprise entre 20°C et 100°C, notamment, entre 30°C et 70°C et, en particulier, de l'ordre de 50°C (i.e. 50°C ± 5°C).The reduction step (b 1 ) can be carried out at a temperature between 20 ° C and 100 ° C, in particular between 30 ° C and 70 ° C and, in particular, of the order of 50 ° C (ie 50 ° C ± 5 ° C).

De plus, l'étape de réduction (b1) peut durer entre 30 sec et 1 h, notamment entre 1 et 30 min et, en particulier, entre 2 et 20 min.In addition, the reduction step (b 1 ) can last between 30 sec and 1 h, in particular between 1 and 30 min and, in particular, between 2 and 20 min.

Les précurseurs du matériau métallique réduits suite à l'étape (b1) du procédé selon l'invention, présentent majoritairement un degré d'oxydation de 0. Ainsi, la métallisation peut alors avoir lieu par immersion dans un bain de métallisation et croissance sur les particules de précurseurs à un degré d'oxydation de 0.The precursors of the metallic material reduced following step (b 1 ) of the process according to the invention mainly have an oxidation degree of 0. Thus, the metallization can then take place by immersion in a metallization bath and growth on the precursor particles at an oxidation degree of 0.

Il convient de noter que cette étape de réduction (étape (b1)) peut être optionnelle. En effet, dans certains cas, le précurseur du matériau métallique peut être réduit lors de la mise en contact avec la solution contenant au moins un ion du matériau métallique lors de l'étape (b2) sans qu'une étape de réduction préalable ne soit nécessaire. En effet, si le précurseur du matériau métallique a un potentiel d'oxydo-réduction supérieur au métal déposé par Electroless, le précurseur du matériau métallique peut être, dans un premier temps, réduit lors de la mise en contact avec l'ion du matériau métallique avant que la croissance métallique ne soit initiée.It should be noted that this reduction step (step (b 1 )) may be optional. Indeed, in some cases, the precursor of the metallic material can be reduced during contacting with the solution containing at least one ion of the metallic material during step (b 2 ) without a prior reduction step be necessary. Indeed, if the precursor of the metallic material has a higher oxidation-reduction potential than the metal deposited by Electroless, the precursor of the metallic material can be, initially, reduced upon contact with the ion of the metallic material before the metal growth is initiated.

L'étape (b2) consiste donc à mettre en contact ledit précurseur réduit suite à l'étape (b1) dans une solution contenant au moins un ion du matériau métallique. La solution contenant un ion du matériau métallique ci-après désignée SM correspond à un bain de métallisation bien connu de l'homme du métier, tout comme ses composants.Step (b 2 ) therefore consists in bringing said reduced precursor into contact following step (b 1 ) in a solution containing at least one ion of the metallic material. The solution containing an ion of the metal material hereinafter designated S M corresponds to a metallization bath well known to those skilled in the art, just like its components.

A titre d'exemple, la solution contenant au moins un ion du matériau métallique SM mise en oeuvre à l'étape (b2) comprend des ions du matériau métallique, un agent complexant les ions du matériau métallique, un agent réducteur et un régulateur de pH. Avantageusement, ladite solution SM est une solution aqueuse. De plus, plusieurs solutions de métallisation sont disponibles dans le commerce.By way of example, the solution containing at least one ion of the metallic material S M implemented in step (b 2 ) comprises ions of the metallic material, a complexing agent for the ions of the metallic material, a reducing agent and a pH regulator. Advantageously, said solution S M is an aqueous solution. In addition, several metallization solutions are commercially available.

Le (ou les) ion (s) du matériau métallique mis en oeuvre dans le cadre de la présente invention peu(ven)t être tout ion d'un matériau métallique. La présente invention concerne plus particulièrement les ions d'un métal de transition. Avantageusement, le (ou les) ion(s) du matériau métallique selon l'invention est(sont) choisi(s) dans le groupe constitué par Ag+, Ag2+, Ag3+, Au+, Au3+, Co2+, Cu+, Cu2+, Fe2+, Ni2+, Pd+, et Pt+.The ion (s) of the metallic material used in the context of the present invention may be any ion of a metallic material. The present invention relates more particularly to the ions of a transition metal. Advantageously, the ion (s) of the metallic material according to the invention is (are) chosen from the group consisting of Ag + , Ag 2+ , Ag 3+ , Au + , Au 3+ , Co 2+ , Cu + , Cu 2+ , Fe 2+ , Ni 2+ , Pd + , and Pt + .

Dans la solution SM, le (ou les) ion(s) du matériau métallique est(sont) associé(s) à un contre-ion anionique. A titre de contre-ions anioniques utilisables, on peut citer un chlorure, un bromure, un fluorure, un iodure, un sulfate, un nitrate, un phosphate, un acétate et tout sel d'acide organique ou inorganique.In the solution S M , the ion (s) of the metallic material is (are) associated with a counter-ion anionic. As anionic counterions that may be used, mention may be made of a chloride, a bromide, a fluoride, an iodide, a sulphate, a nitrate, a phosphate, an acetate and any organic or inorganic acid salt.

L'agent complexant les ions du matériau métallique est nécessaire pour compenser la perte de solubilité de ces ions dans les conditions basiques utilisées et éviter leur précipitation. Un tel agent complexant est notamment choisi parmi les acides organiques et leurs sels tels que l'acide tartarique, de l'EDTA ou de l'EDTP.The complexing agent ions of the metallic material is necessary to compensate for the loss of solubility of these ions under the basic conditions used and avoid their precipitation. Such a complexing agent is in particular chosen from organic acids and their salts such as tartaric acid, EDTA or EDTP.

L'agent réducteur avantageusement mis en oeuvre peut être notamment du formaldéhyde, du DMAB ou du H2PO2. L'homme du métier connaît différents couples ions du matériau métallique/agent réducteur utilisables dans le cadre de la présente invention. De même, en fonction du couple particulier choisi, l'homme du métier les conditions de pH et de température de la solution SM à mettre en oeuvre.The reducing agent advantageously used may especially be formaldehyde, DMAB or H 2 PO 2 . Those skilled in the art know different ion pairs of the metallic material / reducing agent used in the context of the present invention. Similarly, depending on the particular couple chosen, those skilled in the art the pH and temperature conditions of the solution S M to implement.

A titre d'exemple dans une solution SM contenant des ions du cuivré, l'agent réducteur avantageusement mis en oeuvre dans des conditions basiques est du formaldéhyde en une quantité comprise entre 0,1 et 5% (v/v) par rapport au volume total de la solution SM. Par « conditions basiques », on entend une solution dont le pH est compris, entre 10 et 14 et notamment entre 12 et 13, un tel pH est atteint en utilisant du NaOH en tant que régulateur du pH.By way of example in a solution S M containing copper ions, the reducing agent advantageously used under basic conditions is formaldehyde in an amount of between 0.1 and 5% (v / v) with respect to total volume of the solution S M. By "basic conditions" is meant a solution whose pH is between 10 and 14 and in particular between 12 and 13, such a pH is reached using NaOH as a pH regulator.

A titre d'exemple dans une solution SM contenant des ions du cuivre, l'étape de métallisation (b2) peut être effectuée à une température comprise entre 20°C et 80°C, notamment, entre 30°C et 60°C et, en particulier, de l'ordre de 40°C (i.e. 40°C ± 5°C).By way of example in a solution S M containing copper ions, the metallization step (b 2 ) can be carried out at a temperature of between 20 ° C. and 80 ° C., in particular between 30 ° C. and 60 ° C. and, in particular, of the order of 40 ° C. (ie 40 ° C. ± 5 ° C.). ° C).

De plus, l'étape de métallisation (b2) peut durer entre 1 min et 1 h, notamment entre 5 et 45 min et, en particulier, entre 10 et 30 min.In addition, the metallization step (b 2 ) can last between 1 min and 1 h, in particular between 5 and 45 min and, in particular, between 10 and 30 min.

La métallisation de la surface du substrat i.e. la présence d'une fine couche de matériau métallique à la surface du substrat est facilement vérifiable, typiquement, visuellement et notamment à l'oeil nu.The metallization of the surface of the substrate i.e. the presence of a thin layer of metallic material on the surface of the substrate is easily verifiable, typically, visually and in particular with the naked eye.

Dans le cadre de la présente invention, préalablement à l'étape (a) du procédé, la surface du substrat à métalliser peut éventuellement subir différents pré-traitements. Ces prétraitements peuvent être des traitements classiques du domaine de la métallisation des surfaces tels que dégraissage ou polissage.In the context of the present invention, prior to step (a) of the method, the surface of the substrate to be metallized may possibly undergo different pre-treatments. These pretreatments may be conventional treatments in the field of metallization of surfaces such as degreasing or polishing.

En variante, la surface du substrat peut éventuellement être soumise, préalablement à l'étape (a) du procédé selon l'invention à un traitement apte à augmenter son hydrophilie et/ou sa rugosité, ledit traitement étant choisi dans le groupe constitué par un sablage, une abrasion, un traitement chimique avec bain de décapage, un traitement par flamme, un traitement par effet corona et un traitement par plasma et leurs combinaisons.As a variant, the surface of the substrate may optionally be subjected, prior to step (a) of the process according to the invention, to a treatment capable of increasing its hydrophilicity and / or roughness, said treatment being chosen from the group consisting of a sandblasting, abrasion, chemical treatment with pickling bath, flame treatment, corona treatment and plasma treatment and combinations thereof.

