ATBECHDEDKESFRGBGRITLILUNLSEMCPTIESILTLVFIROMKCYALTRBGCZEEHUPLSK..HRIS..MTNORS..SM..................JBDM Ver 0.1.63 (23 May 2017) - 2100000/02730682EUROPEAN PATENT SPECIFICATIONB120180725EP12192458.3201211132014111020151008enenen20180725201830201405142014202018072520183020180309C25D 3/58 20060101AFI20140312BHEP C25D 3/62 20060101ALI20140312BHEP deALKALISCHE, CYANIDFREIE LÖSUNG ZUR ELEKTROPLATTIERUNG VON GOLDLEGIERUNGEN, VERFAHREN ZUR ELEKTROPLATTIERUNG UND SUBSTRAT MIT EINER HELLER, KORROSIONSFREIEN ABLAGERUNG EINER GOLDLEGIERUNGenALKALINE, CYANIDE-FREE SOLUTION FOR ELECTROPLATING OF GOLD ALLOYS, A METHOD FOR ELECTROPLATING AND A SUBSTRATE COMPRISING A BRIGHT, CORROSION-FREE DEPOSIT OF A GOLD ALLOYfrSOLUTION ALCALINE SANS CYANURE POUR L'ÉLECTRODÉPOSITION D'ALLIAGES D'OR, PROCÉDÉ D'ÉLECTRODÉPOSITION ET SUBSTRAT COMPRENANT UN DÉPÔT ANTICORROSION BRILLANT D'UN ALLIAGE D'OREP-A1- 1 321 468EP-A2- 1 728 898US-A- 5 340 529US-A- 5 750 018US-B1- 6 511 589Nelias, Coline76 rue Sedaine75011 ParisFRPommier, Nicolas4 rue Yvonne de Gaulle92600 Asnières sur SeineFRDuprat, Jean-Jacques18 rue Yves Montand33510 Andernos les BainsFRCoventya SAS101347040129P 1184 FWParc d'Activités des Chanteraines 7, rue du Commandant d'Estienne d'Orves CS 3000192396 Villeneuve-la-Garenne CedexFRPfenning, Meinig & Partner mbB100060642Patent- und Rechtsanwälte Theresienhöhe 11a80339 MünchenDEALATBEBGCHCYCZDEDKEEESFIFRGBGRHRHUIEISITLILTLULVMCMKMTNLNOPLPTRORSSESISKSMTR

The present invention relates to an electroplating solution which is free of cyanides and toxic compounds for the electrodeposition of bright deposits of gold-copper alloys. Thus, substrates are provided which comprise a bright gold-copper alloy deposit which is corrosion resistant according to NFS 80772, ISO 4538 and/or ISO 9227 and has 14 to 22 karats of gold in the alloy. Remarkably, the inventive electroplating solution allows electroplating of gold-copper alloy deposits which have a color matching the Swiss standard ISO 8654 from 0.5 N to 5 N. Furthermore, the invention provides a method for electroplating a gold-copper alloy deposit on a substrate. The inventive electroplating solution may be used for electroplating a substrate selected from the group consisting of decorative substrates, jewelry, watches and eyeglass trade.

Currently, cyanide processes are used for most decorative applications, but in order to reduce environmental risks and ensure manipulator safety, the demand of non-toxic and especially non-cyanide processes rose suddenly. Therefore, various kinds of non-cyanide gold plating baths have been developed in order to generate cyanide-free gold depositions.

For example, many non-cyanide gold plating solutions use Na3Au(SO3)2 as gold salt. However, in a gold plating bath using Na3Au(SO3)2, sulfite ions in the solution are unstable and easily oxidized. Consequently, the stability of complexes of gold in the gold plating solution becomes lower and gold may precipitate.

Japanese Patent publication No. 2005-256072 discloses a different complex discovered few years ago, using hydantoin compounds as chelating agent and starting from trivalent gold compounds e.g. gold hydroxide salt or chloroaurate gold. However, this gold complex was found to be unstable regarding the electroless deposit that occurs after a month when complexed gold and conductive salts were in the same bath.

