Classifications

• • 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
  • 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
  • C25D5/48—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, by single or multilayer metal films.
• the present invention relates to metallization processes of substrates for decoration, for example applicable to hollow glasses, bottles, cosmetic parts, parts for aeronautics, automotive and home automation.
• the present invention also relates to the metallization for functional purposes, for example for the manufacture of substrates for electronics, in particular printed circuits, integrated circuits on semiconductor substrate, radio identification chips (RFID), pictograms
• RFID radio identification chips
• the substrates more specifically concerned with metallization are materials of any kind, especially non-conductors such as glass, plastics (polyolefins-polypropylene, polycarbonates, polyesters, styrenics - acrylonitrile-butadiene-styrene). -), ceramics, wood, textiles, minerals, plaster or cement articles; semiconductors, conductors.
• non-conductors such as glass, plastics (polyolefins-polypropylene, polycarbonates, polyesters, styrenics - acrylonitrile-butadiene-styrene).
• plastics polyolefins-polypropylene, polycarbonates, polyesters, styrenics - acrylonitrile-butadiene-styrene.
• ceramics wood, textiles, minerals, plaster or cement articles
• semiconductors conductors.
• Electroplating processes are based on an oxidation-reduction reaction using an electric current.
• the metal is provided 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 disadvantages 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.
• Non-electrolytic metallization processes do not use electric current.
• the metal is deposited by other means, dry or wet.
• dry methods include PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition), which have the major disadvantage of the need to put the substrate under vacuum to perform the metallization.
• electroless non-electrolytic metallization called "electroless method”.
• the metal is also provided 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 so that although the metal salt and the reducing agent are present together in the bath, the direct oxidation reaction is prevented. This is only possible in the presence of a catalyst. This is why the surface of the substrate that is to be metallized is pretreated with sensitizing and optionally activating agents which will render 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.
• Deposition baths may be unstable, and the metal salt may precipitate before the introduction of the substrate.
• the treatment ranges include many stages.
• JetMetal makes it possible to obtain, on an industrial scale, with little or no polluting, at ambient temperature and at atmospheric pressure, substrates metallized with a homogeneous and continuous metallic film.
• additives metal deposit: printing of silver-based ink; temporary masking;
• direct printed (serigraphy or ink jet) conductive patterns are produced using silver-laden inks.
• a heat treatment is necessary in order to evacuate 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 in applying a mask (adhesives, peelable varnishes, stencils ”) on a surface to be protected in order to prevent the metallization of certain zones; this technique is difficult to apply to obtain complex patterns and requires a mechanical action that is not very compatible with mass production.
• the base substrate consists of an assembly comprising a copper layer on an epoxy / glass fiber support.
• the copper is covered with a photoresist (photosoresist) which is insolated through a piece of artwork (printed mask with patterns): this is the step of insolation.
• the insolated resin is polymerized under the effect of light.
• a suitable development solution is then used to solubilize the unpolymerized resin.
• a chemical etching solution is then applied to attack the unprotected copper by the polymerized resin (etching step).
• the substrate is brought into contact with an extraction solution in order to remove any traces of polymerized resin ("stripping" or "stripping” step). (see Fig. 1 attached).
• Laser engraving involves using a laser to selectively extract the metal already present on a substrate. Although very accurate this method can be expensive and difficult to implement for extended reasons.
• the present invention therefore aims to satisfy at least one of the following objectives:
• - » provide a process for producing metallic patterns that can be thin, precise and complex on any type of substrates, which lead to metal patterns that are sufficiently thick especially for electrical conduction applications;
• - » provide a method of producing metal patterns that can be thin, precise and complex on any type of substrates, which lead to hard metal patterns and resistant to assaults of all kinds;
• F. optionally rinsing the surface of the substrate bearing the metallic patterns; G. optionally drying the surface of the substrate bearing the metallic patterns;
• step E of eliminating the temporary protection is carried out, during step D, or at least partly during step D, and / or after step D, or at least partly during and / or after the metallization step D and partly before the metallization step D.