En effet, le traitement mis en oeuvre lors de l'étape (a) n'apporte aucune rugosité supplémentaire à la surface du substrat ce qui peut être vérifié par mesure AFM. Aussi, suivant la rugosité initiale du (co)polymère constituant la surface du substrat ou le substrat, un prétraitement précédent l'étape (a) afin d'amener une rugosité de surface doit être effectué.Indeed, the processing implemented during step (a) does not bring any additional roughness to the surface of the substrate which can be verified by AFM measurement. Also, according to the initial roughness of the (Co) polymer constituting the surface of the substrate or the substrate, a pretreatment preceding step (a) to bring a surface roughness must be performed.

De plus, il peut être nécessaire d'augmenter l'hydrophilie du (co)polymère constituant la surface du substrat ou le substrat à traiter. Certains (co)polymères possèdent déjà des groupes azotés ou oxygénés tels que les poly(acide acrylique), les polyanilines et les polyamides. Si ces oxygènes ou azotes sont accessibles en surface du substrat à métalliser, l'étape apportant l'hydrophilie n'est pas obligatoire.In addition, it may be necessary to increase the hydrophilicity of the (co) polymer constituting the surface of the substrate or the substrate to be treated. Some (co) polymers already have nitrogen or oxygen groups such as poly (acrylic acid), polyanilines and polyamides. If these oxygens or nitrogens are accessible on the surface of the substrate to be metallized, the step providing hydrophilicity is not mandatory.

Selon le polymère, la rugosité de surface avec ou sans apport de fonctions hydrophiles peut être ainsi apportée par prétraitement mécanique, chimique ou par voie sèche et sera, pour certains cas, accompagnée d'une oxydation de surface.Depending on the polymer, the surface roughness with or without hydrophilic function can be provided by mechanical pretreatment, chemical or dry and will, in some cases, accompanied by surface oxidation.

Un prétraitement mécanique de la surface à traiter consiste en un sablage ou une abrasion avec des papiers de grains plus ou moins gros. Il ne modifie en aucun cas la composition chimique de la surface et n'oxyde donc pas la surface du (co)polymère constituant la surface du substrat ou le substrat à traiter. En outre, il n'est pas toujours efficace et ne reste possible que dans le cas des substrats de taille adéquate tels que les substrats se présentant sous forme de grosses pièces planes.Mechanical pretreatment of the surface to be treated consists of sandblasting or abrasion with grains of larger or smaller size. It does not modify in any way the chemical composition of the surface and therefore does not oxidize the surface of the (co) polymer constituting the surface of the substrate or the substrate to be treated. In addition, it is not always effective and remains possible only in the case of substrates of adequate size such as substrates in the form of large flat parts.

Un prétraitement chimique (acide/base) (ou traitement chimique avec bain de décapage) est basé sur la mise en contact de la surface à traiter avec un bain de décapage acide ou basique et est spécifique aux (co)polymères à métalliser. Il apporte rugosité de surface et très généralement oxydation de surface. A chaque fois, le décapage, appelé également « satinage », va dégrader en surface le (co)polymère constituant la surface du substrat ou le substrat à traiter par attaque chimique. Ce décapage suit les lois de la réactivité chimique des chaînes polymériques.A chemical pretreatment (acid / base) (or chemical treatment with pickling bath) is based on contacting the surface to be treated with a bath acid or basic pickling and is specific to the (co) polymers to be metallized. It brings surface roughness and very generally surface oxidation. In each case, etching, also called "satin", will degrade the surface (co) polymer constituting the surface of the substrate or the substrate to be treated by etching. This stripping follows the laws of the chemical reactivity of the polymer chains.

En effet, cette dégradation entraîne une rupture de chaînes de (co)polymères en surface, entraînant de ce fait leur solubilisation afin de faire apparaître une rugosité à la surface du (co)polymère. A titre d'exemples, une attaque acide sur des polymères de type polyamide permet une dégradation de la matière organique. De la même façon, une attaque basique permet la dégradation et la dissolution du polycarbonate contenu en surface dans l'ABS-PC augmentant la rugosité de surface. Ces traitements acido-basiques apportent donc rugosité et oxydation.Indeed, this degradation causes a rupture of chains of (co) polymers on the surface, thereby causing their solubilization in order to reveal a roughness on the surface of the (co) polymer. By way of examples, an acid attack on polyamide-type polymers allows degradation of the organic material. In the same way, a basic attack allows the degradation and the dissolution of the polycarbonate contained in the surface in the ABS-PC increasing the surface roughness. These acid-base treatments provide roughness and oxidation.

A titre d'exemple de bain de décapage, on peut citer une solution aqueuse acide comprenant au moins un acide inorganique. Ledit acide inorganique est notamment choisi dans le groupe constitué par l'acide chromique, l'acide sulfurique, l'acide nitrique, l'acide hypochloreux et leurs mélanges. Par « mélange », on entend un mélange d'au moins deux acides inorganiques différents tels qu'un mélange d'acide chromique et d'acide sulfurique ou un mélange d'au moins trois acides inorganiques différents tels qu'un mélange d'acide nitrique, d'acide hypochloreux et d'acide sulfurique.As an example of a pickling bath, mention may be made of an acidic aqueous solution comprising at least one inorganic acid. Said inorganic acid is especially selected from the group consisting of chromic acid, sulfuric acid, nitric acid, hypochlorous acid and mixtures thereof. By "mixture" is meant a mixture of at least two different inorganic acids such as a mixture of chromic acid and sulfuric acid or a mixture of at least three different inorganic acids such as an acid mixture nitric acid, hypochlorous acid and sulfuric acid.

Le pré-traitement chimique est avantageusement effectué pendant une durée comprise entre 1 et 60 min, notamment entre 2 et 30 min et, en particulier, entre 5 et 20 min et à une température comprise entre 20 et 120°C, notamment entre 40 et 110°C et, en particulier, entre 60 et 100°C.The chemical pre-treatment is advantageously carried out for a period of between 1 and 60 min, in particular between 2 and 30 min and, in particular, between 5 and 20 min and at a temperature of between 20 and 120 ° C, in particular between 40 and 110 ° C and in particular between 60 and 100 ° C.

La surface à traiter peut également être soumise à un pré-traitement par voie sèche. De tels traitements physico-chimiques comprenant un traitement par flamme, un traitement par effet corona et un traitement par plasma ont également un double effet : i) l'oxydation des liaisons chimiques en surface et ii) l'augmentation de la rugosité.The surface to be treated may also be subjected to a dry pretreatment. Such physicochemical treatments comprising a flame treatment, a corona treatment and a plasma treatment also have a double effect: i) the oxidation of chemical bonds on the surface and ii) the increase in roughness.

Le traitement par flamme également appelé « flammage » consiste à exposer la surface du substrat et/ou le substrat à l'action d'une flamme et notamment à l'action d'une flamme stable et légèrement oxydante. Les hautes températures de ce traitement génèrent des espèces actives qui peuvent correspondre à des radicaux, des ions ou des molécules excitées. Le (co)polymère constituant la surface du substrat et/ou le substrat est oxydé sur une épaisseur de l'ordre de 4 à 9 mm. En surface, se fixent des groupements fonctionnels de type carboxylique (-COOH), hydroxyle (-OH), carbonyle (-C=O), amine (-NH2), nitrile (-CN) et parfois amide (-CONH). On observe un phénomène de diffusion à l'intérieur du polymère d'espèces chimiques provenant de sa dégradation. Il y a une véritable restructuration de la surface. Ces modifications se traduisent par une amélioration de la mouillabilité et de la rugosité de la surface à revêtir.The flame treatment also known as "flaming" consists in exposing the surface of the substrate and / or the substrate to the action of a flame and in particular to the action of a stable and slightly oxidizing flame. The high temperatures of this treatment generate active species that can correspond to radicals, ions or excited molecules. The (co) polymer constituting the surface of the substrate and / or the substrate is oxidized to a thickness of about 4 to 9 mm. On the surface, functional groups of carboxylic type (-COOH), hydroxyl (-OH), carbonyl (-C = O), amine (-NH 2 ), nitrile (-CN) and sometimes amide (-CONH) are fixed. A diffusion phenomenon is observed inside the polymer of chemical species resulting from its degradation. There is a real restructuring of the surface. These changes are result in an improvement of the wettability and roughness of the surface to be coated.

La flamme est notamment disposée à une distance de la surface du substrat et/ou du substrat comprise entre 0,1 et 20 cm, en particulier, entre 0,3 et 10 cm et, plus particulièrement, entre 0,5 et 5 cm.The flame is in particular disposed at a distance from the surface of the substrate and / or the substrate of between 0.1 and 20 cm, in particular between 0.3 and 10 cm and more particularly between 0.5 and 5 cm.

