EP3256620B1 - Verfahren zur herstellung von metallmustern auf einem substrat für dekorativen und/oder funktionale zwecke, herstellung von gegenständen mithilfe dieses verfahrens und verwendetes set an verbrauchsmitteln - Google Patents

Verfahren zur herstellung von metallmustern auf einem substrat für dekorativen und/oder funktionale zwecke, herstellung von gegenständen mithilfe dieses verfahrens und verwendetes set an verbrauchsmitteln Download PDF

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Publication number
EP3256620B1
EP3256620B1 EP16709990.2A EP16709990A EP3256620B1 EP 3256620 B1 EP3256620 B1 EP 3256620B1 EP 16709990 A EP16709990 A EP 16709990A EP 3256620 B1 EP3256620 B1 EP 3256620B1
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EP
European Patent Office
Prior art keywords
substrate
metallization
optionally
temporary protection
patterns
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EP16709990.2A
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English (en)
French (fr)
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EP3256620A1 (de
Inventor
Samuel Stremsdoerfer
Arnaud JAMMES
Edouard MOURIER DES GAYETS
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Jet Metal Technologies
Jet Metal Tech
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Jet Metal Technologies
Jet Metal Tech
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Priority to HRP20201758TT priority Critical patent/HRP20201758T1/hr
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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
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1605—Process or apparatus coating on selected surface areas by masking
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • 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
    • C23C18/1689—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
    • C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/022—Electroplating of selected surface areas using masking means
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics

Definitions

  • the technical field of the invention is that of the surface coating of substrates, with single or multi-layered metal films.
  • the present invention relates to processes for the metallization of substrates for decoration, for example applicable to hollow glasses, to bottles, to cosmetic parts, to parts for aeronautics, for the automobile industry and for home automation.
  • the present invention also relates to metallization for functional purposes, for example for the manufacture of substrates for electronics, in particular printed circuits, integrated circuits on a semiconductor substrate, radio-identification chips (RFID), pictograms. coding readable by electronic readers ....
  • RFID radio-identification chips
  • the substrates more specifically concerned with metallization are materials of all kinds, in particular non-conductors such as glass, plastics (polyolefins-polypropylene-, polycarbonates, polyesters, styrenics - Acrylonitrile-Butadiene-Styrene -), ceramics, wood, textiles, minerals, articles in plaster or cement; semiconductors, conductors.
  • non-conductors such as glass, plastics (polyolefins-polypropylene-, polycarbonates, polyesters, styrenics - Acrylonitrile-Butadiene-Styrene -), ceramics, wood, textiles, minerals, articles in plaster or cement; semiconductors, conductors.
  • electrolytic metallization processes There are conventionally two main types of surface metallization processes for substrates: electrolytic metallization processes and non-electrolytic metallization processes.
  • Electrolytic metallization processes are based on an oxidation-reduction reaction using an electric current.
  • the metal is supplied in cationic form in an aqueous medium.
  • An electric current is imposed between the substrate that is to be metallized and a counter electrode.
  • the metal cation is then reduced to the surface of the substrate.
  • One of the major drawbacks of electrolytic deposition is that the substrate that is to be metallized must necessarily be conductive. This type of metallization is therefore not possible for substrates made of polymer, glass, etc.
  • the non-electrolytic metallization processes do not use an electric current.
  • the metal is deposited by other means, dry or wet.
  • dry method methods include PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition), which have the major drawback of the need to put the substrate under vacuum in order to carry out the metallization.
  • wet methods which are technologically simpler to implement, are more common, and among them, mention may in particular be made of the non-electrolytic metallization by immersion called the "electroless method".
  • the metal is also supplied in cationic form in an aqueous medium.
  • a reducing agent is also present in the medium, as well as generally a complexing agent.
  • the bath is prepared in such a way that although the metal salt and the reducing agent are present together in the bath, the direct oxidation-reduction reaction is prevented. This is only possible in the presence of a catalyst. This is why the surface of the substrate which is to be metallized is treated beforehand with sensitizing and possibly activating agents which will make the surface catalytic. In the presence of the catalytic surface, the metal salts are reduced by direct reaction with the reducing agent present in the medium.
  • This non-electrolytic immersion metallization technique is conventionally used in the surface treatment industry.
  • JetMetal® aerosol metallization process is described in particular in the documents FR2763962B1 , EP2326747B1 , EP2318564B1 . It has notable advantages over other existing non-electrolytic metallization processes. JetMetal® makes it possible in particular to obtain, on an industrial scale, with little or no pollution, at room temperature and at atmospheric pressure, substrates metallized with a homogeneous and continuous metal film.
  • conductive patterns are produced by direct printing (screen printing or inkjet printing), using inks loaded with silver particles. A heat treatment is necessary in order to remove the solvent contained in the inks and to obtain a conductive pattern.
