EP2312021A1 - Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals - Google Patents

Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals Download PDF

Info

Publication number
EP2312021A1
EP2312021A1 EP09173198A EP09173198A EP2312021A1 EP 2312021 A1 EP2312021 A1 EP 2312021A1 EP 09173198 A EP09173198 A EP 09173198A EP 09173198 A EP09173198 A EP 09173198A EP 2312021 A1 EP2312021 A1 EP 2312021A1
Authority
EP
European Patent Office
Prior art keywords
copper
process according
gold
bath
silver
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.)
Granted
Application number
EP09173198A
Other languages
German (de)
French (fr)
Other versions
EP2312021B1 (en
Inventor
Christophe Henzirohs
Guido Plankert
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.)
Swatch Group Research and Development SA
Original Assignee
Swatch Group Research and Development SA
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
Priority to EP09173198.4A priority Critical patent/EP2312021B1/en
Application filed by Swatch Group Research and Development SA filed Critical Swatch Group Research and Development SA
Priority to US12/905,788 priority patent/US20110089040A1/en
Priority to CN201010552012.7A priority patent/CN102041527B/en
Priority to JP2010232903A priority patent/JP5563421B2/en
Priority to KR1020100100585A priority patent/KR101297476B1/en
Publication of EP2312021A1 publication Critical patent/EP2312021A1/en
Priority to HK11111618.6A priority patent/HK1157415A1/en
Priority to US14/452,364 priority patent/US9567684B2/en
Priority to US15/898,330 priority patent/US20180171499A1/en
Application granted granted Critical
Publication of EP2312021B1 publication Critical patent/EP2312021B1/en
Priority to US16/847,699 priority patent/US20200240030A1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight 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
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins

Definitions

  • the invention relates to electrolytic deposition in the form of a gold alloy in a thick layer, as well as to its method of manufacture.
  • the deposits obtained by these known methods have cadmium contents of between 1 and 10%.
  • Cadmium facilitates the deposition of thick layers, that is to say between 1 and 800 microns and makes it possible to obtain a yellow-colored alloy by decreasing the quantity of copper contained in the alloy; however, cadmium is extremely toxic and banned in some countries.
  • the object of the present invention is to overcome all or part of the disadvantages mentioned above a manufacturing process for the deposition in thick layer of a yellow gold alloy having neither zinc nor cadmium as main constituents.
  • the invention relates to a method for the electroplating of a gold alloy on an electrode immersed in a bath comprising gold metal in the form of alkaline aurocyanide, organometallic compounds, a wetting agent, a complexant, free cyanide characterized in that the alloying metals are copper in the form of double cyanide of copper and potassium, and silver in cyanide form for depositing on the electrode a gold alloy of the yellow type brilliant mirror.
  • the invention also relates to an electrolytic deposit in the form of a gold alloy obtained from a process according to one of the preceding claims whose thickness is between 1 and 800 microns and which comprises copper characterized in that it comprises silver as the third main compound to obtain a brilliant shade 3N, preferably in a proportion of 75% gold, 21% copper and 4% silver.
  • the invention relates to an electrolytic deposition of a 3N gold alloy which, surprisingly, comprises principal Au-Cu-Ag compounds whose proportions are not known to obtain the 3N hue, that is to say say bright yellow.
  • a gold alloy free of toxic metals or metalloids, in particular free of cadmium, 3N yellow color, a thickness of 200 microns, excellent gloss and having a very high high resistance to wear and tarnishing.
  • the electrolysis is preferably followed by a heat treatment at a temperature between 200 and 450 degrees Celsius for 1 to 30 minutes to obtain an optimal quality deposit.
  • the bath according to the invention makes it possible to obtain a deposit substantially in a proportion of 75% of gold, 21% of copper and 4% of silver corresponding to a deposit of shade 3N to 18 carats which is a very different proportion of the usual electrolytic deposits for this shade which are rather deposits according to substantially 75% of gold, 12.5% of copper and 12.5% of silver.
  • the bath may further contain a brightener.
  • a brightener This is preferably a butynediol derivative, a pyridinio-propanesulfonate or a mixture of both, a tin salt, sulfonated beaver oil, methylimidozole, dithiocarboxylic acid such as thiourea, thiobarbituric acid, imidazolidinthione or thiomalic acid.
  • the electrolytic bath contained in a polypropylene or PVC tank with heat-insulating coating. Bath heating is achieved by thermo-plungers in quartz, PTFE, porcelain or stabilized stainless steel. Good cathodic agitation as well as a circulation of the electrolyte must be maintained.
  • the anodes are platinized titanium, stainless steel, ruthenium, iridium or alloys of the latter two.
  • the bath may contain the following metals Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi in negligible quantity.
  • the wetting agent may be of any type capable of wetting in an alkaline cyanide medium.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