Cette flamme est avantageusement générée par un mélange d'au moins deux gaz, le premier et le second gaz étant respectivement choisis dans le groupe constitué par l'hydrogène, le méthane, l'éthane et le propane et le groupe constitué par l'air, l'ozone et l'oxygène. La température de la flamme ainsi obtenue est comprise entre 500 et 1600°C, notamment entre 800 et 1400°C et, en particulier, de l'ordre de 1200°C (i.e. 1200 ± 100°C).This flame is advantageously generated by a mixture of at least two gases, the first and second gases being respectively chosen from the group consisting of hydrogen, methane, ethane and propane and the group consisting of air , ozone and oxygen. The temperature of the flame thus obtained is between 500 and 1600 ° C, especially between 800 and 1400 ° C and, in particular, of the order of 1200 ° C (i.e. 1200 ± 100 ° C).

La durée du traitement par flamme est comprise entre 0,01 et 10 sec, notamment entre 0,015 et 1 sec, et, en particulier, entre 0,02 à 0,1 sec.The duration of the flame treatment is between 0.01 and 10 sec, in particular between 0.015 and 1 sec, and in particular between 0.02 and 0.1 sec.

Le traitement par l'effet corona est aussi appelé « traitement par effet couronne » ou « traitement par décharge corona » et consiste à exposer la surface du substrat et/ou le substrat à un champ d'ionisation créé en faisant passer un courant alternatif de haut voltage entre deux électrodes distantes de quelques mm et notamment de 1 à 2 mm. Ainsi, une décharge électrique entraînée par l'ionisation du milieu entourant un conducteur se produit lorsque le potentiel électrique dépasse une valeur critique mais que les conditions ne permettent pas la formation d'un arc.Corona treatment is also referred to as "corona treatment" or "corona discharge treatment" and involves exposing the surface of the substrate and / or the substrate to an ionization field created by passing an alternating current of high voltage between two electrodes distant a few mm and in particular 1 to 2 mm. Thus, an electrical discharge driven by the ionization of the medium surrounding a conductor occurs when the electric potential exceeds a critical value but the conditions do not allow the formation of an arc.

Lors de cette ionisation, les électrons émis sont précipités dans le champ électrique et transmettent leur énergie aux molécules du milieu entourant la surface du substrat et/ou le substrat qui est avantageusement de l'air ou un gaz inerte éventuellement enrichi en oxygène. Cela entraîne une déshydrogénation et une rupture de chaînes du (ou des) (co)polymère(s) du substrat ainsi que des réactions spontanées avec les espèces chimiques présentes dans le milieu. La surface du (co)polymère constituant la surface du substrat et/ou le substrat est oxydée.During this ionization, the emitted electrons are precipitated in the electric field and transmit their energy to the molecules of the medium surrounding the surface of the substrate and / or the substrate which is advantageously air or an inert gas optionally enriched with oxygen. This leads to dehydrogenation and chain failure of the substrate (or co) polymer (s) as well as spontaneous reactions with the chemical species present in the medium. The surface of the (co) polymer constituting the surface of the substrate and / or the substrate is oxidized.

La densité de la` décharge corona est avantageusement comprise entre 10 et 500 W.min/m2, notamment entre 20 et 400 W.min/m2 et, en particulier, entre 30 et 300 W.min/m2.Density be sitting corona discharge is advantageously between 10 to 500 W.min / m 2, in particular from 20 to 400 W.min / m 2 and, particularly, from 30 to 300 W.min / m 2.

La durée du traitement par l'effet corona est comprise entre 0,1 et 600 sec, notamment entre 1 et 120 sec, et, en particulier, entre 10 à 50 sec.The duration of treatment with the corona effect is between 0.1 and 600 sec, especially between 1 and 120 sec, and in particular between 10 to 50 sec.

Le traitement par plasma consiste à exposer la surface du support solide et/ou le support solide à un plasma.Plasma treatment involves exposing the surface of the solid support and / or the solid support to a plasma.

Pour rappel, le plasma est un gaz à l'état ionisé, classiquement considéré comme un quatrième état de la matière. On apporte l'énergie nécessaire à l'ionisation d'un gaz au moyen d'une onde électromagnétique (radio fréquence ou micro onde). Le plasma est composé de molécules neutres, d'ions, d'électrons, d'espèces radicalaires (chimiquement très actives) et d'espèces excitées qui vont réagir avec la surface des matériaux. Si le gaz plasmagène contient de l'oxygène ou de l'azote, ces atomes vont réagir instantanément avec la surface du (co)polymère et y créér des sites actifs. La modification des (co)polymères par les plasmas se traduit par la formation de radicaux et de doubles liaisons, par la réticulation et la fonctionnalisation de la surface. Le traitement par plasma est habituellement limité à l'extrême surface et la rugosité de surface apportée est limitée.As a reminder, plasma is a gas in the ionized state, classically considered as a fourth state of matter. The energy required for the ionization of a gas is provided by means of an electromagnetic wave (radio frequency or microwave). Plasma is composed of neutral molecules, ions, electrons, radical species (chemically very active) and excited species that will react with the surface of materials. If the plasma gas contains Oxygen or nitrogen, these atoms will react instantly with the surface of the (co) polymer and create active sites there. The modification of the (co) polymers by the plasmas results in the formation of radicals and double bonds, by the crosslinking and the functionalization of the surface. Plasma treatment is usually limited to the extreme surface and the surface roughness provided is limited.

On distingue les plasmas dits « froids » et les plasmas dits « chauds » qui se distinguent les uns des autres vis-à-vis du taux de ionisation des espèces contenus dans le plasma. Pour les plasmas dits « froids », le taux d'ionisation des espèces réactives est inférieur à 10-4 alors que pour les plasmas dits « chauds », il est supérieur à 10-4. Les termes « chauds » et « froids » viennent du fait que le plasma dit « chaud » est beaucoup plus énergétique que le plasma dit « froid ». Dans le cas d'un prétraitement dans le cadre du procédé selon l'invention, un plasma dit « froid » est plus adapté. Le plasma est avantageusement généré par un (ou plusieurs) gaz plasmagène(s). Dans le cas où le gaz plasmagène est un mélange d'au moins deux gaz, le premier et le second gaz sont respectivement choisis dans le groupe constitué par les gaz inertes et le groupe constitué par l'air et l'oxygène.We distinguish the so-called "cold" plasmas and the so-called "hot" plasmas which are distinguished from each other with respect to the ionization rate of the species contained in the plasma. For so-called "cold" plasmas, the ionization rate of the reactive species is less than 10 -4 while for so-called "hot" plasmas it is greater than 10 -4 . The terms "hot" and "cold" come from the fact that the so-called "hot" plasma is much more energetic than the so-called "cold" plasma. In the case of a pretreatment in the context of the process according to the invention, a so-called "cold" plasma is more suitable. The plasma is advantageously generated by one (or more) plasma gas (s). In the case where the plasma gas is a mixture of at least two gases, the first and second gases are respectively selected from the group consisting of inert gases and the group consisting of air and oxygen.

La durée du traitement par plasma est comprise entre 1 sec et 5 min, notamment, entre 10 à 60 sec et, en particulier, entre 20 et 40 sec.The duration of the plasma treatment is between 1 sec and 5 min, especially between 10 to 60 sec and, in particular, between 20 and 40 sec.

Dans le cadre du procédé selon la présente invention, il peut être nécessaire entre deux étapes de traitements ; préalablement à l'étape (a) ; entre les étapes (a) et (b) ou entre les étapes (b1) et (b2) de soumettre la surface du substrat et/ou substrat à un rinçage ou à plusieurs rinçages mettant en oeuvre des solutions de rinçage identiques ou différentes.In the context of the process according to the present invention, it may be necessary between two treatment steps; prior to step (a); between steps (a) and (b) or between steps (b 1 ) and (b 2 ) subjecting the surface of the substrate and / or substrate to rinsing or rinsing using identical or different rinsing solutions .

Toute solution de rinçage connue de l'homme du métier est utilisable. Avantageusement, cette solution de rinçage est choisie parmi l'eau, l'eau distillée, l'eau désioniséé, l'eau MilliQ, une solution aqueuse contenant un détergent tel que du TDF4 ou de la soude notamment de la soude en une concentration comprise entre 0,01 et 1 M. La solution de rinçage, lorsqu'elle est mise en contact, avec la surface du substrat ou le substrat peut être agitée notamment en utilisant un agitateur, un barreau magnétique, un bain à ultrasons ou un homogénéisateur. Chaque étape de rinçage peut durer de 1 à 30 min et notamment de 5 à 20 min.Any rinse solution known to those skilled in the art is usable. Advantageously, this rinsing solution is selected from water, distilled water, deionized water, MilliQ water, an aqueous solution containing a detergent such as TDF4 or sodium hydroxide including sodium hydroxide in a concentration of between 0.01 and 1 M. The rinsing solution, when it is brought into contact with the surface of the substrate or the substrate, can be agitated, in particular by using a stirrer, a magnetic bar, an ultrasound bath or a homogenizer. Each rinsing step can last from 1 to 30 min and in particular from 5 to 20 min.

La présente invention concerne enfin un substrat dont la surface est revêtue par un matériau métallique susceptible d'être obtenu par le procédé de l'invention tel que précédemment défini.The present invention finally relates to a substrate whose surface is coated with a metallic material that can be obtained by the method of the invention as previously defined.

