Abstract:
Cyanide-free electroplating baths for deposition of gold and gold alloy coatings, using sulphurous gold complexes that are stable for a relatively long time, can be used with current density over 1 A/dm 2  and are practically odor-free, are obtained when the sulphurous compounds used are mercaptosulfonic acids, dye sulfide sulfonic acids or salts thereof.

Description:
This application is a 35 U.S.C. 371 National Stage filing of PCT/EP97/03903 published as WO 98/03700 on Jan. 29, 1998. 
    
    
     DESCRIPTION 
     This invention relates to a cyanide-free, electroplating bath for the deposition of gold and gold alloy coatings, containing 0.5 to 30 g/l of gold in the form of a complex of a sulphurous compound, 0 to 50 g/l of an alloy metal in the form of water-soluble compounds of silver, copper, indium, cadmium, zinc, tin, bismuth, arsenic and/or antimony, 1 to 200 g/l of the free sulphurous compound, 0 to 200 g/l of conductive and buffer salts in the form of alkali metal borates, phosphates, citrates, tartrates and/or gluconates and optionally wetting agents and brighteners. 
     Today, electrodeposition of gold is primarily performed using electrolytes based on gold cyanide complexes which, at least under alkaline conditions, also contain relatively large quantities of toxic alkali metal cyanides. Under acidic and neutral conditions, the cyanide liberated on electrolysis escapes at least in part as highly toxic hydrocyanic acid. Apart from severe toxicity, baths containing cyanide also occasion problems when detoxifying the cyanide, which, in practice, is predominantly performed with alkali metal hypochlorite. This may result in the formation of so-called adsorbable halogen compounds (AOX) which cause waste water treatment problems. Efforts have accordingly long been made to produce gold electroplating baths without using the toxic complexing agent cyanide. However, with the exception of baths based on gold sulphite complexes, it has not hitherto proved possible to produce an industrially viable bath. 
     However, such gold/sulphite complexes have the disadvantage of low stability and, even with a large excess of free sulphite ions, form elemental gold once the solution has stood for a relatively extended period, so rendering the solution unusable. 
     Electroplating baths which contain the gold in the form of a thiosulphate complex (DE-PS 24 45 538) are also not substantially more stable. Like other known gold complexes with sulphurous compounds, they decompose partially if they are kept for a relatively extended period. In published application EP 0 611 840, the gold thiosulphate complexes are thus stabilised by the addition of sulphinates. The current density usable in these baths is limited and decomposition generally occurs at current densities of above 1 A/dm 2 . Moreover, these baths usually cause an odour nuisance. 
     The object of the present invention was accordingly to provide a cyanide-free electroplating bath for the deposition of gold and gold alloy coatings, containing 0.5 to 30 g/l of gold in the form of a complex of a sulphurous compound, 0 to 50 g/l of an alloy metal in the form of a water-soluble compound of silver, copper, indium, cadmium, zinc, tin, bismuth, arsenic and/or antimony, 1 to 200 g/l of the free sulphurous compound, 0 to 200 g/l of conductive and buffer salts in the form of alkali metal borates, phosphates, citrates, tartrates and/or gluconates and optionally wetting agents and brighteners, which was also to be stable over a relatively extended period, to be operated at current densities of above 1 A/dm 2  and, to the greatest extent possible, to be neutral in odour. 
     SUMMARY OF THE INVENTION 
     This object is achieved according to the invention by the bath&#39;s containing the gold complex of a mercaptosulphonic acid, a disulphidesulphonic acid or mixtures of these compounds as the sulphurous compound. 
     The salts, preferably the alkali metal salts, of these compounds are also suitable. 
     The baths preferably contain 1 to 200 g/l of the free sulphurous compound or the alkali metal salts thereof in excess of the stoichiometric composition of the corresponding gold complex. 
     It is furthermore advantageous for the baths to contain 0.01 to 10 g/l of wetting agents in the form of surfactants and 0.1 to 1000 mg/l of brighteners in the form of selenium and/or tellurium compounds. 
     The bath is advantageously operated at a pH value of 7 to 12. 
     The sulphurous compounds which are suitable for the baths according to the invention exhibit good solubility in water and elevated stability, combined with a low vapour pressure, such that there is no perceptible unpleasant odour. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The sulphurous compounds to be used according to the invention may be characterised by the general formula I 
     
         X--S--CHR--(CR&#39;R&#34;).sub.n --SO.sub.3 H                      (I) 
    