  • the electrical conductivity of the patterns thus formed is less than that of a continuous metal film obtained by other metal deposition techniques.
  • Temporary masking consists of applying a mask (adhesives, peelable varnishes, stencils, etc.) to a surface to be protected in order to prevent the metallization of certain areas; this technique is difficult to apply to obtain complex patterns and requires a mechanical action which is not very compatible with mass production.
  • the base substrate consists of an assembly comprising a layer of copper on an epoxy / glass fiber support.
  • the copper is covered with a photosensitive resin ("photoresist") which is exposed through a typon (printed mask presenting the patterns): this is the exposure stage.
  • the insolated resin is polymerized under the effect of light.
  • a suitable development solution is then used to solubilize the uncured resin.
  • a chemical etching solution is then applied to attack the copper not protected by the polymerized resin (etching or "etching” step).
  • the substrate is brought into contact with an extraction solution, in order to remove any trace of polymerized resin (“stripping” or “stripping” step). (see Fig. 1 annexed).
  • Laser engraving involves using a laser to selectively extract the metal already present on a substrate. Although very precise, this method can be expensive and difficult to implement for extensive reasons.
  • This temporary protection has the particularity of being able to be easily and cleanly removed from the surface of the substrate intended to receive the metallic patterns, so that the fineness and precision of the metallic patterns, even complex, are not damaged during this removal operation.
  • the inventors propose a removal of the temporary protection by dissolution in a solvent contained in at least one of the metallization solutions during step D, or at least partially during and after this metallization D, or at least partially during and after the metallization step D and partly before the metallization step D.
  • this elimination E takes place partly during metallization D and in part after this metallization D. According to another alternative, this elimination E takes place partly during and after the metallization step D and in part before the metallization step D.
  • the metal of step D is chosen from the following group of metals: silver, nickel, copper, tin, iron, gold, cobalt, their oxides, their alloys and their combinations.
  • the method comprises a step A of preparing the surface of the substrate intended to receive the metallic patterns
  • said step A comprises the deposition of at least one layer of varnish and / or the degreasing of said surface.
  • the deposited varnish may consist of at least one organic layer containing or not containing (pigments / dyes) crosslinked in temperature (for example a polyurethane, such as that in the form of water-soluble powder) and / or under exposure by a actinic radiation, for example UV.
  • the metallization process to which it relates can include the first mode and possibly the second mode and / or the third mode of implementation referred to above.
  • the solvent allowing the dissolution of the temporary protection is contained in at least one of the liquids used for the metallization step D and also in the liquids used in at least one rinsing step and the duration of this metallization step D is preferably less than or equal to the duration of dissolution of the temporary protection.
  • the metallic patterns obtained are decorative and / or functional and are, preferably, included in the group comprising -preferably constituted by: printed circuits, integrated circuits on a semiconductor substrate, radio-identification chips (RFID ) coding pictograms likely to be read by electronic devices, figurative and / or scriptural information identifying a product, in particular a commercial product, such as a visual or a decorative design on a cosmetic and / or automobile product.
  • RFID radio-identification chips
  • the method according to the invention is implemented continuously / in line on industrial equipment, for example lacquering and / or liquid metallization.
  • the present invention relates to a method of manufacturing objects comprising metallic patterns, preferably decorative and / or functional, characterized in that it implements the method according to at least one of the preceding claims.
  • this device can be on-line on industrial installations, for example on a liquid coating and / or metallization line.
  • any singular designates indifferently a singular or a plural.
  • aerosol is understood to mean that it is eg a mist of droplets of size less than 100 ⁇ m, preferably less than 60 ⁇ m, and more preferably still from 0.1 to 50 ⁇ m, which is carried out by nebulization and / or atomization of solution (s) and / or dispersion (s).
  • non-electrolytic metallization relate in particular to the process described in FR2763962B1 , EP2326747B1 , or EP2318564B1 .
  • the substrate may be a non-conductive material, a semiconductor material or a conductive material.
  • it is a non-conductive material
  • it can be chosen from the group comprising - or ideally constituted by: glass, plastics / (co) polymer (polyolefins-polypropylene-, polycarbonates, polyesters, styrenics -Acrylonitrile-Butadiene-Styrene-), composite materials, ceramics, textiles, wood, minerals, articles made of plaster or cement.
  • plastics / (co) polymer polyolefins-polypropylene-, polycarbonates, polyesters, styrenics -Acrylonitrile-Butadiene-Styrene-
  • composite materials ceramics, textiles, wood, minerals, articles made of plaster or cement.
  • a conductive material is contemplated as the substrate, this could be a metal.
  • the semiconductor material capable of being a substrate is one of those commonly used in the semiconductor industry.
  • the substrate is a rigid, conductive or non-conductive substrate as defined above.
  • Particularly preferred are rigid hollow glass substrates and rigid polymeric substrates.
