EP2505691B1 - Verfahren zur Herhaltung einer Beschichtung aus einer Goldlegierung 18 Karat 3N - Google Patents
Verfahren zur Herhaltung einer Beschichtung aus einer Goldlegierung 18 Karat 3N Download PDFInfo
- Publication number
- EP2505691B1 EP2505691B1 EP11160669.5A EP11160669A EP2505691B1 EP 2505691 B1 EP2505691 B1 EP 2505691B1 EP 11160669 A EP11160669 A EP 11160669A EP 2505691 B1 EP2505691 B1 EP 2505691B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- gold
- copper
- silver
- metal
- 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
- 238000000034 method Methods 0.000 title claims description 22
- 229910001020 Au alloy Inorganic materials 0.000 title claims description 11
- 239000003353 gold alloy Substances 0.000 title claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 19
- 239000010931 gold Substances 0.000 claims description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 17
- 229910052737 gold Inorganic materials 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 8
- 239000000080 wetting agent Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 3
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical group I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 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
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910001097 yellow gold Inorganic materials 0.000 claims description 2
- 239000010930 yellow gold Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 2
- 239000010452 phosphate Substances 0.000 claims 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical group [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229910002065 alloy metal Inorganic materials 0.000 claims 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims 1
- 229940050410 gluconate Drugs 0.000 claims 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims 1
- 239000003352 sequestering agent Substances 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 229940095064 tartrate Drugs 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005494 tarnishing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 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 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 229940043264 dodecyl sulfate Drugs 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 150000003892 tartrate salts Chemical class 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
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000009736 wetting Methods 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
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 241000499489 Castor canadensis Species 0.000 description 1
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- 235000011779 Menyanthes trifoliata Nutrition 0.000 description 1
- 150000001204 N-oxides Chemical class 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- QOGLYAWBNATGQE-UHFFFAOYSA-N copper;gold;silver Chemical compound [Cu].[Au][Ag] QOGLYAWBNATGQE-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 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
- 239000000463 material Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007747 plating Methods 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
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
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 the cadmium is extremely toxic and banned in some countries.
- the document EP 1 728 898 discloses a bath for the electroplating of 18K gold alloys in 2N or 3N colors using a gold-copper-silver alloy. To obtain the 3N color, the document EP 1 728 898 discloses a deposit of 75% gold, 12.5% copper and 12.5% silver.
- the object of the present invention is to overcome all or part of the aforementioned drawbacks by proposing a manufacturing method for the thick-layer deposition of a 3N yellow gold 18-carat gold alloy having neither zinc nor nickel. cadmium as major constituents.
- the invention relates to a method for the electroplating of a gold alloy on an electrode immersed in a bath comprising gold metal, organometallic compounds, a wetting agent, a complexing agent, free cyanide, the alloying metals are copper metal and silver metal making it possible to deposit on the electrode a golden alloy of the brilliant mirror yellow type, characterized in that the bath has a mass proportion of about 21.53% gold, 78.31% copper and 0.16% silver.
- the bath even with a very high concentration of copper makes it possible, according to the invention, to obtain a deposit substantially in a proportion of 75% of gold, 19% of copper and 6% of silver. corresponding to a deposit of 18 carats of yellow tint 3N and not pink 5N.
- 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 ⁇ m and which comprises copper characterized in that it comprises silver as the third main compound in a mass proportion of 75% gold, 19% copper and 6% silver to obtain a brilliant shade 3N.
- the invention relates to an electrolytic deposition of a 3N gold alloy which, surprisingly, comprises principal compounds in order of importance which are Au-Cu-Ag and whose proportions are not known to obtain the 3N color, that is to say bright yellow.
- gold alloy free of toxic metals or metalloids, in particular free of cadmium and zinc, 3N yellow, 200 ⁇ m thick, excellent gloss and having a very high resistance to wear and tarnishing.
- the bath has a mass proportion of about 21.53% gold, 78.31% copper and 0.16% silver between these three main materials.
- 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, 19% of copper and 6% 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 stirring as well as a flow 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)
Claims (14)
- Verfahren zum galvanoplastischen Abscheiden einer Goldlegierung auf einer Elektrode, die in ein Bad eingetaucht ist, das Goldmetall, organometallische Verbindungen, ein Tensid, einen Komplexbildner und freies Cyanid, enthält, wobei die Legierungsmetalle Kupfermetall und Silbermetall sind, die ermöglichen, auf der Elektrode eine Legierung aus Gelbgold, das brillant spiegelt, abzulagern, dadurch gekennzeichnet, dass das Bad einem Massenverhältnis von etwa 21,53 % Gold, 78,31 % Kupfer und 0,16 % Silber gehorcht.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Bad 1 bis 10 g/l Goldmetall in Doppelcyanidform aus Gold und Kalium enthält.
- Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Bad 10 bis 60 g/l Kupfermetall in Kupferjodid-Form enthält.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Bad 10 mg/l bis 1 g/l Silbermetall in Doppelcyanidform aus Silber und Kalium enthält.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Bad 3 bis 35 g/l Cyanid enthält.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Tensid eine Konzentration im Bereich von 0,05 bis 10 ml/l aufweist.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Tensid unter den folgenden Typen gewählt ist: Polyoxyalkoilenic, Etherphosphat, Laurylsulfat, Diamethydodezylamin-N-Oxid, Dimethyldodecyl-Ammonium-Propansulfonat.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Bad ein Amin mit einer Konzentration im Bereich von 0,01 bis 5 ml/l enthält.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Bad ein Depolarisationsmittel mit einer Konzentration im Bereich von 0,1 bis 20 mg/l enthält.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Bad leitende Salze des Typs Phosphate, Carbonate, Citrate, Sulfate, Tartrate, Gluconate und/oder Phosphonate enthält.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Temperatur des Bades im Bereich von 50 bis 90 °C gehalten wird.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der pH-Wert des Bades im Bereich von 8 bis 12 gehalten wird.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Verfahren mit einer Stromdichte im Bereich von 0,05 bis 1,5 A/dm2 verwirklicht wird.
- Elektrolytische Ablagerung in Form einer Goldlegierung, die mit einem Verfahren nach einem der vorhergehenden Ansprüche erhalten wird, deren Dicke im Bereich von 1 bis 800 µm liegt und die Kupfer enthält, dadurch gekennzeichnet, dass sie als dritte Hauptkomponente Silber gemäß einem Massenverhältnis von 75 % Gold, 19 % Kupfer und 6 % Silber enthält, was ermöglicht, ein 3N-brilliantes Aussehen zu erhalten.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11160669.5A EP2505691B1 (de) | 2011-03-31 | 2011-03-31 | Verfahren zur Herhaltung einer Beschichtung aus einer Goldlegierung 18 Karat 3N |
| US13/427,558 US10053789B2 (en) | 2011-03-31 | 2012-03-22 | Method of obtaining a 18 caracts 3N gold alloy |
| CN201210113840.XA CN102732920B (zh) | 2011-03-31 | 2012-03-30 | 18开3n金合金的制备方法 |
| JP2012083556A JP5627629B2 (ja) | 2011-03-31 | 2012-04-02 | １８カラット３ｎ金合金およびこれの析出方法 |
| HK13104533.1A HK1177235A1 (zh) | 2011-03-31 | 2013-04-15 | 金合金的製備方法 |
| US16/038,662 US10793961B2 (en) | 2011-03-31 | 2018-07-18 | Method of obtaining a 18 carats 3N gold alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11160669.5A EP2505691B1 (de) | 2011-03-31 | 2011-03-31 | Verfahren zur Herhaltung einer Beschichtung aus einer Goldlegierung 18 Karat 3N |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2505691A1 EP2505691A1 (de) | 2012-10-03 |
| EP2505691B1 true EP2505691B1 (de) | 2014-03-12 |
Family
ID=44021909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP11160669.5A Active EP2505691B1 (de) | 2011-03-31 | 2011-03-31 | Verfahren zur Herhaltung einer Beschichtung aus einer Goldlegierung 18 Karat 3N |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US10053789B2 (de) |
| EP (1) | EP2505691B1 (de) |
| JP (1) | JP5627629B2 (de) |
| CN (1) | CN102732920B (de) |
| HK (1) | HK1177235A1 (de) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2505691B1 (de) | 2011-03-31 | 2014-03-12 | The Swatch Group Research and Development Ltd. | Verfahren zur Herhaltung einer Beschichtung aus einer Goldlegierung 18 Karat 3N |
Family Cites Families (18)
| 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 |
| US3642589A (en) * | 1969-09-29 | 1972-02-15 | Fred I Nobel | Gold alloy electroplating baths |
| JPS62164890A (ja) * | 1986-01-16 | 1987-07-21 | Seiko Instr & Electronics Ltd | 金銀銅合金めつき液 |
| JPS62164889A (ja) * | 1986-01-16 | 1987-07-21 | Seiko Instr & Electronics Ltd | 金銀銅合金めつき液 |
| EP0304315B1 (de) * | 1987-08-21 | 1993-03-03 | Engelhard Limited | Bad für das Elektroplattieren einer Gold-Kupfer-Zink-Legierung |
| DE3929569C1 (de) * | 1989-09-06 | 1991-04-18 | Degussa Ag, 6000 Frankfurt, De | |
| US5045411A (en) * | 1990-01-10 | 1991-09-03 | P.M. Refining, Inc. | Alloy compositions |
| JPH051393A (ja) * | 1990-07-19 | 1993-01-08 | Electroplating Eng Of Japan Co | 銀銅合金メツキ浴及び銀銅合金ロウ材 |
| US5256275A (en) * | 1992-04-15 | 1993-10-26 | Learonal, Inc. | Electroplated gold-copper-silver alloys |
| JP2832344B2 (ja) * | 1996-05-21 | 1998-12-09 | 大蔵省造幣局長 | メッキ体の製造方法 |
| US7273540B2 (en) * | 2002-07-25 | 2007-09-25 | Shinryo Electronics Co., Ltd. | Tin-silver-copper plating solution, plating film containing the same, and method for forming the plating film |
| SG127854A1 (en) * | 2005-06-02 | 2006-12-29 | Rohm & Haas Elect Mat | Improved gold electrolytes |
| CH714243B1 (fr) * | 2006-10-03 | 2019-04-15 | Swatch Group Res & Dev Ltd | Procédé d'électroformage et pièce ou couche obtenue par ce procédé. |
| JP2008291287A (ja) * | 2007-05-22 | 2008-12-04 | Nippon New Chrome Kk | 耐連続衝撃性に優れた銅−錫合金めっき製品の製造方法 |
| 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. |
| CN101392392A (zh) * | 2008-10-22 | 2009-03-25 | 山东招金万足金珠宝有限公司 | 硬质千足金黄金饰品加工工艺 |
| EP2312021B1 (de) * | 2009-10-15 | 2020-03-18 | The Swatch Group Research and Development Ltd. | Verfahren zum erhalten einer gelben goldlegierungsablagerung durch galvanoplastik ohne verwendung von giftigen metallen |
| EP2505691B1 (de) | 2011-03-31 | 2014-03-12 | The Swatch Group Research and Development Ltd. | Verfahren zur Herhaltung einer Beschichtung aus einer Goldlegierung 18 Karat 3N |
-
2011
- 2011-03-31 EP EP11160669.5A patent/EP2505691B1/de active Active
-
2012
- 2012-03-22 US US13/427,558 patent/US10053789B2/en active Active
- 2012-03-30 CN CN201210113840.XA patent/CN102732920B/zh active Active
- 2012-04-02 JP JP2012083556A patent/JP5627629B2/ja active Active
-
2013