     in which 
     X means H or the residue --S--CHR--(CR&#39;R&#34;) n  --SO 3  H R&#39; and R&#34; 
     R means H, alkyl or aryl containing up to 12 C atoms, SO 3  H, OH, SH, NH 2   
     n means the numbers from 0 to 6. 
     Typical compounds of the formula I are: 
     2-mercaptoethanesulphonic acid, 
     3-mercaptopropanesulphonic acid, 
     2,3-dimercaptopropanesulphonic acid and homologues together with 
     bis-(2-sulphoethyl)disulphide 
     bis-(3-sulphopropyl)disulphide and homologues. 
     The compounds are preferably used in the form of the alkali metal salts thereof. 
     The corresponding gold complexes are obtained by simply reacting soluble gold compounds, such as for example tetrachloroauric acid, sodium aurate solutions or the like, with the stoichiometric quantity or an excess of these sulphurous compounds in an aqueous solution. Care must be taken to provide the stoichiometric quantity of sulphurous compounds required for reduction to gold(I). If the electroplating bath is to contain no chloride ions, the gold should first be precipitated with ammonia solution as fulminating gold, thoroughly washed and dissolved in an aqueous solution of the sulphurous compound. 
     The solution of the gold complex may be used directly for preparation of the electroplating bath. The bath preferably contains an excess of sulphurous compounds of 1-200 g/l. 
     Codeposition of further metals as well as gold from this system is possible in order to influence properties of the deposit. Codeposition of silver, copper, indium, cadmium, tin, zinc, bismuth and the semi-metals arsenic and antimony is of interest. They are used either in the form of the corresponding sulphur compounds, as is preferably the case with silver and copper, or in the form of other complexes with hydroxyl ions, with nitrilotriacetic acid or ethylenediaminetetraacetic acid (EDTA), as complexes with hydroxycarboxylic acids, such as gluconic acid, citric acid and tartaric acid, as complexes with dicarboxylic acids, such as oxalic acid, with amines, such as ethylenediamine, with phosphonic acids, such as 1-hydroxyethanediphosphonic acid, aminotrimethylenephosphonic acid or ethylenediaminetetramethylenephosphonic acid. 
     Bismuth is thus preferably used as a citrate or EDTA complex, tin preferably as oxalatostannate(IV) or tin(II) gluconate complex and indium as gluconate or EDTA complex. Arsenic and antimony are largely used to increase hardness and for brightening. Arsenic is preferably used in the form of alkali metal antimonyltartrate. The concentration of the alloy metals may vary within broad limits between 10 mg/l and 50 g/l. The concentration of the free complexing agent in the bath may be between 0.1 and 200 g/l. 
     Bright alloy deposits may be obtained by adding further brighteners, such as compounds of selenium and tellurium, for example as an alkali metal selenocyanate, selenite or tellurite, in concentrations of 0.1 mg/l to 1 g/l. 
     The addition of conductive and buffer salts, such as borates, tetraborates, phosphates, citrates, tartrates or gluconates of the alkali metals, in concentrations of 1-200 g/l increases the conductivity and throwing power of the bath. 
     The addition of 0.01-10 g/l of wetting agent not only reduces surface tension, but may also have a positive effect on brightening. Wetting agents used are, for example, ionic and nonionic surfactants of the ethylene oxide adduct type, such as alkyl (fatty acid) or nonylphenol polyglycol ethers with alcohol, sulphate, sulphonate or phosphate end groups together with perfluorinated compounds, such as perfluoroalkane carboxylates or sulphonates, together with cationic surfactants, for example tetraalkyammonium(sic)perfluoroalkane sulphonates. 
     According to the invention, the baths thus contain: 
     0.5-30 g/l of gold complexed with sulphurous compounds from the group comprising mercaptosulphonic acids or the alkali metal salts thereof. 
     1-200 g/l of free sulphurous compounds or the alkali metal salts. 
     0-200 g/l of conductive and buffer substances from the group comprising alkali metal borates, phosphates, citrates, tartrates, gluconates. 
     0-50 g/l of alloy metals from the group comprising silver, copper, cadmium, indium, tin, zinc, bismuth, arsenic and antimony in the form of the stated complexes and compounds. 
     0-1000 mg/l of brighteners from the group comprising selenium and tellurium in the form of selenite, selenocyanate or telluride of the alkali metals. 
     0-10 g/l of wetting agents, for example ionic and nonionic surfactants of the ethylene oxide adduct type such as alkyl(fatty acid) or nonylphenol polyglycol ethers having alcohol, sulphate, sulphonate or phosphate end groups together with perfluorinated compounds such as perfluoroalkane carboxylates or sulphonates together with cationic surfactants, for example tetraalkyammonium(sic)perfluoroalkane sulphonates. 
    
    
     The following Examples are intended to illustrate the invention in greater detail: 
     1. 5 g of gold as gold 2-mercaptoethanesulphonate complex, 20 g of 2-mercaptoethanesulphonic acid and 50 g of dipotassium phosphate are dissolved to yield a liter of solution. The pH value is adjusted to pH 10 with sodium hydroxide solution. On subsequent electrolysis at 50° C. and 1.5 A/dm 2 , a smooth, uniformly adhering gold coating of a thickness of 5 μm is obtained on a copper cathode. The bath is virtually odourless and exhibits no signs of decomposition even after relatively extended electrolysis. 
     2. If 2 g of a copper 2-mercaptopropanesulphonic acid complex are added to the bath from Example 1, reddish gold/copper deposits are obtained on electrolysis. 
     3. If a further 0.3 g of potassium oxalatostannate(IV) and 400 μg of potassium selenocyanate are added as brighteners to the bath from Example 2 and electrolysis performed at 50° C. and 2 A/dm 2 , bright, rose-coloured coatings of a gold/copper/tin alloy are obtained. 
     4. 4 g of gold and 2 g of silver as bis-(3-sulphopropyl)disulphide complexes, 30 g of (3-sulphopropyl)disulphide, 50 g of sodium gluconate and 20 mg of potassium tellurite are dissolved to yield a liter of solution. The pH value is adjusted to pH 12 with sodium hydroxide solution. On electrolysis at 55° C. and 1.5 A/dm 2 , a bright, greenish-yellow, ductile deposit of a gold/silver alloy is obtained on a copper cathode.