EP0907767A1 - Cyanide-free electroplating bath for deposition of gold and gold alloys - Google Patents

Cyanide-free electroplating bath for deposition of gold and gold alloys

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Publication number
EP0907767A1
EP0907767A1 EP97933686A EP97933686A EP0907767A1 EP 0907767 A1 EP0907767 A1 EP 0907767A1 EP 97933686 A EP97933686 A EP 97933686A EP 97933686 A EP97933686 A EP 97933686A EP 0907767 A1 EP0907767 A1 EP 0907767A1
Authority
EP
European Patent Office
Prior art keywords
gold
cyanide
free
acid
bath
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97933686A
Other languages
German (de)
French (fr)
Other versions
EP0907767B1 (en
Inventor
Werner Kuhn
Wolfgang Zilske
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Umicore Galvanotechnik GmbH
Original Assignee
Degussa GmbH
Degussa Huels AG
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Publication of EP0907767A1 publication Critical patent/EP0907767A1/en
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Publication of EP0907767B1 publication Critical patent/EP0907767B1/en
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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 a cyanide-free galvanic bath for the deposition of gold and gold alloy coatings, with 0.5 to 30 g / 1 gold in the form of a complex of a sulfur-containing compound, 0 to 50 g / 1 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 / 1 of the free sulfur-containing compound, 0 to 200 g / 1 conductive and buffer salts in the form of alkali borates, phosphates, citrates, tartrates and / or gluconates and given all wetting agents and brighteners.
  • Electrolytic deposition of gold is mainly used for the electrodeposition of gold
  • Gold cyanide complexes are used, which also contain larger amounts of toxic alkali cyanides, at least in the alkaline range. In the acidic and neutral range, the cyanide released during electrolysis at least partially escapes as highly toxic hydrocyanic acid. In addition to the strong toxicity, cyanide baths cause problems in detoxifying the cyanide, which in practice is mainly done with alkali hypochlorite. So-called adsorbable halogen compounds (AOX) can form, which cause difficulties in wastewater treatment. The efforts to produce galvanic gold baths without the use of the toxic complexing agent cyanide therefore go back a long time. However, apart from baths based on gold sulfite complexes, no technically usable bath has yet been produced.
  • AOX adsorbable halogen compounds
  • Contain thiosulfato complex (DE-PS 24 45 538), are not much more stable. They decompose, like other well-known gold complexes with sulfur-containing compounds, sometimes when standing for a long time. In EP-OS 0 611 840, the gold thiosulfato complexes are therefore stabilized by adding sulfinates. The applicable current density is limited in these baths and decomposition usually occurs at current densities above 1 A / dm. In addition, these baths usually cause unpleasant smells.
  • the bath contains a mercaptosulfonic acid, a disulfide sulfonic acid, or mixtures of these compounds as the sulfur-containing compound of the gold complex.
  • the salts preferably the alkali salts, of these compounds are also suitable.
  • the baths preferably contain 1 to 200 g / l of the free sulfur-containing compound or its alkali metal salts in excess of the stoichiometric composition of the corresponding gold complex.
  • the baths contain 0.01 to 10 g / l of wetting agent in the form of surfactants and 0.1 to 1000 mg / l of brightener in the form of selenium and / or tellurium compounds.
  • the bath is advantageously operated at a pH of 7 to 12.
  • the sulfur-containing compounds which are suitable for the baths according to the invention show good solubility in water and great stability, combined with a low vapor pressure, so that no bad smell is perceptible.
  • the sulfur-containing compounds to be used according to the invention can be represented by the general formula I.
  • Typical compounds of formula I are:
  • 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 amount or an excess of these sulfur-containing compounds in aqueous solution. Note the stoichiometric amount of sulfur-containing compounds required for the reduction to gold (I). If the electroplating bath is to be free of chloride ions, gold must first be precipitated with ammonia solution as gold, washed thoroughly and dissolved in an aqueous solution of the sulfur-containing compound.
  • the solution of the gold complex can be used directly to prepare the galvanic bath.
  • the bath preferably contains an excess of sulfur-containing compounds of 1-200 g / 1.