  • a hollow glass substrate is a non-planar glass substrate, in particular a glass container such as a flask or a glass bottle.
  • the substrate is a flexible substrate. It is, for example, chosen from the following compounds: polymers, metals, textiles, metal strips and paper.
  • the flexible substrate is a textile or a polymer film.
  • the flexible substrate is a polyester film whose thickness is 100 ⁇ m to 5 mm, a fabric or a sheet of paper whose density is 50 to 600 g / m2.
  • the term “flexible substrate” is understood to mean a substrate which can be bent, bent by human force alone without breaking or being damaged.
  • the term “rigid substrate” is understood to mean a substrate which cannot be bent or bent by human force alone without breaking or being damaged.
  • Step A Preparation of the surface of the substrate intended to receive the metallic patterns
  • This surface preparation step can take place before or after the application of the temporary protection.
  • the preparation of the substrate before application of the temporary protection makes it possible not to subject this layer to physico-chemical modifications, which could lead to its attachment to the substrate and a more difficult elimination (preferably solubilization) of the protection. temporary.
  • the surface preparation can intervene voluntarily after application of the temporary protection, in order to reinforce its cohesion and to slow down its elimination (preferably solubilization).
  • Such a preparation can comprise a cleaning / degreasing of the surface, by means of any products known per se and suitable.
  • a varnish for example a UV crosslinking varnish applied by spraying, by any known and appropriate means such as a paint gun.
  • compressed air eg HVLP: high volume low pressure
  • step A can include at least one treatment for increasing the energy of the surface (step I.).
  • Step B Deposit of a temporary protection on the surface of the substrate corresponding to the negative of the patterns to be produced
  • this temporary protection is a coating corresponding to the negative of the desired patterns.
  • This coating is obtained from a liquid product which dries and / or which hardens once applied to the surface of the substrate and / or which crosslinks under actinic radiation, for example UV.
  • This liquid product has the singularity of being soluble in at least one of the solvents subsequently employed in the process according to the invention. It may in particular be a product soluble in an alkaline solvent.
  • This temporary protection product can comprise, for example, an ink and or any other organic product having a high solubility in an appropriate solvent.
  • the liquid product used for producing the protective coating can be a product which, after drying and / or curing and / or crosslinking under actinic radiation, for example UV, gives rise to a coating whose adhesion to the substrate. can be reduced by at least one of the substances - preferably liquid -, in particular solvents, subsequently employed in the process according to the invention.
  • actinic radiation for example UV
  • Step C Activation of the surface of the substrate, in particular of the areas corresponding to the patterns to be produced
  • step D is non-electrolytic metallization by spraying one or more redox solutions in aerosol form, activation C is necessary for certain metals. It aims to accelerate the oxidation-reduction reaction involved in this step D.
  • step C at least one sensitizing chemical species is adsorbed on the surface of the material and thus accelerates the metallization reaction.
  • the sensitizing chemical species (s) adsorb onto the unprotected substrate and onto the protective layer.
  • a sensitizing solution will preferably be applied by spraying on the surface of the substrate, preferably coated with the temporary protection.
  • This spraying is carried out by any known and appropriate means such as a compressed air paint gun (eg HVLP: high volume low pressure). According to one variant, it may be an immersion.
  • HVLP high volume low pressure
  • a first sensitizing solution based on stannous chloride (SnCl 2 ) or SnSO 4 / H 2 SO 4 / quinol / alcohol is applied by spraying or immersion.
  • a palladium or silver solution capable of reacting with Sn 2+ to form nucleation centers on the surface of the substrate, or else a PdSn colloidal solution formed ex situ, is then deposited in the same way.
  • metal Finishing Guidebook and Directory Issue 1996 Metal Finishing publication, pages 354, 356 and 357 .
  • the step of sensitizing the surface of the substrate is carried out by means of a sensitizing solution based on stannous chloride, for example in accordance with the mode of implementation described in FR-A-2 763 962 .
  • a rinsing step using a rinsing liquid as described below is carried out just after the sensitization step, without an intermediate step.
  • the activation of the surface of the substrate is carried out by means of a sensitizing solution, in particular of palladium chloride, for example in accordance with the mode of implementation described in FR2763962B1 .
  • a rinsing step using a rinsing liquid as described in the examples below is carried out just after the activation step, without an intermediate step.
  • step D is a chemical metallization (called “electroless") without electric current / auto-catalytic, by immersion in one (or more) suitable metallization solution (s), activation C which aims to accelerate the catalytic oxidation-reduction reaction occurring in this step D, is generally essential. It consists in depositing on the surface of the substrate, coated with the temporary protection, a chemical metallization catalyst without current, for example a catalyst of the Sn / Pd type. The catalyst is adsorbed over the entire surface of the substrate (unprotected areas corresponding to the patterns to be affixed and temporary protective layer).