EP 1 728 898 A2 discloses compositions and methods for depositing gold alloys, wherein the compositions comprise certain dithiocarboxylic acids, salts and esters thereof and mercapto group containing compounds.

In fact, the prior art fails to provide a cyanide-free and toxic compounds free-solution for electroplating of a gold alloy with the following required characteristics:

Thus, the object of the present invention was to provide a cyanide-free and toxic compounds free solution for electroplating of a gold-copper alloy which meets the characteristics cited above.

The solution to the problem is provided with the alkaline, cyanide-free solution for electroplating of a gold-copper alloy according to claim 1, the method for electroplating a gold-copper alloy deposit on a substrate according to claim 10, the substrate comprising a bright, electroplated deposit of a gold-copper alloy according to claim 11 and the use according to claim 13. The dependent claims show advantageous embodiments.

The present invention provides an alkaline, cyanide-free electroplating solution for electroplating a gold-copper alloy, comprising

  1. a) 0.5 to 10 g/L of gold ions;
  2. b) 0 to 3 g/L of zinc, iron and/or indium ions;
  3. c) 0 to 75 g/L of a complexing agent which is different from hydantoin, a salt thereof or 5,5-dimethylhydantoin,
characterized in that the electroplating solution further comprises

The inventive electroplating solution is suitable for electroplating a gold-copper alloy deposit on a substrate, wherein the deposit has the following characteristics:

It was discovered that the inventive alkaline, cyanide-free electroplating solution must comprise a sulfite salt concentration of at least 60 g/L, preferably in the range of 60 to 200 g/L. At this concentration, the sulfite salt may prevent deposit of gold on tank walls over time. The concentration of the sulfite salt in the electroplating solution according to the invention is 70 to 200 g/L and may be 70 to 160 g/L, preferably 70 to 120 g/L, more preferably 75 to 100 g/L. Especially at concentrations ≥ 70 g/L, it was discovered that the stability of the electroplating solution over time is significantly improved.

Sulfite salts which are comprised in the inventive solution are sodium sulfite and/or potassium sulfite.

In a preferred embodiment of the invention, the gold ions in the inventive solution are at least partially complexed by hydantoin or 5,5-dimethylhydantoin.

In a further preferred embodiment, the molar ratio between gold ions and hydantoin, a salt thereof or 5,5-dimethylhydantoin, is 1:2 to 1:6, preferably 1:2.5 to 1:5, more preferably 1:3 to 1:4. A ratio in this range is favorable for complexing gold ions by hydantoin and thus increasing the stability of the electroplating solution.

The concentration of the copper ions may be 0.2 to 10 g/L more preferably 0.5 to 7.5 g/L and most preferably 1 to 5 g/L.

The electroplating solution according to the present invention may further comprise ions of metals which can improve the final characteristics of the plated gold-copper alloy deposit. For example, it was discovered that if zinc, iron and/or indium ions are comprised in the inventive alkaline plating solution, the final gold-copper alloy deposit has an improved brightness. Furthermore, the addition of said metal ions allows to selectively regulate the color of the deposit which is produced after electroplating.

In this regard, a suitable concentration range of the zinc, iron and/or indium ions is 10 mg/L to 3 g/L, preferably 20 mg/L to 1 g/L, more preferably 50 mg/L to 500 mg/L. As a matter of fact, the brightness of the electrode or substrate which is electroplated with the inventive solution can be further improved if all three metal ions i.e. zinc, iron as well as indium ions are comprised in the solution.

In a further preferred embodiment of the invention, the electroplating solution comprises a brightening agent. Suitable brightening agents increase the codeposition of zinc, iron and/or indium metal in the deposit. For example, the addition of a brightening agent allows obtaining a 1 N color when zinc ions are comprised in the inventive solution. Examples for brightening agents according to the invention are pyridine sulfonic acid, trans pyridyl acrylic acid, nicotinic acid and/or antimony. Antimony may be in the form of KSb(OH)6. Antimony was found to be suitable for significantly improving the brightness of the deposit.

The concentration of the brightening agent will be comprised between 0.01 to 1 g/L more preferably between 10 and 500 mg/L.