  • Semi-metals arsenic and antimony They are used either in the form of the corresponding sulfur compounds, as is preferred for 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-hydroxyethane diphosphonic acid, e
  • Bismuth is preferably used as citrate or EDTA complex
  • tin is preferably used as oxalatostannnate (IV) or tin (II) - gluconate complex and indium is used as gluconate or EDTA complex.
  • Arsenic and antimony are used primarily to increase hardness and gloss. Arsenic is preferably used in the form of alkali arsenite compounds, antimony is preferably used in the form of alkali mononyl tartrate.
  • the concentration of the alloy metals can vary within wide limits between 10 mg / 1 and 50 g / 1.
  • the concentration of free complexing agents in the bath can be between 0.1 and 200 g / l.
  • conductive and buffer substances such as borates, tetraborates, phosphates, citrates, tartrates or gluconates of the alkali metals in concentrations of 1-200 g / 1 increase the conductivity and spreadability of the bath.
  • ionic and nonionic surfactants of the ethylene oxide adduct type such as alkyl (fatty acid) or nonylphenol polyglycol ethers with end groups as alcohol, sulfate, sulfonate or phosphate, and perfluorinated compounds, such as Perfluoroalkane carboxylates or sulfonates and cationic surfactants, for example tetraalkyammonium perfluoroalkane sulfonates.
  • the baths thus contain:
  • conductive and buffer substances from the group of alkali borates, phosphates, citrates, tartrates,
  • 0-50 g / 1 alloy metal from the group silver, copper, cadmium, indium, tin, zinc, bismuth, arsenic and antimony in the form of the complexes and compounds mentioned.
  • wetting agent e.g. ionic and nonionic surfactants of the ethylene oxide adduct type such as alkyl (fatty acid) or nonylphenol polyglycol ether with end groups as alcohol, sulfate, sulfonate or phosphate and perfluorinated compounds such as perfluoroalkane carboxylates or sulfonates as well as cationic surfactants, e.g.
  • ionic and nonionic surfactants of the ethylene oxide adduct type such as alkyl (fatty acid) or nonylphenol polyglycol ether with end groups as alcohol, sulfate, sulfonate or phosphate and perfluorinated compounds such as perfluoroalkane carboxylates or sulfonates as well as cationic surfactants, e.g.
  • Tetraalkyammonium perfluoroalkanesulfonates are intended to illustrate the invention:

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  • 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)

Abstract

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

Description

Cyaiiidfreies galvanisches Bad zur .Abscheidung von Gold und Cyaiiid-free galvanic bath for the deposition of gold and
GoldlegierungenGold alloys
Beschreibung :Description :
Die Erfindung betrifft ein cyanidfreies galvanisches Bad zur Abscheidung von Gold- und Goldlegierungsüberzügen, mit 0,5 bis 30 g/1 Gold in Form eines Komplexes einer schwefelhaltigen Verbindung, 0 bis 50 g/1 eines Legierungsmetalls in Form wasserlöslicher Verbindungen von Silber, Kupfer, Indium, Cadmium, Zink, Zinn, Wismut, Arsen und/oder Antimon, 1 bis 200 g/1 der freien schwefelhaltigen Verbindung, 0 bis 200 g/1 Leit- und Puffersalzen in Form von Alkaliboraten, -phosphaten, -citraten, -tartraten und/oder -gluconaten und gegebenen alls Netzmitteln und Glanzbildnern.The invention relates to a cyanide-free galvanic bath for the deposition of gold and gold alloy coatings, with 0.5 to 30 g / 1 gold in the form of a complex of a sulfur-containing compound, 0 to 50 g / 1 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 / 1 of the free sulfur-containing compound, 0 to 200 g / 1 conductive and buffer salts in the form of alkali borates, phosphates, citrates, tartrates and / or gluconates and given all wetting agents and brighteners.
