EP2205778B1 - Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques - Google Patents
Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques Download PDFInfo
- Publication number
- EP2205778B1 EP2205778B1 EP08804009A EP08804009A EP2205778B1 EP 2205778 B1 EP2205778 B1 EP 2205778B1 EP 08804009 A EP08804009 A EP 08804009A EP 08804009 A EP08804009 A EP 08804009A EP 2205778 B1 EP2205778 B1 EP 2205778B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- copper
- gold
- gold alloy
- cyanide
- 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.)
- Active
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 23
- 229910045601 alloy Inorganic materials 0.000 title abstract description 8
- 239000000956 alloy Substances 0.000 title abstract description 8
- 239000010930 yellow gold Substances 0.000 title abstract description 4
- 229910001097 yellow gold Inorganic materials 0.000 title abstract description 4
- 150000002739 metals Chemical class 0.000 title description 5
- 231100000331 toxic Toxicity 0.000 title description 4
- 230000002588 toxic effect Effects 0.000 title description 4
- 229910052752 metalloid Inorganic materials 0.000 title description 3
- 150000002738 metalloids Chemical class 0.000 title description 3
- 239000011248 coating agent Substances 0.000 title description 2
- 238000000576 coating method Methods 0.000 title description 2
- 238000009713 electroplating Methods 0.000 title description 2
- 239000010949 copper Substances 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010931 gold Substances 0.000 claims abstract description 13
- 229910052738 indium Inorganic materials 0.000 claims abstract description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 9
- 239000000080 wetting agent Substances 0.000 claims abstract description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 239000011591 potassium Substances 0.000 claims abstract description 5
- 239000008139 complexing agent Substances 0.000 claims abstract description 4
- 125000002524 organometallic group Chemical group 0.000 claims abstract 2
- 229910001020 Au alloy Inorganic materials 0.000 claims description 9
- 239000003353 gold alloy Substances 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 235000021317 phosphate Nutrition 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 150000003892 tartrate salts Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- NYUQKKWCYPVQGE-UHFFFAOYSA-N dodecyl(dimethyl)azanium;propane-1-sulfonate Chemical compound CCCS([O-])(=O)=O.CCCCCCCCCCCC[NH+](C)C NYUQKKWCYPVQGE-UHFFFAOYSA-N 0.000 claims description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000017858 Laurus nobilis Nutrition 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 claims 1
- 244000125380 Terminalia tomentosa Species 0.000 claims 1
- 229910002065 alloy metal Inorganic materials 0.000 claims 1
- 230000000536 complexating effect Effects 0.000 claims 1
- 230000002999 depolarising effect Effects 0.000 claims 1
- 230000003340 mental effect Effects 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 abstract description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- 238000009736 wetting Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 238000005494 tarnishing Methods 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 150000001204 N-oxides Chemical class 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 2
- 229940043264 dodecyl sulfate Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- IPZMTZLUAIKVKD-UHFFFAOYSA-N 1-pyridin-1-ium-1-ylpropane-1-sulfonate Chemical compound CCC(S([O-])(=O)=O)[N+]1=CC=CC=C1 IPZMTZLUAIKVKD-UHFFFAOYSA-N 0.000 description 1
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 241000499489 Castor canadensis Species 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000011779 Menyanthes trifoliata Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- WREDNSAXDZCLCP-UHFFFAOYSA-N methanedithioic acid Chemical compound SC=S WREDNSAXDZCLCP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
-
- 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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
Definitions
- the invention relates to an electrolytic deposit in the form of a gold alloy in a thick layer and its production process.
- the object of the present invention is to overcome all or part of the disadvantages mentioned above by proposing a method for the deposition in thick layer of a yellow gold alloy having neither zinc nor cadmium as main constituents.
- the invention relates to an electrolytic deposit in the form of a gold alloy whose thickness is between 1 and 800 microns and comprises copper characterized in that it comprises indium as third main compound.
- the invention also 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 complexing agent, a free cyanide characterized in that the alloying metals are copper in the form of copper and potassium double cyanide, and indium in aminocarboxylic or aminophosphonic complexed form for depositing on the electrode a yellow gold alloy brilliant mirror.