  • This activation C is preferably preceded by a step L (satin finish) followed by a step M (rinsing).
  • This satin-finishing step is in fact a treatment for increasing the surface energy of the substrate and / or for increasing the roughness of the substrate, which may be of the type defined below for step I.
  • the satin finish is preferably carried out by physical treatment (corona discharge, plasma treatment) or chemical (eg sulfo-chromic treatment or other) in order to give sufficient adhesion to the metallic patterns to be deposited. .
  • step I. treatment to increase the surface energy of the substrate
  • step J wetting the surface of the substrate
  • step K rinsesing the surface of the substrate
  • the treatment for increasing the surface energy of the substrate according to step I is chosen from physical treatments, preferably the following physical treatments: flame treatment, plasma treatment and their combinations, and / or chemical treatments, preferably the following chemical treatments: application of a solution based on silane, depassivation of the surface using one or more acid solutions, polishing based on rare earth oxide, fluorination and combinations thereof .
  • the physical treatment of step I is a flame treatment.
  • the physical treatment is advantageously a treatment by flame treatment and / or by plasma, when the substrate is a rigid substrate made of plastic, of composite material, of polymer or of a flexible support of polymer, metal such as a metal strip. , textile or paper.
  • Flaming is, for example, the passage of the substrate to be metallized under a flame, the temperature of which is eg from 1200 ° C to 1700 ° C.
  • the duration of flaming is generally 4 to 50 seconds.
  • the flame is preferably obtained by combustion of a fuel such as propane gas (or town gas) in the presence of an oxidizer such as oxygen.
  • the (by) plasma treatment corresponds, for example, to the passage of the substrate to be metallized in a plasma torch, for example those marketed by ACXYS® or PLASMATREAT®.
  • the chemical treatment is preferably chosen from the following treatments: application of a solution based on silane, passivation of the surface using one or more acid solutions, polishing based on silane rare earth oxide, fluorination and combinations thereof. Even more preferably, the chemical treatment is an application of a silane-based solution, a passivation by spraying of one or more acid solutions, a fluorination or their combinations. In addition, this chemical treatment is more especially implemented when the substrate is a rigid substrate made of hollow glass, metal or alloy. Passivation means, for example, that the surface of the substrate is corroded until the oxide layer covering it is removed, by the action of a corrosive substance projected onto the surface.
  • the substrate such as a strong acid solution, for example based on nitric, citric or sulfuric acid and their mixtures.
  • the "rare earth oxide-based polishing" means, for example, that a rare earth oxide-based solution is applied to the substrate to be metallized and that pads come to polish the surface of the substrate, in particular by friction against the substrate. its surface, until a possible oxide layer present on the surface is removed and smoothed.
  • the solution based on rare earth oxide is a solution based on cerium oxide, which is for example of the type marketed by the company POLIR-MALIN® under the name GLASS POLISHING®.
  • the polishing based on rare earth oxide comprises a step of rinsing the surface thus polished, in particular with distilled water.
  • Fluorination corresponds, for example, to bringing the substrate to be metallized and a gaseous solution based on inert gas (argon) containing a fluorine additive into contact, in an enclosure under reduced pressure.
  • the fluorination is carried out for example with an apparatus of the type of those marketed by AIR LIQUIDE®.
  • the surface energy of the substrate is greater than or equal to 50 or 55 dynes, preferably greater than or equal to 60 or 65 dynes , and even more preferably greater than or equal to 70 dynes.
  • the wetting of the substrate is insufficient and the metallic coating obtained after metallization has unsatisfactory characteristics of adhesion, gloss and reflectivity.
  • the value of the surface energy can be measured, for example, by techniques known to those skilled in the art consisting in applying to the substrate, using a brush or a felt-tip pen, a specific solution and to measure the retraction time of the solution thus applied.
  • the wetting step J consists in coating the surface of the substrate with a liquid film to promote the spreading of the redox solutions.
  • the choice of the wetting liquid is made from the following group: deionized water or not, optionally added with one or more anionic, cationic or neutral surfactants, an alcoholic solution comprising one or more alcohols (for example isopropanol, l ethanol and their mixture), and their mixtures.
  • deionized water added with an anionic surfactant and ethanol is chosen as the wetting liquid.
  • the liquid be essentially aqueous for obvious reasons of industrial convenience.
  • the wetting time depends on the surface of the substrate considered and the rate of projection of the wetting aerosol.
  • the wetting step can optionally replace the activation step C of the substrate.
  • Step K
  • this rinsing step K consist of bringing all or part of the surface of the substrate into contact with a or more source (s) of rinsing liquid, which are produced at different stages of the process of the invention, are produced by spraying an aerosol of rinsing liquid, preferably demineralized water.