Galvanoplastic deposition of a gold alloy on an electrode dipped into a bath including gold metal in alkaline aurocyanide form, organometallic compounds, a wetting agent, a sequestering agent and free cyanide, where the alloy metal is copper, which is in double copper and potassium cyanide form, and silver, or in cyanide form, comprises depositing a mirror-bright yellow gold alloy on the electrode, where the bath respects a proportion of 9.08% gold, 90.85% copper and 0.07% silver containing neither cadmium nor zinc. Independent claims are also included for: (1) an electrolytic deposition in the form of a gold alloy obtained from the above method having a thickness of 1-800 mu and comprising copper and silver as the third main compound, allowing a bright 3N color to be obtained; and (2) an electrolytic deposition is in the form of a gold, copper, and silver alloy, where the deposition is made of gold (75%), copper (21%) and silver (4%), allowing a bright 3N color to be obtained.

Description

Domaine de l'inventionField of the invention

L'invention se rapporte à dépôt électrolytique sous forme d'un alliage d'or en couche épaisse ainsi que son procédé de fabrication.The invention relates to electrolytic deposition in the form of a gold alloy in a thick layer, as well as to its method of manufacture.

Arrière plan de l'inventionBackground of the invention

Dans le domaine décoratif du placage, on connaît des procédés pour la production de dépôts électrolytiques d'or, de couleur jaune, dont le titre est supérieur ou égal à 9 carats, ductile à une épaisseur de 10 microns, et de grande résistance au ternissement. Ces dépôts sont obtenus par une électrolyse dans un bain galvanique alcalin contenant, en plus de l'or et du cuivre, du cadmium à raison de 0,1 à 3 g.l-1.In the decorative field of plating processes are known for the production of electrolytic deposits of gold, yellow color, whose title is greater than or equal to 9 carats, ductile to a thickness of 10 microns, and high resistance to tarnishing . These deposits are obtained by electrolysis in an alkaline galvanic bath containing, in addition to gold and copper, cadmium at a rate of 0.1 to 3 gl -1 .

Les dépôts obtenus par ces procédés connus présentent cependant des teneurs en cadmium comprises entre 1 et 10 %. Le cadmium facilite le dépôt de couches épaisses, c'est-à-dire entre 1 et 800 microns et permet d'obtenir un alliage de couleur jaune en diminuant la quantité de cuivre contenue dans l'alliage; toutefois le cadmium est extrêmement toxique et interdit dans certains pays.The deposits obtained by these known methods, however, have cadmium contents of between 1 and 10%. Cadmium facilitates the deposition of thick layers, that is to say between 1 and 800 microns and makes it possible to obtain a yellow-colored alloy by decreasing the quantity of copper contained in the alloy; however, cadmium is extremely toxic and banned in some countries.

On connaît aussi des alliages d'or de 18 carats sans cadmium, contenant du cuivre et du zinc. Cependant, ces dépôts sont de teinte trop rose (titre trop riche en cuivre). Enfin, ces dépôts ont une mauvaise résistance à la corrosion ce qui implique un ternissement rapideAlso known are cadmium-free 18-carat gold alloys containing copper and zinc. However, these deposits are too pink (title too rich in copper). Finally, these deposits have a poor resistance to corrosion which implies a rapid tarnishing

Résumé de l'inventionSummary of the invention

Le but de la présente invention est de pallier tout ou partie les inconvénients cités précédemment un procédé de fabrication permettant le dépôt en couche épaisse d'un alliage d'or de couleur jaune n'ayant ni de zinc ni de cadmium comme constituants principaux.The object of the present invention is to overcome all or part of the disadvantages mentioned above a manufacturing process for the deposition in thick layer of a yellow gold alloy having neither zinc nor cadmium as main constituents.

A cet effet, l'invention se rapporte à un procédé de dépôt galvanoplastique d'un alliage d'or sur une électrode plongée dans un bain comportant de l'or métal sous forme d'aurocyanure alcalin, des composés organométalliques, un mouillant, un complexant, du cyanure libre caractérisé en ce que les métaux d'alliage sont du cuivre sous forme de cyanure double de cuivre et potassium, et de l'argent sous forme cyanure permettant de déposer sur l'électrode un alliage d'or du type jaune miroir brillant.For this purpose, the invention relates to a method for the electroplating of a gold alloy on an electrode immersed in a bath comprising gold metal in the form of alkaline aurocyanide, organometallic compounds, a wetting agent, a complexant, free cyanide characterized in that the alloying metals are copper in the form of double cyanide of copper and potassium, and silver in cyanide form for depositing on the electrode a gold alloy of the yellow type brilliant mirror.