D'autres caractéristiques et avantages de la présente invention apparaîtront encore à l'homme du métier à la lecture des exemples ci-dessous donnés à titre illustratif et non limitatif, en référence aux figures annexées.Other features and advantages of the present invention will become apparent to those skilled in the art on reading the examples below given for illustrative and non-limiting, with reference to the accompanying figures.

BRÈVE DESCRIPTION DES DESSINSBRIEF DESCRIPTION OF THE DRAWINGS

  • La Figure 1 présente le diagramme de voltamétrie cyclique sur une plaque d'ABS métallisée par du cuivre de façon électroless selon le procédé de la présente invention.The Figure 1 presents the cyclic voltammetry diagram on a copper electroless electroless ABS plate according to the method of the present invention.
  • La Figure 2 présente le diagramme de voltamétrie cyclique sur une plaque d'ABS-PC métallisée par du cuivre de façon électroless selon le procédé de la présente invention.The Figure 2 presents the cyclic voltammetry diagram on a electroless electroless metallized copper ABS-PC plate according to the method of the present invention.
  • La Figure 3 présente le diagramme de voltamétrie cyclique sur une plaque de PA métallisée par du cuivre de façon électroless selon le procédé de la présente invention.The Figure 3 presents the cyclic voltammetry diagram on a copper electroless plated AP plate according to the method of the present invention.
  • La Figure 4 présente le diagramme de voltamétrie cyclique sur une plaque d'ABS métallisée par du cuivre de façon électroless selon le procédé de la présente invention (exemple II ci-après).The Figure 4 presents the cyclic voltammetry diagram on an electroless electroless metallized copper ABS plate according to the method of the present invention (Example II hereinafter).
  • La Figure 5 présente le diagramme de voltamétrie cyclique sur une plaque d'ABS-PC métallisée par du cuivre de façon électroless selon le procédé de la présente invention (exemple III ci-après).The Figure 5 presents the cyclic voltammetry diagram on an electroless electroless metallized copper ABS-PC plate according to the method of the present invention (Example III hereinafter).
EXPOSÉ DÉTAILLÉ DE MODES DE RÉALISATION PARTICULIERSDETAILED PRESENTATION OF PARTICULAR EMBODIMENTS I. Métallisation via un traitement de Fenton de plaques d'acrylonitrile butadiène styrène (ABS), d'acrylonitrile butadiène styrène/polycarbonate (ABS/PC) et de polyamide (PA).I. Metallization via Fenton treatment of acrylonitrile butadiene styrene (ABS), acrylonitrile butadiene styrene / polycarbonate (ABS / PC) and polyamide (PA) plates .

Ce procédé de métallisation s'effectue en 3 étapes (Traitement de Fenton/Réduction/Métallisation électroless) et avant de traiter le polymère, il convient de le préparer, dégraisser et nettoyer.This metallization process is carried out in 3 steps (Fenton Treatment / Reduction / Metallization electroless) and before treating the polymer, it should be prepared, degreased and cleaned.

I.1. PolissageI.1. Polishing

Dans un 1er temps, les plaques sont soumises à un polissage pour minimiser les effets de bords et autres défauts apportés lors de la coupe des plaques.In a 1st step, the plates are subjected to polishing to minimize edge effects and other defects introduced during the cutting of the plates.

I.2. RinçageI.2. Rinsing

Dans un 2nd temps, les plaques sont rincées à l'aide d'une solution savonneuse industrielle TDF4 mélangée à l'eau (1 mL de TDF4 pour 4 mL d'H2O MilliQ), sous ultrasons pendant 10 min. Les plaques sont ensuite rincées à l'eau MilliQ, sous ultrasons pendant 10 min.In a 2 nd time, the plates are rinsed with a soap solution industrial TDF4 mixed with water (1 mL of TDF4 for 4 mL of H 2 O MilliQ), under ultrasound for 10 min. The plates are then rinsed with MilliQ water, under ultrasound for 10 min.

I.3. Prétraitement de FentonI.3. Pretreatment of Fenton

Du sulfate de fer (II) (6,961 g, 0,1 mol), a été solubilisé dans 50 mL d'acide sulfurique à 10-3 M dans l'eau. Dans cette solution, ont été immergées les plaques de polymères. 10 mL (0,124 mol) de peroxyde d'hydrogène à 35% dans l'eau ont été ensuite ajoutés, goutte à goutte. Après 25 min, les échantillons ont été rincés à l'eau MilliQ avant d'être séchés.Iron (II) sulfate (6.961 g, 0.1 mol) was solubilized in 50 mL of 10 -3 M sulfuric acid in water. In this solution, the polymer plates were immersed. 10 mL (0.124 mol) of 35% hydrogen peroxide in water was then added dropwise. After 25 min, the samples were rinsed with MilliQ water before being dried.

Les résultats obtenus pour les mesures d'angle de contact d'une goutte de 2 µl d'eau déposée sur les échantillons traités selon le traitement de Fenton (« Après ») ou sans traitement (« Vierge ») sont présentés dans le Tableau 1 ci-après. Tableau 1 : Mesure des angles de contact d'une goutte ABS ABS/PC PA Vierge 90° 81,8° 63,2° Après Fenton 0 à 14° 32,4° 0 à 15° The results obtained for the contact angle measurements of a droplet of 2 μl of water deposited on the samples treated according to the treatment of Fenton ("After") or without treatment ("Virgin") are presented in Table 1. below. <i><b> Table 1 </ b>: Measuring the contact angles of a drop </ i> ABS ABS / PC PA Virgin 90 81.8 ° 63.2 ° After Fenton 0 to 14 ° 32.4 ° 0 to 15 °

L'angle de contact est clairement abaissé. La surface est devenue très hydrophile de par son oxydation.The contact angle is clearly lowered. The surface has become very hydrophilic because of its oxidation.

L'analyse des spectres IR est présentée dans le Tableau 2 ci-après. Tableau 2 : Bandes IR apparues après le traitement oxydatif de Fenton sur les échantillons Plaques de polymères ABS ABS/PC PA Après Fenton 3600-3200 cm-1 3600-3100 cm-1 3600-3100 cm-1 1700-1640 cm-1 1700-1640 cm-1 1150-1100 cm-1 1150-1100 cm-1 The analysis of the IR spectra is presented in Table 2 below. <i><b> Table 2 </ b></i>:<i> IR bands that appeared after the oxidative treatment of Fenton on the samples </ i> Polymer plates ABS ABS / PC PA After Fenton 3600-3200 cm -1 3600-3100 cm -1 3600-3100 cm -1 1700-1640 cm -1 1700-1640 cm -1 1150-1100 cm -1 1150-1100 cm -1

L'apparition des bandes à 3600-3200 cm-1 et entre 1150-1100 cm-1 est typique de l'apport de liaisons C-OH. Pour l'ABS et l'ABS-PC, la bande à 1700-1640 cm-1 pourrait signifier l'apparition de groupements amides provenant de l'oxydation des groupements nitrile du polyacrylonitrile. Dans le cadre du polyamide, les bandes à 1150-1100 et à 1700 sont confondues avec les bandes du polymère vierge.The appearance of bands at 3600-3200 cm -1 and between 1150-1100 cm -1 is typical of the contribution of C-OH bonds. For ABS and ABS-PC, the band at 1700-1640 cm -1 could mean the appearance of amide groups originating from the oxidation of the nitrile groups of polyacrylonitrile. In the context of the polyamide, the bands 1150-1100 and 1700 are confused with the strips of the virgin polymer.

L'analyse XPS de la plaque d'ABS avant/après traitement de Fenton montre un apport d'ion Fe2+/Fe3+ et une forte oxydation de la surface par un apport d'oxygène. Les rapports atomiques par rapport au signal du carbone sont présentés dans le Tableau 3 ci-après. Tableau 3 : Rapport des intensités obtenues à l'analyse XPS des différents éléments par rapport aux électrons de la couche 1s du carbone Rapport Intensité X /C1s Electrons ABS Vierge ABS Fenton C1s 1 1 O1s 0,028 1,130 N 1s 0,097 0,049 Fe 2p3/2 0 0,141 Fe 2p1/2 0 0,122 B 1s 0 0 S 2p 0 0,132 The XPS analysis of the ABS plate before / after treatment of Fenton shows a Fe 2+ / Fe 3+ ion supply and a strong oxidation of the surface by an oxygen supply. The atomic ratios with respect to the carbon signal are shown in Table 3 below. <i><b> Table 3 </ b>: Report of the intensities obtained at the XPS analysis of the different elements with respect to the electrons of the carbon layer 1s </ i> Intensity Report X / C1s Electrons ABS Virgin ABS Fenton C1s 1 1 O1s 0,028 1,130 N 1s 0.097 0.049 Fe 2p3 / 2 0 0.141 Fe 2p1 / 2 0 0.122 B 1s 0 0 S 2p 0 0.132

I.4. Réduction des ions ferrique/ferreuxI.4. Reduction of ferric / ferrous ions

Du borohydrure de sodium NaBH4 (0,316 g, 0,8 X 10-2 mol) est dissout dans 25 mL d'une solution de soude (NaOH) à 0,1 M. Cette solution est chauffée à 80°C à l'aide d'un bain-marie et les échantillons y sont immergés. Après 12 min, les échantillons ont été rincés à l'eau MilliQ avant d'être séchés.NaBH 4 sodium borohydride (0.316 g, 0.8 X 10 -2 mol) is dissolved in 25 ml of a 0.1 M sodium hydroxide solution (NaOH). This solution is heated to 80 ° C. at room temperature. using a water bath and the samples are immersed in it. After 12 min, the samples were rinsed with MilliQ water before being dried.