  • the reducing agent is advantageously strong enough to reduce the metal cation to metal, that is to say that the standard oxidation-reduction potential of the oxidizing / reducing couple of the reducing agent must be lower than that of the oxidizing / reducing couple of the oxidant ( gamma rule).
  • the redox solutions used during the non-electrolytic metallization step are sprayed in the form of aerosols on the substrate and are preferably obtained from solutions, advantageously aqueous, of one or more oxidizing metal cations and of one or more reducing compounds. These redox solutions are preferably obtained by dilution of concentrated stock solutions.
  • the diluent is preferably demineralized water.
  • the spraying aerosol (s) are produced by nebulization and / or atomization of solution (s) and / or dispersion (s), so in obtaining a mist of droplets of size less than 100 ⁇ m, preferably than 60 ⁇ m, and more preferably still from 0.1 to 50 ⁇ m.
  • the projection of metallic solutions preferably takes place continuously and the substrate is set in motion and subjected to the projection.
  • the projection is preferably continuous.
  • the spraying is preferably carried out alternately with relaxation times.
  • the projection lasts from 0.5 to 200 seconds, preferably from 1 to 50 seconds and more preferably still from 2 to 30 seconds for a metallized surface of 1 dm2.
  • the duration of projection has an effect on the thickness of the metal deposit and therefore on the opacity of this deposit. For most metals, if the projection time is less than 15 seconds, the deposit is qualified as semi-transparent and if the projection time is greater than 60 seconds, the deposit is qualified as opaque.
  • the substrate can be rotated at least partially during the metallization spraying.
  • one or more solutions of metallic cation (s) and one or more solutions of reducing agent (s) are simultaneously sprayed onto the surface to be treated, in one or more aerosols.
  • the mixture between the oxidizing solution and the reducing solution can be carried out just before the formation of the projection aerosol or even by melting an aerosol produced from the oxidizing solution and a aerosol produced from the reducing solution, preferably before coming into contact with the surface of the substrate to be metallized.
  • one or more solutions of metallic cation (s) and then one or more solutions of reducing agent (s) are successively projected, via one or more aerosols.
  • the projection of the redox solution is carried out by separate projection (s) of one or more solutions of one or more metal oxidants and of one or more solutions of one or more reducers.
  • This second possibility corresponds to an alternating projection of the reducing solution (s) and of the metal salt (s).
  • the association of several oxidizing metal cations to form a multilayer of different metals or alloys is such that the different salts are preferably sprayed naturally separately from the reducing agent but also separately the from each other and successively. It goes without saying that, in addition to the different nature of the metal cations, it is possible to envisage using counter-anions which are different from one another.
  • the mixture of the oxidant (s) and of the reducing agent (s) is metastable and, after spraying the mixture, the latter is activated so that the transformation into metal is triggered, of preferably by bringing into contact with an initiator, advantageously provided by means of one or more aerosols, before, during or after the projection of the reaction mixture.
  • an initiator advantageously provided by means of one or more aerosols, before, during or after the projection of the reaction mixture.
  • This variant makes it possible to premix the oxidant and the reducing agent while delaying their reaction until they cover the surface of the substrate after spraying.
  • the initiation or activation of the reaction is then obtained by any appropriate physical (temperature, UV, etc.) or chemical means.
  • the redox solutions projected during the metallization step of the substrate are one or more solutions of a metallic oxidant and one or more solutions of a reducing agent.
  • the concentrations of metal salts in the oxidizing solution to be sprayed are from 0.1 g / l to 100 g / l and preferably from 1 to 60 g / l, and the concentrations of metal salts in the stock solutions are from 0.5 g / l to 500 g / l, or else the dilution factor of the stock solutions is 5 to 5000.
  • the metal salts are chosen from silver nitrate, nickel sulphate, copper sulphate and dichloride. tin, aurochloric acid, iron chloride, cobalt chloride and mixtures thereof.
  • reducing agents is preferably made from among the following compounds: borohydrides, dimethylaminoborane, hydrazine, sodium hypophosphite, formalin, lithium aluminum hydride, reducing sugars such as glucose derivatives or erythorbate sodium, and mixtures thereof.
  • the selection of the reducing agent requires taking into account the pH and the properties targeted for the metallization film. These routine adjustments are within the abilities of those skilled in the art.
  • the concentrations of reducing agent in the reducing solution to be sprayed are from 0.1 g / l to 100 g / l and preferably from 1 to 60 g / l, and the concentrations of reducing agent in the stock solutions are 0.5 g / l to 250 g / l, or else the dilution factor of the stock solutions is from 5 to 2500.
  • particles are incorporated into at least one of the redox solutions in order to be projected at the time. metallization. The particles are thus trapped in the metal deposit.
  • hard particles are for example diamond, ceramic, carbon nanotubes, metal particles, rare earth oxides, PTFE (Polytetrafluoroethylene), graphite, metal oxides and their mixtures.
