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WO2017005284A1 - Monture pour pierre décorative, pourvue d'une couche de cuivre à aspect patiné - Google Patents

Monture pour pierre décorative, pourvue d'une couche de cuivre à aspect patiné Download PDF

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Publication number
WO2017005284A1
WO2017005284A1 PCT/EP2015/065270 EP2015065270W WO2017005284A1 WO 2017005284 A1 WO2017005284 A1 WO 2017005284A1 EP 2015065270 W EP2015065270 W EP 2015065270W WO 2017005284 A1 WO2017005284 A1 WO 2017005284A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
gemstone
acid
socket
brass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2015/065270
Other languages
German (de)
English (en)
Inventor
Martin Rauch
Christoph TRIENDL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
D Swarovski KG
Original Assignee
D Swarovski KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by D Swarovski KG filed Critical D Swarovski KG
Priority to PCT/EP2015/065270 priority Critical patent/WO2017005284A1/fr
Publication of WO2017005284A1 publication Critical patent/WO2017005284A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/52—Treatment of copper or alloys based thereon
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper or alloys based thereon
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/60—Adding a layer before coating
    • B05D2350/65—Adding a layer before coating metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect

Definitions

  • the invention relates to a method for producing an artificial copper patina on a gemstone socket, which has a copper-containing layer and a protective layer.
  • the method is characterized in particular by the fact that a protective layer is applied to a thermally treated copper layer.
  • the metallic jewelry parts assume a characteristic appearance created by weathering and aging.
  • copper is known for its characteristic blue-green appearance due to weathering and aging.
  • the layer that forms is called patina.
  • the gemstone setting itself is not completely made of copper, as copper is too soft for jewelry processing.
  • a jewelery base is often made of, for example, brass, a copper-zinc alloy or pure zinc. These materials are easy to coat.
  • Object of the present invention is to realize an artificial copper patina on a gemstone setting, which is also friendly to the skin, does not react with sweat, has good adhesion and protects against mechanical erosion, such as scratches. Description of the invention
  • the subject matter of the present application is therefore a process for coating a gemstone socket, characterized by the following steps: a) optional cleaning of the surface of the gemstone socket,
  • the gemstone socket is optionally cleaned or degreased in step a) before the copper plating.
  • Degreasing is the removal of adhering fats, oils or other contaminants with degreasing agents. This improves the adhesion of the copper layer.
  • the cleaning can be done mechanically, for example by grinding and polishing, with solvents, for example ethyl acetate, or else with ultrasound, for example with the Evolution WP-K device from German Sonic.
  • Another option for pretreatment is electrolytic degreasing.
  • the gemstone socket is in a solution and is then cleaned by applying a current.
  • electrolytic degreasing a distinction is made between cathodic and anodic degreasing.
  • the cathodic degreasing proceeds under hydrogen evolution and the anodic degreasing under evolution of oxygen.
  • the cathodic degreasing is preferably used because it can be achieved with jewelry bodies such as brass very good cleaning.
  • the surface of the gemstone socket may be treated with acids to remove oxide layers.
  • Sulfuric acid has proven to be advantageous for the cleaning of brass jewel casings.
  • electroless processes in solution or electrolytic processes or also processes such as physical vapor deposition (PVD) or chemical vapor deposition (CVD).
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • a thin metal layer is deposited on the surface of a material to be coated. All of these methods are suitable in principle according to the invention.
  • the electrolytic processes are electrochemical depositions of metal layers on surfaces to be coated. Conductive materials, such as conductive metals, conductive metal alloys or conductive plastics, are suitable for this type of surface coating.
  • the material to be coated is placed in a solution of the coating material. By applying an external current, the coating material deposits on the material to be coated.
  • Electroless coating processes in solution such as reductive, occur without the use of an external power source.
  • Such a metal deposition with the addition of reducing agents to the electrolyte is based on the oxidation of the reducing agent with release of electrons, which lead to a reduction of the metal ions.
  • the inventive method allows for jewelry in terms of aesthetics and design very many design options.
  • the copper patina can be applied electrolytically in principle to any conductive material, for example on brass or on electrically conductive plastics.
  • gemstone frames are used, which are made of brass or a brass-containing alloy, since brass is particularly suitable for processing technical reasons. Brass is easy to coat and is easy to machine. Brass and all other metals listed here are used in the purity known to those skilled in the art.
  • a gemstone mount is made of zinc die-cast, it is advantageous to pre-clad first with a cyanide copper electrolyte. The resulting, usually thin copper layer is then reinforced with an acidic copper electrolyte. Pre-coppering is necessary because it is not possible to directly coat zinc die-cast parts due to the low pH of an acidic copper electrolyte. The zinc would dissolve. In contrast, brass jewel casings can be directly coated with an acidic copper electrolyte.