In order to increase the solubility or improve the electrodeposition of the alloy metals, the copper ions or the zinc, iron and/or indium ions may be complexed in solution by a complexing agent. According to the invention, the complexing agent may be selected from the group consisting of carbohydrates, amino acids, sulfur compounds and sugar alcohols, preferably selected from the group consisting of sorbitol, mannitol, gluconate, erithrytol, xylitol, nitrilotriacetic acid, cysteine. Said complexing agents were found to be perfectly suited for complexing e.g. copper, zinc, iron and/or indium ions.

The complexing agent may have a concentration of 0.1 to 60 g/L, preferably 0,5 to 40 g/L, more preferably 1 to 20 g/L, most preferably 1.5 to 10 g/L. A concentration in these ranges is sufficient for complexing the copper ions which are comprised in the inventive alkaline electroplating solution as well as optionally zinc, iron and/or indium ions. A concentration of complexing agent above 75 g/L was found to be detrimental for some type of metal ions. For example, for copper ions, a concentration of a chelating agent above 75 g/L will lead to the reduction of copper (II) into copper (0) and lead to the formation of a brick-red copper precipitate.

In a further preferred embodiment, the concentration of the complexing agent is dependent on the concentration of the copper ions or optionally the zinc, iron and/or indium ions. Preferably, the ratio of the chelating agent concentration to the concentration of alloy metal ions (e.g. copper ions) ranges from 1 : 0.25 to 1:1. This range was found to be sufficient for suitable complexation of the alloy metal ions.

The electroplating solution according to the present invention may further comprise a buffering agent, preferably a buffering agent which is selected from the group consisting of phosphate (e.g. K3PO4, HK2PO4, H2KPO4, or the corresponding sodium phosphate salt), formiate (e.g. sodium formiate), pyrophosphate (e.g. tetrapotassium pyrophosphate) and citrate (e.g. sodium citrate). The advantage of citrate as a buffering agent is that citrate not only acts as a buffering agent, but also as a complexing agent for many metal ions. Phosphate as buffering agent has the advantage that it acts both as buffering agent and as conductive agent.

The buffering agent may have a concentration of 30 to 300 g/L, preferably 40 to 200 g/L, more preferably 50 to 100 g/L. A concentration in this range is suitable for keeping the pH of the inventive electroplating solution constant for many turnovers (TOs) of the electroplating solution.

The pH of the alkaline electroplating solution may be pH 10 to 14, preferably pH 11 to 13, more preferably pH 12 to 13. It was discovered that a pH in this range was found to improve the bath stability and brightness of the deposits. This is especially true for a pH above pH 11. Importantly, it was discovered that the copper complex in the electroplating solution becomes unstable at a pH < 11. In terms of long term stability of components which contact the inventive solution, a pH lower or equal to 13 is beneficial compared to a pH which is higher than pH 13 since the corrosive potential (concentration of the OH- ions) of the solution is higher at pH > 13 and the aspect of the deposit becomes drabber.

The electroplating solution may be at a temperature of 20 to 80 °C, preferably 30 to 70 °C, more preferably 40 to 60 °C. This temperature range was found to be the best compromise between bath stability and process efficiency during electroplating. This is especially true for a temperature in the range of 40 to 60 °C.

The inventive electroplating solution can further comprise a wetting agent. The advantage of a wetting agent in the electroplating solution is that hydrogen formation during electroplating is reduced. Preferred wetting agents are selected from the group consisting of cocamido propyl betaine, ethoxy ester phosphate and sodium lauryl ether sulfate.

The invention further provides a method for electroplating a gold alloy deposit on an electrode or substrate, the method comprising electroplating the electrode or substrate with a solution for 5 to 30 minutes at a current density of 0.1 to 4 A/dm2, characterized in that the electroplating solution is an electroplating solution according to the invention, wherein the electroplating solution is kept at a constant temperature of 20 to 80 °C.

The current density preferably ranges from 0.8 A/dm2 to 2.2 A/dm2, more preferably 1.0 A/dm2 to 2.0 A/dm2. It was discovered that a current density lower than 1 A/dm2 leads to a satin aspect and with more than 2 A/dm2, the deposit is burned.

In a preferred embodiment of the inventive method, the electroplating solution is kept at a constant temperature of 30 to 70 °C, more preferably at a temperature of 40 to 60 °C.