  • PTFE Polytetrafluoroethylene
  • graphite graphite
  • metal oxides and their mixtures.
  • the incorporation of these particles into the metallic film confers particular mechanical, tribological, electrical, functional and aesthetic properties on the metallized substrate.
  • step D is preceded by at least one of the following steps: step L (satin finish treatment of the surface of the substrate) and a step M (rinsing of the surface of the substrate).
  • step L is in accordance with step I as described above in chapter D.1 relating to non-electrolytic metallization by spraying aerosols. The same goes for the M.
  • This metallization D.2 is preferably carried out by immersing the substrate, preferably after removing the temporary protection, in an "electroless" bath containing the oxidizing and reducing species as well as the stabilizers and surfactants.
  • metallization takes place on all the zones catalyzed by the catalyst seeds (eg Palladium) adsorbed.
  • the surface protected by the temporary protection (from preference eliminated during step E) is not catalyzed and therefore cannot be the site of metallization.
  • currentless immersion metallization reference will be made to the examples which follow as well as to the numerous documents describing this technology, such as electroplating treatments.
  • Step E Removal of temporary protection
  • the elimination of the temporary protection can take place during, or at least partly during and after the metallization step D, or in part during and after the metallization step D and in part before the metallization step D.
  • the elimination of the temporary protection, at least in part during the metallization supposes that the means employed in the latter allow it and that the residue produced by this elimination is not of a nature to thwart the metallization. This is particularly the case for metallization by spraying aerosols.
  • the elimination of the temporary protection after metallization will have its place in the case where the metallization means, for example metallization solutions, are not able to dissolve the temporary protection; as in metallization by spraying aerosols with certain metals such as nickel, for example. According to the invention, this elimination is dissolution in a solvent used in the process.
  • the method comprises a rinsing step F, and step E of removing the temporary protection is carried out partly during step D and at least partly during step F.
  • the method comprises a step G of drying, and step E of removing the temporary protection is carried out partly during step D and at least partly during step G.
  • the elimination of the temporary protection can take place during the metallization step.
  • the temporary protection is alkali-soluble (eg ink) the metallization solutions have a strongly alkaline pH, which allows them to solubilize this temporary protection.
  • the unprotected areas are metallized while the protective layer is solubilized and discharged into the effluents, thus allowing the metallic patterns to appear. It is preferable that the duration of metallization is limited so as to prevent any possibility of metallization on the areas initially covered by the temporary protection.
  • a suitable solution that is to say one containing a solvent for the temporary protection, is therefore applied to the surface of the substrate. This can be done, for example, by immersion followed by rinsing. This dissolution reveals the areas of the surface of the substrate corresponding to the negative of the metallic patterns to be produced. Since the deprotected areas of the surface are not activated (adsorption of the catalyst), they do not allow initiation of metallization for a sufficient period of time to form metal patterns.
  • the term “sufficient time” is understood to mean the time required for the formation of metallic patterns on the activated zones of the surface of the substrate.
  • the rinses which mark the separations between the various deposits involved in the process are carried out in a known and appropriate manner, for example by spraying / spraying rinsing liquid or immersing in a rinsing liquid.
  • the latter is advantageously and preferably water, and more particularly demineralized water.
  • Step G Drying / Blowing
  • the drying or blowing which can take place in particular after each rinsing step, consists in the evacuation of the rinsing water. It can advantageously be carried out at a temperature of 20 at 60 ° C using, for example, a pulsed compressed air system at eg 5 bars / pulsed air, at a temperature of 20 to 60 ° C. Drying in the open air or in an oven are also possible.
  • Step H finishing treatment on the surface of the substrate bearing the metallic patterns
  • a finishing treatment variant may be the deposit of at least one topcoat of a crosslinkable liquid composition on the surface of the substrate bearing the metallic patterns.
  • This liquid composition crosslinkable on the protective layer is for example a paint or a varnish, preferably a finishing varnish.
  • This varnish can be based on water-soluble or organic, preferably organic.
  • the crosslinkable liquid finishing composition can be crosslinked by UV or thermal curing and can contain pigments or dyes for coloring.
  • the effluents resulting from the various stages of the process are advantageously reprocessed and recycled to be reused in the process, and to limit the ecological impact.
  • the invention therefore provides in so doing these new advantageous industrial processes, integrating the technique of selective deposition of metallic units described and claimed here.
  • Example 1 Production of metallic patterns (silver) on a varnished plastic substrate for decorative purposes
  • Example 2 Production of an electronic unit on a rigid polymer substrate
  • a conductive circuit is thus obtained corresponding to the negative of the ink deposited initially - see Fig. 6 annexed - (The non-metallized parts correspond to the areas covered by the screen printing ink).
  • the silver deposit is sufficiently conductive to achieve an electrolytic thickening of copper with a conventional bath of acidic copper based on copper sulfate and sulfuric acid.