Zur galvanischen Abscheidung von Gold werden heute überwiegend Elektrolyte auf der Basis vonElectrolytic deposition of gold is mainly used for the electrodeposition of gold
Goldcyanidkomplexen verwendet, die zumindest im alkalischen Bereich auch größere Mengen giftiger Alkalicyanide enthalten. Im sauren und neutralen Bereich entweicht das bei der Elektrolyse freiwerdendes Cyanid zumindest teilweise als hochtoxische Blausäure. Neben der starken Toxizität bereiten cyanidische Bäder Probleme bei der Entgiftung des Cyanids, die in der Praxis überwiegend mit Alkalihypochlorit erfolgt. Dabei können sich sogenannte adsorbierbare Halogenverbindungen (AOX) bilden, die Schwierigkeiten in der Abwasseraufbereitung verursachen. Die Bemühungen zur Herstellung galvanischer Goldbäder ohne den Einsatz des giftigen Komplexbildner Cyanid reichen deshalb lange zurück. Außer Bädern auf der Basis von Goldsulfitkomplexen konnte jedoch bisher kein technisch verwertbares Bad hergestellt werden.Gold cyanide complexes are used, which also contain larger amounts of toxic alkali cyanides, at least in the alkaline range. In the acidic and neutral range, the cyanide released during electrolysis at least partially escapes as highly toxic hydrocyanic acid. In addition to the strong toxicity, cyanide baths cause problems in detoxifying the cyanide, which in practice is mainly done with alkali hypochlorite. So-called adsorbable halogen compounds (AOX) can form, which cause difficulties in wastewater treatment. The efforts to produce galvanic gold baths without the use of the toxic complexing agent cyanide therefore go back a long time. However, apart from baths based on gold sulfite complexes, no technically usable bath has yet been produced.
Derartige Goldsulfito-Komplexe haben jedoch den Nachteil einer geringen Stabilität und bilden selbst bei hohem Überschuß an freien Sulfitionen bei längerem Stehen der Lösung elementares Gold, womit die Lösung unbrauchbar wird.However, such gold sulfito complexes have the disadvantage of low stability and form elemental gold even with a high excess of free sulfite ions when the solution is left for a long time, which makes the solution unusable.
Auch galvanische Bäder, die das Gold in Form einesAlso galvanic baths, which are gold in the form of
Thiosulfatokomplexes enthalten (DE-PS 24 45 538) , sind nicht wesentlich stabiler. Sie zersetzen sich, wie auch andere bekannte Goldkomplexe mit schwefelhaltigen Verbindungen zum Teil bei längerem Stehen. In der EP-OS 0 611 840 werden die Goldthiosulfatokomplexe daher durch Zusatz von Sulfinaten stabilisiert. Die anwendbare Stromdichte ist bei diesen Bädern begrenzt und bei Stromdichten über 1 A/dm tritt meist eine Zersetzung ein. Außerdem entstehen bei diesen Bädern normalerweise Geruchsbelästigungen.Contain thiosulfato complex (DE-PS 24 45 538), are not much more stable. They decompose, like other well-known gold complexes with sulfur-containing compounds, sometimes when standing for a long time. In EP-OS 0 611 840, the gold thiosulfato complexes are therefore stabilized by adding sulfinates. The applicable current density is limited in these baths and decomposition usually occurs at current densities above 1 A / dm. In addition, these baths usually cause unpleasant smells.
Es war daher Aufgabe der vorliegenden Erfindung, ein cyanidfreies galvanisches Bad zur Abscheidung von Gold- und Goldlegierungsüberzügen zu entwickeln, mit 0,5 bis 30 g/1 Gold in Form eines Komplexes einer schwefelhaltigen Verbindung, 0 bis 50 g/1 eines Legierungsmetalls in Form einer wasserlöslichen Verbindung von Silber, Kupfer, Indium, Cadmium, Zink, Zinn, Wismut, Arsen und/oder Antimon, 1 bis 200 g/1 der freien schwefelhaltigen Verbindung, 0 bis 200 g/1 Leit- und Puffersalzen in Form von Alkaliboraten, -phosphaten, -citraten, -tartraten und/oder -gluconaten und gegebenenfalls Netzmitteln und Glanzbildnern, das auch über längere Zeit stabil sein, mit Stromdichten über 1 A/dm betrieben werden und weitestgehend geruchsneutral sein sollte.It was therefore an object of the present invention to develop a cyanide-free galvanic bath for the deposition of gold and gold alloy coatings, with 0.5 to 30 g / 1 gold in the form of a complex of a sulfur-containing compound, 0 to 50 g / 1 of an alloy metal in the form a water-soluble compound of silver, copper, indium, cadmium, zinc, tin, bismuth, arsenic and / or antimony, 1 to 200 g / 1 of the free sulfur-containing compound, 0 to 200 g / 1 conductive and buffer salts in the form of alkali borates, phosphates, citrates, tartrates and / or gluconates and optionally wetting agents and brighteners, which should also be stable over a long period of time, be operated with current densities above 1 A / dm and should be largely odorless.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß das Bad als schwefelhaltige Verbindung des Goldkomplexes eine Mercaptosulfonsäure, eine Disulfidsulfonsäure, oder Gemische dieser Verbindungen enthält.This object is achieved in that the bath contains a mercaptosulfonic acid, a disulfide sulfonic acid, or mixtures of these compounds as the sulfur-containing compound of the gold complex.