- the electrolysis is preferably followed by a heat treatment at least 450 degrees Celsius for at least 30 minutes to obtain an optimal quality deposit.
- 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.
- a gold alloy free of toxic metals or metalloids, in particular free of cadmium, of 2N color. yellow, with a thickness of 200 microns, excellent gloss and having a very high resistance to wear and tarnishing.
- the electrolytic bath is 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 stirring as well as a flow of the electrolyte must be maintained.
- the anodes are platinum titanium, stainless steel, ruthenium, iridium or alloys of the latter two.
- the bath may contain the following metals Ag, Cd, 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 alkaline cyanide medium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH01494/07A CH710184B1 (fr) | 2007-09-21 | 2007-09-21 | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques. |
| PCT/EP2008/062042 WO2009037180A1 (fr) | 2007-09-21 | 2008-09-11 | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2205778A1 EP2205778A1 (fr) | 2010-07-14 |
| EP2205778B1 true EP2205778B1 (fr) | 2011-02-23 |
Family
ID=39967872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08804009A Active EP2205778B1 (fr) | 2007-09-21 | 2008-09-11 | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques |
Country Status (12)
| Country | Link |
|---|---|
| US (3) | US10233555B2 (zh) |
| EP (1) | EP2205778B1 (zh) |
| JP (2) | JP5563462B2 (zh) |
| KR (1) | KR101280675B1 (zh) |
| CN (1) | CN101815814B (zh) |
| AT (1) | ATE499461T1 (zh) |
| CH (1) | CH710184B1 (zh) |
| DE (1) | DE602008005184D1 (zh) |
| HK (1) | HK1147782A1 (zh) |
| IN (1) | IN2014CN02464A (zh) |
| TW (2) | TWI441959B (zh) |
| WO (1) | WO2009037180A1 (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH714243B1 (fr) * | 2006-10-03 | 2019-04-15 | Swatch Group Res & Dev Ltd | Procédé d'électroformage et pièce ou couche obtenue par ce procédé. |
| CH710184B1 (fr) | 2007-09-21 | 2016-03-31 | Aliprandini Laboratoires G | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques. |
| EP2312021B1 (fr) | 2009-10-15 | 2020-03-18 | The Swatch Group Research and Development Ltd. | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques |
| EP2505691B1 (fr) * | 2011-03-31 | 2014-03-12 | The Swatch Group Research and Development Ltd. | Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N |
| ITFI20120103A1 (it) * | 2012-06-01 | 2013-12-02 | Bluclad Srl | Bagni galvanici per l'ottenimento di una lega di oro a bassa caratura e processo galvanico che utilizza detti bagni. |
| WO2016020812A1 (en) * | 2014-08-04 | 2016-02-11 | Nutec International Srl | Electrolytic bath, electrolytic deposition method and item obtained with said method |
| CN109504991B (zh) * | 2019-01-21 | 2020-08-07 | 南京市产品质量监督检验院 | 一种无氰18k金电铸液、其制备方法及其应用 |
Family Cites Families (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (fr) | 1952-05-08 | 1952-10-15 | Spreter Victor | Bain pour le dépôt par voie galvanique d'alliages d'or. |
| US2976180A (en) | 1957-12-17 | 1961-03-21 | Hughes Aircraft Co | Method of silver plating by chemical reduction |
| FR1259407A (fr) | 1960-03-10 | 1961-04-28 | Maison Murat | Bain électrolytique pour dépôt épais d'alliage or-cuivre |
| CH455434A (de) * | 1963-08-15 | 1968-07-15 | Werner Fluehmann Galvanische A | Verfahren zur Herstellung von Weissgoldüberzügen |
| DE1460993A1 (de) | 1965-07-23 | 1970-07-23 | Kieninger & Obergfell | Elektrisches Programmsteuergeraet,vorzugsweise fuer elektrische Haushaltsgeraete,insbesondere Waschmaschinen und Geschirrspuelmaschinen |
| 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 (de) * | 1969-01-07 | 1970-07-30 | Western Electric Co | Elektroniederschlag von Edelmetallen |
| 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 (de) | 1971-04-24 | 1980-08-21 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Verfahren zur galvanischen Abscheidung von Goldlegierungen |