  • Example 3 Online production of decorative metal patterns by inkjet printing
  • Metallic decorative silver patterns with a mirror effect are thus obtained corresponding to the negative of the ink deposited initially.
  • the non-metallic areas reveal the color of the red base varnish.
  • the pictogram characters can be made in order to show the name of a brand or a logo.
  • Example 4 Realization of a silver pattern with electrolytic copper thickening in line
  • the polyimide film is unwound at the start of treatment, undergoes each step and is then wound up again at the end of the process.

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Claims (11)

  1. Verfahren zur Herstellung von Metallmustern auf einem beinhaltend die folgenden wesentlichen Schritte:
    A. eventuell Vorbereitung der Oberfläche des Substrats, das zur Aufnahme der Metallmuster bestimmt ist;
    B. Aufbringen eines temporären Schutzes auf die Oberfläche des Substrats entsprechend dem Negativ der herzustellenden Muster mittels einer Sieb-/Schablonenmaske mit Aussparungen entsprechend dem Negativ der herzustellenden Muster; und/oder durch Direktdruck, vorzugsweise Tintenstrahldruck;
    C. gegebenenfalls Aktivierung der Substratoberfläche, insbesondere der Bereiche, die den herzustellenden Mustern entsprechen;
    D. Metallisierung durch Abscheidung mindestens eines Metalls auf den Flächen, die den herzustellenden Mustern entsprechen;
    E. Entfernen des temporären Schutzes der Stufe B;
    F. eventuell Spülen der Oberfläche des Substrats, das die Metallmuster trägt;
    G. möglicherweise Trocknen der Oberfläche des Substrats, das die Metallmuster trägt;
    H. eventuell Nachbehandlung auf der Oberfläche des Substrats, das die Metallmuster trägt;
    • wobei der Schritt E der Aufhebung des temporären Schutzes während des Schrittes D, oder zumindest teilweise während und nach dem Schrittes D, oder zumindest teilweise während und nach dem Plattierungsschritt D und teilweise vor dem Plattierungsschritt D durchgeführt wird,
    • wobei der Schritt E im Wesentlichen aus dem Lösen des temporären Schutzes durch mindestens ein Lösungsmittel, das in mindestens einer der Metallisierungslösungen enthalten ist, wobei das Lösemittel bevorzugt alkalisch und der temporäre Schutz bevorzugt alkali-löslich ist, um durch das bevorzugte Lösemittel gelöst zu werden.
    • dass die Metallablagerung D eine nicht-elektrolytische Metallisierung durch Versprühen einer oder mehrerer oxidreduzierender Lösungen in Form eines Aerosols (von Aerosolen) ist;
    • und dass sie gegebenenfalls vor der Plattierung D mindestens einen der folgenden Schritte beinhaltet, vorzugsweise in der folgenden Reihenfolge:
    I. Behandlung zur Erhöhung der Oberflächenenergie des Substrats; wobei in dem Fall, dass das Verfahren einen C-Aktivierungsschritt beinhaltet, optional vor der C-Aktivierung ein Schritt I. zur Erhöhung der Oberflächenenergie des Substrats vorgesehen werden kann.
    J. Benetzung der Substratoberfläche;
    K. Spülen der Substratoberfläche.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Schritt E weiterhin mindestens einen der folgenden Schritte beinhaltet:
    • Eine Behandlung in flüssiger Phase,
    • Eine mechanische Behandlung durch ein Gas, vorzugsweise Luft.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Metall der Stufe D aus der Gruppe der folgenden Metalle ausgewählt wird: Silber, Nickel, Zinn, Eisen, Gold, Kobalt, Kupfer, deren Oxide, Legierungen und Kombinationen davon.
  4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, dass es einen Schritt A beinhaltet, der die Abscheidung mindestens einer Lackschicht und/oder das Entfetten der Oberfläche des Substrats beinhaltet, das dazu bestimmt ist, die Metallmuster aufzunehmen.
  5. Verfahren nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Behandlung zur Erhöhung der Oberflächenenergie des Substrats nach Schritt I ausgewählt ist aus physikalischen Behandlungen, vorzugsweise den folgenden physikalischen Behandlungen: Flammenbehandlung, Plasmabehandlung und Kombinationen davon, und/oder chemischen Behandlungen, vorzugsweise den folgenden chemischen Behandlungen: Aufbringen einer Lösung auf Silanbasis, Depassivierung der Oberfläche mittels einer oder mehrerer Säurelösungen, Polieren auf der Basis von Seltenerdoxiden, Fluorierung und Kombinationen davon.
  6. Verfahren nach Anspruch 1 bis 5, dadurch gekennzeichnet, dass die Veredelungsbehandlung H die Herstellung einer oder mehrerer Lackschichten und/oder einer elektrolytischen Verdickung, bestehend aus einem oder mehreren Metallen, ist.