Conformément à d'autres caractéristiques avantageuses de l'invention :

  • le bain comporte de 1 à 10 g.l-1 d'or métal sous forme d'aurocyanure alcalin ;
  • le bain comporte de 30 à 80 g.l-1 de cuivre métal sous forme de cyanure double alcalin ;
  • le bain comporte de 10 mg.l-1 à 1 g.l-1 d'argent métal sous forme complexé ;
  • le bain comporte de 15 à 35 g.l-1 de cyanure libre ;
  • le mouillant comporte une concentration comprise entre 0,05 et 10 ml.l-1 ;
  • le mouillant est choisi parmi les types polyoxyalcoilenique, étherphosphate, lauryl sulfate, diaméthydodécylamine-N-oxide, diméthyldodécyl ammonium propane sulfonate ;
  • le bain comporte une amine de concentration comprise entre 0,01 et 5 ml.l-1 ;
  • le bain comporte un dépolarisant de concentration comprise entre 0,1 mg.l-1 à 20 mg.l-1 ;
  • le bain comporte des sels conducteurs du type phosphates, carbonates, citrates, sulfates, tartrates, gluconates et/ou phosphonates ;
  • la température du bain est maintenue entre 50 et 80°C ;
  • le pH du bain est maintenu entre 8 et 12 ;
  • le procédé est réalisé à une densité de courant comprise entre 0,05 et 1,5 A.dm-2 ;
  • le bain respecte une proportion de 9,08 % d'or, de 90,85 % de cuivre et de 0,07 % d'argent.
According to other advantageous features of the invention:
  • the bath comprises from 1 to 10 g -1 of gold metal in the form of alkaline aurocyanide;
  • the bath comprises from 30 to 80 gl -1 of copper metal in the form of double alkaline cyanide;
  • the bath comprises from 10 mg.l -1 to 1 gl -1 of silver metal in complexed form;
  • the bath comprises 15 to 35 g -1 of free cyanide;
  • the wetting agent has a concentration of between 0.05 and 10 ml.l -1 ;
  • the wetting agent is chosen from the polyoxyalcoilene, etherphosphate, lauryl sulfate, diamethydodecylamine-N-oxide and dimethyldodecylammonium propane sulfonate types;
  • the bath comprises an amine concentration of between 0.01 and 5 ml.l -1 ;
  • the bath comprises a depolarizer with a concentration of between 0.1 mg.l -1 and 20 mg.l -1 ;
  • the bath comprises conducting salts of phosphates, carbonates, citrates, sulphates, tartrates, gluconates and / or phosphonates;
  • the temperature of the bath is maintained between 50 and 80 ° C;
  • the pH of the bath is maintained between 8 and 12;
  • the process is carried out at a current density of between 0.05 and 1.5 A.dm -2 ;
  • the bath has a proportion of 9.08% gold, 90.85% copper and 0.07% silver.

L'invention se rapporte également à un dépôt électrolytique sous forme d'un alliage d'or obtenu à partir d'un procédé conforme à l'une des revendications précédentes dont l'épaisseur est comprise entre 1 et 800 microns et qui comporte du cuivre caractérisé en ce qu'il comprend de l'argent comme troisième composé principal permettant d'obtenir une teinte brillante 3N, préférentiellement selon une proportion de 75 % d'or, de 21 % de cuivre et de 4 % d'argent.The invention also relates to an electrolytic deposit in the form of a gold alloy obtained from a process according to one of the preceding claims whose thickness is between 1 and 800 microns and which comprises copper characterized in that it comprises silver as the third main compound to obtain a brilliant shade 3N, preferably in a proportion of 75% gold, 21% copper and 4% silver.

Description détaillée des modes de réalisation préférésDetailed Description of the Preferred Embodiments

L'invention concerne un dépôt électrolytique d'un alliage d'or de teinte 3N qui, de manière surprenante, comporte des composés principaux Au-Cu-Ag dont les proportions ne sont pas connues pour obtenir la teinte 3N, c'est-à-dire jaune brillant.The invention relates to an electrolytic deposition of a 3N gold alloy which, surprisingly, comprises principal Au-Cu-Ag compounds whose proportions are not known to obtain the 3N hue, that is to say say bright yellow.

Dans un exemple de dépôt ci-dessus, on a un alliage d'or, exempt de métaux ou métalloïdes toxiques, en particulier exempt de cadmium, de teinte 3N jaune, d'une épaisseur de 200 microns, de brillance excellente et ayant une très grande résistance à l'usure et au ternissement.In an example of deposit above, there is a gold alloy, free of toxic metals or metalloids, in particular free of cadmium, 3N yellow color, a thickness of 200 microns, excellent gloss and having a very high high resistance to wear and tarnishing.