• this selective metallization technique that can be put online, which is based in particular on the use of temporary protection on certain areas of the substrate surface which form the negative of the metallization patterns. revised.
• This temporary protection has the particularity of being able to be removed easily and cleanly from the surface of the substrate intended to receive the metallic patterns, so that the fineness and precision of the metallic patterns, even complex ones, are not damaged during this removal operation.
• the inventors propose a withdrawal of the temporary protection, in particular by a non-mechanical route, for example by dissolving in a solvent used in a subsequent phase of the process, at least partly during or during the process for producing the patterns. and / or after this metallization D, or at least partly during and / or after the metallization step D and in part before the metallization step D.
• the elimination E of the temporary protection can be completely achieved during the metallization.
• the duration of this elimination E is less than or equal to the duration of the metallization D.
• this elimination E takes place partly during the metallization D and partly, after and / or before this metallization D.
• this elimination E takes place partly before and partly after this metallization D.
• this elimination E takes place completely after this metallization D.
• step E essentially consists of at least one of the following operations:
• the metal deposit D is a non-electrolytic metallization by spraying one or more redox solutions in the form of aerosol (s).
• this first embodiment optionally comprises, before metallization D, at least one of the following steps, preferably in the following order:
• step I surface energy increase treatment of the substrate; knowing that in the case where the method comprises an activation step C, a step I. of increasing the surface energy of the substrate may be optionally provided before activation C. J. wetting the surface of the substrate;
• the metal of step D is selected from the group of the following metals: silver, nickel, copper, tin, iron, gold, cobalt, their oxides, their alloys and combinations thereof.
• the method comprises a step A of preparing the surface of the substrate for receiving 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 (pigments / dyes) crosslinked in temperature (for example a polyurethane, such as that in the form of water-soluble powder) and / or under insolation by a actinic radiation, for example UV.
• the optional treatment for increasing the surface energy of the substrate according to step I which may be comparable to a step A. of preparing the surface of the substrate, is chosen from among the physical treatments, preferably the following physical treatments. : a flaming, a plasma treatment and combinations thereof, and / or among the chemical treatments, preferably the following chemical treatments: application of a silane-based solution, surface depassivation using one or more acidic solutions, a polishing based on rare earth oxide, fluorination and combinations thereof.
• the metal deposit D is an electroless chemical metallization (electroless type) or displacement metallization, by immersion in one (or more) suitable metallization solution (s) and in that it comprises an activation C and possibly, before the activation C, at least one of the following steps, preferably in the following order:
• the substrate is a conductive material as such or treated to become it (that is to say made previously conductive by the techniques of the art) and the metal deposit D is a metallization electrolytic.
• the metallization process it concerns may include the first mode and / or the second mode and / or the third mode of implementation referred to above.
• the solvent for the dissolution of the temporary protection is contained in at least one of the liquids used for the metallization step D and / or optionally in liquids used in at least one rinsing step and in that the duration of this metallization step D is unlimited and, preferably, is 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: printed circuits, integrated circuits on semiconductor substrate, radio identification chips (RFID) ) coding pictograms that can 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 drawing on a cosmetic and / or automobile product.
• RFID radio identification chips
• the method according to the invention is implemented continuously / online 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.
• the present invention relates to a device for implementing the method according to the invention, characterized in that it comprises:
• a module for depositing temporary protection on the surface of the substrate i. a module for depositing temporary protection on the surface of the substrate; ii. a metallization module;
• iii optionally a module for producing a finishing layer, and / or; iv. optionally a module for preparing the surface of the substrate intended to receive the metallic patterns; and or ;
• step B optionally at least one screen / stencil mask useful in one of the variants of step B; and or ;
• step E of the temporary protection of step B optionally an elimination module according to step E of the temporary protection of step B; and or ;
• step F optionally a rinsing module according to step F; and or ; ix. optionally a deposition module of at least one topcoat according to step H.