Furthermore, a substrate comprising a bright, electroplated deposit of a gold-copper alloy is producible by the method according to the invention, wherein the deposit has 14 to 22 karats of gold in the alloy and is corrosion resistant according to NFS 80772, ISO 4538 and/or ISO 9227.

Preferably, the electrode or substrate has a color matching the Swiss standard ISO 8654 from 0.5 N to 5 N and/or has excellent stability. The color of the electrode or substrate matching the Swiss standard ISO 8654 may be regulated by varying the ratio of alloy metal ions to gold ions in the inventive solution and may e.g. be 0,5 N, 1 N, 1.5 N, 2 N, 2.5 N, 3 N, 3.5 N, 4 N, 4.5 N or 5 N, or any value in between said values. Stability of the color is excellent i.e. the color is stable for at least 6 months without modification of the Lab color coordinates.

The inventive electroplating solution may be used for electroplating an electrode or substrate selected from the group consisting of decorative substrates, jewelry, watches and eyeglass trade.

With reference to the following figures and examples, the subject according to the present invention is intended to be explained in more detail without wishing to restrict said subject to the special embodiments shown here.

Example 1 Production of the gold stock solution

First of all, a complex of gold and hydantoin is obtained after a reaction between trivalent gold coming from HAuCl4 and an hydantoin-based compound, preferably 5,5 dimethylhydantoin. Finally, the complex is stabilized by adding a sulfite salt to the solution, preferably Na2SO3 or K2SO3. The solution is kept between pH 12 and 13.

Additional sulfite is only added after the formation of the gold complex. It was discovered that it is beneficial to separate the sulfite addition from the gold complexation, because otherwise a substantial extra time will be needed to obtain a bright deposit; this waiting period is not suitable for an industrial application and is avoided by adding directly the sufficient amount of sulfite compound to the already complexed gold solution with at least a 1:1 molar ratio.

Example 2 Production of the copper stock solution

First of all, a complex of copper ions with a complexing agent is to be produced. The copper ions remain equimolar or in a molar excess to the sugar alcohol, preferably equimolar to a 4-fold molar excess. To promote complex formation, a base (e.g. NaOH) is added to the solution to generate an alkaline pH (pH ≈ 14). Consequently, at least a certain part of the copper ions forms a complex with the sugar alcohol molecules.

This copper complex solution is then mixed with the solution obtained in Example 1 to produce an alkaline, cyanide-free solution for electroplating of a gold-copper alloy.

Example 3 Production of zinc, iron and indium stock solutions

It was discovered that if the cyanide-free solution comprises up to 3 g/L of zinc, iron and/or indium ions, the brightness and the color tone of the gold alloy deposit obtained with the present invention is improved. If desired, the amount or type of chelating agent in the cyanide-free solution may be adjusted. In order to achieve excellent brightness and color tone, certain molar ratios or molarities of chelating agents dependent on the type of ions (Fe3+, Zn2+ or In3+) were found to be beneficial (see Tables 1 and 2). Table 1 Iron as Fe3+ Stable in alkali media with a solubility bottom limit for the molar ratio between Fe : chelating compound* = 1:3 Zinc as Zn2+ Stable in alkali media with a solubility bottom limit for the molar ratio between Zn : chelating compund = 2:1 Zinc as [ZnOH4]2- not complexed Indium as In3+ Stable in alkali media with a solubility bottom limit for the molar ratio between In : chelating compound = 1:5 * The chelating compound may e.g. be a sugar alcohol
 Table 2 chelating compound sugar-alcohol amino acid sulfur compound Iron as Fe3+ 0.55 - 55 g/L 0.025 g/L - 2.5 g/L Harmful for Fe deposition Zinc as Zn2+ 0.730 g/L - 73 g/L 0.017 g/L - 1.7 g/L Harmful for Zn deposition Zinc as [ZnOH4]2- Doesn't need to be complexed Indium as In3+ 0.38 g/L - 38 g/L 0.16 g/L - 16 g/L 0.057 g/L - 5.68 g/L

Example 4 Production of a coating of a gold-copper-zinc alloy on a brass substrate, bronze substrate and nickel substrate

First of all, the conductive substrate to be treated, in the first case a substrate made of brass, was prepared using the Coventya S.A.S. brass substrate preparation product PRESOL 7073 as cleaner and PICKLANE 33 as activator of the surface.