Ce dépôt est obtenu par une électrolyse dans un bain électrolytique du type :

  • Au : 5,5 g.l-1
  • Cu : 55 g.l-1
  • Ag : 40 mg.l-1
  • KCN : 26 g.l-1
  • pH : 10,5
  • Température : 65°C
  • Densité de Courant : 0,3 A.dm-2
  • Mouillant : 0,05 ml.l-1 NN-Diméthyldodecyl N-Oxide
  • Iminodiacétique : 20 g.l-1
  • Ethylènediamine : 0.5 ml.l-1
  • Gallium, sélénium ou tellure : 10 mg.l-1
This deposit is obtained by electrolysis in an electrolytic bath of the type:
  • Au: 5.5 gl -1
  • Cu: 55 gl -1
  • Ag: 40 mg.l -1
  • KCN: 26 g . l -1
  • pH: 10.5
  • Temperature: 65 ° C
  • Current Density: 0.3 A.dm -2
  • Wetting: 0.05 ml.l -1 NN-Dimethyldodecyl N-Oxide
  • Iminodiacetic: 20 gl -1
  • Ethylenediamine: 0.5 ml.l -1
  • Gallium, selenium or tellurium: 10 mg.l -1

L'électrolyse est de préférence suivie d'un traitement thermique à une température comprise entre 200 et 450 degrés Celsius pendant 1 à 30 minutes afin d'obtenir un dépôt de qualité optimale.The electrolysis is preferably followed by a heat treatment at a temperature between 200 and 450 degrees Celsius for 1 to 30 minutes to obtain an optimal quality deposit.

Ces conditions permettent d'obtenir un rendement cathodique de 98 mg.A.min-1 avec une vitesse de déposition d'environ 10 µm par heure dans le cas de l'exemple.These conditions make it possible to obtain a cathodic efficiency of 98 mg.A.min -1 with a deposition rate of approximately 10 μm per hour in the case of the example.

Ainsi, de manière étonnante, le bain selon l'invention permet d'obtenir un dépôt sensiblement selon une proportion de 75 % d'or, de 21 % de cuivre et de 4 % d'argent correspondant à un dépôt de teinte 3N à 18 carats qui est une proportion très différente des dépôts électrolytiques habituels pour cette teinte qui sont plutôt des dépôts selon sensiblement 75 % d'or, 12,5 % de cuivre et 12,5 % d'argent.Thus, surprisingly, the bath according to the invention makes it possible to obtain a deposit substantially in a proportion of 75% of gold, 21% of copper and 4% of silver corresponding to a deposit of shade 3N to 18 carats which is a very different proportion of the usual electrolytic deposits for this shade which are rather deposits according to substantially 75% of gold, 12.5% of copper and 12.5% of silver.

Le bain peut contenir en outre un brillanteur. Celui-ci est, de préférence, un dérivé du butynediol, un pyridinio-propanesulfonate ou un mélange des deux, un sel d'étain, de l'huile de castor sulfonées, du méthylimidozole, de l'acide dithiocarboxylique tels que du thiourée, de l'acide thiobarbiturique, de l'imidazolidinthione ou de l'acide thiomalique.The bath may further contain a brightener. This is preferably a butynediol derivative, a pyridinio-propanesulfonate or a mixture of both, a tin salt, sulfonated beaver oil, methylimidozole, dithiocarboxylic acid such as thiourea, thiobarbituric acid, imidazolidinthione or thiomalic acid.

Dans ces exemples, le bain électrolytique, contenu dans une cuve en polypropylène ou en PVC avec revêtement calorifuge. Le chauffage du bain est réalisé grâce à des thermo-plongeurs en quartz, en PTFE, en porcelaine ou en acier inoxydable stabilisé. Une bonne agitation cathodique ainsi qu'une circulation de l'électrolyte doit être maintenue. Les anodes sont en titane platiné, en acier inoxydable, en ruthénium, en iridium ou alliages de ces deux derniers.In these examples, the electrolytic bath, contained in a polypropylene or PVC tank with heat-insulating coating. Bath heating is achieved by thermo-plungers in quartz, PTFE, porcelain or stabilized stainless steel. Good cathodic agitation as well as a circulation of the electrolyte must be maintained. The anodes are platinized titanium, stainless steel, ruthenium, iridium or alloys of the latter two.

Bien entendu, la présente invention ne se limite pas à l'exemple illustré mais est susceptible de diverses variantes et modifications qui apparaîtront à l'homme de l'art. En particulier, le bain peut contenir les métaux suivants Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi en quantité négligeable.Of course, the present invention is not limited to the illustrated example but is susceptible of various variations and modifications that will occur to those skilled in the art. In particular, the bath may contain the following metals Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi in negligible quantity.

De plus, le mouillant peut être de tout type susceptible de mouiller en milieu cyanuré alcalin.In addition, the wetting agent may be of any type capable of wetting in an alkaline cyanide medium.