L'analyse IR révèle la conservation de l'oxydation obtenue après Fenton avec les bandes à 3600-3100 cm-1, et les bandes 1700-1640 cm-1, quel que soit le polymère.IR analysis reveals the preservation of the oxidation obtained after Fenton with the bands at 3600-3100 cm -1 , and the bands 1700-1640 cm -1 , whatever the polymer.

L'analyse XPS de la plaque d'ABS avant/après réduction montre une légère diminution de tous les éléments hormis l'apparition de bohr. D'après les spectres XPS, celui-ci est sous forme oxydée et confirme ainsi la réduction des ions Fe2+/Fe3+ par le borohydrure BH4 -. Le fer est, quant à lui, oxydé à l'air et l'eau avant l'analyse XPS et se présente sous forme oxydée. Les rapports atomiques par rapport au signal du carbone sont présentés dans le Tableau 4 ci-après. Tableau 4 : Rapport des intensités obtenues à l'analyse XPS des différents éléments par rapport aux électrons de la couche 1s du carbone Rapport Intensité X /C1s Electrons ABS Fenton ABS Fenton + Réduction C1s 1 1 O1s 1,130 0,860 N 1s 0,049 0,027 Fe 2p3/2 0,141 0,124 Fe 2p1/2 0,122 0,108 B 1s 0 0,088 S 2p 0,132 0,116 The XPS analysis of the ABS plate before / after reduction shows a slight decrease of all elements except the appearance of bohr. According to the XPS spectra, it is in oxidized form and thus confirms the reduction of Fe 2+ / Fe 3+ ions by borohydride BH 4 - . The iron is, in turn, oxidized in air and water before the XPS analysis and is in oxidized form. The atomic ratios with respect to the carbon signal are shown in Table 4 below. <i><b> Table 4 </ b>: Report of the intensities obtained in the XPS analysis of the different elements with respect to the electrons of the carbon layer 1s </ i> Intensity Report X / C1s Electrons ABS Fenton ABS Fenton + Reduction C1s 1 1 O1s 1,130 0.860 N 1s 0.049 0,027 Fe 2p3 / 2 0.141 0.124 Fe 2p1 / 2 0.122 0.108 B 1s 0 0.088 S 2p 0.132 0.116

I.5. Bain de métallisation Electroless de cuivreI.5. Copper electroless metallization bath

Les échantillons sont immergés dans la solution décrite dans le Tableau 5 ci-après, chauffée à 40°C dans un bain-marie : Tableau 5 : Composition du bain de métallisation de cuivre Bain de métallisation Réactifs m(g) pour 100 mL C (g/l) CuSO4, 7H2O 0,5 5 Tartrate de dissodium C4H4Na2O6 2,96 25 NaOH 0,5 7 Formaldehyde HCHO (37% dans H2O) 2,94 10 mL/L The samples are immersed in the solution described in Table 5 below, heated to 40 ° C. in a water bath: <b><i> Table 5 </ i></b>:<i> Composition of copper plating bath </ i> Metallic bath Reagents m (g) for 100 mL C (g / l) CuSO 4 , 7H 2 O 0.5 5 Dissodium tartrate C 4 H 4 Na 2 O 6 2.96 25 NaOH 0.5 7 Formaldehyde HCHO (37% in H 2 O) 2.94 10 mL / L

Après 15 min, les échantillons ont été rincés à l'eau MilliQ, sous ultrasons pendant 10 min avant d'être séchés.After 15 min, the samples were rinsed with MilliQ water, under ultrasound for 10 min before being dried.

L'analyse Infrarouge révèle la disparition des pics des différents polymères.Infrared analysis reveals the disappearance of the peaks of the different polymers.

L'analyse XPS confirme la présence d'une couche de cuivre métallique (sous sa forme réduite, Cu0). Les rapports atomiques par rapport au signal du carbone sont présentés dans le Tableau 6 ci-après. Tableau 6 : Rapport des intensités obtenues à l'analyse XPS des différents éléments par rapport aux électrons de la couche 1s du carbone Rapport Intensité X /C1s Electrons ABS Fenton + Réduction ABS après métallisation C1s 1 1,000 O1s 0,860 0,501 N 1s 0,027 0,030 Fe 2p3/2 0,124 0 Fe 2p1/2 0,108 0 B 1s 0,088 0 S 2p 0,116 0 Cu 2p3/2 0 0,816 Cu 2p1/2 0 0,713 XPS analysis confirms the presence of a metallic copper layer (in its reduced form, Cu 0 ). The atomic ratios with respect to the carbon signal are shown in Table 6 below. <i><b> Table 6 </ b>: Report of the intensities obtained in the XPS analysis of the different elements with respect to the electrons of the 1s carbon layer </ i> Intensity Report X / C1s Electrons ABS Fenton + Reduction ABS after metallization C1s 1 1,000 O1s 0.860 0.501 N 1s 0,027 0,030 Fe 2p3 / 2 0.124 0 Fe 2p1 / 2 0.108 0 B 1s 0.088 0 S 2p 0.116 0 Cu 2p3 / 2 0 0.816 Cu 2p1 / 2 0 0.713

La couche de cuivre est également visible à l'oeil. La présence de carbone, azote et oxygène après métallisation est due à la présence d'impuretés organiques à l'extrême surface du substrat métallisé. L'oxygène peut également provenir de l'oxydation à l'air de la couche de cuivre avant l'analyse.The copper layer is also visible to the eye. The presence of carbon, nitrogen and oxygen after metallization is due to the presence of organic impurities at the extreme surface of the metallized substrate. Oxygen can also come from the air oxidation of the copper layer prior to analysis.

I.6. Dépôt de cuivre par électrodépositionI.6. Electroplating copper deposit

Afin de confirmer la présence d'une couche métallique, du cuivre a été déposé par électrodéposition. Cette technique n'est possible qu'en présence de substrats conducteurs.In order to confirm the presence of a metal layer, copper was deposited by electroplating. This technique is only possible in the presence of conductive substrates.

Ainsi les plaques d'ABS, ABS-PC et PA ayant subi une métallisation au cuivre ont été utilisées, tour à tour, comme électrode de mesure. Le système électrochimique mis en place était constitué d'une électrode de référence au calomel à KCl saturée et d'une contre-électrode au graphite.Thus the plates of ABS, PC-PC and PA having undergone a metallization with copper were used, in turn, like measuring electrode. The system Electrochemical set up consisted of a saturated KCl calomel reference electrode and a graphite counter electrode.

Les électrodes ont été trempées dans une solution de CuSO4 à 10 g/L, le potentiel initial était d'environ 0,1 V.The electrodes were soaked in a solution of CuSO 4 at 10 g / L, the initial potential was about 0.1 V.

Un cycle de voltamétrie allant jusqu'à -0,6 V en 30 s a été imposé au système. Lors de la remontée en tension, l'expérience a été stoppée aux alentours de -0,45 V (Figures 1, 2 et 3).A voltammetry cycle of up to -0.6 V was imposed on the system. During the voltage rise, the experiment was stopped at around -0.45 V ( Figures 1, 2 and 3 ).

Ce cycle a mis en évidence le dépôt de cuivre sur l'électrode de mesure. En effet, le courant a augmenté quand la tension a diminué et le cuivre s'est déposé sur les plaques faisant office d'électrode de mesure. La réduction du cuivre a eu lieu à l'électrode de mesure.This cycle showed the deposition of copper on the measuring electrode. Indeed, the current increased when the voltage decreased and the copper was deposited on the plates acting as measuring electrode. Copper reduction took place at the measuring electrode.

La confirmation du dépôt de cuivre est également visuelle. En effet, la couche de cuivre déposée par électrochimie a un aspect légèrement plus homogène.The confirmation of the copper deposit is also visual. Indeed, the copper layer deposited by electrochemistry has a slightly more homogeneous appearance.

II. Métallisation via un prétraitement accompagné d'un traitement de Fenton de plaques d'ABS. II. Metallization via pretreatment with Fenton treatment of ABS plates.

Ce procédé de métallisation s'effectue en 4 étapes (Prétraitement Oxydant/Traitement de Fenton/Réduction/Métallisation électroless) et avant de, traiter le polymère, il convient de le préparer, dégraisser et nettoyer.This metallization process is carried out in 4 stages (Pretreatment Oxidizer / Fenton Treatment / Reduction / Electroless Metallization) and before treating the polymer, it is necessary to prepare it, degrease and clean.

II.1. PolissageII.1. Polishing

Dans un 1er temps, les plaques sont soumises à un polissage pour minimiser les effets de bords et autres défauts apportés lors de la coupe des plaques.In a 1st step, the plates are subjected to polishing to minimize edge effects and other defects introduced during the cutting of the plates.