• this device can be online on industrial installations, for example on a lacquering line and / or liquid metallization.
• the present invention relates to a set of consumables for implementing the method according to the invention characterized in that it comprises:
• step D b. consumable (s) for the metallization of step D;
• step B optionally at least one screen / stencil mask useful in one of the variants of step B; and or ;
• step C optionally consumable (s) for activating the surface of the substrate of step C; and or ;
• step E optionally consumable (s) for elimination according to step E of the temporary protection of step B; and or ;
• any singular denotes indifferently a singular or a plural.
• aerosol is meant that it is eg a mist of droplets of size less than 100 ⁇ , preferably less than 60 ⁇ , and still more preferably from 0.1 to 50 ⁇ , which is performs nebulization and / or atomization solution (s) and / or dispersion (s).
• non-electrolytic metallization refer in particular to the process described in FR2763962B1, EP2326747B1, or EP2318564B1. Detailed description of the invention
• the substrate may be a nonconductive material, a semiconductor material, or a conductive material.
• non-conductive material it may be chosen from the group comprising -or ideally consisting of: glass, plastics / (co) polymer (polyolefins-polypropylene-, polycarbonates, polyesters, styrenics -Acrylonitrile-Butadiene-Styrene-), composite materials, ceramics, textiles, wood, minerals, plaster or cement articles.
• plastics / (co) polymer polyolefins-polypropylene-, polycarbonates, polyesters, styrenics -Acrylonitrile-Butadiene-Styrene-
• composite materials ceramics, textiles, wood, minerals, plaster or cement articles.
• a conductive material is envisaged as a substrate, it could be a metal.
• the semiconductor material likely to be a substrate is one of those commonly used in the semiconductor industry.
• the substrate is a rigid substrate, conductive or non-conductive as defined above.
• Rigid hollow glass substrates and polymeric rigid substrates are particularly preferred.
• a hollow glass substrate is a non-flat glass substrate, in particular a glass container such as a glass bottle or 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 .mu.m to 5 mm, a tissue or a sheet of paper whose density is 50 to 600 g / m2.
• the term "flexible substrate” a substrate that can be bent, bent by the mere force of man without breaking or damage.
• the term "rigid substrate” a substrate that can not be bent, bent by the mere force of man without breaking or damage.
• Step A Preparation of the surface of the substrate for receiving 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 undergo physico-chemical modifications of this layer, which could lead to its attachment to the substrate and elimination (preferably solubilization) more difficult 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 may comprise a cleaning / degreasing of the surface, by means of all products known in themselves and appropriate.
• a varnish for example a UV-curing varnish applied by projection
• any known and appropriate means such as a spray gun compressed air (eg HVLP: high volume low pressure).
• step A may include at least one surface energy increase treatment (step I).
• Step B Deposition of a temporary protection on the surface of the substrate corresponding to the negative of the reasons to be realized
• this temporary protection is a coating corresponding to the negative of the desired patterns.
• This coating is obtained from a liquid product that dries and / or hardens when 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 used in the process according to the invention. It may be in particular a product soluble in an alkaline solvent.
• This temporary protection product may comprise, for example, an ink and any other organic product having a high solubility in a suitable solvent.
• the liquid product used for producing the protective coating may be a product which gives rise after drying and / or hardening and / or crosslinking under actinic radiation, for example UV radiation, to a coating whose adhesion to the substrate can be reduced by at least one of the substances - preferably liquids -, in particular solvents, used later in the process according to the invention.
• actinic radiation for example UV radiation
• the ink is pigmented. Nevertheless, an ink containing a dye will make it possible to visualize the temporary protection applied to the surface of the substrate, which may be practical.
• the temporary protection may be deposited by any known technique of application, for example by means of a screen / stencil mask, offset, flexography, pad printing, or any other transfer technology .