Claims (16)

Procédé de dépôt galvanoplastique d'un alliage d'or sur une électrode plongée dans un bain comportant de l'or métal sous forme d'aurocyanure alcalin, des composés organométalliques, un mouillant, un complexant, du cyanure libre caractérisé en ce que les métaux d'alliage sont du cuivre sous forme de cyanure double de cuivre et potassium, et de l'argent sous forme cyanure permettant de déposer sur l'électrode un alliage d'or du type jaune miroir brillant.Process for the electroplating of a gold alloy on an electrode immersed in a bath comprising gold metal in the form of alkaline aurocyanide, organometallic compounds, a wetting agent, a complexing agent, free cyanide, characterized in that the metals alloys are copper in the form of cyanide double copper and potassium, and silver in cyanide form for depositing on the electrode a gold-type bright mirror yellow type. Procédé selon la revendication 1, caractérisé en ce que le bain comporte de 1 à 10 g.l-1 d'or métal sous forme d'aurocyanure alcalin.Process according to Claim 1, characterized in that the bath contains from 1 to 10 gl -1 of gold metal in the form of alkaline aurocyanide. Procédé selon la revendication 1 ou 2, caractérisé en ce que le bain comporte de 30 à 80 g.l-1 de cuivre métal sous forme de cyanure double alcalin.Process according to claim 1 or 2, characterized in that the bath comprises from 30 to 80 gl -1 of copper metal in the form of double alkaline cyanide. Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain comporte de 10 mg.l-1 à 1 g.l-1 d'argent métal sous forme complexé.Process according to one of the preceding claims, characterized in that the bath comprises from 10 mg.l -1 to 1 gl -1 of silver metal in complexed form. Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain comporte de 15 à 35 g.l-1 de cyanure libre.Process according to one of the preceding claims, characterized in that the bath comprises from 15 to 35 gl -1 of free cyanide. Procédé selon l'une des revendications précédentes, caractérisé en ce que le mouillant comporte une concentration comprise entre 0,05 et 10 ml.l-1.Process according to one of the preceding claims, characterized in that the wetting agent has a concentration of between 0.05 and 10 ml.l -1 . Procédé selon la revendication 1 ou 6, caractérisé en ce que le mouillant est choisi parmi les types polyoxyalcoilenique, étherphosphate, lauryl sulfate, diaméthydodécylamine-N-oxide, diméthyldodécyl ammonium propane sulfonate.Process according to claim 1 or 6, characterized in that the wetting agent is chosen from the polyoxyalcoilene, etherphosphate, lauryl sulfate, diamethydodecylamine-N-oxide and dimethyldodecylammonium propane sulphonate types. Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain comporte une amine de concentration comprise entre 0,01 et 5 ml.l-1.Process according to one of the preceding claims, characterized in that the bath comprises an amine with a concentration of between 0.01 and 5 ml.l -1 . Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain comporte un dépolarisant de concentration comprise entre 0,1 mg.l-1 à 20 mg.l-1.Process according to one of the preceding claims, characterized in that the bath comprises a depolarizer with a concentration of between 0.1 mg.l -1 and 20 mg.l -1 . Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain comporte des sels conducteurs du type phosphates, carbonates, citrates, sulfates, tartrates, gluconates et/ou phosphonates.Process according to one of the preceding claims, characterized in that the bath comprises conducting salts of the phosphates, carbonates, citrates, sulphates, tartrates, gluconates and / or phosphonates type. Procédé selon l'une des revendications précédentes, caractérisé en ce que la température du bain est maintenue entre 50 et 80°C.Process according to one of the preceding claims, characterized in that the bath temperature is maintained between 50 and 80 ° C. Procédé selon l'une des revendications précédentes, caractérisé en ce que le pH du bain est maintenu entre 8 et 12.Process according to one of the preceding claims, characterized in that the pH of the bath is maintained between 8 and 12. Procédé selon l'une des revendications précédentes, caractérisé en ce que le procédé est réalisé à une densité de courant comprise entre 0,05 et 1,5 A.dm-2 Method according to one of the preceding claims, characterized in that the process is carried out at a current density of between 0.05 and 1.5 A.dm -2. Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain respecte une proportion de 9,08 % d'or, de 90,85 % de cuivre et de 0,07 % d'argent.Method according to one of the preceding claims, characterized in that the bath has a proportion of 9.08% gold, 90.85% copper and 0.07% silver. Dépôt électrolytique sous forme d'un alliage d'or obtenu à partir d'un procédé conforme à l'une des revendications précédentes dont l'épaisseur est comprise entre 1 et 800 microns et qui comporte du cuivre caractérisé en ce qu'il comprend de l'argent comme troisième composé principal permettant d'obtenir une teinte brillante 3N.Electrolytic deposit in the form of a gold alloy obtained from a process according to one of the preceding claims, the thickness of which is between 1 and 800 microns and which comprises copper, characterized in that it comprises silver as the third main compound to obtain a brilliant shade 3N. Dépôt électrolytique sous forme d'un alliage d'or obtenu à partir d'un procédé conforme à la revendication 14 dont l'épaisseur est comprise entre 1 et 800 microns et qui comporte du cuivre caractérisé en ce qu'il comprend de l'argent comme troisième composé principal selon une proportion de 75 % d'or, 21 % de cuivre et 4 % d'argent permettant d'obtenir une teinte brillante 3N.Electrolytic deposit in the form of a gold alloy obtained from a process according to Claim 14, having a thickness of between 1 and 800 microns and comprising copper, characterized in that it comprises silver as the third main compound in a proportion of 75% gold, 21% copper and 4% silver to obtain a brilliant shade 3N.
EP09173198.4A 2009-10-15 2009-10-15 Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals Active EP2312021B1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP09173198.4A EP2312021B1 (en) 2009-10-15 2009-10-15 Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals
CN201010552012.7A CN102041527B (en) 2009-10-15 2010-10-15 Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals
JP2010232903A JP5563421B2 (en) 2009-10-15 2010-10-15 Method for obtaining yellow gold alloy deposits by electroplating without using toxic metals
KR1020100100585A KR101297476B1 (en) 2009-10-15 2010-10-15 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals
US12/905,788 US20110089040A1 (en) 2009-10-15 2010-10-15 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
HK11111618.6A HK1157415A1 (en) 2009-10-15 2011-10-27 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals
US14/452,364 US9567684B2 (en) 2009-10-15 2014-08-05 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
US15/898,330 US20180171499A1 (en) 2009-10-15 2018-02-16 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
US16/847,699 US20200240030A1 (en) 2009-10-15 2020-04-14 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP09173198.4A EP2312021B1 (en) 2009-10-15 2009-10-15 Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals

Publications (2)

Publication Number Publication Date
EP2312021A1 true EP2312021A1 (en) 2011-04-20
EP2312021B1 EP2312021B1 (en) 2020-03-18

Family

ID=41820241

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09173198.4A Active EP2312021B1 (en) 2009-10-15 2009-10-15 Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals

Country Status (6)

Country Link
US (4) US20110089040A1 (en)
EP (1) EP2312021B1 (en)
JP (1) JP5563421B2 (en)
KR (1) KR101297476B1 (en)
CN (1) CN102041527B (en)
HK (1) HK1157415A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2505691A1 (en) * 2011-03-31 2012-10-03 The Swatch Group Research and Development Ltd. Process for obtaining a gold alloy deposit of 18 carat 3N

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018066007A1 (en) * 2016-10-06 2018-04-12 Valmet Plating S.R.L. A galvanic and thermal process to obtain the coloration of metals, in particular precious metals
CN107299364A (en) * 2017-06-07 2017-10-27 常州富思通管道有限公司 A kind of zinc-plating brightener and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1400492A (en) 1971-07-09 1975-07-16 Oxy Metal Finishing Corp Gold alloy plating solutions
EP0193848A1 (en) * 1985-03-01 1986-09-10 Heinz Emmenegger Galvanic bath for the electrodeposition of gold alloys
JPS62164890A (en) * 1986-01-16 1987-07-21 Seiko Instr & Electronics Ltd Gold-silver-copper alloy plating solution
EP0416342A1 (en) * 1989-09-06 1991-03-13 Degussa Aktiengesellschaft Galvanic gold alloy bath
EP0566054A1 (en) * 1992-04-15 1993-10-20 LeaRonal, Inc. Electroplated gold-copper-silver alloys
US5340529A (en) * 1993-07-01 1994-08-23 Dewitt Troy C Gold jewelry alloy
US6576114B1 (en) * 1995-11-03 2003-06-10 Enthone Inc. Electroplating composition bath
EP1728898A2 (en) * 2005-06-02 2006-12-06 Rohm and Haas Electronic Materials LLC Electrolytes for the deposition of gold alloys