Geeignet sind auch die Salze, vorzugsweise die Alkalisalze, dieser Verbindungen.The salts, preferably the alkali salts, of these compounds are also suitable.
Vorzugsweise enthalten die Bäder 1 bis 200 g/1 der freien schwefelhaltigen Verbindung oder deren Alkalisalze im Überschuß gegenüber der stöchiometrischen Zusammensetzung des entsprechenden Goldkomplexes.The baths preferably contain 1 to 200 g / l of the free sulfur-containing compound or its alkali metal salts in excess of the stoichiometric composition of the corresponding gold complex.
Weiterhin ist es von Vorteil, wenn die Bäder 0,01 bis 10 g/1 Netzmittel in Form von Tensiden und 0,1 bis 1000 mg/1 Glanzbildner in Form von Selen- und/oder Tellurverbindungen enthalten.It is also advantageous if the baths contain 0.01 to 10 g / l of wetting agent in the form of surfactants and 0.1 to 1000 mg / l of brightener in the form of selenium and / or tellurium compounds.
Vorteilhafterweise wird das Bad bei einem pH-Wert von 7 bis 12 betrieben.The bath is advantageously operated at a pH of 7 to 12.
Die schwefelhaltigen Verbindungen, die für die erfindungsgemäßen Bäder geeignet sind, zeigen eine gute Wasserlöslichkeit und eine große Stabilität, verbunden mit einem geringen Dampfdruck, so daß kein übler Geruch wahrnehmbar ist . Die erfindungsgemäß einzusetzenden schwefelhaltigen Verbindungen lassen sich durch die allgemeine Formel IThe sulfur-containing compounds which are suitable for the baths according to the invention show good solubility in water and great stability, combined with a low vapor pressure, so that no bad smell is perceptible. The sulfur-containing compounds to be used according to the invention can be represented by the general formula I.
X-S-CHR- (CR'R' ' )n-S03H (I)XS-CHR- (CR'R '') n -S0 3 H (I)
worin bedeutetwhere means
X H oder der Rest -S -CHR- (CR > R ' ' ) n-S03HXH or the rest -S -CHR- (CR > R '') n -S0 3 H
R H , Alkyl oder Aryl mit bis zu 12 C- Atomen , S03HRH, alkyl or aryl with up to 12 C atoms, S0 3 H
R ! , R ' ' R , OH , SH , NH2 R ! , R ″ R, OH, SH, NH 2
n die Zahlen 0 bis 6n the numbers 0 to 6
charakterisieren .characterize.
Typische Verbindungen der Formel I sind:Typical compounds of formula I are:
2 -Mercaptoethansulfonsäure , 3 -Mercaptopropansulfonsäure , 2 , 3 -Dimercaptopropansulfonsäure und Homologe sowie2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 2, 3-dimercaptopropanesulfonic acid and homologues as well
Bis- (2-Sulfoethyl) -disulfidBis (2-sulfoethyl) disulfide
Bis- (3-Sulfopropyl) -disulfid und Homologe.Bis (3-sulfopropyl) disulfide and homologues.