• the screen / stencil mask is for example made of a material consisting of a polymeric material and in the manner traditionally known to those skilled in the art.
• the temporary protection deposit may be performed by a technique allowing a fine, precise and clean impression on a substrate. Inkjet printing, or removal by a pen containing the appropriate ink, are examples that meet these specifications.
• Step C Activation of the surface of the substrate, in particular zones corresponding to the patterns to be produced
• Step D is a non-electrolytic metallization by spraying one or more oxy-red reducing solutions in aerosol form
• activation C is required for certain metals. It aims to accelerate the oxy-reducting reaction involved in this stage 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 (s) adsorb to the unprotected substrate and the protective layer.
• an awareness solution is preferably sprayed onto the surface of the substrate, preferably coated with temporary protection.
• This projection is carried out by any known and appropriate means such as a compressed air paint gun (eg HVLP: high volume low pressure).
• a compressed air paint gun eg HVLP: high volume low pressure
• it may be an immersion.
• a first sensitization solution based on stannous chloride (SnCl 2 ) or SnSO 4 / H 2 SO 4 / quinol / alcohol is applied by spraying or immersion.
• a solution of palladium or silver capable of reacting with Sn 2+ is then deposited in the same manner to form nucleation centers on the surface of the substrate, or else of a colloidal solution PdSn formed ex situ.
• the substrate surface sensitization step is carried out by means of a stannous chloride-based sensitization solution, for example according to the embodiment 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 intermediate step.
• the activation of the surface of the substrate is carried out by means of a sensitization solution, in particular palladium chloride, for example according to the embodiment described in FR2763962B1.
• a rinsing step using a rinsing liquid as described in the examples below is performed just after the activation step, without intermediate step.
• step D is a chemical metallization (called “electroless") without electric / autocatalytic current, 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.
• electroless chemical metallization
• activation C which aims to accelerate the catalytic oxidation-reduction reaction occurring in this step D, is generally essential.
• an electroless chemical metallization catalyst for example an Sn / Pd type catalyst.
• the catalyst is adsorbed on the entire surface of the substrate (unprotected areas corresponding to the patterns to be applied and temporary protective layer).
• This activation C is preferably preceded by a step L (saturation) followed by a step M (rinsing).
• This saturation step is in fact a treatment for increasing the surface energy of the substrate and / or increasing the roughness of the substrate, which may be of the type defined below for step I.
• satinization is preferably carried out by physical treatment (Corona discharge, plasma treatment) or chemical treatment (eg sulfochromic treatment or other) in order to impart sufficient adhesion to the metallic patterns to be deposited.
• physical treatment Corona discharge, plasma treatment
• chemical treatment eg sulfochromic treatment or other
• step I substrate surface energy increase treatment
• step J wetting the substrate surface
• step K Rinse the substrate surface
• the treatment for increasing the surface energy of the substrate according to stage I is chosen from the physical treatments, preferably the following physical treatments: a fiammage, a plasma treatment and their combinations, and / or the chemical treatments, preferably the following chemical treatments: application of a silane solution, surface depassivation using one or more acidic solutions, rare earth oxide polishing, fluorination and combinations thereof .
• the physical treatment of step I is a fiammage treatment.
• the physical treatment is advantageously a fiammage and / or plasma treatment, when the substrate is a rigid substrate of plastic, composite material, polymer or a flexible support of polymer, metal such as a metal strip , textile or paper.
• the fiammage is, for example, the passage of the substrate to metallize under a flame whose temperature is e.g. from 1200 ° C to 1700 ° C.
• the duration of the fiammage is generally from 4 to 50 seconds.
• the flame is preferably obtained by combustion of a fuel such as propane gas (or city 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 silane-based solution, passivation of the surface with the aid of one or more acidic solutions, polishing based on rare earth oxide, fluorination and combinations thereof.
• the chemical treatment is an application of a silane-based solution, a passivation by projection of one or more acidic solutions, a fluorination or combinations thereof.