Family Cites Families (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2127676A (en) * 1938-04-21 1938-08-23 Claude H Coleman Process of tempering gold and silver alloys
US2141157A (en) * 1938-08-23 1938-12-20 Metals & Controls Corp Alloy
US2229463A (en) * 1939-10-21 1941-01-21 Handy & Harman Alloy
US2596454A (en) * 1949-09-10 1952-05-13 Metals & Controls Corp Gold alloys
US2660554A (en) * 1950-11-10 1953-11-24 Barnet D Ostrow Bright gold and gold alloy plating baths
CH286123A (en) * 1952-05-08 1952-10-15 Spreter Victor Bath for the galvanic deposition of gold alloys.
US2976180A (en) * 1957-12-17 1961-03-21 Hughes Aircraft Co Method of silver plating by chemical reduction
FR1259407A (en) 1960-03-10 1961-04-28 Maison Murat Electrolytic bath for thick deposit of gold-copper alloy
DE1460993A1 (en) 1965-07-23 1970-07-23 Kieninger & Obergfell Electrical program control device, preferably for electrical household appliances, especially washing machines and dishwashers
US3475292A (en) * 1966-02-10 1969-10-28 Technic Gold plating bath and process
GB1156186A (en) 1966-09-26 1969-06-25 Sel Rex Corp Gold Plating
DE1965768A1 (en) 1969-01-07 1970-07-30 Western Electric Co Electronic precipitation of precious metals
US3642589A (en) * 1969-09-29 1972-02-15 Fred I Nobel Gold alloy electroplating baths
US3666640A (en) * 1971-04-23 1972-05-30 Sel Rex Corp Gold plating bath and process
DE2121150C3 (en) 1971-04-24 1980-08-21 Schering Ag, 1000 Berlin Und 4619 Bergkamen Process for the electrodeposition of gold alloys
FR2181455B1 (en) * 1972-04-25 1974-08-30 Parker Ste Continentale
DE2244434C3 (en) * 1972-09-06 1982-02-25 Schering Ag, 1000 Berlin Und 4619 Bergkamen Aqueous bath for the galvanic deposition of gold and gold alloys
US3834879A (en) * 1973-05-11 1974-09-10 J Chin Plated coins
JPS6014115B2 (en) * 1977-07-05 1985-04-11 オクシ メタル インダストリ−ズ コ−ポレ−シヨン Shiny low karat silver-gold electrodeposition
CH621367A5 (en) 1977-07-08 1981-01-30 Systemes Traitements Surfaces Electrolytic bath for plating gold-copper-cadmium alloys and its use in galvanoplasty
JPS5433834A (en) * 1977-08-22 1979-03-12 Citizen Watch Co Ltd Golddcopper alloy plating solution
CH622829A5 (en) * 1977-08-29 1981-04-30 Systemes Traitements Surfaces
FR2405312A1 (en) 1977-10-10 1979-05-04 Oxy Metal Industries Corp Bath for electrodeposition of gold-zinc alloys - contains alkali sulphite, gold-sulphite complex, zinc salt, complex or chelate, complexing or chelating agent and metal
US4168214A (en) * 1978-06-14 1979-09-18 American Chemical And Refining Company, Inc. Gold electroplating bath and method of making the same
DE3020765A1 (en) * 1980-05-31 1981-12-10 Degussa Ag, 6000 Frankfurt ALKALINE BATH FOR GALVANIC DEPOSITION OF LOW-CARAINE PINK TO YELLOW-COLORED GOLD ALLOY LAYERS
GB8334226D0 (en) * 1983-12-22 1984-02-01 Learonal Uk Ltd Electrodeposition of gold alloys
US4626324A (en) 1984-04-30 1986-12-02 Allied Corporation Baths for the electrolytic deposition of nickel-indium alloys on printed circuit boards
JPS62164889A (en) * 1986-01-16 1987-07-21 Seiko Instr & Electronics Ltd Gold-silver-copper alloy plating solution
JPH067210B2 (en) * 1986-08-12 1994-01-26 沖電気工業株式会社 Plug-in optical connector
DE3878783T2 (en) * 1987-08-21 1993-07-22 Engelhard Ltd BATH FOR ELECTROPLATING A GOLD-COPPER-ZINC ALLOY.
JPH01247570A (en) 1988-03-29 1989-10-03 Furukawa Electric Co Ltd:The Formation of film of multicomponent substance by beam sputtering
GB8903818D0 (en) 1989-02-20 1989-04-05 Engelhard Corp Electrolytic deposition of gold-containing alloys
US5045411A (en) * 1990-01-10 1991-09-03 P.M. Refining, Inc. Alloy compositions
GB2242200B (en) * 1990-02-20 1993-11-17 Omi International Plating compositions and processes
CH680927A5 (en) 1990-10-08 1992-12-15 Metaux Precieux Sa
US5085744A (en) * 1990-11-06 1992-02-04 Learonal, Inc. Electroplated gold-copper-zinc alloys
US5244593A (en) * 1992-01-10 1993-09-14 The Procter & Gamble Company Colorless detergent compositions with enhanced stability
JPH067210A (en) * 1992-06-29 1994-01-18 Mitsubishi Materials Corp Method for manufacturing metallic article having inclined pattern
JP2832344B2 (en) * 1996-05-21 1998-12-09 大蔵省造幣局長 Manufacturing method of plated body
DE19629658C2 (en) 1996-07-23 1999-01-14 Degussa Cyanide-free galvanic bath for the deposition of gold and gold alloys
JP3933930B2 (en) * 1999-06-17 2007-06-20 デグサ ガルヴァノテヒニク ゲゼルシャフト ミット ベシュレンクテル ハフツング Acid bath and electrodeposition brightener for electrodeposition of shiny gold and gold alloy layers
JP4023138B2 (en) * 2001-02-07 2007-12-19 日立金属株式会社 Compound containing iron-based rare earth alloy powder and iron-based rare earth alloy powder, and permanent magnet using the same
FR2828889B1 (en) * 2001-08-24 2004-05-07 Engelhard Clal Sas ELECTROLYTIC BATH FOR THE ELECTROCHEMICAL DEPOSITION OF GOLD AND ITS ALLOYS
KR100442519B1 (en) * 2002-04-09 2004-07-30 삼성전기주식회사 Alloy Plating Solution for Surface Treatment of Modular PCB
EP1548525B2 (en) * 2003-12-23 2017-08-16 Rolex Sa Ceramic element for watch case and method of manufacturing the same
JP4566667B2 (en) * 2004-01-16 2010-10-20 キヤノン株式会社 Plating solution, method of manufacturing structure using plating solution, and apparatus using plating solution
JP2005214903A (en) 2004-01-30 2005-08-11 Kawaguchiko Seimitsu Co Ltd Method of manufacturing dial with index, and dial with index manufactured using the same
EP3170924A1 (en) * 2007-04-19 2017-05-24 Enthone, Inc. Electrolyte and method for electrolytic deposition of gold-copper alloys
CH710184B1 (en) * 2007-09-21 2016-03-31 Aliprandini Laboratoires G Process for obtaining a yellow gold alloy deposit by electroplating without the use of toxic metals or metalloids.
WO2015038636A1 (en) * 2013-09-10 2015-03-19 Apple Inc. Crystalline gold alloys with improved hardness