II.2. RinçageII.2. Rinsing

Dans un 2nd temps, les plaques sont rincées à l'aide d'une solution savonneuse industrielle TDF4 mélangée à l'eau (1 mL de TDF4 pour 4 mL d'H20 MilliQ), sous ultrasons pendant 10 min. Les plaques sont ensuite rincées à l'eau MilliQ, sous ultrasons pendant 10 min.In a 2 nd time, the plates were rinsed using an industrial soap solution TDF4 mixed with water (1 mL TDF4 4 mL of MilliQ H 2 0) under ultrasound for 10 min. The plates are then rinsed with MilliQ water, under ultrasound for 10 min.

II.3. Prétraitement acideII.3. Pretreatment acid

Les plaques sont immergées pendant 10 min dans une solution d'acide nitrique à 60% à une température de 60°C. Les plaques sont ensuite rincées dans une solution NaOH (0.1M) sous ultrashons pendant 10 min puis à l'eau MilliQ sous ultrasons pendant 10 min.The plates are immersed for 10 min in a 60% nitric acid solution at a temperature of 60 ° C. The plates are then rinsed in a NaOH solution (0.1M) in ultrashons for 10 min and then in MilliQ water under ultrasound for 10 min.

Les résultats obtenus pour les mesures d'angle de contact d'une goutte de 2 µl d'eau déposée sur les échantillons traités selon le traitement de Fenton (« Après ») ou sans traitement (« Vierge ») sont présentés dans le Tableau 7 ci-après. Tableau 7: Mesure des angles de contact d'une goutte ABS Vierge 90° Après prétraitement acide 67° The results obtained for the contact angle measurements of a droplet of 2 μl of water deposited on the samples treated according to the treatment of Fenton ("After") or without treatment ("Virgin") are presented in Table 7. below. <i><b> Table 7 </ b>: Measuring the contact angles of a drop </ i> ABS Virgin 90 After acid pretreatment 67 °

L'angle de contact est abaissé. La surface est devenue plus hydrophile de par son oxydation et la rugosité de surface a augmenté.The contact angle is lowered. The surface has become more hydrophilic due to its oxidation and the surface roughness has increased.

L'analyse des spectres IR est présentée dans le Tableau 8 ci-après. Tableau 8 : Bandes IR apparues après le prétraitement acide Plaques de polymères ABS Après Traitement acide 3600-3200 cm-1 1660-1610 cm-1 1570-1530 cm-1 1320-1280 cm-1 The analysis of the IR spectra is presented in Table 8 below. <i><b> Table 8 </ b>: IR Bands Appeared After Acid Pretreatment </ i> Polymer plates ABS After acid treatment 3600-3200 cm -1 1660-1610 cm -1 1570-1530 cm -1 1320-1280 cm -1

L'apparition des bandes à 3600-3200 cm-1 et 1660-1610 cm-1 peut-être due à la présence de traces d'eau.The appearance of bands at 3600-3200 cm -1 and 1660-1610 cm -1 may be due to the presence of traces of water.

En revanche, les bandes à 1570-1530 cm-1 et à 1320-1280 cm-1 sont caractéristiques des groupes carbonyles, type carboxylate COO-. Ceci confirme l'oxydation de surface.On the other hand, the bands at 1570-1530 cm -1 and at 1320-1280 cm -1 are characteristic of carbonyl groups, carboxylate type COO - . This confirms surface oxidation.

II.4. Prétraitement de FentonII.4. Pretreatment of Fenton

Du sulfate de fer(II) (6,961 g, 0,1 mol) a été solubilisé dans 50 mL d'acide sulfurique à 10-3 M dans l'eau. Dans cette solution, ont été immergées les plaques de polymères. 10 mL (0,124 mol) de peroxyde d'hydrogène à 35% dans l'eau ont été ensuite ajoutés, goutte à goutte. Après 25 min, les échantillons ont été rincés à l'eau MilliQ avant d'être séchés.Iron (II) sulfate (6.961 g, 0.1 mol) was solubilized in 50 mL of 10 -3 M sulfuric acid in water. In this solution, the polymer plates were immersed. 10 mL (0.124 mol) of 35% hydrogen peroxide in water were then added, drip. After 25 min, the samples were rinsed with MilliQ water before being dried.

Les résultats obtenus pour les mesures d'angle de contact d'une goutte de 2 µl d'eau déposée sur les échantillons traités selon le traitement de Fenton (« Après Fenton ») ou avant traitement (« Après traitement acide ») sont présentés dans le Tableau 9 ci-après. Tableau 9 : Mesure des angles de contact d'une goutte ABS Après traitement acide 67° Après Fenton 0 à 5° The results obtained for the contact angle measurements of a droplet of 2 μl of water deposited on the samples treated according to the Fenton treatment ("After Fenton") or before treatment ("After acid treatment") are presented in Table 9 below. <i><b> Table 9 </ b>: Measuring the contact angles of a drop </ i> ABS After acid treatment 67 ° After Fenton 0 to 5 °

L'angle de contact est clairement abaissé. La surface est devenue très hydrophile de par son oxydation.The contact angle is clearly lowered. The surface has become very hydrophilic because of its oxidation.

L'analyse des spectres IR est présentée dans le Tableau 10 ci-après. Tableau 10 : Bandes IR apparues après le traitement oxydatif de Fenton sur les échantillons Plaques de polymères ABS Après Fenton 3600-3200 cm-1 1700-1600 cm-1 1320-1280 cm-1 1150-1100 cm-1 The analysis of the IR spectra is presented in Table 10 below. <i><b> Table 10 </ b>: IR Bands Appeared After Fenton's Oxidative Treatment on Samples </ i> Polymer plates ABS After Fenton 3600-3200 cm -1 1700-1600 cm -1 1320-1280 cm -1 1150-1100 cm -1

L'amplification de la bande à 3600-3200 cm-1 après traitement Fenton ainsi que l'apparition de la bande entre 1150-1100 cm-1 sont typiques de l'apport de liaisons C-OH. L'apparition de la bande à 1700-1600 cm-1 et l'amplification de la bande 1320-1280 cm-1 confirment la présence de groupements carbonyles à la surface des plaques d'ABS.The amplification of the 3600-3200 cm -1 band after Fenton treatment as well as the appearance of the band between 1150-1100 cm -1 are typical of the addition of C-OH bonds. The appearance of the band at 1700-1600 cm -1 and the amplification of the band 1320-1280 cm -1 confirm the presence of carbonyl groups on the surface of the ABS plates.

II.5. Réduction des ions ferrique/ferreuxII.5. Reduction of ferric / ferrous ions

Du borohydrure de sodium NaBH4 (0,316 g, 0,8 10-2 mol) est dissout dans 25 mL d'une solution de soude (NaOH) à 0,1 M. Cette solution est chauffée à 80°C à l'aide d'un bain-marie et les échantillons y sont immergés. Après 12 min, les échantillons ont été rincés à l'eau MilliQ avant d'être séchés.NaBH 4 sodium borohydride (0.316 g, 0.8 × 10 -2 mol) is dissolved in 25 ml of a 0.1 M sodium hydroxide solution (NaOH). This solution is heated to 80 ° C. using a bain-marie and the samples are immersed in it. After 12 min, the samples were rinsed with MilliQ water before being dried.

L'analyse IR révèle la conservation de l'oxydation obtenue après Fenton avec les bandes à 3600-3200 cm-1 et les bandes 1700-1640 cm-1.IR analysis reveals the conservation of oxidation obtained after Fenton with bands at 3600-3200 cm -1 and bands 1700-1640 cm -1 .

II.6. Bain de métallisation Electroless de cuivreII.6. Copper electroless metallization bath

Les échantillons sont immergés dans un bain de métallisation Electroless commercial (M Copper 85, MacDermid) avec comme réducteur le formaldéhyde. Néammoins les plaques y sont immergées pendant 10 min à 48°C.The samples are immersed in a commercial Electroless plating bath (M Copper 85, MacDermid) with formaldehyde as reducing agent. At least the plates are immersed for 10 minutes at 48 ° C.

Après 10 min, les échantillons ont été rincés à l'eau MilliQ, sous ultrasons pendant 10 min avant d'être séchés.After 10 min, the samples were rinsed with MilliQ water, under ultrasound for 10 min before being dried.

L'analyse Infrarouge révèle la disparition des pics des différents polymères.Infrared analysis reveals the disappearance of the peaks of the different polymers.

La couche de cuivre est visible à l'oeil.The copper layer is visible to the eye.

II.7. Scotch testII.7. Scotch test

Pour vérifier la tenue mécanique des couches qui ont été greffées précédemment, un test avec un ruban adhésif a été effectué. Il consiste à coller sur la couche un morceau de ruban adhésif puis de le retirer de la couche.To check the mechanical strength of the layers that have been grafted previously, a test with an adhesive tape was performed. It consists in sticking on the layer a piece of adhesive tape and then removing it from the layer.

Si la couche déposée part avec l'adhésif, la tenue mécanique est considérée comme mauvaise. Si la couche reste insensible à l'adhésif, la tenue mécanique est considérée comme bonne.If the deposited layer leaves with the adhesive, the mechanical strength is considered bad. If the layer remains insensitive to the adhesive, the mechanical strength is considered good.