• this chemical treatment is more particularly 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 of the substrate.
• substrate such as a strong acid solution, for example based on nitric acid, citric acid, sulfuric acid and mixtures thereof.
• the "rare earth oxide polishing" means, for example, that a solution based on rare earth oxide is applied to the substrate to be metallized and that pads come to polish the surface of the substrate, in particular by rubbing against its surface, until the elimination of a possible layer of oxide present on the surface and the smoothing thereof.
• 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 GLAS S POLISHING®.
• the rare earth oxide polishing comprises a step of rinsing the surface thus polished, especially with distilled water.
• the fluorination corresponds, for example, to the contacting, in an enclosure under reduced pressure, of the substrate to be metallized and of a gaseous solution based on an inert gas (argon) containing a fluorine additive.
• the fluorination is carried out for example with an apparatus of the type sold by AIR LIQUIDE®.
• the wetting step J consists of coating the surface of the substrate with a liquid film in order to promote the spreading of the oxy-reducing solutions.
• the choice of the wetting liquid is carried out in the following group: the 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 ethanol and mixtures thereof), and mixtures thereof.
• deionized water added with anionic surfactant and ethanol is chosen as wetting liquid.
• the liquid is essentially aqueous for obvious reasons of industrial convenience.
• the wetting time depends on the surface of the substrate considered and the fountain aerosol spray rate.
• the wetting step may optionally be substituted for the activation step C of the substrate.
• this rinsing step K as well as the other rinsing steps which punctuate the process, as in step F or M, consist in bringing into contact all or part of the surface of the substrate with a or several source (s) of rinsing liquid, which are produced at different stages of the process of the invention, are made by spraying an aerosol of rinsing liquid, preferably demineralised water.
• D. l is a non electrolytic metallization by aerosol spraying and relates in particular to the method described in FR2763962B1, EP2326747B1, or EP2318564B1.
• the aerosol (or aerosol) is (are) e.g.:
• each of which may contain either one or more oxidant (s) or one or more reducing agent (s), provided that there is at least one oxidizing solution and at least one reducing solution.
• the reducing agent is advantageously strong enough to reduce the metal metal cation, that is to say that the standard oxidation-reduction potential of the oxidant / reductant pair of the reducing agent must be lower than that of the oxidant / reducing pair of the oxidant ( rule of gamma).
• the oxy-reducing solutions used in the electroless metallization step are projected as aerosols onto the substrate and are preferably obtained from preferably aqueous solutions of one or more oxidizing metal cations and the like. one or more reducing compounds. These oxy-reducing solutions are preferably obtained by dilution of concentrated stock solutions.
• the diluent is preferably demineralised water. It follows that according to a preferred embodiment of the invention, the aerosol (s) spray (s) are produced by nebulization and / or atomization of solution (s) and / or dispersion (s), so to obtain a mist of droplets smaller than 100 ⁇ , preferably 60 ⁇ , and even more preferably from 0.1 to 50 ⁇ .
• the projection of metallic solutions is preferably continuous and the substrate is set in motion and subjected to projection.
• the projection is preferably continuous.
• the projection is preferably alternating with relaxation times.
• the projection has a duration of 0.5 to 200 seconds, preferably 1 to 50 seconds and even more preferably 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 called semi-transparent and if the projection time is greater than 60 seconds, the deposit is called opaque.
• the substrate can be rotated at least partially during the metallization projection.
• one or more solutions of metal cation (s) and one or more solutions of reducer (s) are sprayed simultaneously onto the surface to be treated in one or more aerosols in a continuous manner.
• the mixture between the oxidizing solution and the reducing solution can be carried out just before the formation of the spray aerosol or else 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 metal cation solutions are successively sprayed via one or more aerosols and then one or more reductant solutions.
• the projection of the oxido-reducing 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 the metal salt (s).