| CH529843A (fr) | 1971-07-09 | 1972-10-31 | Oxy Metal Finishing Europ S A | Bain pour le dépôt électrolytique d'alliages d'or et son utilisation en galvanoplastie |
| FR2181455B1 (zh) * | 1972-04-25 | 1974-08-30 | Parker Ste Continentale | |
| DE2244434C3 (de) * | 1972-09-06 | 1982-02-25 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Wäßriges Bad zur galvanischen Abscheidung von Gold und Goldlegierungen |
| US3902977A (en) * | 1973-12-13 | 1975-09-02 | Engelhard Min & Chem | Gold plating solutions and method |
| CH621367A5 (en) | 1977-07-08 | 1981-01-30 | Systemes Traitements Surfaces | Electrolytic bath for plating gold-copper-cadmium alloys and its use in galvanoplasty |
| CH622829A5 (zh) * | 1977-08-29 | 1981-04-30 | Systemes Traitements Surfaces | |
| FR2405312A1 (fr) * | 1977-10-10 | 1979-05-04 | Oxy Metal Industries Corp | Bains electrolytiques pour le depot d'alliages d'or |
| US4168214A (en) | 1978-06-14 | 1979-09-18 | American Chemical And Refining Company, Inc. | Gold electroplating bath and method of making the same |
| DE3020765A1 (de) * | 1980-05-31 | 1981-12-10 | Degussa Ag, 6000 Frankfurt | Alkalisches bad zum galvanischen abscheiden niederkaraetiger rosa- bis gelbfarbener goldlegierungsschichten |
| 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 |
| CH662583A5 (fr) | 1985-03-01 | 1987-10-15 | Heinz Emmenegger | Bain galvanique pour le depot electrolytique d'alliages d'or-cuivre-cadmium-zinc. |
| JPS62164890A (ja) | 1986-01-16 | 1987-07-21 | Seiko Instr & Electronics Ltd | 金銀銅合金めつき液 |
| EP0304315B1 (en) * | 1987-08-21 | 1993-03-03 | Engelhard Limited | Bath for electrolytic deposition of a gold-copper-zinc alloy |
| JPH01247540A (ja) | 1988-03-29 | 1989-10-03 | Seiko Instr Inc | 硬質金合金外装部品の製造方法 |
| GB8903818D0 (en) * | 1989-02-20 | 1989-04-05 | Engelhard Corp | Electrolytic deposition of gold-containing alloys |
| DE3929569C1 (zh) | 1989-09-06 | 1991-04-18 | Degussa Ag, 6000 Frankfurt, De | |
| GB2242200B (en) | 1990-02-20 | 1993-11-17 | Omi International | Plating compositions and processes |
| CH680927A5 (zh) | 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 |
| US5256275A (en) | 1992-04-15 | 1993-10-26 | Learonal, Inc. | Electroplated gold-copper-silver alloys |
| US5340529A (en) | 1993-07-01 | 1994-08-23 | Dewitt Troy C | Gold jewelry alloy |
| ATE220736T1 (de) | 1995-11-03 | 2002-08-15 | Enthone Omi Inc | Elektroplattierungsverfahren, zusammensetzungen und überzügen |
| DE19629658C2 (de) | 1996-07-23 | 1999-01-14 | Degussa | Cyanidfreies galvanisches Bad zur Abscheidung von Gold und Goldlegierungen |
| US6814850B1 (en) * | 1999-06-17 | 2004-11-09 | Umicore Galvanotechnik Gmbh | Acid bath for electrodeposition of glossy gold and gold alloy layers and a gloss additive for same |
| JP2001198693A (ja) | 2000-01-17 | 2001-07-24 | Ishifuku Metal Ind Co Ltd | 工業用及び宝飾用金ろう |
| JP4023138B2 (ja) | 2001-02-07 | 2007-12-19 | 日立金属株式会社 | 鉄基希土類合金粉末および鉄基希土類合金粉末を含むコンパウンドならびにそれを用いた永久磁石 |
| FR2828889B1 (fr) * | 2001-08-24 | 2004-05-07 | Engelhard Clal Sas | Bain electrolytique pour le depot electrochimique de l'or et de ses alliages |
| EP1548525B2 (fr) | 2003-12-23 | 2017-08-16 | Rolex Sa | Elément en céramique pour boîte de montre et procédé de fabrication de cet élément |
| JP4566667B2 (ja) | 2004-01-16 | 2010-10-20 | キヤノン株式会社 | めっき液、めっき液を用いた構造体の製造方法、めっき液を用いた装置 |
| JP2005214903A (ja) * | 2004-01-30 | 2005-08-11 | Kawaguchiko Seimitsu Co Ltd | 指標付き文字板の製造方法及びその製造方法を用いて製造した指標付き文字板。 |
| SG127854A1 (en) * | 2005-06-02 | 2006-12-29 | Rohm & Haas Elect Mat | Improved gold electrolytes |
| CH710184B1 (fr) * | 2007-09-21 | 2016-03-31 | Aliprandini Laboratoires G | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques. |
-
2007
- 2007-09-21 CH CH01494/07A patent/CH710184B1/fr unknown
-
2008
- 2008-09-11 WO PCT/EP2008/062042 patent/WO2009037180A1/fr active Application Filing
- 2008-09-11 AT AT08804009T patent/ATE499461T1/de not_active IP Right Cessation