The electroplating was performed with the following alkaline, cyanide-free electroplating solution:

The gold complex comes from the gold stock solution prepared as described in example 1, the copper complex comes from the copper stock solution prepared as described in example 2 and the zinc complex comes from the zinc stock solution prepared as described in example 3, table 1.

The electroplating was performed at 50 °C, since this temperature turned out to be the best compromise between the electrolyte efficiency and the zinc deposition which is disturbed by high temperature.

After plating for at a current density of 1 A/dm2 for 10 min., an 18 karat gold-copper-zinc alloy deposit was obtained on the brass electrode.

After the first deposition on a brass substrate, the same electrolyte solution was employed for electroplating a brass substrate having a white bronze under layer and a brass substrate having a nickel under layer. The same electroplating parameters were used (1 A/dm2 for 10 min.).

In both cases, the deposit produced was very bright, with a 5 N color (regarding the ISO 8654 standard) and an excellent resistance to tarnishing. Yet, the tarnishing resistance was better with a white under layer. Furthermore, the deposits were free of any faults such as pitting or stress cracking and demonstrated an excellent resistance to corrosion,

The following parameters of the electroplating bath containing the alkaline, cyanide-free solution were found to be beneficial for the properties of the resulting deposit:

Example 5 Production of a coating of a gold-copper-zinc alloy on a brass substrate and nickel substrate

First of all, the conductive substrate to be treated, in the first case a substrate made of brass, was prepared using the Coventya S.A.S. brass substrate preparation product PRESOL 7073 as cleaner and PICKLANE 33 as activator of the surface.

The electroplating was performed with the following alkaline, cyanide-free electroplating solution:

The gold complex comes from the gold stock solution prepared as described in example 1, the copper complex comes from the copper stock solution prepared as described in example 2 and the zinc complex comes from the zinc stock solution prepared as described in example 3, table 1.

The electroplating was performed at 50 °C, since this temperature turned out to be the best compromise between the electrolyte efficiency and the zinc deposition which is disturbed by high temperature.

After plating at a current density of 1 A/dm2 for 10 min., a 18 karat gold-copper-zinc alloy deposit was obtained on the brass electrode.

After the first deposition on a brass substrate, the same electrolyte solution was employed for electroplating a brass substrate having a white bronze under layer and a brass substrate having a nickel under layer. The same electroplating parameters were used (1 A/dm2 for 10 min.).

In both cases, the deposit produced was very bright, with a 1 N color (regarding the ISO 8654 standard) and an excellent resistance to tarnishing. Furthermore, the deposits were free of any faults such as pitting or stress cracking and demonstrated an excellent resistance to corrosion.

Example 6 Production of a coating of a gold-copper alloy on a brass substrate having or not white under layer

The same electrolyte and same operating conditions were used as in examples 3 and 4, but without the zinc (as Zn2(sorbitol)).

The results were deposits having a hazy aspect and burning problems.

Example 7 Production of a coating of an alloy comprising gold, copper and either iron or indium on a brass substrate

The conductive substrates to be treated were brass hull cells. The brass hull cells were prepared using the Coventya S.A.S. brass substrate preparation product PRESOL 7073 as cleaner and PICKLANE 33 as activator of the surface.

The electroplating was performed with the following alkaline, cyanide-free electroplating solutions, comprising different alloy metals and complexing agents, respectively (see Figure 1):

The gold complex comes from the gold stock solution prepared as described in example 1 and the copper complex comes from the copper stock solution prepared as described in example 2.

Plating was performed with a current density of 1 A/dm2 for 10 minutes. Characteristics of the deposits after electroplating are highlighted in Figure 1.

Example 8 Production of a gold-copper alloy on a brass substrate having different karats of gold in the alloy

The conductive substrate to be treated was brass hull cells. The brass hull cells were prepared using the Coventya S.A.S. brass substrate preparation product PRESOL 7073 as cleaner and PICKLANE 33 as activator of the surface.