Le ruban adhésif qui a été utilisé est un ruban adhésif invisible haute performance, de marque PROGRESS.The adhesive tape that was used is a high performance invisible adhesive tape, branded PROGRESS.

Ce test a été effectué sur une plaque d'ABS après métallisation avec à chaque fois une partie prétraitée à l'acide et une partie non prétraitée. La métallisation est homogène. Les résultats de ce test montrent une meilleure résistance sur la partie prétraitée.This test was carried out on an ABS plate after metallization with each time a pretreated part with the acid and an untreated part. The metallization is homogeneous. The results of this test show a better resistance on the pretreated part.

II.8. Dépôt de cuivre par électrodépositionII.8. Electroplating copper deposit

Afin de confirmer la présence d'une couche métallique, du cuivre a été déposé par électrodéposition. Cette technique n'est possible qu'en présence de substrats conducteurs.In order to confirm the presence of a metal layer, copper was deposited by electroplating. This technique is only possible in the presence of conductive substrates.

Ainsi une plaque ABS ayant subi une métallisation au cuivre a été utilisée comme électrode de mesure. Le système électrochimique mis en place était constitué d'une électrode de référence au calomel à KCl saturée et d'une contre-électrode au graphite.Thus a copper-coated ABS plate has been used as an electrode measurement. The electrochemical system put in place consisted of a saturated KCl calomel reference electrode and a graphite counter electrode.

Les électrodes ont été trempées dans une solution de CuSO4 à 10 g/L, le potentiel initial était d'environ 0 V.The electrodes were soaked in a solution of CuSO 4 at 10 g / L, the initial potential was about 0 V.

Un cycle de voltamétrie allant jusqu'à -1 V en 30 s a été imposé au système. Lors de la remontée en tension, l'expérience a été stoppée aux alentours de -0,75 V (Figure 4).A voltammetry cycle of up to -1 V in 30 was imposed on the system. During the voltage rise, the experiment was stopped at around -0.75 V ( Figure 4 ).

Ce cycle a mis en évidence le dépôt de cuivre sur l'électrode de mesure. En effet, le courant a augmenté quand la tension a diminué et le cuivre s'est déposé sur les plaques faisant office d'électrode de mesure. La réduction du cuivre a eu lieu à l'électrode de mesure.This cycle showed the deposition of copper on the measuring electrode. Indeed, the current increased when the voltage decreased and the copper was deposited on the plates acting as measuring electrode. Copper reduction took place at the measuring electrode.

La confirmation du dépôt de cuivre est également visuelle. En effet, la couche de cuivre déposée par électrochimie a un aspect légèrement plus homogène.The confirmation of the copper deposit is also visual. Indeed, the copper layer deposited by electrochemistry has a slightly more homogeneous appearance.

III. Métallisation via un prétraitement accompagné d'un traitement de Fenton de plaques d'ABS-PC.III. Metallization via pretreatment accompanied by Fenton treatment of ABS-PC plates .

Ce procédé de métallisation s'effectue en 4 étapes (Prétraitement Oxydant/Traitement de Fenton/Réduction/Métallisation électroless) et avant de traiter le polymère, il convient de le préparer, dégraisser et nettoyer.This metallization process is carried out in 4 steps (Pretreatment Oxidizer / Fenton Treatment / Reduction / Electroless Metallization) and before treating the polymer, it is necessary to prepare it, degrease and clean.

III.1. PolissageIII.1. Polishing

Dans un 1er temps, les plaques sont soumises à un polissage pour minimiser les effets de bords et autres défauts apportés lors de la coupe des plaques.In a 1st step, the plates are subjected to polishing to minimize edge effects and other defects introduced during the cutting of the plates.

III.2. RinçageIII.2. Rinsing

Dans un 2nd temps, les plaques sont rincées à l'aide d'une solution savonneuse industrielle TDF4 mélangée à l'eau (1 mL de TDF4 pour 4 mL d'H20 MilliQ), sous ultrasons pendant 10 min. Les plaques sont ensuite rincées à l'eau MilliQ, sous ultrasons pendant 10 min.In a 2 nd time, the plates were rinsed using an industrial soap solution TDF4 mixed with water (1 mL TDF4 4 mL of MilliQ H 2 0) under ultrasound for 10 min. The plates are then rinsed with MilliQ water, under ultrasound for 10 min.

III.3. Prétraitement acideIII.3. Pretreatment acid

Les plaques sont immergées pendant 10 min dans une solution NaOH à 30% massique à une température de 90°C. Les plaques sont ensuite rincées dans une solution HCl 0,5 M sous ultrasons pendant 10 min puis à l'eau MilliQ sous ultrasons pendant 10 min.The plates are immersed for 10 min in a 30 wt% NaOH solution at a temperature of 90 ° C. The plates are then rinsed in 0.5M HCl solution under ultrasound for 10 min and then with MilliQ water under ultrasound for 10 min.

Les résultats obtenus pour les mesures d'angle de contact d'une goutte de 2 µl d'eau déposée sur les échantillons traités selon le traitement de Fenton (« Après ») ou sans traitement (« Vierge ») sont présentés dans le Tableau 11 ci-après. Tableau 11 : Mesure des angles de contact d'une goutte ABS-PC Vierge 90° Après prétraitement acide 67° The results obtained for the contact angle measurements of a droplet of 2 μl of water deposited on the samples treated according to the treatment of Fenton ("After") or without treatment ("Virgin") are presented in Table 11. below. <b> Table 11 </ b>: <i> Measuring the contact angles of a drop </ i> ABS-PC Virgin 90 After acid pretreatment 67 °

L'angle de contact est abaissé. La surface est devenue plus hydrophile de par son oxydation et la rugosité de surface a augmenté.The contact angle is lowered. The surface has become more hydrophilic due to its oxidation and the surface roughness has increased.

L'analyse des spectres IR est présentée dans le Tableau 12 ci-après. Tableau 12 : Bandes IR apparues après le prétraitement acide Plaques de polymères ABS-PC Après Traitement basique 3600-3200 cm-1 1660-1610 cm-1 1740-1700 cm-1 1320-1280 cm-1 The analysis of the IR spectra is presented in Table 12 below. <i><b> Table 12 </ b>: IR Bands Appeared After Acid Pretreatment </ i> Polymer plates ABS-PC After basic treatment 3600-3200 cm -1 1660-1610 cm -1 1740-1700 cm -1 1320-1280 cm -1

L'apparition des bandes à 3600-3200 cm-1 et 1660-1610 cm-1 peut-être due à la présence de traces d'eau. En revanche, les bandes à 1740-1700 cm-1 et à 1320-1280 cm-1 sont caractéristiques des groupes carbonyles, type carboxylique COOH. Ceci confirme l'oxydation de surface. D'autre part, la disparition de la bande ester à 1772 cm-1 caractéristique du polycarbonate est constatée.The appearance of bands at 3600-3200 cm -1 and 1660-1610 cm -1 may be due to the presence of traces of water. On the other hand, the bands at 1740-1700 cm -1 and at 1320-1280 cm -1 are characteristic of carbonyl groups, carboxylic type COOH. This confirms surface oxidation. On the other hand, the disappearance of the ester band at 1772 cm -1 characteristic of polycarbonate is noted.

III.4. Prétraitement de FentonIII.4. Pretreatment of Fenton

Du sulfate de fer(II) (6,961 g, 0,1 mol) a été solubilisé dans 50 mL d'acide sulfurique à 10-3 M dans l'eau. Dans cette solution, ont été immergées les plaques de polymères. 10 mL (0,124 mol) de peroxyde d'hydrogène à 35% dans l'eau ont été ensuite ajoutés, goutte à goutte. Après 25 min, les échantillons ont été rincés à l'eau MilliQ avant d'être séchés.Iron (II) sulfate (6.961 g, 0.1 mol) was solubilized in 50 mL of 10 -3 M sulfuric acid in water. In this solution, the polymer plates were immersed. 10 mL (0.124 mol) of 35% hydrogen peroxide in water were then added, drip. After 25 min, the samples were rinsed with MilliQ water before being dried.

Les résultats obtenus pour les mesures d'angle de contact d'une goutte de 2 µl d'eau déposée sur les échantillons traités selon le traitement de Fenton (« Après Fenton ») ou avant traitement (« après traitement basique)) sont présentés dans le Tableau 13 ci-après. Tableau 13 : Mesure des angles de contact d'une goutte ABS-PC Après traitement basique 67° Après Fenton 0 à 5° The results obtained for the contact angle measurements of a droplet of 2 μl of water deposited on the samples treated according to the Fenton treatment ("After Fenton") or before treatment ("after basic treatment)) are presented in Table 13 below. <i><b> Table 13 </ b>: Measuring the contact angles of a drop </ i> ABS-PC After basic treatment 67 ° After Fenton 0 to 5 °

L'angle de contact est clairement abaissé. La surface est devenue très hydrophile de par son oxydation.The contact angle is clearly lowered. The surface has become very hydrophilic because of its oxidation.