Die Verbindungen werden bevorzugt in Form ihrerThe compounds are preferred in the form of their
Alkalisalze eingesetzt. Die entsprechenden Goldkomplexe werden durch einfache Umsetzung von löslichen Goldverbindungen, wie z.B. Tetrachlorogoldsäure, Natriumauratlösungen oder ähnlichen, mit der stöchiometrischen Menge oder einem Überschuß an diesen schwefelhaltigen Verbindungen in wässriger Lösung erhalten. Zu beachten ist die für die Reduktion zu Gold-(I) erforderliche stöchiometrische Menge an schwefelhaltigen Verbindungen. Soll das galvanische Bad frei von Chloridionen sein, so ist Gold zunächst mit Ammoniaklösung als Knallgold zu fällen, gründlich zu waschen und in einer wässrigen Lösung der schwefelhaltigen Verbindung aufzulösen .Alkali salts used. 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 amount or an excess of these sulfur-containing compounds in aqueous solution. Note the stoichiometric amount of sulfur-containing compounds required for the reduction to gold (I). If the electroplating bath is to be free of chloride ions, gold must first be precipitated with ammonia solution as gold, washed thoroughly and dissolved in an aqueous solution of the sulfur-containing compound.
Die Lösung des Goldkomplexes kann direkt zur Bereitung des galvanischen Bades verwendet werden. Das Bad enthält vorzugsweise einen Überschuß an schwefelhaltigen Verbindungen von 1-200 g/1.The solution of the gold complex can be used directly to prepare the galvanic bath. The bath preferably contains an excess of sulfur-containing compounds of 1-200 g / 1.
Die Mitabscheidung weiterer Metalle neben Gold aus diesem System zur Beeinflussung der Schichteigenschaften ist möglich. Interessant ist die Mitabscheidung von Silber, Kupfer, Indium, Cadmium, Zinn, Zink, Wismut sowie derThe co-deposition of other metals besides gold from this system to influence the layer properties is possible. The co-deposition of silver, copper, indium, cadmium, tin, zinc, bismuth and the is interesting
Halbmetalle Arsen und Antimon. Sie werden entweder in Form der entsprechenden Schwefelverbindungen eingesetzt, wie bevorzugt bei Silber und Kupfer, oder in Form anderer Komplexe mit Hydroxylionen, mit Nitrilotriessigsäure, oder Ethylendiamintetraessigsäure (EDTA) , als Komplexe mit Hydroxycarbonsäuren, wie Gluconsäure, Citronensäure und Weinsäure, als Komplexe mit Dicarbonsäuren, wie Oxalsäure, mit Aminen, wie Ethylendiamin, mit Phosphonsäuren, wie 1-Hydroxyethandiphosphonsäure , eSemi-metals arsenic and antimony. They are used either in the form of the corresponding sulfur compounds, as is preferred for 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-hydroxyethane diphosphonic acid, e
Aminotrimethylenphosphonsäure oder Ethylendiamintetramethylenphosphonsäure .Aminotrimethylenephosphonic acid or ethylenediaminetetramethylenephosphonic acid.
So wird Wismut bevorzugt als Citrat oder EDTA-Komplex, Zinn bevorzugt als Oxalatostannnat (IV) oder Zinn(II)- Gluconat -Komplex und Indium als Gluconat- bzw. EDTA-Komplex eingesetzt. Arsen und Antimon dient vorwiegend zur Härtesteigerung und Glanzbildung. Arsen wird bevorzugt in Form von Alkaliarsenitverbindungen, Antimon bevorzugt in Form von Alkaliantimonyltartrat eingesetzt. Die Konzentration der Legierungsmetalle kann in weiten Grenzen zwischen 10 mg/1 und 50 g/1 variieren. Die Konzentration der freien Komplexbildner im Bad kann zwischen 0,1 und 200 g/1 liegen.Bismuth is preferably used as citrate or EDTA complex, tin is preferably used as oxalatostannnate (IV) or tin (II) - gluconate complex and indium is used as gluconate or EDTA complex. Arsenic and antimony are used primarily to increase hardness and gloss. Arsenic is preferably used in the form of alkali arsenite compounds, antimony is preferably used in the form of alkali mononyl tartrate. The concentration of the alloy metals can vary within wide limits between 10 mg / 1 and 50 g / 1. The concentration of free complexing agents in the bath can be between 0.1 and 200 g / l.
Durch Zugabe weiterer Glanzbildner, wie Verbindungen von Selen und Tellur, beispielsweise als Alkaliselenocyanat , -selenit oder -tellurit in Konzentrationen von 0,1 mg/1- 1 g/1 können glänzende Legierungsschichten erhalten werden.By adding further brighteners, such as compounds of selenium and tellurium, for example as alkali selenate, selenite or tellurite in concentrations of 0.1 mg / 1 - 1 g / 1, shiny alloy layers can be obtained.