- 2008-09-11 DE DE602008005184T patent/DE602008005184D1/de active Active
- 2008-09-11 JP JP2010525308A patent/JP5563462B2/ja active Active
- 2008-09-11 KR KR1020107008598A patent/KR101280675B1/ko active IP Right Grant
- 2008-09-11 IN IN2464CHN2014 patent/IN2014CN02464A/en unknown
- 2008-09-11 US US12/678,984 patent/US10233555B2/en active Active
- 2008-09-11 EP EP08804009A patent/EP2205778B1/fr active Active
- 2008-09-11 CN CN200880107881XA patent/CN101815814B/zh active Active
- 2008-09-17 TW TW097135667A patent/TWI441959B/zh active
- 2008-09-17 TW TW103113847A patent/TWI507571B/zh active
-
2011
- 2011-02-24 HK HK11101836.3A patent/HK1147782A1/xx unknown
-
2014
- 2014-04-03 US US14/244,071 patent/US9683303B2/en active Active
- 2014-06-12 JP JP2014121169A patent/JP5887381B2/ja active Active
-
2019
- 2019-01-28 US US16/259,444 patent/US10619260B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| US10619260B2 (en) | 2020-04-14 |
| EP2205778A1 (fr) | 2010-07-14 |
| ATE499461T1 (de) | 2011-03-15 |
| US20140299481A1 (en) | 2014-10-09 |
| TW201428143A (zh) | 2014-07-16 |
| CH710184B1 (fr) | 2016-03-31 |
| KR101280675B1 (ko) | 2013-07-01 |
| JP5887381B2 (ja) | 2016-03-16 |
| JP2014194087A (ja) | 2014-10-09 |
| TW200930844A (en) | 2009-07-16 |
| IN2014CN02464A (zh) | 2015-08-07 |
| HK1147782A1 (en) | 2011-08-19 |
| US20190153608A1 (en) | 2019-05-23 |
| WO2009037180A1 (fr) | 2009-03-26 |
| JP2010539335A (ja) | 2010-12-16 |
| US10233555B2 (en) | 2019-03-19 |
| CN101815814B (zh) | 2012-05-16 |
| TWI507571B (zh) | 2015-11-11 |
| DE602008005184D1 (de) | 2011-04-07 |
| US20100206739A1 (en) | 2010-08-19 |
| US9683303B2 (en) | 2017-06-20 |
| KR20100075935A (ko) | 2010-07-05 |
| CN101815814A (zh) | 2010-08-25 |
| JP5563462B2 (ja) | 2014-07-30 |
| TWI441959B (zh) | 2014-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2205778B1 (fr) | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques | |
| JP4675626B2 (ja) | ブロンズ電析法及び電解質 | |
| US20200240030A1 (en) | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials | |
| EP2505691B1 (fr) | Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N | |
| CH680927A5 (zh) | ||
| CH710185B1 (fr) | Préparation pour bain galvanique d'alliage d'or et bain galvanique. | |
| CH704795A2 (fr) | Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N. | |
| EP2079859A2 (fr) | Procede d'electroformage et piece ou couche obtenue par ce procede | |
| CH701980A2 (fr) | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques. | |
| CH418085A (fr) | Electrolyte pour le dépôt galvanique d'alliages d'or | |
| WO2016020812A1 (en) | Electrolytic bath, electrolytic deposition method and item obtained with said method | |
| CH680370A5 (zh) |
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 |
|
| 17P | Request for examination filed |
Effective date: 20100421 |
|
| 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 MT NL NO PL PT RO SE SI SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL BA MK RS |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| DAX | Request for extension of the european patent (deleted) | ||
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| 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 MT NL NO PL PT RO SE SI SK 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: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
| REF | Corresponds to: |
Ref document number: 602008005184 Country of ref document: DE Date of ref document: 20110407 Kind code of ref document: P |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602008005184 Country of ref document: DE Effective date: 20110407 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: T3 |
|
| LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20110223 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20110223 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: 20110524 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: 20110603 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: 20110223 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: 20110223 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: 20110523 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: 20110623 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: 20110223 |