• the combination of several oxidizing metal cations to form a multilayer of different metals or alloys is such that the different salts are preferably projected naturally separately from the reducer but also separately the each other and successively. It goes without saying that in addition to the different nature of metal cations, it is possible to use different counter-anions between them.
• the mixture of the oxidant (s) and the reducing agent (s) is made to be metastable and, after projection of the mixture, the latter is activated so that the metal transformation is triggered. preferably by contacting with an initiator, advantageously provided via one or more aerosols, before, during or after the projection of the reaction mixture.
• an initiator advantageously provided via 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 line the surface of the substrate after projection.
• the initiation or activation of the reaction is then obtained by any physical means (temperature, UV ...) or appropriate chemical.
• Oxygen-reducing solutions projected during the metallization step of the substrate are one or more solutions of a metal oxidant and one or more solutions of a reducing agent.
• 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 metal salt concentrations of the stock solutions are 0.5 g / 1 to 500 g / l, or the dilution factor of the stock solutions is from 5 to 5000.
• the metal salts are chosen from silver nitrate, nickel sulphate, copper sulphate, sodium chloride and tin, chloroacidic acid, iron chloride, cobalt chloride and mixtures thereof.
• the selection of the reducing agents is preferably made from the following compounds: borohydrides, dimethylaminoborane, hydrazine, sodium hypophosphite, formaldehyde, lithium aluminum hydride, reducing sugars such as glucose derivatives or erythorbate sodium, and mixtures thereof.
• the selection of the gearbox requires consideration of the pH and the target properties for the metallization film. These routine adjustments are within the abilities of those skilled in the art.
• the reducing agent concentrations 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 reducing agent concentrations of the stock solutions are 0.5 g / l.
• particles are incorporated in at least one of the oxy-reducing solutions to be projected at time of metallization.
• the particles are thus trapped in the metal deposit.
• These hard particles are, for example, diamond, ceramic, carbon nanotubes, metal particles, rare earth oxides, PTFE (polytetrafluoroethylene), graphite, metal oxides and mixtures thereof.
• the incorporation of these particles into the metal film confers mechanical, tribo logical, electrical, functional and aesthetic properties particular to the metallized substrate.
• D.2 Electroless immersion metallization
• step D is preceded by at least one of the following steps: step L (saturation 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 aerosol spraying.
• This metallization D.2 is preferably carried out by immersion of the substrate, preferably after elimination of the temporary protection, in an "electroless" bath containing the oxidizing and reducing species as well as the stabilizers and surfactants.
• the metallization intervenes on all the zones catalyzed by the catalyst seeds (eg Palladium) adsorbed.
• the area protected by temporary protection is not catalyzed and therefore can not be the seat of a metallization.
• Step E Elimination of temporary protection
• the elimination of the temporary protection may occur during, or at least partly during, and / or after the metallization step D, or partly during and / or after the metallization step D and partly before the step of metallization D.
• this removal is a dissolution in a solvent used in the process.
• the method comprises a step F of rinsing, and the step E of elimination of 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 the step E of elimination of the temporary protection is carried out partly during step D and at least partly during step G.
• E. l Aerosol spray metallization
• the elimination of the temporary protection can take place during the metallization step.
• the temporary protection is alkaline (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 revealing the metallic patterns.
• the duration of metallization is limited so as to prevent any possibility of metallization on the areas initially covered by the temporary protection.
• the metals that do not require activation eg nickel
• the dissolution of the latter is accompanied by the evacuation of the metal layer which it is coated.
• a suitable solution is thus applied, that is to say containing a solvent for temporary protection, on the surface of the substrate. This can be done for example by immersion followed by rinsing. This dissolution reveals the zones of the surface of the substrate corresponding to the negative of the metallic patterns to be produced.
• the areas of the deprotected surface are not activated (adsorption of the catalyst), they do not allow initiation of the metallization for a sufficient time to form metallic patterns. Sufficient time means the time required for the formation of metal patterns on the activated areas of the substrate surface.