Der Zusatz von Leit- und Puffersubstanzen, wie Borate, Tetraborate, Phosphate, Citrate, Tartrate oder Gluconate der Alkalimetalle in Konzentrationen von 1-200 g/1 erhöhen die Leitfähigkeit und Streufähigkeit des Bades.The addition of conductive and buffer substances such as borates, tetraborates, phosphates, citrates, tartrates or gluconates of the alkali metals in concentrations of 1-200 g / 1 increase the conductivity and spreadability of the bath.
Der Zusatz von 0,01-10 g/1 Netzmittel reduziert nicht nur die Oberflächenspannung, sondern kann auch die Glanzbildung positiv beeinflussen. Verwendung finden z.B. ionische und nichtionische Tenside vom Ethylenoxidaddukttyp, wie Alkyl (Fettsäure-) oder Nonylphenolpolyglycolether mit Endgruppen als Alkohol, Sulfat, Sulfonat oder Phosphat sowie perfluorierte Verbindungen, wie Perfluoralkancarboxylate oder -sulfonate sowie kationische Tenside, z.B. Tetraalkyammoniumperfluoroalkansulfonate .The addition of 0.01-10 g / 1 wetting agent not only reduces the surface tension, but can also have a positive effect on gloss formation. For example, ionic and nonionic surfactants of the ethylene oxide adduct type, such as alkyl (fatty acid) or nonylphenol polyglycol ethers with end groups as alcohol, sulfate, sulfonate or phosphate, and perfluorinated compounds, such as Perfluoroalkane carboxylates or sulfonates and cationic surfactants, for example tetraalkyammonium perfluoroalkane sulfonates.
Erfindungsgemäß enthalten die Bäder somit:According to the invention, the baths thus contain:
0,5-30 g/1 Gold als Komplex mit schwefelhaltigen Verbindungen aus der Gruppe der0.5-30 g / 1 gold as a complex with sulfur-containing compounds from the group of
Mercaptosulfonsäuren bzw. ihrer Alkalisalze.Mercaptosulfonic acids or their alkali salts.
1-200 g/1 freie schwefelhaltige Verbindungen bzw. der Alkalisalze.1-200 g / 1 free sulfur-containing compounds or the alkali salts.
0-200 g/1 Leit- und Puffersubstanzen aus der Gruppe der Alkaliborate, -phosphate, -citrate, -tartrate,0-200 g / 1 conductive and buffer substances from the group of alkali borates, phosphates, citrates, tartrates,
-gluconate .-gluconate.
0-50 g/1 Legierungsmetall aus der Gruppe Silber, Kupfer, Cadmium, Indium, Zinn, Zink, Wismut, Arsen und Antimon in Form der genannten Komplexe und Verbindungen.0-50 g / 1 alloy metal from the group silver, copper, cadmium, indium, tin, zinc, bismuth, arsenic and antimony in the form of the complexes and compounds mentioned.
0-1000 mg/1 Glanzbildner aus der Gruppe Selen und Tellur in Form von Selenit, Selenocyanat oder Tellurid der Alkalimetalle.0-1000 mg / 1 brightener from the group selenium and tellurium in the form of selenite, selenocyanate or telluride of the alkali metals.
0-10 g/1 Netzmittel z.B. ionische und nichtionischeTenside vom Ethylenoxidaddukttyp wie Alkyl (Fettsäure-) oder Nonylphenolpolyglycolether mit Endgruppen als Alkohol, Sulfat, Sulfonat oder Phosphat sowie perfluorierte Verbindungen wie Perfluoralkancarboxylate oder Sulfonate sowie kationische Tenside, z.B.0-10 g / 1 wetting agent e.g. ionic and nonionic surfactants of the ethylene oxide adduct type such as alkyl (fatty acid) or nonylphenol polyglycol ether with end groups as alcohol, sulfate, sulfonate or phosphate and perfluorinated compounds such as perfluoroalkane carboxylates or sulfonates as well as cationic surfactants, e.g.