|
| 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: 20110223 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: 20110223 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: 20110523 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: 20110223 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: 20110223 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20110223 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: 20110223 Ref country code: IE 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: 20110223 |
|
| 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: 20110223 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: 20110223 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: 20110223 |
|
| PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
| 26 | Opposition filed |
Opponent name: UMICORE GALVANOTECHNIK GMBH Effective date: 20111123 |
|
| PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R026 Ref document number: 602008005184 Country of ref document: DE Effective date: 20111123 |
|
| 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: 20110223 |
|
| BERE | Be: lapsed |
Owner name: THE SWATCH GROUP RESEARCH AND DEVELOPMENT LTD. Effective date: 20110930 Owner name: G. ALIPRANDINI Effective date: 20110930 |
|
| PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110930 |
|
| 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: 20110930 |
|
| TPAC | Observations filed by third parties |
Free format text: ORIGINAL CODE: EPIDOSNTIPA |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20110223 |
|
| PLAY | Examination report in opposition despatched + time limit |
Free format text: ORIGINAL CODE: EPIDOSNORE2 |
|
| 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: 20110911 |
|
| PLBC | Reply to examination report in opposition received |
Free format text: ORIGINAL CODE: EPIDOSNORE3 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20110223 |
|
| PLCK | Communication despatched that opposition was rejected |
Free format text: ORIGINAL CODE: EPIDOSNREJ1 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU 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: 20110223 |
|
| PLBN | Opposition rejected |
Free format text: ORIGINAL CODE: 0009273 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: OPPOSITION REJECTED |
|
| 27O | Opposition rejected |
Effective date: 20130913 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R100 Ref document number: 602008005184 Country of ref document: DE Effective date: 20130913 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R008 Ref document number: 602008005184 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R039 Ref document number: 602008005184 Country of ref document: DE Effective date: 20140401 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 8 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 9 |
|
| 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 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 10 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R040 Ref document number: 602008005184 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 11 |
|
| P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230718 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20230822 Year of fee payment: 16 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20230824 Year of fee payment: 16 Ref country code: IT Payment date: 20230822 Year of fee payment: 16 Ref country code: GB Payment date: 20230823 Year of fee payment: 16 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230822 Year of fee payment: 16 Ref country code: DE Payment date: 20230822 Year of fee payment: 16 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20231001 Year of fee payment: 16 |