  7. Verfahren nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, dass das Lösungsmittel zum Auflösen des temporären Schutzes auch in Flüssigkeiten enthalten ist, die in mindestens einem Spülschritt verwendet werden, und dass die Dauer des Metallisierungsschrittes D vorzugsweise kleiner oder gleich der Dauer zum Lösen des temporären Schutzes ist.
  8. Verfahren nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die erhaltenen Metallmuster dekorativ und/oder funktionell sind und vorzugsweise zu der Gruppe gehören, die beinhaltet - vorzugsweise besteht aus -: gedruckte Schaltungen, integrierte Schaltungen auf einem Halbleitersubstrat, Funk-Identifizierungschips (RFID), Kodierungspiktogramme, die von elektronischen Vorrichtungen gelesen werden können, bildliche und/oder schriftliche Informationen, die ein Produkt, insbesondere ein kommerzielles Produkt, identifizieren, wie z.B. ein dekoratives Sicht- oder Muster auf einem Kosmetik- und/oder Automobilprodukt.
  9. Verfahren nach mindestens einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass es kontinuierlich/inline auf industriellen Anlagen durchgeführt wird.
  10. Verfahren zur Herstellung von Gegenständen mit Metallmustern, vorzugsweise dekorativer und/oder funktioneller Art, dadurch gekennzeichnet, dass es das Verfahren gemäß mindestens einem der vorstehenden Ansprüche durchführt.
  11. Satz von Verbrauchsmaterialien zur Durchführung des Verfahrens nach mindestens einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass er beinhaltet:
    a. Verbrauchsmaterial(ien) zur Durchführung des temporären Schutzes der Stufe B, wobei dieser vorübergehende Schutz in einem alkalischen Lösungsmittel löslich ist;
    b. Verbrauchsmaterial(ien) für die Metallisierung von Schritt D, das eine oder mehrere oxidations-reduzierende Lösungen beinhaltet, die ein oder mehrere oxidierende Metallkationen und/oder eine oder mehrere reduzierende Verbindungen enthalten, wobei mindestens eine dieser Lösungen ein alkalisches Lösungsmittel enthält;
    c. gegebenenfalls Verbrauchsmaterial(ien) für die Vorbereitung der Substratoberfläche, die zur Aufnahme der Metallmuster der Stufe A bestimmt ist; und/oder;
    d. optional mindestens eine Bildschirm-/Schablonenmaske, die in einer der Varianten von Schritt B verwendbar ist; und/oder;
    e. wahlweise Verbrauchsmaterial(ien) zur Aktivierung der Substratoberfläche von Schritt C; und/oder;
    f. möglicherweise Verbrauchsmaterial(ien) zur Entsorgung gemäß Schritt E des temporären Schutzes von Schritt B; und/oder;
    g. möglicherweise Verbrauchsmaterial(ien) für die Spülung gemäß Schritt F; und/oder;
    h. eventuell Verbrauchsmaterial(ien) für die Aufbringung von mindestens einer Deckschicht gemäß Schritt H.
EP16709990.2A 2015-02-12 2016-02-12 Verfahren zur herstellung von metallmustern auf einem substrat für dekorativen und/oder funktionale zwecke, herstellung von gegenständen mithilfe dieses verfahrens und verwendetes set an verbrauchsmitteln Active EP3256620B1 (de)

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FR1551169A FR3032724B1 (fr) 2015-02-12 2015-02-12 Procede et dispositif de realisation de motifs metalliques sur un substrat a des fins decoratives et/ou fonctionnelles fabrication d'objets integrant cette realisation et ensemble de consommables utilises
PCT/FR2016/050335 WO2016128695A1 (fr) 2015-02-12 2016-02-12 Procédé et dispositif de réalisation de motifs métalliques sur un substrat a des fins décoratives et/ou fonctionnelles fabrication d'objets intégrant cette réalisation et ensemble de consommables utilises

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CN107250442B (zh) 2021-03-09
US11168398B2 (en) 2021-11-09
JP6845146B2 (ja) 2021-03-17
FR3032724A1 (fr) 2016-08-19
US20180030599A1 (en) 2018-02-01
ES2828691T3 (es) 2021-05-27
KR20170132132A (ko) 2017-12-01
WO2016128695A1 (fr) 2016-08-18
EP3256620A1 (de) 2017-12-20
KR102628252B1 (ko) 2024-01-24
BR112017017268A2 (pt) 2018-04-17
DK3256620T3 (da) 2020-11-02
BR112017017268B1 (pt) 2022-05-03
JP2018506648A (ja) 2018-03-08
FR3032724B1 (fr) 2019-12-13
CN107250442A (zh) 2017-10-13
MX2017010460A (es) 2018-04-24
HRP20201758T1 (hr) 2021-03-19
HUE051202T2 (hu) 2021-03-01

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