• 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 immersion in a rinsing liquid.
• the latter is advantageously and preferably water, and more particularly demineralised water.
• Step G Drying / Blowing
• the drying or blowing which can occur especially after each rinsing step, consists of the evacuation of the rinsing water. It can advantageously be carried out at a temperature of 20 at 60 ° C using for example a compressed air system pulsed 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
• post-metallization a metal identical to or different from the metal of the metallization step D, preferably by electrolytic thickening.
• An alternative finishing treatment may be the deposition of at least one topcoat of a crosslinkable liquid composition on the surface of the substrate bearing the metallic patterns.
• This crosslinkable liquid composition on the protective layer is for example a paint or a varnish, preferably a finishing varnish.
• This varnish may be based on water-soluble or organic, preferably organic. It is chosen from the following group of paints: alkyds, polyurethanes, epoxies, vinyls, acrylics and their mixtures. Preferably, it is chosen from the following compounds: epoxies, alkyds and acrylics and, more preferably still, it is an alkyd varnish.
• the crosslinkable liquid finishing composition may be cross-linked by UV or thermal baking and may 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 these new advantageous industrial processes, incorporating the technique of selective deposition of metal patterns described here and claimed.
• FIG. 1 represents a diagram illustrating known photolithography processes for the manufacture of printed circuits.
• FIG. 2 represents a diagram illustrating the protocol of examples 1 and 2 implementing the method according to the invention with an aerosol spray metallization
• FIG. 3 represents the silkscreen mask of example 1
• FIG. 5 represents the silkscreen mask of example 2.
• a reference UV cross-linking varnish VB330R developed by the company JetMetal Technologies® is applied using an HVLP air gun with an air pressure of between 3 and 4 bar on an ABS (Acrylonitrile Butadiene Styrene) plate of dimensions 25cm x 20cm degreased beforehand.
• the applied plate is desolvated in an oven at 60 ° C for 5 minutes before polymerization in a UV chamber (0.7 to 1.2J / cm 2 UVA).
• a film of alkaline product Propaco SC sold by the company SOCOMORE containing a fast drying alkali-lubine binder is affixed to the varnished plate through a screen-printing mask corresponding to the negative of the metallic pattern to be produced. This mask is shown in the appended FIG. The lighter areas allow the soluble alkali product / ink to form temporary protection. • -I-Treatment of increase of surface energy:
• the unprotected surface After the flaming step, the unprotected surface must be wetting in its entirety (the projection of water on the surface causes the formation of a continuous liquid film).
• the ink film is evacuated in contact with metallization solutions
• the wafer thus metallized is varnished by projection using an HVLP gun and a reference varnish VM112 developed by the company JetMetal Technologies®.
• the wafer is desolvated in an oven at 60 ° C for 5 minutes before polymerization in a UV chamber (0.7 to 1.2J / cm 2 UVA).
• Silver metallic patterns are thus obtained corresponding to the negative of the initially deposited ink -see FIG. 4 annexed- (The non-metallized parts correspond to the areas covered by the screen printing ink)
• a film of alkaline-solubility product Propaco SC sold by the company SOCOMORE containing a quick-drying alkali-soluble binder is affixed to an ABS plate of dimensions 25cm x 20cm through a silkscreen mask corresponding to the negative of the pattern to be made. This mask is shown in the appended FIG. 5, in which the lighter areas allow the soluble alkali product / ink to form the temporary protection.
• a flaming of the surface is carried out by rapid passages for a total duration of 5s with the aid of a flame whose flame temperature has been set at 1400 ° C. (After flaming, the substrate must have a surface energy greater than 50 dynes).
• the unprotected surface After the flaming step, the unprotected surface must be wetting in its entirety (the projection of water on the surface leads to the formation of a continuous liquid film)
• the ink film is evacuated in contact with metallization solutions
• a conductive circuit is thus obtained corresponding to the negative of the initially deposited ink - see FIG. 6 (The non-metallized parts correspond to the areas covered by the screen printing ink).