- 2013-04-15 HK HK13104533.1A patent/HK1177235A1/zh unknown
-
2018
- 2018-07-18 US US16/038,662 patent/US10793961B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102732920B (zh) | 2015-07-22 |
| CN102732920A (zh) | 2012-10-17 |
| US20120247968A1 (en) | 2012-10-04 |
| EP2505691A1 (de) | 2012-10-03 |
| US10053789B2 (en) | 2018-08-21 |
| US20180320283A1 (en) | 2018-11-08 |
| JP2012214899A (ja) | 2012-11-08 |
| HK1177235A1 (zh) | 2013-08-16 |
| JP5627629B2 (ja) | 2014-11-19 |
| US10793961B2 (en) | 2020-10-06 |
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 (de) | Verfahren zur Herhaltung einer Beschichtung aus einer Goldlegierung 18 Karat 3N | |
| CH704795A2 (fr) | Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N. | |
| EP0480876A2 (de) | Elektrolytisch erzeugter Überzug in Form einer Kupfer und Zink enthaltender Goldlegierung sowie Verfahren zu dessen Herstellung | |
| WO2008040761A2 (fr) | Procede d'electroformage et piece ou couche obtenue par ce procede | |
| CH710185B1 (fr) | Préparation pour bain galvanique d'alliage d'or et bain galvanique. | |
| CH701980A2 (fr) | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques. | |
| 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): AL 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 RS SE SI SK SM TR |
|
| AX | Request for extension of the european patent |
Extension state: BA ME |
|
| 17P | Request for examination filed |
Effective date: 20130403 |
|
| 17Q | First examination report despatched |
Effective date: 20130516 |
|
| GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| INTG | Intention to grant announced |
Effective date: 20131217 |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: FROELICHER, THOMAS Inventor name: HENZIROHS, CHRISTOPHE Inventor name: PLANKERT, GUIDO |
|
| 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): AL 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 RS 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: CH Ref legal event code: NV Representative=s name: ICB INGENIEURS CONSEILS EN BREVETS SA, CH Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 656401 Country of ref document: AT Kind code of ref document: T Effective date: 20140315 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602011005330 Country of ref document: DE Effective date: 20140424 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20140312 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20140312 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: 20140612 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 656401 Country of ref document: AT Kind code of ref document: T Effective date: 20140312 |
|
| 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: 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: 20140312 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: 20140312 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: 20140312 |
|
| 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: 20140312 Ref country code: RS 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: 20140312 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: 20140312 |
|
| 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: 20140312 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: 20140312 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: 20140612 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: 20140712 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: 20140312 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: 20140312 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20140312 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: 20140312 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: 20140312 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: 20140312 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602011005330 Country of ref document: DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20140714 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| 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: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140331 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: 20140312 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: 20140312 |
|
| 26N | No opposition filed |
Effective date: 20141215 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS 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: 20140903 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602011005330 Country of ref document: DE Effective date: 20141215 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20140312 |
|
| 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: 20140312 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20150331 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150331 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 6 |
|
| 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: 20140312 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20140312 |
|
| 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: 20140613 |
|
| 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; INVALID AB INITIO Effective date: 20110331 Ref country code: BE 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: 20140331 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: 20140312 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140331 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 7 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 8 |
|
| 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: 20140312 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL 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: 20140312 |
|
| 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: CH Payment date: 20230402 Year of fee payment: 13 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240220 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240221 Year of fee payment: 14 |