Tetraalkyammoniumperfluoroalkansulfonate . Folgende Beispiele sollen die Erfindung näher erläutern:Tetraalkyammonium perfluoroalkanesulfonates. The following examples are intended to illustrate the invention:
1. 5 g Gold als Gold-2-Mercaptoethansulfonat-Komplex, 20 g 2-Mercaptoethansulfonsäure und 50 g Dikaliumphosphat werden zu einem Liter gelöst. Der pH-Wert wird mit Natronlauge auf pH 10 eingestellt. Bei der anschließenden Elektrolyse bei 50°C und 1,5 A/dm2 wird auf einer Kupferkathode ein glatter, gleichmäßig haftender Goldüberzug von 5 μ Dicke erhalten. Das Bad ist nahezu geruchsfrei und zeigt auch bei längerer Elektrolyse keine Zersetzungserscheinungen.1. 5 g of gold as gold-2-mercaptoethanesulfonate complex, 20 g of 2-mercaptoethanesulfonic acid and 50 g of dipotassium phosphate are dissolved in one liter. The pH is adjusted to pH 10 with sodium hydroxide solution. In the subsequent electrolysis at 50 ° C. and 1.5 A / dm 2 , a smooth, uniformly adhering gold coating of 5 μ thickness is obtained on a copper cathode. The bath is almost odorless and shows no signs of decomposition even after prolonged electrolysis.
2. Setzt man dem Bad aus Beispiel 1 2 g eines Kupfer-2-Mercaptopropansulfonsäure-Komplexes zu, so erhält man bei der Elektrolyse rötliche Gold-Kupferschichten .2. If 2 g of a copper-2-mercaptopropanesulfonic acid complex are added to the bath from Example 1, reddish gold-copper layers are obtained in the electrolysis.
3. Setzt man dem Bad aus Beispiel 2 weitere 0,3 g3. Add another 0.3 g to the bath from Example 2
Kaliumoxalatostanna (IV) und 400 μg Kaliumselenocyanat als Glanzbildner zu und elektrolysiert bei 50°C und 2 A/dm2, so erhält man glänzende, rosefarbene Überzüge einer Gold-Kupfer-Zinn-Legierung.Potassium oxalatostanna (IV) and 400 μg potassium selenocyanate as a brightener and electrolyzed at 50 ° C and 2 A / dm 2 , so you get shiny, rose-colored coatings of a gold-copper-tin alloy.
4. 4 g Gold und 2 g Silber als Bis-4. 4 g of gold and 2 g of silver as bis
(3-Sulfopropyl) -disulfid-Komplexe, 30 g (3-Sulfopropyl) -disulfid, 50 g Natriumgluconat und 20 mg Kaliumtellurit werden zu einem Liter gelöst. Der pH-Wert wird mit Natronlauge auf 12 eingestellt. Bei der Elektrolyse bei 55°C und 1,5 A/dm2 erhält man auf einer Kupferkathode eine glänzende, grünlich-gelbe duktile Schicht einer Gold-Silber-Legierung. (3-sulfopropyl) disulfide complexes, 30 g (3-sulfopropyl) disulfide, 50 g sodium gluconate and 20 mg potassium tellurite are dissolved in one liter. The pH is adjusted to 12 with sodium hydroxide solution. Electrolysis at 55 ° C and 1.5 A / dm 2 gives a shiny, greenish-yellow ductile layer of a gold-silver alloy on a copper cathode.

Claims

Patentansprüche : Claims:
1. Cyanidfreies galvanisches Bad zur Abscheidung von Gold- und Goldlegierungsüberzügen, mit 0,5 bis 30 g/1 Gold in Form eines Komplexes einer schwefelhaltigen Verbindung, 0 bis 50 g/1 eines Legierungsmetalls in Form wasserlöslicher Verbindungen von Silber, Kupfer, Indium, Cadmium, Zink, Zinn, Wismut, Arsen und/oder Antimon, 1 bis 200 g/1 der freien schwefelhaltigen Verbindung, 0 bis 200 g/1 Leit- und Puffersalzen in Form von Alkaliboraten, -phosphaten, -citraten, - tartraten und/oder -gluconaten, dadurch gekennzeichnet, daß es als schwefelhaltige Verbindung des Goldkomplexes eine Mercaptosulfonsäure, eine Disulfidsulfonsäure, deren Salze oder Gemische dieser Verbindungen enthält.1. cyanide-free galvanic bath for the deposition of gold and gold alloy coatings, with 0.5 to 30 g / 1 gold in the form of a complex of a sulfur-containing compound, 0 to 50 g / 1 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 / 1 of the free sulfur-containing compound, 0 to 200 g / 1 conductive and buffer salts in the form of alkali borates, phosphates, citrates, tartrates and / or -gluconates, characterized in that it contains a mercaptosulfonic acid, a disulfide sulfonic acid, their salts or mixtures of these compounds as the sulfur-containing compound of the gold complex.