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1400492A (en) 1971-07-09 1975-07-16 Oxy Metal Finishing Corp Gold alloy plating solutions
EP0193848A1 (en) * 1985-03-01 1986-09-10 Heinz Emmenegger Galvanic bath for the electrodeposition of gold alloys
JPS62164890A (en) * 1986-01-16 1987-07-21 Seiko Instr & Electronics Ltd Gold-silver-copper alloy plating solution
EP0416342A1 (en) * 1989-09-06 1991-03-13 Degussa Aktiengesellschaft Galvanic gold alloy bath
EP0566054A1 (en) * 1992-04-15 1993-10-20 LeaRonal, Inc. Electroplated gold-copper-silver alloys
US5340529A (en) * 1993-07-01 1994-08-23 Dewitt Troy C Gold jewelry alloy
US6576114B1 (en) * 1995-11-03 2003-06-10 Enthone Inc. Electroplating composition bath
EP1728898A2 (en) * 2005-06-02 2006-12-06 Rohm and Haas Electronic Materials LLC Electrolytes for the deposition of gold alloys

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 1987-240265, XP002574602 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2505691A1 (en) * 2011-03-31 2012-10-03 The Swatch Group Research and Development Ltd. Process for obtaining a gold alloy deposit of 18 carat 3N
US10053789B2 (en) 2011-03-31 2018-08-21 The Swatch Group Research And Development Ltd Method of obtaining a 18 caracts 3N gold alloy
US10793961B2 (en) 2011-03-31 2020-10-06 The Swatch Group Research And Development Ltd Method of obtaining a 18 carats 3N gold alloy

Also Published As

Publication number Publication date
JP5563421B2 (en) 2014-07-30
HK1157415A1 (en) 2012-06-29
EP2312021B1 (en) 2020-03-18
US20150027898A1 (en) 2015-01-29
JP2011084815A (en) 2011-04-28
CN102041527B (en) 2014-09-17
US9567684B2 (en) 2017-02-14
US20110089040A1 (en) 2011-04-21
KR101297476B1 (en) 2013-08-16
CN102041527A (en) 2011-05-04
US20200240030A1 (en) 2020-07-30
KR20110041424A (en) 2011-04-21
US20180171499A1 (en) 2018-06-21

Similar Documents

Publication Publication Date Title
US10619260B2 (en) Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US20200240030A1 (en) Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
EP2505691B1 (en) Process for obtaining a gold alloy deposit of 18 carat 3N
CH704795A2 (en) Electroplating process useful for the deposition of mirror bright yellow gold alloy on electrode immersed in bath in the manufacture of thick film, where the bath comprises gold metal, organometallic compound and wetting agent
EP0480876A2 (en) Electrodeposition of a gold alloy containing copper and zinc and its method of production
CH710185B1 (en) Preparation for plating and gold alloy electroplating bath tub.
CH701980A2 (en) Process for obtaining a yellow gold alloy deposit by electroplating without the use of toxic metals.
WO2008040761A2 (en) Electroforming method and part or layer obtained using said method
WO2016020812A1 (en) Electrolytic bath, electrolytic deposition method and item obtained with said method

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

17P Request for examination filed

Effective date: 20111020

17Q First examination report despatched

Effective date: 20111128

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20191106

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602009061459

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: ICB INGENIEURS CONSEILS EN BREVETS SA, CH

Ref country code: AT

Ref legal event code: REF

Ref document number: 1246003

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200415

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200618

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200619

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200618

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200812

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200718

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1246003

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200318

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602009061459

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

26N No opposition filed

Effective date: 20201221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20201015

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201015

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20201031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201031

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201015

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201015

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230615

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230920

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20230920

Year of fee payment: 15

Ref country code: CH

Payment date: 20231102

Year of fee payment: 15