The electroplating was performed with the following alkaline, cyanide-free electroplating solutions comprising different amounts of copper as alloy metal:

The gold complex comes from the gold stock solution prepared as described in example 1, the copper complex comes from the copper stock solution prepared as described in example 2 and the zinc complex comes from the zinc stock solution prepared as described in example 3, table 1.

Plating was performed with a current density of 1 A/dm2 for 10 minutes.
The relationship between copper concentration in the electrolyte and the karat of the deposit is highlighted in Table 3: <b>Table 3</b> Cu content 1 g/L 2 g/L 3 g/L 4 g/L Zn content 25 mg/L 50 mg/L 75 mg/L 100 mg/L Karats 20 KT 18 KT 16 KT 14 KT

Table 4 shows the dependency of the aspect and color of a deposit produced with variants of the inventive electroplating solutions. In particular, it can be seen that all deposits are bright if indium, iron or zinc ions were comprised in the inventive electroplating solution. Furthermore, it is evident that the color of the deposit can be selectively regulated by the type of alloy ions (e.g. zinc, indium or iron) which are comprised in the electroplating solution. <b>Table 4</b> Example alloying metal complexing agent molar ratio of alloy metal: complexing agent alloy metal concentration aspect of the deposit color of the deposit 7 indium NTA 1:2 50 - 200 mg/L Bright From pink to grey as indium content increases 7 indium Sorbitol 1:5 50 - 200 mg/L Bright From pink to grey as indium content increases 7 indium Cysteine 1:4 50 - 200 mg/L Bright From pink to grey as indium content increases 7 iron Sorbitol 1:3 50 - 200 mg/L Bright From pink to 0.5 N color as iron content increases