2. Cyanidfreies galvanisches Bad nach Anspruch 1, dadurch geken zeichnet, daß es eine Verbindung der allgemeinen Formel I2. Cyanide-free galvanic bath according to claim 1, characterized in that it is a compound of general formula I.
X-S-CHR- (CR'R' ' )n-S03H (I)XS-CHR- (CR'R '') n -S0 3 H (I)
worin bedeutetwhere means
X H oder der Rest -S-CHR- (CR' R' ' ) n-S03HXH or the rest -S-CHR- (CR 'R'') n -S0 3 H
R H, Alkyl oder Aryl mit bis zu 12 C-Atomen, S03HRH, alkyl or aryl with up to 12 C atoms, S0 3 H
R' ,R- ' R, OH, SH, NH2 R ', R-' R, OH, SH, NH 2
n die Zahlen 0 bis 6n the numbers 0 to 6
enthält. contains.
3. Cyanidfreies galvanisches Bad nach Ansprüchen 1 oder 2, dadurch gekennzeichnet , daß es 2 -Mercaptoethansulfonsäure, 3- Mercaptopropansulfonsäure, 2,3- Dimercaptopropansulfonsäure, Bis- (2 -Sulfopropyl) - disulfid, Bis- (3 -Sulfopropyl) -disulfid oder deren Alkalisalze enthält.3. Cyanide-free galvanic bath according to claims 1 or 2, characterized in that there are 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 2,3-dimercaptopropanesulfonic acid, bis (2-sulfopropyl) disulfide, bis (3-sulfopropyl) disulfide or whose alkali salts contains.
4. Cyanidfreies galvanisches Bad nach den Ansprüchen 1 bis 3 , dadurch gekennzeichnet, daß es 0,01 bis 10 g/1 Netzmittel in Form eines Tensids und 0,1 bis 1000 mg/1 Glanzmittel in Form von Selen- und/oder Tellurverbindungen enthält.4. Cyanide-free galvanic bath according to claims 1 to 3, characterized in that it contains 0.01 to 10 g / 1 wetting agent in the form of a surfactant and 0.1 to 1000 mg / 1 brightening agent in the form of selenium and / or tellurium compounds .
5. Verfahren zur galvanischen Abscheidung von Gold und Goldlegierungen aus einem cyanidfreien galvanischen5. Process for the galvanic deposition of gold and gold alloys from a cyanide-free galvanic
Bad, dadurch gekennzeichnet , daß die Abscheidung aus einem Bad nach den Ansprüchen 1 bis 4 erfolgt.Bath, characterized in that the separation from a bath is carried out according to claims 1 to 4.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet , daß das Bad bei einem pH-Wert von 7 bis 12 betrieben wird. 6. The method according to claim 5, characterized in that the bath is operated at a pH of 7 to 12.
EP97933686A 1996-07-23 1997-07-21 Cyanide-free electroplating bath for deposition of gold and gold alloys Expired - Lifetime EP0907767B1 (en)

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DE19629658A DE19629658C2 (en) 1996-07-23 1996-07-23 Cyanide-free galvanic bath for the deposition of gold and gold alloys
DE19629658 1996-07-23
PCT/EP1997/003903 WO1998003700A1 (en) 1996-07-23 1997-07-21 Cyanide-free electroplating bath for deposition of gold and gold alloys

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DE19629658A1 (en) 1998-01-29
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EP0907767B1 (en) 2002-02-13
US6165342A (en) 2000-12-26
JPH11513078A (en) 1999-11-09
DE19629658C2 (en) 1999-01-14
WO1998003700A1 (en) 1998-01-29

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