  • the copper layer is preferably deposited electrolytically. With electrolytic processes, the copper layer can be selectively deposited.
  • the Thickness of the deposited copper layer is preferably 5 to 200 ⁇ , in particular 5 to 100 ⁇ and particularly preferably 10 to 50 ⁇ .
  • a minimum layer thickness of 5 ⁇ is necessary because material is removed by further process steps.
  • a layer thickness of more than 200 ⁇ is not very advantageous because no additional advantages are associated with it.
  • the copper-plated parts are treated in process step c) with a mixture of acid and copper salt solution or base and copper salt solution.
  • Nitric acid or acetic acid is preferably used according to the invention as the acid.
  • copper salt copper nitrate is preferably used.
  • the copper-plated gemstone socket can be treated first with the acid or base and then with the copper salt solution.
  • the use of the mixture of acid or base and copper salt solution has the advantage that two process steps can be handled in one.
  • nitric acid it is also possible to use a base, preferably ammonia.
  • the combination of ammonia and copper sulfate is preferred.
  • the copper-plated gemstone setting discolors bluish with a solution of ammonia and copper sulfate and a solution of acetic acid and copper acetate greenish.
  • the gemstone socket is thermally treated.
  • the thermal aftertreatment is preferably carried out at temperatures in the range of 50 ⁇ -190 ⁇ .
  • the thermal post-treatment has proven to be advantageous for the desired color change.
  • temperatures above 190 ° the gemstone setting discolors towards black, which is undesirable for aesthetic reasons.
  • the cooled gemstone setting is optionally treated again with a copper salt solution.
  • the copper salt according to the invention is copper nitrate, Cu (II) acetate or copper sulfate.
  • the gemstone setting in the temperature range of 50 ⁇ - 190 ⁇ thermally treated.
  • the process step e) can be carried out in any repetition and serves to reinforce the copper patina effect.
  • a protective varnish is applied to the gemstone socket.
  • the protective varnish prevents the metal parts from reacting and improving with the sweat of the skin also the resistance of the metal layers.
  • varnish is understood as meaning a liquid or pulverulent coating material which is applied thinly to objects and is built up by chemical or physical processes, for example evaporation of the solvent, to form a continuous, solid layer. Paints often contain binders, fillers, pigments, solvents, resins and / or acrylates and additives, such as biocides. For example, acrylic lacquers, epoxy lacquers or polyurethane lacquers are suitable according to the invention.
  • Acrylic paints are manufactured on the basis of acrylic resins.
  • Acrylic resins are synthetic resins and are considered particularly durable.
  • Acrylic resins are based on polymers or copolymers of acrylic acid or methacrylic acid and their esters. They are often copolymerized with other unsaturated monomers, such as styrene or acrylonitrile.
  • Acrylic paints are either dissolved in solvents or dispersed in water and applied to the coated gemstone mount.
  • Acrylic coatings have a high weather resistance and are UV-resistant and are therefore particularly well suited according to the invention.
  • Epoxy paints often contain the two components epoxy resin and hardener.
  • Epoxy resins are polyadducts of epichlorohydrin with bisphenol derivatives, for example A, F or S. These are crosslinked with a hardener. Usually, the two components epoxy resin and hardener are mixed shortly before processing. Epoxy coatings are characterized by high chemical and mechanical resistance, but are not optimal in terms of UV resistance.
  • the urethane group is characteristic. They are commercially available as single-component and multicomponent coatings, for example the hardener is already mixed with the master varnish in the case of one-component varnish, and the two-component varnish contains hardener and stock varnish. Polyurethane coatings are particularly hard, abrasion resistant and resistant to water, oils and chemicals.
  • a polyurethane varnish is preferably used as the protective varnish.
  • Polyurethane paints have good adhesion properties and are resistant.
  • Two-component polyurethane acrylic resin coatings have proved to be advantageous according to the invention, in particular the products DE 4259x the company Hesse and Lignal, since they are saliva and sweat resistant according to DIN 53160. They can be applied without thermal aftertreatment and are lightfast.
  • Another object of the application are gemstone versions, which are obtainable by the method according to the invention.
  • the preferred embodiments of the method lead to inventively preferred products.
  • the gemstone socket is optionally cleaned or degreased.
  • the electrolytic solution contains, for example, caustic soda and surfactants.
  • the degreasing is carried out for a period of at least 1 minute, a temperature of 35 ⁇ - 55 ⁇ and a current density of at least 3 A / dm 2, for example with the 1018 agent IWG-Plating Vienna.
  • treatment of the gemstone casing with 5-15% sulfuric acid (% by weight) has proved to be advantageous.
  • the gemstone socket is immersed in the sulfuric acid according to the invention for about 1 minute. Thereafter, the gemstone socket is cleaned with deionized water. Inadequate cleaning can damage both the electrolytes and the quality of the copper layer.
  • the gemstone socket is coated electrolytically with copper.