 Alkaline, cyanide-free electroplating solution for electroplating of a gold-copper alloy, comprising a) 0.5 to 10 g/L of gold ions; b) 0 to 3 g/L of zinc, iron or indium ions; c) 70 to 200 g/L of a sulfite salt; d) 0.1 to 8 g/L of copper ions; e) 0 to 75 g/L of a complexing agent which is different from hydantoin, a salt thereof or 5,5-dimethylhydantoin, characterized in that the electroplating solution further comprises 1.0 to 40 g/L of hydantoin, a salt thereof or 5,5-dimethylhydantoin, wherein the sulfite salt is sodium sulfite and/or potassium sulfite. Electroplating solution according to one of the preceding claims, characterized in that the concentration of the sulfite salt is 70 to 120 g/L, preferably 75 to 100 g/L. Electroplating solution according to one of the preceding claims, characterized in that the molar ratio between gold ions and hydantoin, a salt thereof or 5,5-dimethylhydantoin, is 1:2 to 1:6, preferably 1:2.5 to 1:5, more preferably 1:3 to 1:4. Electroplating solution according to one of the preceding claims, characterized in that the concentration of the copper ions is 0.2 to 10 g/L, preferably 0.5 to 7.5 g/L, more preferably 1 to 5 g/L. Electroplating solution according to one of the preceding claims, characterized in that the concentration of zinc, iron or indium ions is 10 mg/L to 3 g/L, preferably 20 mg/L to 1 g/L, more preferably 50 mg/L to 500 mg/L. Electroplating solution according to one of the preceding claims, characterized in that the complexing agent is selected from the group consisting of carbohydrates, amino acids, sulfur compounds and sugar alcohols, preferably selected from the group consisting of sorbitol, mannitol, gluconate, erithrytol, xylitol, nitrilotriacetic acid and cysteine. Electroplating solution according to one of the preceding claims, characterized in that the complexing agent has a concentration 0.1 to 60 g/L, preferably 0.5 to 40 g/L, more preferably 1 to 20 g/L, most preferably 1.5 to 10 g/L. Electroplating solution according to one of the preceding claims, characterized in that the electroplating solution further comprises a buffering agent, preferably a buffering agent which is selected from the group consisting of phosphate, formiate, pyrophosphate and citrate. Electroplating solution according to one of the preceding claims, characterized in that the pH of the solution is pH 10 to 14, preferably pH 11 to 13, more preferably pH 12 to 13. Method for electroplating a gold-copper alloy deposit on a substrate, the method comprising electroplating the electrode with an electroplating solution for 5 to 30 minutes at a current density of 0.1 to 4 A/dm2, characterized in that the electroplating solution is an electroplating solution according to one of claims 1 to 9, wherein the electroplating bath is kept at a constant temperature of 20 to 80 °C. Use of the electroplating solution according to one of claims 1 to 9 for electroplating a gold-copper alloy on a substrate selected from the group consisting of decorative substrates, jewelry, watches and eyeglass trade. Alkalische, cyanidfreie Elektroplattierungslösung zur Elektroplattierung einer Gold-Kupfer Legierung, umfassend a) 0,5 bis 10 g/L Goldionen; b) 0 bis 3 g/L Zink-, Eisen- oder Indiumionen; c) 70 bis 200 g/L eines Sulfitsalzes; d) 0,1 bis 8 g/L Kupferionen; e) 0 bis 75 g/L eines Komplexierungsmittels welches von Hydantoin, einem Salz davon oder 5,5-Dimethylhydantoin verschieden ist, dadurch gekennzeichnet, dass die Elektroplattierungslösung weiterhin 1,0 bis 40 g/L Hydantoin, ein Salz davon oder 5,5-Dimethylhydantoin umfasst, wobei das Sulfitsalz Natriumsulfit und/oder Kaliumsulfit ist. Elektroplattierungslösung gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Konzentration des Sulfitsalzes 70 bis 120 g/L, bevorzugt 75 bis 100 g/L beträgt. Elektroplattierungslösung gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Molverhältnis zwischen Goldionen und Hydantoin, einem Salz davon oder 5,5-Dimethylhydantoin von 1:2 bis 1:6, bevorzugt von 1:2,5 bis 1:5, besonders bevorzugt von 1:3 bis 1:4, beträgt. Elektroplattierungslösung gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Konzentration der Kupferionen von 0,2 bis 10 g/L, bevorzugt von 0,5 bis 7,5 g/L, besonders bevorzugt von 1 bis 5 g/L, beträgt. Elektroplattierungslösung gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Konzentration von Zink-, Eisen- oder Indiumionen von 10 mg/L bis 3 g/L, bevorzugt von 20 mg/L bis 1 g/L, besonders bevorzugt von 50 mg/L bis 500 mg/L, beträgt. Elektroplattierungslösung gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Komplexierungsmittel ausgewählt ist aus der Gruppe bestehend aus Kohlenhydraten, Aminosäuren, Schwefelverbindungen und Zuckeralkoholen, bevorzugt ausgewählt aus der Gruppe bestehend aus Sorbit, Mannit, Gluconat, Erythrit, Xylit, Nitrilotriessigsäure und Cystein. Elektroplattierungslösung gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Komplexierungsmittel eine Konzentration von 0,1 bis 60 g/L, bevorzugt 0,5 bis 40 g/L, besonders bevorzugt 1 bis 20 g/L, insbesondere 1,5 bis 10 g/L, aufweist. Elektroplattierungslösung gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Elektroplattierungslösung weiterhin ein Puffermittel umfasst, bevorzugt ein Puffermittel, welches ausgewählt ist aus der Gruppe bestehend aus Phosphat, Formiat, Pyrophosphat und Citrat. Elektroplattierungslösung gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der pH der Lösung pH 10 bis 14, bevorzugt pH 11 bis 13, besonders bevorzugt pH 12 bis 13, ist. Verfahren zur Elektroplattierung einer Gold-Kupfer Ablagerung auf einem Substrat, wobei die Methode Elektroplattieren der Elektrode mit einer Elektroplattierungslösung für 5 bis 30 Minuten bei einer Stromdichte von 0,1 bis 4 A/dm3 umfasst, dadurch gekennzeichnet, dass die Elektroplattierungslösung eine Elektroplattierungslösung gemäß einem der Ansprüche 1 bis 9 ist, wobei die Elektroplattierungslösung bei einer konstanten Temperatur von 20 bis 80°C gehalten wird. Verwendung der Elektroplattierungslösung gemäß einem der Ansprüche 1 bis 9 zur Elektroplattierung einer Gold-Kupfer Ablagerung auf einem Substrat ausgewählt aus der Gruppe bestehend aus dekorativen Substraten, Schmuck, Uhren und Brillenwaren. Solution de dépôt électrolytique alcaline sans cyanure pour le dépôt électrolytique d'un alliage d'or et de cuivre, comprenant a) 0,5 à 10 g/l d'ions or ; b) 0 à 3 g/l d'ions zinc, fer ou indium ; c) 70 à 200 g/l d'un sel sulfite ; d) 0,1 à 8 g/l d'ions cuivre ; e) 0 à 75 g/l d'un agent complexant qui est différent de l'hydantoïne, d'un sel de celle-ci, ou de la 5,5-diméthylhydantoïne, caractérisée en ce que la solution de dépôt électrolytique comprend en outre 1,0 à 40 g/l d'hydantoïne, d'un sel de celle-ci ou de 5,5-diméthylhydantoïne,
dans laquelle le sel sulfite est le sulfite de sodium et/ou le sulfite de potassium. Solution de dépôt électrolytique selon la revendication précédente, caractérisée en ce que la concentration du sel sulfite est de 70 à 120 g/l, de préférence de 75 à 100 g/l. Solution de dépôt électrolytique selon l'une des revendications précédentes, caractérisée en ce que le rapport molaire entre les ions or et l'hydantoïne, un sel de celle-ci ou la 5,5-diméthylhydantoïne, est de 1/2 à 1/6, de préférence de 1/2,5 à 1/5, mieux encore de 1/3 à 1/4. Solution de dépôt électrolytique selon l'une des revendications précédentes, caractérisée en ce que la concentration des ions cuivre est de 0,2 à 10 g/l, de préférence de 0,5 à 7,5 g/l, mieux encore de 1 à 5 g/l. Solution de dépôt électrolytique selon l'une des revendications précédentes, caractérisée en ce que la concentration des ions zinc, fer ou indium est de 10 mg/l à 3 g/l, de préférence de 20 mg/l à 1 g/l, mieux encore de 50 mg/l à 500 mg/l. Solution de dépôt électrolytique selon l'une des revendications précédentes, caractérisée en ce que l'agent complexant est choisi dans le groupe constitué par les hydrates de carbone, les acides aminés, les composés soufrés et les alcools de sucre, de préférence choisi dans le groupe constitué par le sorbitol, le mannitol, le gluconate, l'érythritol, le xylitol, l'acide nitrilotriacétique et la cystéine. Solution de dépôt électrolytique selon l'une des revendications précédentes, caractérisée en ce que l'agent complexant a une concentration de 0,1 à 60 g/l, de préférence de 0,5 à 40 g/l, mieux encore de 1 à 20 g/l, tout spécialement de 1,5 à 10 g/l. Solution de dépôt électrolytique selon l'une des revendications précédentes, caractérisée en ce que la solution de dépôt électrolytique comprend en outre un agent tampon, de préférence un agent tampon qui est choisi dans le groupe constitué par le phosphate, le formiate, le pyrophosphate et le citrate. Solution de dépôt électrolytique selon l'une des revendications précédentes, caractérisée en ce que le pH de la solution est un pH de 10 à 14, de préférence un pH de 11 à 13, mieux encore un pH de 12 à 13. Procédé pour effectuer un dépôt électrolytique d'un alliage d'or et de cuivre sur un substrat, lequel procédé comprend le dépôt électrolytique de l'électrode avec une solution de dépôt électrolytique pendant 5 à 30 minutes à une densité de courant de 0,1 à 4 A/dm2, caractérisé en ce que la solution de dépôt électrolytique est une solution de dépôt électrolytique selon l'une des revendications 1 à 9, dans lequel le bain de dépôt électrolytique est maintenu à une température constante de 20 à 80°C. Utilisation de la solution de dépôt électrolytique selon l'une quelconque des revendications 1 à 9 pour le dépôt électrolytique d'un alliage d'or et de cuivre sur un substrat choisi dans le groupe constitué par les substrats décoratifs, les bijoux, les montres et le secteur de la lunetterie.
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