• the silver deposit is sufficiently conductive to achieve electrolytic copper thickening with a conventional acid copper bath based on copper sulfate and sulfuric acid.
• Example 3 Online Production of Metal Decorative Patterns by Inkjet Printing
• the polypropylene plastic part (cylinder 2.5 cm in diameter and 8 cm high) is attached to the inverted conveyor on the ground. • The conveyor is started at a constant speed of 3m / min and the workpiece is rotated at 350rpm.
• the part is degreased by rubbing with isopropanol alcohol, then is applied a layer of base UV curing varnish reference VB330R containing a level of 3% red dye from JetMetal Technologies by means of 3 HVLP guns.
• the PP piece moves in a thermal oven at 50 ° for a de-solvation step for 4 min and then passes into a UV oven or the surface of the room is irradiated with a power of 0.9J / cm 2 .
• a flaming of the rotating part is carried out on the conveyor by rapid passages for a total duration of 5s with the aid of a flamer whose flame temperature has been set at 1400 ° C. (After flaming, the substrate must present a surface energy greater than 50 dynes).
• the surface After the flaming step, the surface must be wetting in its entirety (the projection of water on the surface causes the formation of a continuous liquid film).
• an ink jet print using Ricoh Gen4 printhead is performed online (without unloading the conveyor part) using a Tiger Alkali-sensitive Heavy Duty Ink reference ink containing alkali binder sensitive.
• This ink is crosslinked by UV irradiation by means of a mercury bulb with a power of 40 mJ / cm 2 .
• This impression corresponds to the negative of the desired pattern.
• the film-forming agent contained in the ink guarantees the masking of the surface; the pigments are not essential for the proper functioning of the process.
• the adhesion of the alkali sensitive ink film is affected to the contact of the solutions during metallization.
• the wafer thus metallized is varnished by projection using an HVLP gun and a reference varnish VM112 developed by the company JetMetal Technologies®.
• the wafer is desolvated in an oven at 60 ° C for 5 minutes before polymerization in a UV chamber (0.7 to 1.2J / cm 2 UVA).
• Decorative silver metallic patterns with 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 to reveal the name of a mark or logo.
• a fast-drying 1070 LINX alkali-soluble ink film is applied by ink jet projection (Seiko head) on a flexible polyimide film 75 ⁇ thick lying flat on a conveyor equipped with a winder / unwinder .
• the inked pattern corresponds to the negative of the pattern to be made.
• an atmospheric plasma pretreatment rotating plasma head
• the substrate must have a surface energy greater than 50 dynes.
• the surface After the plasma step, the surface must be wetting in its entirety (the projection of water on the surface leads to the formation of a continuous liquid film).
• the ink film is solubilized and discharged during metallization in contact with the solutions.
• the film with silver pattern is then guided by the conveyor of a tank containing an acid copper bath based on copper sulfate and sulfuric acid at 20 ° C to undergo a thickening of electrolytic copper of ⁇ .
• the polyimide film is connected on a silver areas to a cathode contact placed next to the soluble anodes of copper.
• a current density of 3 A / dm 2 makes it possible to carry out a copper deposition of ⁇ in 20 minutes.
• the polyimide film is unwound at the beginning of treatment, undergoes each step and is wound up again at the end of the process.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Mechanical Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Electrochemistry (AREA)
• Chemically Coating (AREA)
• Printing Methods (AREA)
• Other Surface Treatments For Metallic Materials (AREA)
• Laminated Bodies (AREA)
• Manufacturing Of Printed Wiring (AREA)
• Electroplating Methods And Accessories (AREA)
• Application Of Or Painting With Fluid Materials (AREA)

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• 2015
  • 2015-02-12 FR FR1551169A patent/FR3032724B1/fr active Active
• 2016
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