L'analyse des spectres IR est présentée dans le Tableau 14 ci-après. Tableau 14 : Bandes IR apparues après le traitement oxydatïf de Fenton sur les échantillons Plaques de polymères ABS-PC Après Fenton 3600-3200 cm-1 1700-1600 cm-1 1320-1280 cm-1 1150-1100 cm-1 The analysis of the IR spectra is presented in Table 14 below. <i><b> Table 14 </ b>: IR Bands Appearing After Fenton's Oxidative Treatment on Samples </ i> Polymer plates ABS-PC After Fenton 3600-3200 cm -1 1700-1600 cm -1 1320-1280 cm -1 1150-1100 cm -1

L'amplification de la bande à 3600-3200 cm-1 après traitement Fenton ainsi que l'apparition de la bande entre 1150-1100 cm-1 sont typiques de l'apport de liaisons C-OH. L'apparition des bandes à 1700-1600 cm-1 et l'amplification de la bande 1320-1280 cm-1 confirment la présence de groupements carbonyles à la surface des plaques d'ABS-PC.The amplification of the 3600-3200 cm -1 band after Fenton treatment as well as the appearance of the band between 1150-1100 cm -1 are typical of the addition of C-OH bonds. The appearance of bands at 1700-1600 cm -1 and the amplification of the band 1320-1280 cm -1 confirm the presence of carbonyl groups on the surface of ABS-PC plates.

III.5. Réduction des ions ferrique/ferreuxIII.5. Reduction of ferric / ferrous ions

Du borohydrure de sodium NaBH4 (0,316 g, 0,8 10-2 mol) est dissout dans 25 mL d'une solution de soude (NaOH) à 0,1 M. Cette solution est chauffée à 80°C à l'aide d'un bain-marie et les échantillons y sont immergés. Après 12 min, les échantillons ont été rincés à l'eau MilliQ avant d'être séchés.NaBH 4 sodium borohydride (0.316 g, 0.8 × 10 -2 mol) is dissolved in 25 ml of a 0.1 M sodium hydroxide solution (NaOH). This solution is heated to 80 ° C. using a bain-marie and the samples are immersed in it. After 12 min, the samples were rinsed with MilliQ water before being dried.

L'analyse IR révèle la conservation de l'oxydation obtenue après Fenton avec les bandes à 3600-3200 cm-1 et les bandes 1700-1640 cm-1.IR analysis reveals the conservation of oxidation obtained after Fenton with bands at 3600-3200 cm -1 and bands 1700-1640 cm -1 .

III.6. Bain de métallisation Electroless de cuivreIII.6. Copper electroless metallization bath

Les échantillons sont immergés dans un bain de métallisation Electroless commercial (M Copper 85, MacDermid) avec comme réducteur le formaldehyde. La composition exacte du bain de cuivre n'est pas connue. Néammoins les plaques y sont immergées pendant 10 min à 48°C.The samples are immersed in a commercial Electroless plating bath (M Copper 85, MacDermid) with formaldehyde as reducing agent. The exact composition of the copper bath is not known. At least the plates are immersed for 10 minutes at 48 ° C.

Après 10 min, les échantillons ont été rincés à l'eau MilliQ, sous ultrasons pendant 10 min avant d'être séchés.After 10 min, the samples were rinsed with MilliQ water, under ultrasound for 10 min before being dried.

L'analyse Infrarouge révèle la disparition des pics des différents polymères.Infrared analysis reveals the disappearance of the peaks of the different polymers.

La couche de cuivre est visible à l'oeil.The copper layer is visible to the eye.

III.7. Dépôt de cuivre par électrodépositionIII.7. Electroplating copper deposit

Afin de confirmer la présence d'une couche métallique, du cuivre a été déposé par électrodéposition. Cette technique n'est possible qu'en présence de substrats conducteurs.In order to confirm the presence of a metal layer, copper was deposited by electroplating. This technique is only possible in the presence of conductive substrates.

Ainsi une plaque ABS-PC ayant subi une métallisation au cuivre a été utilisée comme électrode de mesure. Le système électrochimique mis en place était constitué d'une électrode de référence au calomel à KCl saturée et d'une contre-électrode au graphite.Thus a copper-metallized ABS-PC plate was used as the measuring electrode. The electrochemical system put in place consisted of a saturated KCl calomel reference electrode and a graphite counter electrode.

Les électrode ont été trempées dans une solution de CuSO4 à 10 g/L, le potentiel initial était d'environ 0 V.The electrodes were soaked in a solution of CuSO 4 at 10 g / L, the initial potential was about 0 V.

Un cycle de voltamétrie allant jusqu'à -1 V en 30 sec a été imposé au système. Lors de la remontée en tension, l'expérience a été stoppée aux alentours de -0,75 V (Figure 5).A voltammetry cycle of up to -1 V in 30 sec has been imposed on the system. During the voltage rise, the experiment was stopped at around -0.75 V ( Figure 5 ).

Ce cycle a mis en évidence le dépôt de cuivre sur l'électrode de mesure. En effet, le courant a augmenté quand la tension a diminué et le cuivre s'est déposé sur les plaques faisant office d'électrode de mesure. La réduction du cuivre a eu lieu à l'électrode de mesure.This cycle showed the deposition of copper on the measuring electrode. Indeed, the current increased when the voltage decreased and the copper was deposited on the plates acting as measuring electrode. Copper reduction took place at the measuring electrode.

La confirmation du dépôt de cuivre est également visuelle. En effet, la couche de cuivre déposée par électrochimie a un aspect légèrement plus homogène.The confirmation of the copper deposit is also visual. Indeed, the copper layer deposited by electrochemistry has a slightly more homogeneous appearance.

RÉFÉRENCESREFERENCES

  1. [1] Charbonnier, M., et al., "Plasma treatment process for palladium chemisorption onto polymers before electroless deposition", Journal of the Electrochemical Society 1996, 143, (2), 472-480 .[1] Charbonnier, M., et al., "Plasma treatment process for palladium chemisorption onto polymers before electroless deposition", Journal of the Electrochemical Society 1996, 143, (2), 472-480 .
  2. [2] Demande de brevet CA 1 203 720 au nom de OMI Int. Corp. publiée le 29 avril 1986.[2] Patent application CA 1 203 720 on behalf of OMI Int. Corp. published on April 29, 1986.
  3. [3] Naudin, « Nomenclature, classification et formules chimiques des polymères » Techniques de l'Ingénieur 1995: A3035 .[3] Naudin, "Nomenclature, classification and chemical formulas of polymers"Engineer's Techniques 1995: A3035 .

Claims (9)

  1. A method for coating a surface of a substrate in (co)polymer with a metal material comprising the successive steps of:
    a) subjecting said surface to an oxidizing treatment by a chemical reaction of the Fenton type in the presence of at least one precursor of said metal material;
    b) transforming said precursor into said metal material,
    characterized in that the oxidizing treatment of said step (a) consists in putting said surface of the substrate in contact with a solution containing at least one precursor of the metal material and a compound of formula ROOR in which R represents a hydrogen, an alkyl group comprising from 1 to 15 carbon atoms, an acyl group -COR' with R' representing an alkyl group comprising from 1 to 15 carbon atoms or an aroyl group -COAr with Ar representing an aromatic group comprising from 6 to 15 carbon atoms.
  2. The method according to claim 1, characterized in that said substrate is selected from the group consisting of a nanoparticle, a microparticle, a button, a plug of cosmetic products, an electronic element, a door handle, a home electric appliance, glasses, a decorative object and a vehicle body element.
  3. The method according to claim 1 or 2, characterized in that said (co)polymer is selected from the group consisting of acrylonitrile-butadiene-styrene (ABS), acrylonitrile-butadiene-styrene/polycarbonate (ABS/PC), a polyamide (PA), a polyamine, a poly(acrylic acid), a polyaniline and a polyethylene terephthalate (PET).
  4. The method according to any of claims 1 to 3, characterized in that said solution comprising at least one precursor of the metal material and a compound of formula ROOR is an acid solution.
  5. The method according to any of the preceding claims, characterized in that said precursor of the metal material is selected from the group consisting of copper, silver, gold, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum ions.
  6. The method according to any of the preceding claims, characterized in that said step (b) has successirre sub steps consisting in:
    b1) optionally reducing said precursor of the metal material present at the surface of said substrate;
    b2) putting into contact said precursor optionally reduced following step (b1) in a solution containing at least one ion of the metal material.
  7. The method according to claim 6, characterized in that the ion(s) of the metal material is(are) selected from the group consisting of Ag-, Ag2+, Ag3+, Au+, Au3+, Co2+, Cu+, Cu2+, Fe2+, Ni2+, Pd+ and Pt+.
  8. The method according to any of the preceding claims, characterized in that the surface of the substrate is subject, prior to said step (a) of the method, to a treatment capable of increasing its hydrophilicity and/or its roughness, said treatment being selected from the group consisting of sanding, abrasion, chemical treatment with a pickling bath, flame treatment, corona effect treatment and plasma treatment and combinations thereof.
  9. The method according to claim 8, characterized in that said pickling bath is an acid aqueous solution comprising at least one inorganic acid notably selected from the group consisting of chromic acid, sulfuric acid, nitric acid, hypochlorous acid and mixtures thereof.
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