  • the electrolyte used can be, for example, Cupracid® 210 from Atotech. When coppering the metal parts is particularly preferably a copper layer thickness of 10 - 50 ⁇ deposited.
  • the gemstone socket is treated in step c) of the process with an aqueous solution of acid or base and copper salt, for example by immersing it in the aqueous solution of acid or base and copper salt.
  • an aqueous solution of acid or base and copper salt for example by immersing it in the aqueous solution of acid or base and copper salt.
  • For the treatment of brass has proven due to good adhesion properties nitric acid (about 0.1 to 1 mol / l) and copper nitrate (about 3 - 7 mol / l).
  • the gemstone socket is usually treated for about 30 seconds with the aqueous solution of nitric acid and copper nitrate or with the aqueous solution of acetic acid (about 3 - 5 wt .-%) and Cu (II) acetate (about 0.5 - 1 mol / l).
  • Another alternative is an aqueous solution of Cu (II) SO 4 (about 0.1-0.3 mol / l) and ammonia (about 0.02-0.04 mol / l).
  • Acid or base and copper salt do not have to be used in a solution.
  • the gemstone socket can also be treated first with the acid or base and then in a further step with the copper salt.
  • the use of the acid or base and copper salt in a solution has the advantage that two process steps can be handled in one.
  • the gemstone casing is dried at about 20 ° to 30 ° C. and, in process step d), thermally treated with a hot air blower in the range of 50 ° C.-190 ° C.
  • the cooled gemstone socket is optionally cleaned with deionized water and then treated again in process step e) with an aqueous copper salt solution by immersing the socket.
  • copper salt copper nitrate, Cu (II) acetate or Copper sulphate.
  • the gemstone version is again at about 20 ⁇ - 30 ⁇ ge dried and thermally treated.
  • the gemstone socket is again dried with a hot air blower in the range of 50 ⁇ - 190 ⁇ .
  • the process step e) can be repeated as often as desired.
  • a protective lacquer is applied in step f), for example, to prevent the reaction of skin sweat with the gemstone setting.
  • a protective varnish acrylic varnish, epoxy varnish, for example Duralit® 1516-754 S from Rohm and Haas or also polyurethane varnish can be used.
  • a gemstone setting made of brass was coated in the following manner with a copper patina.
  • the gemstone frame made of the FRMSBR alloy from AGS Alpha Guss Metals and Alloys GmbH Pforzheim was degreased electrolytically with the agent 1018 from IWG-Plating Wien for 5 minutes at a temperature of 45 ° and a current density of 5 A / dm 2 . Thereafter, the degreased brass parts were washed with deionized water. For removal of oxide layers, the brass jewelry frame was immersed for about 1 minute in a 10% sulfuric acid (wt .-%). Thereafter, the gemstone socket was washed again with deionized water.
  • the brass jewel case was dipped wet in a copper bath and coated in the bright copper bath Cupracid® 210 from Atotech at 25 ° and a current density of 3 A / dm 2 for about 20 minutes.
  • the copper-plated gemstone socket was immersed for about 20 seconds in an aqueous solution of nitric acid (1 mol / l) and copper nitrate (7 mol / l) and then dried for about 20 minutes at about 25. Thereafter, the frame was thermally treated with a hot air blower and a temperature of about 180 °.
  • the cooled gemstone socket was again washed with deionized water and then immersed for about 20 seconds in an aqueous copper nitrate solution (3 mol / l). Then the gemstone setting was dried for about 20 minutes at about 25 ⁇ and then with a hot air blower at about 180 ⁇ thermally aftertreated It.
  • the cooled gem stone mount was coated with the protective varnish by immersing it in the two-component polyurethane acrylic resin paint DE 42597-0040 the company Hesse & Lignal and dried at about 25 ⁇ for a period of about 14 hours.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'une couche de cuivre à aspect artificiellement patiné sur une monture pour pierre décorative. Ladite patine se caractérise par un aspect qui correspond au processus de vieillissement naturel. La présente invention concerne également des produits fabriqués selon ledit procédé.
PCT/EP2015/065270 2015-07-05 2015-07-05 Monture pour pierre décorative, pourvue d'une couche de cuivre à aspect patiné Ceased WO2017005284A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2015/065270 WO2017005284A1 (fr) 2015-07-05 2015-07-05 Monture pour pierre décorative, pourvue d'une couche de cuivre à aspect patiné

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2015/065270 WO2017005284A1 (fr) 2015-07-05 2015-07-05 Monture pour pierre décorative, pourvue d'une couche de cuivre à aspect patiné

Publications (1)

Publication Number Publication Date
WO2017005284A1 true WO2017005284A1 (fr) 2017-01-12

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PCT/EP2015/065270 Ceased WO2017005284A1 (fr) 2015-07-05 2015-07-05 Monture pour pierre décorative, pourvue d'une couche de cuivre à aspect patiné

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3497401A (en) * 1967-09-20 1970-02-24 Intern Copper Research Ass Inc Patination of copper
GB2167444A (en) * 1984-11-22 1986-05-29 Risis Private Limited Electroforming
US6212745B1 (en) * 1996-10-09 2001-04-10 Pgcm Conception, Societe Civile D'inventeurs Method for setting stones in the surface of a jewel produced by electroforming

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3497401A (en) * 1967-09-20 1970-02-24 Intern Copper Research Ass Inc Patination of copper
GB2167444A (en) * 1984-11-22 1986-05-29 Risis Private Limited Electroforming
US6212745B1 (en) * 1996-10-09 2001-04-10 Pgcm Conception, Societe Civile D'inventeurs Method for setting stones in the surface of a jewel produced by electroforming

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